Metal Additive

Manufacturing
State of the Art 2020
Edited by
Nader Asnafi
Printed Edition of the Special Issue Published in Metals

www.mdpi.com/journal/metals
Metal Additive Manufacturing – State
of the Art 2020
Metal Additive Manufacturing – State
of the Art 2020

Editor
Nader Asnafi

MDPI • Basel • Beijing • Wuhan • Barcelona • Belgrade • Manchester • Tokyo • Cluj • Tianjin
Editor
Nader Asnafi
School of Science and Technolog
Örebro University
Örebro
Sweden

Editorial Office
MDPI
St. Alban-Anlage 66
4052 Basel, Switzerland

This is a reprint of articles from the Special Issue published online in the open access journal Metals
(ISSN 2075-4701) (available at: www.mdpi.com/journal/metals/special issues/metal additive
manufacturing 2020).

For citation purposes, cite each article independently as indicated on the article page online and as
indicated below:

LastName, A.A.; LastName, B.B.; LastName, C.C. Article Title. Journal Name Year, Volume Number,
Page Range.

ISBN 978-3-0365-1324-9 (Hbk)

ISBN 978-3-0365-1323-2 (PDF)

© 2021 by the authors. Articles in this book are Open Access and distributed under the Creative
Commons Attribution (CC BY) license, which allows users to download, copy and build upon
published articles, as long as the author and publisher are properly credited, which ensures maximum
dissemination and a wider impact of our publications.
The book as a whole is distributed by MDPI under the terms and conditions of the Creative Commons
license CC BY-NC-ND.
Contents

About the Editor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii

Preface to ”Metal Additive Manufacturing – State of the Art 2020” . . . . . . . . . . . . . . . . . ix

Nader Asnafi
Application of Laser-Based Powder Bed Fusion for Direct Metal Tooling
Reprinted from: Metals 2021, 11, 458, doi:10.3390/met11030458 . . . . . . . . . . . . . . . . . . . . 1

Suvi Santa-aho, Mika Kiviluoma, Tuomas Jokiaho, Tejas Gundgire, Mari Honkanen, Mari
Lindgren and Minnamari Vippola
Additive Manufactured 316L Stainless-Steel Samples: Microstructure, Residual Stress and
Corrosion Characteristics after Post-Processing
Reprinted from: Metals 2021, 11, 182, doi:10.3390/met11020182 . . . . . . . . . . . . . . . . . . . . 47

Stefan Roos and Lars-Erik Rännar

Process Window for Electron Beam Melting of 316LN Stainless Steel
Reprinted from: Metals 2021, 11, 137, doi:10.3390/met11010137 . . . . . . . . . . . . . . . . . . . . 63

Óscar Teixeira, Francisco J. G. Silva, Luı́s P. Ferreira and Eleonora Atzeni

A Review of Heat Treatments on Improving the Quality and Residual Stresses of the Ti–6Al–4V
Parts Produced by Additive Manufacturing
Reprinted from: Metals 2020, 10, 1006, doi:10.3390/met10081006 . . . . . . . . . . . . . . . . . . . 75

Markus Köhler, Jonas Hensel and Klaus Dilger

Effects of Thermal Cycling on Wire and Arc Additive Manufacturing of Al-5356 Components
Reprinted from: Metals 2020, 10, 952, doi:10.3390/met10070952 . . . . . . . . . . . . . . . . . . . . 99

Stefan Gneiger, Johannes A. Österreicher, Aurel R. Arnoldt, Alois Birgmann and Martin
Fehlbier
Development of a High Strength Magnesium Alloy for Wire Arc Additive Manufacturing
Reprinted from: Metals 2020, 10, 778, doi:10.3390/met10060778 . . . . . . . . . . . . . . . . . . . . 111

Gregory Peter Le Sage

Thermal Frequency Drift of 3D Printed Microwave Components
Reprinted from: Metals 2020, 10, 580, doi:10.3390/met10050580 . . . . . . . . . . . . . . . . . . . . 125

Anika Langebeck, Annika Bohlen, Rüdiger Rentsch and Frank Vollertsen

Mechanical Properties of High Strength Aluminum Alloy EN AW-7075 Additively
Manufactured by Directed Energy Deposition
Reprinted from: Metals 2020, 10, 579, doi:10.3390/met10050579 . . . . . . . . . . . . . . . . . . . . 137

Martin R. Gotterbarm, Alexander M. Rausch and Carolin Körner

Fabrication of Single Crystals through a µ-Helix Grain Selection Process during Electron Beam
Metal Additive Manufacturing
Reprinted from: Metals 2020, 10, 313, doi:10.3390/met10030313 . . . . . . . . . . . . . . . . . . . . 145

Diana Chioibasu, Liviu Duta, Gianina Popescu-Pelin, Nicoleta Popa, Nichita Milodin,
Stefana Iosub, Liliana Marinela Balescu, Aurelian Catalin Galca, Adrian Claudiu Popa, Faik
N. Oktar, George E. Stan and Andrei C. Popescu
Animal Origin Bioactive Hydroxyapatite Thin Films Synthesized by RF-Magnetron Sputtering
on 3D Printed Cranial Implants
Reprinted from: Metals 2019, 9, 1332, doi:10.3390/met9121332 . . . . . . . . . . . . . . . . . . . . 161

v
Wadea Ameen, Muneer Khan Mohammed and Abdulrahman Al-Ahmari
Evaluation of Support Structure Removability for Additively Manufactured Ti6Al4V
Overhangs via Electron Beam Melting
Reprinted from: Metals 2019, 9, 1211, doi:10.3390/met9111211 . . . . . . . . . . . . . . . . . . . . 183

vi
About the Editor
Nader Asnafi
Nader Asnafi is a Professor of Mechanical Engineering at ¨Orebro University. Nader has
extensive academic and industrial experience as the Director of Studies at Luleå University of
Technology, Researcher and Research Group Leader at the Swedish Institute for Metals Research,
Head of Mechanical Properties at Sapa Technology, Manager of Product Design, Advanced
Engineering and Technology Development at Volvo Cars Body Components, Senior Manager of
Research and Advanced Engineering at Volvo Cars, Dean of the School of Engineering at Blekinge
Institute of Technology, Vice President—R&D at Uddeholms AB, and Vice President and Head of
Development at VA Automotive.

vii
Preface to ”Metal Additive Manufacturing – State of
the Art 2020”
Additive manufacturing (AM), more popularly known as 3D printing, comprises a group
of technologies used to produce objects through the addition (rather than removal) of material.
AM is used in many industries—aerospace, defense, automotive, consumer products, industrial
products, medical devices, and architecture. AM is transforming the industry, and this industrial
transformation is expected to become more comprehensive and quicker during the coming years.
Additive manufacturing of metal components with virtually no geometric limitations has
enabled new product design options and opportunities, increased product performance, shorter cycle
time in part production, total cost reduction, shortened lead time, improved material efficiency, more
sustainable products and processes, full circularity in the economy, and new revenue streams.
This Special Issue of Metals focuses on metal additive manufacturing with respect to:
- business models and engineering;
- product/component design (including generative design, topology optimization, and lattice
and surface optimization);
- industrial applications (aerospace, defense, automotive, consumer, medical, and industrial
products);
- material and process design and engineering;
- new materials;
- powder production and characterization;
- systems and equipment engineering;
- post-processing;
- process control and optimization and quality assurance.

The papers presented in this Special Issue give an up-to-date account of the scientific,
technological, and industrial state of the art for metal additive manufacturing from the perspectives
mentioned above.
I would like to express my sincere gratitude to the authors, reviewers, Section Managing Editor
Ms Lyra Xing, and Editorial Office of Metals who have made this 2020 account possible through
high-quality research and development, highly valuable perspectives and comments, and highly
efficient collaboration in a pleasant and collegial environment.

Nader Asnafi
Editor

ix
 metals
Review
Application of Laser-Based Powder Bed Fusion for Direct
Metal Tooling
Nader Asnafi

School of Science and Technology, Örebro University, SE-701 82 Örebro, Sweden; [email protected];
Tel.: +46-19-301-493

Abstract: The journey of production tools in cold working, hot working, and injection molding from
rapid tooling to additive manufacturing (AM) by laser-based powder bed fusion (L-PBF) is described.
The current machines and their configurations, tool steel powder materials and their properties, and
the L-PBF process parameters for these materials are specified. Examples of production tools designed
for and made by L-PBF are described. Efficient design, i.e., high tooling efficiency and performance
in operation, should be the primary target in tool design. Topology and lattice structure optimization
provide additional benefits. Using efficient design, L-PBF exhibits the greatest potential for tooling in
hot working and injection molding. L-PBF yields high tooling costs, but competitive total costs in
hot working and injection molding. Larger object sizes that can be made by L-PBF, a larger number
of powder metals that are designed for different tooling applications, lower feedstock and L-PBF
processing costs, further L-PBF productivity improvement, improved surface roughness through
L-PBF, and secured quality are some of the targets for the research and development in the future.
A system view, e.g., plants with a high degree of automation and eventually with cyber-physically
controlled smart L-PBF inclusive manufacturing systems, is also of great significance.





 Keywords: rapid tooling; additive manufacturing (AM); laser-based powder bed fusion (L-PBF);
production tools; cold working; hot working; injection molding
Citation: Asnafi, N. Application of
Laser-Based Powder Bed Fusion for
Direct Metal Tooling. Metals 2021, 11,
458. https://doi.org/10.3390/
met11030458 1. Introduction
To build objects by adding many very thin layers of material, layer on top of layer,
Academic Editor: Massimo Pellizzari has historically attracted some attention. The progress made during the past 40 years has,
however, been the greatest and most profound.
Received: 30 January 2021 Technologically, it was held that such a layer-by-layer manufacturing was the com-
Accepted: 6 March 2021 mon denominator of (a) computer aided design (CAD), i.e., solid modelling, (b) enabling
Published: 10 March 2021
technologies, i.e., laser, ink-jet printers and motion control, and (c) traditional technolo-
gies, i.e., powder metallurgy, welding, extrusion, computerized or computer numerically
Publisher’s Note: MDPI stays neutral controlled (CNC) machining, and lithography.
with regard to jurisdictional claims in
Industrially, rapid prototyping would enable a fast visualization and evaluation of
published maps and institutional affil-
the product design and a rapid tooling would shorten the time-critical toolmaking in the
iations.
industrialization of new products (and thereby reduce the time to market).
Rapid tooling, particularly direct rapid tooling, through layer-by-layer toolmaking
evolved in the middle of 1990s. Direct rapid tooling was defined as an industrial concept
aimed at the realization of production tooling through layered manufacturing directly from
Copyright: © 2021 by the author. CAD data files.
Licensee MDPI, Basel, Switzerland. As far as layered manufacturing is concerned, several methods have been developed.
This article is an open access article
Selective laser sintering (SLS), one of the methods that were developed initially, was
distributed under the terms and
launched in 1995. This method evolved to selective laser melting (SLM). In these methods,
conditions of the Creative Commons
a thin layer of metal powder is sintered or melt. A steel powder based SLM machine was
Attribution (CC BY) license (https://
launched in 1999.
creativecommons.org/licenses/by/
4.0/).

Metals 2021, 11, 458. https://doi.org/10.3390/met11030458 https://www.mdpi.com/journal/metals

Metals 2021, 11, 458

At the same, a similar technology, in which an electron beam is used instead of a laser
beam, was developed for metallic materials. This paper is focused on metallic materials
and SLM.
Now after two decades, the so-called layered manufacturing and SLM are standard-
ized to additive manufacturing (AM) and laser-based powder bed fusion (L-PBF). The
remarkable advances in AM and L-PBF in the past two decades have resulted in production
tooling that is highly advanced both in design and performance.
This paper is an account of how production tools can be made today thanks to the
scientific and technological advances during the past 20 years. To be brief, this account
focuses on the “newness”. For instance, machining and heat treatment are not mentioned
in this paper. (Machining is in many cases used to post-process a production tool made by
L-PBF to improve its surface roughness).
This account comprises:
• A brief history of direct rapid tooling by SLS/SLM.
• A brief description of L-PBF.
• A brief account of applications and materials for production tooling.
• The L-PBF process parameters for these materials.
• The new tooling design ingredients, i.e., generative design and topology and lattice
structure optimization, primarily as an amplifier of and important complement to L-PBF.
• Examples of tooling applications designed for and made by L-PBF. These examples,
which are from cold and hot working and injection molding, illustrate the results
of the advances made during the past 20 years and the yet greater future potential
in toolmaking.
• Discussions including a future outlook and
• Conclusions.
The methodology used to create this review is described in Appendix A.

2. Direct Rapid Tooling by Selective Laser Sintering/Melting—Brief History as a Baseline

The process of building objects by adding many very thin layers of material, layer on
top of layer, has historically had several names. Solid freeform fabrication (SFF) through
layered manufacturing in order to accomplish rapid prototyping (RP) can trace its roots
back to the 19th century, particularly the fields of topography and photosculpture [1,2].
Early SFF examples were proposed by Swainson in 1968, Ciraud in 1971, Kodama
in 1981, and Herbert in 1982 [1]. After a few years, Hull invented the stereolithography
machine (SLA) in 1986. This machine is considered to be the first 3D printer [2].
It was held that SFF was the common denominator of the following [1]:
• Computer aided design (CAD): Solid modelling.
• Enabling component technologies: Laser, ink-jet printers and motion control.
• Traditional technologies: Powdered metallurgy, welding, extrusion, CNC machining
and lithography.
The various SFF building strategies and deposition/fusion processes included pho-
tolithography, laser fusion, lamination, extrusion, and ink-jet printing.
Product creation comprises chiefly product design/development and industrializa-
tion. Once the design is accepted, the realization of the production line, in particular the
preparation of complex production tooling (tools, dies, and molds), is time-critical in the
industrialization phase and has therefore a direct and strong influence on time-to-market.
RP through SFF (or layered manufacturing), used to visualize and evaluate the results of
product design (or development phase of a product), evolved in the middle of 1990s toward
rapid tooling (RT). This extension was caused by the need to further reduce the time-to-
market by shortening, not only the development phase, but also the industrialization phase
of product creation [3–6].
RT was divided into non-direct RT and Direct RT (DRT):

2
Metals 2021, 11, 458

• Non-direct RT: SFF techniques shortening the classical/traditional toolmaking meth-

ods, e.g., using SLA to make a pattern for investment casting, resin tooling, etc., [7].
SLA, FDM (fused material deposition), LOM (laminated object manufacturing), and
SLS-P (P = polymers) were used to accomplish non-direct RT.
• DRT: techniques requiring no intermediate steps in the manufacture of tools. In
other words, DRT was defined as an industrial concept aimed at the realization of
production tooling directly from CAD data files, with the smallest possible process
chain (number of operations). Its purpose was the manufacture of tools that can be
used under normal production conditions, in terms of durability, accuracy and surface
quality. LG (laser generation), SLS-M (M = metals), SLS-PM (selective laser sintering
of polymer-coated metal powder), and 3DP (three-dimensional printing) were used to
accomplish DRT [8–10].
The present paper is focused on DRT by SLS-M. As far as SLS-M is concerned, several
parallel tracks were followed by different researchers. The research and development by
Deckard and Beaman at the University of Texas in Austin, [11], resulted in Sinterstation
2000—the first proper commercial system for laser-sintering launched by DTM Corporation
of Austin in December 1992 [12,13]. DTM used the Sintersation to laser-sinter a polymer-coated
metal powder to form a green part, followed by a furnace process to remove the polymer,
bond the metal matrix and infiltrate it with a secondary metal to remove the porosity [14]. This
process was called “RapidTool” and commercially released at the end of 1995.
EOS GmbH of Munich collaborated with Electrolux Rapid Development (ERD) of
Rusko, Finland, and Nyrhilä that were involved in the development of Direct Metal Laser
Sintering (DMLS). ERD was focused on powder metallurgy development and Nyrhilä
had invented a novel powder concept for pressureless metal sintering with very low
shrinkage in 1989 [15]. This collaboration resulted in development and installation of the
first commercial DMLS system, EOSINT M 250, in the summer of 1995 [12,13]. This opened
up the first real commercial use of DMLS for rapid tooling [12].
This equipment was used in 1996 to make injecting molding tools. One of these
tools (which comprised 11 parts) was laser-sintered in the nickel-bronze mixture (Ni-Bz)
developed by ERD and infiltrated with high temperature epoxy resin within 45 h. After
sanding, polishing, integrating the gating system and the ejectors, Electrolux assembled
the mold and produced approximately 100 mobile phone housings in PC/ABS using
standard parameters. An overall accuracy of ±0.1 mm was reached [10]. The same mold
was traditionally made in aluminium.
The time from completed CAD data to producing the injected parts in series material
took Electrolux four weeks and cost DM 30,000 (DM = Deutsche Mark). This was considered
as a remarkable reduction in time and costs for manufacturing injection mold prototypes
and small batches of components [10].
SLS-M attracted great attention and many studies were conducted to explore the
possibilities, optimize the process and develop DRT further [16–19].
At the same time, the researchers and device/equipment manufacturers were aware
of the shortcoming of the DRT techniques that were available in 1995. These techniques
allowed only the fabrication of pre-series or short-run tools, could not yield sufficiently
high properties for demanding tools, e.g., forging dies, and required time consuming
post-sintering through infiltration.
Porosity, part shrinkage, and thermal and mechanical instability were some additional
problems. The nickel-bronze mixture developed by Nyrhilä and ERD, [15], exhibited a
near-zero shrinkage and minimal curl and warpage [10] when laser-sintered without any
protecting gas. However, it was known that oxidation before, during and after sintering of
other metal powders would result in lower yield strength, cracks etc., and must therefore
be prevented. Parameters influencing the accuracy, such as laser scan speed, laser power,
powder delivery, powder properties, powder compaction, post-processing, etc. should be
tested, evaluated, and optimized [3,10].
Many research projects were carried out to remedy these shortcomings [12,13,20–22].

3
Metals 2021, 11, 458

The successful efforts at Fraunhofer ILT to accomplish fully dense metal objects by
complete melting (SLM) showed how the SLS process needed to be altered. For SLM, the
chamber needed to be closed/shielded and flooded with an inert gas like argon so that
the wetting properties of the melt were not reduced by formation of an oxide skin layer.
The metal powder was, as wished, processed without any binder material and without
any kind of pre-treatment. However, the particle shape must be spherical with a size in
the range of 20–50 µm. To melt the powder particles completely, as shown in Figure 1,
fundamental investigations of the physical interrelations between the process parameters
and the behavior of the metal melt were carried out. Laser power, scan speed, hatch
distance and layer thickness appeared to be interrelated and crucial for the processing
results. The influence of scanning strategies and protection gas flow was determined. In
addition, a special scanning strategy with a limited length of each scan vector had to be
used to achieve a high density of the parts [20,22].

Figure 1. Melting process of single component powder with a laser beam: (a) porous structure with
SLS and (b) dense structure with SLM [22].

With this developed procedure, objects in stainless steel 316L, TiA16V4 and DIN 1.2343
(H11) were made with a density of 99%. Infiltration to improve density and strength was no
longer necessary. Figure 2 shows a couple of tools made by the then newly developed SLM.
The slider for a die casting tool made by SLM in DIN 1.2343, Figure 2a), was fitted into the
conventionally made tool. 4800 housings in AlSi12 were produced in this tool at a casting
temperature of 700 ◦ C and a pressure of approx. 800 bar without any visible tool wear. The
injection molding tool in Figure 2b) was made by SLM in stainless steel 316L. It took ca 4 h to
make the core and ca 7 h to make the cavity. After SLM, the mold release surfaces had to be
manually smoothed and the core and cavity had to be fitted into the mother tool. This tool
was used to produce thermoplastic parts as well as rubber parts [22]. See also [23].

Figure 2. Tools made by the then (1999) newly developed selective laser melting (SLM): (a) slider for
a die casting tool made in 1.2343 and (b) injection molding tool made in 316L [22].

4
Metals 2021, 11, 458

3. Laser-Based Powder Bed Fusion (L-PBF)

During the past 15 years, layered manufacturing has been subject to further research
studies, standardization and industrialization. According to the developed standards, the
technology is named Additive Manufacturing (AM). Laser-based powder Bed Fusion
(L-PBF), formerly SLM (Figure 1b), is one of the seven AM basic process categories in the
new standards [24–27]. For a detailed description of L-PBF, see [28–32].
Table 1 displays the features of the current (2020) machines for AM by L-PBF. This
table, which is based on the machine makers specifications, show that the maximum object
size that can be 3D-printed today is 600 × 600 × 600 mm3 (although the largest height is
850 mm in one of the other machines). This size has more than doubled compared to that
in the 1995 machine for selective laser sintering. In addition to higher laser power, some of
the current machines have more than one laser and therefore a much higher productivity.
Due to the complexity of L-PBF, the manufacturers of metal AM systems have de-
veloped sets of optimized processing conditions for some existing powder metals. The
machine manufacturer sets the process parameters for one or some specific powder metals
as the default values for additive manufacturing based on the customer preferences before
machine delivery and installation, Table 2. The number of these powder metals is much
larger than those in 1995. However, this number is still very small, compared to the number
of existing materials made and used conventionally.
Table 1. The features of the current L-PBF machines [33–39].

Laser Power Build Volume Layer Scan

Number and Build
Manufacturer Model (per Laser) (l × w × h) Thickness Speed
Type of Lasers Rate (cm3 /hr)
(W) (mm3 ) (µm) (m/s)
DMP Factory 500 Printer Module 3 fiber 500 500 × 500 × 500 1 - 2–200, Typical: 30, 60 & 90 -
DMP Factory/Flex 350 1 fiber 500 275 × 275 × 420 - 5–200, Typical: 30, 60 & 90 -
3D Systems DMP Flex 100 1 fiber 100 100 × 100 × 90 - 10–100 -
ProX DMP 300 1 fiber 500 250 × 250 × 330 - 10–100, preset: 40 -
ProX DMP 200 1 fiber 300 140 × 140 × 115 - 10–100, preset: 30 -
Additive
MetalFAB1 1 to 4 Yb fiber 500 420 × 420 × 400 - 20–100 -
Industries
X Line 2000R 2 (cw) fibre 1000 800 × 400 × 500 - - -
Concept Laser M Line Factory 4 fiber 1000 500 × 500 × 400 - - -
M2 Multilaser 2 (cw) fiber 400 250 × 250 × 350 - - -
EOS M 400-4 4 Yb-fiber 400 1 100 80 7
400 × 400 × 400
EOS M 400 1 Yb-fiber 400 400 × 400 × 400 1 50 - 7

EOS EOS M 300-4 4 Yb-fiber 400 300 × 300 × 400 10 - 7

EOS M 290 1 Yb-fiber 400 250 × 250 × 325 1 - - 7
EOS M 100 1 Yb-fiber 200 1&2 - - 7
f100 × 95
SLM® NXG XII 600 12 1000 600 × 600 × 600 1000 - -
SLM® 800 4 400 or 700 500 × 280 × 850 1 Up to 171 20–90 10

SLM Solutions SLM® 500 4 IPG fiber 700 500 × 280 × 365 1 Up to 171 20–75 10

® 400, 700, or 1
SLM 280 1, 2, 3 or dual 280 × 280 × 365 Up to 113 20–90 10
700 & 1000
SLM® 125 1 IPF fiber 400 125 × 125 × 125 1 Up to 25 20–75 10
RenAM 500Q/S 1 or 4 Yb-fiber 500 1 Up to 150 20–100 10
250 × 250 × 350
RenAM 500E 1 Yb-fiber 500 1 Up to 150 20–100 10
250 × 250 × 350
Renishaw RenAM 500M 1 Yb-fiber 500 250 × 250 × 350 1 Up to 150 20–100 10
AM 400 1 400 250 × 250 × 300 1 - - -
AM 250 is now replaced by AM 400 1 - - -
250 × 250 × 300
TruPrint 1000 1 fiber 200 f100 × 100 1 & 2 2–18 10–50 -
TruPrint 2000 1 fiber 300 f200 × 200 2 - 20–100 -
Trumpf
TruPrint 3000 1 fiber 500 2 5–60 20–150 -
f300 × 400
TruPrint 5000 3 fiber 500 f300 × 400 2 5–180 30–150 -
1 Height includes the thickness of the substrate/building plate. 2 Diameter × height.
5
Metals 2021, 11, 458

Table 2. Materials the current machines L-PBF machines can be set in for upon installation [33–39].

Manu- Powder Metals Based on . . .

Facturer Model
Al Co Cu Fe Ni Ti W
DMP Factory 500 Printer Module By request Nickel alloys By request
AlSi7Mg0.6, Maraging Steel, Ti Gr1, Ti Gr5,
DMP Factory/Flex 350 CoCrF75 - Ni625, Ni718 -
AlSi10Mg 17-4PH, 316L Ti Gr23
3D
Systems DMP Flex 100 - CoCr - 17-4PH, 316L - - -
Maraging steel,
ProX DMP 300 AlSi12 CoCr - - - -
17-4PH
Maraging steel,
ProX DMP 200 AlSi12 CoCr - - - -
17-4PH, 316 L
Additive AlSi10Mg,
MetalFAB1 - - Tool steel 1.2709, 316L IN718 Ti6Al4V -
Industries ScalmAlloy©
AlSi10Mg—
Ti6AL4V
X Line 2000R Balanced & - - - Nickel 718 -
Grade 23
Productivity
Concept
Laser M Line Factory A205 CoCrMo - - Nickel 718 CL - -
AlSi10Mg, Maraging M300, Nickel 625, Ti6AL4V
M2 Multilaser CoCrMo - -
AlSi7Mg 316L, 17-4PH Nickel 718 Grade 23
Ti64, TiCP
EOS M 400-4 AlSi10Mg - - MS1, 316L HX, IN718 -
Grade 2
EOS M 400 AlSi10Mg - - MS1 IN718 Ti64, Ti64ELI -
EOS EOS M 300-4 AlSi10Mg - - MS1 IN718 Ti64 -
MS1, CX, PH1, HX, IN625, Ti64, Ti64ELI,
EOS M 290 AlSi10Mg MP1 - -
17-4PH, 316L IN718 TiCP Grade 2
EOS M 100 - SP2 - 316L - Ti64 W1
ALSi10Mg (No IN718 (No
SLM® NXG XII 600 No limitations No limitations
limitations) limit.)
SLM® 800
SLM Maraging 1.2709, Ti6Al4V ELI
Solutions SLM® 500 AlSi10Mg, CoCr28Mo6, 316L (1.4404), 15-5PH (Grade 23),
CuSn10, HX, IN625, -
AlSi7Mg0.6, SLM® (1.4545), 17-4PH TA15, and Ti
SLM® 280 CuNi2SiCr IN718, IN939
AlSi9Cu3 MediDent (1.4542), H13 (1.2344), (Grade 2)
Invar 36®
SLM® 125
RenAM 500Q/S
RenAM 500E
Renishaw RenAM 500M AlSi10Mg CoCr - Maraging M300, 316L IN625, IN718 Ti6Al4ELI -
AM 400
AM 250
TruPrint 1000 Yes to all except W + precious metal alloys + amorphous metals
TruPrint 2000 Yes to all except Cu and W + amorphous metals
Trumpf
TruPrint 3000 Yes to all except Co, Cu and W
TruPrint 5000 Yes to all except Co, Cu and W

4. Production Tooling—Applications and Materials

Production tooling is required in many different industrial applications. Cutting
(material removal), cold working, hot working, and injection molding are some of these
applications. However, cutting tools (material removal) are not covered in this review.
As displayed in Figure 3, the tool material has a large influence on the tool life.
Tool material selection is based on (a) the required tool performance during the intended
application and (b) the manufacturing of the tool. As far as the tool production is concerned,
the tool material machinability, polishability, and heat treatment response are of great
significance. Toughness, wear resistance, hot hardness, and resistance to softening are
some of the important performance factors.
The failure mechanism encountered in cold working tools, e.g., stamping tools and
dies, comprise abrasive and adhesive wear or mixed wear (caused by sliding contact),
chipping at cutting edges and corners (fatigue), plastic deformation (exceeding the yield
strength locally), cracking (fatigue), and galling (the same mechanism as in adhesive wear).
The tool concept (tool material, hardness, surface roughness and treatment) is highly
6
Metals 2021, 11, 458

related to the workpiece material (sheet material grade, surface and thickness). The tool
concept for 1-mm thick hot-dip galvanized DP600 steel sheet differs therefore from that for
1-mm thick uncoated DP1000 steel sheet [40–42].

Figure 3. Factors that influence the tool life.

For hot-working tools, i.e., tools and dies in high pressure die casting, hot forging, hot
stamping, or extrusion, thermal fatigue (heat checking), corrosion/erosion, cracking (total
failure), and indentation are some of the failures that need to be avoided. Thermal fatigue
is dependent upon thermal expansion coefficient (should be low), thermal conductivity
(should be high), hot yield strength (should be high), temper resistance (a good resistance
to softening at high temperature exposure), creep strength (should be high), and ductility.
In other words, the tool should display resistance to deformation, softening, wear, impact
loading and corrosion/erosion at the working temperature, [43–45].
Some injection molds are likely to be exposed to corrosion, since the plastic materials
can produce corrosive by-products, e.g., PVC, and/or due to condensation caused by
prolonged production stoppages, humid operating or storage conditions. In such cases, a
stainless tool steel is required. Through-hardened molds are used, if the production runs
are long, abrasion from certain molding materials needs to be avoided, and/or the closure
or injection pressures are high. However, large molds and molds with low demands on
wear resistance can be made in pre-hardened steel. Good polishability and excellent surface
finish are key requirements for many injection molds [46,47].
Tool steels are classified according to composition, hardness, properties, or application.
According to the classification system developed by the American Iron and Steel Institute
(AISI), tool steels can be subdivided in seven different groups, based on prominent char-
acteristics such as alloying elements, heat treatment and application. These groups are
displayed in Table 3. The properties of some of these conventionally common tool steels
are displayed in Table 4.

Table 3. AISI classification of (conventional) tool steels [48,49].

AISI Prefix Important Group Principal Alloying

Examples of Applications
Classification (AISI Standards) Characteristics Elements
M
C, Mo, W, V, Cr
(Mo type) High hardness for high speed cutting of materials,
High speed steels Cutting (material removal) tools.
T red hardness.
C, W, V, Cr, Co
(W type)
A
(medium alloy Deep hardening in air (up to 100 mm). C, Mn, Cr, Mo
air hardening)
D Tools/dies/punches for blanking,
High wear resistance at normal temperatures. C, Cr, (Mo) coining and forming.
(high C, high Cr)
Cold-work steels
O
High wear resistance at normal temperatures. Varies
(oil hardening)
W
Group W exhibits higher toughness than group L. C Woodworking tools, coining tools.
(water hardening)

7
Metals 2021, 11, 458

Table 3. Cont.

AISI Prefix Important Group Principal Alloying

Examples of Applications
Classification (AISI Standards) Characteristics Elements
H Dies for extrusion of Al and Mg.
Deep hardening, high toughness. C, Cr, W, (V)
(Cr type) Hot rolling, hot forging.
H
Hot-work steels C, W, V, Cr, Co Hot rolling, hot forging.
(W type) Greater thermal stability than the Cr type.
Extrusion dies for brass,
H, Properties similar to high speed steels.
C, Mo, W, V, Cr, Co Ni alloys and steels.
(Mo type)
Shock-resisting steels S High shock loading resistance. Mn, Si, Cr, W, Mo Chisels, hammers, and punches.
Molds,
Mold steels P Low softening resistance at elevated temperature. Cr, Ni
Critical finish molds.
Special purpose steels L Low alloyed steels. Cr, V, Ni, Mo Various.

Table 5 shows the most common powder steels used to make tools by L-PBF. The
number of these tool steels for L-PBF is, as displayed in this table, still very limited. M789
AMPO, L-40, W360 AMPO and AM Corrax were launched within the past 2–3 years, while
the maraging steel grade 300, the stainless steels 316L and 17-4PH, and the tool steel H13
have been studied more thoroughly in tooling applications much longer.

Table 4. Some of the properties of some common conventional tool steels. All values labelled with 1 are from [50]. All
other values are extracted from [48].

Yield Ultimate Tensile Usual Working Thermal

AISI AISI W.-Nr. Wear Hot
Strength Strength Hardness Conductivity Machinability Tougness
Classification (USA) (Germany) Resistance Hardness
(MPa) (MPa) (HRC) (W/(mK)) 1
2210 1
M3:2 1.3344 - (hardened to 63–66 26 4 8 3 8
High speed 68 HRC)
steels 2240 1
T15 1.3202 - (hardened to 64–68 21 1 9 1 9
69 HRC)
A2 1.2363 - 1858 2 57–62 38 8 6 4 5
1510 1 2000 1
D2 1.2379 (hardened (hardened 58–64 31 3 8 2 6
Cold-work to 62 HRC) to 62 HRC)
steels
O1 1.2510 1538 3 1710 3 57–62 43 8 4 3 3
2320 1
W1 1.1545 - 72 1 48
(hardened)
H11 1.2343 1482 1806 38–55 42 8 3 9 6
1820 1
H13 1.2344 - (hardened to 40–53 29 8 3 9 6
Hot-work 56 HRC)
steels
H21 1.2581 1193 1379 50–55 27 6 4 8 8
2210 1
H41 - - 68 1 28
(hardened)
Shock- 1840 1
resisting S1 1.2550 - (hardened to 50–58 41 8 4 8 5
steels 57 HRC)
Mold steels P20 1.2311 1172 4 1310 4 30–50 45 8 1a 8 2a
Special
1546 5 1605 5
purpose L2 1.2210 45–60 44 8 1 7 2
with V with V
steels

1 The values are from [50]. (All other values are extracted from [48].). 2 Hardened from 945 ◦ C/Tempered at 540 ◦ C. 3 Oil quenched/tempered
at 425 ◦ C. 4 After oil quenching from 845 ◦ C and tempering 2 h at 205 ◦ C. 5 Oil quenched from 840 ◦ C/tempered at 425 ◦ C.

Table 5. L-PBF: the major tool powder steels so far and the associated tooling applications.

Class Name/AISI Designation DIN Designation Tooling Applications

18Ni-Grade 300
1.2709 Cold and hot forming, injection molding etc.
(See also Böhler M722 AMPO)
Maraging steel
Böhler M789 AMPO - Injection molding, plastic extrusion, tool holders etc.
Formetrix L-40 - Injection molding etc.

8
Metals 2021, 11, 458

Table 5. Cont.

Class Name/AISI Designation DIN Designation Tooling Applications

316L 1.4404 Injection molding etc.
Extrusion (metal powder and additives (polymers and waxes)),
Stainless steel 17-4PH 1.4542
Injection molding etc.
420 1.4021 Injection molding etc.
M2 1.3343 Cutting etc.
H13 1.2344 Hot forging, die casting, extrusion and injection molding
Tool steel Extrusion, hot forging, hot stamping, injection molding,
Böhler W360 AMPO -
high-pressure die casting
Uddeholm AM Corrax - Extrusion of plastic, injection molding

The chemical compositions of these powder steels are shown in Table 6. The properties
of the tools made by L-PBF in these powder steels are displayed in Table 7. These tables are
based on [33,51–62].
Maraging steel has been used widely in additive manufacturing for applications,
where high strength, toughness and ductility at high hardness and dimensional stability
are required. Maraging steel’s low-carbon soft martensitic matrix is mostly free from
interstitial alloying elements, which rank it as an excellent candidate for synthesis by AM
and welding [63].
316L is used in a large variety of applications where the tool is in contact with corro-
sive media at moderate temperatures during service. In, for instance, injection molding,
where an overlap of corrosion resistance and increased mechanical strength and hardness
(compared to austenitic stainless steels) is required, the so-called PH steel grades such
as 17-4PH (i.e., the maraging-type precipitation-hardened martensitic stainless steels) are
used [51]. See also Tables 5–7.
420 is the only martensitic stainless steel grade in use so far. The phase content of the
microstructure depends strongly on the chosen process parameters. In L-PBF (where the
laser power is high), the process can result in retained austenite as well. This will in turn
yield a hardness that is comparable with the wrought material [57]. See Tables 6 and 7.
As displayed in Table 6, low carbon maraging steels and carbon-bearing tool steels
(e.g., M2 and H13) are used in toolmaking by L-PBF. Martensite with precipitates is the
microstructure in both. In the case of carbon-bearing tool steels, the martensitic matrix
without precipitates obtained upon quenching is hard and brittle and tempering serves
to regain some ductility by precipitating carbon from the martensite matrix in the form
of carbides. In the case of the high-Ni maraging steels, quenching leads to a comparably
soft and ductile martensitic microstructure which gains its strength by precipitation of
intermetallic-phase particles upon ageing [51,63]. See also Table 7.
Since the cooling rates in L-PBF are high, martensite is formed in both maraging and
tool steels during AM. Therefore, maraging steels with a ductile martensitic microstructure
are well processable in AM while carbon-bearing tool steels (M2 and H13) with a brittle
martensitic microstructure tend to crack due to the thermal stresses during the AM. A
considerable fraction of the literature on carbon-bearing tool steels regard the optimum
process parameters to make crack free, dense samples. In contrast, for maraging steels most
studies are aimed at optimizing microstructures, mechanical properties and post process
heat treatments [51,63]. See also Tables 6 and 7.
The conducted investigations show that crake free and fully dense tools can be made
by L-PBF in the materials displayed in Tables 5–7 [51,54–60,63]. See also [62].

9
Metals 2021, 11, 458

Table 6. The chemical composition of the major tool powder steels for additive manufacturing.

Alloying Elements (wt.%), (Fe = Balance)

Class Name/Designation
C Mn P Si Cr Mo Co Ni V Al Ti Nb Cu N S W Ref.
18Ni-Grade 300 (M722 AMPO, [33], see
≤0.03 ≤0.15 ≤0.01 ≤0.10 - 4.5–5.20 8.5–10.0 17.0–19.0 - - 0.8–1.2 - - - ≤0.01 -
DIN 1.2709) also [51]
Maraging
steel M789 AMPO <0.02 - - - 12.2 1.0 - 10.0 - 0.6 1.0 - - - - - [52]]
Formetrix L-40 <0.1 - - - >10.5 <5.0 - <5.0 - - - <1.0 <1.0 <1.0 - - [53]
AISI 316L [33], see
≤0.03 ≤2.0 ≤0.045 ≤1.0 16.5–18.5 2.0–2.5 - 10.0–13.0 - - - - - ≤0.11 ≤0.03 -
(DIN 1.4404) also [54]
Stainless 17-4PH +Ta [33], see
<0.07 <1.0 < 0.04 <1.0 15.0–17.5 - - 3.0–5.0 - - - 3.0–5.0 - <0.03 -
steel (DIN 1.4542) 0.15–0.45 also [51]
AISI 420
0.3 0.72 0.012 0.79 12.8 0.5 - 1.0 - - - - - 0.09 0.008 - [56]
(DIN 1.4021)
AISI M2
0.9 0.38 - 0.35 3.97 4.89 - 0.3 1.82 - - - 0.25 - 0.03 6.15 [58]
(DIN 1.3343)
H13 [51], see
0.32–0.45 0.2–0.6 - 0.8–1.2 4.75–5.5 1.1–1.75 - - 0.8–1.2 - - - - - - -
(DIN 1.2344) also [59]
Tool steel W360 AMPO 0.5 0.25 - 0.2 4.5 3.0 - - 0.55 - - - - - - - [52]
P20 *
0.4 0.83 - 0.45 1.95 0.33 - - - - - - 0.02 - - - [60]
(DIN 1.2311)
AM Corrax 0.03 0.3 - 0.3 12.0 1.4 - 9.2 - 1.6 - - - - - - [61]

* P20 is a common conventional material for conventionally designed and manufactured injection moulds. Its chemical composition is given here only for comparison.
Metals 2021, 11, 458

Table 7. The properties of the tools made by additive manufacturing through L-PBF in the powder steels shown in Table 6.

Yield Strength (MPa) Ultimate Tensile Strength (MPa) Elongation at Break (%) Hardness (HRC) Impact Toughness (J) Thermal
Building
Class Name/Designation After Heat After Heat After Heat After Heat After Heat Conductivity Ref.
Direction As-Built As-Built As-Built As-Built As-Built
Treatment1 Treatment 1 Treatment 1 Treatment 1 Treatment 1 (W/(m.K)

18Ni-300 Horizontal 1080 ± 90 2180 ± 40 1230 ± 70 2260 ± 30 13 ± 2 5±2 [33], see

(DIN 1.2709) 35 ± 3 55 ± 3 64 ± 5 7±2 20.9 at 25 ◦ C
Maraging Vertical 1090 ± 50 2070 ± 80 1220 ± 20 2160 ± 90 13 ± 2 2±1 also [51]
steel M789 AMPO - - 1720 ± 50 - 1850 ± 50 - 6±2 - 52 ± 1 - 6–14 - [52]
Formetrix L-40 - 1300 1350 1500 1650 14 10 46–48 50–52 60 18 16.3 at 20 ◦C [53]

AISI 316L Horizontal 530 ± 20 2 370 ± 30 3 660 ± 20 2 610 ± 30 3 39 ± 5 2 51 ± 5 3 [33], see

90 ± 6 HRB 83 ± 4 HRB 215 ± 15 220 ± 15 15 at 20 ◦ C
(DIN 1.4404) Vertical 440 ± 20 2 320 ± 20 3 570 ± 30 2 540 ± 30 3 49 ± 5 2 66 ± 5 3 also [54]

Stainless 17-4PH Horizontal - 1280 ± 30 4 - 1450 ± 10 4 - 11 ± 1 4 [33], see

steel (DIN 1.4542) 4 4
32 ± 4 40 ± 2 4 71 ± 20 7±24 18 at 100 ◦ C
also [55]
Vertical 830 ± 110 1260 ± 100 1100 ± 90 1380 ± 20 19 ± 4 12 ± 2 4
AISI 420 [56], see
- 700 ± 15 950 ± 20 1050 ± 25 1520 ± 30 2.5 ± 0.2 6.3 ± 0.2 55 ± 1 53 ± 1 - - -
(DIN 1.4021) also [57]
AISI M2
- - - 1280 - 0.8 - 57 64 5 - - - [58]
(DIN 1.3343)
H13 1580 ± 14.7 [59], see
- 1003 ± 8.5 2 1370 ± 175.1 1860 ± 55.8 2 1.7 ± 0.6 2.2 ± 0.8 2 59 ± 4.6 51 ± 3.7 2 - - 27 at 500 ◦ C
Tool steel (DIN 1.2344) also [51]
W360 AMPO - - 1500–1670 - 1970–2010 - 6.6–8.1 - 55–57 - 8–14 - [52]
[61], see
AM Corrax - 760 1600 1150 1700 16 10 34 50 - 18.7 -
also [62]
1 Ageing. 2 After stress relief. 3 Full anneal. 4 H900. 5 Every layer is remelted during L-PBF.
Metals 2021, 11, 458

5. L-PBF Process Parameters

The quality of the feedstock (metal powder) and the process parameters used in L-PBF
are of key significance for the process performance and determine the microstructure and
thereby the quality of the end part (in this case, the tool) [64–92].
Table 8 displays the L-PBF processing parameters that result in fully dense objects
(tool in this case) in the shown materials. Compare Table 8 with Tables 5–7.

Table 8. The L-PBF processing parameters that result in fully dense objects. See also Tables 5–7.

Layer Scan Hatch

Used Laser Power
Class Material Thickness Speed Distance Scan Stratgey Ref.
3D Printer (W)
(µm) (mm/s) (µm)
18Ni-300 3D Systems
40 185 1200 70 Line [62], see also [91]
Maraging steel (DIN 1.2709) ProX DMP 300
M789 AMPO Trumpf TruPrint 1000 20 160 763 87 NA [92]
316L Stripe pattern,
Renishaw AM250 50 200 1000 100 [87], See also [88,91]
(DIN 1.4404) 20 mm overlap
17-4PH 3D SystemsProX [89]
Stainless steel 40 150 1200 50 NA
(DIN 1.4542) DMP 300 See also [90]
420 Line, 90◦ rotation
Concept Laser Mlab R 20 90 600 120 [56]
(DIN 1.4021) (−45◦ /+ 45◦ )
M2 Concept Laser
30 105 150 128 Island (chess) [58]
(DIN 1.3343) M3 Linear
H13
SLM250HL 30 175 607.64 120 NA [59], see also [91]
(DIN 1.2344)
Tool steel
P20
DiMetal-100 30 160 350 80 NA [60], see also [91]
(DIN 1.2311)
[62],
AM Corrax EOS M290 30 170 1250 100 Line
See also [61]

Table 9 summarizes the proposed measures to combat build and microstructural

problems in L-PBF.

Table 9. Measures to combat build and microstructural problems in L-PBF. Based on [74].

Problem Primary Approach Secondary Approach

Build defects - -
Increase laser velocity
Keyhole porosity Reduce laser power
Remelting/reheating
Reduce laser velocity
Reduce scan line spacing
Lack-of-fusion porosity Increase laser power
Reduce layer thickness
Remelting/reheating
Reduce laser power Increase scan line spacing
Composition change
Increase laser velocity Increase layer thickness
Reduce scan vector length
Residual stress and distortion Reduce laser velocity
Use heated substrate/chamber
Microstructural/materials related - -
Microsegregation Increase laser velocity Strongly reduce laser velocity
Undesired texture Reduce laser velocity Reduce laser power
Coarse/columnar grains Reduce laser velocity Reduce laser power
Meta-stable phases (e.g., martensite) Remelting/reheating Reduce laser velocity

The difference between maraging steel, DIN 1.2709, and tool steel, H11 and H13, can
be used to illustrate how the measures to combat build and microstructural problems
vary from material to material. Since the cooling rates in L-PBF are high, 105 –106 K·s−1 ,
martensite formation is induced in both steel types. The so-called carbon-free DIN 1.2709
obtains a ductile martensitic microstructure (and is well processable in L-PBF), while the
carbon-bearing H11 and H13 display a brittle martensitic microstructure that tends to crack
due to the thermal stresses built up by the high cooling rates [51,85]. The conducted studies
show that a pre-heating of the base plate (building platform) eliminate the cracking [30,51].

12
Metals 2021, 11, 458

Martensitic microstructure is found in crack-free H13 for all pre-heating tempera-

tures up to 300 ◦ C. Cracking is, in other words, avoided due to lower thermal gradients
and reduced residual stresses. A base plate heated to 400 ◦ C results in a change in the
phase transformation and a bainitic microstructure (the part is kept above the martensite
start temperature) is formed instead. The bainitic microstructure displays higher hard-
ness and tensile strength than the martensitic microstructure formed at lower heating
temperatures [51].
The roughness of the functional tool surfaces is of great significance in all tooling
applications. Figure 4 displays (a) the different surface types on a part fabricated by and
(b) the staircase effect in L-PBF.

Figure 4. (a) schematic presentation of the different surface types on a part fabricated by L-PBF [93]. (b) Schematic
presentation of the staircase effect.

The staircase effect increases with layer thickness and decreasing θ angle. The con-
ducted studies show that the downskin exhibits the highest roughness in L-PBF, since the
material is built upon powder (and not on solid material). The downskin surface exhibits a
roughness of 20–65 µm in these investigations [94,95]. For the top surface, a roughness of
5 µm can be achieved in L-PBF [62].
L-PBF is not yet capable to accomplish the surface roughness required in the tooling ap-
plications [96–101]. The tool made by L-PBF needs to be machined during post-processing
to obtain the required surface roughness. The functional tool surfaces must therefore have
an allowance of 0.2–0.5 mm [65].
Benchmarking artifacts have been proposed, designed, fabricated by L-PBF and
evaluated during the past years to assess the capabilities and limitations of the process
and the performance of different machines. The evaluation of the geometrical performance
of L-PBF and the dimensional accuracy of objects made by L-PBF has been one of the
purposes for such artifacts [102–105]. Figure 5 displays such artifacts.
Seven (7) state-of-the-art L-PBF machines were used to produce the artifact in Figure 5
in maraging steel 18Ni-300 (DIN 1.2709). Each machine made three complete jobs (artifacts).
Table 10 shows the minimum dimensions in the artifact in Figure 5 compared with the
minimum dimensions the most capable machine manufacturers claimed to be able to
produce. This benchmarking study overcame most of the limitations stated by the machine
manufacturers in Table 10. It showed that user experience and expertise were of great
significance. The newest machines did not outperform the oldest machine due to this
user’s experience and expertise. To create an own space in industrial production, L-PBF
needs to become more robust, i.e., less dependent upon the user experience and better
repeatability [105].
This observation in [105], i.e., the large role played by the user experience and expertise,
was made also in [106]. Rings 1-mm thick and 30-mm high were made by L-PBF in the
diameters 25, 50 and 85 mm in tool steel H13 (DIN 1.2344). The dimensional accuracy
was then measured and analyzed. These rings were made using two different L-PBF
scanning strategies—a stripe scan strategy that is automatically generated and provided

13
Metals 2021, 11, 458

by the machine manufacturer and a (manually designed) sectional scan strategy, Figure 6.
The dimensional accuracy of ring specimens could be improved by up to 81% with the
introduced sectional strategy compared to the standard approach [106].

Figure 5. The Artifact with spiral on benchmarking in [105]. The figure is from [104].

Table 10. The minimum dimensions in the artifact in Figure 5 compared with the minimum dimension
the most capable machine manufacturers claimed to be able to produce. Material = 18Ni-300 (DIN
1.2709). Seven (7) state-of-the-art L-PBF machines were used to produce 3 complete jobs (artifacts)
each [105].

Feature Minimum Dimension Min Dimension in Artifact

Wall thickness 0.15 mm 0.10 mm
Overhang structure 45◦ 25◦
Circular holes (diameter) 0.50 mm 0.20 mm
Circular pins (diameter) 0.50 mm 0.10 mm

Figure 6. (a) The stripe scan strategy automatically generated and provided by the machine manu-
facturer and (b) the manually designed sectional scan strategy [106].

6. Tool Design for Metal Additive Manufacturing by L-PBF

Additive manufacturing provides a significantly larger design freedom (compared
to conventional manufacturing), the benefits of which can be maximized by the emerg-
ing computer-aided design (CAD) technologies like generative design (GD). It is now
possible to:
(1) Generate a wide range of design alternatives by artificial intelligence-based algorithms
(GD software) after setting the part/object design space, constraints, criteria and
objectives. The designer reviews the different design options and chooses the best-
suited for the application [107,108].

14
Metals 2021, 11, 458

(2) Topology optimize the selected design alternative, the purpose of which is to remove
unnecessary material while meeting (or exceeding) the performance criteria. The goal
is to optimize a part properly (weight, stiffness, frequency . . . ) while respecting a cer-
tain set of constraints. The topology optimization process uses various mathematical
algorithms and methods (each having several versions) [109–112].
(3) Optimize the internal lattice and surface structure of the topology optimized ob-
ject by creating an internal mesh while meeting (or exceeding) the performance
criteria [113–116].
(4) Produce this complex object by L-PBF (and post-processing).
During the past two decades, different new design methodologies have emerged,
among them the Design for X (DfX). X represents a particular perspective to improve
during the product design as well as the design process [117,118]. DfX applied to the
Additive Manufacturing process is named DfAM. It aims at using the full potential of the
AM technologies for design, for which there are two methods [108,119,120].
A new detailed DfAM process has been proposed including the available design
support (methods, design rules, guidelines and software tools), the tools and methods that
are best suited at different stages of the design process are specified, and the possibility to
achieve a more automated DfAM is indicated [121].
As far as the L-PBF process design (i.e., the preparation of the L-PBF process) is
concerned, the part orientation, support structures, overhangs and part supporting angles,
channels and holes, wall thickness, tolerances and offsets are addressed in [122–124]. VDI
3405 Part 2, [122], addresses the qualification, quality assurance and post processing. The
procedure described in this standard is applied to DIN 1.2709 in a VDI inter-laboratory test.
The obtained properties in this inter-laboratory test are accounted for in [122]. The values
for DIN 1.2709 in Tables 6 and 7 are in parity with the values stated for the same material
in [122].
The angle between the building platform and the building direction is also of great
significance for the properties of the as-built object. In other words, the properties of the
as-built object are anisotropic due to the layered manufacturing, the loading direction etc.
Table 11 and Figure 7 display 7 different configurations, in which tensile specimens in 316L
(1.4404) were built with an oversize of 0.4 mm in width and thickness. After milling to
final shape, the specimens were tested. Table 12 displays the tensile properties of these
specimens. The maximum strength is obtained at a 45◦ layer versus loading offset [125].

Figure 7. The tensile samples in 1.4404 (316L) on the building platform: overview of the positioning, building angles and
arrangement (configurations). See also Tables 11 and 12. The figure is from [125].

15
Metals 2021, 11, 458

Table 11. The tested configurations. See also Figure 7 and Table 12. The table is from [125].

Config. Polar Angle Φ; αXY (◦ ) Azimuth Angle Θ; αX (◦ ) Total Runtime (h)

(a) 0 0 -
(b) 0 90 39.5
(c) 15 0 -
(d) 45 0 -
(e) 75 0 86.5
(f) 90 0 -
(g) 90 90 -

Table 12. The tensile properties of 1.4404 (316L) in different building configurations. See also Table 11 and Figure 7. The
specimens were built with an oversize of 0.4 mm in width and thickness and milled to final shape before tensile testing. The
table is from [125].

Young’s Modulus Yield Strength Ultimate Tensile Elongation at Poisson’s Ratio

Config. E (GPa) Rp0.2 (MPa) Strength Rm (MPa) Failure At (%) ν (-)
Average STDEV Average STDEV Average STDEV Average STDEV Average STDEV
(a) 151.01 25.56 516.51 7.16 634.43 7.39 33.24 0.57 0.444 0.031
(b) 207.57 24.22 539.47 3.29 643.67 3.25 42.74 0.82 0.155 0.014
(c) 147.87 23.59 501.32 7.70 624.65 4.36 34.09 1.12 0.479 0.058
(d) 227.35 25.12 589.89 11.86 698.98 23.65 32.56 10.17 0.203 0.024
(e) 151.43 18.80 485.65 11.93 571.23 18.63 22.84 7.27 0.558 0.020
(f) 137.78 14.25 438.60 9.69 511.99 17.95 11.76 5.38 0.453 0.005
(g) 137.83 16.25 457.21 17.29 530.22 8.09 17.46 4.42 0.170 0.085

Design demands knowledge of the precise material properties. These properties are
anisotropic and the component orientation on the build platform needs therefore to be
considered [125]. (Post L-PBF heat treatment affects also these properties. See the properties
of 316L (1.4404) before and after heat treatment in Table 7.)
It is possible to achieve ±0.2% in tolerance, with the minimal value being 0.2 mm. It is
also possible to achieve a wall thickness of 0.5 mm. However, the wall shape is dependent
upon the orientation, its height (in relation to the thickness), and the possibility to have
support if needed. As far as gaps (between walls or solid portions) are concerned, the
minimum gap width should be larger than at least the melt pool width. It is also important
to add an allowance of 0.3–0.5 mm to the locations and surfaces that require post-processing
by machining to reach the required tolerance and surface roughness [114,122].

7. Examples of Tooling Applications Designed for and Made by L-PBF

Research and development have been conducted on toolmaking for cold working, hot
working and injection molding by an L-PBF inclusive process, i.e., design for L-PBF (metal
AM), L-PBF, and post-processing. In the following, some examples of the studied tooling
applications are accounted for. These examples display the scientific and technological
achievements and the commercial benefits of an L-PBF inclusive toolmaking.

7.1. Cold Working

7.1.1. Piercing Punches
100-mm long cylindrical punches with a piercing diameter of ϕ10 mm were made by
L-PBF in H13, M300, and KP4. These punches were made vertically with a layer thickness
of 50 µm. Durability studies were conducted by using these punches to make round holes
in 1.2-mm thick CP1180 sheet steel with a tensile strength of 1200 MPa. Conventionally
manufactured punches in conventional solid SKD11 and HWS were used in this investi-
gation for comparison. The M300 punch had the best mechanical properties among the
additively manufactured punches and exhibited the same performance, i.e., managed

16
Metals 2021, 11, 458

10,000 strokes, as the conventional SKD11 and HWS punches. Process optimization and the
application of other powder metals are indicated as topics for further investigations [126].

7.1.2. Stamping: Case 1

In a comparison of different additive manufacturing methods, a small prototyping
sheet metal forming tool (bending matrix, holding block and die) was made in ABS,
VeroGrey, PEAK, and H13. The variant made by L-PBF in H13 (vertically built with a layer
thickness of 30 µm) exhibited the smallest form deviations, took the longest time to print,
and had the highest production costs [127].

7.1.3. Stamping: Case 2

To study the potential of additive manufacturing in automotive stamping, 3 cutting
inserts (the largest being 200 × 135 × 65 mm3 ), a calibration insert (205 × 97 × 56 mm3 )
and a blankholder insert (95 × 44 × 44 mm3 ) were made by an L-PBF inclusive process in
DIN 1.2709. These inserts were printed as solid objects and hade a hardness of 38 HRC
after L-PBF. After heat treatment in a vacuum at 490 ◦ C in 6 h, the inserts were machined
to a surface roughness of 0.2 µm. The final hardness was 57 HRC and the inserts managed
one million strokes/hits per insert. The costs were more than doubled and the lead time
was more than halved, compared to conventional toolmaking [128].

7.1.4. Stamping: Case 3

To study the potential of topology optimization of the stamping tools, certify such tools,
and study the options in design and manufacturing of such tools, semi-industrial forming
(u-bending) and trimming tools were made by an L-PBF inclusive process [129–132].
The left U-bending tool half in Figure 8 was topology optimized and 3D-printed
(L-PBF). The right U-bending tool half in the same figure was 3D-printed solidly. Both
tool halves were 3D-printed in DIN 1.2709. LS-TaSC (LS-Dyna) was used for the topology
optimization and the Z-displacement at the tool half profile radius was the compliance
criterion. The volume fraction of 0.45 was selected, since the maximum Z-displacement at
this fraction is very close to that of the solid [129–131]. See Figures 8–10.
After L-PBF, the U-bending tool halves were heat treated at 490◦ C in 6 h and then
machined to a surface roughness of 0.2 µm. The hardness was 55 HRC. This tool was
used to U-bend 2-mm thick hot-dip galvanized DP600 steel sheet with a minimum tensile
strength of 600 MPa. This tool managed 50,000 strokes (U-bends) without any problems
and was approved [129]. See Figure 8.
Compared to the 3D-printed solid tool half, the topology optimized and 3D-printed
tool half exhibited a weight reduction (or improved material usage) by 19.4% and a lead
time reduction by 11.1%. Initially, the profile radius of the left tool half (topology optimized)
was 5.05 mm and that of the right tool half (solid) was 5.04 mm. After 50,000 strokes,
the maximum wear measured as a change in the profile radius was 0.0186 mm [129].
See Figure 8.
Figure 11 displays the 3D-printed (L-PBF) semi-industrial solid and topology opti-
mized trimming tools. The hardness varies between 54 and 56 HRC. The surface roughness
Ra = 0.2 µm. Both the solid and topology optimized tools managed 100,000 strokes in
2-mm thick DP600 sheet steel without any problems and were approved. Figure 12 shows
the wear after 100,000 strokes at the edge (profile) radius on the trim dies. Compared to
the 3D-printed solid tool, the topology optimized and 3D-printed tool exhibits a weight
reduction by 47% and a lead time reduction by 29.6%, Figure 11, [131,132].
Based on the approved semi-industrial results above, a station in an industrial progres-
sive die used to stamp 1-mm thick DP600 sheet steel was chosen and 3D-printed (L-PBF) in
DIN 1.2709 with a honeycomb inner structure. This station comprises a punch and a puller,
as shown in Figure 13 [62] (see also [129]).
The punch in this industrial stamping tool, Figure 13, was topology optimized using
LS-TaSC with a volume fraction of 0.45 as the target, and using NX12 with a weight reduc-

17
Metals 2021, 11, 458

tion by 70% as the target. The shape and the resultant displacements prior to unloading (in
stamping) in the punch with the original design and the topology optimized versions are
displayed in Figure 14 [62,131]. These topology optimized versions, both 3D-printed in
DIN 1.2709, are shown in Figure 15.

Figure 8. The U-bending tool: the right tool half was 3D-printed (L-PBF) as a solid piece. The left
tool half was topology optimized at the volume fraction of 0.45 (Figure 9) and 3D-printed (L-PBF).
Both tool halves were 3D-printed in maraging steel DIN 1.2709. Both tool halves managed 50,000
U-bends and were approved [129]. All displayed dimensions are in mm.

Figure 9. Topology optimization of the U-bend tool (Figure 11) with different volume fractions [130].

Figure 10. The Z-displacement at the U-bending tool profile radius for different volume fractions (Figure 9) [131].

18
Metals 2021, 11, 458

Figure 11. The 3D-printed (L-PBF) solid and topology optimized trimming tools. Both versions were 3D-printed (L-PBF) in
DIN 1.2709 [131]. All displayed dimensions are in mm.

Figure 12. The wear after 100,000 strokes at the edge (profile) radius on the trim dies [132].

19
Metals 2021, 11, 458

Figure 13. A station in an industrial progressive die, used to stamp 1-mm thick DP600 sheet steel, 3D-
printed (L-PBF) in DIN 1.2709 with a honeycomb inner structure [62] (see also [129]). The displayed
dimension is in mm.

Figure 14. The shape and the resultant displacements prior to unloading in the punch (a) with the original design and
(b) topology optimized with the volume fraction 0.45 using LS-TaSC, and (c) topology optimized using NX12 and targeting a
weight reduction by 70% (compared to the conventionally designed solid version) [62,131]. All displayed dimensions are in mm.

20
Metals 2021, 11, 458

Figure 15. Three (3) versions of the industrial punch (Figure 13)—all 3D-printed (L-PBF) in DIN
1.2709: (left) with a honeycomb inner structure, (middle) after topology optimization using LS-TaSC
and (right) after topology optimization using NX12 [62]. See also Figure 14.

Compared to a 3D-printed solid punch, both the honeycomb inner structure and the
topology optimization with the volume fraction of 0.45 improved the material usage (and
thereby reduced the weight) and the printing time by ca 45% & ca 34% respectively. This
means that the same printing time reduction and improved material efficiency can be
accomplished in at least two different fashions—topology optimization and a honeycomb
inner structure [62]. See Figure 15.
The topology optimization targeting a weight reduction by 70% (compared to the
solid version made conventionally) led to much larger displacements held to have a large
negative impact on the trimming result and the die life length [62]. See Figure 15.

7.2. Hot Working

7.2.1. Hot Stamping
Hot stamping, or press hardening, is a process used to form lightweight high strength
(2000 MPa) structural car body parts. The thin steel sheet is heated to the austenitizing
temperature (ca 950 ◦ C), formed, and rapidly cooled down to 200 ◦ C in the forming tool.
This leads to martensitic high strength structure. The cooling, the time the die must be kept
closed after forming and before unloading (the holding time), dominates the cycle time. To
accomplish the cooling, channels are drilled (ca one hour per meter borehole) [114].
To accomplish improved cooling and maximize the benefits, a so-called hybrid tooling
approach was selected. The tool base was made by conventional milling of a conventionally
made solid block. The functional structure was made by L-PBF in DIN 1.2709 over this
tool base, as shown in Figures 16 and 17. Before L-PBF, this functional structure was
optimized through thermo-fluidic simulations and by placing the cooling channels very
close and conformal to the surface. Due to the optimized cooling, the part was cooled down
more rapidly and evenly. The holding time could be reduced from initially 10 to 5 s [133].
See Figure 18.

7.2.2. Extrusion: Case 1

During extrusion, the feedstock is heated up and pushed through a forming tool. The
formed shape needs to be cooled down and maintained. To do so, a calibration tool is
used directly after the extrusion. The cooling is accomplished by a fluid flowing through
the cooling channels. The vacuum, accomplished through the vacuum channel, forces the
extruded material to adopt the cylindrical inner surface of the calibration tool. Thereby, the
extruded geometry is fixed and “calibrated” [114].
The tool described above was specially designed for AM by integrating the complex
internal channels in a limited design space. After design, the calibration tool was made
by L-PBF in 17-4PH. For the internal channels, tolerances in the range of ± 0.5 mm were

21
Metals 2021, 11, 458

met. The channel diameter had to be about 3 mm to be able to get rid of the not bound
powder [114]. See Figures 19 and 20.
There is no conventionally manufactured predecessor. Comparable conventionally
manufactured tools use compressed air for calibration. Better thermal and calibration perfor-
mance and the reduced size are the main benefits of the calibration tool in Figures 19 and 20
compared to the conventional less effective tools [114].

Figure 16. Tool insert for hot stamping made by the so-called hybrid tooling. The tool base was
made by conventional milling of a conventionally made solid block (left). The functional structure
including the optimized cooling channel was made by L-PBF in DIN 1.2709 over this tool base (right).
The figure (right) shows the hybrid tool ready for final machining [133].

Figure 17. The assembled hot stamping punch [114].

Figure 18. The temperature distribution in the hot stamping punch: (left) the conventional tool and
(right) the tool designed for and made by L-PBF [133].
22
Metals 2021, 11, 458

Figure 19. The calibration tool: The internal cooling and vacuum channels were integrated in a very
compact design space. The minimum distance between the channels is about 1 mm [114].

Figure 20. The calibration tool was made by L-PBF in 17-4PH [114].

7.2.3. Extrusion: Case 2

In another study, the thermal control and the maintenance of a uniform temperature
in the extrusion process of aluminum alloys was at the focus. The purpose was to generate
sound profiles with high press productivities. Numerical studies were conducted to check
the mechanical and thermal performances of die inserts both in uncooled and cooled
conditions. Conformal cooling channels through which liquid nitrogen flowed was the
targeted cooling system. A thermally controlled die insert was designed and made in
H13 by L-PBF. Initially, cracks due to thermally induced stresses caused problems. This
problem was solved by reducing the waiting time for one layer to another layer melting.
The crack-free insert made by L-PBF is shown in Figure 21. This insert was then integrated
into a conventionally machined steel housing [134]. The height and outer diameter of the
insert in Figure 21 are 20 mm and 25 mm respectively [135].

7.2.4. Die Casting: Case 1

The bedplate for a passenger car engine was to be manufactured regularly by alu-
minium die casting in the alloy EN AC-Al Si9Cu3 (Fe). Gas and shrink porosity were some
of the chief problems encountered in the initial testing phases. The conducted investiga-
tions resulted in an insert made by L-PBF in DIN 1.2709 mounted as a component in the
die [133], as shown in Figure 22.
The optimization of the cooling channels in this insert comprised [133]:
• FE-simulations to obtain the shortest possible distance between the cooling and the
cavity on one hand and sufficient insert strength on the other.
• Thermal simulations to optimize the cooling channels in steps, ranging from spiral
design to a complex system of small channels, as shown in Figure 23.
23
Metals 2021, 11, 458

The optimized insert reduced the gas and shrinkage porosity to a permissible level,
the scrap rate by 10% and the cycle time by 3% [133].

Figure 21. An extrusion die insert with conformal cooling channels through which liquid nitrogen
flow. This die insert was made by L-PBF in H13 and integrated into a conventionally machined steel
housing [134]. The height = 20 mm and the outer diameter = 25 mm [135].

Figure 22. Aluminium die casting: (left) The tool insert was made in DIN 1.2709 by L-PBF, after
which it was installed as a component in the die [133].

7.2.5. Die Casting: Case 2

In another study, the main objective was to investigate the benefits of conformal
cooling in the tool used to manufacture sample batches of zinc alloy castings. A hybrid
approach was chosen to reduce the process and material costs. The impression block in
Figure 24 was made of two pieces separated at the dashed line [136]:
• The upper piece, which includes the cores and the conformal cooling channels, was
built by L-PBF from powders of AISI H11 (DIN 1.2343). An allowance of 0.3 mm was
left for CNC finish milling after a thermal treatment.
• The lower piece, which is 25 mm thick and includes the inlet and outlet ports for the
coolant, was built by CNC machining from a blank made of the same steel.
The main lines of the cooling system were placed on the parting plane to ease powder
removal. The whole process took 180 h, of which 91 h for the additive manufacturing
phase [136].

24
Metals 2021, 11, 458

Figure 25 displays the redesigned impression block with the conformal cooling chan-
nels. The conformal cooling improved the surface finish of the castings (due to a reduced
need of spray cooling) and reduced the time and shrinkage porosity [136].

Figure 23. The insert in Figure 22: Stepwise optimization of the cooling channels, ranging from spiral
design to a complex system of small channels [133].

Figure 24. The impression block, a die for zinc alloy castings, was made by applying a hybrid approach. The upper piece
was made by selective laser melting (SLM) or L-PBF from powders of AISI H11 (DIN 1.2343). The lower piece was built by
CNC machining from a blank made of the same steel [136]. See also Figure 25. All displayed dimensions are in mm.

7.2.6. Sheet Molding Compound (SMC) Technology

Isothermally heated compression mold for an aircraft component was subject to
a study. The pre-impregnated chopped long fiber fabrics are cut, stacked, placed into
the heated mold and extruded by high pressure and at temperatures between 130 and

25
Metals 2021, 11, 458

145 ◦ C. The modular tooling concept, selected and used in this study, comprised standard
tool rack with four guide pins made of hardened steel and a quick-change mold system
manufactured by L-PBF [137]. See Figure 26.
The mold system consisted of a die and a punch. For an optimum heat conduction and
temperature distribution (on the surfaces of the shape) the heated channels were integrated
close to the cavity surface and meander-shaped. The mold was made by L-PBF with island
strategy in DIN 1.2709. After heat treatment and milling, the surfaces of the die and punch
were chromized with a coating thickness of 10–15 µm. This mold was used to make the
carbon fiber SMC cleat in Figure 26 [137].
Improved FRP (fiber reinforced plastics) part quality, reproducibility, and temperature
distribution and heat conduction due to surface compliant heating channels were the
obtained benefits [137].

Figure 25. Redesigned impression block, a die for zinc alloy castings, with conformal cooling
channels [136]. (a) The impression block. (b) The conformal cooling channels inside the impression
block. See also Figure 24.

Figure 26. The selected modular tooling concept comprised standard tool rack with four guide pins made of hardened steel
and a quick-change mold system manufactured by L-PBF. (a) the tool, (b) CAD model of the tool, and (c) carbon fiber SMC
cleat [137,138].

26
Metals 2021, 11, 458

7.2.7. Vulcanisation Mold for Tyres

The last step in production of tyres (for cars, motorcycles, trucks and agricultural
vehicles) is the vulcanisation in a closed mould, which gives the tyre its final shape and
tread pattern. In this process, the rubber material of the tyre is cured and converted into an
elastomer at approximately 200 ◦ C. The tyre mould consists of eight to sixteen segments
and each segment is conventionally made in a wear resistant aluminium–silicon alloy by
casting and 5 axis CNC milling [139,140], Figure 27.
Tyre profiles comprise an array of broad and narrow grooves (also called sipes). Broad
grooves can be integrated in the aluminium mold. However, the hardness and stiffness
of aluminium is insufficient for narrow grooves with a width of less than approximately
3 mm. Instead, thin steel inserts called sipes are mounted in the aluminium mold [140],
Figure 27.
The manufacture and installation of sipes is extremely costly and time consuming.
Sipes are made by stamping and cold bending. Four to five sets of stamping and bending
tools are therefore required for a specific sipe geometry. Each tyre mold contains various
sipe geometries. Sipes (sipes with undercut) made by L-PBF have therefore attracted a
large interest, particularly for the running performance of snow tyres, during the past
years [140].

Figure 27. Tyre tread segment and tread ring vulcanisation mould segment [139].

In 2009, a feasibility study was conducted in which one-pitch-segment (1/128 of the

tread ring mold) was made by Direct Metal Laser Sintering (DMLS) as a Rapid Tooling (RT)
strategy [139].
Today, the size of the each 8–16 tyre mold segments can fit into the L-PBF building
chamber. It is held that steel mold segments with sipes of 0.3 mm thickness can be made by
L-PBF. However, the present concept of an AM tyre mold is a twin shell design. The outer
shell is a machined aluminium ring with the required strength, stability and roundness that
supports the inner profile. Inside the supporting outer ring is the additively manufactured
shell forming the tyre profile. This is as thin as possible for cost reduction [140].

7.3. Injection Moulding

An L-PBF inclusive manufacturing of the tooling for injection molding has been
addressed in many studies. The possibility to design, manufacture and use conformal
cooling channels has been subject to investigation from different perspectives in the many
of these studies [59,141–145].

7.3.1. Injection Molding: Case 1

Figures 28 and 29 display a case in which an existing injection molding core was
redesigned and made by L-PBF in a new powder material. Simulations were conducted
27
Metals 2021, 11, 458

to optimize the injection molding core (inserts) with respect to cooling and solidification
of the molded part. Conformal cooling channels were designed based on solidification,
cooling, heat flux, average mold temperature per cycle, average mold temperature at the
end of the cycle, and warpage of the molded part [62], Figure 28. The inserts optimized
by these simulations were 3D-printed (L-PBF) in AM Corrax, hardened to 48 HRC and
post-machined to the surface roughness Ra = 0.2 µm [62], Figure 29.
The 3D-printed inserts were tested in real production and compared with the exist-
ing conventionally designed and manufactured core. This comparison showed that the
water flow was reduced by 86.4% and the cycle time somewhat with the core shown in
Figure 29 [62].

Figure 28. The core/inserts for injection molding optimized by the simulations. Red color = the
cooling channels after optimization [62]. The displayed dimension is in mm.

Figure 29. The core/inserts for injection molding optimized by simulations (Figure 28) 3D-printed (L-PBF) in AM Corrax [62].
The displayed dimensions are in mm.

7.3.2. Injection Molding: Case 2

High performance thermal management of molds for injection molding and tools
for die casting with conformal cooling cavities has been studied in several investigations
and noted as one of the great benefits of L-PBF. In addition, the use of flexible lattice

28
Metals 2021, 11, 458

structure inside the mould provides better thermal fatigue resistance, leak protection,
defined thermal management and weight reduction. The use of internal lattice structure
leads to a reduction of the L-PBF production time and material usage, which in turn
reduce the costs [143], Figure 30. The height = the outer diameter = 200 mm, the outer skin
thickness = 6 mm, and the lattice diameter = 0.5 mm in Figure 30 [144].

Figure 30. A split mould tool with internal lattice structure in green (a) and a close view of the same mold (b) [143].
(a) Height = outer diameter = 200 mm. (b) Outer skin thickness = 6 mm and lattice structure = 0.5 mm [144].

7.3.3. Injection Molding: Case 3

As mentioned above, the implementation of conformal cooling channels to enhance
the cooling efficiency has been the most common example of L-PBF design freedom in the
injection molding sector and corresponding academic research. To benefit further from the
L-PBF potential, the removal of excessive non-contributing material, topology optimization,
should also be considered [145].
In this study, two topology optimization methods were considered and used [145]:
• A commercially available software, which adopts the geometry-based constraints and
achieves a mass reduction of ≈50%.
• A topology optimization method developed in-house, which integrates a simplified
AM process model within the standard topology optimization algorithm. The un-
derlying thermal aspect of L-PBF is therefore included with a sequential localized
steady-state thermal analysis and, thus, local overheating issues during manufacturing
are avoided.
Figure 31 displays the original design of the studied injection molding insert. Figure 32
shows the “same” injection molding insert topology optimized with the standard density-
based topology optimization (TO) algorithm and with the in-house novel TO algorithm
with the AM thermal constraint (hotspot detection) [145]. The topology optimized inserts
in Figure 32 have the same dimensions as the original, i.e., 220 mm × 110 mm × 25 mm.
For simplicity, the authors display only half of each insert (110 mm × 110 mm × 25 mm) in
Figure 32 [146].
The use of the novel in-house algorithm with the thermal AM constraint limits the
occurrence of heat accumulation, local overheating and accumulated residual stresses, and
results in a greater geometrical accuracy and surface quality [145].
The proposed algorithm that includes AM related thermal aspects indicates that there
is room for further improvements [145].

29
Metals 2021, 11, 458

Figure 31. Original design of the injection molding insert [145].

Figure 32. The injection molding insert, topology optimized with the standard density-based topology optimization (TO)
algorithm and the in-house novel TO algorithm with AM thermal constraint (hotspot detection) [145]. The topology
optimized inserts have the same dimensions as the original, Figure 31. For simplicity, the authors display only half of each
insert (110 mm × 110 mm × 25 mm) in this figure [146].

8. Discussion
Three categories have been proposed for dividing the research in DfAM (design
for additive manufacturing)—system design, part design, and process design [121]. The
following selection criteria can be applied to identify whether a redesign for additive
manufacturing would be beneficial [147]:
• Integrated design, the objective of which is to identify assemblies or groups of parts
that can be re-designed into one single part.
• Individualization, which is driven by the wish to meet different customers’ needs.
• Lightweight design, where the reduced weight improves the performance of the product.
• Efficient design, the objective of which is to improve the efficiency and performance
of the product (the tool in this paper) in operation.

30
Metals 2021, 11, 458

The tooling examples in the previous section illustrate, emphasize the correctness of,
and confirm the importance of using the system, part and process design approach and
having efficient design as the selection criteria. Efficient design is of particular significance
for the production tools in hot working and injection molding. The importance of process
design and its close relationship to part and system design is illustrated in Figure 32
and [145].
While the primary target is high efficiency and performance in operation, using genera-
tive design and topology and lattice structure optimization will also lead to lightweight design.
Using the efficient design, i.e., high efficiency and performance in operation, as the
criterion, the tooling examples in the previous section show that L-PBF (combined with
conformal cooling and topology and lattice structure optimization) has its greatest potential
in production tools for hot working and injection molding.
In injection molding, cooling stands for 60–90% of the total cycle time [143]. The
related tooling examples in the previous section display the importance of efficient de-
sign. Conformal cooling channels in topology and lattice structure optimized inserts/core
provide high efficiency and performance in injection molding.
In a 2003 review, design for layer manufacturing (LM) was identified as a topic that
“required attention in the future”. To take full advantage of the design freedom offered by
LM, the need for “research and development in the area of dedicated CAD design software
incorporating design for LM modules” was highlighted [148]. Today, it is interesting to
note the accuracy of this prediction.
In hot working, it is important to avoid thermal fatigue. The linear tensile or compres-
sive stress that occurs in the tool can be calculated by [143]
σ = α E (Ti − Tf ) = α E ∆T (1)
in which σ = thermal stress developed due to the thermal change ∆T, Ti = initial tempera-
ture, Tf = final temperature, α = expansion coefficient and E = modulus of elasticity.
Thermal fatigue is related to the parameter [143]
σf k/α E (2)
where σf = the mean fatigue strength and k = the thermal conductivity. An increase in this
parameter indicates better resistance to thermal fatigue.
Fast cooling by a large temperature difference ∆T will increase the thermal stress.
Choosing a material with low α and E will decrease the thermal stresses, while an increased
tensile strength will directly increase the effect the thermal stress has on the material.
AISI H13 has a thermal stress of σ = 2.604∆T N/mm2 ◦ C and a thermal conductivity
of k = 27 W/mK at 500 ◦ C. DIN 1.2709 has the properties σ = 2.124∆T N/mm2 ◦ C and
k = 24 W/mK at 500 ◦ C. Both steels have an almost equal ability to withstand thermal
fatigue [143].
Samples tested with as-produced surface conditions usually show a poor fatigue life,
since fatigue strength depends mostly on surface and internal defects. Therefore and for
instance, surface machining improves fatigue properties considerably (in some cases to a
comparable fatigue life as conventionally-produced specimens) [51]. See also [149].
H11 and H13 have superior wear resistance compared to 1.2709 [150]. As discussed
in Section 5, the carbon-bearing H11 and H13 tend, however, to crack during L-PBF.
Preheating the base plate, which lowers the thermal gradients and reduces the thermal
stresses, has been identified as a measure to obtain crack-free H11 and H13 in L-PBF.
High tool efficiency and performance in operation is also affected by the corrosion
properties in injection molding (of for instance reinforced polyamide). The corrosion prop-
erties of AM-produced steels, mainly stainless steels, is typically superior to those of
conventionally produced material, mainly due to the fine microstructure and sometimes
also due to the special texture and the two-phase nature of AM-produced stainless steels.
The research into the reasons for the improved corrosion resistance is still in its early
stages [51].

31
Metals 2021, 11, 458

DIN 1.2709 (18Ni-300), the most established maraging grade, combines high values
of mechanical properties (strength, hardness, toughness and ductility) with very good
processability in L-PBF. However, due to the lack of chromium this steel grade does not ex-
hibit corrosion resistance. The stainless steels 316L and 17-4PH are also well established as
powder materials for additive manufacturing but have relatively low mechanical strength
and hardness [151]. See also Table 7.
The recently developed M798 AMPO displays mechanical properties that are close to
those of DIN 1.2709 but has better corrosion resistance than 17-4PH [151]. See also Table 7.
The recently developed AM Corrax displays also high strength and hardness, Table 7.
Both untreated and surface treated AM Corrax samples were subject to corrosion tests,
the salt spray testing and the cyclic polarization. The samples were surface treated with
physical vapor deposition (PVD) coatings—TiN, CrN, and diamond-like carbon (DLC)—at
temperatures below 450 ◦ C, as well as with plasma nitriding treatments for conventional
steel grades (PN1) and suitable for stainless steel grades (PN2). These tests showed that
the corrosion resistance is high and can be summarized as untreated > PN2 > CrN > TiN >
DLC > PN1 [152].
The number of powder steels for L-PBF of production tools is however very limited
today, both in general and particularly for hot working (and injection molding). See Tables 5–7
and [51].
It was noted in the 2003 review that “a lot remains to be done to develop better
base materials (powders, liquid photopolymers, etc.) . . . ” for LM [148]. Metals, plastics,
ceramics and composites are mentioned [148]. Many materials have been developed since
then. However, the number of powder steels for L-PBF of production tools is, as noted
above, still very limited.
As far as the feedstock (powder) is concerned, the metal powder should, according to
some investigations, exhibit high sphericity, a clean and smooth surface, and low amount
of satellites—features that are associated with gas-atomized powder [66]. The particle
size distribution of the powder used in L-PBF is nominally 10–45 µm [65]. Some other
investigations show that fine particles (D90 = 24.17 µm in the used powder) can easily be
melted and are therefore beneficial for high part density and mechanical strength, while
bigger particles (D90 = 55.54 µm in the used powder) are beneficial for higher breaking
elongations. The selection of the appropriate particle size distribution must therefore take
care of these contrary effects [153]. 316L is the powder material used in [66] and [153].
Water-atomized powder results in irregular shapes and low flowability but lower
atomization costs. Water-atomized Fe-4800 powder has been successfully used to make
objects by L-PBF. The low powder flowability was overcome through in-situ-alloying of
carbon black nanoparticles in the range of 20–100 nm [154]. Compared to gas atomization,
water atomization reduces the costs significantly. The costs will be discussed more later on
in this section.
Spherical, ovoidal, and irregular particle shapes using powders atomized with argon,
nitrogen and air (non-spherical N/air atomized powder were not possible to use before
due to severe wiper blocking) have been successfully applied in L-PBF using nanoparticles
as spacers. This process has been used for aluminium-silicon powder. However, since the
principle of using nanoparticles is based on geometry, the same principle can be transferred
to other material systems [155].
Research and development in the area of feedstock (powder) production and qual-
ity is therefore highly important from process, property, part quality, cost, and lead
time perspectives.
Figure 33 displays a comparison of different metal AM methods with respect to part
performance, cost and lot size. Production tools are normally made in single or few units
and required to perform well in operation to avoid stops, minimize or eliminate rejections
and maximize the production efficiency. L-PBF (PBF-L in Figure 33) is, other words, in a
good position from these perspectives. The high L-PBF costs indicated in Figure 33 are
observed in many AM tooling related investigations. See, for instance, [62,128].

32
Metals 2021, 11, 458

Figure 33. A 2018 comparison of different metal AM methods with respect to part performance, cost and lot size [32].

For the parts that require production tooling, the costs of this tooling constitute an
initial investment which in majority of the cases are larger for an AM inclusive process.
However, the total cost per produced part can be reduced due to e.g., improved cooling and
shorter cycle time using production tools made by an AM inclusive process [62], Figure 34.
For hot working and injection molding, the tools, dies, molds, cores and inserts made
by L-PBF cost more but lead to lower total costs (the part costs) since such tools enable
shorter cycle time, improved quality etc.
For cold working, both the tooling and part costs are, however, higher (than the
conventionally made tool and the part made in it), in case the tools are made by L-PBF. A
lead time reduction in toolmaking is reported particularly for the (cold) stamping tools
made by an L-PBF inclusive process [62,128]. For (cold) stamping tools, the cost increase
can in some cases be motivated by the significant lead time reduction. A so-called late
change in the industrialization of a car body component can be considered as such a case.

Figure 34. The part costs and revenues: conventional versus AM inclusive fabrication. The lower
running AM costs is valid only for the cases in which the tooling enables a shorter cycle time,
e.g., conformally cooled injection molding cores [62].
33
Metals 2021, 11, 458

The cost of feedstock (powder) production was mentioned above. The cost and pro-
ductivity of L-PBF is closely related to the number of lasers that are active at the same
time, Table 1. As displayed in this table, up to 12 lasers can be active at the same time. The
costs for L-PBF have been reduced significantly during the past six years and will continue
to fall in the coming years. However, these costs are still much higher than the costs for
conventional toolmaking [32].
To accomplish a significant improvement of the process efficiency (productivity and
cost), different technologies and methods need to be studied. As an example, the multi-spot
array system based on multi-diode lasers can be mentioned. The machine design uses
no scanner systems and instead relies on a printer head featuring several individually
controllable diode lasers that is moved using linear axes [156]. See also [157].
It was noted in the 2003 review that productivity had been improved partially and
that “a lot of effort is still required to further boost production rate” [148]. In addition,
“exaggerated equipment and material cost” was observed due to the “great divergence
of machines offered and their costs” [148]. The 2003 review concerned all LM methods
(not only SLM/L-PBF). A great progress has been made since then. The build rate has
improved significantly. In one of the current L-PBF machines, the build rate is 71 times
higher than that in 1995. However, the productivity and cost need, as indicated above, to
be improved further.
The 2003 review indicated “From near to net-shape” as another topic that “required
attention in the future” [148]. Improved accuracy, repeatability and secured quality were
mentioned in this context. “The combination with traditional processes in multiprocessing
equipment might be explored” [148]. This topic has been addressed and a large progress
has been made since 2003. However, post-processing is and will be an important topic also
during the coming years.
In tooling applications, the roughness of the functional tool surfaces is of great sig-
nificance. As mentioned in Section 5, L-PBF is not yet capable of providing the surface
roughness required in tooling applications. The tool made by L-PBF needs therefore to
be machined during post-processing to obtain the required surface roughness. Further
improvement of L-PBF is, in other words, required in the future from this perspective.
Laser surface re-melting might be a track to explore further to accomplish improved
surface roughness.
Heat treatment is frequently needed in different tooling applications.
Multiprocessing equipment has been subject to exploration and will be important
to explore further also in the future. Plants with a L-PBF inclusive production process,
high degree of automation, digitization and digitalization is also a track that needs to be
explored further in the future.
The size of the object than can be made by L-PBF is of great significance for many
tooling applications. As mentioned in Section 3, the maximum object size that can be made
by L-PBF today is 600 × 600 × 600 mm3 (although the largest height is 850 mm in one of
the other current machines), Table 1. This size has more than doubled compared to that in
the 1995 machine for SLS.
However, many production tools, particularly (cold) stamping, press-hardening,
die casting tools are larger than 600 × 600 × 600 mm3 . L-PBF can be used to make
tool/die/mold inserts, which then are mounted in a core or shoe that is made by e.g., cast-
ing. Another option is to design the tool modularly and make each module by L-PBF. The
object size that can be made by L-PBF will still be an important topic in the future. The
challenge will then be to realize a homogenous shielding gas flow over the entire powder
bed in combination with high productivity (due to the large object size).
According to a non-peer-reviewed assessment in 2018, metal AM is on the brink of
industrialization [32]. The manufacturing readiness level (MRL) is the highest for L-PBF
compared to the other metal AM methods [32]. According to another non-peer-reviewed
assessment in 2020, L-PBF has reached the highest technology maturity index and the
highest industrialization index (compared to other metal AM methods) and thereby a

34
Metals 2021, 11, 458

widespread industrial use [158]. L-PBF is almost fully industrialized [158]. Two other
non-peer-reviewed assessments from 2013 and 2015 show that [159,160]
• dental/medical applications have reached the highest MRL (full- rate production),
• tooling applications the second highest MRL (low-rate production),
• aerospace industry the third highest MRL (capability in operational environment
demonstrated—low rate production), and
• automotive industry the lowest MRL (technology validated in laboratory environment—basic
capabilities shown).
The assessment in [160] is stated to be based on expert interviews.
In spite of this high MRL for L-PBF of tooling (low-rate production), further research
and development is required to improve toolmaking by a L-PBF inclusive process: larger
maximum objects sizes than be made by L-PBF, a larger number of powder metals that
are designed for different tooling applications, lower feedstock (powder) costs, lower
L-PBF processing costs, further L-PBF productivity and lead time improvement, minimized
post-processing, improved surface roughness (both through L-PBF and in combination
with efficient post-processing), and secured quality (including the L-PBF portion of the
process). As indicated above, these improvements require research and development both
within “single” topics, e.g., L-PBF in a multi-spot array system based on multi-diode
lasers or laser re-melting, and from a toolmaking system view, e.g., plants with a high
degree of automation and eventually cyber-physically controlled smart L-PBF inclusive
manufacturing systems.

9. Summary and Conclusions

For laser-based powder bed fusion (L-PBF) of production tooling, the following
summary and conclusions apply:
• Generative design and topology and lattice structure optimization enable, amplify
and are a complement to the design freedom provided by L-PBF.
• A focus on efficient design, the objective of which is to improve the efficiency and
performance of the tooling in operation, should be the primary target in tool de-
sign. Lightweight solutions can be obtained through topology and lattice structure
optimization as a complement.
• Using high tooling efficiency and performance as the primary target, L-PBF exhibits
the greatest potential for hot working and injection molding tools, dies and molds.
• The tools made by L-PBF cost more than those made conventionally. However, the total
costs (the part costs) can be lower than those of the parts made in conventional tools,
since the cycle time is reduced significantly in the tools made by L-PBF. Hot working
and injection molding are the processes in which lower total costs can be obtained.
• For cold working, e.g., (cold) stamping, both the tooling and part costs are higher
with tools made by L-PBF. However, the reported lead time reduction for toolmaking
through L-PBF can be used to motivate higher tooling costs for e.g., the so-called late
changes in the industrialization of car body components.
• The largest objects that can be made by L-PBF are currently 600 × 600 × 600 mm3 and
800 × 400 × 500 mm3 .
• The number of metal powder alloys for tooling applications is limited. Currently,
maraging steels 18Ni-300 (or DIN 1.2709) and M789 AMPO, stainless steels 316L,
17-4PH and 420, and the tool steels M2, H13, P20, and AM Corrax can be selected as
tool material.
• According to some investigations, the metal powder should exhibit high sphericity, a
clean and smooth surface, and low amount of satellites—features that are associated
with inert gas atomization. The nominal particle size distribution used for L-PBF is
10–45 µm. Other investigations show that it is possible to L-PBF metal powder with irreg-
ular particle shapes—metal powder made by water or N/air atomization—successfully.
This improves the resource efficiency, since larger percentages of atomized powder
can be used in L-PBF.
35
Metals 2021, 11, 458

• Laser power (W), scan velocity (mm/s), and hatch distance (mm) between neighboring
melt tracks, and the layer thickness (µm) determine the process window in L-PBF.
• The path of the scan vector and thereby the scan strategy are essential for the fi-
nal quality, i.e., defect types and numbers, microstructure, residual stresses, and
surface roughness.
• A chess strategy (or island scanning) is effective in reducing the residual stresses.
• User experience and expertise play a large roll in some cases, e.g., selection of a
scan strategy other than the one pre-set by the machine builder might lead to better
dimensional accuracy and higher quality.
• The values of the process parameters and the size of the process window which
provide fully dense and high quality objects in the above-mentioned metal powder
tool materials can be found in this paper (Table 8).
• The downskin surface exhibits a roughness of 20–65 µm after L-PBF. For the upskin and
the top surface, a roughness of 5 µm can be achieved in L-PBF. In other words, L-PBF
is not yet capable of providing the surface roughness required in tooling applications.
Smaller roughness requires post-processing by machining.
• The properties of the built object are anisotropic and dependent upon the build
directions and angles.
• Faces with the downskin angle <45◦ require support structure.
• Internal channels should be built vertically.
• Several examples from different tooling applications in cold working, hot working
and injection molding made by L-PBF are showcased in this paper.
• The corrosion properties of AM-produced steels, mainly stainless steels, are superior
to those of the conventionally produced materials. The research into the reasons for
the improved corrosion resistance is still in its early stages.
• The so-called carbon-free DIN 1.2709 obtains a ductile martensitic microstructure and
is well processable in L-PBF, while the carbon-bearing H11 and H13 display a brittle
martensitic microstructure that tends to crack due to the thermal stresses built up by
the high cooling rates. A pre-heating of the base plate (building platform) eliminates,
however, this cracking. H11 and H13 have superior wear resistance compared to
DIN 1.2709. L-PBF yields excellent performance and is suitable for small lot sizes (in
tooling, only a single or a few objects are made).
• According to non-peer-reviewed assessments, metal AM is on the brink of industri-
alization. The manufacturing readiness level is the highest for L-PBF compared to
the other metal AM methods and the second highest for L-PBF of tooling (low-rate
production) compared to L-PBF in other industrial/application segments.
• Rapid tooling has made a remarkable journey to AM of production tools by L-PBF
thanks to the enormous efforts in research, development, entrepreneurial endeavors
and company building.
• Further research and development is required to improve toolmaking by a L-PBF
inclusive process: larger object sizes that can be made by L-PBF, a larger number of
powder metals that are designed for different tooling applications, lower feedstock
(powder) costs, lower L-PBF processing costs, further L-PBF productivity and lead
time improvement, minimized post-processing, improved surface roughness (both
through L-PBF and in combination with efficient post-processing) and secured quality
(including the L-PBF portion of the process). These improvements require research
and development both on “single” topics, e.g., L-PBF in a multi-spot array system
based on multi-diode lasers, and from a toolmaking system view, e.g., plants with a
high degree of automation and eventually cyber-physically controlled smart L-PBF
inclusive manufacturing systems.

Funding: This research received no external funding.

Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.

36
Metals 2021, 11, 458

Data Availability Statement: The data presented in this study are openly available in the referred
publications. See the reference list.
Acknowledgments: The author expresses his sincere gratitude to Vegard Brøtan, SINTEF Manufac-
turing AS, Norway, Marc Fette, Airbus/CTC GmbH, Germany, Gerhard Hackl, ASMET, Austria,
Professor Em. Jean-Pierre Kruth, KU Leuven, Belgium, Bernhard Langefeld, Roland Berger GmbH,
Germany, Alexander Leicht, RISE Research Institutes of Sweden, Bernhard Mueller, Fraunhofer IWU,
Germany, Professor Barbara Reggiani, UNIMORE, Italy, and Mirko Sinico, KU Leuven, Belgium, for
providing valuable information and in some cases permissions.
Conflicts of Interest: The author declares no conflict of interest.

Appendix A
In this appendix, the methodology and process used to create and structure this review
manuscript is described.
The purpose of this study was to conduct a review of the journey of the production
tools for cold working, hot working and injection molding from rapid tooling to Additive
Manufacturing (AM) by Laser-based Powder Bed Fusion (L-PBF).
To conduct this review, the keywords and the search profile were discussed with the
university library staff resulting in the following search profile:
metals (”direct rapid tooling” OR ”metal additive manufacturing” OR ”laser powder
bed fusion” OR ”selective laser melting” OR ”selective laser sintering”) (tools OR dies
OR molds)
This search profile was then used in the available engineering databases at the university
library: Materials Science and Engineering Database/Collection, Science Direct, Springer
Link and Wiley Online.
Table A1 displays the number of search results in this first step. See also Figure A1.

Table A1. The number of search results in the first step.

The Database Number of Results

Materials Science and Engineering Collection 401
Science Direct 5366
Springer Link 929
Wiley Online 972
Total 7668

To reduce the number of results, the obtained results (Table A1) were limited by using
a number of selection criteria. Table A2 displays the used selection criteria per database
and the number of the obtained results. See also Figure A1.
In step 3, the abstracts were reviewed and the duplications (or papers with “similar”
contents), papers that were not related to direct rapid tooling, papers that were not related
to production tools for cold working, hot working and injection molding, and the papers
that were related to selective laser sintering (SLS) published after 2005 were removed. See
also Figure A1.
In Step 4, the full papers were reviewed and
• similar papers were “neglected”, review papers were given a higher priority and
industrial tooling applications were focused, and
• the remaining papers were classified based on Metallic materials for tooling applica-
tions, Design, simulations and modelling, Equipment for SLS/SLM/L-PBF, Process de-
sign and parameters, Properties and performance, and Examples of tooling applications.

37
Metals 2021, 11, 458

Table A2. The selection criteria per database and the number of results. The indicated selection
criteria were applied to the results obtained in the first step, i.e., Table A1.

The Database Number of Results

Materials Science and Engineering Collection
Peer-reviewed, English 239
Science Direct
Open access,
Procedia CIRP, Additive Manufacturing, 325
Journal of Materials Processing Technology
Springer Link
Subdiscipline Manufacturing,
Machines, Tools, Processes, 212
English
Wiley Online
Journals,
Advanced Engineering Materials, 112
English
Total 888

Figure A1. The method applied for creating this review.

The selected review targets at this stage were to

1. set a baseline for the review by providing a brief historical background until 2005,
2. provide the capabilities of the 2020 L-PBF equipment/machines,
3. provide the chemical compositions and properties of the current materials for L-PBF
of production tools in cold working, hot working and injection molding,
4. describe the impact of feedstock and process parameters on the properties and performance,
5. provide the L-PBF process parameters for the above-mentioned tool materials,
6. provide a brief description of system, part and process design,
7. review some examples of tooling applications designed for and made by L-PBF,
8. discuss the advances made during the past 20 years and
9. draw some conclusions.

38
Metals 2021, 11, 458

Based on these selected targets, the remaining papers were kept in accordance with
the above-mentioned classification.
In step 5, relevant standards were reviewed. The papers presented at some relevant
conferences, such as the Tooling Conference, Metal Additive Manufacturing Conference
(MAMC), and Solid Freeform Fabrication symposium (SFF) were selected based on the
above-mentioned criteria and targets and reviewed. The websites of the material devel-
opers/producers and L-PBF machine builders were visited and the relevant material and
machine information were gathered from these websites. A google search was conducted,
the purpose of which was to find papers about the tooling materials mentioned above.
These papers were then reviewed. The same classification was used for this information.
See also Figure A1.
The review (manuscript) was then outlined based on the above-mentioned procedure
and submitted. As this manuscript was peer-reviewed, the reviewers suggested:
• that items 4 and 6 above should be focused on tooling applications, and
• some improvements. To facilitate these improvements, the reviewers provided addi-
tional 10 publication titles.
These publications were reviewed and the manuscript was modified in accordance
the reviewer suggestions.
As far as the machine builders are concerned, it is worth noting that Table 1 in the
manuscript is limited to seven machine builders.
The present review manuscript does not comprise tools made by “conventional”
powder metallurgy-based processes.
There is no bias in this review.

References
1. Prinz, F.B.; Atwood, C.L.; Aubin, R.F.; Beaman, J.J.; Brown, R.L.; Fussel, P.S.; Lightman, A.J.; Sachs, E.; Weiss, L.E.; Wozny, M.J.
Japanese and World Technology Evaluation Centers Panel Report on Rapid Prototyping in Europe and Japan; Analytical Chapters; Rapid
Prototyping Association of the Society of Manufacturing Engineers: Baltimore, MD, USA, 1997; Volume 1, ISBN 1-883712-44-0.
2. Matias, E.; Rao, B. 3D Printing: On Its Historical Evolution and the Implications for Business. In Management of the Technology Age,
Proceedings of the PICMET ‘15 Conference, Portland International Center for Management of Engineering and Technology (PICMET),
Portland, OR, USA, 2–6 August 2015; IEEE: Portland, OR, USA, 2015; pp. 551–558.
3. Karapatis, N.P.; van Griethuysen, J.-P.S.; Glardon, R. Direct rapid tooling: A review of current research. Rapid Prototyp. J. 1998, 4,
77–89. [CrossRef]
4. Kruth, J.-P. Rapid prototyping, a new application of physical and chemical processes for material accretion manufacturing. In
Proceedings of the 11th International Symposium for Electromachining, Lausanne, Switzerland, 17–21 April 1995; pp. 3–28.
5. Gebhardt, A. Rapid prototyping– laser-gestützte Revolution der Produktentwicklung. Laser Magazin 1996, 1, 6–9.
6. Wohlers, T. Rapid Prototyping State of the Industry: 1995–96 Worldwide Progress Report; Society of Manufacturing Engineers
Symposium: Dearborn, MI, USA, April 1996.
7. Styger, L. Rapid Prototyping and Tooling: The Enabling Technology of the ‘90s. IEE Manufacturing Division Colloquium on
Rapid Prototyping in the UK: Coventry, UK, 1994.
8. Rapid Prototyping: Rewriting the Rule Book; IEE Manufacturing Division Colloquium on Rapid Prototyping in the UK: Coventry,
UK, 1994.
9. CRIF-Liège Information Leaflet; CRIF: Liège, Belgium, 1996.
10. Lohner, A. Laser sintering ushers in new route to PM parts. Metal Powder Rep. 1997, 52, 24–30.
11. Girouard, D. The SLSTM selective laser sintering process: Technology, applications, and materials for advanced rapid prototyping.
In Proceedings of the IBEC ‘93, Detroit, MI, USA, 21–23 September 1993; pp. 10–14.
12. Shellabear, M.; Nyrhilä, O. Dmls—Development history and state of the art. In Proceeding of the 4th LANE (Laser Assisted Net
Shape Engineering), Erlangen, Germany, 21–24 September 2004.
13. Wohler, T.; Gornet, T. History of additive manufacturing. Wohler Rep. 2016, 24, 118.
14. Hejmadi, U.; McAlea, K. Selective laser sintering of metal molds: The RapidToolTM process. In Proceedings of the Annual
International Solid Freeform Fabrication Symposium, Austin, TX, USA, 12–14 August 1996; pp. 97–104.
15. Nyrhilä, O.; Syrjälä, S. Manufacture of Dimensionally Precise Pieces by Sintering. U.S. Patent 5,061,439, 5 December 1990.
16. Holger, D.; Pilz, R.; Eleser, N.S. Rapid tooling of EDM electrodes by means of selective laser sintering. Comput. Ind. 1999, 39,
35–45.

39
Metals 2021, 11, 458

17. Majewski, C.; Hopkinson, N. The Effect of Layer Thickness on Ejection Forces for Injection Moulded Parts Made Using DMLS
Tools. In Proceedings of the Annual International Solid Freeform Fabrication Symposium, Austain, TX, USA, 5–7 August 2002;
pp. 73–82.
18. King, D.; Tansey, T. Rapid tooling: Selective laser sintering injection tooling. J. Mater. Process. Technol. 2003, 132, 42–48. [CrossRef]
19. Kruth, J.-P.; Mercelis, P.; Van Vaerenbergh, J.; Froyen, L.; Rombouts, M. Advances in selective laser sintering. In Proceedings of
the 1st International Conference on Advanced Research in Virtual and Rapid Prototyping (VR@P), Leiria, Portugal, 1–4 October
2003; pp. 59–69.
20. Meiners, W.; Wissenbach, K.; Gasser, A. Selective Laser Sintering at Melting Temperature. U.S. Patent 6,215,093, 10 April 2001.
21. Neikov, O.D. Powders for Metal Additive Processing. In Handbook for Non-Ferrous Metal Powders—Technologies and Applications,
2nd ed.; Neikov, O.D., Naboychenko, S.S., Yefimov, N.A., Eds.; Elsevier: Amsterdam, The Netherlands, 2019; pp. 373–399,
ISBN 978-0-08-100543-9.
22. Meiners, W.; Over, C.; Wissenbach, K.; Poprawe, R. Direct Generation of Metal Parts and Tools by Selective Laser Powder
Remelting (SLPR). In Proceedings of the Annual International Solid Freeform Fabrication Symposium, Austain, TX, USA, 9–11
August 1999; pp. 655–661.
23. Kruth, J.-P.; Vandenbroucke, B.; Van Vaerenbergh, J.; Mercelis, P. Benchmarking of different sls/slm processes as rapid manufac-
turing techniques. In Proceeding of International Conference Polymers & Moulds Innovations (PMI), Gent, Belgium, 20–23 April
2005; pp. 1–7.
24. Sprinkle, T. The 5 Most Important Standards in Additive Manufacturing. ASTM Standardization News. 11 May 2020. Available
online: https://www.astm.org/standardization-news/?q=features/5-most-important-standards-additive-manufacturing-.html
(accessed on 25 November 2020).
25. ISO. International Standard ISO 52900, 2016—Additive manufacturing—General principles—Terminology (ISO/ASTM 52900, 2015, IDT);
ISO: Geneva, Switzerland, 2016.
26. ISO. International Standard ISO 17296-2, 2016—Additive manufacturing—General principles—Part 2, Overview of process categories and
feedstock (ISO 17296-2, 2015); ISO: Geneva, Switzerland, 2016.
27. Ålgårdh, J.; Strondl, A.; Karlsson, S.; Farre, S.; Joshi, S.; Andersson, J.; Ågren, J. State-of-the-Art for Additive Manufacturing of Metals;
Report 2016-03898—State-of-the-Art—Version 2.1; Swedish Arena for Additive Manufacturing of Metals: Stockholm, Sweden, 2017.
28. Criales, L.E.; Arısoy, Y.M.; Lane, B.; Moylan, S.; Donmez, A.; Özel, T. Laser powder bed fusion of nickel alloy 625, Experimental
investigations of effects of process parameters on melt pool size and shape with spatter analysis. Int. J. Mach. Tool Manuf. 2017,
121, 22–36. [CrossRef]
29. Schwarze, D. Auswirkungen der Bauraumvorheizung auf die thermomechanischen Bauteileigenschaften; Anwender Zentrum Augsburg,
IWB: München, Germany, 2010.
30. Over, C. Generative Fertigung von Bauteilen aus Werkzeugstahl X38CrMoV5-1 und Titan TiAl6V4 mit “Selective Laser Melting”; Shaker:
Aachen, Germany, 2003.
31. Niendorf, T.; Leuders, S.; Riemer, A.; Richard, H.A.; Tröster, T.; Schwarze, D. Highly Anisotropic Steel Processed by Selective
Laser Melting. Metall. Mater. Trans. B 2013, 44B, 794–796. [CrossRef]
32. Langefeld, B.; Moehrle, M.; Balzer, C.; Schildbach, P. Advancements in Metal 3D Printing—Beyond Powder Bed—Additive Manufactur-
ing on the Brink of Industrialization; Roland Berger: Munich, Germany, 2018.
33. 3D Systems, Printers and Materials Specifications. Available online: https://www.3dsystems.com (accessed on 27 November 2020).
34. Additive Industries, Printers and Materials Specifications. Available online: https://www.additiveindustries.com (accessed on
27 November 2020).
35. Concept Laser, Printers and Materials Specifications. Available online: https://www.ge.com/additive/who-we-are/concept-
laser (accessed on 27 November 2020).
36. EOS (Electro Optical Systems), Printers and Materials Specifications. Available online: https://www.eos.info/en (accessed on 27
November 2020).
37. SLM Solutions, Printers and Materials Specifications. Available online: https://www.slm-solutions.com/ (accessed on 27
November 2020).
38. Renishaw, Printers and Materials Specifications. Available online: https://www.renishaw.com/en/metal-3d-printing--32084
(accessed on 27 November 2020).
39. Trumpf, Printers and Materials Specifications. Available online: https://www.trumpf.com/en_INT/products/machines-
systems/additive-production-systems (accessed on 27 November 2020).
40. Liljengren, M.; Kjellsson, K.; Johansson, T.; Asnafi, N. Die Materials, Hardening Methods and Surface Coatings for Forming
of High, Extra High & Ultra High Strength Steel Sheets (HSS/EHSS/UHSS). In Proceedings of the Annual Conference of the
International Deep Drawing Research Group’s (IDDRG), Porto, Portugal, 19–21 June 2006; pp. 507–603.
41. Asnafi, N.; Johansson, T.; Miralles, M.; Ullman, A. Laser Surface-Hardening of Dies for Cutting, Blanking or Trimming of
Uncoated DP600. Proceeding of the Recent Advances in Manufacture & Use of Tools & Dies and Stamping of Steel Sheets,
Olofström, Sweden, 5–6 October 2004; pp. 169–190.
42. Asnafi, N. Tooling and Technologies for Processing of Ultra High Strength Sheet Steels. In Proceedings of the Tools and
Technologies for Processing Ultra High Strength Materials, Graz University of Technology, Graz, Austria, 19–21 September 2011.

40
Metals 2021, 11, 458

43. Sjöström, J. Chromium Martensitic Hot-Work Tool Steels—Damage, Performance and Microstructure. Ph.D. Thesis, Karlstad
University Studies, Karlstad, Sweden, 2004; p. 52, ISBN 91-85335-21-5.
44. Fuchs, K.-D. Hot-Work Tool Steels with Improved Properties for Die casting Applications. In Proceedings of the 6th International
Conference on Tooling, Karlstad, Sweden, 10–13 September 2002; pp. 17–26.
45. Klobčar, D.; Tušek, J.; Taljat, B. Thermal fatigue of materials for die-casting tooling. Mater. Sci. Eng. A 2008, 472, 198–207.
[CrossRef]
46. Vasco, J.; Capela, C.; Bártolo, P.; Granja, D. Material Selection for High Performance Moulds. In Proceedings of the SPE Meeting
Improving Quality and Tool Efficiency within Injection Moulding K2007, Düsseldorf, Germany, 25 October 2007; pp. 1–7.
47. Rebeggiani, S. On Polishability of Tool Steels; Chalmers University of Technology: Göteborg, Sweden, 2013; ISBN 978-91-7385-828-1.
48. Roberts, G.; Krauss, G.; Kennedy, R. Tool Steels, 5th ed.; ASM International: Novelty, OH, USA, 1998; ISBN 978-0-87170-599-0.
49. Højerslev, C. Tool steels. Risoe-R, No. 1244(EN); Risø National Laboratory, Forskningscenter Risoe: Roskilde, Denmark, 2001.
50. The online Material Properties Database MakeItFrom.com. Available online: https://www.makeitfrom.com (accessed on 12
September 2020).
51. Bajaj, P.; Hariharan, A.; Kini, A.; Kürnsteiner, P.; Raabe, D.; Jägle, E.A. Steels in additive manufacturing: A review of their
microstructure and properties. Mater. Sci. Eng. A 2020, 772, 138633. [CrossRef]
52. Böhler Edelstahl, Material Specifications. Available online: https://www.bohler-edelstahl.com/en/applications/3d-printing-
selective-laser-melting/ (accessed on 27 November 2020).
53. FORMETRIX, L-40 Specification. Available online: https://www.formetrixmetals.com/products/formetrix-l-40/ (accessed on 27
November 2020).
54. Eriksson, P. Evaluation of Mechanical and Microstructural Properties for Laser Powder-Bed Fusion 316L; Uppsala University: Uppsala,
Sweden, 2018.
55. Zai, L.; Zhang, C.; Wang, Y.; Guo, W.; Wellmann, D.; Tong, X.; Tian, Y. Laser Powder Bed Fusion of Precipitation-Hardened
Martensitic Stainless Steels: A Review. Metals 2020, 10, 255. [CrossRef]
56. Nath, S.D.; Irrinki, H.; Gupta, G.; Kearns, M.; Gulsoy, O.; Are, S. Micostructure-property relationships of 420 stainless steel
fabricated by laser-power bed fusion. Powder Technol. 2019, 343, 738–746. [CrossRef]
57. Zhao, X.; Wei, Q.; Song, B.; Liu, Y.; Luo, X.; Wen, S.; Shi, Y. Fabrication and Characterization of AISI 420 Stainless Steel Using
Selective Laser Melting. Mater. Manuf. Process. 2015, 30, 1283–1289. [CrossRef]
58. Kempen, K.; Vrancken, B.; Buls, S.; Thijs, L.; Van Humbeek, J.; Kruth, J.-P. Selective Laser Melting of Crack-Free High Density M2
High Speed Steel Parts by Baseplate Preheating. J. Manuf. Sci. Eng. 2014, 136, 061026-1. [CrossRef]
59. Mazur, M.; Brincat, P.; Leary, M.; Brandt, M. Numerical and experimental evaluation of conformally cooled H13 steel injection
mould manufactured with selective laser melting. Int. J. Adv. Manuf. Technol. 2017, 93, 881–900. [CrossRef]
60. Li, H.X.; Qi, H.L.; Song, C.H.; Li, Y.L.; Yan, M. Selective laser melting of P20 mould steel: Investigation on the resultant
microstructure, high-temperature hardness and corrosion resistance. Powder Metall. 2018, 61, 21–27. [CrossRef]
61. Uddeholm, AM Corrax Specification. Available online: https://www.uddeholm.com/sweden/sv/products/uddeholm-am-
corrax (accessed on 27 November 2020).
62. Asnafi, N.; Rajalampi, J.; Aspenberg, D.; Alveflo, A. Production Tools Made by Additive Manufacturing Through Laser-based
Powder Bead Fusion. Berg Huettenmaenn Mon. 2020, 165, 125–136. [CrossRef]
63. Mooney, B.; Kourousis, K.I. A Review if Factors Affecting the Mechanical Properties of Maraging Steel 300 Fabricated via Laser
Powder Bed Fusion. Metals 2020, 10, 1273. [CrossRef]
64. Vock, S.; Klöden, B.; Kirchner, A.; Weißgärber, T.; Kieback, B. Powders for powder bed fusion: A review. Prog. Addit. Manuf. 2019,
4, 383–397. [CrossRef]
65. Sames, W.J.; List, F.A.; Pannala, S.; Dehoff, R.R.; Babu, S.S. The metallurgy and processing science of metal additive manufacturing.
Int. Mater. Rev. 2016, 61, 315–360. [CrossRef]
66. Leicht, A. Aspects of Building Geometry and Powder Characteristics in Powder Bed Fusion; Tech Technical report no. IMS-2018-1; Ph.D.
Thesis; Chalmers University of Technology: Göteborg, Sweden, 2018.
67. Li, R.; Shi, Y.; Wang, Z.; Wang, L.; Liu, J.; Jiang, W. Densification behavior of gas and water atomized 316 L stainless steel powder
during selective laser melting. Appl. Surface Sci. 2010, 256, 4350–4356. [CrossRef]
68. Hoeges, S.; Zwiren, A.; Schade, C. Additive manufacturing using water atomized steel powders. Metal Powder Rep. 2017, 72,
111–117. [CrossRef]
69. Abdelwahed, M.; Casati, R.; Bengtsson, S.; Larsson, A.; Riccio, M.; Vedani, M. Effects of Powder Atomization on Microstructural
and Mechanical Behaviour of L-PBF Processed Steels. Metals 2020, 10, 1474. [CrossRef]
70. ASTM. F3049-14 Standard Guide for Characterizing Properties of Metal Powders Used for Additive Manufacturing Processes; ASTM
International: West Conshohocken, PA, USA, 2014.
71. Spierings, A.B.; Voegtlin, M.; Bauer, T.; Wegener, K. Powder flowability characterization methodology for powder-bed-based
metal additive manufacturing. Prog. Addit. Manuf. 2016, 1, 9–20. [CrossRef]
72. A Guidebook to Particle Size Analysis. Horiba Scientific. Available online: https://www.horiba.com (accessed on 27 November 2020).

41
Metals 2021, 11, 458

73. Karg, M.C.H.; Hentschel, O.; Ahuja, B.; Junker, D.; Hassler, U.; Schäperkötter, C.S.; Haimerl, A.; Arnet, H.; Merklein, M.; Schmidt, M.
Comparison of process characteristics and resulting microstructure of maraging steel 1.2709 in Additive Manufacturing via
Laser Metal Deposition and Laser Beam Melting in Powder Bed. In Proceedings of the 6th International Conference on Additive
Technologies, ICAT2016, Nürnberg, Germany, 29–30 November 2016; pp. 39–50.
74. Oliveira, J.P.; LaLonde, A.D.; Ma, J. Processing parameters in laser powder bed fusion metal additive manufacturing. Mater. Design
2020, 193, 108762. [CrossRef]
75. Metens, R.; Dadbakhsh, S.; Van Humbeeck, J.; Kruth, J.-P. Application of base plate preheating during selective laser melting.
Procedia CIRP 2018, 74, 5–11. [CrossRef]
76. Leicht, A. Laser Powder Bed Fusion of 316L Stainless Steel—Microstructure and Mechanical Properties as a Function of Process Param-
eters, Design and Productivity. Ph.D. Thesis, Chalmers University of Technology, Göteborg, Sweden, 2020; ISBN 978-91-7905-289-8.
77. Ali, H.; Ghadbeigi, H.; Mumtaz, K. Effect of scanning strategies on residual stress and mechanical properties of Selective Laser
Melted Ti6Al4V. Mater. Sci. Eng. A 2018, 712, 175–187. [CrossRef]
78. Bartlett, J.L.; Li, X. An overview of residual stresses in metal powder bed fusio. Addit. Manuf. 2019, 27, 131–149.
79. Saunders, M. How process parameters drive successful metal ALM part production. Metal AM 2018, 4, 127–135.
80. Kou, S. Welding Metallurgy, 2nd ed.; John Wiley & Sons: Hoboken, NJ, USA, 2003.
81. Wang, Z.; Denlinger, E.; Michaleris, P.; Stoica, A.D.; Ma, D.; Beese, A.M. Residual stress mapping in Inconel 625 fabricated
through additive manufacturing: Method for neutron diffraction measurements to validate thermomechanical model predictions.
Mater. Design 2017, 11, 3169–3177. [CrossRef]
82. Rodrigues, T.A.; Duarte, V.; Avila, J.A.; Santos, T.G.; Miranda, R.; Oliveira, J. Wire and arc additive manufacturing of HSLA steel:
Effect of thermal cycles on microstructure and mechanical properties. Addit. Manuf. 2019, 27, 440–450. [CrossRef]
83. Bobbio, L.D.; Bocklund, B.; Otis, R.; Borgonia, J.P.; Dillon, R.P.; Shapiro, A.A.; McEnerney, B.; Liu, Z.-K.; Beese, A.M. Characteriza-
tion of a functionally graded material of Ti-6Al-4V to 304L stainless steel with an intermediate V section. J. Alloys Compd. 2018,
742, 1031–1036. [CrossRef]
84. Carroll, B.E.; Otis, R.A.; Borgonia, J.P.; Suh, J.O.; Dillon, R.P.; Shapiro, A.A.; Hofmann, D.C.; Liu, Z.K.; Beese, A.M. Function-
ally graded material of 304L stainless steel and inconel 625 fabricated by directed energy deposition: Characterization and
thermodynamic modeling. Acta Mater. 2016, 108, 46–54. [CrossRef]
85. DebRoy, T.; Wei, H.L.L.; Zuback, J.S.S.; Mukherjee, T.; Elmer, J.W.W.; Milewski, J.O.O.; Beese, A.M.M.; Wilson-Heid, A.; De, A.;
Zhang, W. Additive manufacturing of metallic components—Process, structure and properties. Prog. Mater. Sci. 2018, 92, 112–224.
[CrossRef]
86. Dai, D.; Gu, D. Effect of metal vaporization behavior on keyhole-mode surface morphology of selective laser melted composites
using different protective atmospheres. Appl. Surface Sci. 2015, 355, 310–319. [CrossRef]
87. Zhong, Y.; Liu, L.; Wikman, S.; Cui, D.; Shen, Z. Intragranular cellular segregation network structure strengthening 316L stainless
steel prepared by selective laser melting. J. Nucl. Mater. 2016, 470, 170–178. [CrossRef]
88. Kluczyński, J.; Śnieżek, L.; Grzelak, K.; Janiszewski, J.; Płatek, P.; Torzewski, J.; Szachogłuchowicz, I.; Gocman, K. Influence of
Selective Laser Melting Technological Parameters on the Mechanical Properties of Additively Manufactured Elements Using
316L Austenitic Steel. Materials 2020, 13, 1449. [CrossRef] [PubMed]
89. Burns, D.E.; Kudzal, A.; McWilliams, B.; Manjarres, J.; Hedges, D.; Parker, P.A. Investigating Additively Manufactured 17-4 PH
for Structural Applications. J. Mater. Eng. Perform. 2019, 28, 4943–4951. [CrossRef]
90. Irrinki, H.; Dexter, M.; Barmore, B.; Enneti, R.; Pasebani, S.; Badwe, S.; Stitzel, J.; Malhotra, R.; Are, S. Effects of Powder Attributes
and Laser Powder Bed Fusion (L-PBF) Process Conditions on the Densification and Mechanical Properties of 17-4 PH Stainless
Steel. JOM 2016, 68, 860–868. [CrossRef]
91. Yan, J.; Zhou, Y.; Gu, R.; Zhang, X.; Quach, W.-M.; Yan, M. A Comparison Study of Steel Powders (316L, H13, P20 and 18Ni300)
for Their Selective Melting Additive Manufacturing. Metals 2019, 9, 86. [CrossRef]
92. Turk, C.; Zunko, H.; Aumayr, C.; Leitner, H.; Kapp, M. Advances in Maraging Steels for Additive Manufacturing. Berg-und
Hüttenmännische Mon. 2019, 164, 112–116. [CrossRef]
93. Jiang, J.; Chen, J.; Ren, Z.; Mao, Z.; Ma, X.; Zhang, D.Z. The influence of Process Parameters and Scanning Strategy on Lower
Surface Quality of TA 15 Parts Fabricated by Selective Laser Melting. Metals 2020, 10, 1228. [CrossRef]
94. Chen, Z.; Wu, X.; Tomus, D.; Davies, C.H.J. Surface roughness of Selective Laser Melted Ti-6Al-4V alloy components. Addit. Manuf.
2018, 21, 91–103. [CrossRef]
95. Snyder, J.C.; Thole, K.A. Understanding Laser Powder Bed Fusion Surface Roughness. J. Manuf. Sci. Eng. 2020, 142, 71003.
[CrossRef]
96. Wang, D.; Liu, Y.; Yang, Y. Theoretical and experimental study on surface roughness of 316L stainless steel metal parts obtained
through selective laser melting. Rapid Prototyp. J. 2016, 22, 706–716. [CrossRef]
97. Spierings, A.B.; Levy, G. Comparison of density of stainless steel 316L parts produced with selective laser melting using different
powder grades. In Proceedings of the Annual International Solid Freeform Fabrication Symposium, Austin, TX, USA, 3–5 August
2009; pp. 342–353.
98. Yang, T.; Liu, T.; Liao, W.; Macdonald, E.; Wei, H.; Chen, X. The Influence of Process Parameters on Vertical Surface Roughness of
the AlSi10Mg Parts Fabricated by Selective Laser Melting. J. Mater. Process. Technol. 2019, 266, 26–36. [CrossRef]

42
Metals 2021, 11, 458

99. Casalino, G.; Campanelli, S.L.; Contuzzi, N.; Ludovico, A.D. Experimental Investigation and Statistical Optimisation of the
Selective Laser Melting Process of a Maraging Steel. Opt. Laser Technol. 2015, 65, 151–158. [CrossRef]
100. Liu, B.; Wildman, R.; Tuck, C.; Ashcroft, I.; Hague, R. Investigation the Effect of Particle Size Distribution on Processing
Parameters Optimisation in Selective Laser Melting Process. In Proceedings of the Annual International Solid Freeform Fabrication
Symposium, University of Texas at Austin, Austin, TX, USA, 8–10 August 2011; pp. 227–238.
101. Sendino, S.; Martinez, S.; Lartategui, F.; Diaz, J.; Lamikiz, A.; Ukar, E. Surface Roughness Dependant Factors in Metal Bed
Fusion Processes. In Proceedings of the Joint Special Interest Group meeting between euspen (the European Society for Precision
Engineering and Nanotechnology) and ASPE (the American Society of Precision Engineering) on Advancing Precision in Additive
Manufacturing, Ecole Centrale de Nantes, Nantes, France, 16–18 September 2019.
102. Moylan, S.; Slotwinski, J.; Cooke, A.; Jurrens, K.; Donmez, M.A. An Additive Manufacturing Test Artifact. J. Res. Natl. Inst. Stand. Technol.
2014, 119, 429–459. [CrossRef] [PubMed]
103. Rebaioli, L.; Fassi, I. A review on benchmark artifacts for evaluating the geometrical performance of additive manufacturing
processes. Int. J. Adv. Manuf. Technol. 2017, 93, 2571–2598. [CrossRef]
104. Moshiri, M.; Tosello, G.; Mohanty, S. A new design for an extensive benchmarking of additive manufacturing machines. In
Proceedings of the 18th International Conference of the European Society for Precision Engineering and Nanotechnology (Euspen
18), Venice, Italy, 4–8 June 2018.
105. Moshiri, M.; Candeo, S.; Carmignato, S.; Mohanty, S.; Tosello, G. Benchmarking of Laser Powder Bed Fusion Machines. J. Manuf.
Mater. Process. 2019, 3, 85. [CrossRef]
106. Tomas, J.; Hitzler, L.; Köller, M.; von Kobylinski, J.; Sedlmajer, M.; Werner, E.; Merkel, M. The Dimensional Accuracy of
Thin-Walled Parts Manufactured by Laser-Powder Bed Fusion Process. J. Manuf. Mater. Process. 2020, 4, 91. [CrossRef]
107. Krish, S. A practical generative design method. Comput. Aided Des. 2011, 43, 88–100. [CrossRef]
108. Briard, T.; Segonds, F.; Zamariola, N. G-DfAM: A methodological proposal of generative design for additive manufacturing in the
automotive industry. Int. J. Interact. Des. Manuf. 2020, 14, 875–886. [CrossRef]
109. Bendsoe, M.P.; Sigmund, O. Topology Optimization: Theory, Methods and Applications; Springer: Berlin/Heidelberg, Germany, 2004.
110. Liu, X.; Yi, W.J.; Li, Q.S.; Shen, P.S. Genetic evolutionary structural optimization. J. Constr. Steel Res. 2008, 64, 305–311. [CrossRef]
111. Zhao, F. A nodal variable ESO (BESO) method for structural topology optimization. Finite Elem. Anal. Des. 2014, 86, 34–40.
[CrossRef]
112. Guo, X.; Zhang, W.; Zhang, J.; Yuan, J. Explicit structural topology optimization based on moving morphable components (MMC)
with curved skeletons. Comput. Methods Appl. Mech. Eng. 2016, 310, 711–748. [CrossRef]
113. Niendorf, T.; Brenne, F.; Schaper, M. Lattice Structures Manufactured by SLM: On the Effect of Geometrical Dimensionson
Microstructure Evolution During Processing. Metall. Mater. Trans. B 2014, 45B, 1181–1185. [CrossRef]
114. Schnabel, T.; Oettel, M.; Mueller, B.; Hoschke, K.; Pfaff, A.; Amund-Kopp, C.; Klöden, B.; Gebauer, M.; Töppel, T. Design for Additive
Manufacturing, Guidelines and Case Studies for Metal Applications; Fraunhofer IWU, EMI and IFAM: Dresden, Germany, 2017.
115. Pan, C.; Han, Y.; Lu, J. Design and Optimization of Lattuce Structures: A Review. Appl. Sci. 2020, 10, 6374. [CrossRef]
116. Dong, G.; Tang, Y.; Zhao, Y.F. A Survey of Modeling of Lattice Structures Fabricated by Additive Manufacturing. J. Mech. Des.
2017, 139, 100906. [CrossRef]
117. Kuo, T.C.; Huang, S.H.; Zhang, H.C. Design for manufacture and design for ‘X’: Concepts, applications, and perspectives.
Comput. Ind. Eng. 2001, 41, 241–260. [CrossRef]
118. Tomiyama, T.; Gu, P.; Jin, Y.; Lutters, D.; Kind, C.; Kimura, F. Design methodologies: Industrial and educational applications.
CIRP Ann. Manuf. Technol. 2009, 58, 543–565. [CrossRef]
119. Laverne, F.; Segonds, F.; Answer, N.; Le Coq, M. Assembly Based Methods to Support Product Innovation in Design for Additive
Manufacturing: An Exploratory Case Study. J. Mech. Des. 2015, 137, 121701. [CrossRef]
120. Reiher, T.; Lindemann, C.; Jahnke, U.; Deppe, G.; Koch, R. Holistic approach for industrializing AM technology: From part
selection to test and verification. Prog. Addit. Manuf. 2017, 2, 43–55. [CrossRef]
121. Wiberg, A.; Persson, J.; Ölvander, J. Design for additive manufacturing—A review of available design methods and software.
Rapid Prototyp. J. 2019, 25, 1080–1094. [CrossRef]
122. VDI. VDI Guideline 3405 Part 2—Additive Manufacturing Processes, Rapid Manufacturing—Beam Melting of Metallic Parts—Qualification,
Quality Assurance and Post Processing; VDI: Düsseldorf, Germany, 2013.
123. International Standard ISO/ASTM 52911-1. Additive Manufacturing—Design—Part 1, Laser-Based Powder Bed Fusion of Metals; ISO:
Geneva, Switzerland, 2019.
124. Reinarz, B.; Sehrt, J.T.; Witt, G.; Deiss, O.; van Kampen, J.; Münzer, J.; Ott, M. Optimization of media feed channels in laser beam
melting. Proc. ASPE. Berkeley 2014, 57, 13–18.
125. Hitzler, L.; Hirsch, J.; Heine, B.; Merkel, M.; Hall, W.; Öchsner, A. On the Anisotropic Mechanical Properties of Selective
Laser-Melted Stainless Steel. Materials 2017, 10, 1136. [CrossRef] [PubMed]
126. Li, R.; Kim, Y.S.; Tho, H.V.; Yum, Y.J.; Kim, W.J.; Yang, S.Y. Additive manufacturing (AM) of piercing punches by the PBF method
of metal 3D printing using mold steel powder materials. J. Mech. Sci. Technol. 2019, 33, 809–817. [CrossRef]
127. Zelený, P.; Váňa, T.; Stryal, J. Application of 3D Printing for Specific Tools. Mater. Sci. Forum 2016, 862, 316–323. [CrossRef]
128. Leal, R.; Barreiros, F.M.; Alves, L.; Romeiro, F.; Vasco, J.C.; Santos, M. Additive manufacturing tooling for the automotive industry.
Int. J. Adv. Manuf. Technol. 2017, 92, 1671–1676. [CrossRef]

43
Metals 2021, 11, 458

129. Asnafi, N.; Shams, T.; Aspenberg, D.; Öberg, C. 3D Metal Printing from an Industrial Perspective—Product Design, Production
and Business Models. BHM Berg-und Hüttenmännische Mon. 2019, 164, 91–100. [CrossRef]
130. Aspenberg, D.; Asnafi, N. Topology optimization of a U-bend tool using LS-TaSC. In Proceedings of the 12th European LS-DYNA
Conference, Koblenz, Germany, 14–16 May 2019.
131. Asnafi, N.; Rajalampi, J.; Aspenberg, D. Design and Validation of 3D-Printed Tools for Stamping of DP600. In Proceedings of the
IOP Conference Series: Materials Science and Engineering, 3–7 June 2019; Volume 651, p. 12010.
132. Skåre, T.; Asnafi, N. Forming and trimming of 2-mm thick DP600 sheet steel in tools and dies 3D-printed in maraging steel by
laser-based powder bed fusion. In Proceedings of the IOP Conference Series: Materials Science and Engineering, 26–30 October
2020; Volume 67, p. 12040.
133. Müller, B.; Gebauer, M.; Hund, R.; Malek, R.; Gerth, N. Metal Additive Manufacturing for tooling applications—Laser Beam
Melting technology increases efficiency of dies and molds. In Proceedings of the Metal Additive Manufacturing Conference 2014
(MAMC 2014) Meet the Future of Industrial Manufacturing Now! Vienna, Austria, 20–21 November 2014.
134. Reggiani, B.; Todaro, I. Investigation on the design of a novel selective laser melted insert for extrusion dies with conformal
cooling channels. Int. J. Adv. Manuf. Technol. 2019, 104, 815–830. [CrossRef]
135. Reggiani, B.; (University of Modena and Reggio Emilia (UNIMORE), Reggio Emilia, Italy). Personal communication, 15 February 2021.
136. Armillotta, A.; Baraggi, R.; Fasoli, S. SLM tooling for die casting with conformal cooling channels. Int. J. Adv. Manuf. Technol.
2014, 71, 573–583. [CrossRef]
137. Fette, M.; Sander, P.; Wulfsberg, J.; Zierk, H.; Herrmann, A.; Stoess, N. Optimized and Cost-Efficient Compression Molds Manufac-
tured by Selective Laser Melting for the Production of Thermoset Fiber Reinforced Plastic Aircraft Components. Procedia CIRP
2015, 35, 25–30. [CrossRef]
138. Fette, M.; (Airbus/CTC GmbH, Stade, Germany). Personal communication, 15 February 2021.
139. Milovanovic, J.; Stojkovic, M.; Trajanovic, M. Rapid tooling of tyre treat ring mould using direct metal laser sintering. J. Sci. Ind. Res.
2009, 68, 1038–1042.
140. Schlieper, G. Metal Additive Manufacturing grains ground in the tyre industry. Metal AM 2017, 3, 81–86.
141. Shellabear, M.; Weilhammer, J. Tooling Applications with EOSINT M; EOS Whitepaper: München, Germany, 2007.
142. Mazur, M.; Leary, M.; McMillan, M.; Elambasseril, J.; Brandt, M. ALM additive manufacture of H13 tool steel with conformal
cooling and structural lattices. Rapid Prototyp. J. 2016, 22, 504–518. [CrossRef]
143. Brøtan, V.; Åsebø Berg, O.; Sørby, K. Additive manufacturing for enhanced performance of molds. Procedia CIRP 2016, 54, 186–190.
[CrossRef]
144. Brøtan, V.; (SINTEF Manufacturing AS, Trondheim, Norway). Personal communication, 15 February 2021.
145. Sinico, M.; Ranjan, R.; Moshiri, M.; Ayas, C.; Langelaar, M.; Witvrouw, A.; van Keulen, F.; Dewulf, W. A Mold Case Study
on Topology Optimized Design for additive Manufacturing. In Proceedings of the 30th Annual International Solid Freeform
Fabrication Symposium, Solid Freeform Fabrication 2019—An Additive Manufacturing Conference 2019, Austin, TX, USA, 12–14
August 2019; pp. 1921–1931.
146. Sinico, M.; (KU Leuven, Leuven, Belgium). Personal communication, 15 February 2021.
147. Klahn, C.; Leutenecker, B.; Meboldt, M. Design for additive manufacturing—Supporting the Substitution of Components in
Series Products. Procedia CIRP 2014, 21, 138–143. [CrossRef]
148. Levy, G.N.; Schindel, R.; Kruth, J.P. Rapid manufacturing and rapid tooling with layer manufacturing (LM) technologies, state of
the art and future perspectives. CIRP Ann. 2003, 2, 589–609. [CrossRef]
149. Spierings, A.B.; Starr, T.L.; Wegener, K. Fatigue performance of additive manufactured metallic parts. Rapid Prototyp. J. 2013, 19,
88–94. [CrossRef]
150. Florian, H.; Bischof, C.; Hentschel, O.; Heberle, J.; Zettl, J.; Nagulin, K.Y.; Schmidt, M. Laser beam melting and heat treatment of
1.2343 (AISI H11) tool steel—Microstructure and mechanical properties. Mater. Scienec Eng. A 2019, 742, 109–115.
151. Zunko, H.; Turk, C.; Kapp, M.; Hofer, C. Corrosion resistant maraging steel for AM-produced plastic mold inserts. In Proceedings
of the 11th Tooling 2019 Conference & Exhibition—Communication along the Supply Chain in the Tooling Industry, Aachen,
Germany, 12–16 May 2019.
152. Oikonomou, C.; Karamchedu, S. A complete solution in metal AM for tooling applications—A case study on plastic injection
molding. In Proceedings of the 11th Tooling 2019 Conference & Exhibition—Communication Along the Supply Chain in the
Tooling Industry, Aachen, Germany, 12–16 May 2019.
153. Spierings, A.B.; Herres, N.; Levy, G. Influence of the particle size distribution on surface quality and mechanical properties in
additive manufactured stainless steel parts. Rapid Prototyp. J. 2011, 17, 195–202. [CrossRef]
154. Bischof, C.; Nitsch, G.; Scheitler, C.; Dressler, A.; Schmidt, M. Laser beam melting of water atomized iron base alloy FE 4800 with
in-situ alloying of carbon nanoparticles. In Proceedings of the 17th Annual international Conference of RAPDASA, Building on
the Foundations, Johannesburg, South Africa, 2–4 November 2016.
155. Karg, M.C.H.; Munk, A.; Ahuja, B.; Backer, M.V.; Schmitt, J.P.; Stengel, C.; Kuryntsev, S.V.; Schmidt, M. Expanding particle size
distribution and morphology of aluminium-silicon powders for Laser Beam Melting by dry coating with silica nanoparticles.
J. Mater. Process. Technol. 2019, 264, 155–171. [CrossRef]
156. Hinke, C.; Merkt, S.; Eibl, F.; Schrage, J.; Bremen, S. Additive Manufacturing: Perspectives for Diode Lasers. In Proceedings of the
IEEE High Power Diode Lasers and Systems Conference 2015, Coventry, UK, 14–15 October 2015; pp. 39–40.

44
Metals 2021, 11, 458

157. Zavala-Arredondo, M.; Boone, N.; Willmott, J.; Childs, D.T.D.; Ivano, P.; Groom, K.M.; Mumtaz, K. Laser diode area melting for
high speed additive manufacturing of metallic components. Mater. Des. 2017, 117, 305–315. [CrossRef]
158. AMPOWER GmbH & Co. KG. Additive Manufacturing, New Metal Technologies, Ampower Insights; AMPOWER GmbH & Co. KG:
Hamburg, Germany, 2020; Volume 6.
159. Roland Berger. Additive Manufacturing—A Game Changer for the Manufacturing Industry? Roland Berger: Munich, Germany, 2013.
160. Roland Berger. Additive Manufacturing (AM)—Opportunities in a Digitalized Production; Roland Berger: Munich, Germany, 2015.

45
 metals
Article
Additive Manufactured 316L Stainless-Steel Samples:
Microstructure, Residual Stress and Corrosion Characteristics
after Post-Processing
Suvi Santa-aho 1, * , Mika Kiviluoma 1 , Tuomas Jokiaho 1 , Tejas Gundgire 1 , Mari Honkanen 2 ,
Mari Lindgren 3 and Minnamari Vippola 1

1 Materials Science and Environmental Engineering, Tampere University, P.O. Box 589, 33014 Tampere, Finland;
[email protected] (M.K.); [email protected] (T.J.); [email protected] (T.G.);
[email protected] (M.V.)
2 Tampere Microscope Center, Tampere University, P.O. Box 692, 33014 Tampere, Finland;
[email protected]
3 Metso Outotec Research Center, Kuparitie 10, 28330 Pori, Finland; [email protected]
* Correspondence: [email protected]; Tel.: +358-408-4901-45

Abstract: Additive manufacturing (AM) is a relatively new manufacturing method that can pro-
duce complex geometries and optimized shapes with less process steps. In addition to distinct
microstructural features, residual stresses and their formation are also inherent to AM components.
AM components require several post-processing steps before they are ready for use. To change the
traditional manufacturing method to AM, comprehensive characterization is needed to verify the
suitability of AM components. On very demanding corrosion atmospheres, the question is does AM



lower or eliminate the risk of stress corrosion cracking (SCC) compared to welded 316L components?


This work concentrates on post-processing and its influence on the microstructure and surface and
Citation: Santa-aho, S.; Kiviluoma, subsurface residual stresses. The shot peening (SP) post-processing levelled out the residual stress
M.; Jokiaho, T.; Gundgire, T.; differences, producing compressive residual stresses of more than −400 MPa in the AM samples and
Honkanen, M.; Lindgren, M.; Vippola, the effect exceeded an over 100 µm layer below the surface. Post-processing caused grain refinement
M. Additive Manufactured 316L
and low-angle boundary formation on the sample surface layer and silicon carbide (SiC) residue
Stainless-Steel Samples: Microstructure,
adhesion, which should be taken into account when using the components. Immersion tests with
Residual Stress and Corrosion
four-point-bending in the heated 80 ◦ C magnesium chloride solution for SCC showed no difference
Characteristics after Post-Processing.
between AM and reference samples even after a 674 h immersion.
Metals 2021, 11, 182. https://
doi.org/10.3390/met11020182
Keywords: powder methods; additive manufacturing (AM); post-processing; residual stresses;
Received: 22 December 2020 316L stainless-steel; electron microscopy
Accepted: 18 January 2021
Published: 20 January 2021

Publisher’s Note: MDPI stays neutral 1. Introduction

with regard to jurisdictional claims in The additive manufacturing (AM) of metals is becoming more and more popular due
published maps and institutional affil- to its ability to produce complex geometries and parts on-demand from many different
iations. available powder materials with efficient material use [1,2]. Powder bed fusion (PBF) is
one of the metal AM methods which uses either laser (L-PBF) or electron beam (EB-PBF)
as a heat source to build the component in a layer-by-layer fashion and can produce
accurate, sub-millimeter features [3,4]. One widely used powder material in PBF (especially
Copyright: © 2021 by the authors. L-PBF) is austenitic stainless-steel 316L. Due to its superior corrosion resistance, 316L is
Licensee MDPI, Basel, Switzerland. widely used in different components facing demanding corrosion atmosphere in chemical,
This article is an open access article petrochemical, process and marine industry [5]. The microstructure of PBF 316L is usually
distributed under the terms and composed of columnar [6–9] grains oriented parallel to the thermal gradients, i.e., the build
conditions of the Creative Commons direction. These microstructural features are originated by the anisotropic heat removal
Attribution (CC BY) license (https:// and re-melting of previous layers, also leading to anisotropic mechanical properties [8,10].
creativecommons.org/licenses/by/
Compared to the wrought sheet materials, AM-produced 316L components have better
4.0/).

47

Metals 2021, 11, 182. https://doi.org/10.3390/met11020182 https://www.mdpi.com/journal/metals

Metals 2021, 11, 182

mechanical properties [8,9,11,12]. In the PBF manufactured components, the motion of

dislocations is hindered by various methods that all strengthen the 316L stainless-steel
material. The grain boundary strengthening according to the Hall-Petch effect [8] of the
very fine microstructure is formed due to the high cooling rate of the melt pool. In addition,
other strengthening mechanisms are the production of high dislocation density in the
as-built material [8], as well as the high amount of low-angle grain boundaries [9] and the
fine cellular structure with cell sizes from 0.5 to 1 µm [9,10,13,14].
In addition to the distinct microstructural features, the residual stresses and their
formation are also inherent to L-PBF manufactured components [15] due to the rapid
localized heating–cooling thermal cycling of the material. At first, the laser beam heats
the material and causes it to expand against the surrounding material and thus creates
compressive stresses. Then, while the laser beam moves on, the material cools rapidly
and its shrinking is constrained by the surrounding material, generating tensile residual
stresses [16]. However, the produced residual stress field is said to be very complicated due
to the complex heating and heat transfer [16]. The generating residual stresses may lead the
material to crack, delaminate [17] and deform [18], and thus the result may be broken or
warped components. Therefore, the controlling of the generation and end effects of residual
stresses both in-situ and after the actual manufacturing process are of great interest.
During the AM process, the controlling of residual stresses is done in-situ with either
feedback control, thermal gradient control, scanning strategy control and/or mechanical
control [15,19]. However, often the scan strategy is an important parameter in controlling the
formulating residual stresses in the printing [16,20,21]. For example, Robinson et al. [16,21]
noticed that the greatest magnitudes of residual stresses are parallel to the scan vector
and the scan vector direction determines the direction of primary residual stress. Residual
stresses can be controlled by the scanning strategy, but it requires a high amount of
designing and planning. Many characteristics of the component can be controlled during
the printing but usually, the printed components are treated with different post-processing
methods. These methods to control and mitigate residual stresses include heat treatments,
shot and laser shock peening [22,23] and machining [15]. In addition, other traditional
surface treatments could be applied, such as abrasive blasting, electropolishing and plasma
spraying. Surface finish optimization can also be done to improve the corrosion resistance
of the component [24]. Other reasons for post-processing are to increase the density of
component, tailor the mechanical properties [15] or homogenize the microstructure [3,15],
for instance.
The post-processing for residual stress controlling of AM 316L often includes a
stress relief annealing heat treatment (“a build-on-plate stress relief heat treatment” [15]).
Shiomi et al. [25] stated that the post-annealing reduces the residual stresses with 70% of
the as-built AM component manufactured from chrome molybdenum steel (JIS SCM440)
powder mixed with copper phosphate and nickel powders. The stress relief annealing
can be done in different steps: at first, the lower temperatures are used for relieving the
residual stresses and then higher temperatures for microstructure manipulation to produce
microstructures involving recrystallized equiaxed grains [26]. Kirka et al. [27] reported
for EB-PBF built Alloy 718 that the equiaxed grain structure could be beneficial for the
applications demanding isotropic mechanical properties. Cruz et al. [28] studied AM 316L
specimens subjected to three different stress-relieving heat treatments generating different
residual stresses after printing. They concluded that after 4 h at 400 ◦ C, no microstruc-
tural variations were found, and the cellular substructure became invisible after 5 min
at 1100 ◦ C [28], whereas the magnitude of the residual stress was closely related to the
temperature and duration of the heat treatment and the varying temperatures produced
23%, 64% and 92% stress relief at 400 ◦ C for 4 h, 650 ◦ C for 2 h, and 1100 ◦ C for 5 min
heat-treated specimens, respectively.
Mechanical treatments such as a shot peening (SP) as a post-treatment are used to
improve the as-built surface quality [29]. The shot peening also offers beneficial compres-
sive residual stresses to the component surface and subsurface. In addition, some novel

48
Metals 2021, 11, 182

post-processing methods have been studied. Chen et al. [24] used laser polishing for a
stainless-steel 316L surface and studied the corrosion behavior. The laser polishing melts
the top surface and therefore reduces the surface roughness. Additionally, it was observed
to refine the columnar structure in as-built sample into a fine cellular structure. The surface
roughness reduction and a fine cellular structure were also noticed to improve the corrosion
resistance. Wang et al. [23] utilized an ultrasonic impact peening and a laser shot peening
for AM 316L. They noticed the different effects of the two methods on the surface hardness,
yield strength and tendency of producing mechanical twins to the surface layer. Therefore,
it can be stated that the different post-processing methods would provide lots of tools to
manipulate or to tailor the surface layer characteristics [22,23].
Even though traditional stainless-steel 316L has a good corrosion resistance and it is
used in demanding applications where superior corrosion resistance is needed, the very
aggressive environments may cause pitting corrosion in chloride-bearing environments [30].
The corrosion responses of AM 316L have not been widely studied and more research in
this field is definitely needed. For example, the porosity has been noticed to affect the
corrosion properties of the AM component. Cruz et al. [28] used AM 316L specimens
(three different stress-relieving heat treatments generating different residual stresses after
printing) for pitting corrosion behavior tests in acidic FeCl3 solution. The weight loss
measurements after exposure showed that the residual stress did not significantly impact
the kinetics of pitting to AM 316L samples. New properties of the AM components have
merited testing under simulated operation conditions. Lou et al. [31] studied the AM
316L in a high-temperature annealed condition and its stress corrosion cracking (SCC) in
high-temperature water (288 ◦ C) with either dissolved oxygen or hydrogen. They did
not find any significant differences in crack growth rate between AM and traditionally
manufactured 316L. However, the intragranular oxide inclusions on grain boundaries were
found to cause oxidation and cracking.
In the present study, basic sheet AM 316L components were characterized by the
presence of residual stress, distinct microstructural features, etc., which could be detrimen-
tal in an actual working environment. In order to change the traditional manufacturing
method of certain 316L components to AM, thorough characterization is needed to verify
the suitability of AM components. Therefore, it is important to study these components
and the post-processing methods and investigate their effect on the microstructure, resid-
ual stress formation and corrosion behavior. On very demanding corrosion atmospheres,
the question is does AM lower or eliminate the risk of SCC compared to the welded 316L
component? Here, the AM 316L samples were tested in different conditions: as-built,
stress relief annealed and shot peened. A systematic investigation of surface and subsur-
face residual stresses as well as microstructure was also done in as-built and post-treated
conditions. The SCC behavior of the selected samples was also investigated. In our future
work, we will study more complex AM 316L shapes after different shot peening post-
processing variations to consider the effects of the shape. The complex shapes might need
more adjustment of the correct post-processing and may influence the functionality of the
component in demanding conditions.

2. Materials and Methods

In this study, simple strip geometry samples were printed with L-PBF and stud-
ied with various material characterization methods. The high molybdenum austenitic
stainless steel (EN 1.4432) 316L powder was used in AM (Table 1) manufactured by EOS
Finland. The AM samples were manufactured to match B-type U-bend samples according
to American Society for testing and Materials (ASTM) G30 [32], giving them dimensions
of 100 mm × 9 mm × 3 mm, as illustrated in Figure 1. For the reference in the SP and
immersion tests, similar samples (100 mm × 9 mm) were cut from the cold-rolled sheet.
Low molybdenum variant 316L (EN 1.4404) was used for the shot peening and high molyb-
denum variant 316L (EN 1.4432) for the immersion tests. The low molybdenum variant

49
Metals 2021, 11, 182

was provided in 3 mm thick sheets, while the high molybdenum variant was only available
in 1.95 mm thick sheets.

Table 1. Nominal chemical composition of studied 316L variant [33].

Element Fe Cr Ni Mo C Mn Cu P S Si N
– – –
(wt.%) balance 17–19 13–15 2.25–3 0.03 2 0.5 0.025 0.01 0.75 0.1

– – –

(a) (b)

Figure 1. (a) Additive manufacturing (AM) strip sample geometry from 316L stainless-steel. (b) Locations of residual stress
measurements from top and bottom sides (35, 50 and 65 mm from other end) and residual stress depth profiles from middle
of sample (50 mm).

The AM strip samples were manufactured by 3DFormtech (Jyväskylä, Finland) with an

EOS M290 L-PBF machine (Krailling, Germany) to a solid support structure. In total, 11 sam-
ples were printed to the solid structure build plate, at the same time, the 100 mm × 9 mm
surface was parallel to the build plate. All samples were oriented in the same direction and
they were located on two columns side by side with six or five samples on separate rows,
one below another. The printing parameters were the standard recommended settings
given by EOS-printing software. Hatch angle rotation of 47◦ and layer height of 40 µm was
used. The edges of samples were printed with 100 W laser power and 900 mm/s scanning
speed. The infill was done with 214 W laser power, 928 mm/s scanning speed and 100 µm
hatch spacing. The top surfaces of the samples were printed with 150 W laser power,
515 mm/s scanning speed and 100 µm hatch spacing. The bottom sides of the samples
were printed with the infill parameters. Eleven strips were treated with four different
post-process treatments introduced in the process diagram in Figure 2. After the printing,
five as-built samples were cut from the build plate with a band saw. The remaining six on
the build plate were heat-treated with a stress relief annealing at 1030 ◦ C for 60 min under
vacuum. The samples were cooled using flowing nitrogen gas. After this, the remaining
samples were cut from the build plate using a band saw.

Figure 2. Process chart of samples.

Shot peening was done as a post-treatment for two as-built samples, for three stress
relief annealed samples and for three reference samples. The shot peening was carried
out in the manual shot peening (SP) cabinet with silicon carbide (SiC) shots with hardness
50
Metals 2021, 11, 182

reported at 2000 HV [34], being much harder than the samples (as-built average hardness
220 HV0.05 ). Pressure in the SP system was 7 bar, and the flow rate of the shots were
calculated to be 11.4 g/s. The peening was carried out at a 20 cm distance from the sample
surface for either 1, 2 or a total of 3 s per surface. Overall, three of the samples were in
the as-built (AsB) condition, three were stress relief annealed (AsB HT), three were both
annealed and shot peened (HT SP), two samples were as-built and shot peened (AsB SP)
and three reference samples were shot peened, as illustrated in Figure 2.
The metallographic cross-sectional samples were prepared by grinding them with
320–4000 SiC papers and then electrolytical polisher (Struers, Ballerup, Denmark) with 10%
oxalic acid using 10 s etching time, 20 V as the voltage and a flow rate of 10. The hardness
depth profiles were done from the cross-sectional samples using the MMT-X7 (Matsuzawa,
Toshima, Japan) microhardness measurement device with a test load of 50 g.
The microstructure of the cross-sectional samples was studied by an optical microscope
DM 2500 M (Leica Microsystems, Renens, Switzerland) and a field emission scanning
microscope (FESEM) ULTRAplus (Zeiss, Jena, Germany). The microstructure of the samples
was also studied by a Symmetry electron backscatter diffraction (EBSD) system (Oxford
Instruments, Abingdon, United Kingdom) combined to the FESEM. A step size of 0.15 µm
and an acceleration voltage of 15 kV were used. The cross-sectional EBSD samples were
prepared by a traditional metallographic method followed by a final polishing using
colloidal silica suspension (0.04 µm). The EBSD data were collected by the AZtec software
(Oxford Instruments, Abingdon, United Kingdom) and post-processed and analyzed by
the CHANNEL 5 software (Oxford Instruments, Abingdon, United Kingdom). In the EBSD
results, a band contrast (BC) map represents the quality of the Kikuchi diffraction pattern for
each measurement pixel. In the BC map, bright color means that the pattern quality is good,
and the crystal orientation can be determined. Black signifies that the pattern quality is poor,
and indexing is not possible. The colors in the inverse pole figure (IPF) maps correspond to
the crystallographic orientations parallel to the observed plane (z direction), as indicated
by a colored stereographic triangle, i.e., an IPF coloring key. Different boundaries were also
analyzed and marked on the BC + IPF maps. Low-angle boundaries were considered when
the misorientation angle was 2–10◦ , high-angle boundaries with the angles >10◦ and twin
boundaries (Σ3) were defined by a 60◦ misorientation along the axis <111>. Phase maps
show the distribution of iron and silicon carbide.
The residual stresses (RS) were measured with a portable X-ray diffraction (XRD)-
based system XStress 3000 residual stress diffractometer (Stresstech Oy, Jyväskylä, Finland)
with the modified Chi method [35]. Measurements from all the samples were done along
the longitudinal (0) and transverse directions (90) in relation to the specimen surfaces
(illustrated in Figure 1a). The residual stresses from an austenitic steel at lattice plane (311)
with a diffraction angle of 148.9◦ were used with chromium K beta radiation. Measurements
were done with 3 mm diameter collimator. In total, six different surface RS measurements
were taken from one sample (Figure 1b). The measurement locations were from both
surfaces A (top) and B (bottom), from 35, 50 and 65 mm from the other end in the centerline
of the sheet sample. One of the locations (50 mm) was in the middle of the samples.
Residual stress depth profiles were taken from as-built, HT and reference samples together
with certain shot peened samples (one reference sheet, as-built and shot peened sample).
At first, the surface residual stress measurement was done. Next, material was removed
by electrolytical polishing with the MoviPol-5 electrolytical polisher (Struers, Ballerup,
Denmark) with A2 electrolyte containing perchloric acid and ethanol. The removed layer
was measured with a dial gage. This routine was repeated up to 100–120 µm depth below
the surface.
In order to verify the SCC behavior, the corrosion testing was performed in two test
series containing one as-built AM sample, one stress relief annealed AM sample and two
reference samples. One reference sample had high Mo content and other was similar,
having a weld in the middle. The samples were fixed to specially prepared 4-point bending
rigs manufactured from aluminum and painted with epoxy paint. The immersion was

51
Metals 2021, 11, 182

performed at 80 ◦ C in a thermal cabinet in a 50% magnesium chloride solution with 75% of

yield strength condition with the 4-point bending rigs. The corrosion test series exposure
times were 237 and 674 h for two separate test series. After the immersion tests, sample
cross-sections were analyzed with an optical microscope in order to reveal possible stress
corrosion cracks.

3. Results
3.1. Microstructural Observations
The microstructure of the AM 316L in as-built and after stress relief annealing condi-
tions was studied by the optical microscope and FESEM-EBSD (Figures 3 and 4). The L-PBF
selectively melts the powder layers which then solidify, bowl-shaped fusion boundary
structures are visible in the as-built structure and the elongated, different-sized grains are
oriented parallel to the build direction, where temperature is higher in the upper printed
layer (Figure 3a). The overlapping features are resulting from the solidification of the melt
pool after each laser scan. The layer thickness in the AM was 40 µm. The surface layer
thickness was, however, larger, as seen in the Figure 3a, because the top layer processing
parameters (lower laser power, lower speed) were different. In the stress relief annealed
AM sample (Figure 3b), the melt pool boundaries were no longer as visible as in the as-built
sample (Figure 3a). Figure 4 presents the FESEM images of the AsB 316L sample, showing
the cellular structure within the grains. The cell size was measured to be, on average,
0.7 µm in diameter with the intercept technique. The cellular structure changed at the
austenite grain boundaries and some of the grains continued across the fusion boundaries.

Figure 3. Optical microscope image from surface (left) and inverse pole figure (IPF) map superim-
posed on band contrast (BC) map from bulk (right) for (a) AsB AM sample and (b) AsB HT AM
sample. The colors in the IPF maps
– correspond to the orientations (z direction), as indicated by (c) IPF
coloring key for austenite (iron face-centered cubic structure, Fe-FCC). In IPF + BC maps, low-angle
boundaries (2–10◦ ) are marked by white lines and high-angle boundaries (>10◦ ) by black lines.
52
Metals 2021, 11, 182
–

Figure 4. Scanning electron microscopy images of AsB AM 316L sample.

The microstructure of the reference sheet sample and AsB AM 316L was studied by
FESEM-EBSD after the shot peening (Figure 5). The AsB HT AM 316L had similar structure
as the as-built condition and it is not shown separately. In the bulk of the reference sheet
sample, homogenous, round-shaped austinite grains existed, with some twin boundaries
(Σ3). All samples studied had a non-indexable or weakly identified 10–20 µm thick surface
layer, indicating the formation of extremely refined or heavily deformed crystals during
the SP. Below this non- or weakly indexable surface layer, many strain-induced, mainly
low-angle, boundaries were formed within the austenitic grains (Figure 5). In the refer-
ence sample, also a very small amount of the martensitic structure was observed in the
subsurface layer. However, no martensite was observed in the AM samples. The hardness
depth profiles of the cross-sectional samples presented in Figure 6 verified the increased
hardness values after the SP (from 200 to 250 HV0.05 base level to 300–400 HV0.05 ) in the
subsurface layer. Based on the phase maps (Figure 5), SiC residues from the SP existed on
all sample surfaces.

Figure 5. Inverse pole figure (IPF) map superimposed on band contrast (BC) map (with two magnifications, left side and
right side) and phase map (middlemost) superimposed on BC map collected after shot peening from (a) reference sheet
sample (SP, 3 s) and (b) AsB AM sample (SP, 2 s). Colors in IPF maps correspond to orientations (z direction), –as indicated
by (c) IPF coloring key for austenite (Fe-FCC) and silicon carbide (SiC). On BC + IPF maps, low-angle boundaries (2–10◦ ) are
marked by white lines, high-angle boundaries (>10◦ ) by black lines and twin boundaries (60◦ <111>) by red lines. In phase
maps, iron (austenite) is blue and silicon carbide is yellow, and some of the residual silicon carbides are marked by arrows.
53
 –
Metals 2021, 11, 182

Figure 6. Hardness depth profiles of the cross-sectional samples: AsB HT SP, AsB SP, Ref SP (1 s peening) and REF SP
(3 s peening).

3.2. Residual Stresses

Surface residual stresses were measured from all different sample categories presented
in the Figure 2 process chart. It should be noted that the penetration of the X-rays exceeds
only few microns into the material with the XRD method. AsB AM components (numbered
as 1, 2, 3) had different residual stress states on the top and bottom surfaces, as presented
in Figure 7a. Figure 7b presents the surface residual stress results from three stress relief
annealed samples (top and bottom). The annealing treatment decreased the surface residual
stresses compared to the AsB samples in top and bottom surfaces (Figure 7a). The effect
of the SP is shown in Figure 7c. As expected, all the shot peened samples (AsB SP, HT SP
and reference (Ref) sheet SP) had compressive residual stresses on both measurement
directions and measured surfaces. The SP created much more compressive stresses to the
AM component surface (both as-built and heat-treated) compared to the reference sheet
sample (average of −555 MPa on the as-built HT SP and −502 MPa on the as-built SP
versus −186 MPa on the Ref SP).
Figure 8 presents the residual stress depth profiles measured from the longitudinal
(0) and the transverse (90) directions from the middle of the samples. Three RS profiles
were measured for the as-built sample (the top and bottom surfaces) and the stress relief
annealed sample (the bottom surface). The other RS profiles were measured for the shot
peened samples: the AsB was shot peened for 1 s and the reference sheet samples were shot
peened either for 1 s (Ref sheet SP1) or 3 s (Ref sheet SP3). Residual stress depth profiles
measured from the shot peened samples (Figure 8) showed a typical profile of compressive
residual stress reaching a maximum compression below the surface of the component and
then constantly decreasing towards zero. The reference sample shot peened once (1 s) had a
maximum of −620 MPa and a minimum of −130 MPa at 100 µm below the surface, and the
three times (totally 3 s) shot peened sample had more intense compressive stresses under
its surface, ranging from a maximum of −700 to −400 MPa. The shot peened AsB AM
sample stands between the shot peened reference samples, at −600 to −280 MPa at 100 µm
below the surface. The effect of the SP exceeded over the measured 100 µm layer (Figure 8)
in all samples. The SP for 1 s was almost able to transform the 200 MPa tensile residual
stress to a maximum of −600 MPa compression below (20 µm) the surface. In addition,

54
Metals 2021, 11, 182

−5 RS state to the surface and below the

as supposed, the SP produced a uniform −5surface if
the different measurement
−1 directions 0 and 90 are compared.

Figure 7. (a) Surface residual stresses of three AsB AM samples (top) and (bottom) surfaces in longitudinal and tangential
directions. Typical deviation was–20–40 MPa. (b) Surface residual stresses of three stress relief annealed AM samples (top)
and (bottom) surfaces in longitudinal and tangential directions. Typical deviation was 20–40 – MPa. (c) Surface residual
stresses of shot peened samples AsB, HT and Ref (top), and (bottom) surfaces in longitudinal and tangential directions.

55
 −7 −4
−6
−2

Metals 2021, 11, 182 −6

Figure 8. Residual stress depth profiles from 0 and 90 measurement direction for as-built (top and bottom surfaces) and
heat-treated samples (bottom surface), and the as-built sample shot peened 3 s and Ref sheet shot peened either 1 or 3 s.

3.3. Immersion Tests in Magnesium Chloride

The possibility of SCC was studied by the 237 and the 674 h immersions in magnesium
chloride at 80 ◦ C in four-point bending rigs. The cross-sections of the samples after
immersion tests were studied with an optical microscope at two different depths: surface
and 0.5 mm depth from the surface. Any signs of corrosion or cracking were not detected
in the AM components, AsB, AsB + HT or references (the 316L sheet and the 316L sheet
with the weldment). Figure 9 shows examples of optical micrographs of (a) AsB sample
and (b) AsB HT material after first corrosion test, and (c) AsB sample and (d) AsB HT
material after second corrosion test with no signs of SCC.

56
Metals 2021, 11, 182

Figure 9. Optical micrographs of (a) AsB sample and (b) AsB HT after first corrosion test, and (c) AsB sample and (d) AsB
HT after second corrosion test.

4. Discussion
Different post-processing treatments (as-built, stress relief annealed and shot peening)
for simple AM 316L samples were investigated and their effect on the residual stress state
and microstructure were determined. The microstructures of AsB AM 316L consisted of
bowl-shaped fusion boundary structures and the elongated, different-sized grains were
oriented parallel to the build direction. In addition, there were many low-angle boundaries
within the austenitic grains, agreeing with the literature that a large fraction of low-angle
grain boundaries exist in AM 316L, e.g., References [9,14]. The melt pool boundaries were
no longer as visible in the stress relief annealed AM sample compared to the as-built
sample. The AsB sample contained cellular structure within the grains which changed
at the austenite grain boundaries, and some of the grains continued across the fusion
boundaries. This kind of hierarchical and inhomogeneous microstructure is typical for
AM 316L [9,14,36].
Microstructural studies showed that the bulk reference sheet sample consisted of ho-
mogenous, round-shaped austenite grains with some twin boundaries (Σ3), (Σ3) considered as
annealing twins. All studied samples had a non-indexable or weakly identified 10–20 – µm
thick surface layer, indicating the formation of extremely refined or heavily deformed
crystals during the SP. Below this surface layer, many strain-induced, mainly low-angle,
boundaries were formed within the austenitic grains. Very small amount of martensite
was observed in the subsurface layer of the reference sample. However, martensite was
not observed from AM samples. The hardness depth profiles of the cross-sectional samples
verified the increased hardness values after the SP in the subsurface layer, probably because
of the grain refinement and formation of low-angle boundaries. Our findings here agree
well with the literature. Based on the studies by Shakhova et al. [37], cold-working of
conventional austenitic stainless-steel results in strain-induced boundaries, mainly asso-
ciated with deformation twin boundaries, and then a martensitic transformation starts

57
Metals 2021, 11, 182

primarily at these twins. Both strain-induced martensitic transformation and deformation

twins promote the grain refinement [37]. Hong et al. [14] noticed that in the AM 316L
sample, no martensite and deformation twins existed after a tensile test at room temper-
ature. They assumed that the high density of low-angle boundaries and a fine cellular
microstructure hinder dislocation slip and deformation twinning, decreasing the nucleation
sites for martensite. Pham et al. [38] noticed deformation-induced twins (Σ3) in AM 316L
after tensile tests at room temperature but no martensite transformation.
AsB AM components had different surface residual stresses on the top and bottom
surfaces. One reason for this is the different printing parameters on the top and bottom
surfaces. In addition, a sample removal with a band saw from the build plate affected the
bottom surface stresses. The difference in residual stress values between measurement
directions in the as-built samples can be explained by the fact that they have different orien-
tation on the build plate while printing, or that the sample had different orientation during
band sawing. It should be noted that the surface residual stresses on all as-built samples
(1, 2, 3) had variations between the different measurement locations on the AM strip and
some variations existed also on the band saw bottom surface results. In addition, normally,
the components are removed from the build plate after the heat treatment. The causes
for the surface residual stress variations might also be the anisotropic heat removal and
re-melting of previous layers producing thermal gradients and their effects on the produced
residual stresses [16,21]. The surface residual stress results from the top surfaces of the
as-built samples are similar to the results reported by Ghasri-Khouzani et al. [18] with
5 mm thick disks of 316L after being removed from the build plate. The varying residual
stresses in the different surface regions may be caused by the heterogeneous microstructure
and the location-dependent lattice spacings, as suggested in Li et al. [15].
The annealing treatment was noticed to decrease the surface residual stresses com-
pared to the AsB samples in top and bottom surfaces. One reason for the different stress
levels for the bottom surface is that the heat-treated samples were cut in a different orientation
than the as-built samples, which was verified by visual observations of the cutting marks
on the samples. When comparing the top surface results, the stress state was, somewhat
unexpectedly, slightly more compressive in the annealed sample than in the as-built sam-
ple. The stress state after the heat treatment was expected to be more homogeneous and
stress-free. Regardless of the original AM condition (as-built or heat-treated), the post-
processing shot peening decreased the surface residual stress results approximately −400
to −600 MPa in both directions. Even if the SP was rather quick, it produced notable
compressive residual stresses.
The AsB sample had almost a constant tensile RS depth profile in the top surface in
both measured directions. This result is in line with previous studies [18,39]. While the
metal powder is added on to the surface of the build plate, it causes the molten metal to
cool rapidly and to contract. Tensile residual stresses are developing in the material as
the shrinking material is constrained. Correspondingly, compressive residual stresses are
developing in the build plate. These stresses are relieved when a new powder is added on
the top of the first layer, while layers re-melt and new hot powder effectively anneals it [8].
This continuous process of cooling and annealing generates a residual stress state such that
the bottom of the component is in compression while the top is in tension, with a neutral
axis somewhere in between.
Based on the measurements here, it is obvious that a stress state with compression
at the bottom and tension at the top was present in the as-built samples if they were cut
from the build plate prior to the heat treatment. The stress relief annealed samples were
cut from the build plate after the heat treatment. The residual stress profile from the
heat-treated bottom surface showed compressive residual stresses both in longitudinal
and in transverse directions. The transverse direction showed even higher compression
on the surface. The band saw might also affect 90 µm below the surface from the bottom
surface because the residual stress was closer to zero, compared to the bottom surface of
the as-built sample, but it still compressed.

58
Metals 2021, 11, 182

In addition, the stress corrosion cracking resistance of AM 316L was tested in magne-
sium chloride atmosphere. The magnesium chloride solution was chosen as it is widely
known, and it has been shown to be more aggressive than sodium chloride [40]. Due to our
testing equipment limitations, the standardized ASTM G36 boiling magnesium chloride
test was not possible, but an 80 ◦ C study was conducted. Any signs of corrosion or cracking
were not detected in the AM components or reference samples. Therefore, it can be sum-
marized that the AM components had similar tolerance against stress corrosion cracking to
the 316L sheet and the sheet with the weldment. It is generally known that SCC might be
rapid in sheet 316L, and the failure can occur, in the worst case, also in a short time [41].
Some results of the SCC behavior of austenitic stainless-steels in chloride solutions have
been reported. SCC of 316 stainless-steel at 3.5 and 9.35 wt.% NaCl solutions at room
temperature under a constant load was studied by Elsariti and Haftirman [41]. They [41]
reported that no cracks were detected after 404 h of exposure. After 838 h in the 9.35 wt.%
NaCl solution and after 1244 h in 3.5 wt.% NaCl, the samples had cracked [41]. The tests
here were performed for AM 316L steel in 50 wt.% MgCl2 solution at 80 ◦ C for up to
674 h. The conditions and materials here and in Reference [41] are quite different, making a
comparison hard, but possible. 316L is generally considered to be more corrosion-resistant
owing to its added molybdenum content [42]. Elsariti’s and Haftirman’s [41] observa-
tions about SCC in 316 steel in the 9.35 wt.% NaCl solution indicated a relation between
chloride concentration and SCC incubation time. Therefore, it is surprising that no SCC
was observed in our study on 316L at much higher chloride concentration at an exposure
time between the two observation times of 404 and 838 h of Elsariti and Haftirman [41].
The immersion in this study was carried out at 80 ◦ C, while their [41] tests were done at
room temperature. The intensity of loading was not mentioned in Reference [41], stating
only that a constant load setup was used. The studied materials (316 vs 316L) were also
slightly different, although 316L is generally considered more corrosion-resistant only after
welding, where the low carbon content of 316L inhibits the precipitation of chromium
carbides [42]. The tensioning of the samples might have been influenced and caused the
stress to be under the threshold stress required to initiate SCC. In the future, immersion
tests will be performed also for the shot peened AM samples to verify the possible effect of
SiC residues on the corrosion behavior.

5. Conclusions
Regardless of the benefits of the metal AM, the method still requires several post-
processing steps before the component is ready for use. Residual stress generation during
the whole processing chain is one important aspect when considering the performance
of the part in very demanding atmospheres where, e.g., stress corrosion cracking (SCC)
might be possible. In this study, we investigated the effect of different post-treatments
on the residual stress state and microstructure of AM 316L and its corrosion resistance
in magnesium chloride atmosphere. The main findings of this study are summarized
as follows:
• The surface residual stresses varied according to the location due to the complex
heating–cooling cycles in AM. The range of surface residual stress variation was
150 MPa in the AsB and 90 MPa in the AsB HT sample. The band sawing produced
more compressive surface residual stresses that were also dependent on the saw-
ing orientation.
• Subsequent shot peening levelled out the residual stress differences in different mea-
surement directions, producing compressive residual stresses of more than −400 MPa
in the AM samples and the effect of the shot peening exceeded the measured 100 µm
layer below the surface.
• The shot peening left residues of SiC on the surfaces, which should be taken into
account during the use of the components. In addition, the grain refinement and the
formation of low-angle boundaries on the sample surfaces were observed after the
shot peening.

59
Metals 2021, 11, 182

• The immersion testing for 273 and 674 h in the magnesium chloride atmosphere at
80 ◦ C with four-point bending did not produce any signs of pitting corrosion nor
cracking in the AM components or sheet 316L references.

Author Contributions: Conceptualization, M.K., S.S.-a. and M.H.; methodology, M.K.; software,
S.S.-a.; validation, T.J.; formal analysis, S.S.-a.; investigation, M.K., S.S.-a., M.H. and T.J.; resources,
S.S.-a.; data curation, S.S.-a.; writing—original draft preparation, M.K., S.S.-a., M.H., T.G. and
T.J.; writing—review and editing, S.S.-a., M.H., M.L., T.J., T.G. and M.V.; visualization, T.J. and
S.S.-a.; supervision, M.L. and M.V. All authors have read and agreed to the published version of
the manuscript.
Funding: This research was partly funded by Association of Finnish Steel and Metal Producers,
grant number 750/19.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data presented in this study are available on request from the
corresponding author. The data are not publicly available due the data also forms part of an
ongoing study.
Acknowledgments: 3D Formtech Oy (especially Sami Koivulahti and Toni Järvitalo) is thanked for
the collaboration with sample preparation. SEM and EBSD studies made use of Tampere Microscopy
Center facilities at Tampere University.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Gausemeier, J.; Echterhoff, N.; Wall, M. Thinking Ahead the Future of Additive Manufacturing–Innovation Roadmapping of Required
Advancements; Direct Manufacturing Research Center, University of Paderborn: Paderborn, Germany, 2013; p. 110.
2. Attaran, M. The rise of 3-D printing: The advantages of additive manufacturing over traditional manufacturing. Bus. Horiz. 2017,
60, 677–688. [CrossRef]
3. Bourell, D.; Kruth, J.P.; Leu, M.; Levy, G.; Rosen, D.; Beese, A.M.; Clare, A. Materials for additive manufacturing. CIRP Ann.
Manuf. Technol. 2017, 66, 659–681. [CrossRef]
4. SFS-EN ISO 17296-2: Additive manufacturing. In General Principles; Part 2: Overview of process categories and feedstock
(ISO 17296-2:2015); Finnish Standards Association SFS: Helsinki, Finland, 2016.
5. Tucho, W.M.; Lysne, V.H.; Austbø, H.; Sjolyst, K.A.; Hansen, V. Investigation of effects of process parameters on microstructure
and hardness of SLM manufactured SS316L. J. Alloys Compd. 2018, 740, 910–925. [CrossRef]
6. Thijs, L.; Verhaeghe, F.; Craeghs, T.; Humbeeck, J.; Kruth, J.P. A study of the microstructural evolution during selective laser
melting of Ti-6Al-4V. Acta Mater. 2010, 58, 3303–3312. [CrossRef]
7. Vilaro, T.; Colin, C.; Bartout, J.D. As-fabricated and heat-treated microstructures of the Ti-6Al-4V alloy processed by selective
laser melting. Metall Mater. Trans. A Phys. Metall Mater. Sci. 2011, 42, 3190–3199. [CrossRef]
8. Gorsse, S.; Hutchinson, C.; Gouné, M.; Banerjee, R. Additive manufacturing of metals: A brief review of the characteristic
microstructures and properties of steels, Ti-6Al-4V and high-entropy alloys. Sci. Technol. Adv. Mater. 2017, 18, 584–610. [CrossRef]
[PubMed]
9. Wang, Y.M.; Voisin, T.; Keown, J.T.; Ye, J.; Calta, N.P.; Li, Z.; Zheng, Z.; Zhang, Y.; Chen, W.; Roehling, T.T.; et al. Additively
manufactured hierarchical stainless steels with high strength and ductility. Nat. Mater. 2018, 17, 63–70. [CrossRef] [PubMed]
10. Casati, R.; Lemke, J.; Vedani, M. Microstructure and Fracture Behavior of 316L Austenitic Stainless Steel Produced by Selective
Laser Melting. J. Mater. Sci. Technol. 2016, 32, 738–744. [CrossRef]
11. Montero, M.; Nardone, S.; Hautfenne, C.; Humbeeck, J. Effect of Heat Treatment of 316L Stainless Steel Produced by Selective
Laser Melting (SLM). In Proceedings of the 27th Annual International Solid Freeform Fabrication Symposium-An Additive
Manufacturing Conference, Austin, TX, USA, 8–10 August 2016; pp. 558–565.
12. Herzog, D.; Seyda, V.; Wycisk, E.; Emmelmann, C. Additive manufacturing of metals. Acta Mater. 2016, 117, 371–392. [CrossRef]
13. Lou, X.; Song, M.; Wang, M.; Was, G.S.; Rebak, R.B. Radiation damage and irradiation-assisted stress corrosion cracking of
additively manufactured 316L stainless steels. J. Nucl. Mater. 2018, 513, 33–44.
14. Hong, Y.; Zhou, C.; Zheng, Y.; Zhang, L.; Zheng, J.; Chen, X.; An, B. Formation of strain-induced martensite in selective laser
melting austenitic stainless steel. Mater. Sci. Eng. A 2019, 740–741. [CrossRef]
15. Li, C.; Liu, Z.Y.; Fang, X.Y.; Guo, Y.B. Residual Stress in Metal Additive Manufacturing. Procedia CIRP 2018, 71, 348–353. [CrossRef]
16. Robinson, J.H.; Ashton, I.R.T.; Jones, E.; Fox, P.; Sutcliffe, C. The effect of hatch angle rotation on parts manufactured using
selective laser melting. Rapid Prototyp. J. 2018, 25, 289–298. [CrossRef]

60
Metals 2021, 11, 182

17. Humbeeck, J.; Buls, S.; Thijs, L.; Kempen, K.; Vrancken, B.; Kruth, J.P. Selective Laser Melting of Crack-Free High Density M2
High Speed Steel Parts by Baseplate Preheating. J. Manuf. Sci. Eng. 2014, 136, 061026.
18. Ghasri, K.M.; Peng, H.; Rogge, R.; Attardo, R.; Ostiguy, P.; Neidig, J.; Billo, R.; Hoelzle, D.; Shankar, M.R. Experimental
measurement of residual stress and distortion in additively manufactured stainless steel components with various dimensions.
Mater. Sci. Eng. A 2017, 707, 689–700.
19. Kim, H.; Lin, Y.; Tseng, T.L.B. A review on quality control in additive manufacturing. Rapid Prototyp. J. 2018, 24, 645–669.
[CrossRef]
20. Cheng, B.; Shrestha, S.; Chou, K. Stress and deformation evaluations of scanning strategy effect in selective laser melting.
Addit. Manuf. 2016, 12, 240–251.
21. Robinson, J.; Ashton, I.; Fox, P.; Jones, E.D.; Sutcliffe, D. Determination of the effect of scan strategy on residual stress in laser
powder bed fusion additive manufacturing. Addit. Manuf. 2018, 23, 13–24. [CrossRef]
22. Kalentics, N.; Boillat, E.; Peyre, P.; Ciric, K.S.; Bohojevic, N.; Loge, R.E. Tailoring residual stress profile of Selective Laser Melted
parts by Laser Shock Peening. Addit. Manuf. 2017, 16, 90–97. [CrossRef]
23. Wang, Z.D.; Sun, G.F.; Lu, Y.; Chen, M.Z.; Bi, K.D.; Ni, Z.H. Microstructural characterization and mechanical behavior of ultrasonic
impact peened and laser shock peened AISI 316L stainless steel. Surf. Coat. Technol. 2020, 385. [CrossRef]
24. Chen, L.; Richter, B.; Zhang, X.; Ren, X.; Pfefferkorn, F.E. Modification of surface characteristics and electrochemical corrosion
behavior of laser powder bed fused stainless-steel 316L after laser polishing. Addit. Manuf. 2020, 32. [CrossRef]
25. Shiomi, M.; Osakada, K.; Nakamura, K.; Yamashita, T.; Abe, F. Residual stress within metallic model made by selective laser
melting process. CIRP Ann. Manuf. Technol. 2004, 53, 195–198. [CrossRef]
26. Kong, D.; Ni, X.; Dong, C.; Zhang, L.; Man, C.; Yao, J.; Xiao, K.; Li, X. Heat treatment effect on the microstructure and corrosion
behavior of 316L stainless steel fabricated by selective laser melting for proton exchange membrane fuel cells. Electrochim. Acta
2018, 276, 293–303. [CrossRef]
27. Kirka, M.M.; Lee, Y.; Greeley, D.A.; Okello, A.; Goin, M.J.; Prearce, M.T.; Dehoff, R.R. Strategy for Texture Management in Metals
Additive Manufacturing. JOM 2017, 69, 523–531. [CrossRef]
28. Cruz, V.; Chao, Q.; Birbilis, N.; Fabijanic, D.; Hodgson, P.D.; Thomas, S. Electrochemical studies on the effect of residual stress on
the corrosion of 316L manufactured by selective laser melting. Corros. Sci. 2020, 164, 108314. [CrossRef]
29. Sugavaneswaran, M.; Vinoth, J.A.; Barath, K.M.J.; Lokesh, K.; John, R.A. Enhancement of surface characteristics of direct metal
laser sintered stainless steel 316L by shot peening. Surf. Interface Anal. 2018, 12, 31–40. [CrossRef]
30. Lodhi, M.J.K.; Deen, K.M.; Greenlee, W.M.C.; Haider, W. Additively manufactured 316L stainless steel with improved corrosion
resistance and biological response for biomedical applications. Addit. Manuf. 2019, 27, 8–19. [CrossRef]
31. Lou, X.; Andersen, P.L.; Rebak, R.B. Oxide inclusions in laser additive manufactured stainless steel and their effects on impact
toughness and stress corrosion cracking behaviour. J. Nucl. Mater. 2019, 499, 182–190. [CrossRef]
32. ASTM G30-97. Standard Practice for Making and Using U-Bend Stress-Corrosion Test Specimens; ASTM International: West Conshohocken,
PA, USA, 2016; p. 7.
33. EOS Stainless Steel 316L. Material Data Sheet. Available online: https://www.eos.info/en/additive-manufacturing/3d-printing-
metal/dmls-metal-materials/stainless-steel (accessed on 22 December 2020).
34. Ćurković, L.; Rede, V.; Grilec, K. Utjecaj opterećenja na izmjerenu tvrdoću silicijeve karbidne keramike. Kem. Ind. Chem. Eng.
2010, 59, 483–488.
35. SFS-EN 15305. Non-Destructive Testing-Test Method for Residual Stress Analysis by X-ray Diffraction; Finnish Standards Association
SFS: Helsinki, Finland, 2008.
36. Valente, E.H.; Christiansen, T.L.; Somers, M.A.J. High-temperature solution nitriding and low-temperature surface nitriding of
3D printed stainless steel. In Proceedings of the European Conference on Heat Treatment (ECHT), Friedrichshafen, Germany,
12–13 April 2018.
37. Shakhova, I.; Dudko, V.; Belyakov, A.; Tsuzaki, K.; Kaibyshev, R. Effect of large strain cold rolling and subsequent annealing on
microstructure and mechanical properties of an austenitic stainless steel. Mat. Sci. Eng. A 2012, 545, 176–186. [CrossRef]
38. Pham, M.; Dovgyy, B.; Hooper, P.A. Twinning induced plasticity in austenitic stainless steel 316L made by additive manufacturing.
Mat. Sci. Eng. A 2017, 704, 102–111. [CrossRef]
39. Brown, D.W.; Bernardin, J.D.; Carpenter, J.S.; Clausen, B.; Spernjak, D.; Thompson, J.M. Neutron diffraction measurements of
residual stress in additively manufactured stainless steel. Mater. Sci. Eng. A 2016, 678, 291–298. [CrossRef]
40. Prosek, T.; Iversen, A.; Taxén, C.; Thierry, D. Low-Temperature Stress Corrosion Cracking of Stainless Steels in the Atmosphere in
the Presence of Chloride Deposits. CORROSION 2009, 65, 105–117. [CrossRef]
41. Elsariti, S.M.; Haftirman, W.H. Behaviour of stress corrosion cracking of austenitic stainless steels in sodium chloride solutions.
Proc. Eng. 2013, 53, 650–654. [CrossRef]
42. Outokumpu. Stainless steels for highly corrosive environments Outokumpu Supra range datasheet. Available online: https:
//www.outokumpu.com/fi-fi/products/product-ranges/supra (accessed on 12 November 2020).

61
 metals
Article
Process Window for Electron Beam Melting of 316LN Stainless
Steel
Stefan Roos * and Lars-Erik Rännar

Sports Tech Research Centre, Department of Quality Management and Mechanical Engineering,
Mid Sweden University, Akademigatan 1, SE-83125 Östersund, Sweden; [email protected]
* Correspondence: [email protected]; Tel.: +46-10-142-85-32

Abstract: Electron beam melting (EBM) is currently hampered by the low number of materials
available for processing. This work presents an experimental study of process parameter development
related to EBM processing of stainless steel alloy 316LN. Area energy (AE) input and beam deflection
rate were varied to produce a wide array of samples in order to determine which combination of
process parameters produced dense (>99%) material. Both microstructure and tensile properties were
studied. The aim was to determine a process window which results in dense material. The range of
AE which produced dense materials was found to be wider for 316LN than for many other reported
materials, especially at lower beam deflection rates. Tensile and microstructural analysis showed that
increasing the beam deflection rate, and consequently lowering the AE, resulted in material with
a smaller grain size, lower ductility, lower yield strength, and a narrower window for producing
material that is neither porous nor swelling.

Keywords: powder bed fusion; electron beam melting (EBM); process window; stainless steel; 316LN

1. Introduction





 One advantage that laser-based powder bed fusion (laser-PBF) methods still have
over the electron beam melting (EBM) method is the sheer number of different materials
Citation: Roos, S.; Rännar, L.-E.
available for processing. The dominant EBM machine supplier for industrial applica-
Process Window for Electron Beam
Melting of 316LN Stainless Steel.
tions, Arcam (Arcam AB, Gothenburg, Sweden), currently supports six different materials,
Metals 2021, 11, 137. https://
while the numerous suppliers of laser-based equipment offer more than 20 different ma-
doi.org/10.3390/met11010137 terials. EBM process windows for pure copper [1–3], Inconel 718 [4], and Ti64 [5,6] have
previously been reported. Wang et al. [7] presented work on EBM process development for
Received: 21 December 2020 316L, and other researchers [8–11] have also presented work on EBM of 316LN, which is a
Accepted: 8 January 2021 nitrogen-enriched version of 316L, although without disclosing their process development
Published: 12 January 2021 methods. Stainless steel alloy 316L is a versatile engineering material that features out-
standing corrosion resistance, good weldability, high strength, and high ductility [10]; it is
Publisher’s Note: MDPI stays neu- readily available in a powder form suitable for additive manufacturing and offers a lower
tral with regard to jurisdictional clai- material cost than, for instance, the commonly used alloy Ti6Al4V. Therefore, 316L is a
ms in published maps and institutio- desirable choice for industrial adaptation for EBM. Using 316L(N) for additive manufactur-
nal affiliations. ing is not novel in itself; laser-PBF [12–14] and directed energy deposition [15–17] methods
have been used to process 316L feedstock into solid parts. The novelty is found with the
adaptation of the EBM process to the 316LN powder feedstock, and where previously
Copyright: © 2021 by the authors. Li-
mentioned research has demonstrated the feasibility of using EBM for 316LN for producing
censee MDPI, Basel, Switzerland.
parts, this work explores the processing parameter space for which good, solid parts can
This article is an open access article
be manufactured.
distributed under the terms and con- When using EBM to produce materials with high relative density and low top surface
ditions of the Creative Commons At- roughness, it is vital to find the correct process parameters [18,19]. The present work focuses
tribution (CC BY) license (https:// on managing two of the critical process parameters: electron beam deflection rate and
creativecommons.org/licenses/by/ electron beam power input. The combination of said parameters determines the amount
4.0/). of beam energy applied to each part of the powder bed, often described as area energy

63

Metals 2021, 11, 137. https://doi.org/10.3390/met11010137 https://www.mdpi.com/journal/metals

Metals 2021, 11, 137

(AE) (J/mm2 ). The parameters also determine the build temperature and solidification
rate, which influence microstructure [20,21], as well as the build time, which relates to the
overall productivity of the machine.
This study presents a well-defined process window for 316LN stainless steel, along
with an investigation into the relationship between varying process parameters. The result-
ing microstructure and mechanical properties are investigated for a selection of process
parameter settings. From an industrial standpoint, the important productivity aspect is
presented, and one can relate the productivity to material properties.

2. Materials and Methods

2.1. Sample Manufacturing and Process Parameters
All samples were manufactured using a modified Arcam S20 EBM machine (GE
Additive, Mölnlycke, Sweden) facilitating a 3 kW tungsten filament electron gun with
an approximately 200 µm powder bed interaction diameter. Each build consisted of 30
pieces of 15 mm × 15 mm × 15 mm cubes arranged on a 170 mm × 170 mm stainless steel
substrate (Figure 1a), with each cube assigned a unique set of process parameters. The
process area energy (AE), calculated by Equation (1)

J 60 × Beam Current (mA)

 
AE = (1)
mm 2 Line spaceing (mm) × Beam deflection rate mm


s

was varied by changing beam deflection rate and beam current while layer thickness (70
µm), line spacing (0.1 mm), process temperature (initially 810–820 ◦ C, measured below
start plate), hatch scanning strategy (snake pattern with layer-wise directional change),
and focus offset (5 mA) remained constant. Equations (2) and (3) were used for calculating
volumetric processing rate and volumetric energy input.

J
 

J
 AE mm 2
Volumetric energy input = (2)
mm3 layer thickness (mm)
 2
mm

mm 3  Processing rate s
Volumetric processing rate = (3)
s layer thickness (mm)

Figure 1. Layouts of builds for sample manufacturing: (a) cubes for evaluation of different process parameters; (b) layout
for tensile bar build.

Automatic temperature control features were deactivated, and process temperature

was regulated by altering preheat theme parameters during manufacturing. Each sample–

64

−
Metals 2021, 11, 137

top surface was visually analyzed using light microscopy (Nikon Instruments, Tokyo,
Japan) to determine porosity or swelling tendencies, and these observations were later
quantified by Archimedes-type density measurements. A total of 120 sample cubes
were manufactured over 4 builds. Tensile specimens were manufactured in the form
of 15 mm × 15 mm × 90 mm rectangular blocks. Specimens arranged lengthwise in the
xy-plane were angled at 45◦ with respect to the x- and y-axes in order to maintain a constant
scan length between layers (Figure 1b). All specimens were built on 3.5 mm supports to
facilitate ease of post-build removal and assurance of initial process stability. A total of 30
tensile bars were manufactured.

2.2. Powder Material

A gas-atomized 316LN precursor powder (Carpenter, Torshälla, Sweden) with 53–150
µm grain size range was used for this study. The chemical composition of the powder
was 17.6 wt.% Cr, 12.3 wt.% Ni, 2.46 wt.% Mo, 1.7 wt.% Mn, 0.5 wt.% Si, 0.075 wt.% N,
0.013 wt.% C, and Fe for balance. The morphology of the powder was analyzed using
scanning electron microscopy, flowability using a Hall flow funnel, and packing ratio using
a scale with 10−4 g resolution. The powder used for this study had been recycled in the
standard Arcam powder recovery system several times.

2.3. Density Measurement

Sample relative density was determined using Archimedes’ method. From Archimedes’
principle, sample density ( ρsample ) was calculated via Equation (4)

Win air × ρliq.

ρsample = (4)
Win air − Win liq.

where W in air and W in liq . are the measured sample weight in air and distilled water, respec-
tively, and ρliq. is the density of the liquid for submersion. Three repetitive measurements
were taken for each sample.

2.4. Testing of Mechanical Properties

Tensile specimens were machined from 15 mm × 15 mm × 90 mm rectangular blocks
into circular cross-section rods of dimensions compliant with the “Small size specimen 3”
of ASTM E8/E8M-13a (Ø6 mm and length 56 mm of reduced section). Tensile tests were
carried out at room temperature using an Instron 5969 Universal Testing System (Instron,
Norwood, MA, USA) with a clip-on extensometer. Four tensile specimens were tested for
each selected process parameter setting: 1000/2.7, 3000/1.8, and 5000/1.5 (beam deflection
rate (mm/s)/AE (J/mm2 )). The process parameters were selected based on AE location
being in the center of their approved respective beam deflection rate in the process window.
Rockwell B hardness was determined using a Mitutoyo HR200 with a type B ball indenter.

2.5. Microstructural Characterization

Samples were encapsulated in acrylic resin and mechanically polished using colloidal
silica as final polishing medium. Microstructural features were revealed via electrochemical
etching with oxalic acid (saturated solution + 10% H20) for 30–60 s at 2 V with approx-
imately 0.03 A (no current limit). Scanning electron microscopy and energy-dispersive
X-ray spectroscopy (EDS) (Tescan Maia 3, Tescan, Brno, Czech Republic) were used to
analyze the elemental composition of the processed material and to produce imagery for
grain size analysis. EDS data was acquired and analyzed using AZtec software (Oxford
Instruments, Abingdon, Oxfordshire, UK).
Optical spectroscopy was used to analyze and retrieve images of melt tracks revealed
by the etching process. Image analysis was used to quantify the melt track width.
The grain dimensions were examined using particle analysis in ImageJ software
(National Institutes of Health, Bethesda, Maryland, MD, USA).

65
Metals 2021, 11, 137

2.6. Statistical Analysis

A null hypothesis stating that group arithmetic means are equal was used. Alpha of
0.05 (p ≤≤ 0.05) was used for rejection of the null hypothesis. Group means were compared
with a t-test method. Since the expectation of the results was unknown, the t-test results
were evaluated for double-sided variance. The arithmetic mean and standard deviation
were used to present the test data.

3. Results and Discussion

The powder was mainly spherical in shape with some satellites attached, although
some oddly shaped powder grains were observed (Figure 2). Particles deviating from
spherical shape did not influence flowability (14.7 s/50 g Hall flow) or spreadability
(visually determined) to the point of affecting the quality of powder distribution during
processing. The bulk density of powder was approximately 4.98 g/cm3 , or 62.3%.

Figure 2. Scanning electron microscope image of 316LN precursor powder, showing mainly spherical
powder grains with some satellites attached.

At lower beam deflection rates, there was a wide AE spectrum for producing dense
material, but the acceptable AE span decreased as the deflection rate increased (Figure 3).
Three process settings of varying beam deflection rates and AE were selected from the
processwindow:
process window: samples
samples “a”
“a”(1000
(1000 mm/s, 2.7 J/mm ), “b”
2 ), (3000
“b” (3000 mm/s, 1.8 ), and “c”
J/mm 2 ),

and “c” (5000 mm/s, 1.5 J/mm ). 2

Density measurements showed a well-defined point of AE below which the samples

had decreasing density (Figure 4). In addition, the density of the samples increased as the
AE increased, even when entering the swelling region of the process window.
The impact of different process parameters on surface topography was visually clear.
While density measurement showed that lower beam deflection rates resulted in higher
relative density, the visual surface quality in terms of apparent surface roughness improved
with higher deflection rates (Figure 3). One could hypothesize that this was an effect of melt
pool dynamics, where the lower beam deflection rate caused the material to completely
solidify between beam passes. The higher beam deflection rate may have entered a dynamic
regime where the adjacent melt track was at least partly in a liquid state, thus combining
the two melt tracks more seamlessly. This would also explain why the melt tracks appeared
narrower at lower beam deflection rates, even though the opposite situation would be a
reasonable assumption given the higher area energy input. This hypothesis is supported
by the cross sections of samples a, b, and c (see Figure 5), with melt track widths of average
(SD): 254 µm (38.3), 442 µm (78.8), and 649 µm (27.5), respectively.

66
Metals 2021, 11, 137

Figure 3. Process window for

–
electron beam melting (EBM)-processed 316LN stainless steel at 70 um layer thickness and 0.1
mm line spacing; (a–c) the top surfaces of the specimens and their respective positions in the process window. For ease
of comparison to other process development studies, volumetric energy (accounting for layer thickness), and volumetric
processing rate have been added as secondary axes.

Figure 4. Relative density measurement results (arithmetic mean ± SD) for different beam deflection
rates and area energies.

67
Metals 2021, 11, 137

Figure 5. Melt tracks from samples with different process settings: (a) sample a (1000 mm/s), (b) sample b (3000 mm/s), (c)
sample c (5000 mm/s).

All z-axis-oriented samples showed material properties that were inferior in all aspects
to their xy-oriented counterparts. Figure 6 shows the difference in breaking behavior for
z-oriented bars at 5000 mm/s, which appeared more brittle than all other samples.

Figure 6. Results from tensile testing of EBM-processed 316LN stainless steel.

68
Metals 2021, 11, 137

All of the xy-oriented tensile bars exceeded the specifications for both cast and wrought
316LN described by the ASTM standards ASTM240 (cast), ASTM A276 (wrought), and
ASTM F3184 (316L AM) (Table 1). The z-oriented tensile bars fulfilled the yield strength
requirement for all tested process settings but failed to comply with the ultimate tensile
strength and elongation requirements.

Table 1. Tensile test results of 316LN stainless steel processed via EBM (arithmetic mean ± standard
deviation (n-1)).

EBM-Built Samples YS (MPa) UTS (MPa) Elongation at Break (%) *

xy 1000 mm/s 271.3 ± 7.8 592.7 ± 5.5 63.2 ± 2.2/72.4 ± 4.3
xy 3000 mm/s 284.2 ± 4.6 587.4 ± 5.2 63.5 ± 1.7/75.0 ± 0.0
xy 5000 mm/s 290.1 ± 5.9 585.2 ± 2.4 62.2 ± 3.9/78.1 ± 2.1
z 1000 mm/s 262.4 ± 2.5 508.9 ± 1.7 40.2 ± 2.6/39.6 ± 8.8
z 3000 mm/s 273.0 ± 3.3 518.1 ± 7.0 34.5 ± 5.5/35.9 ± 9.2
z 5000 mm/s 279.4 ± 1.6 483.2 ± 16.7 20.0 ± 4.0/16.7 ± 3.8
ASTM A743M (cast) 205 515 40 ***
ASTM A276 (wrought) 255 515 ** 35 ***
ASTM F3184 (316L AM) 205 515 30
* Values show post-test measurements for gauge lengths 50/24 mm respectively; ** Annealed, thickness > 12.7
mm (1/2”); *** Gauge length = 50 mm.

Anisotropic mechanical properties in additively manufactured components are a

common occurrence and are known to originate in the microstructure [17,22,23]. Thermal
treatment throughout the entire build cycle due to elevated build temperatures in the EBM-
build chamber have a history of producing as-built materials with good strength, high
ductility, and low residual stress [24], which explains the high elongation at break recorded
for the xy-oriented tensile bars. Microstructural heterogeneity, such as elongated grains,
tends to yield inferior strength and ductility in the building direction, an effect which was
also present in this study and explains the difference between xy-oriented tensile bars and
z-oriented tensile bars. Lack of fusion between layers due to melting errors can also play
a significant role if such a defect is present in the tensile bar. The fact that all tensile bars
within each parameter set displayed a similar tensile behavior makes the presence of lack
of fusion defects improbable.
Hardness tests showed that the Rockwell B hardness (HRB) value did not differ
significantly between the samples, with HRB values of 78.3 ± 3.6, 77.5 ± 2.3, and 78.6 ± 2.0
for samples with process settings of 1000 mm/s, 3000 mm/s, and 5000 mm/s, respectively—
all well below the maximum of 95 specified by ASTM A240.
Microstructural analysis revealed that the grains and sub-grains were non-equiaxed.
The grains showed elongation along the build direction for all examined specimens,
while elongated sub-grains were oriented in multiple directions (Figure 7).
Grain size measurements in the xy-plane showed grain areas of 1847 ± 2509, 1485 ± 1977,
and 1101 ± 1483 µm2 for samples a, b, and c, respectively. When a t-test was used to evaluate
the null hypothesis of equal arithmetic means, the probability of accepting the null hypothesis
was p = 0.50 for a and b, p = 0.19 for b and c, and p = 0.14 for a and c. Despite a trend where a
faster beam deflection rate and lower AE led to finer grains, the statistical analysis did not
support any conclusive statements.
EDS analysis showed that there were no statistically significant differences in elemental
composition between the samples resulting from different sets of process parameters.
Typical area scan location, contained within a single grain, can be seen in Figure 8.

69
Metals 2021, 11, 137

Figure 7. Microstructure of EBM-built 316LN stainless steel samples: (a) overview of magnified areas of interest, (b) low and
(c) high magnification scanning electron microscope image of cross section perpendicular to build direction, highlighting
cellular sub-grains, (d) low and (e) high magnification of cross section parallel to build direction showing boundaries of
elongated grains, grain boundary precipitates, and cellular dendrites.

Figure 8. Representative SEM image of cross section oriented in the xy-plane used for EDS analysis.
sis.spectrum
EDS EDS spectrum collected
collected from
from area area marked
marked “ 1” contained
“Spectrum 1” contained within
within a single a single microstruc-
microstructural grain.

The scan was performed in the xy cross sections (building direction towards reader) at
approximately 50% build height.
Levels of chromium and molybdenum were consistently slightly higher than man-
ufacturer specification in all samples. One possible explanation for this is that the EDS
scanning was performed within the boundaries of individual grains, and so any migration

70
Metals 2021, 11, 137

of elements towards the grain surfaces would not be included in the results. The precipitate
scan should be seen as comparative rather than absolute. The interaction volume of the
EDS scanning was of the same size magnitude as the precipitates themselves, causing the
surrounding material to influence readings. Grain boundary precipitate scans did show a
minor elevation in chromium levels, while nickel, molybdenum, and silicon all showed
slightly lower levels than bulk material scans (Table 2). No manganese was detected in the
precipitates.

Table 2. EBM-manufactured 316LN stainless steel sample elemental weight percentage and (SD)
acquired via EDS. Sample designation a, b, and c referenced from process window presented in
Figure 3.

Element Cr Ni Mo Si Mn Fe
Sample a 18.18 (0.05) 12.24 (0.08) 2.82 (0.05) 0.62 (0.02) 1.6 (0.04) 64.44 (0.09)
Sample b 18.17 (0.07) 12.30 (0.10) 2.78 (0.07) 0.64 (0.02) 1.66 (0.06) 64.35 (0.11)
Sample c 18.23 (0.05) 12.35 (0.08) 2.78 (0.05) 0.67 (0.02) 1.75 (0.05) 64.12 (0.09)
Grain
boundary 19.25 (0.07) 11.96 (0.10) 1.97 (0.06) 0.45 (0.02) - 66.28 (0.11)
inclusions

The statistical analysis (Table 3) revealed several cases where the null hypothesis was
rejected, with a significant difference between mean values for samples a, b, and c.

Table 3. p-values for a true null hypothesis of equal means between groups. Alpha of 0.05 used for
determination of statistical significance. Data from tests of samples with process settings a, b, and c
(Figure 3). p-values less than 0.05 are highlighted.

Compared Data a and b b and c a and c

Grain size 0.5 0.194 0.135
Melt track width 0.003 0.002 3.09 × 10−7
Ultimate tensile
0.215 0.477 0.068
strength xy
Ultimate tensile
0.085 0.018 0.054
strength z
Yield strength xy 0.036 0.169 0.008
Yield strength z 0.002 0.025 8.73 × 10−5
Elongation xy 0.865 0.586 0.672
Elongation z 0.133 0.008 0.0004
Hardness 0.582 0.439 0.822

Statistical analysis of the test data showed that changing the beam deflection rate and
AE significantly changed the melt track width and yield strength in the z-direction for all
tested process settings. Comparing properties for samples a and c meant a greater change in
beam deflection rate and beam power than comparing a and b, or b and c. The comparison
between a and c also revealed statistically significant differences in yield strength in the xy-
direction and elongation in the z-direction, but the impact was not of sufficient magnitude
to show statistical relevance for each change in process settings. The analysis did not show
any statistically significant differences between samples in terms of grain size, ultimate
tensile strength in the xy-direction, elongation in the xy-direction, or hardness.
Future research should include the optimization of process parameters to process the
precursor powder into solid material that is compliant with the current ASTM material
specifications and corresponds to or exceeds the material properties of laser-based powder
bed fusion-processed material. In order to keep the layer time to a minimum, the process
window width for the higher beam deflection rates should, if possible, be increased by
altering the parameters that were kept fixed in this study. Developing an understanding

71
Metals 2021, 11, 137

of how the dynamic melting characteristics of high deflection rates affect the thermal
history of the processed material is the key to success in producing high-quality parts in
the shortest possible timeframe.

4. Conclusions
Increasing the beam deflection rate and lowering the area energy counterintuitively
led to a wider melt track. It also led to lower ductility and ultimate tensile strength in
the z-direction.
Changing the beam deflection rate and area energy produced no significant differences
in material grain size, ultimate tensile strength in the xy-direction, elongation in the xy-
direction, or hardness.
Changes in the beam deflection rate and area energy had a greater influence on the
z-direction properties than the xy-direction properties, with the sole exception of yield
strength.
Even though the elemental composition was retained, the EBM-processed 316LN in
this study failed to comply with existing ASTM standards for 316 L and 316 LN material.
The main issue was the z-direction properties.

Author Contributions: S.R. has performed the research design and experiments, also performed
the writing of this paper. L.-E.R. has proofread this paper and facilitated the use of equipment and
resources. All authors have read and agreed to the published version of the manuscript.
Funding: Research is conducted with financial support from the European Regional Development
Fund through the Interreg Sweden–Norway program.
Institutional Review Board Statement: Not Applicable.
Informed Consent Statement: Not Applicable.
Data Availability Statement: The raw/processed data required to reproduce these findings cannot
be shared at this time as the data also forms part of an ongoing study.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Frigola, P.; Harrysson, O.A.; West, H.A.; Aman, R.L.; Rigsbee, J.M.; Ramirez, D.A.; Murr, L.E.; Medina, F.; Wicker, R.B.; Rodriguez,
E. Fabricating copper components with electron beam melting. Adv. Mater. Process. 2014, 172, 20–24.
2. Lodes, M.A.; Guschlbauer, R.; Körner, C. Process development for the manufacturing of 99.94% pure copper via selective electron
beam melting. Mater. Lett. 2015, 143, 298–301. [CrossRef]
3. Guschlbauer, R.; Momeni, S.; Osmanlic, F.; Körner, C. Process development of 99.95% pure copper processed via selective electron
beam melting and its mechanical and physical properties. Mater. Charact. 2018, 143, 163–170. [CrossRef]
4. Helmer, H.E.; Körner, C.; Singer, R.F. Additive manufacturing of nickel-based superalloy Inconel 718 by selective electron beam
melting: Processing window and microstructure. J. Mater. Res. 2014, 29, 1987–1996. [CrossRef]
5. Kirchner, A.; Klöden, B.; Luft, J.; Weißgärber, T.; Kieback, B. Process window for electron beam melting of Ti-6Al-4V. Powder Metall.
2015, 58, 246–249. [CrossRef]
6. Pobel, C.R.; Osmanlic, F.; Lodes, M.A.; Wachter, S.; Körner, C. Processing windows for Ti-6Al-4V fabricated by selective electron
beam melting with improved beam focus and different scan line spacings. Rapid Prototyp. J. 2019, 25, 665–671. [CrossRef]
7. Wang, C.; Tan, X.; Liu, E.; Tor, S.B. Process parameter optimization and mechanical properties for additively manufactured
stainless steel 316L parts by selective electron beam melting. Mater. Des. 2018, 147, 157–166. [CrossRef]
8. Rännar, L.-E.; Koptyug, A.; Olsén, J.; Saeidi, K.; Shen, Z. Hierarchical structures of stainless steel 316L manufactured by electron
beam melting. Addit. Manuf. 2017, 17, 106–112. [CrossRef]
9. Olsén, J.; Shen, Z.; Liu, L.; Koptyug, A.; Rännar, L.-E. Micro- and macro-structural heterogeneities in 316L stainless steel prepared
by electron-beam melting. Mater. Charact. 2018, 141, 1–7. [CrossRef]
10. Zhong, Y.; Rännar, L.-E.; Liu, L.; Koptyug, A.; Wikman, S.; Olsen, J.; Cui, D.; Shen, Z. Additive manufacturing of 316L stainless
steel by electron beam melting for nuclear fusion applications. J. Nucl. Mater. 2017, 486, 234–245. [CrossRef]
11. Zhong, Y.; Rännar, L.-E.; Wikman, S.; Koptyug, A.; Liu, L.; Cui, D.; Shen, Z. Additive manufacturing of ITER first wall panel parts
by two approaches: Selective laser melting and electron beam melting. Fusion Eng. Des. 2017, 116, 24–33. [CrossRef]
12. Zhang, M.; Sun, C.-N.; Zhang, X.; Goh, P.C.; Wei, J.; Hardacre, D.; Li, H. Fatigue and fracture behaviour of laser powder bed
fusion stainless steel 316L: Influence of processing parameters. Mater. Sci. Eng. A 2017, 703, 251–261. [CrossRef]

72
Metals 2021, 11, 137

13. Li, Z.; Voisin, T.; McKeown, J.T.; Ye, J.; Braun, T.; Kamath, C.; King, W.E.; Wang, Y.M. Tensile properties, strain rate sensitivity, and
activation volume of additively manufactured 316L stainless steels. Int. J. Plast. 2019, 120, 395–410. [CrossRef]
14. Choo, H.; Sham, K.-L.; Bohling, J.; Ngo, A.; Xiao, X.; Ren, Y.; Depond, P.J.; Matthews, M.J.; Garlea, E. Effect of laser power on
defect, texture, and microstructure of a laser powder bed fusion processed 316L stainless steel. Mater. Des. 2019, 164, 107534.
[CrossRef]
15. Feenstra, D.R.; Cruz, V.; Gao, X.; Molotnikov, A.; Birbilis, N. Effect of build height on the properties of large format stainless steel
316L fabricated via directed energy deposition. Addit. Manuf. 2020, 34, 101205. [CrossRef]
16. Azinpour, E.; Darabi, R.; de Sa, J.C.; Santos, A.; Hodek, J.; Dzugan, J. Fracture analysis in directed energy deposition (DED)
manufactured 316L stainless steel using a phase-field approach. Finite Elem. Anal. Des. 2020, 177, 103417. [CrossRef]
17. Saboori, A.; Aversa, A.; Marchese, G.; Biamino, S.; Lombardi, M.; Fino, P. Microstructure and mechanical properties of AISI 316L
produced by directed energy deposition-based additive manufacturing: A review. Appl. Sci. 2020, 10, 3310. [CrossRef]
18. Safdar, A.; He, H.Z.; Wei, L.Y.; Snis, A.; de Paz, L.E.C. Effect of process parameters settings and thickness on surface roughness of
EBM produced Ti-6Al-4V. Rapid Prototyp. J. 2012, 18, 401–408. [CrossRef]
19. Klingvall, E.R.; Rännar, L.E.; Bäckstöm, M.; Carlsson, P. The effect of EBM process parameters upon surface roughness. Rapid Pro-
totyp. J. 2016, 22, 495–503. [CrossRef]
20. Pushilina, N.; Syrtanov, M.; Kashkarov, E.; Murashkina, T.; Kudiiarov, V.; Laptev, R.; Lider, A.; Koptyug, A. Influence of
manufacturing parameters on microstructure and hydrogen sorption behavior of electron beam melted titanium Ti-6Al-4V alloy.
Materials 2018, 11, 763. [CrossRef]
21. Hrabe, N.; Quinn, T. Effects of processing on microstructure and mechanical properties of a titanium alloy (Ti–6Al–4V) fabricated
using electron beam melting (EBM), Part 2: Energy input, orientation, and location. Mater. Sci. Eng. A 2013, 573, 271–277.
[CrossRef]
22. Kok, Y.; Tan, X.P.; Wang, P.; Nai, M.L.S.; Loh, N.H.; Liu, E.; Tor, S.B. Anisotropy and heterogeneity of microstructure and
mechanical properties in metal additive manufacturing: A critical review. Mater. Des. 2018, 139, 565–586. [CrossRef]
23. Carroll, B.E.; Palmer, T.A.; Beese, A.M. Anisotropic tensile behavior of Ti–6Al–4V components fabricated with directed energy
deposition additive manufacturing. Acta Mater. 2015, 87, 309–320. [CrossRef]
24. Zhao, X.; Li, S.; Zhang, M.; Liu, Y.; Sercombe, T.B.; Wang, S.; Hao, Y.; Yang, R.; Murr, L.E. Comparison of the microstructures and
mechanical properties of Ti–6Al–4V fabricated by selective laser melting and electron beam melting. Mater. Des. 2016, 95, 21–31.
[CrossRef]

73
 metals
Review
A Review of Heat Treatments on Improving the
Quality and Residual Stresses of the Ti–6Al–4V
Parts Produced by Additive Manufacturing
Óscar Teixeira 1 , Francisco J. G. Silva 1, * , Luís P. Ferreira 1 and Eleonora Atzeni 2
1 ISEP—School of Engineering, Polytechnic of Porto, Rua Dr. António Bernardino de Almeida, 431,
4249-015 Porto, Portugal; [email protected] (Ó.T.); [email protected] (L.P.F.)
2 Department of Management and Production Engineering (DIGEP), Politecnico di Torino,
Corso Duca degli Abruzzi, 24, 10129 Torino (TO), Italy; [email protected]
* Correspondence: [email protected]; Tel.: +351-228-340-500




Received: 4 July 2020; Accepted: 24 July 2020; Published: 27 July 2020


Abstract: Additive manufacturing (AM) can be seen as a disruptive process that builds complex
components layer upon layer. Two of its distinct technologies are Selective Laser Melting (SLM) and
Electron Beam Melting (EBM), which are powder bed fusion processes that create metallic parts with
the aid of a beam source. One of the most studied and manufactured superalloys in metal AM is
the Ti–6Al–4V, which can be applied in the aerospace field due to its low density and high melting
point, and in the biomedical area owing to its high corrosion resistance and excellent biocompatibility
when in contact with tissues or bones of the human body. The research novelty of this work is
the aggregation of all kinds of data from the last 20 years of investigation about Ti–6Al–4V parts
manufactured via SLM and EBM, namely information related to residual stresses (RS), as well as
the influence played by different heat treatments in reducing porosity and increasing mechanical
properties. Throughout the report, it can be seen that the expected microstructure of the Ti–6Al–4V
alloy is different in both manufacturing processes, mainly due to the distinct cooling rates. However,
heat treatments can modify the microstructure, reduce RS, and increase the ductility, fatigue life,
and hardness of the components. Furthermore, distinct post-treatments can induce compressive RS
on the part’s surface, consequently enhancing the fatigue life.

Keywords: additive manufacturing; metal powder bed fusion; selective laser melting; electron beam
melting; Ti–6Al–4V; residual stresses; heat treatments; microstructure

1. Introduction
Additive manufacturing (AM), also known by many as three-dimensional printing (3DP), was born
in 1981 through Hideo Kodama [1] and can be described, according to the International Organization
for Standardization (ISO) 52900-15 standard [2], as a manufacturing process that creates 3D objects from
scratch, typically layer after layer. As a matter of fact, this technology can be seen as a disruptive one,
as it completely changed the creation of parts through the addition of material instead of the common
subtraction of it, something that is characteristic of subtractive manufacturing [3]. Furthermore, it can
be classified as a sustainable process as it enables the production of complex geometry components with
minimal waste of material [4]. One of the process categories associated with this new manufacturing
process is called Powder Bed Fusion, which agglomerates three distinct technologies, namely Selective
Laser Sintering (SLS), Selective Laser Melting (SLM), and Electron Beam Melting (EBM) (Figure 1) [5].
However, if one desires to produce exclusively metal components, then it must employ the last two
mentioned technologies. Thus, from now on, this paper review will solely focus on SLM and EBM,
as they are seen as metal Powder Bed Fusion technologies.

Metals 2020, 10, 1006; doi:10.3390/met10081006 75 www.mdpi.com/journal/metals

Metals 2020, 10, 1006

In fact, SLM appeared in 1996 through Wilhelm Meiners, Konrad Wissenbach, and Andres
Gasser [6], and it is a process that must be done in a closed chamber surrounded by an inert gas, such as
argon or nitrogen, to avoid oxidation of the material after melting, remove spatter, metal vapor, and plasma
plumes [7–10]. In addition, the parts are usually connected to a substrate plate by support structures,
in order to reduce deformations when manufacturing. The operating method is done by firstly heating
up the building platform in order to reduce deformations caused by temperature differences (only on
some machines); then, the powder cartridge rises, thanks to an actuator, and dispenses a predefined
amount of powder. After that, the leveling roller/blade creates a uniform layer of powder on the
construction platform and places the substrate excess in another cartridge opposite the first one, after
which a high-energyμdensity laser melts the powder, forming a melt pool of approximately 100 µm
width [11]. Finally, the construction platform lowers according toμthe thickness of each layer, which
usually varies between 20 and 100 µm depending on the material, and the process is repeated until the
final part is completed [12].
ARCAM was founded in 1997 and is the only enterprise that manufactures EBM machines, as they
own the patent [13]. This technology uses accelerated electrons in the order of 0.1 to 0.4 times the
speed of light [14] as a beam source, and the process is done in a vacuum chamber [15]. Furthermore,
the additive manufacturing steps are the same as the SLM technology; however, the temperature of the
build chamber is much higher (500–800 ◦ C) [16–19]. Hence, one should expect fewer residual stresses
(RS) because of the lower temperature gradient during manufacturing (Tmelt–Tambient). μ In addition,
the typical layer thickness of the parts is between 50 and 200 µm, due to the deeper penetration and
higher energy of the beam, making the manufacturing process quicker than SLM [16].

(a) (b)
Figure 1. Main components of (a) Selective Laser Melting (SLM) machine, (b) Electron Beam Melting
(EBM) machine. Adapted from [20], under CC BY 4.0. Original sources: (a) EMPA, (b) ARCAM.

Titanium alloys have been receiving special attention from the aerospace industry, thanks to the
low density and the high melting point of this material (around 1650 ◦ C) [21]. In other words, several
companies turn to titanium when they need a light component that is capable of safely supporting
high loads and/or when working temperatures are high [22]. In addition, it has also a high corrosion
resistance [23–25], and it is often used in medical implants due to its excellent biocompatibility when
in contact with tissues or bones of the human body [26]. Note that this material is quite difficult and
expensive to machine, so its use and diffusion in AM is of great interest [27,28]. In fact, the titanium
alloy most studied by the scientific community and used to manufacture final components is Ti–6Al–4V
(UNS R56400) [29]. The crystalline structure of this alloy is composed of a compact hexagonal structure
(phase α) and body-centered
α cubic (phase β). The existence
β of aluminum and vanadium causes the α
and β phasesα to stabilize,
β respectively, maintaining the dual phase at room temperature [22]. In general,
the microstructure, when depositing material, presents a martensitic phase (α′ ) due to the rapid cooling
α′
α′

76
Metals 2020, 10, 1006

of the manufacturing process. In addition to the quick cooling, the α′ phase will only form if the build
temperature is kept below the martensite start temperature (Ms) [30]. The aforementioned temperature
varies from 575 ◦ C up to 800 ◦ C [31–33] as the impure elements along with the initial microstructure
and composition homogeneity affect the Ms temperature [34]. In Figure 2, it is possible to analyze how
the phase transformation is affected by the distinct cooling rates, i.e., in the region of 525–410 ◦ C/s the
α′ phase will be formed; however, if the cooling rate is kept under 20 ◦ C/s, it will lead to the formation
of the phase α. α′
α

Figure 2. Diagram that explains how the cooling rate affects the phase transformation. Reproduced
from [35], under CC BY 4.0.

In laser-based additive manufacturing processes, RS are induced by thermal principles, as the

gradient temperature is high because of the heating and thermal expansion upon the deposition
of a new layer, and its subsequent cooling and contraction [36]. Therefore, production errors in the
components might occur due to geometrical distortion. Thus, it is mandatory to understand the expected
orientation and magnitude of the RS in order to do accurate predictions of the final part properties.
Moreover, high magnitude (100–500 MPa) RS are more prone to occur in the SLM rather than in the
EBM process [37].
As a matter of fact, residual stresses can be divided into three different types, Type I, II, and III,
depending on the operational length scale, as shown in Figure 3. Type I are macroscopic stresses that
act on the scale of component geometry, Type II, often called intergranular stresses, are microstresses
acting at the individual grain scale, and Type III act at the atomic scale [38]. Nowadays, multiple
techniques are employed to measure residual stresses, and they can be divided into two major groups:
destructive, and non-destructive testing. On one hand, if one seeks to find residual stresses located on
the surface level in a non-destructive way, X-ray Diffraction (XRD) is one of the most suitable techniques
for that effect due to its great accuracy (±20 MPa) and the large variety of equipment available [39].
On the other hand, if the goal is to investigate internal residual stresses in a destructive way, one can
use the stripping method, crack compliance method, or the contour method. Furthermore, there is
also an economic semi-destructive way to discover surface residual stresses called the hole-drilling
strain gage method [40]. It is considered a semi-destructive method as it does not affect, in a significant
way, the structural integrity of the part. Currently, an ISO standard does not exist; however, according
to American Society for Testing and Materials (ASTM) E837-08 [41] standard, the aforementioned
method can be described as a technique that computes residual stresses near the surface of a material
by sticking a strain rosette to the part’s surface and then drilling a hole at the center of the rosette,
which later determines the relieved strains.

77
Metals 2020, 10, 1006

(a) (b)
Figure 3. (a) Residual stresses classification and (b) plastic deformation development. Reproduced
from [36], with permission of Elsevier, 1996.

The research novelty of this work is the aggregation of all kinds of information from the last 20 years
of research about the Ti–6Al–4V alloy in a structured way, namely information related to residual
stresses, as well as the influence played by different heat treatments in reducing porosity, increasing
mechanical properties, and the stress relief of additive manufactured components. The authors strongly
believe that the compilation of the aforementioned data is essential because it allows understanding the
research evolution of this titanium alloy, and it provides a good starting point for those who want to
learn about additive manufacturing. Furthermore, the reading of this review paper can also be useful
to understand some key aspects of the Ti–6Al–4V alloy, thus improving the quality and performance of
the manufactured parts.
Total Articles: 537

2. Methodology
The methodology followed in this article started with the selection of the theme, which is heat
treatments and residual stresses on metal powder bed fusion Ti–6Al–4V parts. In this way, the authors
tried to analyze the amount of information available on the ScienceDirect platform in order to get a
general idea of the number of articles published on this topic. When performing an advanced search
by title, abstract, and keywords on the topics “Additive Manufacturing + Ti-6Al-4V”, 537 articles were
found, of which only 11 were review articles, as shown in Figure 4.

Total Articles: 537

Figure 4. Pareto’s chart of the research “Additive Manufacturing + Ti–6Al–4V” on ScienceDirect.

Then, after a thorough research for the topics “Heat Treatments + Selective Laser Melting +
Ti-6Al-4V”, as shown in Figure 5a, it was concluded that the number of results had decreased

78
Metals 2020, 10, 1006

considerably, with a total of 61 research articles. After that, the authors searched for “Residual Stresses
+ Selective Laser Melting + Ti–6Al–4V”, as shown in Figure 5b, and they found that there were only
31 research articles. Lastly, the authors removed the word “Selective Laser Melting” on the last two
searches and added the word “Electron Beam Melting”, and they found out 18 articles about heat
treatments and 10 about residual stresses, as shown in Figure 6. Note that if the research had not been
done in an advanced way, the results would have been much higher; however, more than 50% of the
results would not be relevant for this review article.

Total Articles: 61 Total Articles: 31

(a) (b)
Figure 5. Pareto’s charts of the research, (a) “Heat Treatments + Selective Laser Melting + Ti–6Al–4V”,
and (b) “Residual Stresses + Selective Laser Melting + Ti–6Al–4V”, on ScienceDirect.

Total Articles: 18 Total Articles: 10

(a) (b)

Figure 6. Pareto’s charts of the research, (a) “Heat Treatments + Electron Beam Melting + Ti–6Al–4V”,
and (b) “Residual Stresses + Electron Beam Melting + Ti–6Al–4V”, on ScienceDirect.

79
Metals 2020, 10, 1006

3. Literature Review
Before heading to the first subsection of the literature review, the authors thought that the SLMed
and EMBed as-built microstructures of the titanium alloy should be compared as they are heavily
dependent on the manufacturing process. Furthermore, the microstructure also plays a crucial role
in governing the material properties of the components. Therefore, several investigators studied
the as-built microstructure of SLMed titanium samples [42–46]. Thijs et al. [42] reported that all the
as-built specimens produced via SLM showed a microstructure with fine acicular α′ precipitates in the
columnar original β grains, which was due to the rapid cooling of the manufacturing process, as shown
in Figure 7a. Similarly, Facchini et al. [43] and Gong et al. [44] found the same microstructureα′ results
β
as the aforementioned study, while Benedetti et al. [45] reported that the as-built titanium specimens
had a very fine acicular α′ microstructure. On the contrary, Xu et al. [46] managed to accomplish an
ultrafine lamellar α + β structure of SLMed titanium as-built
α′ specimens without having notable grain
coarsening. The authors used the following process αvariables:β layer thickness of 60 µm, focal offset
distance of 2 mm, and energy density of 50.62 J/mm3 , they and reported that a careful selection of the
printing parameters was the key for μ such microstructure.
Several other authors studied the microstructure of as-built titanium specimens produced via
EBM [47–51]. Xu et al. [47] reported that an α + β lamellar microstructure, as shown in Figure 7b,
was achieved for the following processing parameters:
α β accelerated voltage of 60 kV, beam current of
10 mA, filament current of 432 mA, focus current of 670 mA, gun vacuum pressure of 3.4 × 10−3 Pa,
chamber vacuum pressure of 7 × 10−2 Pa, and work distance of 150 mm. Likewise, Galarraga −
et al. [48],
−
Zhao et al. [49], Chern et al. [50], and Murr et al. [51] found an α + β lamellar microstructure in the
α β
EBMed as-built specimens.

(a) (b)
α′ α′ in columnar original
Figure 7. Characteristic microstructure of (a) SLM process (fine acicular β β
α β
grains), and (b) EBM process (α + β lamellar). Reproduced from [45,48] respectively, with permission
of Elsevier 2017, 2016.

Furthermore, it is also relevant to understand the influence played by distinct additive

manufacturing processes on the mechanical properties, profile surface roughness (Ra), and porosity
of Ti–6Al–4V components. Thus, in Table 1, it is possible to analyze the distinct as-built mechanical
properties of titanium samples. From the aforementioned table, it is worth noting that the SLMed
samples, when compared to the EBMed ones, exhibit a 20% to 30% increase of the yield strength (YS)
α′
and ultimateβ tensile strength (UTS); however, the ductility is much lower due to the inherent rapid
cooling of the SLM process which promotes an α′ martensitic microstructure within long columnar
prior β grains. Regarding the Ra, it is known that different scan speeds, powder sizes, and layer
thicknessesμof the EBM and SLM manufacturing processes promote distinct surface roughness [35].
Edwards et al. [52] stated that the titanium specimens produced via SLM had an Ra between 32 and
μ μ
38.5 µm, depending on the build orientation. Moreover, Chan et al. [53] compared the surface roughness

80
Metals 2020, 10, 1006

of Ti–6Al–4V samples manufactured via SLM and EBM and reported that the latter manufacturing
process revealed an Ra of 131 µm, while the former presented 38.5 µm. The authors associated the
high surface roughness of the EBMed sample to the presence of unfilled gaps and unmelted powder
attached to the surface. Fousová et al. [54] studied the effect of internal defects and surface roughness
on the mechanical properties of Ti–6Al–4V samples produced via SLM and EBM. In order to achieve a
similar microstructure as the EBM as-built specimens, the SLM ones underwent a heat treatment at
820 ◦ C for 5.5 h. After analyzing the microstructure and conducting a uniaxial tension test and a fatigue
test, the authors reported that both EBMed and SLMed specimens exhibited a two-phase lamellar
microstructure; however, internal defects were distinct due the manufacturing process. EBMed samples
showed spherical pores resulting from gas entrapment, while SLMed ones revealed insufficient melting
defects. Despite that, the researchers concluded that the static properties in the tension of both samples
reached comparable values, but the fatigue test demonstrated that the SLMed specimens exhibited
greater fatigue strength (220 ± 24 MPa) than the EBMed ones (115 ± 13 MPa) due to the lower surface
roughness. Besides, Qiu et al. [55] studied the effect of laser power and layer thickness on surface
roughness and porosity level of SLMed titanium as-built samples. The researchers reported that a low
layer thickness combined with a high laser power leads to the production of specimens with a porosity
level inferior to 1 vol%. In fact, when it comes to part porosity, several authors [44,49,56] reported
that in the SLM process, one should expect porosities between 0.1 and 0.5 vol%, while others [44,57]
stated that components produced through EBM present an inherent porosity between 0.1 and 0.3 vol%.
Recently, Ning et al. [58] created an analytical model based on the relationship between porosity
evolution and the thermal behavior of the material, which predicted part porosity in metal powder
bed additive manufacturing without resorting to any iteration-based simulations or Finite Element
Modeling (FEM). For that, the authors followed the algorithm that can be seen in Figure 8. The molten
pool dimensions were computed through the comparison of the material’s melting temperature with
the expected temperatures using an analytical thermal model. The porosity evaluation was computed
by subtracting the volume fraction of the powder bed void from the post-processed porosity of the part.
The volume fraction of the powder was investigated by image analysis and through an advancing front
approach. Then, after determining the analytical results of the expected porosity, the authors compared
the values with additively manufactured Ti–6Al–4V specimens from the literature and concluded that
their model could predict porosity with a high amount of precision. Furthermore, the authors stated
that the computational time of the model was short, allowing a quick and precise prediction for distinct
processing parameters.

Figure 8. Schematic illustration of the algorithm used in the porosity prediction model. Adapted
from [58], with permission of Elsevier, 2020.

81
Metals 2020, 10, 1006

In another report, Zhang et al. [59] studied and compared the wear resistance of as-built SLM,
as-built EBM, and forged Ti–6Al–4V samples. Then, the authors performed friction and wear tests to
the three types of samples and concluded that when compared to the forged specimens, the additively
manufactured ones exhibited a better wear resistance owing to their weaker delamination and higher
hardness. Moreover, the SLMed samples showed a higher wear rate than the EBMed ones due to the
higher number of horizontal cracks of the former, as shown in Figure 9.

Table 1. Mechanical properties of as-built Ti–6Al–4V specimens in tensile testing. UTS: ultimate tensile
strength, YS: yield strength.

Manufacturing Process YS [MPa] UTS [MPa] ε [%] Ref.

EBM 881 ± 12.5 978.5 ± 11.5 10.7 ± 1.5 [60]
EBM 851.8 ± 5.8 964.5 ± 0.3 16.3 ± 0.8 [61]
SLM 1056 ± 29 1351 ± 34 5.5 ± 0.8 [62]
SLM 1143 ± 30 1219 ± 20 4.9 ± 0.6 [63]

(a) (b) (c)

Figure 9. Wear mechanisms in the Ti–6Al–4V samples built by (a) forging, (b) SLM, and (c) EBM.
Reproduced from [59], under CC BY 4.0.

3.1. Heat Treatments

Heat treatments are known for reducing residual stresses, improving mechanical properties,
and changing the microstructure of titanium components. Balyakin et al. [64] studied the heat treatment
ε
effect on the surface roughness of titanium specimens manufactured via SLM. The researchers conducted
distinct heat treatments followed by mechanical brushing and chemical polishing and reported that
after heating the samples to 950 ◦ C for 30 min followed by oil quenching and subsequent aging at
650 ◦ C for 120 min, the specimens exhibited the worst surface roughness (Ra = 4.41 µm) measured just
before undergoing mechanical polishing and chemical polishing, whilst the best final surface roughness
(Ra = 0.27 µm) was achieved through the following preliminary heat treatments: annealing at 650 ◦ C
for 120 min followed by furnace cooling (FC) plus heating up to 950 ◦ C for 30 min followed by water
quenching (WQ). Vayssette et al. [65] investigated the roughness influence on multiaxial high-cycle
fatigue of titanium samples manufactured via SLM and EBM. Firstly, when producing the specimens,
the authors used processing parameters that minimized the RS formation due to high-thermal gradients.
Secondly, the samples were post-treated with a stress relief heat treatment followed by Hot Isostatic
Pressing (HIP), which aimed to reduce each part’s porosity. After that, the researchers analyzed the
microstructure and reported that both samples exhibited a lamellar microstructure with a mean 2 μ µm
lamella size. Then, the authors measured the Ra values of both samples before and after chemical polishing,
which for the SLM samples were μ 18.9 µm and 11.2 µm, and for the EBM, they were 38.9 µm and 17.7 µm,
respectively. Finally, the researchers conducted fatigue tests and reported that despite the roughness
improvement induced by the chemical etching, the fatigue properties did not improve significantly.
Similarly, Yuan et al. [66] investigated the heat treatment effect on the compressive fatigue properties of
titanium samples produced via EBM. For that, after manufacturing the samples, the authors conducted
an annealing treatment with three different temperatures (750 ◦ C, 850 ◦ C, and 950 ◦ C) for 1.5 h followed
by FC to room temperature. Then, they compared the as-built microstructure to the post-treated one
and concluded that the heat treatment promoted the decomposition of the acicular α′ martensite into
μ
μ μ
82
μ μ
Metals 2020, 10, 1006

an α + β phase. After conducting fatigue tests, the researchers concluded that when annealing at
950 ◦ C, near the phase boundary, the width of the α lamellae coarsens up to 20 µm and promotes a
ductility improvement of the struts, an increase of the fatigue strength, and the fatigue endurance ratio
raises to nearly 0.6, which is almost three times more than that reported in another work [67].
Several authors [68–73] studied the fatigue properties of the titanium alloy manufactured via metal
powder bed fusion. Chastand et al. [68] investigated the influence of different manufacturing processes,
build orientation, surface roughness, and HIP treatment on the fatigue life of titanium samples. To do
that, the researchers manufactured several specimens in SLM and EBM machines with different build
orientations, namely XY and Z. Then, all the SLMed specimens underwent a stress relief treatment at
640 ◦ C for 4 h, while others undertook a stress relief + HIP treatment at 920 ◦ C under 1020 bar for 2 h.
After that, the authors conducted the same HIP treatment to 12 EBMed specimens and then machined
and polished the surface of several SLMed and EBMed samples. After conducting the fatigue tests,
Chastand et al. [68] reported that the manufacturing processes (SLM and EBM) effect is negligible on
the fatigue properties, as a similar type of defects was found in both cases. Moreover, machining and
polishing improved the fatigue properties of the titanium alloy because it lowered the surface roughness
and removed superficial defects. Furthermore, the HIP treatment led to the size decrease of the internal
defects, hence improving the fatigue properties. To conclude, the authors also reported that the effect of
the build direction highly depends on the presence of unmelted zones. In a similar study, Wu et al. [71]
investigated the porosity and HIP treatment effect on the fatigue endurance ratio of SLMed titanium
samples. For that, the researchers purposely manufactured cellular structures with three different
porosities (33 vol%, 50 vol%, and 84 vol%) and then subjected some of them to an HIP treatment at
1000 ◦ C and a pressure of 150 MPa for 1 h. After studying the microstructure, the authors reported that
the heat treatment promoted the transformation of the martensitic microstructure into a lamellar α + β
α β
phase. Then, the researchers conducted fatigue tests and concluded that the porosity increase in the
as-built samples led to a decrease in the fatigue endurance ratio, as shown in Figure 10, due to the low
α′
ductility of α′ . However, in the HIPed samples, as the porosity increased from 33 vol% to 50 vol%,
the fatigue endurance ratio at 106 cycles increased from 0.5 up to nearly 0.55, Figure 10. Moreover,
⁶
when compared to the as-built specimens, the HIPed ones exhibited far better fatigue endurance
ratios as the porosity increased. Similarly, Vispoli et al. [72] investigated the surface roughness effect
on the fatigue behaviour of Ti–6Al–4V samples produced via SLM. The authors reported that the
fatigue resistance of the as-built specimens, when compared to the machined ones, evidenced a drastic
reduction due to the elevated roughness.

Figure 10. Porosity influence on the fatigue endurance ratios at 106 cycles of as-built and specimens
⁶
subject to Hot Isostatic Pressing (HIP). Reproduced from [71], with permission of Elsevier, 2020.

Likewise, Yu et al. [73] studied the influence of distinct heat treatments and surface finishing
processes on the fatigue performance of titanium samples produced via SLM. The authors employed

83
Metals 2020, 10, 1006

four different finishing processes, namely turning, 400 mesh sandpaper grinding, 400 mesh sandpaper
grinding + sandblasting, and polishing. Furthermore, the researchers also conducted three distinct
heat treatments, which can be seen in Table 2. After the fatigue tests, the authors concluded that
all the surface-finishing processes reduced the as-built arithmetic mean roughness (Ra = 12.16 µm),
hence significantly improving the fatigue performance of the samples. Furthermore, as is possible to
analyze in Figure 11a, when compared to the as-built specimens, the HIPed and HT-920 ones showed
lower YS and UTS; however, the ductility was greatly improved. On the contrary, the HT-850-550
specimens showed no obvious reduction in the YS and UTS when compared to the as-built ones,
and the ductility of the former specimens was also better than the latter. Finally, the heat treatments
promoted the increase of the fatigue limit, as the HT-920 and HT-850-550 samples exhibited a stress
amplitude of approximtaely 400 MPa for 106 cycles, and the HIPed samples showed a stress amplitude
of approximtaely 500 MPa for the same number of cycles, as shown in Figure 11b.

Table 2. Distinct heat treatments performed by Yu et al. [73]. FC: furnace cooling, WQ: water quenching.

Code Name in Figure 11a Condition

SLMed As-built
HIPed HIP at 920 ◦ C and a pressure of 100 MPa for 2 h
HT-920 Heat treatment at 920 ◦ C for 2 h followed by FC
Double heat treatment, firstly done at 850 ◦ C for 2 h
HT-850-550
followed by WQ and then 550 ◦ C for 4 h followed by AC

(a) (b)
Figure 11. (a) Tensile properties and elongation of the different specimens, (b) Fatigue performances of
the distinct specimens. Adapted from [73], with permission of Elsevier, 2019.

Kim et al. [74] investigated the effect of microstructure control through heat treatments on
the high-temperature creep behavior of Ti–6Al–4V specimens manufactured via SLM. The authors
conducted a heat treatment at 1040 ◦ C for 1 h and then analyzed the microstructure of the as-built
and heat-treated specimens. The former exhibit a typical martensitic microstructure, while the latter
showed a β phase at the interface of a large α colony area, meaning that a Widmanstätten’s structure
was formed. Subsequently, the researchers did two different mechanical tests, namely a compressive
test at 500 ◦ C and a high-temperature creep test, and they reported that the compressive yield strength
of the as-built specimens was approximately 930 MPa and that in the heat-treated specimens was
557 MPa. Nevertheless, the high-temperature creep test results confirmed that the heat-treated samples
exhibited a lower steady-state creep rate, proving that the martensitic microstructure has a lower creep
performance than the Widmanstätten one.
In a different study, Ettefagh et al. [75] investigated the influence of the annealing heat treatment
on the corrosion resistance of SLMed titanium components. For that, the authors conducted two
distinct post-treatments at 600 ◦ C and 800 ◦ C for 2 h. The microstructure analysis revealed that the

84
Metals 2020, 10, 1006

heat treatment done at 600 ◦ C did not provide the proper condition for the vanadium diffusion, hence
the microstructure remained similar to the as-built one (α′ needle-like). However, the 800 ◦ C heat
treatment led to the formation of the β phase and the stress relief of the α′ phase. Then, the researchers
performed the corrosion tests and ascertained that the corrosion rate of the as-built specimens was
nearly 16 times worse than the cold-rolled commercial titanium samples, which were used as a
benchmark. Moreover, the martensitic phase stress relief and the formation of the β phase on the
800 ◦ C post-treated samples greatly improved the corrosion behavior of the material, which exhibited
results comparable to the benchmark.
Wang et al. [76] studied the heat treatment effect on the biocompatibility and osseointegration of
SLMed titanium samples. For that, the researchers employed an annealing treatment at a temperature
of 820 ◦ C for 4 h to half of the manufactured specimens. Then, all the specimens were ultrasonic
degreased in acetone and anhydrous ethanol baths for 1 h, respectively. Later, the authors applied
human bone mesenchymal stem cells (hBMSCs) to both types of specimens, measured cell proliferation
on the first, fourth, and seventh day of incubation, and reported that the heat-treated specimens
showed a significant enhancement of hBMSCs adhesion and proliferation. The authors concluded
that the annealing treatment promoted better mechanical properties, a more homogeneous, rougher,
and more hydrophilic surface, as well as the formation of a crystalline rutile (TiO2) layer, which
elevated the corrosion resistance and biocompatibility of the implant. Similarly, Pazhanivel et al. [77]
investigated the post-treatment effect on the corrosion resistance of titanium specimens produced
via SLM. Firstly, the authors produced several specimens on an EOS M290 machine using different
laser power and scan speed parameters. After performing a tensile test, the researchers reported
that the specimen that achieved the best elongation (10.88%) was manufactured with a laser power
of 310 W and a scan speed of 1340 mm/s. Then, the researchers subjected some specimens to a heat
treatment at 850 ◦ C for 2 h and continued for 2 h more to go through isothermal heating. After that,
the furnace temperature was set below 200 ◦ C to reduce the specimen’s temperature to 200 ◦ C within
1 h, and, besides, the samples were also shot-peened. Later, the authors studied the microstructure of
the as-built and post-treated Ti–6Al–4V samples and reported that the former exhibited the α′ as a
major phase, while the latter was composed of ultrafine grain lamellar α + β phases. Subsequently,
corrosive tests were performed in a NaCl and phosphate buffer corrosion media, and the researchers
concluded that due to the microstructural change, the post-treated samples demonstrated lower
corrosion rates. Likewise, Leon et al. [78] investigated the HIP effect on the corrosion performance of
Ti–6Al–4V samples manufactured by EBM. After producing the specimens, the authors conducted a
thermal treatment at 925 ◦ C with a pressure of 100 MPa for 3 h and then performed electrochemical
measurements and stress-corrosion examination by means of slow strain-rate testing. After analyzing
the results, the authors concluded that the heat treatment had a slightly advantageous effect on the
mechanochemical performance and corrosion resistance of the titanium alloy due to the reduction of
α/β interphase area, the increased amount of β phase, as well as the amplified passivation film stability.
Despite not using any thermal treatment, Sharma et al. [79] investigated the corrosion resistance
of as-built Ti–6Al–4V bioimplants manufactured through SLM, having in mind that their dissolution
inside the human body usually leads to inflammations in the internal organs. The authors used three
types of corrosion media (NaOH, NaCl, and H2SO4), which varied from alkaline to acidic and also
used a physiological simulated body fluid (SBF) medium as a comparison. Then, after manufacturing
the samples, the researchers studied the microstructure of the SLMed and commercial cast titanium,
which was used as a reference, and determined that the former exhibited a martensitic microstructure,
while the latter showed a uniform distribution of α + β phases. Subsequently, the authors conducted
several corrosion tests and reported that the SLMed samples had a worse corrosion resistance than the
reference because of the α′ phase and the higher surface porosity. Nevertheless, the charge transfer
resistance, which measures the difficulty faced when an electron is moved from one atom/compound to
another, and the polarization of both samples were noticeably high in NaOH, NaCl, and SBF, meaning

85
Metals 2020, 10, 1006

that the samples exhibited a good corrosion resistance in the aforementioned media. However, in a
more acidic and aggressive solution (H2SO4), they showed an enormously poor corrosion resistance.
Nalli et al. [80] investigated the barrel finishing and heat treatment effect on the mechanical properties
of Ti–6Al–4V samples manufactured through SLM. For that, some specimens were heat-treated with
distinct temperatures (482 ◦ C, 704 ◦ C, 788 ◦ C, and 800 ◦ C) and holding times (3 h, 4 h, 5 h, 6 h, 8 h,
and 10 h). Furthermore, others were barrel finished at 30 and 42 rpm, and as a reference, the authors
left some specimens in the as-built state. Then, mechanical tests were performed, and after analyzing
the results, the researchers reported that as the temperature of the heat treatment and the intensity of
the barrel finishing increased, the elongation at break of the specimens improved as well. However,
as the elongation increased, the YS and UTS decreased; nevertheless, the authors concluded that the
heat treatment temperature of 788 ◦ C and barrel finishing speed of 30 rpm provided the best results in
terms of ductility versus strength.
In order to have a better understanding of the effects caused by distinct post-treatments on the
mechanical properties of Ti–6Al–4V components, the authors of the current work agglomerated distinct
information from diverse scientific reports related to YS, UTS, and elongation at break (ε), which can
be analyzed in Table 3.

Table 3. Manufacturing process and post-treatment effect on the mechanical properties of the
Ti–6Al–4V alloy.

Mnf. Process Condition Orientation YS [MPa] UTS [MPa] ε [%] Ref.

Wrought - Vertical 836 ± 9 942 ± 8 12.5 ± 1.2 [81]
Wrought - Horizontal 832 ± 10 933 ± 7 13.0 ± 1.5 [81]
Forged Mill Annealed - 970 1030 16 [82]
Forged Mill Annealed - 960 ± 10 1006 ± 10 18.37 ± 0.88 [83]
Cast - - 865 980 13.5 [84]
Cast - - 750 ± 2 875 ± 10 4.5 ± 0.2 [85]
ASTM F136 - - ≥795 ≥860 ≥10 [86]
EBM As-built Vertical 812 ± 12 851 ± 19 3.6 ± 0.9 [87]
EBM As-built Horizontal 783 ± 15 833 ± 22 2.7 ± 0.4 [87]
EBM As-built Vertical 869 ± 7.2 928 ± 9.8 9.9 ± 1.7 [63]
EBM As-built Horizontal 899 ± 4.7 978 ± 3.2 9.5 ± 1.2 [63]
EBM As-built Vertical 1001–1051 1073–1116 11–15 [82]
EBM As-built Horizontal 973–1006 1032–1066 12–15 [82]
EBM HIPed - 723–817 817–918 3–9 [88]
EBM Two-stage HIPed - 885 ± 6 985 ± 12 - [89]
EBM Annealed - 741–842 837–918 3–9 [88]
EBM Stress Relieved - 778–943 885–1015 3–9 [88]
SLM As-built Vertical 1150 ± 67 1246 ± 134 1.4 ± 0.5 [81]
SLM As-built Horizontal 1273 ± 53 1421 ± 120 3.2 ± 0.5 [81]
SLM As-built Vertical 1143 ± 30 1219 ± 20 4.89 ± 0.6 [63]
SLM As-built Horizontal 1195 ± 19 1269 ± 9 5.0 ± 0.5 [63]
SLM HIPed Vertical 883–888 973 – 974 18.5–19.4 [90]
SLM HIPed - 912 ± 30 1005 ± 30 8.3 ± 2 [91]
SLM Annealed Vertical 1045–1054 1115–1116 9.5–12.4 [90]
SLM Annealed Vertical 905–911 987–989 7.4–12.5 [90]
SLM Annealed Horizontal 913 ± 7 1019 ± 11 8.9 ± 1 [84]
SLM Annealed Horizontal 944 ± 8 1036 ± 30 8.5 ± 1 [84]
SLM Stress Relieved Vertical 937 ± 9 1052 ± 11 9.6 ± 0.9 [92]

Similarly, several authors [92–100] also studied the heat treatment effect on the mechanical
properties and microstructure of Ti–6Al–4V components. For instance, Benzing et al. [92] demonstrated
the efficiency of a novel HIP treatment strategy employed to EBMed specimens. The heat treatment
consisted of a two-stage HIP, which can be described as follows: 1050 ◦ C with a pressure of 100 MPa
for 2 h with a 12 ◦ C/min heating rate and a nearly 1600 ◦ C/min cooling rate done between 1050 and
500 ◦ C + temper HIP at 800 ◦ C with a pressure of 30 MPa for 2 h and 12 ◦ C/min heating and cooling
rates. After studying the microstructure and performing mechanical tests, the authors reported that
the new heat treatment maintained the α lath thickness of 1.20 µm ± 0.32 µm, created prior-β grains,

86
Metals 2020, 10, 1006

sealed the internal porosity, removed microstructural heterogeneities, and maintained the YS and UTS
identical to the as-built specimens. In another report, Sabban et al. [96] applied an innovative heat
α μ μ
treatment strategy that
β achieves a bimodal globularized microstructure without the need for a previous
plastic deformation process. After manufacturing the specimens in an SLM machine, the researchers
employed a heat treatment, as shown in Figure 12, with a thermal cycle between 875 and 975 ◦ C,
a heating rate of 2.5 ◦ C/min, and a cooling rate of 1 ◦ C/min. The authors reported that the numerous
heating cycles transformed the lamellar α phase into the β phase, which later transformed into globular
α upon slow cooling. Moreover, the Electron Backscatter Diffraction (EBSD) micrograph showed that
the heating cycles also aided to break the α lamella into smaller segments,α β
which subsequently were
α
converted into spatially separated globular α. Besides, the ductility of the heat-treated specimens, when
α
compared to the as-built ones, was enhanced, the YS and UTS suffered a small decrease, the toughness
α
increased from 98 to 163 MJ/m3 , and beneficial compressive residual stresses were created at the surface
level. Likewise, Galarraga et al. [98] submitted EBMed titanium specimens to different solution heat
treatments with distinct cooling rates and reported that the water-cooled samples, when compared
to the furnace-cooled ones, exhibited an utterly α′ martensitic microstructure which promoted an
increase of 31 % of the UTS; however, they lowered the ductility by 86%. Haar et al. [100] developed a
α′
novel duplex anneal treatment that was firstly done at 910 ◦ C for 8 h followed by water-quenching and
then 750 C for 4 h followed by furnace-cooling. The first step of the heat treatment created a bimodal
◦

microstructure of α in the α′ matrix, while the second step promoted the decomposition of α′ into
α α′
α + β lamellar. Subsequently, the authors conducted tensile tests and verified that when compared to
α′ α β
the as-built SLMed and conventionally annealed samples, the duplex annealed ones demonstrated a
far greater ductility.

Figure 12. Schematic of the heat treatment employed for a period of 24 h. Reproduced from [96],
with permission of Elsevier, 2019.

3.2. Residual Stresses

In additive manufacturing, residual stresses are spatially nonuniform and can lead to worse
fatigue life and mechanical properties of the built components, as well as layer delamination
and part distortion [101]. Moreover, the length of the scan vectors used when producing the
components can also influence the distribution and magnitude of RS, as a longer scan vector results
in a higher temperature gradient, which is opposite to shorter scan vectors that are preferable to
create lower residual stresses [102]. Hence, one of the most usual scanning strategies employed
is the chessboard scanning [103]. Ali et al. [104] investigated the effect of the scan strategy and
vector length on SLMed Ti–6Al–4V specimens. For that, the authors used distinct scan strategies,
namely 45◦ alternating, 90◦ alternating, 2 mm × 2 mm chessboard, 3 mm × 3 mm chessboard,
5 mm × 5 mm chessboard, 5 mm × 5 mm chessboard with scan vectors rotated 45◦ in adjacent blocks,
and 5 mm × 5 mm chessboard with scan vectors rotated 90◦ in adjacent blocks. After analyzing the
finite element simulation results, the researchers reported that a 90◦ alternating scan strategy caused
the lowest residual stresses. Furthermore, the growth of the scan vector length in the chessboard
scanning strategy resulted in increased residual stresses. Likewise, Song et al. [105] used finite element
simulation and experimental verification to ascertain the effect of scanning strategies on the residual
stresses of SLMed Ti–6Al–4V samples. The authors employed three distinct scan strategies, which were

87
Metals 2020, 10, 1006

line scan, 15◦ alternating scan, and 90◦ alternating scan. After conducting several tests, they reported
that the scan strategy had little to no influence on the molten pool size, and the 15◦ alternating scan
strategy produced the lowest residual stresses. Lu et al. [106] investigated the RS evolution on distinct
chessboard scanning areas through Vickers micro-indentation. After performing the aforementioned
test, the authors reported that the lowest RS were found in the 2 × 2 mm2 sample; however, that only
happened because cracks were formed, and stresses were released. Thus, the authors concluded that
the 5 × 5 mm2 scanning area was the best to produce end parts with the lowest RS.
Laser Shock Peening (LSP) has been widely studied by several authors [107–114], which state that
the aforementioned post-treatment refines the microstructure and induces compressive residual stresses
on the surface level, thus enhancing the fatigue lifetime of the components made from distinct titanium
alloys. Zhang et al. [110] conducted a residual stress analysis through XRD and a micro-hardness
test through Vickers indentation and reported that the LSP treatment induced compressive residual
stresses and enhanced the micro-hardness of the Ti–6Al–4V samples. Plus, multiple laser shocks had a
positive effect on the surface hardening. Furthermore, the authors also ascertained that the number of
overlapped laser spots, which were meant to act as the laser peening intensity, provided better fatigue
life properties when set to 3. In another study, Ren et al. [111] reported that the LSP treatment was
able to reduce the surface roughness and repair surface details of Ti–6Al–4V samples if done with
a lower laser pulse energy (6.3 J). Besides, when the authors employed a higher laser pulse energy
(7.9 J), the surface hardness significantly increased. Likewise, Jin et al. [113] investigated the influence
of LSP on the fatigue behavior and microstructure of Ti–6Al–4V samples manufactured via EBM.
For the post-treatment, the authors used a Nd:YAG laser with a frequency of 1 Hz, a wavelength of
1064 nm, a beam diameter of 2.5 mm, and a pulse duration of 12 ns. Then, the microstructure was
studied, and the researchers reported that the EBMed specimens showed a microstructure composed
of α + β phases, as shown in Figure 13a. Besides, the LSP treatment caused grain refinement of the
α phase via deformation twinning, as shown in Figure 13b. Subsequently, the authors performed
mechanical tests and concluded that the LSPed samples, when compared to the as-built ones, exhibited
a micro-hardness increase of 11%, as well as a run-out fatigue strength (2 × 106 cycles) increase of
100 MPa. Moreover, the LSP treatment inhibited the crack initiation and enhanced the required work of
fatigue fracture, which, according to the literature reviewed by the authors, was due to the formation of
compressive residual stresses and the grain refinement. In a similar study, Lan et al. [114] investigated
the effect of the LSP treatment on the microstructural evolution and mechanical properties of Ti–6Al–4V
specimens. The authors employed the same LSP parameters as Jin et al. [113] and then studied the
microstructural evolution of the as-built and post-treated samples. They reported that when compared
to the as-built samples, the post-treated ones exhibited a refined α lamella into sub-micro-equiaxed
grains and nano-equiaxed grains. Later, the researchers measured the residual stresses of both types of
samples through XRD and concluded that the LSP treatment changed the surface stress state from
nearly 45 MPa to −380 MPa. Finally, the authors conducted a tensile test and ascertained that the
LSP-treated samples possessed a higher tensile strength and elongation, due to the grain refinement
and the induced compressive RS.

(a) (b)
Figure 13. Transmission Electron Microscopy (TEM) image of (a) EBM as-built specimens, and (b) Laser
Shock Peening (LSP)-treated specimens. Adapted from [113], with permission of Elsevier, 2020.

88
Metals 2020, 10, 1006

Eyzat et al. [115] studied the effect of distinct post-treatments on the mechanical properties,
residual stresses, and roughness of Ti–6Al–4V samples manufactured via SLM. For that, the researchers
employed a stress relief heat treatment at 400 ◦ C for 2 h to some specimens and the previous heat
treatment + Surface Mechanical Attrition Treatment (SMAT) to the others. The latter post-treatment
− subsequent impact
uses a high frequency (20 kHz) ultrasonic generator, which leads to the vibration and
of spherical balls into the specimen’s surface and promotes plastic deformation. After performing
mechanical tests, investigating the specimen’s surface roughness, and analyzing the residual stresses
through the XRD method, the authors concluded that SMAT treatment changed the RS from tensile
(approximately 100 MPa) to compressive (approximately −300 MPa) as it can be seen in Figure 14,
reducing by 80% the high surface roughness, and boosting the mechanical properties (YS, UTS,
μ
and micro-hardness) by 10% to 15%. Yakout et al. [116] studied the correlation between residual
stresses and process parameters of SLMed Ti–6Al–4V samples. For that, the authors used the Renishaw
AM 400 machine and the titanium grade 23 powder from the same enterprise. Then, several specimens
were manufactured using distinct laser power (P), scanning speed (v), and hatch spacing (h), while the
layer thickness (t) was kept constant at 40 µm. Note that the aforementioned process parameters are
all correlated in the Volumetric Energy Density (Ev) formula, which is:

P
Ev = (1)
v×h×t

(a) (b)

Figure 14. Post-treatment effects on (a) longitudinal residual stresses and (b) transversal residual
stresses. Adapted from [115], under CC BY 4.0.

Later, after conducting distinct studies of the produced samples, the researchers concluded that
the Ev increase led to a growth in the part’s thermal expansion and density up to a maximum point,
which was considered the critical energy density (Ev = 86.8 J/mm3 ). Furthermore, the components
manufactured with a volumetric energy density inferior to the critical one exhibited less residual
stresses, as the XRD analysis exposed.
In a similar study, Vastola et al. [117] investigated, through FEM, the effect of beam scan speed,
beam power density, beam size, and chamber bed temperature on the distribution and magnitude of
residual stresses on EBMed Ti–6Al–4V samples. The authors reported that lower scan speeds deepened
the Heat-Affected Zone (HAZ), while higher speeds reduce the HAZ. Furthermore, a 20% increase
of the beam power caused an approximate 15% growth of the HAZ. Moreover, the researchers also
stated that small beam sizes provided higher stresses within a smaller Heat-Affected Zone. Finally,
it was concluded that the bed pre-heating temperature was the most crucial parameter for reducing
the residual stresses, as a 50 ◦ C increase of the pre-heating temperature promoted an approximate 20%
decrease of residual stresses, as shown in Figure 15.

89
Metals 2020, 10, 1006

Figure 15. Quantitative effect of bed pre-heating temperature on residual stresses, where SMises is the
Von Mises Stress. Adapted from [117], with permission of Elsevier, 2016.

In another study, Ning et al. [118] developed an analytical model that predicts RS and part distortion
without the need for any iteration-based simulations or FEM. The inputs for the aforementioned model
were the laser parameters, scan parameters, and material parameters, and the thermal model was
calculated by a moving point heat source solution along with a heat sink solution. Then, the thermal
stress model was calculated from the thermal model and the RS were computed from the thermal stress
model by applying an elastoplastic relaxation method. After that, part distortion was computed using
a surface displacement model, which finally outputted the distortion at distinct locations. The authors
validated the accuracy of their analytical model by manufacturing several cantilever-like Ti–6Al–4V
specimens on an SLM machine and measuring the part distortion on a Coordinate Measuring Machine
(CMM). After comparing the experimental results with the analytical ones, the researchers ascertained
that similar agreements were seen in terms of part distortion at distinct locations. Furthermore,
the authors also emphasized that the computational time of the analytical model was only 10 s on a
personal computer, thus allowing a high computational efficiency.
Finally, in Figures 16 and 17, it is possible to analyze two similar diagrams that explain and
summarize the expected mechanical properties and microstructures of as-built and heat-treated EBMed
and SLMed Ti–6Al–4V components, respectively.

Figure 16. Diagram of the expected microstructure and mechanical properties of as-built and heat-treated
EBMed Ti–6Al–4V samples.

90
Metals 2020, 10, 1006

Figure 17. Diagram of the expected microstructure and mechanical properties of as-built and heat-treated
SLMed Ti–6Al–4V samples.

4. Concluding Remarks and Outlook

One of the most used and studied superalloys in additive manufacturing is the Ti–6Al–4V, which
can be applied in several distinct areas, namely in the aerospace field due to its low density and high
melting point (around 1650 ◦ C), and the biomedical area owing to its high corrosion resistance and
excellent biocompatibility when in contact with tissues or bones of the human body. For this review
work, the authors analyzed roughly 22% of the 537 different publications seen in Figure 4, and more
than half of those 22% were about heat treatments and residual stresses of Ti–6Al–4V components
produced via SLM and/or EBM in order to provide a solid and unbiased overview. The main ideas can
be described as follows:

• Owing to the inherent characteristics of the SLM process, i.e., high cooling rates andα′quick
β
solidification, the expected microstructure in the as-built α by βfine acicular α′
state is characterized
martensitic precipitates in columnar original β grains, opposed to an α + β lamellar microstructure
obtained through EBM. The latter manufacturing process achieves superior building chamber
temperatures; therefore, it reduces the part’s cooling rate and forms a bimodal microstructure.
• If one seeks to improve the mechanical properties, such as ductility and hardness, and decrease the
residual stresses of SLMed Ti–6Al–4V parts, then heat treatments should be conducted. A duplex
anneal treatment can be firstly done at 910 ◦ C for 8 h followed by water-quenching and then
750 ◦ C for 4 h followed by furnace-cooling. The first step of the heat treatment creates a bimodal
microstructure of α in the α′ matrix, while the second step promotes the decomposition of α′ into
α + β lamellar.
• Hot Isostatic Pressing must be done if one desires to increase the density and fatigue life of
the manufactured component, as the aforementioned treatment is responsible for decreasing
the size of the internal defects. Besides, one can also predict the expected porosity of the final
pieces due to recent developments of trustworthy and efficient computer analytical models.
Furthermore, the surface roughness also plays a crucial role in the fatigue life of the final part and
is heavily dependent of the manufacturing process, i.e., SLM leads to lower Ra values than EBM;
nevertheless, post-machining, sandblasting, and polishing can greatly decrease the Ra values,
consequently weakening the crack initiation and improving the fatigue life.
• It has been seen that residual stresses can be lowered through heat treatments as well as optimized
printing parameters, such as the bed pre-heating temperature in EBM or the correlation of distinct
process parameters in the Volumetric Energy Density formula on SLMed components. Besides,
high scanning speeds coupled with shorter scan vectors, i.e., chessboard scanning, has been
demonstrated to lower the residual stresses. Furthermore, LSP and SMAT post-treatments can
also enhance the fatigue life as they induce compressive residual stresses on the surface and
increase the microhardness of the components.

91
Metals 2020, 10, 1006

Despite the tremendous research over the last years about additively manufactured Ti–6Al–4V
parts, there are still some problems to overcome—namely, the mechanical properties variability when
subjected to different heat treatments and process parameters. Furthermore, heat treatments should be
further investigated and improved, because often one sacrifices yield and ultimate tensile strength
for ductility. In addition, there is still room to improve regarding the residual stresses of Ti–6Al–4V
components, i.e., researching the RS evolution under different heat treatments and printing parameters.
Lastly, the main limitations felt by the authors upon writing this review paper were the restricted
access of several scientific articles as well as the comprehension of a small number of results exhibited
by distinct authors. Moreover, as one can analyze in the Pareto charts (Figures 5 and 6), the scientific
community has studied more SLMed Ti–6Al–4V components than EBMed ones, and only a few works
focus on residual stresses, which ultimately was a big limitation of information.

Author Contributions: Conceptualization: Ó.T. and F.J.G.S.; methodology: Ó.T., L.P.F., E.A. and F.J.G.S.;
investigation: Ó.T.; formal analysis: E.A., L.P.F. and F.J.G.S.; supervision: F.J.G.S. and E.A.; validation: F.J.G.S.,
L.P.F. and E.A.; writing original draft: Ó.T.; writing, reviewing and editing: F.J.G.S.; resources: E.A.; project
administration: F.J.G.S., L.P.F. and E.A. All authors have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Acknowledgments: The main author would like to acknowledge his mentor for all the help and support given
through the writing of this report.
Conflicts of Interest: The authors declare no conflict of interest.

List of Symbols and Abbreviations

3DP Three-Dimensional Printing
AM Additive Manufacturing
ASTM American Society for Testing and Materials
CMM Coordinate Measuring Machine
EBM Electron Beam Melting
EBSD Electron Backscatter Diffraction
Ev Volumetric Energy Density
FC Furnace Cooling
FEM Finite Element Modeling
h Hatch Spacing
H2SO4 Sulfuric Acid
HAZ Heat-Affected Zone
hBMSCs Human Bone Mesenchymal Stem Cells
HIP Hot Isostatic Pressing
ISO International Organization for Standardization
LSP Laser Shock Peening
Ms Martensite Start Temperature
NaCl Sodium Chloride
NaOH Sodium Hydroxide
P Laser Power
Ra Surface Roughness
Ref. Reference
RS Residual Stresses
SBF Simulated Body Fluid
SLM Selective Laser Melting
SLS Selective Laser Sintering
SMAT Surface Mechanical Attrition Treatment
t Layer Thickness
Tambient Ambient Temperature
Tmelt Melting Temperature

92
Metals 2020, 10, 1006

UTS Ultimate Tensile Strength

v Scanning Speed
WQ Water Quenching
XRD X-ray Diffraction
YS Yield Strength
ε Elongation at Break

References
1. Goldberg, D. History of 3D Printing: It’s Older than You Are (That Is, If You’re Under 30). AutoDesk. 2018.
Available online: https://www.autodesk.com/redshift/history-of-3d-printing/ (accessed on 4 December 2019).
2. ISO/ASTM 52900-15. Standard Terminology for Additive Manufacturing–General Principles–Terminology;
ASTM International: West Conshohocken, PA, USA, 2015.
3. Silva, F.J.G.; Campilho, R.D.S.G.; Gouveia, R.M.; Pinto, G.; Baptista, A. A Novel Approach to Optimize the
Design of Parts for Additive Manufacturing. Procedia Manuf. 2018, 17, 53–61. [CrossRef]
4. Gouveia, R.M.; Silva, F.J.G.; Atzeni, E.; Sormaz, D.; Alves, J.L.; Pereira, A.B. Effect of Scan Strategies and Use
of Support Structures on Surface Quality and Hardness of L-PBF AlSi10Mg Parts. Materials 2020, 13, 2248.
[CrossRef]
5. ASTM F2792-12a. Standard Terminology for Additive Manufacturing Technologies (Withdrawn 2015);
ASTM International: West Conshohocken, PA, USA, 2012; pp. 1–3.
6. Meiners, W. Shaped Body Especially Prototype or Replacement Part Production. German Patent 19649865,
12 February 1998.
7. Giganto, S.; Zapico, P.; Castro-Sastre, M.Á.; Martínez-Pellitero, S.; Leo, P.; Perulli, P. Influence of the scanning
strategy parameters upon the quality of the SLM parts. Procedia Manuf. 2019, 41, 698–705. [CrossRef]
8. Anwar, A.B.; Ibrahim, I.H.; Pham, Q.C. Spatter transport by inert gas flow in selective laser melting:
A simulation study. Powder Technol. 2019, 352, 103–116. [CrossRef]
9. Ferrar, B.; Mullen, L.; Jones, E.; Stamp, R.; Sutcliffe, C.J. Gas flow effects on selective laser melting (SLM)
manufacturing performance. J. Mater. Process. Technol. 2012, 212, 355–364. [CrossRef]
10. Konečná, R.; Nicoletto, G.; Riva, E. Notch fatigue behavior of Inconel 718 produced by selective laser melting.
Procedia Struct. Integr. 2019, 17, 138–145. [CrossRef]
11. Contuzzi, N.; Campanelli, S.L.; Ludovico, A.D. 3D finite element analysis in the Selective Laser Melting
process. Int. J. Simul. Model. 2011, 10, 113–121. [CrossRef]
12. Nguyen, Q.B.; Luu, D.N.; Nai, S.M.L.; Zhu, Z.; Chen, Z.; Wei, J. The role of powder layer thickness on the
quality of SLM printed parts. Arch. Civ. Mech. Eng. 2018, 18, 948–955. [CrossRef]
13. Arcam, A.B. Arrangement for the Production of a Three-Dimensional Product. U.S. Patent 20060141089,
29 June 2006.
14. Körner, C.; Attar, E.; Heinl, P. Mesoscopic simulation of selective beam melting processes. J. Mater. Process.
Technol. 2011, 211, 978–987. [CrossRef]
15. Galati, M.; Iuliano, L. A literature review of powder-based electron beam melting focusing on numerical
simulations. Addit. Manuf. 2018, 19, 1–20. [CrossRef]
16. Li, P.; Warner, D.H.; Fatemi, A.; Phan, N. Critical assessment of the fatigue performance of additively
manufactured Ti-6Al-4V and perspective for future research. Int. J. Fatigue 2016, 85, 130–143. [CrossRef]
17. Prabhakar, P.; Sames, W.J.; Dehoff, R.; Babu, S.S. Computational modeling of residual stress formation during
the electron beam melting process for Inconel 718. Addit. Manuf. 2015, 7, 83–91. [CrossRef]
18. Smith, C.J.; Derguti, F.; Hernandez Nava, E.; Thomas, M.; Tammas-Williams, S.; Gulizia, S.; Fraser, D.;
Todd, I. Dimensional accuracy of Electron Beam Melting (EBM) additive manufacture with regard to weight
optimized truss structures. J. Mater. Process. Technol. 2016, 229, 128–138. [CrossRef]
19. Gokuldoss, P.K.; Kolla, S.; Eckert, J. Additive manufacturing processes: Selective laser melting, electron
beam melting and binder jetting-selection guidelines. Materials 2017, 10, 672. [CrossRef]
20. Azam, F.I.; Abdul Rani, A.M.; Altaf, K.; Rao, T.V.V.L.N.; Zaharin, H.A. An In-Depth Review on Direct
Additive Manufacturing of Metals. IOP Conf. Ser. Mater. Sci. Eng. 2018, 328, 012005. [CrossRef]
21. Properties of Titanium Ti-6Al-4V (Grade 5). Matweb. Available online: http://www.matweb.com/search/
datasheet.aspx?MatGUID=10d463eb3d3d4ff48fc57e0ad1037434 (accessed on 6 December 2019).

93
Metals 2020, 10, 1006

22. Zuback, J.S.; DebRoy, T. The hardness of additively manufactured alloys. Materials 2018, 11, 2070. [CrossRef]
23. Dai, N.; Zhang, L.C.; Zhang, J.; Zhang, X.; Ni, Q.; Chen, Y.; Wu, M.; Yang, C. Distinction in corrosion resistance
of selective laser melted Ti-6Al-4V alloy on different planes. Corros. Sci. 2016, 111, 703–710. [CrossRef]
24. Lin, J.; Lv, Y.; Liu, Y.; Sun, Z.; Wang, K.; Li, Z.; Wu, Y.; Xu, B. Microstructural evolution and mechanical
property of Ti-6Al-4V wall deposited by continuous plasma arc additive manufacturing without post heat
treatment. J. Mech. Behav. Biomed. Mater. 2017, 69, 19–29. [CrossRef]
25. Tamilselvi, S.; Raman, V.; Rajendran, N. Corrosion behaviour of Ti–6Al–7Nb and Ti–6Al–4V ELI alloys in
the simulated body fluid solution by electrochemical impedance spectroscopy. Electrochim. Acta 2006, 52,
839–846. [CrossRef]
26. Castellanos, S.D.; Alves, J.L.; Neto, R.J. A comparative study of manufacturing processes of complex surface
parts in Titanium Ti6Al4V. Ciência Tecnol. Dos Mater. 2017, 29, 73–78. [CrossRef]
27. Lütjering, G.; Williams, J.C. Titanium, 2nd ed.; Springer: New York, NY, USA, 2007. [CrossRef]
28. Huang, R.; Riddle, M.; Graziano, D.; Warren, J.; Das, S.; Nimbalkar, S.; Cresko, J.; Masanet, E. Energy
and emissions saving potential of additive manufacturing: The case of lightweight aircraft components.
J. Clean. Prod. 2016, 135, 1559–1570. [CrossRef]
29. Ngo, T.D.; Kashani, A.; Imbalzano, G.; Nguyen, K.T.Q.; Hui, D. Additive manufacturing (3D printing):
A review of materials, methods, applications and challenges. Compos. Part B Eng. 2018, 143, 172–196.
[CrossRef]
30. Ducato, A.; Fratini, L.; La Cascia, M.; Mazzola, G. An automated visual inspection system for the classification
of the phases of Ti-6Al-4V titanium alloy. Lect. Notes Comput. 2013, 8048, 362–369. [CrossRef]
31. Ahmed, T.; Rack, H.J. Phase transformations during cooling in α+β titanium alloys. Mater. Sci. Eng. A 1998,
243, 206–211. [CrossRef]
32. Boyer, R.; Collings, E.W.; Welsch, G. Materials Properties Handbook: Titanium Alloys; ASM International:
Cleveland, OH, USA, 1994.
33. Gil Mur, F.X.; Rodríguez, D.; Planell, J.A. Influence of tempering temperature and time on the α′ -Ti-6Al-4V
martensite. J. Alloys Compd. 1996, 234, 287–289. [CrossRef]
34. Reisgen, U.; Olschok, S.; Sharma, R.; Gach, S. Influence on martensite-start-temperature and volume
expansion of low-transformation-temperature materials used for residual stress relief in beam welding.
Mater. Sci. Eng. Technol. 2017, 48, 1276–1282. [CrossRef]
35. Liu, S.; Shin, Y.C. Additive manufacturing of Ti6Al4V alloy: A review. Mater. Des. 2019, 164, 107552.
[CrossRef]
36. Bartlett, J.L.; Li, X. An overview of residual stresses in metal powder bed fusion. Addit. Manuf. 2019, 27,
131–149. [CrossRef]
37. Vayssette, B.; Saintier, N.; Brugger, C.; Elmay, M.; Pessard, E. Surface roughness of Ti-6Al-4V parts obtained
by SLM and EBM: Effect on the High Cycle Fatigue life. Procedia Eng. 2018, 213, 89–97. [CrossRef]
38. Liu, D.; Flewitt, P.E.J. Raman measurements of stress in films and coatings. Spectrosc. Prop. Inorg. Organomet.
Compd. 2014, 45, 141–177. [CrossRef]
39. Guo, J.; Fu, H.; Pan, B.; Kang, R. Recent progress of residual stress measurement methods: A review.
Chin. J. Aeronaut. 2020. [CrossRef]
40. Barros, R.; Silva, F.J.G.; Gouveia, R.M.; Saboori, A.; Marchese, G.; Biamino, S.; Salmi, A.; Atzeni, E. Laser
Powder Bed Fusion of Inconel 718: Residual Stress Analysis Before and After Heat Treatment. Metals 2019,
9, 1290. [CrossRef]
41. ASTM E 837-08. Standard Test Method for Determining Residual Stresses by the Hole-Drilling Strain-Gages;
ASTM International: West Conshohocken, PA, USA, 2008; Volume 1, pp. 1–17.
42. Thijs, L.; Verhaeghe, F.; Craeghs, T.; Humbeeck, J.V.; Kruth, J.P. A study of the microstructural evolution
during selective laser melting of Ti-6Al-4V. Acta Mater. 2010, 58, 3303–3312. [CrossRef]
43. Facchini, L.; Magalini, E.; Robotti, P.; Molinari, A.; Höges, S.; Wissenbach, K. Ductility of a Ti-6Al-4V alloy
produced by selective laser melting of prealloyed powders. Rapid Prototyp. J. 2010, 16, 450–459. [CrossRef]
44. Gong, H.; Rafi, K.; Gu, H.; Janaki Ram, G.D.; Starr, T.; Stucker, B. Influence of defects on mechanical properties
of Ti-6Al-4V components produced by selective laser melting and electron beam melting. Mater. Des. 2015,
86, 545–554. [CrossRef]

94
Metals 2020, 10, 1006

45. Benedetti, M.; Torresani, E.; Leoni, M.; Fontanari, V.; Bandini, M.; Pederzolli, C.; Potrich, C. The effect of
post-sintering treatments on the fatigue and biological behavior of Ti-6Al-4V ELI parts made by selective
laser melting. J. Mech. Behav. Biomed. Mater. 2017, 71, 295–306. [CrossRef]
46. Xu, W.; Sun, S.; Elambasseril, J.; Liu, Q.; Brandt, M.; Qian, M. Ti-6Al-4V Additively Manufactured by Selective
Laser Melting with Superior Mechanical Properties. JOM 2015, 67, 668–673. [CrossRef]
47. Xu, J.; Zhu, J.; Fan, J.; Zhou, Q.; Peng, Y.; Guo, S. Microstructure and mechanical properties of Ti–6Al–4V
alloy fabricated using electron beam freeform fabrication. Vacuum 2019, 167, 364–373. [CrossRef]
48. Galarraga, H.; Lados, D.A.; Dehoff, R.R.; Kirka, M.M.; Nandwana, P. Effects of the microstructure and
porosity on properties of Ti-6Al-4V ELI alloy fabricated by electron beam melting (EBM). Addit. Manuf. 2016,
10, 47–57. [CrossRef]
49. Zhao, X.; Li, S.; Zhang, M.; Liu, Y.; Sercombe, T.B.; Wang, S.; Hao, Y.; Yang, R.; Murr, L.E. Comparison of the
microstructures and mechanical properties of Ti-6Al-4V fabricated by selective laser melting and electron
beam melting. Mater. Des. 2016, 95, 21–31. [CrossRef]
50. Chern, A.H.; Nandwana, P.; McDaniels, R.; Dehoff, R.R.; Liaw, P.K.; Tryon, R.; Duty, C.E. Build orientation,
surface roughness, and scan path influence on the microstructure, mechanical properties, and flexural fatigue
behavior of Ti–6Al–4V fabricated by electron beam melting. Mater. Sci. Eng. A 2020, 772, 138740. [CrossRef]
51. Murr, L.E.; Esquivel, E.V.; Quinones, S.A.; Gaytan, S.M.; Lopez, M.I.; Martinez, E.Y.; Medina, F.;
Hernandez, D.H.; Martinez, E.; Martinez, J.L.; et al. Microstructures and mechanical properties of electron
beam-rapid manufactured Ti-6Al-4V biomedical prototypes compared to wrought Ti-6Al-4V. Mater. Charact.
2009, 60, 96–105. [CrossRef]
52. Edwards, P.; Ramulu, M. Fatigue performance evaluation of selective laser melted Ti-6Al-4V. Mater. Sci. Eng. A
2014, 598, 327–337. [CrossRef]
53. Chan, K.S.; Koike, M.; Mason, R.L.; Okabe, T. Fatigue life of titanium alloys fabricated by additive layer
manufacturing techniques for dental implants. Metall. Mater. Trans. A Phys. Metall. Mater. Sci. 2013, 44,
1010–1022. [CrossRef]
54. Fousová, M.; Vojtěch, D.; Doubrava, K.; Daniel, M.; Lin, C.F. Influence of inherent surface and internal defects
on mechanical properties of additively manufactured Ti6Al4V alloy: Comparison between selective laser
melting and electron beam melting. Materials 2018, 11, 537. [CrossRef] [PubMed]
55. Qiu, C.; Panwisawas, C.; Ward, M.; Basoalto, H.C.; Brooks, J.W.; Attallah, M.M. On the role of melt flow into
the surface structure and porosity development during selective laser melting. Acta Mater. 2015, 96, 72–79.
[CrossRef]
56. Stef, J.; Poulon-Quintin, A.; Redjaimia, A.; Ghanbaja, J.; Ferry, O.; De Sousa, M.; Gouné, M. Mechanism of
porosity formation and influence on mechanical properties in selective laser melting of Ti-6Al-4V parts.
Mater. Des. 2018, 156, 480–493. [CrossRef]
57. Tammas-Williams, S.; Zhao, H.; Léonard, F.; Derguti, F.; Todd, I.; Prangnell, P.B. XCT analysis of the influence
of melt strategies on defect population in Ti-6Al-4V components manufactured by Selective Electron Beam
Melting. Mater. Charact. 2015, 102, 47–61. [CrossRef]
58. Ning, J.; Sievers, D.E.; Garmestani, H.; Liang, S.Y. Analytical modeling of part porosity in metal additive
manufacturing. Int. J. Mech. Sci. 2020, 172, 105428. [CrossRef]
59. Zhang, W.; Qin, P.; Wang, Z.; Yang, C.; Kollo, L.; Grzesiak, D.; Prashanth, K.G. Superior wear resistance in
EBM-Processed TC4 alloy compared with SLM and forged samples. Materials 2019, 12, 782. [CrossRef]
60. Mohammadhosseini, A.; Fraser, D.; Masood, S.H.; Jahedi, M. Microstructure and mechanical properties of
Ti–6Al–4V manufactured by electron beam melting process. Mater. Res. Innov. 2013, 17, 106–112. [CrossRef]
61. Tan, X.; Kok, Y.; Tan, Y.J.; Descoins, M.; Mangelinck, D.; Tor, S.B.; Leong, K.F.; Chua, C.K. Graded
microstructure and mechanical properties of additive manufactured Ti-6Al-4V via electron beam melting.
Acta Mater. 2015, 97, 1–16. [CrossRef]
62. Losertová, M.; Kubeš, V. Microstructure and mechanical properties of selective laser melted Ti6Al4V alloy.
IOP Conf. Ser. Mater. Sci. Eng. 2017, 266, 012009. [CrossRef]
63. Rafi, H.K.; Karthik, N.V.; Gong, H.; Starr, T.L.; Stucker, B.E. Microstructures and mechanical properties of
Ti6Al4V parts fabricated by selective laser melting and electron beam melting. J. Mater. Eng. Perform. 2013,
22, 3872–3883. [CrossRef]

95
Metals 2020, 10, 1006

64. Balyakin, A.; Zhuchenko, E.; Nosova, E. Study of heat treatment impact on the surface defects appearance on
samples obtained by selective laser melting of Ti-6Al-4V during chemical polishing. Mater. Today Proc. 2019,
19, 2307–2311. [CrossRef]
65. Vayssette, B.; Saintier, N.; Brugger, C.; El May, M. Surface roughness effect of SLM and EBM Ti-6Al-4V on
multiaxial high cycle fatigue. Theor. Appl. Fract. Mech. 2020, 108, 102581. [CrossRef]
66. Yuan, W.; Hou, W.; Li, S.; Hao, Y.; Yang, R.; Zhang, L.C.; Zhu, Y. Heat treatment enhancing the compressive
fatigue properties of open-cellular Ti-6Al-4V alloy prototypes fabricated by electron beam melting. J. Mater.
Sci. Technol. 2018, 34, 1127–1131. [CrossRef]
67. Zhao, S.; Li, S.J.; Hou, W.T.; Hao, Y.L.; Yang, R.; Misra, R.D.K. The influence of cell morphology on the
compressive fatigue behavior of Ti-6Al-4V meshes fabricated by electron beam melting. J. Mech. Behav.
Biomed. Mater. 2016, 59, 251–264. [CrossRef]
68. Chastand, V.; Quaegebeur, P.; Maia, W.; Charkaluk, E. Comparative study of fatigue properties of Ti-6Al-4V
specimens built by electron beam melting (EBM) and selective laser melting (SLM). Mater. Charact. 2018, 143,
76–81. [CrossRef]
69. Pegues, J.W.; Shao, S.; Shamsaei, N.; Sanaei, N.; Fatemi, A.; Warner, D.H.; Li, P.; Phan, N. Fatigue of additive
manufactured Ti-6Al-4V, Part I: The effects of powder feedstock, manufacturing, and post-process conditions
on the resulting microstructure and defects. Int. J. Fatigue 2020, 132, 105358. [CrossRef]
70. Molaei, R.; Fatemi, A.; Sanaei, N.; Pegues, J.; Shamsaei, N.; Shao, S.; Li, P.; Warner, D.H.; Phan, N. Fatigue of
additive manufactured Ti-6Al-4V, Part II: The relationship between microstructure, material cyclic properties,
and component performance. Int. J. Fatigue 2020, 132, 105363. [CrossRef]
71. Wu, M.-W.; Chen, J.-K.; Lin, B.-H.; Chiang, P.-H.; Tsai, M.-K. Compressive fatigue properties of
additive-manufactured Ti-6Al-4V cellular material with different porosities. Mater. Sci. Eng. A 2020,
790, 139695. [CrossRef]
72. Viespoli, L.M.; Bressan, S.; Itoh, T.; Hiyoshi, N.; Prashanth, K.G.; Berto, F. Creep and high temperature
fatigue performance of as build selective laser melted Ti-based 6Al-4V titanium alloy. Eng. Fail. Anal. 2020,
111, 104477. [CrossRef]
73. Yu, H.; Li, F.; Wang, Z.; Zeng, X. Fatigue performances of selective laser melted Ti-6Al-4V alloy: Influence of
surface finishing, hot isostatic pressing and heat treatments. Int. J. Fatigue 2019, 120, 175–183. [CrossRef]
74. Kim, Y.K.; Park, S.H.; Yu, J.H.; AlMangour, B.; Lee, K.A. Improvement in the high-temperature creep
properties via heat treatment of Ti-6Al-4V alloy manufactured by selective laser melting. Mater. Sci. Eng. A
2018, 715, 33–40. [CrossRef]
75. Hemmasian Ettefagh, A.; Zeng, C.; Guo, S.; Raush, J. Corrosion behavior of additively manufactured
Ti-6Al-4V parts and the effect of post annealing. Addit. Manuf. 2019, 28, 252–258. [CrossRef]
76. Wang, M.; Wu, Y.; Lu, S.; Chen, T.; Zhao, Y.; Chen, H.; Tang, Z. Fabrication and characterization of selective
laser melting printed Ti–6Al–4V alloys subjected to heat treatment for customized implants design. Prog. Nat.
Sci. Mater. Int. 2016, 26, 671–677. [CrossRef]
77. Pazhanivel, B.; Sathiya, P.; Sozhan, G. Ultra-fine bimodal (α + β) microstructure induced mechanical strength
and corrosion resistance of Ti-6Al-4V alloy produced via laser powder bed fusion process. Opt. Laser Technol.
2020, 125, 106017. [CrossRef]
78. Leon, A.; Levy, G.K.; Ron, T.; Shirizly, A.; Aghion, E. The effect of hot isostatic pressure on the corrosion
performance of Ti-6Al-4 V produced by an electron-beam melting additive manufacturing process.
Addit. Manuf. 2020, 33, 101039. [CrossRef]
79. Sharma, A.; Oh, M.C.; Kim, J.T.; Srivastava, A.K.; Ahn, B. Investigation of electrochemical corrosion behavior
of additive manufactured Ti–6Al–4V alloy for medical implants in different electrolytes. J. Alloys Compd.
2020, 830, 154620. [CrossRef]
80. Nalli, F.; Bottini, L.; Boschetto, A.; Cortese, L.; Veniali, F. Effect of industrial heat treatment and barrel
finishing on the mechanical performance of Ti6AL4V processed by selective laser melting. Appl. Sci. 2020,
10, 2280. [CrossRef]
81. Wysocki, B.; Maj, P.; Sitek, R.; Buhagiar, J.; Kurzydłowski, K.J.; Świeszkowski, W. Laser and electron beam
additive manufacturing methods of fabricating titanium bone implants. Appl. Sci. 2017, 7, 657. [CrossRef]
82. Zhai, Y.; Galarraga, H.; Lados, D.A. Microstructure, static properties, and fatigue crack growth mechanisms in
Ti-6Al-4V fabricated by additive manufacturing: LENS and EBM. Eng. Fail. Anal. 2016, 69, 3–14. [CrossRef]

96
Metals 2020, 10, 1006

83. Vrancken, B.; Thijs, L.; Kruth, J.P.; Van Humbeeck, J. Heat treatment of Ti6Al4V produced by Selective Laser
Melting: Microstructure and mechanical properties. J. Alloys Compd. 2012, 541, 177–185. [CrossRef]
84. Vilaro, T.; Colin, C.; Bartout, J.D. As-fabricated and heat-treated microstructures of the Ti-6Al-4V alloy
processed by selective laser melting. Metall. Mater. Trans. A Phys. Metall. Mater. Sci. 2011, 42, 3190–3199.
[CrossRef]
85. Koike, M.; Greer, P.; Owen, K.; Lilly, G.; Murr, L.E.; Gaytan, S.M.; Martinez, E.; Okabe, T. Evaluation of
titanium alloys fabricated using rapid prototyping technologies-electron beam melting and laser beam
melting. Materials 2011, 4, 1776–1792. [CrossRef]
86. ASTM F136-08. Standard Specification for Wrought Titanium-6Aluminum-4Vanadium ELI (Extra Low Interstitial)
Alloy for Surgical Implant Applications (UNS R56401); ASTM International: West Conshohocken, PA, USA,
2008. Available online: www.astm.org (accessed on 24 June 2020).
87. Edwards, P.; O’Conner, A.; Ramulu, M. Electron Beam Additive Manufacturing of Titanium Components:
Properties and Performance. J. Manuf. Sci. Eng. 2013, 135, 061016. [CrossRef]
88. Hayes, B.J.; Martin, B.W.; Welk, B.; Kuhr, S.J.; Ales, T.K.; Brice, D.A.; Ghamarian, I.; Baker, A.H.; Haden, C.V.;
Harlow, D.G.; et al. Predicting tensile properties of Ti-6Al-4V produced via directed energy deposition.
Acta Mater. 2017, 133, 120–133. [CrossRef]
89. Benzing, J.; Hrabe, N.; Quinn, T.; White, R.; Rentz, R.; Ahlfors, M. Hot isostatic pressing (HIP) to achieve
isotropic microstructure and retain as-built strength in an additive manufacturing titanium alloy (Ti-6Al-4V).
Mater. Lett. 2019, 257, 126690. [CrossRef]
90. Kasperovich, G.; Hausmann, J. Improvement of fatigue resistance and ductility of TiAl6V4 processed by
selective laser melting. J. Mater. Process. Technol. 2015, 220, 202–214. [CrossRef]
91. Leuders, S.; Thöne, M.; Riemer, A.; Niendorf, T.; Tröster, T.; Richard, H.A.; Maier, H.J. On the mechanical
behaviour of titanium alloy TiAl6V4 manufactured by selective laser melting: Fatigue resistance and crack
growth performance. Int. J. Fatigue 2013, 48, 300–307. [CrossRef]
92. Simonelli, M.; Tse, Y.Y.; Tuck, C. Effect of the build orientation on the mechanical properties and fracture
modes of SLM Ti-6Al-4V. Mater. Sci. Eng. A 2014, 616, 1–11. [CrossRef]
93. Galati, M.; Saboori, A.; Biamino, S.; Calignano, F.; Lombardi, M.; Marchiandi, G.; Minetola, P.; Fino, P.;
Iuliano, L. Ti-6Al-4V lattice structures produced by EBM: Heat treatment and mechanical properties.
Procedia CIRP 2020, 88, 411–416. [CrossRef]
94. Morita, T.; Tsuda, C.; Nakano, T. Influences of scanning speed and short-time heat treatment on fundamental
properties of Ti-6Al-4V alloy produced by EBM method. Mater. Sci. Eng. A 2017, 704, 246–251. [CrossRef]
95. Zhang, X.Y.; Fang, G.; Leeflang, S.; Böttger, A.J.; Zadpoor, A.A.; Zhou, J. Effect of subtransus heat treatment
on the microstructure and mechanical properties of additively manufactured Ti-6Al-4V alloy. J. Alloys Compd.
2018, 735, 1562–1575. [CrossRef]
96. Sabban, R.; Bahl, S.; Chatterjee, K.; Suwas, S. Globularization using heat treatment in additively manufactured
Ti-6Al-4V for high strength and toughness. Acta Mater. 2019, 162, 239–254. [CrossRef]
97. Tsai, M.T.; Chen, Y.W.; Chao, C.Y.; Jang, J.S.C.; Tsai, C.C.; Su, Y.L.; Kuo, C.N. Heat-treatment effects on
mechanical properties and microstructure evolution of Ti-6Al-4V alloy fabricated by laser powder bed fusion.
J. Alloys Compd. 2020, 816, 152615. [CrossRef]
98. Galarraga, H.; Warren, R.J.; Lados, D.A.; Dehoff, R.R.; Kirka, M.M.; Nandwana, P. Effects of heat treatments
on microstructure and properties of Ti-6Al-4V ELI alloy fabricated by electron beam melting (EBM). Mater. Sci.
Eng. A 2017, 685, 417–428. [CrossRef]
99. Zhang, D.; Wang, L.; Zhang, H.; Maldar, A.; Zhu, G.; Chen, W.; Park, J.S.; Wang, J.; Zeng, X. Effect of
heat treatment on the tensile behavior of selective laser melted Ti-6Al-4V by in situ X-ray characterization.
Acta Mater. 2020, 189, 93–104. [CrossRef]
100. Ter Haar, G.M.; Becker, T.H. Selective laser melting produced Ti-6Al-4V: Post-process heat treatments to
achieve superior tensile properties. Materials 2018, 11, 146. [CrossRef]
101. Mercelis, P.; Kruth, J.P. Residual stresses in selective laser sintering and selective laser melting. Rapid Prototyp. J.
2006, 12, 254–265. [CrossRef]
102. Kruth, J.P.; Deckers, J.; Yasa, E.; Wauthlé, R. Assessing and comparing influencing factors of residual stresses
in selective laser melting using a novel analysis method. Proc. Inst. Mech. Eng. Part B J. Eng. Manuf. 2012,
226, 980–991. [CrossRef]

97
Metals 2020, 10, 1006

103. Zaeh, M.F.; Branner, G. Investigations on residual stresses and deformations in selective laser melting.
Prod. Eng. 2010, 4, 35–45. [CrossRef]
104. Ali, H.; Ghadbeigi, H.; Mumtaz, K. Effect of scanning strategies on residual stress and mechanical properties
of Selective Laser Melted Ti6Al4V. Mater. Sci. Eng. A 2018, 712, 175–187. [CrossRef]
105. Song, J.; Wu, W.; Zhang, L.; He, B.; Lu, L.; Ni, X.; Long, Q.; Zhu, G. Role of scanning strategy on residual
stress distribution in Ti-6Al-4V alloy prepared by selective laser melting. Optik 2018, 170, 342–352. [CrossRef]
106. Lu, Y.; Wu, S.; Gan, Y.; Huang, T.; Yang, C.; Junjie, L.; Lin, J. Study on the microstructure, mechanical
property and residual stress of SLM Inconel-718 alloy manufactured by differing island scanning strategy.
Opt. Laser Technol. 2015, 75, 197–206. [CrossRef]
107. Maawad, E.; Sano, Y.; Wagner, L.; Brokmeier, H.G.; Genzel, C. Investigation of laser shock peening effects on
residual stress state and fatigue performance of titanium alloys. Mater. Sci. Eng. A 2012, 536, 82–91. [CrossRef]
108. Tong, Z.; Ren, X.; Ren, Y.; Dai, F.; Ye, Y.; Zhou, W.; Chen, L.; Ye, Z. Effect of laser shock peening on
microstructure and hot corrosion of TC11 alloy. Surf. Coat. Technol. 2018, 335, 32–40. [CrossRef]
109. Huang, S.; Zhu, Y.; Guo, W.; Peng, P.; Diao, X. Impact toughness and microstructural response of Ti-17
titanium alloy subjected to laser shock peening. Surf. Coat. Technol. 2017, 327, 32–41. [CrossRef]
110. Zhang, X.C.; Zhang, Y.K.; Lu, J.Z.; Xuan, F.Z.; Wang, Z.D.; Tu, S.T. Improvement of fatigue life of Ti-6Al-4V
alloy by laser shock peening. Mater. Sci. Eng. A 2010, 527, 3411–3415. [CrossRef]
111. Ren, X.D.; Zhou, W.F.; Liu, F.F.; Ren, Y.P.; Yuan, S.Q.; Ren, N.F.; Xu, S.D.; Yang, T. Microstructure evolution and
grain refinement of Ti-6Al-4V alloy by laser shock processing. Appl. Surf. Sci. 2016, 363, 44–49. [CrossRef]
112. Guo, W.; Sun, R.; Song, B.; Zhu, Y.; Li, F.; Che, Z.; Li, B.; Guo, C.; Liu, L.; Peng, P. Laser shock peening of laser
additive manufactured Ti6Al4V titanium alloy. Surf. Coat. Technol. 2018, 349, 503–510. [CrossRef]
113. Jin, X.; Lan, L.; Gao, S.; He, B.; Rong, Y. Effects of laser shock peening on microstructure and fatigue behavior
of Ti–6Al–4V alloy fabricated via electron beam melting. Mater. Sci. Eng. A 2020, 780, 139199. [CrossRef]
114. Lan, L.; Jin, X.; Gao, S.; He, B.; Rong, Y. Microstructural evolution and stress state related to mechanical
properties of electron beam melted Ti-6Al-4V alloy modified by laser shock peening. J. Mater. Sci. Technol.
2020, 50, 153–161. [CrossRef]
115. Eyzat, Y.; Chemkhi, M.; Portella, Q.; Gardan, J.; Remond, J.; Retraint, D. Characterization and mechanical
properties of As-Built SLM Ti-6Al-4V subjected to surface mechanical post-treatment. Procedia CIRP 2019, 81,
1225–1229. [CrossRef]
116. Yakout, M.; Elbestawi, M.A.; Veldhuis, S.C. A study of the relationship between thermal expansion and
residual stresses in selective laser melting of Ti-6Al-4V. J. Manuf. Process. 2020, 52, 181–192. [CrossRef]
117. Vastola, G.; Zhang, G.; Pei, Q.X.; Zhang, Y.W. Controlling of residual stress in additive manufacturing of
Ti6Al4V by finite element modeling. Addit. Manuf. 2016, 12, 231–239. [CrossRef]
118. Ning, J.; Praniewicz, M.; Wang, W.; Dobbs, J.R.; Liang, S.Y. Analytical modeling of part distortion in metal
additive manufacturing. Int. J. Adv. Manuf. Technol. 2020, 107, 49–57. [CrossRef]

© 2020 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).

98
 metals
Article
Effects of Thermal Cycling on Wire and Arc Additive
Manufacturing of Al-5356 Components
Markus Köhler *, Jonas Hensel and Klaus Dilger
Institute of Joining and Welding, Technische Universität Braunschweig, Langer Kamp 8,
38106 Braunschweig, Germany; [email protected] (J.H.); [email protected] (K.D.)
* Correspondence: [email protected]; Tel.: +49-531-391-955-32




Received: 23 June 2020; Accepted: 12 July 2020; Published: 15 July 2020


Abstract: Wire and arc additive manufacturing (WAAM) provides a promising alternative to
conventional machining for the production of large structures with complex geometry, as well
as individualized low quantity components, using cost-efficient production resources. Due to the
layer-by-layer build-up approach, process conditions, such as energy input, deposition patterns and
heat conduction during the additive manufacturing process result in a unique thermal history of the
structure, affecting the build-up properties. This experimental study aims to describe the effects of
thermal cycling on the geometrical and material properties of wire arc additive manufactured Al-5356
aluminum alloy. Under consideration, that Al-5356 is a non-heat treatable alloy, a significant effect
on geometrical formation is expected. Linear wall samples were manufactured using pulsed cold
metal transfer (CMT-P) under variation of wire-feed rate, travel speed and interpass temperatures.
The samples were analyzed in terms of geometry; microstructural composition; hardness and residual
stress. Furthermore, the mechanical properties were determined in different building directions.

Keywords: direct energy deposition; WAAM; cold metal transfer; 5356-aluminum; temperature
distribution; mechanical properties

1. Introduction
In recent years, additive manufacturing (AM) of metallic components gained growing interest in a
wide range of industrial sectors such as civil engineering, turbine construction as well as automotive and
aerospace industry [1–4]. Thereby, the economic efficiency compared to conventional manufacturing
processes is mainly determined by high geometrical complexity and/or small series production [5,6].
In order to meet the requirements of different industrial sectors, a variety of AM processes, following
different approaches of material deposition, have been developed. These processes can mainly be
classified into powder-bed, powder and wire-feed processes [7]. Due to higher deposition rates
and significantly higher maximum part size, wire-based processes such as wire and arc additive
manufacturing (WAAM) are particularly suitable for near net-shape production of large components [8].
Furthermore, wire filler metals are more cost-efficient and available in a wider range of materials
compared to powder materials [9,10]. On the other hand, the geometrical accuracy and the attainable
component complexity are lower compared to powder-based processes [7].
During WAAM processing, the component is generated by a layer-wise deposition of molten
filler metal. Melting of the filler material is achieved using electric arc or plasma as a heat source,
thus combining well known arc welding processes such as gas metal arc welding (GMAW), gas tungsten
arc welding (GTAW) or plasma arc welding (PAW) with wire as the feedstock [11–13]. Due to a
simultaneously energy input and wire feed, the wire-feed orientation during GMAW is perpendicular
to the forming substrate, offering advantages in automation and productivity [14].

Metals 2020, 10, 952; doi:10.3390/met10070952 99 www.mdpi.com/journal/metals

Metals 2020, 10, 952

Basic prerequisite for the application of AM technologies is that the resulting component properties
meet the requirements of the operation purpose. This applies in particular to mechanical properties
such as hardness, strength and ductility as well as to specific requirements such as corrosion resistance.
Due to the layer-by-layer build-up approach, both the WAAM process itself and the geometrical and
mechanical properties of the resulting components are directly related to the welding parameters and
the deposited material. Compared to conventionally manufactured components, the primary material
of AM components merely consists of weld metal. Accordingly, there is an increasing number of studies
on material-specific processability and component properties. Regarding the resulting geometry,
studies in [15,16] have shown an increase in surface waviness with increased energy input per length
unit, reporting the main dependencies of geometry formation on heat input and heat accumulation
during the AM process. Other than the effects on the resulting geometry, the welding process always
results in a heat treatment of the surrounding material during deposition, causing microstructural
changes in the current layer and the adjacent material. Depending on the deposited material, this can
lead a non-uniform distribution of the mechanical properties [17]. Regarding this, various studies
on WAAM of low-alloy and high-grade steels reported an increase in hardness and grain refinement
towards the top layers of the deposited structure [11,18,19]. Aiming to reduce the influence of thermal
cycling during WAAM and to actively affect the temperature–time regime during deposition as well
as the resulting grain structure, recent studies have explored the implementation of active cooling
–
systems [20–22]. However, most of the current research regarding the influence of temperature regimes
–
on the resulting properties during additive manufacturing is focused on steel and titanium alloys.
Research on WAAM using various aluminum alloys is mainly focused on microstructural evolution,
pore formation as well as the effects of different arc modes on microstructure characteristics and
mechanical properties [14,23–26]. –
Summarizing, the specific objective of this study is to investigate the heat accumulation and the
influence of different temperature-time regimes on the resulting component properties during wire
and arc additive manufacturing of Al-5356, providing a contribution on geometry formation and
mechanical properties.

2. Materials and Methods

The experimental setup is presented in Figure 1a. A Fronius CMT Advanced 4000 R welding
system (Fronius International GmbH, Wels, Austria) was used in CMT-Pulse mode with current
characteristics according to the deposited material. The welding torch was connected to a KUKA
KR22 6-axis robotic system (KUKA Deutschland GmbH, Augsburg, Germany). The presented studies
have been conducted using thin-walled specimen with a length of 300 mm and a build-up height of
approximately 140 mm. The process sequence is given in Figure 1b. Depending on the underlying
– single pass layers were conducted during sample preparation.
process parameters, 100–120

(a) (b)

Figure 1. Experimental setup (a) and process sequence for sample preparation (b).

100
Metals 2020, 10, 952

The experimental trials were carried out on Al-6082 base plates with dimensions of 400 × 125 × 15 mm3 .
The base plate material was chosen as a typical aluminum alloy ensuring good weldability and thermal
conductivity. As the presented research is focused on the material and geometrical properties of the AM
component, the base plate material does not affect the findings. Prior to welding, organic residues on the
base plate were removed with acetone. The deposited wire was an Al-5356 solid wire electrode with a
diameter of 1.0 mm. The chemical composition of the used materials is given in Table 1.

Table 1. Nominal composition of welding wire and substrate material.

Chemical Composition (wt%)

Alloy
Al Mn Mg Si Fe Cu
Welding Wire: Al-5356 bal 0.15 5.0 0.05 0.15 -
Substrate: Al-6082 bal 0.4–1.0 0.60–1.2 0.7–1.3 <0.5 <0.1

Referring to previous findings, welding parameters such as wire feed and welding speed show a
great influence on the geometrical characteristics of the components processed by WAAM. In order
to further describe the influence of the process parameters on geometrical properties, thin-walled
samples were manufactured with two different settings of process parameters (Series A, Series B).
The process parameters of Series A and Series B were chosen to result in similar energy input per unit
length to ensure a comparable heat input during welding. Aiming to obtain different temperature
profiles during the build-up sequence, thin-walled samples were prepared using different intermediate
times (ti ) between layers. Table 2 provides the welding parameters used for processing the samples.
For all specimens, the preheating temperature of the base plate was set at approximately 100 ◦ C.
During build-up, a contact tube to work piece distance of 10 ± 3 mm was maintained. Pure Argon
(Ar ≥ 99.996%) was used as shielding gas with a flow rate of 14 L/min.

Table 2. Welding parameters for processing of samples.

Parameter Symbol Unit Series A Series B

Wire feed vW m/min 8 10
Welding speed vS cm/min 60 76
Voltage I V 15.5–16.5 16.5–17.5
Current U A 91–92 111–112
Time between layers ti s 30/60/120 30/60/120

In order to describe the occurring temperatures during welding, type-K thermocouples were
positioned at the base plate at a distance of 9.5 ± 0.8 mm to the fusion line. Further, an infrared
pyrometer (Optris CTlaser 3MH, Optris GmbH, Berlin, Germany) with a measuring range from 100 to
600 ◦ C was used to determine the interpass temperature in the middle of the respective topmost layer
during build-up.
Prior to mechanical testing, the specimens were visually examined and measured regarding the
resulting height and width. To assess changes in geometry during build-up, a width measurement
was conducted at ten measurement points in building direction. Further, residual stress was analyzed
by means of X-ray diffraction in the Series A specimen using a cobalt radiation source. Several
measurements were taken in welding direction on the top layer and against the building direction.
To produce a homogeneous surface for the measurement, electrolytic polishing was performed in the
measuring area before testing. Stresses were determined from diffraction patterns by means of the
sin2 Ψ method using the (hkl) crystalline plane {331} of aluminum at eight Ψ-angles between 144◦ and
154◦ . The elastic constant was 0.5S2 = 18.93 mm2 /N.
Samples for metallographic cross-sections, hardness measurement and tensile testing were
sectioned from the AM structures as depicted in Figure 2. The start and end sections of the thin-wall
were discarded. Metallographic samples were polished and etched using 2% hydrofluoric acid for

101
Metals 2020, 10, 952

macroscopic examination and Kroll etchant for microsections. Hardness measurements (HV1) were
conducted equidistant on the cross-sectional samples using hardness testing according to Vickers
(TUKON1202, ITW Test & Measurement GmbH, Esslingen, Germany). In addition, the micro hardness
(HV0.005) was measured at different areas of the microsections depending on the microstructure
composition. Samples for tensile testing were prepared and tested according to EN ISO 6892-1 standards
(Figure 2b) at an extension rate of 3.2 mm/min.

(a) (b)

Figure 2. Schematic representation of sample extraction (a) and dimensions of tensile samples according
to DIN 50125 (b).

3. Results

3.1. Temperature Formation During WAAM

In order to describe temperature related effects on structural and mechanical properties of additive
manufactured structures, temperature measurements were carried out on both the base plate and on
the top layer during build-up. This allowed the determination of the temperature–time regimes during–
WAAM build-up with different intermediate times between layers. Due to similar energy input per
unit length, both regarded parameter settings (Series A, B) resulted in comparable temperature profiles.
Differences in the resulting geometry based on varying parameter settings, as described in Section 3.2,
only showed a minor influence on the heat distribution due to a similar heat input. For the purpose of
improved clarity, only temperature profiles of Series B are discussed below. However, the results can
be transferred to Series A likewise.
The resulting temperature-time regime at the base plate is shown in Figure 3. Particular differences
in temperature distribution can be detected during the first 10 to 15 build-up layers. For intermediate
times of 120 s and 60 s, the graphs show a slight decrease in the average temperature due to heat
dissipation at the base plate and the welding table. During build-up with an intermediate time of 30 s,
no significant decrease in the base plate temperature could be observed. Further progression of the
temperature profiles shows an increase in base plate temperature, reaching a peak at approximately
half of the build-up height. During further build-up the base plate temperature decreases. The visible
discontinuities in the curves for intermediate times of 120 s and 30 s near the top layers are caused
by process interruptions. Due to their location outside of the tensile samples gauge length, the
interruptions have no major effect on further results.

102
Metals 2020, 10, 952

Figure 3. Temperature distribution on the baseplate by example of Series B specimen.

The resulting temperature profiles on the base plate can be explained by basic mechanisms of heat
flow. The heat flow in the thin-walled structure is described by terms of heat conduction, convection
and thermal radiation. Neglecting the heat flow by thermal radiation, the heat flow at the base plate
is mainly determined by heat conduction and convection. The heat conduction in the thin-walled
lled structure is given by (1) with thermal conductivity λ,
structure is given by (1) with thermal conductivity λ, the cross-section area A and the wall height h:

. 𝑑𝑇
dT
𝑄ℎ̇ Q
=h =
−𝜆−λ⋅ · 𝐴A ⋅· (1)
𝑑ℎ
dh
Further, the heat flow to the environment due to convection is given by (2) with the heat
coefficient η,
transfer coefficient η, the surface area of the wall S and the temperature difference between wall and
room temperature:
𝑄𝑐̇ =. 𝜂 ⋅ 𝑆 ⋅ (𝑇𝑊 − 𝑇0 )
Qc = η · S · (TW − T0 ) (2)

Relating to the periodically growing

𝑄. ℎ̇ wall structure, the wall height increases over time, leading to
a constant decrease of the heat flow Qh . By contrast, the heat flow due to convection increases over
time as the wall surface increases, leading to a higher heat transfer to the environment. In combination,
the temperature on the base plate decreases with increasing wall height, after reaching a maximum at
a build-up height of about 70 mm.
The following Figure 4 shows the development of interpass temperature for the examined
intermediate times between layers during additive manufacturing. The data indicates a correlation
between interpass and base plate temperature during the first 30 layers. Further build-up leads to
increasing interpass temperatures, reaching saturation depending on the intermediate time between the
layers. Thereby, the determined interpass temperature substantially exceeds the base plate temperature
for intermediate times of 60 s and 30 s.

Figure 4. Interpass temperature depending on number of layers and intermediate time between layers
by example of Series B specimen.

103
Metals 2020, 10, 952

The results on temperature distribution identify that the measuring point is of key importance
in order to describe the heat distribution and correlations between energy input and occurring
temperatures. Based on the examined thin-walled structure, a direct influence of the continuously
changing geometry during additive manufacturing on the temperature distribution within the
component could be shown.

3.2. Effects on Resulting Geometry

During additive manufacturing of complex components with high requirements on geometrical
and material accuracy, information about the effects of process parameters on the resulting geometry is
of primary importance. – Aiming to describe the influence of the underlying welding parameters at
different temperature–time regimes on the resulting geometry, the average layer height as well as the
wall width were determined at the final samples.
The material accumulation during WAAM is presented in Figure 5 by means of cross-section
micrographs taken from the center of the respective thin-walled structures. Overall, the micrographs show
a defined deposition pattern throughout the considered range of the building parameters. What stands
out is a periodical lateral shift of the layers at the Series A (ti = 30 s) sample. These shifts only show minor
influence on the overall waviness of the wall surface. By visual inspection,≤ a more even surface could
be obtained using an intermediate time between layers of ti ≤ 60 s resulting in interpass temperatures
Ti > 125 ◦ C. Further, a fine dispersed porosity could be detected in the Series A (ti = 120 s) sample.

Series A Series B

Figure 5. Cross-section micrographs of wire and arc additive manufacturing (WAAM) samples with
varying process strategies.

Previous findings reported in [27,28] have shown the influence of wire feed and welding speed on
the height and width of the resulting geometry. It was reported that the wall width increases at higher
wire-feed rates and decreases at higher welding speeds, whereas the wire feed shows a dominant
influence. Further, the layer height increases at higher wire feed and decreases at higher welding speed
with dominant influence of the welding speed.
Figure 6 compares the resulting layer height (Figure 6a) and the wall width (Figure 6b) as a
function of the intermediate time ti between each layer for both welding strategies considered. For both
welding strategies, the average layer height shows a steady increase with increasing waiting time
between layers. This indicates that higher interpass temperatures lead to a reduction in layer height.
On average, the layer height of Series A is about 0.15 mm higher compared to Series B, confirming the
dominant influence of the welding speed on the average layer height reported in [27]. Although the
difference in height is low in regard to single layers, the differences add up during build-up and may
cause process instability or errors. The wall width showed higher values for Series B specimen due
to the influence of a higher wire feed used compared to Series A specimen. Further, the wall width
was found to increase in the building direction, indicating an influence of the interpass temperature.

104
Metals 2020, 10, 952

Since the interpass temperatures increase in building direction (Section 3.1.), it can be concluded that
higher interpass temperatures lead to an increase in wall width. This also leads to comparatively high
deviations due to average determination on basis of ten measured values in building direction.

(a) (b)

Figure 6. Effect of building strategy on average layer height (a) and wall width (b).

The investigation of the resulting geometry indicated a different geometrical formation despite
similar energy input per length unit for the welding strategies considered and thus confirming a
different emphasis of the main welding parameters influence on geometrical formation during WAAM.
Accordingly, a verification of the geometry after any adaption of the process parameters is suggested.

3.3. Residual Stress and Mechanical Properties

The longitudinal residual stress was analyzed on samples of Series A in the as-welded condition
manufactured. Figure 7a shows the stress distribution determined on the top layer of the specimens.
The residual stress in welding direction varies along the measuring path from approximately −75 MPa
to +150 MPa. The individual scatter at discrete measuring locations from the sin2 -calculation is in− the
order of ±30 to ±50 MPa due to coarse microstructure. However, a clear influence of the intermediate
time between layers is not visible.

(a) (b)

Figure 7. Residual stress in welding (a) and building (b) direction (Series A).

Figure 7b depicts the residual stress distribution at the side of the specimens, measured from
top layer downwards. The abscissa indicates the distance of the measuring point from the top layer
with positive values directing to the base plate. In addition, shown here are the residual stresses in
the welding direction. The residual stress magnitudes are more homogeneous than on the top layer

105
Metals 2020, 10, 952

and the scatter is smaller. The residual stress ranges from approximately 0 MPa to +50 MPa at an
intermediate time of 120 s. A tendency of decreasing residual stress can be observed near the top layers
at an intermediate time of 30 s.
Overall, the residual stress in the investigated WAAM aluminum structure appears to be of low
magnitude. This can be explained by the heat conduction properties of the alloy in combination with
its low yield strength. This leads to homogeneous temperature distributions during relatively fast
cooling times. Further, the metal is relatively soft causing yielding of residual stress. These effects are
also known from conventional fusion welding of aluminum alloys.
The hardness test according to Vickers was conducted using cross-section samples from the
bottom, middle and top part from the thin-walled samples (see Figure 2). The hardness distributions
for different intermediate time between the layers in the as-build condition are given in Figure 8 by
example of Series B specimen. Hardness values ranged from 66 to 72 HV1 showing no significant
dependency on the build-up height and therefore stating independency of hardness values on
temperature distribution. This result can be explained by the fact that the investigated aluminum
Al-5356 is a non-heat treatable alloy.

Figure 8. Hardness distribution depending on build-up height and intermediate time between layers
by example of Series B.

Aiming to describe the tensile properties of additive manufactured Al-5356 depending on the
investigated process settings, yield strength (Rp0.2 ), tensile strength and elongation were determined
horizontally and vertically to the welding direction. The results on tensile properties can be compared
in Figure 9.

Figure 9. Tensile properties of WAAM processed Al-5356.

Depending on the welding parameters and test direction, the average values of yield strength reach
115–120 MPa, ultimate tensile strength 254–277 MPa and elongation 14–28%. Therefore, all batches
– – –
≥
106
≥ ≥
Metals 2020, 10, 952

achieved both strength and ductility properties of wrought material (EN AW-5019 (F): Rm ≥ 250 MPa;
Rp0,2 ≥ 110 MPa; A ≥ 14%). What stands out is that tensile strength and elongation were generally
found to be lower for batches in vertical direction compared to horizontal samples (see Figure 9).
Especially at long intermediate times between layers, i.e., lower interpass temperatures, the elongation
showed up to 40% lower values in vertical direction. The higher deviation in the values for vertical
specimens from Series B welded with ti = 30 s can be attributed to fracture locations near the end
of the gage length and therefore measurement of elongation could contain errors. The result of an
anisotropic material behavior may be explained by an inhomogeneous microstructure at the fusion
line boundaries, resulting in less favorable conditions for the vertical load direction. On basis of the
microscopic examination shown in Figure 10, three distinct areas of different metallurgical properties
in the layer structure could be determined. Near the fusion line boundary, regions with a fine grain
microstructure and comparatively high micro hardness are formed (Figure 10a). By contrast, regions
below the interlayer boundary are characterized by coarse grain microstructure with an increased
formation of segregations (Al8 Mg5 ) at the grain boundaries and lower hardness (Figure 10c). The grain
growth may be explained by the thermal influence of the following layer. An interlayer boundary
zone with a further increased occurrence of segregations can be identified (Figure 10b). In these
regions, primary stages and segregations merged at the grain boundaries as a result of comparatively
long heat exposure. Due to the difference in hardness, grain size and the formation of segregations,
these areas can act as metallurgical notches, thus affecting the mechanical properties in vertical loading
direction. The most consistent results regarding the anisotropic material behavior could be found for
Series B specimen with intermediate time between layers of 30 s. Although interpass temperature was
increasing during the built-up sequence, no distinct effect of sample allocation on the tensile properties
could be observed.

Figure 10. Microstructure and micro hardness of innerlayer fine grain (a), interlayer boundary (b) and
innerlayer coarse grain (c) regions for Series A specimen with ti = 120 s.

4. Conclusions
Within the underlying study, the effects of different temperature-time regimes during wire and
arc additive manufacturing of Al-5356 on both the geometrical and mechanical properties have
been systematically investigated. Linear thin-walled samples were built and analyzed with the
following conclusions:


107
Metals 2020, 10, 952

• Temperature profiles during WAAM processing indicated that the temperature distribution
is directly related to the geometry of the additive manufactured component. Due to a
continuously changing geometry, a non-steady temperature distribution during WAAM can
be assumed. However, steady geometrical build-up results can be expected by obtaining uniform
temperature fields.
• Although different process strategies, using the same energy input per length unit, lead to
comparable temperature distributions and cooling rates, they showed differences in the resulting
geometry of the component. An increase in wire feed and welding speed resulted in lower layer
height and increased wall width. Furthermore, higher interpass temperatures led to an increase in
wall width and lower layer height.
• Residual stresses in the top layer and on the surface of the wall specimen appeared of low
magnitude due to small temperature gradients combined with a comparably low yield strength of
the regarded material.
• Material properties were evenly distributed over the build-up geometry with values comparable
to AlMg5 wrought material. No significant dependency on the temperature-time regime during
processing could be detected. However, the mechanical properties, especially the elongation at
fracture, showed dependencies on the loading in relation to the build-up direction.

Author Contributions: Conceptualization, M.K. and J.H.; methodology, M.K. and J.H.; validation, J.H.; formal
analysis, M.K.; investigation, M.K.; resources, K.D.; data curation, J.H.; writing—original draft preparation, M.K.;
writing—review and editing, J.H.; visualization, M.K.; supervision, K.D.; project administration, J.H. and K.D.
All authors have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Acknowledgments: We acknowledge support by the German Research Foundation and the Open Access
Publication Funds of the Technische Universität Braunschweig.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Buchanan, C.; Gardner, L. Metal 3D printing in construction: A review of methods, research, applications,
opportunities and challenges. Eng. Struct. 2019, 180, 332–348. [CrossRef]
2. Frazier, W.E. Metal Additive Manufacturing: A Review. J. Mater. Eng. Perform. 2014, 23, 1917–1928.
[CrossRef]
3. Grunwald, R.; Mayer, M.; Schörghuber, M. WAAM-Technologie und aktuelle Anwendungen: DVS-Berichte
Congress 2018. DVS Media GmbH 2018, 344, 97–103.
4. Brandl, E.; Baufeld, B.; Leyens, C.; Gault, R. Additive manufactured Ti-6Al-4V using welding wire:
Comparison of laser and arc beam deposition and evaluation with respect to aerospace material specifications.
Phys. Procedia 2010, 5, 595–606. [CrossRef]
5. Busachi, A.; Erkoyuncu, J.; Colegrove, P.; Martina, F.; Watts, C.; Drake, R. A review of Additive Manufacturing
technology and Cost Estimation techniques for the defense sector. CIRP J. Manuf. Sci. Technol. 2017, 19,
117–128. [CrossRef]
6. Cunningham, C.; Wikshåland, S.; Xu, F.; Kemakolam, N.; Shokrani, A.; Dhokia, V.; Newman, S. Cost
Modelling and Sensitivity Analysis of Wire and Arc Additive Manufacturing. Procedia Manuf. 2017, 11,
650–657. [CrossRef]
7. Ding, D.; Pan, Z.; Cuiuri, D.; Li, H. Wire-feed additive manufacturing of metal components: Technologies,
developments and future interests. Int. J. Adv. Manuf. Technol. 2015, 81, 465–481. [CrossRef]
8. Thomas-Seale, L.E.J.; Kirkman-Brown, J.C.; Attallah, M.M.; Espino, D.M.; Shepherd, D.E.T. The barriers
to the progression of additive manufacture: Perspectives from UK industry. Int. J. Prod. Econ. 2018, 198,
104–118. [CrossRef]
9. Baufeld, B.; Widdison, R.; Dutilleul, T.; Bridger, K. Electron Beam Additive Manufacturing at the Nuclear
AMRC. Elektron. Elektrotech. 2016, 51, 25.

108
Metals 2020, 10, 952

10. Taminger, K.M.; Hafley, R.A. Electron Beam Freeform Fabrication for Cost Effective Near-Net Shape
Manufacturing. In Proceedings of the Meeting on Cost Effective Manufacture via Net Shape Processing,
Amsterdam, The Netherlands, 15–17 May 2006.
11. Liberini, M.; Astarita, A.; Campatelli, G.; Scippa, A.; Montevecchi, F.; Venturini, G.; Durante, M.; Boccarusso, L.;
Minutolo, F.M.C.; Squillace, A. Selection of Optimal Process Parameters for Wire Arc Additive Manufacturing.
Procedia CIRP 2017, 62, 470–474. [CrossRef]
12. Hoefer, K.; Haelsig, A.; Mayr, P. Arc-based additive manufacturing of steel components—Comparison of
wire-and powder-based variants. Weld World 2018, 62, 243–247. [CrossRef]
13. Reisgen, U.; Sharma, R.; Oster, L.; Zanders, E. Plasma-Mehrdraht-Schweißen zum Herstellen gradierter
Strukturen. In Proceedings of the DVS CONGRESS, Friedrichshafen, Germany, 17–18 September 2018;
DVS 344. pp. 109–114.
14. Fang, X.; Zhang, L.; Li, H.; Li, C.; Huang, K.; Lu, B. Microstructure Evolution and Mechanical Behavior of
2219 Aluminum Alloys Additively Fabricated by the Cold Metal Transfer Process. Materials 2018, 11, 812.
[CrossRef]
15. Kazanas, P.; Deherkar, P.; Almeida, P.; Lockett, H.; Williams, S. Fabrication of geometrical features using wire
and arc additive manufacture. Proceedings of the Institution of Mechanical Engineers. Part B J. Eng. Manuf.
2012, 226, 1042–1051. [CrossRef]
16. Venturini, G.; Montevecchi, F.; Scippa, A.; Campatelli, G. Optimization of WAAM Deposition Patterns for
T-crossing Features. Procedia CIRP 2016, 55, 95–100. [CrossRef]
17. Workowski, M.; Nitschke-Pagel, T.; Dilger, K. Load induced inhomogeneous plastic deformations in welded
aluminium joints. Weld. World 2014, 58, 529–538. [CrossRef]
18. Ge, J.; Lin, J.; Chen, Y.; Lei, Y.; Fu, H. Characterization of wire arc additive manufacturing 2Cr13 part: Process
stability, microstructural evolution, and tensile properties. J. Alloys Compd. 2018, 748, 911–921. [CrossRef]
19. Suryakumar, S.; Karunakaran, K.P.; Chandrasekhar, U.; Somashekara, M.A. A study of the mechanical
properties of objects built through weld-deposition. Proc. Inst. Mech. Eng. Part B J. Eng. Manuf. 2013,
227, 1138–1147. [CrossRef]
20. Henckell, P.; Günther, K.; Ali, Y.; Bergmann, J.P.; Scholz, J.; Forêt, P. The Influence of Gas Cooling in Context of
Wire Arc Additive Manufacturing—A Novel Strategy of Affecting Grain Structure and Size. In The Minerals,
Metals & Materials Series, TMS 2017 146th Annual Meeting & Exhibition Supplemental Proceedings; BSpringer
International Publishing: Cham, Switzerland, 2017; pp. 147–156.
21. Li, F.; Chen, S.; Shi, J.; Zhao, Y.; Tian, H. Thermoelectric Cooling-Aided Bead Geometry Regulation in Wire
and Arc-Based Additive Manufacturing of Thin-Walled Structures. Appl. Sci. 2018, 8, 207. [CrossRef]
22. Shi, J.; Li, F.; Chen, S.; Zhao, Y.; Tian, H. Effect of in-process active cooling on forming quality and efficiency of
tandem GMAW–based additive manufacturing. Int. J. Adv. Manuf. Technol. 2019, 101, 1349–1356. [CrossRef]
23. Gu, J.; Ding, J.; Williams, S.; Gu, H.; Ma, P.; Zhai, Y. The effect of inter-layer cold working and post-deposition
heat treatment on porosity in additively manufactured aluminium alloys. J. Mater. Process. Technol. 2016,
230, 26–34. [CrossRef]
24. Cong, B.; Ding, J.; Williams, S. Effect of arc mode in cold metal transfer process on porosity of additively
manufactured Al-6.3%Cu alloy. Int. J. Adv. Manuf. Technol. 2015, 76, 1593–1606. [CrossRef]
25. Fang, X.; Zhang, L.; Chen, G.; Dang, X.; Huang, K.; Wang, L.; Lu, B. Correlations between Microstructure
Characteristics and Mechanical Properties in 5183 Aluminium Alloy Fabricated by Wire-Arc Additive
Manufacturing with Different Arc Modes. Materials 2018, 11, 2075. [CrossRef] [PubMed]
26. Derekar, K.; Lawrence, J.; Melton, G.; Addison, A.; Zhang, X.; Xu, L. Influence of Interpass Temperature on
Wire Arc Additive Manufacturing (WAAM) of Aluminium Alloy Components. MATEC Web Conf. 2019,
269, 5001. [CrossRef]
27. Köhler, M.; Tóth, T.; Hensel, J.; Dilger, K. Prozesscharakteristiken bei der lichtbogenbasierten generativen
Fertigung metallischer Komponenten. DVS Ber. 39 Assist. Fügetechnik 2019, 356, 96–102.
28. Köhler, M.; Fiebig, S.; Hensel, J.; Dilger, K. Wire and Arc Additive Manufacturing of Aluminum Components.
Metals 2019, 9, 608. [CrossRef]

© 2020 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).

109
 metals
Article
Development of a High Strength Magnesium Alloy
for Wire Arc Additive Manufacturing
Stefan Gneiger 1 , Johannes A. Österreicher 1, * , Aurel R. Arnoldt 1 , Alois Birgmann 1 and
Martin Fehlbier 2
1 LKR Light Metals Technologies, Austrian Institute of Technology, A-5282 Ranshofen, Austria;
[email protected] (S.G.); [email protected] (A.R.A.); [email protected] (A.B.)
2 Chair of Foundry Technology, University of Kassel, Kurt-Wolters-Strasse 3, D-34109 Kassel, Germany;
[email protected]
* Correspondence: [email protected]; Tel.: +43-(0)664-825-1151




Received: 23 April 2020; Accepted: 8 June 2020; Published: 10 June 2020


Abstract: Due to their high specific strength, magnesium alloys are promising materials for further
lightweighting in mobility applications. In contrast to casting and forming processes, additive
manufacturing methods allow high degrees of geometrical freedom and can generate significant
weight reductions due to load-specific part design. In wire arc additive manufacturing processes,
large parts can be produced with high material utilization. Process-inherent high melt temperatures
and solidification rates allow for the use of magnesium alloys which are otherwise complicated to
process; this enables the use of unconventional alloying systems. Here, we report the development of
a Mg-Al-Zn-Ca-rare earth alloy for wire arc additive manufacturing (WAAM). Compared to parts
made of commercially available filler wire, the newly developed alloy achieves a higher strength
(approx. +9 MPa yield strength, +25 MPa ultimate tensile strength) in WAAM.

Keywords: wire arc additive manufacturing; WAAM; microstructure; magnesium; mechanical

properties; scanning electron microscopy; electron backscattered diffraction method

1. Introduction
Magnesium is the lightest construction metal available and used mainly in the form of cast
components. It can be processed in a wide variety of casting processes including gravity casting, low-
and high pressure die casting, and thixomolding [1]. Compared to casting, additive layer manufacturing
(ALM) allows for higher part complexity at the cost of reduced productivity. This enables further
potential for weight savings in part design [2,3]. For Mg, two directions of ALM processes have
been proven to be feasible: powder-based and wire-based methods. While powder-based additive
manufacturing of Mg is already in use to produce high quality parts for medical applications [4],
widespread use is prevented by the complex production process and slow building rates. Mg powder
tends to oxidize fast, so the use of a chamber with controlled gas shielding is mandatory, limiting the
maximum part size [5]. In selective laser melting (SLM), the vaporizing metal reduces the visibility in
the chamber and, therefore, the laser efficiency, which further reduces processability [6,7].
Very good mechanical properties can be achieved using Mg additive manufacturing processes.
Typically, SLM Mg parts show similar or even superior strength compared to cast and wrought parts
due to the small volume melt pools where rapid solidification rates and short segregation paths are
achieved [8,9].
Tandon et al. reported the mechanical values of direct energy deposited (DED) as well as powder
bed fusioned MAP + 43 alloy powders in the “HIPed” (hot isostatic pressed) and subsequently T6
treated condition [10]. For the DED material, they achieved a yield strength (YS) of 170 MPa, an ultimate

Metals 2020, 10, 778; doi:10.3390/met10060778 111 www.mdpi.com/journal/metals

Metals 2020, 10, 778

tensile strength (UTS) of 245 MPa, and an elongation of 6.4%. In contrast, the hot isostatic pressing
led to an essentially pore-free material, which showed superior strength and ductility in T6 condition:
194 MPa YS, 312 MPa UTS, and elongation of up to 14%.
Wire-based processes (e.g., wire arc additive manufacturing—WAAM) have the advantage of
easier and safer handling of filler metal compared to powder-based processes because commercial,
state-of-the-art wire arc welding equipment can be used. Due to the existence of a local gas shielding
provided by the welding gun, working inside a chamber is not necessary. Thus, there are practically
no limitations in part size. Mg wire arc additive manufacturing offers the ability to produce large
components with a high material efficiency without the need to handle powders or large quantities of
molten magnesium.
Despite their advantages, wire-based processes for magnesium are relatively uncommon to date,
not least due to insufficient filler wire availability. Only a limited number of filler wire grades are
known, namely AZ31B, AZ61A, AZ91D, EZ33A, AZ101A, QE22A, AM50A, and AZ92A [11–14] and not
all of them are commercially available at the moment. These grades are generally used as all-purpose
wires for magnesium welding, where the filler wire is selected to best fit the base material composition.
As these alloys are not specifically designed for welding or additive layer manufacturing purposes,
their performance is limited.
To date, the number of published results of Mg WAAM is very small. To the best of our knowledge,
no results for WAAM of Mg alloys were published yet using other than the before-mentioned standard
alloys. Guo et al. reported WAAM of AZ31 wires and achieved 104 MPa YS, 263 MPa UTS, and
elongation of 23% by adjusting the pulse frequency during processing [15]. Takagi et al. reported
in [16] the wire arc additive manufacturing of bulk samples using AZ31 wires and varying processing
conditions. They report a very low porosity of 2.5 × 10−4 % in the central part of the object with the
biggest defect being 7.74 × 10−4 mm3 . The mechanical properties achieved are 95 MPa YS, 239 MPa UTS,
and an elongation of 21% in the WAAM part, which is comparable to the values reported by Guo et al.
in [15]. Holguin et al. and Han et al. reported WAAM of AZ91 alloy, showed microstructures and
XRD-analysis but did not report mechanical properties [17,18]. Graf et al. used numerical approaches
for predicting temperature fields of WAAM processes using AZ31 filler wire [19].
Additive manufacturing of magnesium parts is especially promising for applications where
minimum weight and high specific strength are crucial, like aeronautics and space applications.
However, magnesium parts must possess good flame resistance to achieve a certification. Tests carried
out by the Federal Aviation Administration (FAA) showed that typical Mg-Al alloys are not able to
fulfill these requirements while alloys including high amounts of rare earth elements (e.g., WE43 using
around 4 wt.% of Y and 3 wt.% of rare earths or Elektron 21 using around 2.6 wt.% Nd and 1.3 wt.%
Gd) [20,21] or minor amounts of Ca (AZ80 + 0.3 wt.% Ca and 0.35 wt.% Y) [22] are able to successfully
pass the tests. We have previously shown that Mg-Al-Zn alloys using Ca as flame retardant can be
used for welding magnesium sheets [23].
High specific strength values can be achieved using the WAAM process, as the fast solidification
speeds lead to solid solution strengthening which also allows for subsequent precipitation hardening.
Therefore, Mg alloys with high Al contents and additional strengthening phase forming elements are
suitable candidates for generating high strength WAAM parts. A promising strategy is the addition
of rare earth elements which have been shown to increase the strength of Mg-Al alloys due to the
formation of intermetallic phases of the type Mg12 RE, Al2 RE, Al3 RE and Al11 RE3 [24,25]. This approach
was followed in this study.
The novel alloy reported here—AEX11—is based on the casting alloys AZ91 (Mg-Al9-Zn1) and
AZ61A (Mg-Al6-Zn1). Compared to these alloys, it has an increased Al content as well as minor
additions of Ca and rare earth elements (Ce-rich mischmetal). The Al-content was chosen based on
CALPHAD-calculations to match the amount of Mg17 Al12 compared to AZ91 after the formation
of Al-RE- and Al-Ca-phases (Figure 5). This allows the use heat treatment times and temperatures
analogous to the ones used for AZ91. Ca was chosen to increase the flame resistance of the alloy

112
Metals 2020, 10, 778

and rare earth elements to increase the strength. Cerium-rich mischmetal (65 wt.% Ce, 35 wt.% La)
was used due to its low price compared to single rare earth elements. Mechanical properties were
evaluated from thin walled structures made from AZ61A and from plates (walls) made from AEX11,
both produced via WAAM.

2. Materials and Methods

We produced AEX11 wire via casting and subsequent direct extrusion at LKR in Ranshofen,
Austria, as described below. The nominal chemical compositions are given in Table 1 along with the
compositions of AZ61A and AZ91D for comparison.

Table 1. Nominal compositions of the alloys AZ61A (acc. to ASTM B107), AZ91D (acc. to ASTM B94),
and AEX11.

Alloy Al (wt.%) Zn (wt.%) Ce-Mischmetal (wt.%) Ca (wt.%) Mn (wt.%) Mg (wt.%)

AZ61A 5.8–7.2 0.40–1.5 - - 0.15–0.5 Rem.
AZ91D 8.5–9.5 0.45–0.9 - - ≥0.17 Rem.
AEX11 10.1–11.5 0.3–0.6 2.5–3.5 0.2–0.44 0.15–0.5 Rem.

AEX11 was prepared in a resistance heated furnace Nabertherm Liquitherm® (Nabertherm GmbH,
Lilienthal, Germany) T20/H in a mild steel crucible with a melt capacity of 30 kg. The melt was covered
with Ar + 1% SF6 shielding gas during preparation and casting. Casting temperature
≥ was 720 ◦ C.
The alloy was gravity cast into billets with a diameter of 65 mm and a height of 240 mm in
a tempered (150 ◦ C) mild steel mold. The billets were turned to a diameter of 58.5 mm and a length
of 180 mm and homogenized at 420 ◦ C for 8 h with subsequent cooling using forced air resulting in
a cooling rate of approximately 25 K/min. Afterwards, the billets were extruded in two single steps to
the desired filler wire diameter (Φ58.5 mm → Φ19.5 mm → Φ1.2 mm) using a 1.5 MN direct extrusion
press NEHP 1500.01 manufactured by Φ Müller Engineering,
→ Φ Todtenweis,
→ Φ Germany. A more detailed
explanation of the wire manufacturing process can be found elsewhere [17].
Directly before welding, the wires were cleaned using isopropanol and a fiber mat. Wire arc
additive manufacturing of AEX11 was carried out using the gas-metal arc-welding cold metal transfer
(CMT) process (Fronius, Pettenbach, Austria). The power source was a Fronius CMT TPS with the
following parameters: welding curve KL 1904, weld speed 12 mm/s, wire feed rate 3.5 m/min (base
layer) and 2.2 m/min (building layers), current 51 A, pulse frequency 80–120 Hz, layer thickness 2.5 mm
each, and a wall thickness of 5 mm. The distance between workpiece and tip was 13 mm. Ar with
30% He was used as shielding gas. The nozzle diameter was 14 mm and the gas flow was 14 L/min.
Figure 1 shows the AM welding facility at LKR.

Figure 1. Additive manufacturing lab at LKR, Ranshofen.

113
Metals 2020, 10, 778

Thin-walled structures with a height of 80 mm, a length of 130 mm and a width of 30 mm were
manufactured continuously from AZ61 wires on a AZ31 base plate (Mg-3.0Al-0.6Zn). Walls with
dimensions of 140 mm × 120 mm × 5 mm were manufactured discontinuously (layer for layer) using
AEX11 wires for microstructural and mechanical investigations. In the plates, the welding direction
was alternating and changed every single layer. The walls of AEX11 manufactured via WAAM are
intended to represent a section of the structures manufactured out of AZ61A. The AZ61 samples were
obtained from AZ61A filler wires sourced from DRATEC Drahttechnik GmbH, Krefeld, Germany. The
resulting structures can be seen in Figure 2.

(a) (b)

Figure 2. Additive manufactured plate (a) out of AEX11 with schematic representation of sample
extraction. The red area indicates the position of samples for microstructural and EBSD analysis.
Additive manufactured sample structure out of AZ61A (b). The power source was a Fronius CMT
TPS with the following parameters: weld speed 12 mm/s, wire feed rate 3.5 m/min (base layer) and
2.2 m/min (building layers), current 51 A, layer thickness 2.5 mm each, and a wall thickness of 5 mm.

After milling off the wavy surface, tensile test specimens were taken out of the WAAM parts
in welding direction (WD) and transversal direction (TD). The positions of specimen extraction are
shown schematically in Figure 3 (all dimensions in mm), and the geometry of the specimens is shown
in Figure 4. In the as fabricated state, five samples per direction were taken and, in the T6 condition,
four samples per direction were taken. Only one sample per direction was taken for analyzing the
solution heat treatment state. Tensile tests were carried out at room temperature using a DIL 805 A/D
deformation dilatometer (Bähr Thermoanalyse GmbH, Hüllhorst, Germany) at a deformation rate of
0.006 s−1
− .

For solution heat treatment, some of the tensile specimens were placed in a preheated furnace
(415 ◦ C) for 6 h and then heated up to 430 ◦ C with holding for another 6 h, followed by water quenching.
Afterwards, the solution heat treated samples were placed in a preheated furnace (260 ◦ C) for 30 min
with subsequent water quenching.
Thermodynamic calculations were done using Thermo-Calc software (Version 2017a) and database
TCMG5 (both Thermo-Calc Software AB, Solna, Sweden).
The samples for microstructural investigations were extracted from the WAAM parts (Figure 3)
perpendicular to all three directions (WD welding direction, ND normal direction and TD transversal
direction) from at least 30 mm distance to the base plate. The samples were mechanically polished to 14
µm and then finished using colloidal silica suspension. Additionally, selected samples were etched
using picric acid to visualize the grain boundaries and allows for investigating the grain structure.

114
Metals 2020, 10, 778

(a) (b)

Figure 3. Schematic position of specimen extraction for AZ61A (a) and AEX11 (b). Specimens were
extracted in welding direction (WD) and transversal direction (TD). The walls of AEX11 manufactured
via WAAM represent a section of the structures manufactured out of AZ61A.

Figure 4. Dimensions of tensile test specimen.

Microstructural investigations in all directions were carried out using optical light microscopy
and scanning electron microscopy (SEM). A Tescan MIRA3 field emission gun (FEG) scanning electron
microscope (Brno, Czech Republic) operated at 15 kV and a 4-quadrant solid-state backscattered
electron (BSE) detector were used for imaging and energy dispersive X-ray spectroscopy (EDS) with
an EDAX (Mahwah, NJ, USA) Octane Elect silicon drift detector system. Electron backscattered
diffraction (EBSD) was performed at 20 kV and a working distance of ~7 mm on a Zeiss Sigma 500 VP
FEG scanning electron microscope (AZ61A) (Carl Zeiss AG, Oberkochen, Germany) and at ~15 mm
working distance on the aforementioned Tescan Mira 3 (AEX11). On both microscopes, an EDAX
Hikari Plus EBSD camera (AMETEK, Berwyn, PA, USA) was used. EBSD data analysis was carried
out with EDAX OIM 8 (AMETEK, Berwyn, PA, USA). The samples were taken about 30 mm away
from the base plate. For cleanup, we used of grain dilatation with a grain tolerance angle of 5◦ and
a minimum grain size of 2 px (AZ61A) or 20 px (AEX11). For grain size analysis, a misorientation
angle of 15◦ was used to determine grain boundaries.

3. Results and Discussion

Figure 5 shows the results of the equilibrium thermodynamic calculations carried out for AZ61A,
AZ91D, and AEX11 alloys. According to the calculations, the amount of the intermetallic phase
Mg17 Al12 is predicted to be significantly higher in the alloy AEX11 than in AZ61A, whilst, for AZ91D,
it is approximately equal as in AEX11. Additionally, the alloy AEX11 shows small amounts of

115
Metals 2020, 10, 778

intermetallic phases Al11 RE3 and Al2 Ca. While the Mg17 Al12 in the divorced eutectic can be completely
dissolved into the matrix by solution heat treatment, the Al-RE and Al2 Ca phases cannot.

(a) (b)

(c) (d)

Figure 5. Equilibrium thermodynamic calculations of AZ61A (a), AZ91D (b) and AEX11 (c,d).
(d) represents a section of (c).

As the manganese content is about equal in all three alloys, the resulting Alx Mny phases are
almost identical with regard to their stoichiometry depending on the relative Al and Mn amounts
present. The calculated total amount of intermetallic phases is highest for AEX11 because it contains
the highest amount of alloying elements. The calculated solidification ranges are 116 ◦ C for AZ61A,
124 ◦ C for AEX11, and 136 ◦ C for AZ91D.
Figure 6 shows SEM of the microstructure of AEX11 fabricated via WAAM in the “as fabricated”
and the “T6 heat treated” states as well as the microstructure of AZ61A in the “as fabricated” state.
EDS measurements identify the present intermetallic phases as Al-RE, Al-Ca, and Mg/Al-rich phases.
With reference to the thermodynamic calculations and literature [24,26,27], these are presumed to be
Al11 RE3 , Al2 Ca, and β-Mg17 Al12 . By indexing of EBSD patterns, the Al-RE phases were identified
with high confidence as orthorhombic Al11 RE3 phase with large d-spacings (a = 4.4 Å, b = 10.1 Å,
c = 13.0 Å).

116
Metals 2020, 10, 778

Figure 6. Microstructure of parts manufactured via WAAM. (a) AEX11 “as fabricated” state; (b) AEX11
after T6 heat treatment; (c) AZ61A “as fabricated”; (backscattered SEM).

Due to the higher cooling rates of WAAM compared to classical casting processes (with the
exception of high pressure die casting), typical grain sizes and phase fractions of coarsely precipitated
(divorced) Mg17 Al12 are lower, resulting in generally higher mechanical properties [28–30]. The
Al11 RE3 intermetallic phases found in the AEX11 are relatively large and needle-like; therefore, their
contribution to strengthening is not clear. In [31], it is stated that the addition of RE increases the
strength of Mg-Al. Nevertheless, it is also shown that, with an increasing amount of RE, the size
of Al-RE phases increases, leading to a decrease of mechanical properties. Additionally, a positive
contribution to creep resistance is expected due to the high thermal stability of the phases [32,33].
Figure 6b shows that the T6 heat treatment resulted in spheroidization of Mg17 Al12 phases, while
no change can be detected in the Al-RE phases. This is also consistent with the thermodynamic
calculation (Figure 5c,d), which shows that the phase dissolution temperature of Al-RE is significantly
higher than the heat treatment temperature, while the Mg17 Al12 is dissolved and precipitated in the T6
heat treatment.
While in wrought material the grains are deformed and often partially recrystallized, WAAM
material typically possesses columnar grains in the welding direction and a low grain size compared to
conventional casting methods resulting from the low amount of molten volume and high solidification
rates. The resulting grain structure is mainly dependent on the component geometry and the energy
input during processing, which is dependent on the wire feed, the wire thickness, power settings,
and polarity. Additionally, the grain sizes are strongly dependent on the cooling rate. Therefore, the
grain size can be minimized using optimized processing parameters [34]. Guo et al. [15] have achieved
grain sizes of 20–39 µm while the AZ61A shown in this work has a grain size of 31 ± 12 µm and the
grain size of AEX11 is roughly 55 ± 19 µm. The grain size was determined via EBSD (Figure 7). No
formation of columnar grains was observed and the grains were formed approximately equiaxially.

117
Metals 2020, 10, 778

Figure 7. Detail of inverse pole figure [001] map of (a) AZ61A and (b) AEX11; (cross section in welding
direction; TD: transversal direction; ND: normal direction).

Figure 8 gives a comparison of the microstructure of AEX11 (Figure 8a,b) and AZ61A (Figure 8c,d)
in the “as fabricated” state, manufactured via WAAM. In agreement with SEM, potential Al-Mn
(dark grey) and Mg17 Al12 (light grey) can be found. In AZ61A, potential Al-Mn is the dominating
phase while potential Mg17 Al12 is only visible in very small quantities, coming from the high cooling
speed during processing. Al has a high solubility limit in Mg and the formation of Mg17 Al12 can be
suppressed when the solidification speed is fast enough. This is in agreement with the thermodynamic
calculations which show that the phase is only stable at temperatures below 300 ◦ C for AZ61A and
350 ◦ C for AEX11. Due to the higher amount of Al in AEX11, the amount of already precipitated
potential Mg17 Al12 is substantially higher. Additionally, needle shaped Al-RE phases are present
in AEX11. According to the thermodynamic calculations, their temperature of formation is above
the solidus temperature. Thus, achieving a complete solution of these phases via heat treatment is
not possible.
A number of small defects (pores, cavities) were found in the samples. The pores have a size of
<20 µm and are distributed evenly across the cross section of the samples. It is believed that the pores
are mainly a result of impurities in the filler wires and defects in the surface region of underlying
layers [35]. As the process was carried out only using local gas shielding instead of a gas chamber,
insufficient shielding might have led to porosity [36]. The cavities occur preferably in transitions
between layers (Figure 9). Possibly, a reduction of porosity could be achieved by further adaptions of
processing parameters and proper preparation (cleaning) of base material and filler wires in future
research. A better indication of the quantity and size of the voids to take targeted measures could be
provided by a non-destructive in-line analysis method such as that presented by Javadi et al. [37].
Tensile test results of WAAM magnesium parts are given in Figure 10 and Table 2. In the “as
fabricated” state, AEX11 has an elongation at break of around 6% while AZ61A achieved values of
around 16%. The amount of Mg17 Al12 in AEX11 is about equal to the amount of what one would
expect to find in AZ91D; therefore, a T6 heat treatment can be performed with approximately the
same efficiency. A relatively high annealing temperature was chosen to keep the treatment time low.
Nevertheless, reducing this temperature may lead to even higher strength at the cost of increased
treatment time.

118
Metals 2020, 10, 778

(a) (b)

(c) (d)

Figure 8. Microstructures of AEX11 (a,b) and AZ61A (c,d) in the “as fabricated” state, manufactured
via WAAM.

Figure 9. Cross section of AEX11 sample manufactured via WAAM. Voids occur in the transitions
between single layers.

119
 −

− −

Metals 2020, 10, 778

Figure 10. Typical tensile test results of additive manufactured structures out of AZ61 and AEX11
filler wires.

Table 2. Mechanical properties (tensile) of AZ61A and AEX11 in detail.

Alloy State Direction UTS (MPa) SD (MPa) Elongation (%) SD (%)

WD 275 1.0 16.8 0.4
AZ61A as fabricated
TD 272 4.5 17.2 1.3
WD 243 17.3 4.5 2.3
as fabricated
TD 233 12.3 5.2 0.7
AEX11
WD 299 8.0 12.6 1.5
T6
TD 298 6.3 11.0 0.8

After dissolution of Mg17 Al12 , high elongation was achieved while at the same time the strength
was decreased. Annealing at 260 ◦ C was carried out to exploit the precipitation strengthening effect
of Mg17 Al12 . We achieved a maximum UTS of 307 MPa at an elongation of 14% using the alloy
AEX11, designed specifically for WAAM processing in the T6 state. With a density of ~1.84 g/cm3 , this
results in a specific strength of ~166.8 Nms−1 , which is comparable to the aluminum alloy Al-2024-T6
(171.5 Nms−1 ) but inferior to Al-7075-T6 forgings (196.4 Nms−1 ) [38]. The UTS is 15% higher than that
of parts made from our reference material, commercial AZ61A wires in the as fabricated state, using
classical welding parameters without frequency modulation. The strength of the baseline material is
comparable to previous reports [15].
The elongation of the AEX11 samples increased after every single heat treatment step. This can
be attributed to the spheroidization of brittle phases (mainly Mg17 Al12 ). In AZ61A, the amount of
precipitated β-Mg17 Al12 is inherently lower, leading to a good deformability already in the as fabricated
state. It is known that β-Mg17 Al12 has a detrimental effect on the ductility of Mg-Al alloys [11,39]. In
the WAAM AZ61A samples, a large proportion of Al was found to be already in solid solution due
to the rapid solidification as only a small amount of Al-rich phases was found in the microstructural
analysis. Additionally, according to [40,41], hardness increase by heat treatment is not very effective
for AZ61A. Therefore, no further heat treatment was applied.
The mechanical properties of the WAAM manufactured parts shown in this work can be compared
to the ones achieved in wrought processes such as forging [42] and extrusion [43]. Forged AZ61 parts
reach an ultimate tensile strength of 295 MPa and an elongation of 12% [44], while, for extruded AZ61,
UTS values of 310 MPa at elongations of 16% are stated [45].
Figure 11 shows the fracture surface of a tensile test specimen of AEX11 in the as fabricated
state. The matrix deforms around the intermetallic phases before detaching. All samples showed

120
Metals 2020, 10, 778

ductile fracture behavior because no continuous network of intermetallic phases is formed on the grain
boundaries, which could act as crack propagation sites.

Figure 11. Fracture surface of AEX11 tensile test specimen in the as fabricated state (secondary electron
SEM). Al-RE phase indicated with an arrow.

4. Conclusions
WAAM is a suitable production process for low quantity Mg parts and prototypes. Especially for
large dimensional parts, this processing route can be faster and easier to implement than traditional
routes like milling and casting.
In this research, we showed that commercial AZ61 filler wire as well as custom made wire from
AEX11 can be used for the fabrication of WAAM parts. We demonstrated that new alloys with a high
proportion of soluble elements can be used to take advantage of the high cooling rate of the process
and, thus, achieve superior mechanical properties.
While WAAM can be used to produce components with attractive properties, there are still some
challenges along the process chain to be solved. For wire manufacturing, impurities must be reduced
to a minimum as these may lead to porosity in the parts. For WAAM itself, temperature control and
optimization of the welding path are essential to avoid warpage.

Author Contributions: This paper is the work of several authors, the individual contributions are subsequently
listed: conceptualization, S.G., J.A.Ö., and M.F.; methodology, S.G. and J.A.Ö.; software, S.G.; validation, J.A.Ö.;
formal analysis, J.A.Ö. and M.F.; investigation, S.G., J.A.Ö., A.R.A., and A.B.; data curation, S.G.; writing—original
draft preparation, S.G. and J.A.Ö.; writing—review and editing, S.G., J.A.Ö., A.R.A., A.B., and M.F.; visualization,
S.G.; supervision, J.A.Ö. and M.F.; project administration, S.G. All authors have read and agreed to the published
version of the manuscript.
Funding: This research was funded by the European Regional Development Fund (EFRE) in the framework of
the EU-program “IWB Investition in Wachstum und Beschäftigung Österreich 2014–2020” and the federal state
Upper Austria.
Acknowledgments: The authors thank Martin Schnall for his efforts in the search for suitable processing parameters
and his support in the production of AM structures, Iris Baumgartner for the preparation of metallographic
samples, and René de Kloe (EDAX/AMETEK) for providing crystallographic files for Al11 RE3 .
Conflicts of Interest: The authors declare no conflict of interest. The founding sponsors had no role in the design
of the study; in the collection, analyzes, or interpretation of data; in the writing of the manuscript, or in the
decision to publish the results.

References
1. Mordike, B.L.; Ebert, T. Magnesium: Properties—Applications—Potential. Mater. Sci. Eng. A 2001, 302,
37–45. [CrossRef]

121
Metals 2020, 10, 778

2. Emmelmann, C.; Sander, P.; Kranz, J.; Wycisk, E. Laser Additive Manufacturing and Bionics: Redefining
Lightweight Design. Phys. Procedia 2011, 12, 364–368. [CrossRef]
3. Herzog, D.; Seyda, V.; Wycisk, E.; Emmelmann, C. Additive manufacturing of metals. Acta Mater. 2016, 117,
371–392. [CrossRef]
4. Windhagen, H.; Radtke, K.; Weizbauer, A.; Diekmann, J.; Noll, Y.; Kreimeyer, U.; Schavan, R.;
Stukenborg-Colsman, C.; Waizy, H. Biodegradable magnesium-based screw clinically equivalent to titanium
screw in hallux valgus surgery: Short term results of the first prospective, randomized, controlled clinical
pilot study. Biomed. Eng. OnLine 2013, 12, 62. [CrossRef]
5. Gieseke, M.; Kiesow, T.; Noelke, C.; Kaierle, S.; Maier, H.J.; Matena, J.; Kampmann, A.; Nolte, I.; Gellrich, N.-C.;
Haferkamp, H. Challenges of Processing Magnesium and Magnesium Alloys by Selective Laser Melting.
In Proceedings of the World PM 2016 Congress and Exhibition. European Powder Metallurgy Association
(EPMA), Hamburg, Germany, 9–13 October 2016.
6. Jauer, L.; Meiners, W.; Vervoort, S.; Gayer, C.; Zumdick, N.A.; Zander, D. Selective Laser Melting of
Magnesium Alloys. In Proceedings of the World Powder Metallurgy Conference 2016, Hamburg, Germany,
9–13 October 2016.
7. Gieseke, M.; Noelke, C.; Kaierle, S.; Wesling, V.; Haferkamp, H. Selective Laser Melting of Magnesium
and Magnesium Alloys. In Magnesium Technology 2013; Hort, N., Mathaudhu, S.N., Neelameggham, N.R.,
Alderman, M., Eds.; Springer International Publishing: Berlin/Heidelberg, Germany, 2016; pp. 65–68.
ISBN 978-3-319-48150-0.
8. Manakari, V.; Parande, G.; Gupta, M. Selective Laser Melting of Magnesium and Magnesium Alloy Powders:
A Review. Metals 2017, 7, 2. [CrossRef]
9. Frazier, W.E. Metal Additive Manufacturing: A Review. J. Mater. Eng. Perform. 2014, 23, 1917–1928.
[CrossRef]
10. Tandon, R.; Palmer, T.; Gieseke, M.; Noelke, C.; Kaierle, S. Additive manufacturing of magnesium alloy
powders: Investigations into process development using elektron® MAP+43 via laser powder bed fusion
and directed energy deposition. In Proceedings of the World PM 2016 Congress and Exhibition; European
Powder Metallurgy Association (EPMA), Hamburg, Germany, 9–13 October 2016.
11. Avedesian, M.M.; Baker, H. ASM Specialty Handbook: Magnesium and Magnesium Alloys; ASM International:
Russel Township, OH, USA, 1999; ISBN 978-0-87170-657-7.
12. Products–Mag Specialties. Available online: https://www.magspecialtiesinc.com/products/ (accessed on
10 July 2019).
13. Magnesium Alloys|Products|Washington Alloy Company. Available online: https://weldingwire.com/
products/Magnesium-Alloys (accessed on 10 July 2019).
14. Magnesium-DRATEC. Available online: http://www.dratec.de/magnesium.html (accessed on 10 July 2019).
15. Guo, J.; Zhou, Y.; Liu, C.; Wu, Q.; Chen, X.; Lu, J. Wire Arc Additive Manufacturing of AZ31 Magnesium
Alloy: Grain Refinement by Adjusting Pulse Frequency. Materials 2016, 9, 823. [CrossRef]
16. Takagi, H.; Sasahara, H.; Abe, T.; Sannomiya, H.; Nishiyama, S.; Ohta, S.; Nakamura, K. Material-property
evaluation of magnesium alloys fabricated using wire-and-arc-based additive manufacturing. Addit. Manuf.
2018, 24, 498–507. [CrossRef]
17. Han, S.; Zielewski, M.; Martinez Holguin, D.; Michel Parra, M.; Kim, N. Optimization of AZ91D Process and
Corrosion Resistance Using Wire Arc Additive Manufacturing. Appl. Sci. 2018, 8, 1306. [CrossRef]
18. Holguin, D.A.M.; Han, S.; Kim, N.P. Magnesium Alloy 3D Printing by Wire and Arc Additive Manufacturing
(WAAM). MRS Adv. 2018, 3, 2959–2964. [CrossRef]
19. Graf, M.; Hälsig, A.; Höfer, K.; Awiszus, B.; Mayr, P. Thermo-Mechanical Modelling of Wire-Arc Additive
Manufacturing (WAAM) of Semi-Finished Products. Metals 2018, 8, 1009. [CrossRef]
20. Marker, T. Evaluating the Flammability of Various Magnesium Alloys During Laboratory- and Full-Scale Aircraft
Fire Test; US Department of Transportation, Federal Aviation Administration: Atlantic City, NJ, USA, 2013.
21. Marker, T.R. Development of a Laboratory-Scale Flammability Test for Magnesium Alloys Used in Aircraft Seat
Construction; Federal Aviation Administration: Washington, DC, USA, 2014.
22. Gneiger, S.; Frank, S.; Betz, A. Untersuchung des Elementeinflusses von Ca und Y auf Magnesiumlegierungen.
In Proceedings of the 9th Ranshofener Leichtmetalltage, Bad Ischl, Austria, 9–10 November 2016.

122
Metals 2020, 10, 778

23. Gneiger, S.; Gradinger, R.; Betz, A. Manufacturing route for producing tailor-made magnesium wires
for welding and ALM purposes. In Proceedings of the 2017 World Magnesium Conference, Singapore,
21–23 May 2017.
24. Bakke, P.; Westengen, H. The Role of Rare Earth Elements in Structure and Property Control of Magnesium
Die Casting Alloys. In Essential Readings in Magnesium Technology; Springer: Berlin/Heidelberg, Germany,
2016; pp. 313–318. ISBN 978-3-319-48588-1.
25. Rokhlin, L.L. Magnesium Alloys Containing Rare Earth Metals: Structure and Properties; CRC Press: Boca Raton,
FL, USA, 2003; ISBN 978-0-429-17922-8.
26. Li, P.; Tang, B.; Kandalova, E.G. Microstructure and properties of AZ91D alloy with Ca additions. Mater. Lett.
2005, 59, 671–675. [CrossRef]
27. Nami, B.; Shabestari, S.G.; Razavi, H.; Mirdamadi, S.; Miresmaeili, S.M. Effect of Ca, RE elements and
semi-solid processing on the microstructure and creep properties of AZ91 alloy. Mater. Sci. Eng. A 2011, 528,
1261–1267. [CrossRef]
28. Dini, H.; Andersson, N.-E.; Jarfors, A. Effect of Mg17Al12 Fraction on Mechanical Properties of Mg-9%Al-1%Zn
Cast Alloy. Metals 2016, 6, 251. [CrossRef]
29. Cai, H.; Guo, F.; Su, J. Combined effects of cerium and cooling rate on microstructure and mechanical
properties of AZ91 magnesium alloy. Mater. Res. Express 2018, 5, 016503. [CrossRef]
30. Zhu, T.; Chen, Z.W.; Gao, W. Effect of cooling conditions during casting on fraction of β-Mg17Al12 in
Mg–9Al–1Zn cast alloy. J. Alloys Compd. 2010, 501, 291–296. [CrossRef]
31. Cui, X.; Liu, H.; Meng, J.; Zhang, D. Microstructure and mechanical properties of die-cast AZ91D magnesium
alloy by Pr additions. Trans. Nonferrous Met. Soc. China 2010, 20, s435–s438. [CrossRef]
32. Easton, M.; Zhu, S.; Gibson, M.; Abbott, T.; Ang, H.Q.; Chen, X.; Birbilis, N.; Savage, G. Performance
Evaluation of High-Pressure Die-Cast Magnesium Alloys. In Magnesium Technology 2017; Solanki, K.N.,
Orlov, D., Singh, A., Neelameggham, N.R., Eds.; Springer International Publishing: Berlin/Heidelberg,
Germany, 2017; pp. 123–129. ISBN 978-3-319-52391-0.
33. Zhu, S.; Easton, M.A.; Abbott, T.B.; Nie, J.-F.; Dargusch, M.S.; Hort, N.; Gibson, M.A. Evaluation of Magnesium
Die-Casting Alloys for Elevated Temperature Applications: Microstructure, Tensile Properties, and Creep
Resistance. Metall. Mater. Trans. A 2015, 46, 3543–3554. [CrossRef]
34. Klein, T.; Schnall, M. Control of macro-/microstructure and mechanical properties of a wire-arc additive
manufactured aluminum alloy. Int. J. Adv. Manuf. Technol. 2020. [CrossRef]
35. Monteiro, W.A. New Features on Magnesium Alloys; InTech: Rijeka, Croatia, 2012; ISBN 978-953-51-0668-5.
36. Liu, L.; Song, G.; Liang, G.; Wang, J. Pore formation during hybrid laser-tungsten inert gas arc welding of
magnesium alloy AZ31B—Mechanism and remedy. Mater. Sci. Eng. A 2005, 390, 76–80. [CrossRef]
37. Javadi, Y.; MacLeod, C.N.; Pierce, S.G.; Gachagan, A.; Lines, D.; Mineo, C.; Ding, J.; Williams, S.; Vasilev, M.;
Mohseni, E.; et al. Ultrasonic phased array inspection of a Wire + Arc Additive Manufactured (WAAM)
sample with intentionally embedded defects. Addit. Manuf. 2019, 29, 100806. [CrossRef]
38. Kaufman, J.G. Properties of Aluminum Alloys: Tensile, Creep, and Fatigue Data at High and Low Temperatures;
ASM International: Russel Township, OH, USA, 1999; ISBN 978-0-87170-632-4.
39. Kammer, C. Magnesium-Taschenbuch; Aluminium-Verlag: Düsseldorf, Germany, 2000; ISBN 978-3-87017-264-0.
40. Jo, S.M.; Go, Y.; You, B.S.; Kim, Y.M. Precipitation Behavior of Mg–Al–Sn–Zn–(Na) Alloy. In Magnesium
Technology 2017; Solanki, K.N., Orlov, D., Singh, A., Neelameggham, N.R., Eds.; Springer International
Publishing: Berlin/Heidelberg, Germany, 2017; pp. 203–207.
41. Manivannan, S.; Gopalakrishnan, S.K.; Saravana Murthy, L.N.; Babu, K.; Sundarrajan, S. Microstructure
and Mechanical Properties of Cast Mg-6Al- 1Zn-xRE Alloy with Additions of Yttrium at Different Ageing
Temperature. Eur. J. Sci. Res. 2014, 122, 381–391.
42. Papenberg, N.P.; Gneiger, S.; Weißensteiner, I.; Uggowitzer, P.J.; Pogatscher, S. Mg-Alloys for Forging
Applications—A Review. Materials 2020, 13, 985. [CrossRef] [PubMed]
43. Gneiger, S.; Papenberg, N.; Frank, S.; Gradinger, R. Investigations on Microstructure and Mechanical
Properties of Non-flammable Mg–Al–Zn–Ca–Y Alloys. In Proceedings of the Magnesium Technology
2018; Orlov, D., Joshi, V., Solanki, K.N., Neelameggham, N.R., Eds.; Springer International Publishing:
Berlin/Heidelberg, Germany, 2018; pp. 105–113.

123
Metals 2020, 10, 778

44. ASM Handbook Volume 2: Properties and Selection: Nonferrous Alloys and Special-Purpose Materials-ASM
International. Available online: https://www.asminternational.org/materials-resources/results/-/journal_
content/56/10192/06182G/PUBLICATION (accessed on 24 September 2019).
45. Zeng, Z.; Stanford, N.; Davies, C.H.J.; Nie, J.-F.; Birbilis, N. Magnesium extrusion alloys: A review of
developments and prospects. Int. Mater. Rev. 2019, 64, 27–62. [CrossRef]

© 2020 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).

124
 metals
Article
Thermal Frequency Drift of 3D Printed Microwave
Components
Gregory Peter Le Sage
U.S. Government, Washington, DC 20001, USA; [email protected]




Received: 14 March 2020; Accepted: 26 April 2020; Published: 29 April 2020


Abstract: Fabrication of microwave slot array antennas and waveguide bandpass and notch filters
using 3D printing has significant advantages in terms of speed and cost even for parts with high
mechanical complexity. One disadvantage of Stereolithography (SLA) 3D printed, copper plated
microwave components is that some SLA resins have a high Coefficient of Thermal Expansion (CTE),
quoted in micrometers per meter per degree or 10−6 per degree. Compared to typically used metals
such as aluminum (CTE 24 × 10−6 ·K−1 ) and copper (CTE 17 × 10−6 ·K−1 ), SLA resin can have CTE
above 100 × 10−6 ·K−1 . Resonant structures experience significant frequency drift with temperature
changes on the order of 10–50 ◦ C. The issue of 3D printed microwave structures changing frequency
characteristics significantly with temperature shift has not been addressed or reviewed in current
literature. We measured and simulated the effect of temperature change on a slot array, cavity notch
filters, and post loaded waveguide bandpass filters. We tested several types of SLA resin, different
plating techniques, and also Direct Metal Laser Sintering (DMLS) and Binder Infusion metal 3D
printing. Performance as a function of temperature is presented for these alternatives.

Keywords: cavity resonators; filters; microwave; plating; stereolithography; thermal expansion;

three-dimensional printing

1. Introduction
Microwave slot array antennas and bandpass and notch filters can be produced quickly and
inexpensively using 3D printing [1–3]. The high CTE of SLA resins causes frequency drift with
temperature to be notably worse than solid metal structures [4]. Somos Taurus SLA resin [5] has CTE
of 105.3 × 10−6 ·K−1 over the temperature range 0–50 ◦ C. Choosing lower CTE resin, strengthening
metal coatings using multiple layers of nickel and copper, and switching to 3D metal printing with
DMLS or binder infusion improves frequency dependence on temperature. In this paper, the frequency
dependence with temperature is presented for multiple SLA resins, multiple metal coatings, and 3D
metal printed structures. Theoretical fits to expected temperature variation are presented to confirm the
predictability of performance. Armed with these predictions and results, requirements for temperature
stability can be applied to make decisions regarding the materials and processes to use for 3D printed
fabrication of microwave devices.
Another notable advantage of 3D printed parts is that they are much lighter than metal parts.
Invar is a 36% nickel alloy with iron. It is used when temperature stability is important. It is ductile
and weldable. Its CTE over 20–100 ◦ C is <1.3 × 10−6 ·K−1 , with σ = 0.202 × 106 S/m (must be plated
for use in microwave circuits). Its density is 8.1 to 8.2 g·cm−3 . Accura Bluestone [6] has solid density
of 1.78 g·cm−3 at 25 ◦ C, so invar is 4.6 times heavier than Accura Bluestone. Using metals with low
CTE [7] is a conventional way to attack the temperature variation problem. There are also various
methods of compensating temperature variations in microwave structures [8–19].
It is possible to achieve metal CTE characteristics with 3D printing using DMLS. The AlSi10Mg
alloy used for DMLS 3D printing has a CTE of 20.5 × 10−6 ·K−1 [20] and σ = 11.3 × 106 S/m [21], which is

Metals 2020, 10, 580; doi:10.3390/met10050580 125 www.mdpi.com/journal/metals

Metals 2020, 10, 580

better CTE than pure aluminum. There are a range of CTE values from 53 × 10−6 ·K−1 to 145 × 10−6 ·K−1
available for a desktop SLA 3D printer [22]. Electroplating can also use layers of copper and nickel
to strengthen the metal coating and resist the expansion of plastic. Relatively broad band structures
such as slot arrays and bandpass filters are not as badly affected by frequency
− drift
− as narrow
− − band

notch filters.

2. Materials and Methods

We measured the effect of temperature change on a slot array, cavity notch filters with single and
multiple cavities, and post loaded waveguide bandpass filters. We tested several types of SLA resin,
different plating techniques, and also DMLS and Binder Infusion metal 3D printed structures.
Analytical predictions of frequency shifts with temperature and calculation of effective CTE are
estimates based on bulk scaling of resonators. Analytical scaling and HFSS bulk scaling results are
consistent. Mechanical complications of the expansion of the structure causing it to expand in a more
complicated way than bulk scaling cannot be simulated analytically or with HFSS. Metal coatings
decrease the effect of plastic expansion. Quoted commercial CTE values for 3D printed resin are
assumed to be accurate, and their quoted values change with temperature ranges. There is no quoted
CTE for the binder infusion metal. The DMLS metal CTE is based on a publication. Measurements
present the actual frequency drift performance of each device. Calculations and predictions offer a way
to know the impact of material and construction choices.
The oven used for temperature testing was a Test Equity model 107, with temperature range −42
to +130 ◦ C. The network analyzer used in the measurements was a Keysight N5242A. Commercial −
waveguide to coaxial transitions were used to test both filters and a slot array antenna.
An 18 GHz slot array was cycled in temperature from −10 to +60 ◦ C six times in 24 h intervals.
−
Only S11 was measured. After six cycles, there was visible warping of the structure. The S11 minimum
changed permanently after each cycle, so there was a hysteresis effect with a 70 ◦ C temperature
excursion. Our theory is that the plastic expanding during heating pushes the metal plating, and when
the plastic shrinks during cooling, the metal does not return exactly to its original position.
As shown in Figure 1, the minimum S11 was −20.047 dB at 18.07 GHz on the first cycle, −33.16 dB
− −
at 18.12 GHz after the second cycle, −32.11
− dB at 18.13 GHz after the third cycle, −28.94
− dB at 18.14 GHz
after the fourth cycle, −22.19 dB
− at 18.15 GHz after the fifth cycle, and −27.36− dB at 18.14 GHz after the
sixth cycle.

Minimum S11 Frequency of 18 GHz Slot Array

18.16
Minimum S11 Frequency [GHz]

18.15
18.14
18.13
18.12
18.11
18.1
18.09
18.08
18.07
18.06
0 1 2 3 4 5 6 7

Temperature Cycle -10 °C to +60 °C in 24 h

Figure 1. Minimum S11 frequency of slot array temperature cycled

− −10 ◦ C to +60 ◦ C.

126
Metals 2020, 10, 580

The maximum frequency excursion was 80 MHz, which is a 0.44% permanent change. The −10 − dB
bandwidth did not change from 100 MHz or 0.55%. A 70 ◦ C temperature shift, a minimum of −10 − ◦C
and a maximum of +60 ◦ C cause permanent damage to a 3D printed, copper plated microwave slot
array. An obvious alternative that would avoid hysteresis and damage is metal 3D printing. Metal 3D
printing with DMLS becomes expensive for part dimensions greater than six inches.
Three slot arrays were simulated with CTE of 50 × 10−6 − to examine the effects of temperature
− ·K−1

change on gain and S11 parameters. A 315 × 323 mm array designed to operate at 18.4 GHz showed
an S11 minimum at 18.375 GHz, with S11−= −30.52 dB with no temperature offset. The –10 dB S11
width was from 18.3 to 18.44 GHz (140 MHz bandwidth). With a 20-degree temperature offset,
the minimum S11 shifted to 18.356 GHz Δ −(∆f = −19 MHz), with − S11 = −30.78−dB. The −10 dB S11
width was from 18.28 to 18.43 GHz. With a 50-degree temperature offset, the minimum S11 shifted to
Δ
18.330 −GHz (∆f = −45 MHz), with
− S11 = −35.5613−dB. The −10 dB S11 width was from 18.25 to 18.40 GHz.
The temperature scaling is shown in Figure 2. This array used a four-point corporate network, so it
had a wide bandwidth (145 MHz or 7.9%). The realized gain at the design frequency of 18.4 GHz was
34.16 dB with no temperature offset, and reduced to 33.92 dB with a 20-degree temperature offset and
to 33.53 dB with a 50-degree temperatureffoffset− (−0.62 dB). This is due to the shift in optimum S11 .

18.4 GHz Slot Array Temperature Scaling

18,380,000
18,375,000
Minimum S11 Frequency [kHz]

18,370,000
18,365,000
18,360,000
18,355,000
18,350,000
18,345,000
18,340,000
18,335,000
18,330,000 y = -897.37x + 2E+07
18,325,000
0 10 20 30 40 50 60

Temperature Offset [°C]

Figure 2. 18.4 GHz slot array temperature scaling.

A 301 × 319 mm array designed to operate at 10.73 GHz had a minimum S11 at 10.7305 GHz,
with −S11 = −20.26 dB with no temperature offset as shown in Figure − 3. The −10 dB S11 width was
from 10.69 to 10.76 GHz (70 MHz bandwidth). With a 20-degree temperature offset, the minimum
S11 shifted toΔ10.721
− GHz (∆f = −9.5 MHz), − with S11 = −20.1103
− dB. The −10 dB width was from
10.6842 to 10.7530 GHz. With a 50-degree temperature offset, the minimum S11 shifted Δ to−10.705 GHz
(∆f = −25.5− MHz), with S11− = −20.87 dB. The −10 dB S11 width was from 10.67 to 10.74 GHz. This array
was coaxial fed in the center of a centered feeding waveguide. The realized gain at the design frequency
of 10.73 GHz reduced from 28.42 dB with no temperature offset to 28.45 dB with a 20-degree temperature
offset and 28.13 dB with a 50-degree temperature ff offset
− (−0.29 dB).

127
Metals 2020, 10, 580

10.73 GHz Slot Array Temperature Scaling

10,735,000

10,730,000
Minimum S11 Frequency [kHz]

10,725,000

10,720,000

10,715,000

10,710,000

10,705,000 y = -511.84x + 1E+07

10,700,000
0 10 20 30 40 50 60
Temperature Offset [°C]

Figure 3. 10.73 GHz slot array temperature scaling.

A 448 × 420 mm array designed to operate at 8.18 GHz showed an S11 minimum at 8.171 GHz,
− −
with S11 = −30.11 dB with no temperature offset as shown in Figure 4. The −10 dB S11 width was
from 8.13 to 8.22 GHz
Δ (90− MHz bandwidth). − With a 20-degree
− temperature offset, the minimum S11
shifted to 8.161 GHz (∆f = −10 MHz), with S11 = −32.42 dB. The −10 dB SΔ11 width
− was from 8.12 to
8.21 GHz.− With a 50-degree
− temperature offset, the minimum S11 shifted to 8.147 GHz (∆f = −24 MHz),
with S11 = −35.4 dB. The −10 dB S11 width was from 8.11 to 8.19 GHz. The array used a center feeding
waveguide fed from the end, which is why it has smaller bandwidth. The realized gain at the design
−
frequency of 8.18 GHz was 29.84 dB with no temperature offset, reduced to 29.81 dB with a 20 ◦ C offset,
and reduced to 29.66 dB with a 50-degree temperature offset (−0.18 dB).

8.18 GHz Slot Array Temperature Scaling

8,175,000
Minimum S11 Frequency [kHz]

8,170,000

8,165,000

8,160,000

8,155,000

8,150,000

y = -478.95x + 8E+06
8,145,000
0 10 20 30 40 50 60

Temperature Offset [°C]

Figure 4. 8.18 GHz slot array temperature scaling.

128
Metals 2020, 10, 580

Given that all three arrays lose less than one dB of realized gain with a 50 ◦ C temperature increase,
slot array performance is apparently not significantly affected by operating at high temperatures.
The effect of temperature variation is much less pronounced than it is for narrow band notch filters
and to a lesser degree bandpass filters. On the other hand, a high enough temperature will cause
permanent changes to the array, and with a high enough temperature, visible damage.
A microwave notch filter can be created by coupling a single or multiple resonant cavities to
a waveguide [23]. The cavity resonance causes a dip in S21 , notching the frequency out of the passband.
Not only do the resonant cavity dimensions grow with increasing temperature, but the coupling
apertures will also increase in size, which also decreases the resonant frequency assuming that the
cavity was originally under-coupled.
The resonant frequency of a TE101 rectangular cavity is given by
r 
π 2
 2
c π
f101 = √ + (1)
2π µr εr a d

For a resonant frequency of 10 GHz based on WR-90 waveguide (a = 0.9 inches = 22.86 mm),
the guide wavelength is given by
λ0
λg = q  λ 2 (2)
1 − λc0

where λc is the cutoff wavelength given by two times the waveguide width ‘a.’ At 10 GHz,
λ0 = 29.979 mm and λg = 39.707 mm.
The length of a TE101 cavity is exactly λg /2 so d = 19.854 mm. As temperature increases,
cavity dimensions change according to the following formulas:

a = 22.86mm × (1 + CTE × ∆T ) (3)

d = 19.854mm × (1 + CTE × ∆T ) (4)

𝑑 = 19.854𝑚𝑚 × 1 + 𝐶𝑇𝐸 × 𝛥𝑇
The resonant frequency as a function of temperature and CTE is shown in Figure 5 below.

Frequency Scaling With Temperature

CTE 20 CTE 50 CTE 100
10
Cavity Frequency [GHz]

9.995
9.99
9.985
9.98
9.975
9.97
0 5 10 15 20 25 30
Temperature Change [°C]

Figure 5. Frequency scaling of 10 GHz TE101 Resonant Cavity – Temperature versus CTE.
− − − −

− − − − − − − −
129

− −

− −
Metals 2020, 10, 580

For a notch filter centered at 10 GHz, the slope for CTE 20 × 10−6 ·K−1 is −200 kHz·K−1 . For CTE
of 50 × 10−6 ·K−1 , the slope is −499 kHz·K−1 . For CTE of 100 × 10−6 ·K−1 , the slope is −997 kHz·K−1 .
Equation (1) combined with Equations (3) and (4) yields the approximate result that the slope of
resonant frequency change with temperature is –CTE multiplied by the unmodified resonant frequency.
This matches the fit slopes for CTE 20, 50, and 100 × 10−6 ·K−1 .
For a TE101 notch filter centered at 15.7 GHz, using the same analytical scaling, CTE of 20 × 10−6 ·K−1
produces a slope of −300 kHz·K−1 , a CTE of 50 × 10−6 ·K−1 produces a slope of −800 kHz·K−1 , and a
CTE of 100 × 10−6 ·K−1 produces a slope of −1.6 MHz·K−1 . For a DMLS 3D printed cavity filter made
with AlSi10Mg, with a notch at 15.644 GHz, with CTE published as 20.5 × 10−6 ·K−1 , we measured
−16 MHz shift for a temperature range from 23 to 55 ◦ C, corresponding to −500 kHz·K−1 . Measurement
of S21 at 20, 23, 35, 40, 45, and 50 ◦ C was followed by plotting the S21 null versus temperature and
applying a linear fit to the data. An analytical fit to this frequency change corresponds to a CTE of
32 × 10−6 ·K−1 . An image of the single cavity DMLS metal 3D printed notch filter is shown in Figure 6.

Figure 6. DMLS metal 3D printed single cavity notch filter.

A single cavity filter SLA 3D printed with Formlabs Tough resin at 15.9 GHz using WR-62
waveguide, and plated with 12.7 µm μ copper, 25.4 µmμnickel, and 12.7 µm copper
μ measured 15.933 GHz
− −
with S21 = −16.04 dB at 20 C, 15.91 GHz with S21 = −16.26 dB at 35 C, 15.9036 GHz with S21 = −15.48 dB
◦ ◦

− 40 ◦ C, and 15.913 GHz with S21 = −28.97 dB at− 45 ◦ C. The linear slope fit to these data is −856.23 kHz
at
− ◦ C. The analytical fit to CTE for this resonant cavity is 53.95 × 10−6 ·K−1 . The
per − −
published CTE of
− −
Formlabs Tough resin [24] in the cured state is 119 × 10 ·K , so the stronger metal coating did have
−6 −1

an effect. The heated plastic expands, but a stronger metal coating more strongly resists this expansion.
In the limit where the metal coating was very thick, it is obvious that the plastic would be completely
prevented from expanding. Returning to 20 ◦ C, the S21 null was −29.89 dB (−13.85 − −
dB change) at
15.939 GHz (∆f = +6 MHz).Δ There was some hysteresis effect.
Images of SLA 3D printed, copper plated single cavity notch filters using WR-42 and WR-62
waveguide are shown in Figure 7.

130
 − −
Δ
Metals 2020, 10, 580

Figure 7. SLA 3D printed single cavity notch filter using WR-42 and WR-62 waveguide.

A single cavity filter SLA 3D printed with Taurus resin at 17.1 GHz using WR-62 waveguide,
and plated with copper measured an S21 minimum at 17.068 GHz with S21 = –9 dB at 20 ◦ C, 17.037 GHz
with S21 −8.15−dB at 35 ◦ C, 17.027 GHz with S21 = −8.31− dB at 40 ◦ C, 17.015 GHz with S21 = −6.52 − dB
at 45 ◦ C, and 17.001 GHz with S21 = −7.61
− dB at 50 ◦ C. As shown in Figure 8, the linear slope fit to

these data is −−2197.9 kHz per ◦ C. The analytical fit to CTE for this resonant cavity is 129 ×− 10−6
− ·K
−1 .

The published CTE of Somos Taurus is 105.3 × −10 − ·K . Returning to 20 C, the S21 null was –7.61 dB
−6 −1 ◦

(+ 1.39 dB change) at 17.055 GHz Δ (∆f−= −13 MHz). There was some hysteresis effect.

Taurus Resin Copper Plated Notch Filter

17,080,000

17,070,000
Notch Frequency [kHz]

17,060,000

17,050,000

17,040,000

17,030,000

17,020,000

17,010,000
y = -2197.9x + 2E+07
17,000,000

16,990,000
20 25 30 35 40 45 50

Temperature [°C]

Figure 8. Somos Taurus SLA 3D printed copper plated notch filter.

A three-cavity filter at 17.2 GHz was fabricated using binder infusion metal 3D printing. In this
process, a binder is printed on tungsten powder and infused with bronze [25]. The percentage of
tungsten is 50–55%. For a TE101 notch filter centered at 17.2 GHz, using the same analytical scaling,
CTE of 20 × 10−−6 ·K− −1 produces a slope of − −343 kHz·K
−
−1 , a CTE of 50 ×− 10−6
− ·K
−1 produces a slope of
−
−859 kHz
− K , and a CTE of 100 × 10
−1 − −6 ·K produces a slope
−1
− of −1.71 MHz·K
− −1 . The binder infusion
three cavity notch filter measured a frequency shift of 3 MHz over a temperature range from 23 to 50 ◦ C,
corresponding to −111.11
− kHz·K−1− . Compared to analytical scaling, this corresponds to an effective

CTE of 6.5 × 10 − ·K − . Since bronze has CTE of 17 × 10−6− ·K−1

−6 −1 − and tungsten has CTE of 4.5 × 10−6− ·K−1
− ,

− −

131
 − − − − − − −
− − − −

Metals 2020, 10, 580

− −

− − − − − −

− −
assuming 50% of each one should expect overall CTE of 10.75 × 10−6 ·K−1 . An image of the binder
infusion metal 3D printed notch filter is shown in Figure 9.

Figure 9. Binder infusion metal 3D printed cavity notch filter.

One remedy for the temperature drift problem is to adjust the coupling aperture of a single cavity
filter to be near critical coupling. This increases the resonant bandwidth. If the notch width is 150 MHz
and the interfering signal has a bandwidth of 50 MHz or less, significant temperature drift can be
tolerated while still attenuating the target signal. One problem with this technique is that it does not
allow filtering of an interfering signal that is closer in frequency than the notch bandwidth.
The bandpass filter design that was 3D printed is a post loaded waveguide. The inductive posts
form coupled resonant cavities. This filter was designed based on a technique described in [24].
The filter has openings along the center of the waveguide broad wall, following the technique described
in [1] to enable internal electroplating of a 3D printed structure.
The SLA 3D printed, copper electroplated bandpass filter measured a passband shift of
−549 kHz·K−1 . The DMLS 3D printed bandpass filter measured a passband shift of −243.4 kHz·K−1 .
This was determined by measuring the S21 = −15 dB point of each bandpass S21 characteristic plot
as a function of frequency. These were measured at 20, 23, 35, 40, 45, and 50 ◦ C with frequencies
12.6892 GHz (20 ◦ C), 12.6883 GHz (23 ◦ C), 12.6850 GHz (35 ◦ C), 12.6842 GHz (40 ◦ C), 12.6833 GHz
(45 ◦ C), and 12.6817 GHz (50 ◦ C) as shown in Figure 10. The value of f for S21 = −15 dB at each
temperature was plotted and a linear fit was used to characterize the overall temperature variation.
The high temp SLA, copper plated bandpass filter measured a passband shift of −365.89 kHz·K−1 .
The measured frequencies were 12.6742 GHz (20 ◦ C), 12.6733 GHz (23 ◦ C), 12.6708 GHz (35 ◦ C),
12.6658 GHz (40 ◦ C), 12.6650 GHz (45 ◦ C), and 12.6642 GHz (50 ◦ C). Images of the SLA and DMLS 3D
printed, post-loaded, waveguide microwave bandpass filters are shown in Figure 11.

132
 −

− −

Metals 2020, 10, 580

Bandpass Filter -15 dB S21 Points versus Temperature

12,690,000

12,689,000
-15 dB S21 Frequency [kHz]

12,688,000

12,687,000

12,686,000

12,685,000

12,684,000

12,683,000

12,682,000
y = -242.44x + 1E+07
12,681,000
20 25 30 35 40 45 50

Temperature [°C]

Figure 10. Bandpass Filter -15 dB S21 Points versus Temperature.

− −

− −

− − Δ

Figure 11. SLA 3D printed, copper plated and DMLS microwave bandpass filter.

Simulation with HFSS using bulk scaling of the structure corresponding to CTE of 20 × 10−6 ·K−1
showed a frequency shift of −300 kHz·K−1 , very close to the measured value for DMLS with actual
reported CTE of 20 × 10−6 ·K−1 . The HFSS simulation result is shown in Figure 12 for ∆T = 0 to 50 ◦ C.
dB(S(2 1))

133
Metals 2020, 10, 580

dB(S(2,1))

ΔT== 0–50
Figure 12. Bandpass filter scaling in HFSS ∆T 0– ◦ C.

3. Conclusions
Resins used for stereolithography 3D printing typically have high CTE. Microwave structures
manufactured with 3D printing using SLA and copper plated can have strong frequency dependence
on temperature. In particular, multi-cavity filters with narrow bandwidth are strongly affected by
dependence of resonant frequency on temperature. This can preclude their usefulness if the frequency
drift approaches the bandwidth of the device. Electroplating with layers of copper and nickel to
strengthen the metal coating resists the expansion of plastic and reduces temperature dependence.
Using DMLS metal printing approaches metal structure performance, so that metal 3D printed
structures can approach temperature characteristics of solid metal structures. Single cavity notch
filters printed with lower CTE resin can be useful if a wide enough notch bandwidth is used to
accommodate frequency drift. One must choose the right 3D printing materials and processes to
achieve the temperature stability required by the application.

Funding: This research received no external funding.

Conflicts of Interest: Page: 9The authors declare no conflict of interest.

References
1. Le Sage, G.P. 3D printed waveguide slot array antennas. IEEE Access 2016, 4, 1258–1265. [CrossRef]
2. Le Sage, G.P. Dielectric steering of a 3-D printed microwave slot array. IEEE Antennas Wirel. Propag. Lett.
2018, 17, 2141–2144. [CrossRef]
3. Hindle, P. First flight-worthy metal printed RF filter developed by airbus and 3D system. Microw. J. 2017.
4. Tamayo-Dominguez, A.; Fernandez-Gonzales, J.; Sierra-Perez, M. Groove Gap Waveguide in 3-D Printed
Technology for Low Loss, Weigh, and Cost Distribution Networks. IEEE Trans. Microw. Theory Tech. 2017, 65,
4138–4147. [CrossRef]
5. Somos Taurus Resin Specification. Available online: https://www.dsm.com/solutions/additive-
manufacturing/en_US/resource-center/user-guide/somos-taurus.html (accessed on 1 March 2020).
6. Accura Bluestone Specification. Available online: https://www.buildparts.com/materials/accurabluestone
(accessed on 1 March 2020).

134
Metals 2020, 10, 580

7. Martín-Iglesias, P.; Raadik, T.; Teberio, F.; Percaz, J.M.; Martín-Iglesias, S.; Pambaguian, L.; Arregui, I.;
Arnedo, I.; Lopetegui, T.; Laso, M.A.G. Multiphysic Analysis of High Power Microwave Filter Using High
Performance Aluminium Alloy. In Proceedings of the 2019 IEEE MTT-S International Microwave Workshop
Series on Advanced Materials and Processes for RF and THz Applications (IMWS-AMP), Bochum, Germany,
16–18 July 2019; pp. 58–60.
8. Djerafi, T.; Wu, K.; Deslandes, D. A Temperature-Compensation Technique for Substrate Integrated Waveguide
Cavities and Filters. IEEE Trans. Microw. Theory Tech. 2012, 60, 2448–2455. [CrossRef]
9. Keats, B.F. Bimetal Temperature Compensation for Waveguide Microwave Filters. Ph.D. Thesis, University
of Waterloo, Waterloo, ON, Canada, 2007. Available online: https://uwspace.uwaterloo.ca/bitstream/handle/
10012/3529/BFKPhDThesis.pdf;jsessionid=5258AA80CC2EEDBB50BBB511BC90A52E?sequence=1 (accessed
on 1 March 2020).
10. Martin, T.; Ghiotto, A.; Vuong, T.; Lotz, F. Self-Temperature-Compensated Air-Filled Substrate-Integrated
Waveguide Cavities and Filters. IEEE Trans. Microw. Theory Tech. 2018, 66, 3611–3621. [CrossRef]
11. Lisi, M. Temperature compensation of microwave resonators and filters for space applications. Microw. J.
2015, 58, 100–108.
12. Lisi, M. A Review of Temperature Compensation Techniques for Microwave Resonators and Filters.
In Proceedings of the Micro and Millimetre Wave Technology and Techniques Workshop 2014, Estec,
Noordwijk, The Netherlands, 25 November 2014.
13. Temperature Compensated Cavity Filters. EverythingRF. Available online: https://www.everythingrf.com/
product-datasheet/521-334-temperature-compensated-cavity-filters (accessed on 1 March 2020).
14. Hsieh, L.; Dai, S. Temperature Compensated Bandpass Filters in LTCC; SAND2013-2744C; Sandia National Lab.:
Albuquerque, NM, USA, 2013.
15. Temperature Compensated Microwave Resonator. US Patent 4677403, 30 June 1987.
16. Temperature Compensated Resonator and Method. US Patent 6131256A, 17 October 2000.
17. Filter with Temperature Compensated Tuning Screw. US Patent CA2206942C, 17 January 1999.
18. Temperature Compensated Microwave Filter. US Patent US5867077A, 2 February 1999.
19. Temperature Compensated High Power Bandpass Filter. US Patent US6529104B1, 4 March 2003.
20. Gumbleton, R.; Cuenca, J.A.; Klemencic, G.M.; Jones, N.; Porch, A. Evaluating the coefficient of thermal
expansion of additive manufactured AlSi10Mg using microwave techniques. Addit. Manuf. 2019, 30, 100841.
[CrossRef]
21. Silbernagel, C.; Ashcroft, I.; Dickens, P.; Galea, M. Electrical resistivity of additively manufactured AlSi10Mg
for use in electric motors. Addit. Manuf. 2018, 21, 395–403. [CrossRef]
22. Formlabs Resin Specifications. Available online: https://formlabs.com/3d-printers/form-3/tech-specs/#data-
sheets (accessed on 1 March 2020).
23. Matthaei, G.; Young, L.; Jones, E.M.T. Microwave Filters, Impedance-Matching Networks, and Coupling Structures;
Artech House: London, UK, 1980.
24. Available online: https://formlabs-media.formlabs.com/datasheets/Tough_Technical.pdf (accessed on 1
March 2020).
25. Available online: http://exone.com/Admin/getmedia/79471d50-8b99-41e5-945d-4f151409ef42/X1_
MaterialData_Tungsten-Bronze_Tekna_062519.pdf (accessed on 1 March 2020).

© 2020 by the author. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).

135
 metals
Article
Mechanical Properties of High Strength Aluminum
Alloy EN AW-7075 Additively Manufactured by
Directed Energy Deposition
Anika Langebeck 1, * , Annika Bohlen 1 , Rüdiger Rentsch 2 and Frank Vollertsen 1,3
1 BIAS—Bremer Institut für angewandte Strahltechnik GmbH, Klagenfurter Str. 5, 28359 Bremen, Germany;
[email protected] (A.B.); [email protected] (F.V.)
2 Leibniz Institute for Material-Oriented Technologies, Badgasteiner Straße 3, 28359 Bremen, Germany;
[email protected]
3 Faculty Production Technology, University of Bremen, Bibliothekstr. 1, 28359 Bremen, Germany
* Correspondence: [email protected]; Tel.: +49-421-218-58035




Received: 31 March 2020; Accepted: 23 April 2020; Published: 29 April 2020


Abstract: A manifold variety of additive manufacturing techniques has a significant positive impact
on many industry sectors. Large components are often manufactured via directed energy deposition
(DED) instead of using powder bed fusion processes (PBF). The advantages of the DED process
are a high build-up rate with values up to 300 cm3 /h and a nearly limitless build-up volume.
In combination with the lightweight material aluminum it is possible to manufacture large lightweight
components with geometries adapted to customer requirements in small batches. This contributes
the pursuit of higher efficiency of machines through lightweight materials as well as lightweight
design. A low-defect additive manufacturing of high strength aluminum EN AW-7075 powder
via DED is an important challenge. The laser power has a significant influence on the remaining
porosity. By increasing the laser power from 2 kW to 4 kW the porosity in single welding tracks can
be lowered from 2.1% to only (0.09 ± 0.07)% (n = 3). However, when manufacturing larger specimens;
the remaining porosity is higher than in single tracks; which can be attributed to the oxide skin on the
preceding welding tracks. Further investigations regarding the mechanical properties were carried
out. In tensile tests an ultimate tensile strength of (222 ± 17) MPa (n = 6) was measured. The DED
processed EN AW-7075 shows comparable mechanical properties to PBF processed EN AW-7075.

Keywords: directed energy deposition; EN AW-7075; porosity; ultimate tensile strength

1. Introduction
Metal additive manufacturing for producing components and component parts is becoming more
and more relevant, especially in customized single and small series production [1]. Two relevant
process groups are powder bed fusion (PBF) and directed energy deposition (DED) (ISO/ASTM
52900:2018-06). The latter is commercialized by several organizations and known under different
acronyms such as LENS (Laser Engineering Net Shaping) [2]. These DED systems are used besides
additive manufacturing purposes for repairing high-value components [3]. A common classification of
DED processes is to divide them into powder-feed processes and wire-feed processes [4]. For PBF
processes the powder material is supplied in a powder bed. For powder-feed DED, powder nozzles
are used to deliver the powder directly into the process zone. In contrast to PBF processes, DED is
used in case of larger structures with lower resolution [4] due to high build-up rates which can reach
values up to 1.8 kg/h for the powder-feed DED and a nearly limitless build-up volume [5]. Besides a
laser as energy source for DED an electron beam or an arc can be used. A five times higher build-up

Metals 2020, 10, 579; doi:10.3390/met10050579 137 www.mdpi.com/journal/metals

Metals 2020, 10, 579

rate can be achieved in DED with wire feed [6]. However, by using a laser as energy source the heat
input is significantly lower compared to an arc and therefore the distortion is smaller [7].
When aluminum alloys are used in additive processes, hydrogen related porosity is a disadvantage
that must be considered. Hydrogen related porosity is formed during solidification of the melt pool,
when the solubility of the aluminum for hydrogen decreases significantly [8]. An important source
for hydrogen besides the oxide layer on the substrate’s surface is the humidity of the ambient air
near to the process zone [9]. There are two approaches to reduce hydrogen related porosity. First,
by improving the shielding gas coverage to protect the process zone from hydrogen. Secondly, by
adapting the process parameters for a better degassing of hydrogen during the solidification of the
melt pool.
A low porosity is necessary to achieve high mechanical characteristics such as ultimate tensile
strength and Young’s modulus. For additively manufactured tensile specimens made of aluminum EN
AW-7075 laser powder bed fusion (LPBF) is often used [10]. Only few scientists report on produced
tensile specimens using DED [11]. When additively manufactured tensile specimens are tested, it is
shown that the orientation of the specimen’s single tracks to the tensile load direction has a significant
influence on the results for the mechanical characteristics. The ultimate tensile strength is highest
when building direction is parallel to the load direction [11]. EN AW-7xxx alloys can be precipitation
hardened in a subsequent heat treatment that results in higher hardness and therefore in higher
ultimate tensile strength [12]. A T6 heat treatment is often used to achieve an increase in hardness
through precipitation hardening [13]. Therefore, solution heat treatment followed by quenching is
carried out to achieve a supersaturated solid solution. Precipitation of magnesium and zinc take place
during subsequent artificial aging and an increase in hardness is reached. For DED manufactured
specimens of an EN AW-7xxx alloy with high zinc content of 11.9% and high magnesium content
of 2.7% the measured Vickers hardness increased after a T6 heat treatment from (133 ± 6) HV0.05
to (219 ± 4) HV0.05 [13]. When processing EN AW-7xxx alloys in DED processes a loss in volatile
elements such as zinc and magnesium is observed [14]. This alters the initial alloy composition and
can affect the (mechanical) properties.
In this study low-defect specimens of EN AW-7075 will be manufactured via powder-feed DED
with an adapted shielding gas shroud and the influence of the laser power on the porosity will be
determined. The low-defect specimens will be used to examine the influence of artificial aging on
hardness and mechanical characteristics of the low-defect specimens will be evaluated as well.

2. Materials and Methods

The specimens were manufactured by powder-feed DED. Therefore, a lamp pumped Nd:YAG
rod laser (Trumpf GmbH + Co. KG, Ditzingen, Germany) was used. The Trumpf HL 4006 D generates
a wavelength of 1064 nm with a maximum power of 4 kW. The laser beam is guided via an optical
fiber with a core diameter of 600 µm to the processing head. The processing head consists out of an
optical unit by Trumpf (type BEO D70). Collimation lens as well as focus lens have a focal length
of 200 mm. By setting the laser focus with a top-hat profile 24.5 mm above the substrate surface a
calculated spot size of 4.5 mm with a gaussian intensity distribution on the substrate’s surface was
reached. With increasing the laser power to the maximum of 4 kW at a spot size of 4.5 mm a maximum
laser intensity of 251 W/cm2 can be reached. This ensures that the threshold intensity for forming a
keyhole is not exceeded during the DED process. The aluminum powder was supplied by a rotating
disk powder feeder made by Plasma-Technik AG (Twin10C, Wohlen, The Switzerland) to a coaxial
three-jet nozzle by Ixun Lasertechnik GmbH (Aachen, Germany) with a working distance for the
powder focus of 12 mm. Argon was used as carrier and shielding gas. Substrates for the specimens
and the processing head were mounted on a 3-axis CNC by Föhrenbach GmbH (Löffingen-Unadingen,
Germany) and which was driven by a control unit from Power Automation GmbH (type PA8000,
Pleidelsheim, Germany).

138
Metals 2020, 10, 579

As substrate material aluminum wrought alloys EN AW-5083 and EN AW-6082 with a thickness
of 10 mm each were used. The used aluminum powder EN AW-7075 was supplied by NMD—New
Materials Development GmbH (Heemsen, Germany) with a grain size distribution of D10 37 µm, D50
68 µm and D90 122 µm. It was sieved with 50 µm and 125 µm mesh size. See Table 1 for the chemical
composition of the powder material.

Table 1. Chemical composition of EN AW-7075 in wt. % supplied by NMD—New Materials

Development GmbH (Heemsen, Germany). Measurements in accordance with EN 10204 3.1.

Al Si Fe Mn Zn Mg Cu Cr
89.9 0.11 0.09 0.01 5.51 2.42 1.60 0.21

In order to improve the shielding gas coverage of the processing zone an additional shielding
gas shroud was developed. See Figure 1 for a schematic view of the developed shielding gas shroud.
The shroud is made of sinter metal with an internal radius of 19 mm and an external radius of 47 mm
and has four ports for the gas supply to provide an extended and homogenous shielding gas coverage
for the process zone.

Figure 1. Improved shielding gas concept with an additional shielding gas shroud.

The effect of the new shielding gas concept was evaluated by manufacturing single tracks (see
Table 2). The porosity was measured at cross sections. A decrease in porosity from over 7.0% to 5.9%
was measured. This corresponds to a reduction by 1/8 for the used parameter set. For all subsequent
experimental studies regarding DED with EN AW-7075 the additional shielding gas shroud was used.
The influence of the laser power on pore volume was determined at cross sections in the area of
the center of the specimens. The laser power was varied between 2 kW and 4 kW in steps of 0.5 kW.
Each parameter combination was examined in randomized triple determination.
For measuring the tensile strength as well as the hardness of the additively manufactured
aluminum parts larger specimens consisting of 9 layers in total with 6 single tracks per layer were
manufactured. A horizontal overlapping (y-direction) between the single layers of 30% was used.
The vertical overlapping (z-direction) was 13%. Between two subsequent layers an offset in y-direction
of 2.5 mm was chosen. The building direction (x-direction) was parallel to the load direction chosen for
the tensile tests. For the evaluation of the porosity, the microscopic images of non-etched cross-sections
were binarized using Otsu’s method. See Figure 2 for the position of the cross-sections. The binarized
images were used to calculate the porosity by measuring the proportion of black (pores) to white
pixels (EN AW-7075). The Vickers hardness measurements were carried out on ground and polished
cross sections directly after the DED process and after artificial aging according DIN EN ISO 6507-3.
By using wire-cut EDM (electrical discharge machining) tensile specimens were manufactured out of

139
Metals 2020, 10, 579

the artificially aged DED parts with an overall length of 100 mm, a width of grip section of 25 mm,
a width of 10 mm and a thickness of 4 mm (see Figure 2). The artificial aging includes stretching to 2%
elongation, aging for 3 days at room temperature and two step artificial aging for 18 h at 120 ◦ C and
for 5 h at 175 ◦ C.

Table 2. Process parameters for single tracks to determine the influence of shielding gas concept on
pore volume and the influence of energy input per unit length on pore volume.

Single Tracks for Shielding Single Tracks for Porosity

Parameters
Gas Investigations Investigations
Laser power 2.4 kW 2 kW to 4 kW
Laser spot diameter 2.0 mm 4.5 mm
Shielding gas flow conv. 7.5 L/min (centric) -
7.5 L/min (centric) 7.5 L/min (centric)
Shielding gas flow with additional shroud
30 L/min (additional shroud) 30 L/min (additional shroud)
Carrier gas flow 5.5 L/min 4 L/min
Powder feed rate (9.9 ± 0.2) g/min (9.3 ± 0.3) g/min
Substrate material EN AW-5083 EN AW-5083
Welding speed 400 mm/min 400 mm/min

Figure 2. Additively manufactured tensile specimen with building direction parallel to load direction
before and after wire-cut electrical discharge machining (EDM).

3. Results
As shown in Figure 3 with increased laser power from 2 kW to 4 kW the measured porosity
decreased from 2.1% to just (0.09 ± 0.07)% (n = 3). With a powder feed rate of (9.3 ± 0.3) g/min
and a powder usage efficiency of (82.0 ± 3.4)% (n = 14) a build-up rate of (164 ± 10) cm3 /h (n = 14)
was reached.
When manufacturing larger parts consisting of several layers with several single tracks the
low pore volume of (0.09 ± 0.07)% (n = 3) measured in single tracks could not be reached anymore.
However, a pore volume of (2.2 ± 0.9)% (n = 15) was reached. Figure 4 shows an exemplary cross
section. The cross section reveals a preferred localization of the pores in the area of the melt pool
borders. Additionally to porosity some cracks between the lower layers and the substrate material on
the left and right side are visible.

140
Metals 2020, 10, 579

Figure 3. Influence of laser power on porosity.

Figure 4. Schematic view of built-up strategy; cross section of large part for hardness measurements as
well as tensile tests.

After the DED process Vickers hardness measurements were carried out. A hardness of
(85 ± 4) HV0.5 (n = 4) was measured. A slight improvement in hardness up to (93 ± 2) HV0.5 (n = 3)
could be reached after artificial aging.
After artificial aging tensile specimens were manufactured and tested. The results are shown in
Figure 5. An ultimate tensile strength of (222 ± 17) MPa (n = 6) was calculated.

141
Metals 2020, 10, 579

Figure 5. Results of tensile tests for additively manufactured specimens made of EN AW-7075.

4. Discussion
In this work, low-defect specimens were manufactured via DED with an additional shielding gas
shroud. An increase in laser power leads to a significant decrease in porosity. This parameter set were
then used to evaluate the mechanical characteristics of (tensile) specimens made of EN AW-7075.
The pore volume of DED processed EN AW 7075 decreased from 2.09% to just (0.09 ± 0.07)% (n = 3)
in single track experiment by the increase of laser power from 2 kW to 4 kW. The increased laser power
led to a more overheated and larger melt pool. Additionally, the thermo-capillary convection in the
melt pool increases with higher laser power [15]. This aspect results in lower cooling rates which leave
the precipitated gaseous hydrogen and other volatile elements such as zinc and magnesium from the
alloy system longer time for degassing out. When larger specimens are manufactured with the same
parameter set, which was used for single tracks, the low pore volume of single track experiment could
not be achieved. A reason for this can be hydrated oxide layers which form on the substrate surfaces as
well as on previous weld beads [16]. The weld beads have a convex macroscopic geometry and have
a rough surface due to adhering, partially melted powder particles. This significantly increases the
surface area that can oxidize and hydrate. In addition, the increased temperatures during the welding
of the individual layers further increase the thickness of the resulting oxide layer [17]. The surface of
the weld beads can be identified as a significant source for additional hydrogen that causes porosity.
The previous welding tracks are partially remelted during the DED process and the oxide layer with
its hydrogen content can cause porosity in the area of the melt pool borders of the new welding track.
EN AW-7075 can be precipitation hardened. Highest hardness can be reached after a T6 heat
treatment. The large specimens for hardness measurements were artificially aged without a previous
solution heat treatment. The results show a slight increase in hardness from (85 ± 4) HV0.5 (n = 4) to
(93 ± 2) HV0.5 (n = 3). This indicates that after the DED process a microstructure is already present
which achieves precipitation hardening by artificial aging. For conventionally produced EN AW-7075
T6 a Vickers hardness of (177 ± 7) HV0.5 (n = 3) was measured, which is considerably higher. It is
uncertain whether a higher increase in hardness can be achieved by previous solution heat treatment
with quenching and subsequent artificial aging reaching a T6 condition. The measured ultimate tensile
strength of (222 ± 17) MPa (n = 6) and elongation of about 2% for the DED specimens are in good
agreement with the mechanical characteristics of specimens additively manufactured by LPBF (laser
powder bed fusion) with an ultimate tensile strength of (206 ± 26) MPa and an elongation smaller
than 1% [10]. These comparative figures were determined for both as-built specimens and solution
annealed, quenched and artificially aged specimens with no significant deviations [10]. This suggests

142
Metals 2020, 10, 579

that a complete T6 heat treatment after the DED process would have had a similar negligible effect
on the ultimate tensile strength as for the LPBF specimens. Though when comparing the measured
ultimate tensile strength of (222 ± 17) MPa (n = 6) with the tensile strength of conventionally produced
EN AW-7075 for T6 temper with 572 MPa, it becomes apparent that the additively manufactured
specimen’s tensile strength is considerably lower yet it shows good agreement with the tensile strength
of soft annealed aluminum with 228 MPa [18]. However, the elongation of only 2% for the additively
manufactured specimens is uncharacteristic for the aluminum alloy EN AW-7075 which normally
has an elongation of 11% to 17% [18]. This leads to the assumption that the additively manufactured
specimens could reach higher ultimate tensile strength if the elongation could be enlarged. The loss
in elongation can be attributed to the defects within the specimens such as porosity and hot cracks
(see Figure 4) and therefore further improvement for low-defect DED is crucial.

5. Conclusions
Low-defect aluminum specimens can be manufactured via DED by increasing the time for
degassing through an increase in laser power. Whereby the surface of the previous welding tracks
has a significant impact on porosity, too. After the DED process the EN AW-7075 specimens have
a microstructure which allows for a slight increase in hardness from (85 ± 4) HV0.5 (n = 4) to
(93 ± 2) HV0.5 (n = 3) through precipitation hardening. The mechanical characteristics do not reach
those of conventionally produced EN AW-7075 T6 specimens, which is mostly attributable to the
remaining defects. When comparing the measured ultimate tensile strength of (222 ± 17) MPa (n = 6)
with that of other additively manufactured EN AW-7075 specimens, good agreement is obtained
irrespective of whether the specimens were heat treated or not.

Author Contributions: Conceptualization, A.L., A.B. and R.R.; data curation, A.L.; formal analysis, A.L. and R.R.;
investigation, A.L. and R.R.; methodology, A.L. and R.R.; project administration, A.B.; resources, F.V.; supervision,
A.B. and F.V.; validation, A.L., A.B., R.R. and F.V.; visualization, A.L.; writing—original draft, A.L.; writing—review
& editing, A.B. and F.V. All authors have read and agreed to the published version of the manuscript.
Funding: This research was funded by the Federal Ministry for Economic Affairs and Energy (BMWi) via the
German Federation of Industrial Research Associations (AiF) in accordance with the policy to support the Central
Innovations of Medium-Sized Enterprises (ZIM) on the basis of a decision by the German Bundestag, grant
number ZF4063003SU7.
Acknowledgments: The authors gratefully acknowledge the collaboration with the company IBO GmbH regarding
their support of knowledge over the course of the research. The “BIAS ID” numbers are part of the figures and allow
the retraceability of the results with respect to the mandatory documentation required by the funding organization.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Schmidt, M.; Merklein, M.; Bourell, D.; Dimitrov, D.; Hausotte, T.; Wegener, K.; Overmeyer, L.; Vollertsen, F.;
Levy, G.N. Laser based additive manufacturing in industry and academia. CIRP Ann. 2017, 66, 561–583.
[CrossRef]
2. Saboori, A.; Gallo, D.; Biamino, S.; Fino, P.; Lombardi, M. An overview of additive manufacturing of titanium
components by directed energy deposition: Microstructure and mechanical properties. Appl. Sci. 2017,
7, 883. [CrossRef]
3. Saboori, A.; Aversa, A.; Marchese, G.; Biamino, S.; Lombardi, M.; Fino, P. Application of directed energy
deposition-based additive manufacturing in repair. Appl. Sci. 2019, 9, 3316. [CrossRef]
4. Jahn, S.; Matthes, S.; Scheller, D.; Huber, M. Process principles for metal additive manufacturing.
In Proceedings of the IIW Commissions I, IV, XII, SG 212 Joint Intermediate Meeting, Greifswald, Germany,
7–12 July 2019.
5. Ding, D.; Pan, Z.; Cuiuri, D.; Li, H. Wire-feed additive manufacturing of metal components: Technologies,
developments and future interests. Int. J. Adv. Manuf. Technol. 2015, 81, 465–481. [CrossRef]
6. Wohlers, T. Wohlers Report 2014: 3D Printing and Additive Manufacturing State of the Industry Annual Worldwide
Progress Report; Wohlers Associates: Fort Collins Col, CO, USA, 2014.

143
Metals 2020, 10, 579

7. Ding, J.; Colegrove, P.; Mehnen, J.; Ganguly, S.; Sequeira Almeida, P.M.; Wang, F.; Williams, S.
Thermo-mechanical analysis of Wire and Arc Additive Layer Manufacturing process on large multi-layer
parts. Comput. Mater. Sci. 2011, 50, 3315–3322. [CrossRef]
8. Zhao, H.; White, D.R.; DebRoy, T. Current issues and problems in laser welding of automotive aluminium
alloys. Int. Mater. Rev. 1999, 44, 238–266. [CrossRef]
9. Guo, G.; Zhang, M.; Chen, H.; Chen, J.; Li, P.; Yang, Y.P. Effect of humidity on porosity, microstructure and
fatigue strength of A7N01S-T5 aluminum alloy welded joints in high-speed trains. Mater. Des. 2015, 85,
309–317.
10. Reschetnik, W.; Brüggemann, J.-P.; Aydinöz, M.E.; Grydin, O.; Hoyer, K.-P.; Kullmer, G.; Richard, H.A.
Fatigue crack growth behavior and mechanical properties of additively processed EN AW-7075 aluminium
alloy. Procedia Struct. Integr. 2016, 2, 3040–3048. [CrossRef]
11. Khazan, P.; Stroth, M.; Freiße, H.; Köhler, H. Mechanical Properties of Large Three-Dimensional Specimens
Build through Direct Powder Deposition. WGP Congr. 2014, 1018, 525–532. [CrossRef]
12. Brüggemann, J.-P.; Risse, L.; Kullmer, G.; Richard, H.A. Optimization of the fracture mechanical properties of
additively manufactured EN AW-7075. Procedia Struct. Integr. 2018, 13, 311–316. [CrossRef]
13. Wang, P.; Li, H.C.; Prashanth, K.G.; Eckert, J.; Scudino, S. Selective laser melting of Al-Zn-Mg-Cu: Heat
treatment, microstructure and mechanical properties. J. Alloys Compd. 2017, 707, 287–290. [CrossRef]
14. Singh, A.; Ramakrishnan, A.; Dinda, G. Direct laser metal deposition of Al 7050 alloy. SAE Tech. Paper 2017.
[CrossRef]
15. Dai, D.; Gu, D. Influence of thermodynamics within molten pool on migration and distribution state of
reinforcement during selective laser melting of AlN/AlSi10Mg composites. Int. J. Mach. Tools Manuf. 2016,
100, 14–24. [CrossRef]
16. Haboudou, A.; Peyre, P.; Vannes, A.B.; Peix, G. Reduction of porosity content generated during Nd:YAG
laser welding of A356 and AA5083 aluminium alloys. Mater. Sci. Eng. A 2003, 363, 40–52. [CrossRef]
17. Jeurgens, L.P.H.; Sloof, W.G.; Tichelaar, F.D.; Mittemeijer, E.J. Growth kinetics and mechanisms of
aluminum-oxide films formed by thermal oxidation of aluminum. J. Appl. Phys. 2002, 92, 1649–1656.
[CrossRef]
18. Davis, J.R. Properties and Selection, 10th ed.; ASM International: Materials Park, OH, USA, 2000.

© 2020 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).

144
 metals
Article
Fabrication of Single Crystals through a µ-Helix
Grain Selection Process during Electron Beam Metal
Additive Manufacturing
Martin R. Gotterbarm 1,2, *, Alexander M. Rausch 2 and Carolin Körner 1,2
1 Joint Institute of Advanced Materials and Processes, University of Erlangen-Nürnberg, Dr.-Mack-Str. 81,
90762 Fürth, Germany; [email protected]
2 Chair of Materials Science and Engineering for Metals, University of Erlangen-Nürnberg, Martensstr. 5,
91058 Erlangen, Germany; [email protected]
* Correspondence: [email protected]; Tel.: +49-(0)911-65078-65121




Received: 13 January 2020; Accepted: 26 February 2020; Published: 28 February 2020


Abstract: Selective Electron Beam Melting (SEBM) is a powder bed-based additive manufacturing
process for metals. As the electron beam can be moved inertia-free by electromagnetic lenses,
the solidification conditions can be deliberately adjusted within the process. This enables control
over the local solidification conditions. SEBM typically leads to columnar grain structures. Based on
numerical simulation, we demonstrated how technical single crystals develop in IN718 by forcing
the temperature gradient along a µ-Helix. The slope of the µ-Helix, i.e., the deviation of the
thermal gradient from the build direction, determined the effectiveness of grain selection right up to
single crystals.

Keywords: additive manufacturing; powder bed fusion; single crystal; grain selection

1. Introduction
Additive Manufacturing (AM) is an integral part of Industry 4.0, the fourth industrial revolution.
AM is a revolutionary way of manufacturing, and is thus subject to intense research and development
efforts. With respect to powder bed fusion AM of metals, Selective Electron Beam Melting (SEBM) and
the more common Selective Laser Melting (SLM) were investigated. The use of an electron beam as a
heat source offers unique possibilities for the manufacturing process. Namely, operating temperatures
of more than 1000 ◦ C become feasible as the electron beam can not only be used in a focused way for
selective melting. The defocused beam can also be used as a source of global heat input. This makes
SEBM suitable for processing of the most challenging materials like nickel- and cobalt-based superalloys
or intermetallics, such as titanium aluminides [1]. As the grain structure governs the mechanical
properties, it is highly desirable to control or manipulate the developing grain structure within any
manufacturing process. SEBM typically yields a columnar grain structure, resulting in a highly
anisotropic mechanical behavior [2–4]. The elongated grains originate from epitaxial growth and steep
temperature gradients oriented mostly parallel to the build direction (BD) [3,5–7]. However, the grain
structure can be manipulated by altering the SEBM processing strategy, and thus influencing the
solidification conditions. The possibility of tailoring the grain structure towards a more equiaxed one has
been demonstrated in various publications [8–10]. For extremely demanding applications like turbine
blades, single crystalline parts are state-of-the-art. Until now, the successful generation of single crystals
via SEBM has only been reported by Ramsperger et al. [11] and Chauvet et al. [12], and the underlying
mechanisms are not yet fully understood. This study aims to provide a deeper understanding of the
underlying grain selection processes leading to single crystals. The nickel-based superalloy IN718 was

Metals 2020, 10, 313; doi:10.3390/met10030313 145 www.mdpi.com/journal/metals

Metals 2020, 10, 313

used as the model alloy to fabricate technical single crystals via SEBM. The solidification conditions
were subsequently analyzed using numerical simulations of the process.

2. Materials and Methods

In the present study, trapezoidal prisms, as depicted in Figure 1b, were fabricated from IN718
powder on an Arcam A2 machine (Arcam AB, Mölndal, Sweden), which was modified to meet the
specifications of an Arcam A1. As a scan strategy, cross snake hatching (CS, see Figure 1a) without
contour melting was used for all samples. The SEBM processing parameters are listed in Table 1 and
originate from prior processing window experiments. Two different variations of CS were employed.
On the one hand, a standard hatching (SH) approach with a moderate line offset of 100 µm, and a
scan speed of 3 m/s was used. On the other hand, the multi passing (MPCol) strategy introduced by
Helmer et al. [8] was employed, where small line offsets and high scan speeds are used. The µ-Helix
parameter setting is a special variant of multi passing, which enables controlling the solidification
paths to resemble a µm-sized helix. Three trapezoidal prisms with varying aperture angles in the
wedge section were manufactured with each parameter setting. A total of nine samples were built.
Note, that the samples were rotated by 45◦ with respect to the scan vectors SX and SY , in order to
achieve a constant scan length of 15 mm in the middle of the sample. Additionally, cuboid samples
with the dimensions 15 × 15 × 120 mm3 (XYZ) were manufactured with the µ-Helix parameter setting
for comparison. In this case, the edges of the cuboids were aligned with the scan vectors. As a start
plate, a polycrystalline IN718 disk with a thickness of 16 mm, and a diameter of 136 mm was used.
The samples were connected to the start plate via cylindrical support structures. The build temperature
was held constant at 950 ◦ C, as measured by a thermocouple attached to the start plate. A build
chamber pressure of 2 × 10−3 mbar under
− Helium atmosphere was applied during the build. The raw
material IN718 powder, with a particle size distribution of 45–105 µm, was used, provided by TLS
Technik GmbH & Co. Spezialpulver, Bitterfeld, Germany. The powder particles showed spherical
morphology with few satellites and moderate residual porosity. The chemical composition is given
in Table 2. For analysis, all manufactured samples were metallographically prepared as longitudinal
microsections. They were subsequently etched with a HCl + H2 O2 etching solution to reveal the grain
structure. No heat treatments were applied, in order to document the as-built state.

Figure 1. (a) Schematic of the cross snake scan strategy used; (b) Schematic of the trapezoidal prism
geometry used in the present study. The build direction (BD) Z and the scan vectors SX and SY are
indicated. Note the rotation of the sample coordinates X and Y in the longitudinal sections by 45◦ with
respect to SX and SY .

146
Metals 2020, 10, 313

Table 1. Selective Electron Beam Melting (SEBM) processing parameters for trapezoid samples.

Build Layer
Scan Scan Speed Line Offset Beam Power
Parameter Setting Temperature Thickness
Strategy [m/s] [µm] [W]
[◦ C] [µm]
Standard hatching (SH) Cross snake 3 100 660 950 50
Multi passing (MPCol) Cross snake 13 30 858 950 50
Multi passing (µ-Helix) Cross snake 7 30 546 950 50

Table 2. Chemical composition (wt.%) of the IN718 powder used.

Fe Ni Cr Nb Mo Ti Al Co C
Bal. 53.6 18.1 5.38 3.07 0.97 0.6 0.22 0.024

In order to gain further insights into the grain orientation, electron backscatter diffraction
(EBSD) measurements were performed on four samples. Multiple mappings from the center of the
sample, close to the top surface, were collected with a step size of 5 µm, and subsequently stitched.
The measurements and post processing were performed on a Helios NanoLab DualBeam 600 FIB/SEM
(FEI Company, Hillsboro, OR, USA) equipped with a NordlysNano EBSD detector using the AZtecHKL
and the HKL CHANNEL5 software (Oxford Instruments, Abingdon, UK), as well as the MATLAB
toolbox MTEX. In order to allow for a quantitative comparison of the crystallographic texture, the texture
index JODF was computed by MTEX according to Equation (1) [13]:
Z
2
JODF = f ( g) dg, (1)

where f is the orientation distribution function (ODF) that is calculated from the EBSD data, and g
represents an orientation. Accordingly, JODF = 1 for a completely uniform distribution of orientations
and it is infinitely large for a single orientation.
Numerical simulations were used to analyze the solidification conditions during SEBM as a
function of the processing parameters. The simulations were conducted using the 2D version of our
in-house software tool, SAMPLE2D (Simulation of Additive Manufacturing on the Powder scale using
a Laser or Electron beam), which is described elsewhere in detail [14]. It is based on a Lattice Boltzmann
framework that solves full hydrodynamics in the melt pool, and thermodynamics in the entire domain.
The setup used in the current study is depicted in Figure 2a, and the used material parameters [15–17]
are listed in Table 3. As the simulation domain is two dimensional (15 mm width), only rotations of
the hatching pattern by 180◦ are possible. A cell size of 5 × 5 µm2 and a time step of 2 × 10−7 s were
used. The scan vectors, with a length of 15 mm, run perpendicular to the simulation plane. In order to
assess the solidification conditions during SEBM without the stochastic influence of powder, a block of
solid material with a height of 50 µm was added, instead of placing individual powder particles in
each layer. For each parameter setting listed in Table 1, three layers were simulated. While a large
quantity of outputs can be sourced from SAMPLE2D , the main focus of this study was the thermal
gradient G and the solidification interface velocity vs . Both values were taken at the solidification
front. This was implemented by tracking the isotherm of the average temperature between solidus
and liquidus. The orientation of G plays a key role as it dictates the growth direction of the dendrites
during solidification [18]. As depicted in Figure 2b, the maximum deviation of vs from the BD, labeled
ϕint , is always present at the interface between two layers. Consequently, ϕint was tracked directly at
the interface between the first layer and the respective next higher layer.

147
Metals 2020, 10, 313

Figure 2. (a) Schematic of the simulation domain. The temperature field and the melt pool shape are
shown. For convenience, the whole domain (width 15 mm) is not illustrated. The beam’s hatch pattern is
schematically shown. (b) Schematic illustration of the solidification directions within overlapping melt
pools. The maximum angle between thermal gradient G (proportional to the solidification velocity vs )
and the BD, ϕint , is reached at the interface between two layers, while ϕint is about 0◦ at the bottom of
the next layer. φ φ

Table 3. Material parameters for IN718 used in SAMPLE2D [15–17]. The thermal conductivity in the
solid and the liquid are linearly approximated with the temperature (T) in K.
S𝔸𝕄PLE

Parameter Value Unit

Density 7580 Kgm−3
−
Dynamic Viscosity 4.0 × 10−3 Pas
−
Atomic Mass 26.73 u
Surface Tension 1.73 Nm−1
Solidus Temperature 1528 K −

Liquidus Temperature 1610 K

Heat Capacity (solid) 652 JKg−1 K−1
Heat Capacity (liquid) 778 JKg−1 K1 − −

Thermal Conductivity (solid) 1.66 × 10−2 T + 5.80 Wm−1 K−1 −

Thermal Conductivity (liquid) 1.35 × 10−2 T + 5.15

− Wm−1 K−1 − −

Latent Heat of Fusion 2.27·105 − JK−1 − −

∙ −

3. Results and Discussion

3.1. Grain Structure Characterization

Figure 3 shows overview images of macro etched longitudinal sections of the three different
microstructures examined in this study. Deviations from the CAD geometry are mainly due to specimen
preparation. The standard hatching strategy (SH) (Figure 3a) leads to a columnar grain structure,
with grains growing epitaxially over numerous layers. A certain grain coarsening over the build height
is evident. The mean grain width increases from about 100 µm at the very bottom of the sample up to
around 500 µm near the top surface. In the vicinity of the side surfaces, the grain structure is dominated
by inward growing fine columnar grains, which are triggered by nucleation from the surrounding
powder bed. The section is about 1 mm wide, and is a well-known phenomenon in powder bed fusion
additive manufacturing [7]. As can be seen from the detailed picture in Figure 3d, the grain boundaries
are, overall, clearly aligned parallel to the BD, yet somewhat serrated. The corresponding results from
the large area EBSD mappings in Figure 6 provide detailed information about the crystallographic
orientation of the grains. The IPF-Z map, where the coloring is chosen according to the BD, is almost
solely colored in red, which indicates a very strong <100> fiber texture parallel to the BD. This is
quantified by a high texture index of JODF = 26.07, whereas a value of 1 represents no texture at all.
Minor agglomerations of stray grains can also be observed, but these are quickly overgrown by𝐽 <100> =
26.07 grains over the course of a few layers. The IPF-X and Y maps show a different picture. Here,
oriented

148
Metals 2020, 10, 313

green is the predominant color, indicating orientations around <110>. This can be seen even more
clearly as distinct peaks in the pole figures, e.g., on the outer rim of the {100} pole figure. It can thus
be noted that in addition to the strong anisotropy in the orientation of the primary dendrite arms,
there is also anisotropy in the orientation of the secondary dendrite arms. Taking the 45◦ rotation of
the samples with respect to the scan vectors into account, the preferred orientation of the secondary
<100> directions coincides with the scan vectors. This grain structure can be seen as the reference grain
structure for SEBM-IN718, manufactured with standard cross snake hatching scan strategies, and is
comparable to what is reported in the literature [1,5,19,20].

Figure 3. Macro-etched longitudinal sections (a–c) and corresponding detailed pictures (d–f) from
trapezoidal prisms manufactured with different SEBM processing parameters and aperture angles of
35◦ . The build direction is indicated by the black arrows. The µ-Helix parameter setting allows the
fabrication of technical single crystals (SXs). For convenience, the SX region (white), as well as the
areas for the electron backscatter diffraction (EBSD) measurements are highlighted (red). SH—standard
hatching; MPCol—multi passing.

A small line offset combined with a very high scan speed (MPCol) leads to columnar grains,
as depicted in Figure 3b. However, the grain selection along the BD is slightly more pronounced here.
The grain width increases faster within the first 10 mm of the build compared to SH. From the detailed
picture in Figure 3e, it is evident that the grain boundaries are significantly less serrated and generally
tend to run more parallel to the BD. Qualitatively, the grain length appears to be larger as well. With an
expansion of about 2.5 mm, the region affected by nucleation from the powder bed at the side surfaces
is notably enlarged in comparison to SH. This region also exhibits significant notches, which drastically
deteriorate the surface quality. This phenomenon can be explained as follows: During hatching,
the beam generally passes any given spot on the surface multiple times, due to the fact, that the beam
diameter (300–400 µm) is significantly larger than the line offset. Using multi passing, the necessary
energy input per area to produce dense materials is higher compared to standard hatching, although
the line energies are significantly lower. The first hatch lines within any layer are generally needed to

149
Metals 2020, 10, 313

heat up the material and initially form a stable melt pool. The low line energies consequently lead to a
prolonged region of reduced melt depth at the beginning of a layer, and may thus cause delamination
issues at the edges since no contour melting is applied. In terms of crystallographic texture, the grain
structure exhibits similar results in the EBSD measurements compared to the standard hatching sample.
The <100> fiber texture is even more pronounced, as indicated by a texture index of 36.93. However,
the anisotropy of the secondary dendrite arms is not as distinct, which becomes evident from the more
diffuse appearance at the rim of the {100} pole figure.
As can be seen in Figure 3c, a small line offset paired with moderate scan speeds (µ-Helix)
allows the realization of technical single crystals (SXs). It is already evident from the macro etched
state, that the SX region in the center of the sample, which is about 21 mm wide, is surrounded by a
polycrystalline (PX) shell of about 2 mm width, similar to the other samples examined in this study.
There are some isolated stray grains present within the SX region, which are overgrown in subsequent
layers (see Figure 3f). The orientation of the grains within the first layers is rather randomly distributed
due to heterogeneous nucleation from the powder bed [21]. A grain selection region of approximately
9 mm in build height is present at the bottom, until the SX orientation prevails. It is interesting to note,
that the shape of the SX-region is similar to the shape of the sample, as the wedged bottom section
leads to nucleation from the powder, as long as the cross section of the part is still increasing with the
build height. Once the final cross section is established, the SX grain selection process will again take
place over the course of the next approximately 9 mm build height. This behavior is also seen in the
fabrication of SEBM-CMSX-4 technical single crystal samples [11].
In order to analyze the impact of the part geometry on the grain selection process, trapezoid
samples with different aperture angles in the wedge section were manufactured. The corresponding
macro-etched longitudinal sections are depicted in Figure 4. Please note, that the notch-like feature
seen in Figure 4b is due to an error during sample cutting. In all cases, the grain selection in the sample
center takes place within the first 9 mm of build height, regardless of the part geometry. For comparison
purposes, large cuboid samples were manufactured with the µ-Helix parameter setting at a later stage,
with an improved build temperature control during the process. A macro etched longitudinal section
of the lower part of such a cuboid sample is depicted in Figure 5. Again, an SX region is evident in the
center of the sample surrounded by a PX shell. The SX region is stable along the whole build height of
120 mm. The section demonstrates the possibility of obtaining large, high quality SX samples with the
µ-Helix parameter setting, and the importance of tight temperature control during SEBM build jobs.

Figure 4. Macro-etched longitudinal sections from trapezoidal prisms manufactured with the µ-Helix
parameter setting. The build direction is indicated by the black arrows. The aperture angle of (a) 55◦ ,
(b) 45◦ and (c) 35◦ in the wedge section influences the overall shape of the SX region (white), but the SX
selection height of about 9 mm remains constant.

150
Metals 2020, 10, 313

Figure 5. Macro-etched longitudinal section of a cuboid sample manufactured with the µ-Helix
parameter setting. The build direction is indicated by the black arrows. A high quality SX region is
present in the center of the sample. For convenience, the SX region (white), as well as the areas for the
EBSD measurements are highlighted (red).

While there is no generally accepted definition, technical single crystals typically allow for low
angle grain boundaries, with a misorientation angle of up to 10◦ , to be present within the material.
In order to verify the compliance of the presented samples with this requirement, large area EBSD
mapping was performed over the whole sample width. The results are shown in Figure 6c and
confirm that a technical single crystal was indeed built, albeit flawed. The only grain boundaries
exhibiting a misorientation angle of > 10◦ are the isolated stray grains, and the PX shell, which were
both already discussed. Consequently, the texture index of 120.29 within the SX region is extremely
high. It should be noted however, that the present stray grains may significantly affect the material’s
properties. The results of the EBSD analysis of the SX cuboid sample are depicted in Figure 7 (ODF pole
figures) and Figure 8 (IPF maps). This SX exhibits a higher quality by means of the absence of stray
grains. Consequently, the texture index within the SX region of 145.17 is even higher compared to the
trapezoidal prism SX. The resulting pole figures clearly show that there is only one distinct crystal
orientation present in the SX regions. The primary orientation of the dendrites is once again <100>
parallel to the BD, analogous to the columnar grain structures. The key difference lies within the
uniform orientation of all secondary dendrite arms, which are rotated by 45◦ with respect to the
scan vectors (note the orientation of the samples in the build chamber for the trapezoidal prisms,
see Figure 1).

151
Metals 2020, 10, 313

Figure 6. Large area EBSD-IPF maps of trapezoidal prisms manufactured with different SEBM
processing parameters: (a) SH, (b) MPCol, (c) µ-Helix. The build direction is indicated by the black
arrows. Grain boundaries with a misorientation angle of > 10◦ are highlighted with black lines.
The dashed lines indicate the region of interest for the pole figure of the µ-Helix sample.

152
Metals 2020, 10, 313

Figure 7. (100) Orientation distribution function (ODF)

𝐽𝑂𝐷𝐹 of pole figures from the EBSD measurements of
𝐽
Figures 6 and 8. The respective texture indices JODF𝑂𝐷𝐹
and hatching directions are given.

Figure 8. Large area EBSD-IPF maps of a cuboid sample manufactured with the µ-Helix parameter
setting. The build direction is indicated by the black arrows. Grain boundaries with a misorientation
angle of > 10◦ are highlighted with black lines. The dashed lines indicate the region of interest for the
pole figures.

3.2. Numerical Simulation

Numerical simulations of the SEBM process using our in-house software SAMPLE2D [14] were
S𝔸𝕄PLE
performed to reveal the solidification conditions for all hatching strategies. The parameters listed
S𝔸𝕄PLE
in Table 1 were used. The first aim was to assess the resulting melt pools. This is of particular
interest, as the melt pool shape mainly determines the orientation of G during solidification, which is
perpendicular to the melt pool walls, as depicted in Figure 2b. It has been proven to play a key role
in grain structure formation in SEBM [19]. Figure 9 shows results from the SAMPLE2D simulations
S𝔸𝕄PLE
S𝔸𝕄PLE
153
Metals 2020, 10, 313

for the three investigated parameter settings. When comparing the results it is evident, that all melt
pools (dark grey) fundamentally exhibit a similar shape, while the size varies. To understand how
these rather similarly shaped melt pools can lead to such drastically different grain structures, one has
to bare in mind that only a rather small region of interest (ROI) determines the final grain structure,
as highlighted in Figure 9. This is due to the fact that the majority of the meltpool will be remelted in
subsequent beam passes and layers and, thus, does not contribute to the grain structure of the final
part. The height of this ROI is equal to the layer thickness (typically 50 µm) starting from the melt pool
bottom. The lateral dimension of the ROI is mainly determined by the line offset, and can be assessed
by stringing together a series of melt pools with a distance equal to the line offset. It is evident from
these visualizations, that G, on average, diverges from the BD within each layer, as indicated by the
solidification paths. One can also derive that the deviation will always start at 0◦ at the melt pool
bottom and increase up to its maximum, ϕint , at the very φ top of the ROI as the melt pool curvature
increases continuously with the height. In the following, the solidification conditions are analyzed
in detail.

Figure 9. Numerical results from SS𝔸𝕄PLE

AMPLE2D (Simulation of Additive Manufacturing on the Powder
scale using a Laser or Electron beam). The dark grey areas represent the melt pools for (a) SH, (b) MPCol,
(c) µ-Helix. The dashed lines indicate previous pools. Due to remelting in subsequent beam passes and
layers, only a small region of interest (ROI) remains for grain structure development (highlighted in
green). The red streamlines resemble the orientation of G, i.e., the solidification paths.

We investigated the maximum deviation of G from the BD at the interface between the two
layers, ϕφint , for each parameter setting as a function of the lateral position in the part (see Figure 10).
The respective moving averages of ϕφint are shown. It is evident, that there is a strong influence of the
position in the part ϕφint for all settings. These boundary effects can be understood by considering
Figure 10a, where the three simulated layers are arranged schematically, and the respective interface for
the evaluation of ϕint isφhighlighted. Here, the aforementioned melt pool initialization phase becomes
evident: The melt pool depth increases steadily within the first 2–4 mm (depending on the processing
parameters), until it reaches equilibrium. This leads to an overmelting effect of preceding layers in the
boundary regions, as highlighted in Figure 10c. On the very left side, where the initialization phase
of Layer 1 took place, only Layer 2 effectively remains. It overmelts this portion of Layer 1 entirely.
As the interface for the evaluation of ϕint was defined on φ the basis of Layer 1 and the next higher
φ
Layer (see Section 2), ϕint can not be evaluated here. Consequently, there are no data points available
φ

154
Metals 2020, 10, 313

for plotting in Figure 10b. As soon as Layer 1 reaches a sufficient melt depth, ϕint increases at the
melt depth. Once a stable melt pool with a constant melt depth is established, ϕint stays constant φ
and the ROI governs the solidification conditions. Towards the far end of the layer ϕint increases φ
again. This is due to the influence of the initialization phase of Layer 2. As a result of the decreasing
melt depth, the interface is shifted higher within Layer 1, where higher deviations of G from the BD
occur. Subsequently, a second plateau region emerges, as Layer 2 is overmelted completely by Layer 3,
which exhibits a stable melt depth at this position. Finally, ϕint decreases rapidly and φ reaches values
of up to −90 , i.e., G is tilted towards
◦
− −X. As the whole melt pool − solidifies at the very end of the
simulation domain, orientations from across the whole melt pool width show up here. This second
boundary region is once again 2–4 mm wide. The described effects explain the phenomena that could
be seen on the sidewalls of the trapezoid samples.

AMPLE2D . (a) Schematic showing an overlay

Figure 10. Analysis of the solidification conditions via SS𝔸𝕄PLE
of three simulated layers. The resulting location for the evaluation of ϕ
φ int is highlighted. (b) Deviation
of the thermal gradient G from the BD at the interface between two layers φϕint , as a function of the
position within the simulation domain. The plotted curves resemble moving averages of the original
data for enhanced visibility. A section of the EBSD IPF-Z map of the cuboid µ-Helix sample is fit in
for comparison. (c) Detailed results of the simulation of µ-Helix. The red streamlines resemble the
orientation of G, i.e., the solidification paths.

Comparing the results in the stable mid-section, one can see that SH yields the lowest mean
interface angle (18◦ ). The mean ϕφint of 21◦ for MPCol is only slightly larger compared to SH. However,
there still is a noticeable difference in the resulting grain structure, with MPCol yielding a quantifiably
more pronounced grain selection when comparing the texture indices of 26.07 and 36.93, respectively.
Employing µ-Helix leads to the highest mean ϕint of 26◦ , andφthe emergence of an SX. As indicated by
the attached IPF-Z maps of the cuboid µ-Helix sample, the intialization phases coincide perfectly with
the SX region.

155
Metals 2020, 10, 313

4. Discussion
In order to understand the grain selection process to the single crystal during SEBM it is useful to
recall the standard casting process to generate single crystals, see Figure 11a. This two-stage selection
process starts with heterogeneous nucleation and growth of randomly oriented grains at a water-cooled
chill plate. During the solidification process, the temperature gradient G is oriented parallel to the
withdrawal direction. Thus, competitive grain growth based on the primary dendritic orientation
prevails within the starter block. This primary selection process results in a columnar grain structure
with a pronounced <100> fiber texture. During the following secondary spiral section process, ideally,
only one grain survives. Grain selection in this second stage is based on a purely geometric blocking
mechanism [22]. As a consequence, the secondary orientation of the selected grain is at random. Thus,
it is not possible to select a distinct grain orientation with a spiral grain selector [23].
The experimental results in conjunction with the numerical analysis allow for a deeper
understanding of the grain selection process during SEBM. Instead of using directional solidification
within a physical mold, a tailored thermal gradient controls the solidification direction in each layer.
Combining the progression of the thermal gradient G within one layer with the scan pattern rotation
after each layer, G forms a helix on the microscale (µ-Helix) (see Figure 11b). Although G deviates
significantly from the building direction in every layer, the resulting grain structure shows a pronounced
<100> -type texture. The rotation of the scan pattern after each layer leads to an averaging effect over
the course of multiple layers. On average, G is oriented parallel to the BD. In addition, G is oriented
in <100> direction at the bottom of the melt pool. Thus, solidification always starts with the <100>
direction leading to the pronounced <100> fiber texture commonly observed in parts manufactured by
SEBM. As the <100> directions are the fastest growing directions in cubic crystal systems, grains with
their primary dendritic orientation close to <100>, with respect to the BD, are systematically favored.
This initial selection process is based on the well-known principles of competitive grain growth [18]
and is typically finished within the first millimeters of build height, as shown in [21].

Figure 11. Schematic illustration of different approaches to realize single crystals. (a) Physical spiral
grain selector used within an investment casting mold, (b) µ-Helix selector during SEBM formed by
the direction of the local thermal gradient G.

156
Metals 2020, 10, 313

While the mean direction of G explains primary grain selection, the deviation of G from the BD is
responsible for the secondary selection process (see Figure 9). Secondary grain selection takes place in
the plane perpendicular to the building direction. It occurs by competitive growth of the secondary
dendrite arms. At the beginning of solidification, i.e., at the melt pool bottom, G only marginally
diverges from the BD. This indicates that only grain selection based on the primary dendritic orientation
will take place here. As the deviation of G increases steadily within the layer, grain selection based
on the secondary dendritic orientation will attain its maximum at the interface to the subsequent
layer. The deviation of G from the BD depends on the processing parameters, see Figure 10. Obviously,
the velocity of secondary grain selection increases with increasing deviation of G from the BD. However,
a too high deviation of G from the BD will ultimately end in new grain formation [24]. Following the
same arguments as for primary grain selection, secondary grain selection in the plane perpendicular to
the BD should prefer grains with the secondary dendrite arms oriented parallel to the scan vectors.
However, the experimental results do not confirm this expectation. On the contrary, the <110> direction
is determined for the secondary orientation, see Figure 8. That is, the secondary dendrite arms are
rotated by 45◦ with respect to the scan vectors. The origin of this phenomenon is not yet understood
and is still under investigation.

5. Conclusions
The grain structure of SEBM parts can be strongly influenced by the processing parameters.
For this purpose, trapezoidal prism samples from IN718 were produced by SEBM using different
processing strategies.

1. Standard hatching and multi passing yield columnar grains with a pronounced <100> fiber
texture along the build direction. The novel µ-Helix parameter setting, a special variant of multi
passing, allowed for the fabrication of technical single crystals (SXs), which were surrounded by a
polycrystalline shell. Within the SX section, minor agglomerations of stray grains were still present.
This was overcome in a second build job with improved temperature control, which resulted in
high quality cuboid SX samples.
2. In contrast to investment casting, where the secondary orientation of single crystals produced by
a spiral grain selector is random, SEBM leads to a defined and reproducible secondary orientation.
All SXs show a primary orientation of <100> parallel to the build direction, and a secondary
orientation of <110> along the scan vectors.
3. The aperture angle of the trapezoidal prisms determines the height where the SX region reaches
its maximum width as new grain orientations emerge as long as the sample cross section
still increases.
4. Numerical simulations using our in-house software suite SAMPLE2D revealed that the deviation
of the thermal gradient G from the build direction, right at the interface between two layers,
ϕint , correlates with the effectiveness of grain selection. The higher ϕint , the stronger the grain
selection. The µ-Helix parameter setting forces the solidification paths along a µm-sized helix
over the course of multiple layers.
5. The grain selection mechanisms leading to an SX are two-fold. As G deviates only slightly at
the bottom of each melt pool, competitive growth between the grains based on their primary
dendritic orientation is triggered, yielding a columnar grain structure. The increasing deviation
of G from the BD closer to the layer interface leads to grain selection based on the secondary
dendritic orientation. This mechanism is not yet fully understood and still under investigation.

Author Contributions: Conceptualization, M.R.G. and C.K.; methodology, M.R.G., A.M.R. and C.K.; software,
A.M.R.; validation, M.R.G., A.M.R. and C.K.; formal analysis, M.R.G., A.M.R. and C.K.; investigation, M.R.G.;
resources, C.K.; data curation, A.M.R.; writing—original draft preparation, M.R.G.; writing—review and editing,
M.R.G. and C.K.; visualization, M.R.G., A.M.R. and C.K.; supervision, C.K.; project administration, C.K.; funding
acquisition, C.K. All authors have read and agreed to the published version of the manuscript.

157
Metals 2020, 10, 313

Funding: This research was funded by the Deutsche Forschungsgemeinschaft (DFG) through the Collaborative
Research Center SFB/TR 103, Project B2.
Conflicts of Interest: The authors declare no conflicts of interest. The funders had no role in the design of the
study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, or in the decision to
publish the results.

References
1. Körner, C. Additive manufacturing of metallic components by selective electron beam melting—A review.
Int. Mater. Rev. 2016, 61, 361–377. [CrossRef]
2. Strondl, A.; Palm, M.; Gnauk, J.; Frommeyer, G. Microstructure and mechanical properties of nickel based
superalloy IN718 produced by rapid prototyping with electron beam melting (EBM). Mater. Sci. Technol.
2011, 27, 876–883. [CrossRef]
3. Helmer, H.E.; Hartmann, N.; Körner, C.; Singer, R.F. Relation Between Processing Strategy, Grain Structure and
Mechanical Properties in Superalloy Inconel 718 Processed by Selective Electron Beam Melting. In Proceedings
of the DDMC 2014, Fraunhofer Direct Digital Manufacturing Conference, Berlin, Germany, 12–13 March 2014.
4. Sun, S.-H.; Koizumi, Y.; Saito, T.; Yamanaka, K.; Li, Y.-P.; Cui, Y.; Chiba, A. Electron beam additive
manufacturing of Inconel 718 alloy rods: Impact of build direction on microstructure and high-temperature
tensile properties. Addit. Manuf. 2018, 23, 457–470. [CrossRef]
5. Strondl, A.; Fischer, R.; Frommeyer, G.; Schneider, A. Investigations of MX and γ′ /γ′′ precipitates in the
nickel-based superalloy 718 produced by electron beam melting. Mater. Sci. Eng. A 2008, 480, 138–147.
[CrossRef]
6. Al-Bermani, S.S.; Blackmore, M.L.; Zhang, W.; Todd, I. The Origin of Microstructural Diversity, Texture,
and Mechanical Properties in Electron Beam Melted Ti-6Al-4V. MMTA 2010, 41, 3422–3434. [CrossRef]
7. Antonysamy, A.A.; Meyer, J.; Prangnell, P.B. Effect of build geometry on the β-grain structure and texture
in additive manufacture of Ti6Al4V by selective electron beam melting. Mater. Charact. 2013, 84, 153–168.
[CrossRef]
8. Helmer, H.; Bauereiß, A.; Singer, R.F.; Körner, C. Grain structure evolution in Inconel 718 during selective
electron beam melting. Mater. Sci. Eng. A 2016, 668, 180–187. [CrossRef]
9. Raghavan, N.; Dehoff, R.; Pannala, S.; Simunovic, S.; Kirka, M.; Turner, J.; Carlson, N.; Babu, S.S. Numerical
modeling of heat-transfer and the influence of process parameters on tailoring the grain morphology of
IN718 in electron beam additive manufacturing. Acta Mater. 2016, 112, 303–314. [CrossRef]
10. Kirka, M.M.; Lee, Y.; Greeley, D.A.; Okello, A.; Goin, M.J.; Pearce, M.T.; Dehoff, R.R. Strategy for Texture
Management in Metals Additive Manufacturing. JOM 2017, 69, 523–531. [CrossRef]
11. Ramsperger, M.; Carolin, K. Selective Electron Beam Melting Of The Single Crystalline Nickel-Base Superalloy
Cmsx-4® : From Columnar Grains To A Single Crystal. In Superalloys 2016; John Wiley & Sons: Hoboken,
NJ, USA, 2016.
12. Chauvet, E.; Tassin, C.; Blandin, J.-J.; Dendievel, R.; Martin, G. Producing Ni-base superalloys single crystal
by selective electron beam melting. Scr. Mater. 2018, 152, 15–19. [CrossRef]
13. Mainprice, D.; Bachmann, F.; Hielscher, R.; Schaeben, H. Descriptive tools for the analysis of texture projects
with large datasets using MTEX: Strength, symmetry and components. Geol. Soc. Lond. Spec. Publ. 2014,
409, SP409. [CrossRef]
14. Markl, M.; Rausch, A.M.; Küng, V.E.; Körner, C. SAMPLE: A Software Suite to Predict Consolidation and
Microstructure for Powder Bed Fusion Additive Manufacturing. Adv. Eng. Mater. 2019, 1901270. [CrossRef]
15. Pottlacher, G.; Hosaeus, H.; Kaschnitz, E.; Seifter, A. Thermophysical properties of solid and liquid Inconel
718 Alloy *. Scand. J. Metall. 2002, 31, 161–168. [CrossRef]
16. Mills, K.C. Recommended Values of Thermophysical Properties for Selected Commercial Alloys; Woodhead:
Cambridge, UK, 2002.
17. Mills, K.C.; Youssef, Y.M.; Li, Z.; Su, Y. Calculation of Thermophysical Properties of Ni-based Superalloys.
ISIJ Int. 2006, 46, 623–632. [CrossRef]
18. Walton, D.; Chalmers, B. The origin of the preferred orientation in the columnar zone of ingots. Trans. Metall.
Soc. AIME 1959, 215, 447–457.

158
Metals 2020, 10, 313

19. Harald, E.H. Additive Fertigung durch Selektives Elektronenstrahlschmelzen der Nickelbasis
Superlegierung IN718: Prozessfenster, Mikrostruktur und Mechanische Eigenschaften. Ph.D. Thesis,
Friedrich-Alexander-Universität Erlangen-Nürnberg, Erlangen, Germany, 2017.
20. Dehoff, R.R.; Kirka, M.M.; List, F.A.; Unocic, K.A.; Sames, W.J. Crystallographic texture engineering through
novel melt strategies via electron beam melting: Inconel 718. Mater. Sci. Technol. 2015, 31, 939–944. [CrossRef]
21. Koepf, J.A.; Gotterbarm, M.R.; Markl, M.; Körner, C. 3D multi-layer grain structure simulation of powder
bed fusion additive manufacturing. Acta Materialia 2018, 152, 119–126. [CrossRef]
22. Dai, H.J.; D’Souza, N.; Dong, H.B. Grain Selection in Spiral Selectors During Investment Casting of
Single-Crystal Turbine Blades: Part I. Experimental Investigation. Metall. Mater. Trans. A 2011, 42, 3430–3438.
[CrossRef]
23. Dai, H.J.; Dong, H.B.; D’Souza, N.; Gebelin, J.-C.; Reed, R.C. Grain Selection in Spiral Selectors During
Investment Casting of Single-Crystal Components: Part II. Numerical Modeling. Metall. Mater. Trans. A
2011, 42, 3439–3446. [CrossRef]
24. Rausch, A.M.; Gotterbarm, M.R.; Markl, M.; Körner, C. Nucleation Mechanism in Powder Bed Fusion Additive
Manufacturing; 2020; Manuscript in preparation.

© 2020 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).

159
 metals
Article
Animal Origin Bioactive Hydroxyapatite Thin Films
Synthesized by RF-Magnetron Sputtering on 3D
Printed Cranial Implants
Diana Chioibasu 1,2 , Liviu Duta 1 , Gianina Popescu-Pelin 1 , Nicoleta Popa 3 , Nichita Milodin 3 ,
Stefana Iosub 1,4 , Liliana Marinela Balescu 5 , Aurelian Catalin Galca 5 , Adrian Claudiu Popa 5,6 ,
Faik N. Oktar 7,8 , George E. Stan 5, * and Andrei C. Popescu 1, *
1 National Institute for Lasers, Plasma and Radiation Physics, RO-077125 Magurele-Ilfov, Romania;
[email protected] (D.C.); [email protected] (L.D.); [email protected] (G.P.-P.);
[email protected] (S.I.)
2 Department of Physics, Faculty of Applied Sciences, University Politehnica of Bucharest,
RO-060042 Bucharest, Romania
3 National Institute for Mechatronics & Measurement Technique, RO-021631 Bucharest, Romania;
[email protected] (N.P.); [email protected] (N.M.)
4 Department of Molecular Cell Biology, Institute of Biochemistry of the Romanian Academy,
RO-060031 Bucharest, Romania
5 National Institute for Materials Physics, RO-077125 Magurele-Ilfov, Romania;
[email protected] (L.M.B.); [email protected] (A.C.G.); [email protected] (A.C.P.)
6 Army Centre for Medical Research, RO-010195 Bucharest, Romania
7 Center for Nanotechnology & Biomaterials Research, University of Marmara, Goztepe Campus,
34722 Istanbul, Turkey; [email protected]
8 Department of Bioengineering, Faculty of Engineering, University of Marmara, Goztepe Campus,
34722 Istanbul, Turkey
* Correspondence: [email protected] (G.E.S.); [email protected] (A.C.P.);
Tel.: +40-21-241-8128 (G.E.S.); +40-21-457-4550 (A.C.P.)




Received: 18 November 2019; Accepted: 9 December 2019; Published: 10 December 2019


Abstract: Ti6Al4V cranial prostheses in the form of patterned meshes were 3D printed by selective
laser melting in an argon environment; using a CO2 laser source and micron-sized Ti6Al4V powder
as the starting material. The size and shape of prostheses were chosen based on actual computer
tomography images of patient skull fractures supplied in the framework of a collaboration with
a neurosurgery clinic. After optimizations of scanning speed and laser parameters, the printed
material was defect-free (as shown by metallographic analyses) and chemically homogeneous, without
elemental segregation or depletion. The prostheses were coated by radio-frequency magnetron
sputtering (RF-MS) with a bioactive thin layer of hydroxyapatite using a bioceramic powder derived
from biogenic resources (Bio-HA). Initially amorphous, the films were converted to fully-crystalline
form by applying a post-deposition thermal-treatment at 500 ◦ C/1 h in air. The X-ray diffraction
structural investigations indicated the phase purity of the deposited films composed solely of a
hexagonal hydroxyapatite-like compound. On the other hand, the Fourier transform infrared
spectroscopic investigations revealed that the biological carbonatation of the bone mineral phase
was well-replicated in the case of crystallized Bio-HA RF-MS implant coatings. The in vitro acellular
assays, performed in both the fully inorganic Kokubo’s simulated body fluid and the biomimetic
organic–inorganic McCoy’s 5A cell culture medium up to 21 days, emphasized both the good resistance
to degradation and the biomineralization capacity of the films. Further in vitro tests conducted in
SaOs-2 osteoblast-like cells showed a positive proliferation rate on the Bio-HA RF-MS coating along
with a good adhesion developed on the biomaterial surface by elongated membrane protrusions.

Metals 2019, 9, 1332; doi:10.3390/met9121332 161 www.mdpi.com/journal/metals

Metals 2019, 9, 1332

Keywords: biological origin hydroxyapatite; bioactive layers; cranial mesh implants; selective laser
melting; 3D printing; radio-frequency magnetron sputtering

1. Introduction
Ti6Al4V is the most popular titanium alloy used in biomedical applications due to its high strength,
high fracture toughness, superior corrosion resistance, low density, excellent biocompatibility, and
favorable osseointegration [1–3]. Even if Ti6Al4V is considered as a highly biocompatible metallic
material, there have been reports of inflammatory reactions occurring around the prostheses upon
implantation [4–8]. In order to improve the biocompatibility of the metallic alloys, a bioactive material
can be deposited on its surface as a thin film, in order to increase the osseointegration and to ensure
the biomimetism of the implant [9–15]. Hydroxyapatite (HA), with the theoretical chemical formula
Ca10 (PO4 )6 (OH)2 , in its non-stoichiometric multi-cation and anion substituted form, represents the
main constituent of the mineral part of the bone. By the application of such a biomimetic coating, one
can stimulate the osteoblasts to proliferate and to generate osseous matrix, which will culminate with
the new bone formation. As stated, biological apatite (further denoted Bio-HA) is similar, but not
chemically and structurally identical with the pure synthetic HA. Bio-HA can enclose a series of trace
elements (e.g., Na, Mg, Sr, Zn, F), as well as substituting functional groups such as carbonate (CO3 2− ),
silicate (SiO4 3− ), and/or hydrogen phosphate (HPO4 − ) [16–19]. Thereby, an apatite compound similar
to the one produced in the bones of living mammals is very difficult, if not impossible, to replicate by
chemical synthesis. This is why the extraction of Bio-HA from animal bones could represent a viable
solution, not only due to the intrinsic natural doping with ions which can promote specific biofunctional
traits, but also due to their high availability and reduced costs [17,20]. For biomedical research purposes,
bovine [21,22], ovine [23], or swine bones [24] are the most commonly used resources, but also fish [25]
and sea-shells [26], as well as more exotic sources such as camel [27] or shark [28] have been explored.
For depositing calcium phosphate-based coatings onto metallic implants, the industrial technique
of choice is plasma spray (PS), due to the deposition speed, large area coverage, and inexpensive
working atmosphere (i.e., ambient or argon) [29,30]. However, HA coatings produced using this
technique could contain residual decomposition phases because of high-processing temperatures,
having different dissolution speeds, and thereby an unpredictable biological behavior [31]. Pulsed
laser deposition (PLD) is another coating technique which proved reliable for the fabrication of
bioactive layers [6,17,32]. The PLD strength comes from its capability to congruently transfer from
target-to-substrate even materials with complex stoichiometry, but the biggest shortcoming is the
limitation to a very small deposition area of the order of few cm2 [32]. Radio-frequency magnetron
sputtering (RF-MS) was long-time considered a solid alternative to PS since it can produce (by the
control of deposition parameters) dense, pure, highly-adherent films on large area substrates (even
on ones with complex geometry when coupled with rotation-translation facilities) [33–35]. There are
reports in scientific literature on deposition of synthetic pure [7,12,34] or substituted HA [11,13,36]
coatings using RF-MS. However, to the best of our knowledge, no information has been reported yet
on the successful magnetron sputtering of Bio-HA films and consequently on their structural and
biofunctional properties.
Casting and forging are the conventional processing technologies used for implants mass
manufacturing. When customized prostheses with dimensions and complex geometries are in demand,
such technologies are not reliable because of the time, energy, material consumption, and costs [37].
As an alternative, laser-based additive manufacturing (AM) is a method that allows customized,
cost-effective, and rapid production of complex 3D medical parts [38,39].
Selective laser melting (SLM) is an AM process capable of producing metallic, ceramic, plastic,
or composite parts using layer-by-layer manufacturing [40–43]. 3D structures are generated from
a geometric CAD (computer aided design) file. The model is virtually sliced into 2D contour lines

162
Metals 2019, 9, 1332

and imported into the AM machine that builds the new part [44–47]. The energy source is a laser
beam which scans a selected area of a powder bed. The area scanned by the laser beam is molten and
it quickly solidifies. The new solid structure is covered by a powder layer with a leveling system,
and subsequently the laser scanner irradiates the next contour and thus, layer-by-layer, the part is
completed [48,49].
SLM has been used to manufacture hip, ankle, knee, tibia, maxillo-facial, or spinal prostheses
with intricate geometrical parts, based on medical imaging. The correlation between micro-structural
features and mechanical properties has been reported in the literature [37,50–53]. Fatigue strength
of AM components is the primary mechanism of failure, and for this reason many investigations
have been conducted in this area of research [54,55]. Lieverani et al. [56] reported the fabrication of
Co-Cr-Mo endoprosthetic ankle devices using SLM. They identified the optimal process parameters
for obtaining samples with maximum density and high mechanical strength.
We report in this study the manufacturing in two steps of a cranial prosthesis with bioactive
Bio-HA surface with dimensions corresponding to a cranial large defect of a real patient, obtained by
computer tomography. First, the prosthesis is generated by 3D printing using the SLM method, while
in a second step, a thin film is deposited by RF-MS from a target of biological apatite derived from
bovine bones. The focus of this study was to assess for the first time the feasibility of depositing by
RF-MS bioceramic coatings of biogenic origin onto SLM custom-fabricated prosthesis. In this respect,
morphological, compositional, structural, and biofunctional interrogations were conducted for both
the metallic part and the bioceramic coating.

2. Materials and Methods

2.1. Cranial Meshes

2.1.1. 3D Printing of Cranial Meshes

For the manufacturing of meshes, a Ti6Al4V powder with the particle size in the range of 10–30 µm
(Eos GmbH, Krailling, Germany) was used. The SLM machine was a model M270 (Eos GmbH, Krailling,
Germany).
The laser beam used for melting the metallic powder was generated by a CO2 laser source
(λ = 10.6 µm, continuous wave, Gaussian beam) connected to a scanner. The optimal laser parameters
recommended by the producer for SLM of titanium alloys are: 90 W laser power and 450 mm/s
scanning speed, and an under 4 bar argon atmosphere. The laser spot on the powder bed was of
~100 µm. For the manufacturing of a 3 mm thick cranial mesh prosthesis a number of 100 successive
layers were needed, corresponding to an individual layer thickness of 30 µm.
The cranial meshes were designed in the SolidWorks (Dassault Systems, Vélizy-Villacoublay,
France) graphical engineering software, and imported in the EOSPRINT proprietary software of the
SLM machine, which generated the movement of the scanner mirrors.
The prostheses were extracted from the Ti plate by electro-erosion cutting using a Robofil 6030
machine (Charmilles Technologies, Schaffhausen, Switzerland) with 0.25 mm thickness of the wire,
13 m/min wire consumption, and a cutting speed of 1 mm/min. Prostheses of 3 mm thickness were
produced by SLM, so that after cutting, the thickness of the mesh to be of ~2 mm.

2.1.2. Characterization of the 3D Printed Material

First, bulk prisms of 10 × 10 × 20 mm3 were 3D printed in view of metallographic characterization,
in the same experimental conditions as the meshes. The obtained samples were cut in slices using a
disk cutting machine, model Brillant 200 (ATM GmbH, Mammelzen, Germany). The slices were fixed
in Bakelite using a machine Opal 410 (ATM GmbH, Mammelzen, Germany) and polished with a Saphir
520 (ATM GmbH, Mammelzen, Germany) semiautomatic machine. The resulting mirror-polished

163
Metals 2019, 9, 1332

samples were etched with Kroll solution (water 92%, nitric acid 6%, hydrofluoric acid 2%) in order to
reveal the metallographic microstructure of the alloy after SLM.
The metallographic analysis was conducted with a BX51M (Olympus, Tokyo, Japan) optical
microscope and a scanning electron microscope (SEM) Quanta 450 (FEI Company, Hillsboro, OR, USA).
The compositional homogeneity of the prosthesis has been investigated by energy dispersive X-ray
spectroscopy (EDXS) measurements.
The micro-hardness of the printed material was evaluated by the Falcon 500 mechanical testing
machine (Innovatest, Maastricht, Netherlands) equipped with a Vickers indenter. Ten Vickers
indentations have been made on the surface of the specimens using a load of 0.5 kgf/mm2 . The reported
micro-hardness value represents the average of the ten independent values ± standard deviation.

2.2. Coating of the Prosthesis With a Bio-HA Thin Film

The final step of the manufacturing process was to coat the 3D printed prosthesis with a thin
ceramic layer of biological hydroxyapatite (Bio-HA) extracted from bovine bone for increasing the
bioactivity of the surface.

2.2.1. Bio-HA Extraction

The extraction of Bio-HA was performed by applying a previously established work
protocol [17,23,57], conducted in accordance with the European Regulation 722/2012 and ISO
22442-1:2015—Medical devices using animal tissues and their derivatives—Part 1: Application
of risk management. In brief, the bone marrow and the soft tissue residues were removed mechanically
from bovine femoral bodies. The femoral shafts were cut into small pieces and ultrasonicated with
distilled water. The cleaned parts were deproteinized by immersion for 14 days in an alkali water
solution (1% sodium hypochlorite). Next, they were washed with water and dried, and then submitted
to a calcination at 850 ◦ C for 4 h in air. In the end, the calcined (white-colored) bone specimens were
ball-milled into fine Bio-HA powders.

2.2.2. Deposition of Bio-HA Thin Films by RF-MS

Ti6Al4V cranial meshes manufactured by SLM were used as substrates together with
monocrystalline infrared transparent Si <111> wafers (Medapteh, Magurele, Romania). The later ones
were required to enable the structural evaluation of deposited films by Fourier transform infrared
(FTIR) spectroscopy in transmission mode.
The substrates were first degreased in acetone and further on cleaned in iso-propanol using an
ultrasonic bath and a dwell time of 15 min per step. In the end, they were fast-dried by argon gas
purging and mounted on a rotating stage of the deposition chamber of the UVN-75R1 (Vacma, Kazan,
Republic of Tatarstan, Russian Federation) RF-MS equipment.
The target (with the diameter of 110 mm) has been manufactured by mild-pressing the Bio-HA
powder at room-temperature (RT) in a specially designed Ti plate (crucible). Such type of targets are
preferred to the compacted ceramic disks (prone to cracking during prolonged sputtering processes),
as they provide not only consistency, but also reducing significantly the fabrication costs [58,59].
First, a base pressure of ~3 × 10−3 Pa was achieved in the working chamber, such as to ensure a
low contamination level and thus enable the fabrication of good purity films.
Prior to deposition, the substrate and the target were subjected individually to plasma cleaning
treatments. The substrates were cleaned in situ for 15 min by argon ion etching following the protocol
described in [60]. The target was pre-sputtered in the future deposition conditions for 30 min. This step
is essential since it can ensure the removal of contaminants adsorbed on the target surface, and at the
same time, it can allow the stabilization of the sputtering processes before the actual deposition [59,61].
The Bio-HA thin film deposition was performed at an argon pressure of 0.3 Pa, without intentional
substrate heating (the substrate reached a temperature of ~120 ◦ C owned to radiative plasma
bombardment processes only). A 1.78 MHz RF generator and an electrical power of ~100 W

164
Metals 2019, 9, 1332

were used. The target-to-substrate distance was set at 35 mm. Based on the deposition rate of
~3.7 nm/min (previously estimated by spectroscopic ellipsometry (SE) measurements), Bio-HA films
of ~600 nm thickness were deposited. In order to crystallize the initially amorphous as-deposited
Bio-HA films, without inducing a strong oxidation of the Ti6Al4V implant substrate, a post-deposition
thermal-treatment was applied at 500 ◦ C/1 h in air.

2.3. Characterization of Biological HA Thin Films

2.3.1. Physico–Chemical Characterizations

Since the RF-MS technology produces smooth layers [33,62] and the SEM method does not have
enough contrast to distinguish the fine topological details, the morphology of Bio-HA films deposited
onto mirror-polished substrates could be better revealed by atomic force microscopy (AFM) analysis.
An NTEGRA Probe NanoLaboratory System (NT-MDT, Moscow, Russian Federation) equipped with
an NSG01 cantilever with 10 nm tip was used. The AFM images were recorded in non-contact mode
on areas of 25 × 25, 10 × 10, 5 × 5, and 2 × 2 µm2 .
The comparative composition of source material and Bio-HA RF-MS deposited film was evaluated
by EDXS using an EDAX (Ametek, Berwyn, PA, USA) equipment with a Si-Li detector, operated at
20 kV acceleration voltage. The EDXS measurements were performed in at least four regions with an
area of ~240 × 240 µm2 , randomly chosen on the sample surface. For the calibration of Ca/P atomic ratio,
a National Institute of Standards and Technology standard reference sample of HA (i.e., NIST-SRM
2910b) was measured as well. Arithmetic means and standard deviations (SD) have been inferred, and
statistical analyses were carried out using the unpaired two-tailed Student’s t-test, with the differences
being considered significant when p < 0.01.
The evaluation of the crystalline status of source powder and Bio-HA films was performed by
X-ray diffraction (XRD), in the angular range 2θ = 9–54◦ , using a step of 0.04◦ . The source material
and the heat-treated Bio-HA film were investigated comparatively using symmetrical geometry
(Bragg–Brentano) XRD measurements, using a D8 advance diffractometer (Bruker, Karlsruhe, Germany)
with CuKα1 radiation. In addition, the films were measured, before and after the post-deposition
thermal-treatment, also by grazing incidence XRD (GIXRD) at an incidence angle of 0.5◦ , using a
SmartLab 3 kW diffractometer (Rigaku, Tokyo, Japan), in order to maximize their diffracted signal.
The chemical structure of the source powder and deposited Bio-HA films, with a focus on the
short-range order and the transfer of functional groups specific to the bone mineral component, was
investigated by Fourier transform infrared (FTIR) spectroscopy, in transmission mode. A Spectrum BX
II (Perkin Elmer, Waltham, MA, USA) apparatus was used. The spectra were recorded in the wave
numbers range of 400–4000 cm−1 , at a resolution of 4 cm−1 , and represent the average of 32 individual
scans per sample.

2.3.2. In Vitro Tests in Simulated Physiological Solutions

An implant coating has to play a double role: (i) act as a buffer against the release of metallic ions
of the metallic substrate in the internal environment and (ii) promote osteoconductivity. In vitro tests
in synthetic physiological fluids were performed in order to evaluate the resistance to degradation of
the deposited coatings and to explore their biomineralization capability. The tests were carried out
following the indications contained in the ISO 23317:2014 protocol: “Implants for surgery—In vitro
evaluation for apatite-forming ability of implant material”. However, besides the fully inorganic
Kokubo’s simulated body fluid (SBF), recommended by the ISO standard, we have also used for these
tests the complex biomimetic inorganic–organic McCoy’s 5A culture medium supplemented with 15%
fetal bovine serum (FBS)—the same medium formulation used for the in vitro tests on cell cultures.
The immersed samples were kept at 37 ◦ C in a stabilized biology incubator in humid atmosphere (to
avoid the medium evaporation) under the accurate homeostatic conditions (5% CO2 ) up to 21 days
(we note that the ISO 23317:2014 does not provide recommendations for the testing atmosphere, and

165
Metals 2019, 9, 1332

the implied common use of atmospheric pressure seems faulty). After 7 and 21 days, the Bio-HA films
were extracted, gently washed with distilled water, and left to dry in a desiccator. Subsequently, they
were investigated by SE, AFM, and FTIR spectroscopy.
The SE measurements were performed using a spectroscopic ellipsometer (J.A. Woollam Co.,
Lincoln, NE, USA) equipped with a HS-190 monochromator and a goniometer that allows for automatic
acquisition of spectra at different angles of incidence. For Bio-HA films before and after immersion in
biological medium, the measurements were performed at 65◦ , 70◦ , and 75◦ incidence angles in the
spectral range of 1.3–3.5 eV. The Bio-HA material optical properties (refractive index dispersion) were
inferred using a Cauchy formula [63].

2.3.3. In Vitro Tests on Cell Cultures

SLM printed prism samples were cut into 10 × 10 mm2 coupons to serve as substrates for
in vitro cell biocompatibility tests. The SLM coupons were polished down to mirror level to exclude
any possible morphological incongruences between specimens, and their influence on cell behavior.
The Bio-HA coated samples were subjected to sterilization in water vapors at 121 ◦ C for 30 min using
an AES-8 autoclave (Raypa, Barcelona, Spain).
Experiments were performed with human osteosarcoma (SaOs-2) cells which were grown in
McCoy’s 5A medium (Gibco Thermo Fisher Scientific, Waltham, MA, USA) supplemented with
15% FBS (Gibco Thermo Fisher Scientific, Waltham, MA, USA), 50 U/mL penicillin and 50 mg/mL
streptomycin (Gibco Thermo Fisher Scientific, Waltham, MA, USA). Cells were seeded on biomaterials
at a density of 2000 cells/cm2 . All substrates were then kept in a humid atmosphere with 5% CO2
at 37 ◦ C for 1, 3, and 7 days, respectively. Borosilicate glass coverslips were used as experimental
standard control material.
Cell proliferation was assessed by using a CellTiter 96® AQueous one solution cell proliferation
assay (MTS) kit (Promega, Madison, WI, USA). For this, samples were cultured in triplicate for 1, 3,
and 7 days. At each time interval, samples were transferred to new wells and incubated at 37 ◦ C for
1 h 30 min with fresh medium containing the MTS reagent. The absorbance values were recorded at
450 nm using a LB 913 Apollo 11 spectrophotometer (Berthold Technologies, Bad Wildbad, Germany).
The final data was represented as the average of the measured optical density upon background
subtraction. Statistical analysis was performed by using GraphPad Prism 6 (GraphPad, San Diego, CA,
USA) in which an unpaired, two-tailed, Student’s t-test was calculated. Differences were considered
statistically significant for p < 0.05.
Cell adhesion was examined by immunofluorescence microscopy. After 24 and 72 h of culture,
SaOs-2 cells were fixed for 15 min with 4% paraformaldehyde at RT and stored in phosphate buffered
saline solution (PBS) at 4 ◦ C prior to labelling. Fixed cells were then permeabilized for 3 min with 0.2%
TritonX-100 and blocked for 1 h in 0.5% bovine serum albumin (BSA). To visualize the actin filaments,
cells were labelled with 1:100 diluted Alexa Fluor 488 conjugated Phalloidin (Cell Signaling Technology,
Danvers, MA, USA). Cells were subsequently treated with 1 µg/mL Hoechst (Cell Signaling Technology,
Danvers, MA, USA) to stain cell nuclei. Upon each incubation, samples were washed three times with
PBS. Finally, representative images were acquired on each substrate by using a Leica DM 4000 B LED
fluorescence microscope equipped with a DFC 450 C camera (Leica Microsystems GmbH, Wetzlar,
Germany) and the appropriate filters.

3. Results

3.1. Printing of Cranial Mesh Prostheses and Their Structural and Chemical Characterization
A photograph of a cranial mesh grown by SLM is presented in Figure 1. The pattern design
is original, being devised after studying the morphology of several commercial cranial prostheses.
Structures of 50 × 50 × 3 mm3 with the pattern depicted in Figure 1b were built layer-by-layer on a

166
Metals 2019, 9, 1332

50 mm thick Ti plate by laser scanning. Every single contour was ~30 µm tall and 100 layers were
needed to obtain a final product with the desired height.

Figure 1. (a) Photograph of a Ti6Al4V cranial mesh manufactured by SLM (Selective laser melting)
based on a (b) three-dimensional (3D) CAD (computer aided design) model generated in the SolidWorks
Professional software, version 2013 (Dassault Systems, Vélizy-Villacoublay, France).

After polishing and attacking with a metallographic reagent, the grain structure was exposed and
it was studied by optical and SEM microscopies (Figure S1 of Supplemental Information). Optical
and SEM micrographs, characteristic to the printed SLM printed Ti6Al4V sample are presented in
Figure S1a,b, respectively. Figure S1a displays a martensitic acicular structure that developed in islands
in the α phase. More specifically, it is an α‘-type martensite that crystallizes in the hexagonal system
upon the fast cooling of biphasic titanium alloys (α + β) such as Ti6Al4V. The acicular plates displayed
a “clustered” morphology, consisting of structural units with needles exhibiting a certain parallelism.
This distribution includes the microstructure of the printed material in the cryptocrystalline martensite
category. In general, α′ martensite nucleates at the boundaries of the prior β grains and spreads within
their parent β grains, which explains the different orientation of the α’ needles. SEM investigations
allowed for a better visualization of the grains, the parallel distribution of lamellar martensite was
more obvious, with varying lengths of the grains dependent on the micro-regions from which they
were part of (Figure S1b). There are structural units with grains whose average lengths are greater than
100 µm, which correspond to primary α’ martensite, but also units with finer needles, with lengths of
about 15–20 µm, corresponding to secondary α’ phase. These later grains were perpendicular to the
primary α’ ones.
The hardness tests performed in 10 randomly chosen points of the SLM test sample revealed
similar hardness values, which represent an indirect proof of its structural homogeneity. The average
hardness of the SLM prints was 391 ± 5 HV, similar to the casted Ti6Al4V alloy [64].
Subsequently, the same sample was analyzed by EDXS. An EDXS characteristic spectrum of a
Ti6Al4V 3D printed sample is shown in Figure S2a (of Supplemental Information). The elemental
composition was found to be ~90.2 wt% Ti, ~5.6 wt% Al, and ~4.2 wt% V, thus, congruent to the one of
the Ti6Al4V starting powder.
Further, the EDXS mapping analysis (Figure S2b–e) attested the presence of Ti, Al, and V, the
components of the studied alloy (Figure S2b), and offered qualitative information on the uniform
distribution of elements (Figure S2c–e). The brightness is directly proportional to the presence of the
element being tracked. Taking into account this principle, it was confirmed that all the components
were uniformly distributed over the studied area, with no trace of elemental segregation or depletion.

167
Metals 2019, 9, 1332

3.2. Functionalization of the Cranial Mesh With a Bioceramic Layer

Illustrative images of a Ti6Al4V cranial mesh, before and after biofunctionalization with a Bio-HA
thin film by RF-MS, are presented in Figure 2.

Figure 2. (a) Uncoated and (b) Bio-HA (derived from biological hydroxyapatite) sputtered cranial
mesh of Ti6Al4V fabricated by SLM.

3.2.1. Physico–Chemical Characterization of the Bio-HA Functional Layer

AFM micrographs, collected at different magnifications, are depicted in Figure 3. They highlighted
that the crystallized Bio-HA RF-MS film consisted of a compact matrix of polyhedral grains with
diameters in the range ~110–230 nm. An average root mean square roughness (Rrms ) of ~15 nm was
inferred, irrespective of the scanned microscopic field area, which advocates for the good uniformity of
the deposited film.

Figure 3. Characteristic AFM (atomic force microscopy) images of the of Bio-HA films surface acquired
on scanning areas of: (a) 25 × 25; (b) 10 × 10; (c) 5 × 5; and (d) 2 × 2 µm2 , respectively.

168
Metals 2019, 9, 1332

Next, the composition of the Bio-HA sputtered film and parent target were determined by EDXS
and compared. In addition, the Ca, P, and O, also small contents of Na (~3 at%) and Mg (~2 at%) were
detected. Such specific trace elements present in the composition of bone apatite, are known to play
important roles in bone metabolism and health [65,66], and thereby, their successful transfer by RF-MS
into the deposited layers can be emphasized. The mean elemental concentration ± standard deviations
obtained for each of these constituent elements (except oxygen, light element for which the EDXS
quantification yields characteristically large errors) of the Bio-HA target and film are shown in Figure 4.
Significant compositional differences (p < 0.01) were found only in the case of P and Mg. The Ca/P
molar ratios for the source material and the Bio-HA film were of 1.63 ± 0.02 and 1.70 ± 0.01, respectively.
However, in the case of cation substituted HAs, such as those derived from biogenic resources, the
contribution of natural dopants (e.g., Na, Mg) should not be dismissed. In this case, a (Ca + Na + Mg)/P
molar ratio could provide further information on the features of the ceramic compounds. The (Ca +
Na + Mg)/P molar ratios of the Bio-HA target and film were of 1.76 ± 0.01 and 1.85 ± 0.01, respectively
(thus, situated close to the Ca/P ratio of 1.67 of stoichiometric HA, Ca10 (PO4 )6 OH2 ). The higher (Ca +
Na + Mg)/P ratios (than 1.67), obtained in the case of both target and sputtered film, are suggesting a
deficit of orthophosphate groups, most probably due to their substitution with carbonate functional
groups (specific to Bio-HAs). A slight increase of the (Ca + Na + Mg)/P was recorded in the case of the
RF-MS film with respect to the parent target. This is connected with the P evaporation phenomena
taking place during sputtering deposition [34,59].

Figure 4. Elemental composition of the Bio-HA film produced by RF-MS (radio-frequency magnetron
sputtering) with respect to the source target material. The Ca/P and (Ca + Na + Mg)/P molar ratios of
the Bio-HA target and film.

XRD patterns were recorded in symmetric geometry (Figure 5a,b), for both Bio-HA target and
crystallized Bio-HA film, to accommodate an equivalent structural comparison and to survey the
presence of preferred crystallite orientations (if any). It has been revealed that the HA powder
obtained from the bovine cortical bone was monophasic, consisting of a randomly oriented hexagonal
hydroxyapatite compound (ICDD-PDF4: 00-009-0432) only. In the case of the thermal-treated (TT)
Bio-HA film, besides the intense diffraction peaks of the Ti6Al4V substrate (crystallized in the
hexagonal system, ICCD-PDF4: 04-020-7055), only peaks of a well-defined phase of hexagonal HA
were evidenced. The increased intensity of the 002 peak of Bio-HA film with respect to the ICDD file
indicated that the Bio-HA crystallites elicited a preferred orientation along the c-axis, normal to the

169
Metals 2019, 9, 1332

substrate. The c-axis texturing is characteristic to sputtered films synthesized from materials of the
hexagonal system [34,36,60,62,67]. The average crystallite size determined based on the full width
at the half-maximum (FWHM) of (002) planes reflections was estimated by applying the Scherrer
equation [68]. The FWHM was corrected for instrumental breadth using a corundum NIST-SRM
1976a sample. Similar average crystallite sizes of ~167 and ~139 nm were obtained in the case of
the source target material and crystalline Bio-HA film, respectively. This finding demonstrated the
capability of the chosen thermal treatment to yield excellent crystalline quality. Furthermore, the
efficiency of post-deposition thermal treatment performed in air at 500 ◦ C/1 h was highlighted by
GIXRD measurements (Figure 5c,d) which showed the complete conversion of the initial amorphous
as-sputtered film (see the halo centered at 2θ ≈ 30◦ ) into a completely crystallized Bio-HA structure.

Figure 5. XRD (X-ray diffraction) patterns recorded in (a,b) symmetric (Bragg–Brentano) and (b,d)
grazing incidence (α = 0.5◦ ) geometries in the case of (b) Bio-HA source material and (d) as-sputtered
(AS) and (a,c) thermal-treated (TT) Bio-HA film. For comparison, the ICDD-PDF4: 00-009-0432 reference
file of pure hexagonal hydroxyapatite is inserted on the bottom of the figures.

The short-range order of the Bio-HA magnetron sputtered film and the presence and type of
functional groups incorporated within its structure was surveyed by FTIR spectroscopy measurements
(Figure 6). The sharp and well-split IR absorption bands of orthophosphate groups recorded in the
case of the Bio-HA film (Figure 6a) testified for it its high crystallinity [69], in full agreement with the
XRD data. All the characteristic IR bands of HA were evidenced for the Bio-HA sputtered structure: ν4
bending (~565 and ~600 cm–1 ), ν1 symmetrical stretching (~962 cm−1 ), and ν3 asymmetric stretching
(~1032 and ~1088 cm–1 ) vibration modes of orthophosphate groups, and νL libration (~632 cm–1 ) and
νS stretching (~3753 cm–1 ) of structural hydroxyl units [26,36,69]. Only slight shifts and intensity
modification of the Bio-HA film bands (Figure 6a) with respect to the pure HA reference and Bio-HA
source powder (Figure 6b) were noticed. These are denoting minor structural alterations (in terms of
bond length and/or angle and short-range order), and are to be expected for a material deposited by
magnetron sputtering, thus, under non-equilibrium thermodynamic conditions. Furthermore, it can
be emphasized the successful incorporation of carbonate groups in the orthophosphate sites (B-type
carbonatation) of the Bio-HA film crystalline lattice, similarly to the source powder: ν2 symmetrical
(~875 cm−1 ) and ν3 asymmetrical (~1417 and ~1472 cm−1 ) stretching vibrations of (CO3 )2− units [69].
Such type of substitution is also characteristic to the mineral phase of the human bone [36,70].

170
Metals 2019, 9, 1332

Figure 6. Comparative FTIR (Fourier transform infrared) spectra of (a) Bio-HA crystallized film and (b)
pure commercial HA powder (Acros Organics, Geel, Belgium) and Bio-HA source material.

3.2.2. In Vitro Tests in Simulated Physiological Solutions

The first step in the evaluation of in vitro behavior of Bio-HA coatings was to immerse them
in both a fully inorganic SBF solution (as the ISO 23317/2014 standard recommends), as well as in
the McCoy’s 5A cell culture medium supplemented with 15% FBS (to be used in the in vitro tests
on cell cultures). It is our belief that the increased degree of biomimicry of the latter could foster a
more truthful interrogation of the material degradation and bioactivity performance. After 7 days of
immersion, the films thickness decreased by ~6.5% when immersed in SBF and by ~4% in the case of
the tests carried out in the FBS supplemented McCoy’s 5A culture medium. After 21 days of immersion
a decrease of Bio-HA film thickness with ~14% and ~5% was recorded in SBF and FBS supplemented
McCoy’s 5A, respectively.
The AFM investigations revealed that radical morphological changes occurred on the surface of
Bio-HA sputtered film immersed in SBF and FBS supplemented McCoy’s 5A simulated physiological
media (Figure 7). After 7 days of immersion in SBF on the surface of Bio-HA films, initially composed
of a uniform bed of nano-grains (Figure 3c), was signaled the formation of spheroid conglomerates
with a mean diameter of ~1–1.5 µm (Figure 7a). Such type of topography is specific to biomimetic HA
layers formed in SBF solution [71,72] and demonstrates (according to ISO 23317:2014) the bioactivity of
the Bio-HA sputtered film. For comparison, in Figure 7b a SEM image of a fully-developed biomimetic
nano-crystalline HA layer is given, formed in 30 days in SBF on the surface of a bioactive silicate-based
glass film [72]. The higher magnification AFM image (Figure 7c) evidenced that the micron-sized
spheroid aggregates are constituted of randomly-dispersed small round particles (with sizes in the
range of ~35–50 nm). A Rrms value of ~4 nm was inferred. After 21 days of immersion in SBF,
the AFM analyses (Figure 7e,g) indicated that the formation of the biomimetic calcium phosphate
layer progressed, having at this time point a denser morphology (Figure 7g) and an overall lower
Rrms ≈ 1 nm.

171
Metals 2019, 9, 1332

Figure 7. Characteristic AFM images of Bio-HA sputtered films tested in vitro in (a,b,e,f) SBF and
(c,d,g,h) FBS supplemented McCoy’s 5A simulated physiological solutions, for (a–d) 7 and (e–f) 21
days, acquired on scanning areas of: (a,b,e,f) 10 × 10 and (c,d,g,h) 2 × 2 µm2 , respectively. (b’) SEM
images of a fully developed biomimetic nano-crystalline HA layer formed in 30 days in the SBF medium.
Figure 7b’ is adapted after Figure 2a from Reference 72, with permission from Springer, 2019.

In the case of tests performed in FBS supplemented McCoy’s 5A solution, the biomineralization
processes seem to take place at a slower pace. After 7 days of immersion the general appearance of the
surface was found rather uneven. The presence of the spheroid aggregates is only hinted (Figure 7b),
having a smoother morphology with respect to the SBF experiments (Figure 7a). On top of this covering
blanket, smaller grains (~0.2–0.5 µm), randomly distributed, were revealed. Consequently, a larger
Rrms value of ~13 nm was inferred. After 21 days of immersion in the FBS supplemented McCoy’s 5A
solution, the surface of the samples (Figure 7f,h) closely resembled the one observed in the case of films
tested for 7 days in SBF (Figure 7a,c), further suggesting that biomineralization processes are slower
in the FBS supplemented McCoy’s 5A solution with respect to the ones occurring in SBF. Kindred
observations were recently reported by Popa et al. [59], Vladescu et al. [11] and Vranceanu et al. [73]
which showed that the (i) biomineralization processes (i.e., formation and structuring of biomimetic
HA layers) takes place at a lower rate [59] and (ii) the degradation is significantly reduced [11,73] in
media with a complex organic–inorganic composition (such as in the FBS-supplemented McCoy’s 5A
solution) with respect to those encountered in the inorganic SBF solution.
The FTIR comparative spectra of the Bio-HA films after immersion for 7 and 21 days in SBF and
FBS supplemented McCoy’s 5A media are presented in Figure 8. A strong diminution of carbonate
bands intensity is noticed even after seven days, with the allure and intensity of the orthophosphate and
hydroxyl bands basically unaltered. The decrease of the carbonate content of the Bio-HA films could

172
Metals 2019, 9, 1332

be attributed to the weaker Ca–CO3 bonds as compared to the Ca–PO4 ones [74], which makes them
more susceptible to be cleaved and released during the ion exchange processes with the surrounding
medium [71]. No other remarkable structural changes have been revealed by FTIR measurements
(Figure 8) up to 21 days of immersion, which suggests that the modification of the film surface revealed
by AFM (Figure 7) is only superficial. However, one should note that the phase discrimination
between the top biomimetic HA layer and the Bio-HA sputtered film underneath is impeded by their
structural–chemical similarity (i.e., both being nano-structured and having akin compositions).

Figure 8. Comparative FTIR spectra of the Bio-HA sputtered film before and after in vitro testing for 7
and 21 days in SBF (simulated body fluid) and FBS (fetal bovine serum) supplemented McCoy’s 5A
simulated physiological solutions.

Overall, the results suggest a reduced rate of degradation accompanied by a good biomineralization
capacity of the Bio-HA films, with the loss of mass being compensated to a certain extent by growth of
new calcium phosphate layers in contact with the simulated physiological solutions.

3.2.3. In Vitro Cytocompatibility Studies

To determine the effect of Bio-HA coating on cell viability and proliferation, we have carried
out an MTS test at 1, 3, and 7 days after cell seeding. As a control, a borosilicate glass coverslip was
used, which is a cell culture standard [75]. The results are represented in Figure 9 and they show
an enhanced osteoblasts proliferation on the control up to 72 h. However, after 168 h, the Bio-HA
coated substrate was found to encourage cells expansion, as indicated by a significant increase in MTS
absorbance value. This result suggests a slower proliferation dynamic on Bio-HA at early time points,
which is compensated after cells reach semi-confluency.
The adhesion of SaOs-2 cells on the Bio-HA film and the control surface has been investigated by
fluorescence microscopy (Figure 10). The actin filaments were labelled in green to study the cytoskeleton
organization, while the cell nuclei were represented in blue. As it can be seen from Figure 10a,b, after
one day of culture, the cells have successfully attached on both substrates. However, in the case of
the Bio-HA coating (Figure 10a), cells have extended their membrane protrusions and changed their
morphology to a more elongated phenotype. This difference in the cytoskeleton structure is more
pronounced after three days of culture (Figure 10c,d). Cells grown on the control material (Figure 10d)
elicit a more spread cell body compared to those on the Bio-HA substrate where they become rather
elongated with multiple developed filipodia (Figure 10c). However, taking into consideration the

173
Metals 2019, 9, 1332

increased cell number detected after 7 days by MTS (Figure 9) on the Bio-HA sputtered surface, we can
conclude that this biomaterial is compatible with bone cell adhesion and expansion, which are key
early steps important for osseointegration.

Figure 9. SaOs-2 cells proliferation on Bio-HA sputtered film and control substrate, after 1, 3, and 7
days of culture (*** p < 0.001; **** p < 0.0001).

Figure 10. Immunofluorescence microscopy images of SaOs-2 cells grown on the surface of the Bio-HA
coated 3D printed Ti6Al4V substrates (a,c) and control substrate (b,d), after one day (a,b) and three
days (c,d) of seeding. The actin filaments are stained in green and the cell nuclei are labeled in blue.
Scale bar = 200 µm.

174
Metals 2019, 9, 1332

4. Discussion
3D printing is a technique that resonates with medicine. The prospect of custom metal implants
that can be produced rapidly for specific bone fractures is highly appealing. In general, metal printing
techniques are not cheap and neither is prosthesis manufacturing. While 3D printing is not envisaged
for mass production due to its high costs, it is an excellent option for manufacturing prototypes and
complex shape items that cannot be obtained by conventional casting. 3D printed metal implants fall
into this category, as they can be patient specific, fabricated in a low number for targeted needs and can
support the high manufacturing cost. Among laser metal printing techniques, SLM and laser melting
deposition (LMD) are the main options. In the case of cranial meshes, LMD is out of discussion, as it
lacks the resolution for producing lines with submillimeter width. With the LMD experimental setup
in our laboratory, we have not succeeded to produce lines thinner than 2.5 mm. This width increases
in the case of multiple layer patterns, as material flows during deposition. In the case of SLM, this
problem was non-existent, the minimum width of obtained lines being of ~200 µm, thus, allowing to
obtain even cranial prostheses with intricate patterns.
However, one pending drawback of titanium-based implants, in spite of their excellent
biocompatibility and mechanical performance, is their slow osseointegration. One solution to
tackle this downside is the application of coatings of bioactive ceramics [34,76], an ever-growing
and dynamic field of research if taking into account the recent statistics on yearly distribution of
kindred scientific articles published in Reference 76. For this purpose, radio-frequency magnetron
sputtering was selected as the deposition method of choice, due to its ability to generate high purity,
dense, and adherent coatings on large area substrates (dependent only on the cathode gun size),
making it scale-up and mass production ready. This study focused on sputtered hydroxyapatite
films derived from biogenic sources (i.e., cortical bovine bones), which have both cost-efficient and
biofunctionality valances. On the one hand, repurposing highly-abundant waste materials (such
as animal bones, resulting in large quantities from the food industry) represents an inexpensive,
sustainable, and environmentally-preferred alternative. On the other hand, biological apatite is
substituted with low contents of cations (e.g., Na+ , Mg2+ ) and anions (e.g., CO3 2– , F– , SiO4 4– ), each
with specific biofunctional roles [17,18,65,66,74,76–78]. Such trace elements can be directly responsible
for the modifications in crystallinity, degradation speed, biomineralization capacity, or mechanical
performance of apatite [18,74,76].
Thereby, the current study is congruent with the current efforts taking place worldwide to delineate
patient-customized implants capable to warrant a rapid osseointegration process. Furthermore, the
importance of this study stems also from being the first attempt to assess RF-MS technique ability
(to the best of our knowledge) to transfer biological apatite compounds in the form of thin films.
The physical–chemical analysis results showed great promise, with the composition (presenting only
slight deviations, to be expected in the case of a physical vapor deposition technique such as RF-MS)
and structure (similar crystallite size, conservation of the B-type carbonatation) of the source biogenic
apatite material being well reproduced into the crystallized sputtered films. The c-axis preferential
orientation of the Bio-HA sputtered films could constitute a supplemental attribute to be further
explored, since several studies have stressed the superiority of such textured structured with respect to
the randomly oriented ones in terms of chemical stability in physiological environments [79], wear
resistance [80], hardness and Young modulus [81], and bioactivity [81].
The in vitro degradation/bioactivity tests performed in the complex organic–inorganic McCoy’s
5A FBS-supplemented medium (for a more rigorous evaluation), indicated on the one part the stability
of Bio-HA film (a thickness decrease of only ~5% was recorded after three weeks of immersion) and the
good biomineralization capacity highlighted by the formation of the characteristic spherulitic deposits
of biomimetic calcium phosphates. The bone bonding mechanism of dense hydroxyapatite constructs
(here including also magnetron sputtered films) is considered to consist of five consecutive reaction
stages: (i) slight decrease of homeostatic pH at the interface between HA—biological environment;
(ii) dissolution/precipitation processes culminating with the formation of the biomimetic carbonated HA;

175
Metals 2019, 9, 1332

(iii) production of extracellular matrix by collagen and adhesive proteins; (iv) concurrent mineralization
of collagen fibrils and incorporation of carbonated HA within the new bone remodeling process;
and (v) interlocking and strengthening of host bone— HA interface by mineralized collagen [82,83].
The first two stages can be evaluated in vitro in media with ion concentrations equivalent to those
of human blood plasma [59,84], and currently, it is generally viewed that the in vitro capacity of
a material to generate the formation of a biomimetic layer on its surface is a predictor of in vivo
bone-bonding ability [84]. The partial dissolution process (in vivo mediated by extracellular fluids
and/or phagocytosis by osteoclasts) of HA leads to a local concentration increase of Ca2+ and PO4 3−
ions which will upsurge even more the saturation of the micro-environment (already saturated with
respect to calcium and phosphate) and trigger the nucleation and precipitation of apatitic crystals,
which will incorporate in time carbonate, hydroxyl, and various cations in its further crystallization and
structuring process [85,86]. Thereby, a bioactive material will always need to dissolve slightly in order
to induce the formation of biological apatite which will facilitate the chemical bond with the bone [87].
A too fast or extreme degradation could lead to the loss of the osteogenic coating before fulfilling
its role. However, in our case, after 21 days of immersion in the simulated body media solutions
Bio-HA film experienced only a minor thickness reduction (i.e., of ~14% and 5%, in SBF and SBF and
FBS-supplemented McCoy’s 5A, respectively). The formation of biomimetic calcium phosphates layers
(whose nucleation already started at 7 days, and fully developed at 21 days), shown for the Bio-HA
RF-MS film, in both SBF and FBS-supplemented McCoy’s 5A, already started to compensate for any
further implant coating mass loss, and will hinder its further degradation. Thereby, it is expected for
the Bio-HA films to preserve one of its designed roles (i.e., buffer against the release of metallic ions of
the metallic substrate in the internal environment) until the bone regeneration process (typically taking
4–6 weeks) is complete [88].
The biomineralization processes were suggested to be slower in the medium with increased
biomimicry with respect to purely inorganic SBF solution. This could be related to the unnatural high
pH (i.e., ~8) attained typically by the SBF solution with respect to the FBS-supplemented McCoy’s 5A
(which had a constant homeostatic pH of 7.3–7.4 throughout the testing period) and/or to the adsorption
of proteins from the medium [59] on the surface of the Bio-HA film, forming a capping layer which
slightly retards the biomineralization processes. The development at a slower pace of HA in complex
organic–inorganic testing media could be also connected with (i) the inhibitory effect of amino-acids
which are known to chelate Ca2+ and PO4 3− ions or bind to nuclei of calcium phosphate [89] and (ii) the
proficiency of testing medium proteins to increase the free energy of nucleation and thereby, to reduce
the rate of calcium phosphate nucleation by decreasing the supersaturation level [90]. However, since
there is no interaction of an implant with purely inorganic medium such as SBF, it is our belief that
only tests performed in solutions with an increased biomimicry degree could provide accurate gauges
of their real in situ performances.
Furthermore, the cytocompatibility tests indicated that besides their bioactive behavior, the films
were also non-toxic and stimulated the proliferation of osteoblast-like cells. Roughness was long
advertised to play an important role on the biological response of implants [91,92]. Since the Bio-HA
sputtered films were rather smooth (Rrms ≈ 15 nm) and uniform, the in vitro biological response
(i.e., bioactivity, cell shape modifications, and their accelerated proliferation rate) could be associated
prominently to the chemical and structural nature of the biological HA coatings.
Overall the physico–chemical properties and preliminary biological behavior of the sputtered
Bio-HA films hold promise, and thus encourage us to further and more insightfully assess their
potential from mechanical and biofunctional points of view.

5. Conclusions
3D cranial meshes of Ti6Al4V were successfully manufactured by SLM. The microstructure of
Ti6Al4V deposited by SLM was martensitic α’. The irradiation parameters were optimized in order to

176
Metals 2019, 9, 1332

obtain shapes without defects, such as pores or cracks and with homogeneous distribution of alloy
elements in their volume.
In a second technological step the implants produced by SLM were coated by radio-frequency
magnetron sputtering with a ~600 nm layer of hydroxyapatite derived from biogenic
sustainable resources (i.e., calcined cortical bovine bones), which could constitute a cost-efficient,
environmental-friendly, and highly promising biofunctional solution. Remarkably, the composition
and structure of the biological apatite material were well-replicated into the smooth (Rrms ≈ 15 nm)
and uniform sputtered post-deposition crystallized films. Consequently, the Bio-HA films consisted
of a single B-type carbonated hydroxyapatite phase with traces of Na+ and Mg2+ , having a c-axis
preferential texturing, similar to the bone mineral phase.
The Bio-HA sputtered films elicited promising biological performances:

1. Chemical stability in simulated physiological solutions (after 21 days the film thickness was
reduced by ~14% in SBF and ~5% in FBS-supplemented McCoy’s 5A medium);
2. Biomineralization capacity (Bio-HA generated the formation of spherulitic deposits of biomimetic
calcium phosphates in contact with both types of simulated physiological solutions);
3. Absent cytotoxicity;
4. Optimal osteoblast cell proliferation and adhesion.

3D printing is now viewed as a highly appealing approach for the manufacturing of personalized
implants. The most important functional request of such devices should be their capacity to stimulate
fast bone regeneration. Thereby, the materials of choice would be bioceramics that highly resemble the
composition and structure of the mineral bone phase. Unfortunately, such stand-alone bioceramics
lack suitable mechanical properties risking implant failure. Furthermore, they are difficult to be 3D
printed. Therefore, the compromise solution is the fabrication of customized implants by 3D printing
from metallic materials, followed by their coating with bioactive ceramic thin films, closely mimicking
the fine and intricate features of the metallic biomedical device. In this study we aimed to show
that RF-MS could be a candidate deposition technique for the coating of such medical devices with
thin films of biological apatite, on the one hand due to its now demonstrated ability to preserve
the physico–chemical properties of the source material, and on the other hand due to its recognized
capability to synthesize, in a controlled manner, dense and adherent thin films on large area substrates.

Supplementary Materials: The following are available online at http://www.mdpi.com/2075-4701/9/12/1332/s1,

Figure S1: (a) Optical microscopy image and (b) SEM micrograph of the Ti6Al4V sample produced by the SLM
method. (c) A typical EDXS spectrum recorded for the Ti6Al4V sample 3D printed by SLM. Figure S2: (a) A
typical EDXS spectrum recorded for the Ti6Al4V sample 3D printed by SLM. Compositional EDXS maps for (b) all
constitutive elements (overlayed), (c) Ti, (d) Al and (e) V, collected for the area highlighted in the microscopic field
presented in (Figure S1b).
Author Contributions: Conceptualization, A.C.P., G.E.S., F.N.O. and L.D.; SLM manufacturing, N.P. and N.M.;
Metallographic investigations and writing—original draft preparation, D.C. and A.C.P.; SE, SEM, XRD, FTIR,
AFM, EDXS, and in vitro degradation/bioactivity testing, G.P.-P., L.M.B., A.C.G., A.C.P., and G.E.S.; In vitro
cytocompatibility testing, S.I.; writing—review and editing, L.D., G.E.S., and A.C.P.
Funding: INFLPR authors acknowledge the funding of the Core Program contract no. 16N/2019 and of the
Romanian Ministry of Research and Innovation in the framework of the projects PN-III-P2-2.1-PED-2016-1309
(PED241/2017), PN-III-P1-1.1-TE-2016-2015 (TE136/2018), and PN-III-P1-1.1-PD-2016-1568 (PD6/2018).
NIMP authors are thankful for the support of PCCDI—UEFISCDI, in the framework of project
PN-III-P1-1.2-PCCDI-2017-0062 (contract no. 58PCCDI/2018)/component project no. 2 and of Core Program
(contract no. 21N/2019). This work was also supported by a grant of the Romanian Ministry of
Research and Innovation, PCCDI— UEFISCDI, project number PN-III-P1-1.2-PCCDI-2017-0224 (contract no.
77PCCDI/2018)—DigiTech, within PNCDI III.
Acknowledgments: In vitro studies were conducted at the Biology Lab of CETAL Department.
Conflicts of Interest: The authors declare no conflict of interest.

177
Metals 2019, 9, 1332

References
1. Yan, L.; Yuan, Y.; Ouyang, L.; Li, H.; Mirzasadeghi, A.; Li, L. Improved mechanical properties of the new
Ti-15Ta-xZr alloys fabricated by selective laser melting for biomedical application. J. Alloys Compd. 2016, 688,
156–162. [CrossRef]
2. Banerjee, D.; Williams, J.C. Perspectives on titanium science and technology. Acta Mater. 2013, 61, 844–879.
[CrossRef]
3. Agius, D.; Kourousis, K.I.; Wallbrink, C. A review of the as-built SLM Ti-6Al-4V mechanical properties
towards achieving fatigue resistant designs. Metals 2018, 8, 75. [CrossRef]
4. Sargeant, A.; Goswami, T. Hip implants-Paper VI-Ion concentrations. Mater. Des. 2007, 28, 155–171. [CrossRef]
5. Cui, C.; Shen, Y.; Li, Y.; Sun, J.-B. Fabrication, microstructure, and mechanical properties of tip/Al composite.
Adv. Eng. Mater. 2003, 5, 725–729. [CrossRef]
6. Koch, C.; Johnson, S.; Kumar, D.; Jelinek, M.; Chrisey, D.; Doraiswamy, A.; Jin, C.; Narayan, R.J.; Mihailescu, I.N.
Pulsed laser deposition of hydroxyapatite thin films. Mater. Sci. Eng. C 2007, 27, 484–494. [CrossRef]
7. Nelea, V.; Morosanu, C.; Iliescu, M.; Mihailescu, I. Microstructure and mechanical properties of hydroxyapatite
thin films grown by RF magnetron sputtering. Surf. Coat. Technol. 2003, 173, 315–322. [CrossRef]
8. Mahammadi, S.; Wictorin, L.; Ericsonetal, L.E. Cast titanium as implant material. J. Mater. Sci. Mater. Med.
1995, 6, 435–444. [CrossRef]
9. Corpe, R.S.; Steflik, D.E.; Whitehead, R.Y.; Wilson, M.D.; Young, T.R.; Jaramillo, C. Correlative experimental
animal and human clinical retrieval evaluations of hydroxyapatite (HA)-coated and non-coated implants in
orthopaedics and dentistry. Crit. Rev. Biomed. Eng. 2000, 28, 395–398. [CrossRef]
10. Sakkers, R.; Dalmeyer, R.; Brand, R.; Rozing, P.; Van Blitterswijk, C. Assessment of bioactivity for orthopedic
coatings in a gap-healing model. J. Biomed. Mater. Res. 1998, 36, 265–273. [CrossRef]
11. Vladescu, A.; Parau, A.; Pana, I.; Cotrut, C.M.; Constantin, L.R.; Braic, V.; Vranceanu, D.M. In vitro activity
assays of sputtered HAp coatings with SiC addition in various simulated biological fluids. Coatings 2019, 9,
389. [CrossRef]
12. Surmeneva, M.A.; Ivanova, A.A.; Tian, Q.; Pittman, R.; Jiang, W.; Lin, J.; Liu, H.H.; Surmenev, R.A. Bone
marrow derived mesenchymal stem cell response to the RF magnetron sputter deposited hydroxyapatite
coating on AZ91 magnesium alloy. Mater. Chem. Phys. 2019, 221, 89–98. [CrossRef]
13. Prolosov, K.A.; Belyavskaya, O.A.; Linders, J.; Loza, K.; Prymak, O.; Mayer, C.; Rau, J.V.; Epple, M.;
Sharkeev, Y.P. Glancing angle deposition of Zn-doped calcium phosphate coatings by RF magnetron
sputtering. Coatings 2019, 9, 220. [CrossRef]
14. Aydin, I.; Bahcepinar, A.I.; Kirman, M.; Cipiloglu, M.A. HA coating on Ti6Al7Nb alloy using as electrophoretic
deposition method and surface properties examination of the resulting coatings. Coatings 2019, 9, 402.
[CrossRef]
15. Popa, A.C.; Stan, G.E.; Enculescu, M.; Tanase, C.; Tulyaganov, D.U.; Ferreira, J.M.F. Superior biofunctionality
of dental implant fixtures uniformly coated with durable bioglass films by magnetron sputtering. J. Mech.
Behav. Biomed. Mater. 2015, 51, 313–327. [CrossRef] [PubMed]
16. Rey, C.; Combes, C.; Drouet, C.; Glimcher, M.J. Bone mineral: Update on chemical composition and structure.
Osteoporos. Int. 2009, 20, 1013–1021. [CrossRef] [PubMed]
17. Duta, L.; Popescu, A.C. Current status on pulsed laser deposition of coatings from animal origin calcium
phosphate sources. Coatings 2019, 9, 335. [CrossRef]
18. Graziani, G.; Boi, M.; Bianchi, M. A review on ionic substitutions in hydroxyapatite thin films: Towards
complete biomimetism. Coatings 2018, 8, 269. [CrossRef]
19. Miculescu, F.; Miculescu, M.; Ciocan, L.T.; Ernuteanu, A.; Antoniac, I.; Pencea, I.; Matei, E. Comparative
studies regarding heavy elements concentration in human cortical bone. Dig. J. Nanomater. Biostruct. 2011, 6,
1117–1127.
20. Akram, M.; Ahmed, R.; Shakir, I.; Ibrahim, W.A.W.; Hussain, R. Extracting hydroxyapatite and its precursors
from natural resources. J. Mater. Sci. 2013, 49, 1461–1475. [CrossRef]
21. Popescu, A.C.; Florian, P.E.; Stan, G.E.; Popescu-Pelin, G.; Zgura, I.; Enculescu, M.; Oktar, F.N.; Trusca, R.;
Sima, L.E.; Roseanu, A.; et al. Physical-chemical characterization and biological assessment of simple and
lithium-doped biological-derived hydroxyapatite thin films for a new generation of metallic implants. Appl.
Surf. Sci. 2018, 439, 724–735. [CrossRef]

178
Metals 2019, 9, 1332

22. Bianchi, M.; Gambardella, A.; Graziani, G.; Liscio, F.; Maltarello, M.C.; Boi, M.; Berni, M.; Bellucci, D.;
Marchiori, G.; Valle, F.; et al. Plasma-assisted deposition of bone apatite-like thin films from natural apatite.
Mater. Lett. 2017, 199, 32–36. [CrossRef]
23. Duta, L.; Mihailescu, N.; Popescu, A.C.; Luculescu, C.R.; Mihailescu, I.N.; Cetin, G.; Gunduz, O.; Oktar, F.N.;
Popa, A.C.; Kuncser, A.; et al. Comparative physical, chemical and biological assessment of simple and
titanium-doped ovine dentine-derived hydroxyapatite coatings fabricated by pulsed laser deposition. Appl.
Surf. Sci. 2017, 413, 129–139. [CrossRef]
24. Liu, R.; Qiao, W.; Huang, B.; Chen, Z.; Fang, J.; Li, Z.; Chen, Z. Fluorination enhances the osteogenic capacity
of porcine hydroxyapatite. Tissue Eng. Part A 2018, 24, 1207–1217. [CrossRef] [PubMed]
25. Boutinguiza, M.; Pou, J.; Comesaña, R.; Lusquiños, F.; de Carlos, A.; León, B. Biological hydroxyapatite
obtained from fish bones. Mater. Sci. Eng. C 2012, 32, 478–486. [CrossRef]
26. Mocanu, A.C.; Stan, G.E.; Maidaniuc, A.; Miculescu, M.; Antoniac, I.V.; Ciocoiu, R.C.; Voicu, S.I.; Mitran, V.;
Cimpean, A.; Miculescu, F. Naturally-derived biphasic calcium phosphates through increased phosphorous-
based reagent amounts for biomedical applications. Materials 2019, 12, 381. [CrossRef] [PubMed]
27. Jaber, H.L.; Hammood, A.S.; Parvin, N. Synthesis and characterization of hydroxyapatite powder from
natural Camelus bone. J. Aust. Ceram. Soc. 2018, 54, 1–10. [CrossRef]
28. Lopez-Alvarez, M.; Vigo, E.; Rodriguez-Valencia, C.; Outeirino-Iglesias, V.; Gonzalez, P.; Serra, J. In vivo
evaluation of shark teeth-derived bioapatites. Clin. Oral Implant. Res. 2016, 28, 91–100. [CrossRef]
29. Levingstone, T.J.; Khaled Benyounis, M.A.; Looney, L.; Stokes, J.T. Plasma sprayed hydroxyapatite coatings:
Understanding process relationships using design of experiment analysis. Surf. Coat. Technol. 2015, 283,
29–36. [CrossRef]
30. Roy, M.; Bandyopadhyay, A.; Bose, S. Induction plasma sprayed nano hydroxyapatite coatings on titanium
for orthopaedic and dental implants. Surf. Coat. Technol. 2011, 205, 2785–2792. [CrossRef]
31. Heimann, R.B. Plasma-sprayed hydroxylapatite-based coatings: Chemical, mechanical, microstructural, and
biomedical properties. J. Therm. Spray Technol. 2016, 25, 827–850. [CrossRef]
32. Eason, R. (Ed.) Pulsed Laser Deposition of Thin Films: Applications-Lead Growth of Functional Materials; Wiley &
Sons: New York, NY, USA, 2007.
33. Kelly, P.J.; Arnell, R.D. Magnetron sputtering: A review of recent developments and applications. Vacuum
2000, 56, 159–172. [CrossRef]
34. Surmenev, R.A. A review of plasma-assisted methods for calcium phosphate-based coatings fabrication.
Surf. Coat. Technol. 2012, 206, 2035–2056. [CrossRef]
35. Fernandes, H.R.; Gaddam, A.; Rebelo, A.; Brazete, D.; Stan, G.E.; Ferreira, J.M.F. Bioactive glass and
glass-ceramics for healthcare application in bone regeneration and tissue engineering. Materials 2018, 11,
2530. [CrossRef]
36. Sima, L.E.; Stan, G.E.; Morosanu, C.O.; Melinescu, A.; Ianculescu, A.; Melinte, R.; Neamtu, J.; Petrescu, S.M.
Differentiation of mesenchymal stem cells onto highly adherent radio frequency-sputtered carbonated
hydroxyalapatite thin films. J. Biomed. Mater. Res. A 2010, 95, 1203–1214. [CrossRef]
37. Attar, H.; Calin, M.; Zhang, L.C.; Scudino, S.; Eckert, J. Manufacture by selective laser melting and mechanical
behavior of commercially pure titanium. Mater. Sci. Eng. A 2014, 593, 170–177. [CrossRef]
38. Kruth, P.; Vandenbroucke, B.; Van Vaerenbergh, J.; Naert, I. Virtual Prototyping and Rapid Manufacturing—
Advanced Research in Virtual and Rapid Prototyping; Taylor and Francis: London, UK, 2005; pp. 139–146.
39. Zhang, L.C.; Klemm, D.; Eckert, J.; Hao, Y.L.; Sercombe, T.B. Manufacture by selective laser melting and
mechanical behavior of a biomedical Ti-24Nb-4Zr-8Sn alloy. Scr. Mater. 2011, 65, 21–24. [CrossRef]
40. Bose, S.; Ke, D.; Sahasrabudhe, H.; Bandyopadhyay, A. Additive manufacturing of biomaterials. Prog. Mater.
Sci. 2018, 93, 45–111. [CrossRef]
41. Singh, S.; Ramakrishna, S.; Singh, R. Material issues in additive manufacturing: A review. J. Manuf. Process.
2017, 25, 185–200. [CrossRef]
42. Weißmann, V.; Drescher, P.; Bader, R.; Seitz, H.; Hansmann, H.; Laufer, N. Comparison of single Ti6 Al4 V
struts made using selective laser melting and electron beam melting subject to part orientation. Metals 2017,
7, 91. [CrossRef]
43. Zhang, P.; He, A.N.; Liu, F.; Zhang, K.; Jiang, J.; Zhang, D.Z. Evaluation of low cycle fatigue performance of
selective laser melted titanium alloy Ti–6Al–4V. Metals 2019, 9, 1041. [CrossRef]

179
Metals 2019, 9, 1332

44. Jardini, A.L.; Larosa, M.A.; Kaasi, A.; Kharmandayan, P. Additive manufacturing in medicine. In Reference
Module in Materials Science and Materials Engineering; Hasmi, S., Ed.; Elsevier: Amsterdam, The Netherlands,
2017; pp. 1–21. [CrossRef]
45. Jardini, A.L.; Lasora, M.A.; Macedo, M.F.; Bernardes, L.F.; Lambert, C.S.; Zavaglia, C.A.C.; Maciel, R.;
Calderoni, D.R.; Ghizoni, E.; Kharmandayan, P. Improvement in cranioplasty: Advanced prosthesis
biomanufacturing. Procedia CIRP 2016, 49, 203–208. [CrossRef]
46. Ataee, A.; Li, Y.; Brandt, M.; Wen, C. Ultrahigh-strength titanium gyroid scaffolds manufactured by selective
laser melting (SLM) for bone implant applications. Acta Mater. 2018, 158, 354–368. [CrossRef]
47. Sun, J.; Zhang, F.Q. The application of rapid prototyping in prosthodontics. J. Prosthodont. 2012, 21, 641–644.
[CrossRef]
48. Zhang, L.C.; Sercombe, T.B. Selective laser melting of low-modulus biomedical Ti-24Nb-4Zr-8Sn Alloy: Effect
of laser point distance. Key Eng. Mater. 2012, 520, 226–233. [CrossRef]
49. Gu, D.D.; Meiners, W.; Wissenbach, K.; Poprawe, R. Laser additive manufacturing of metallic components:
Materials, processes and mechanisms. Int. Mater. Rev. 2012, 57, 133–164. [CrossRef]
50. Mohammed, M.T. Mechanical properties of SLM-titanium materials for biomedical applications: A review.
Mater. Today Proc. 2018, 5, 17906–17913. [CrossRef]
51. Attar, H.; Bönisch, M.; Calin, M.; Zhang, L.; Scudino, S.; Eckert, J. Selective laser melting of in situ
titanium–titanium boride composites: Processing, microstructure and mechanical properties. Acta Mater.
2014, 76, 13–22. [CrossRef]
52. Attar, H.; Löber, L.; Funk, A.; Calin, M.; Zhang, L.; Prashanth, K.; Scudino, S.; Zhang, Y.; Eckert, J. Mechanical
behavior of porous commercially pure Ti and Ti–TiB composite materials manufactured by selective laser
melting. Mater. Sci. Eng. A 2015, 625, 350–356. [CrossRef]
53. Krakhmalev, P.; Fredriksson, G.; Yadroitsava, I.; Kazantseva, N.; du Plessis, A.; Yadroitsev, I. Deformation
behavior and microstructure of Ti6Al4V manufactured by SLM. Phys. Procedia 2016, 83, 778–788. [CrossRef]
54. Kajima, Y.; Takaichi, A.; Nakamoto, T.; Kimura, T.; Yogo, Y.; Ashida, M.; Doi, H.; Nomura, N.; Takahashi, H.;
Hanawa, T.; et al. Fatigue strength of Co–Cr–Mo alloy clasps prepared by selective laser melting. J. Mech.
Behav. Biomed. 2016, 59, 446–458. [CrossRef] [PubMed]
55. Leuders, S.; Thöne, M.; Riemer, A.; Niendorf, T.; Tröster, T.; Richard, H.A.; Maier, H.J. On the mechanical
behaviour of titanium alloy TiAl6V4 manufactured by selective laser melting: Fatigue resistance and crack
growth performance. Int. J. Fatigue 2013, 48, 300–307. [CrossRef]
56. Liverani, E.; Fortunato, A.; Leardini, A.; Belvedere, C.; Siegler, S.; Ceschini, L.; Ascari, A. Fabrication of
Co–Cr–Mo endoprosthetic ankle devices by means of Selective Laser Melting (SLM). Mater. Des. 2016, 106,
60–68. [CrossRef]
57. Duta, L.; Chifiriuc, M.C.; Popescu-Pelin, G.; Bleotu, C.; (Pircalabioru) Gradisteanu, G.; Anastasescu, M.;
Achim, A.; Popescu, A. Pulsed laser deposited biocompatible lithium-doped hydroxyapatite coatings with
antimicrobial activity. Coatings 2019, 9, 54. [CrossRef]
58. Popa, A.C.; Marques, V.M.F.; Stan, G.E.; Husanu, M.A.; Galca, A.C.; Ghica, C.; Tulyaganov, D.U.; Lemos, A.F.;
Ferreira, J.M.F. Nanomechanical characterization of bioglass films synthesized by magnetron sputtering.
Thin Solid Films 2014, 553, 166–172. [CrossRef]
59. Popa, A.C.; Stan, G.E.; Husanu, M.A.; Mercioniu, I.; Santos, L.F.; Fernandes, H.R.; Ferreira, J.M.F. Bioglass
implant-coating interactions in synthetic physiological fluids with varying degrees of biomimicry. Int. J.
Nanomed. 2017, 12, 683–707. [CrossRef]
60. Galca, A.C.; Stan, G.E.; Trinca, L.M.; Negrila, C.C.; Nistor, L.C. Structural and optical properties of c-axis
oriented aluminum nitride thin films prepared at low temperature by reactive radio-frequency magnetron
sputtering. Thin Solid Films 2012, 524, 328–333. [CrossRef]
61. Popa, A.C.; Stan, G.E.; Besleaga, C.; Ion, L.; Maraloiu, V.A.; Tulyaganov, D.U.; Ferreira, J.M.F. Submicrometer
hollow bioglass cones deposited by radio frequency magnetron sputtering: Formation mechanism, properties,
and prospective biomedical applications. ACS Appl. Mater. Interfaces 2016, 8, 4357–4367. [CrossRef]
62. Besleaga, C.; Dumitru, V.; Trinca, L.M.; Popa, A.C.; Negrila, C.C.; Kołodziejczyk, Ł.; Luculescu, C.R.;
Ionescu, G.C.; Ripeanu, R.G.; Vladescu, A.; et al. Mechanical, corrosion and biological properties of
room-temperature sputtered aluminum nitride films with dissimilar nanostructure. Nanomaterials 2017, 7,
394. [CrossRef]
63. Cauchy, A.L. Sur la refraction et la réflexion de la lumière. Bull. Sci. Math. 1830, 14, 6–10.

180
Metals 2019, 9, 1332

64. Ti6Al4V Properties Datasheet. Available online: http://asm.matweb.com/search/SpecificMaterial.asp?

bassnum=MTP642 (accessed on 1 November 2019).
65. Zofkova, I.; Nemcikova, P.; Matucha, P. Trace elements and bone health. Clin. Chem. Lab. Med. 2013, 51,
1555–1561. [CrossRef] [PubMed]
66. Gaffney-Stomberg, E. The impact of trace minerals on bone metabolism. Biol. Trace Elem. Res. 2019, 188,
26–34. [CrossRef] [PubMed]
67. Besleaga, C.; Stan, G.E.; Galca, A.C.; Ion, L.; Antohe, S. Double layer structure of ZnO thin films deposited by
RF-magnetron sputtering. Appl. Surf. Sci. 2012, 258, 8819–8824. [CrossRef]
68. Patterson, A. The Scherrer formula for X-ray particle size determination. Phys. Rev. 1939, 56, 978–982.
[CrossRef]
69. Markovic, M.; Fowler, B.O.; Tung, M.S. Preparation and comprehensive characterization of a calcium
hydroxyapatite reference material. J. Res. Natl. Inst. Stand. Technol. 2004, 109, 553–568. [CrossRef]
70. Rey, C.; Collins, B.; Goehl, T.; Dickson, I.R.; Glimcher, M.J. The carbonate environment in bone mineral: A
resolution-enhanced Fourier transform infrared spectroscopy study. Calcif. Tissue Int. 1989, 45, 157–164.
[CrossRef]
71. Hench, L.L. The story of Bioglass® . J. Mater. Sci. Mater. Med. 2006, 17, 967–978. [CrossRef]
72. Stan, G.E.; Pina, S.; Tulyaganov, D.U.; Ferreira, J.M.F.; Pasuk, I.; Morosanu, C.O. Biomineralization capability
of adherent bio-glass films prepared by magnetron sputtering. J. Mater. Sci. Mater. Med. 2010, 21, 1047–1055.
[CrossRef]
73. Vranceanu, D.M.; Parau, A.C.; Cotrut, C.M.; Kiss, A.E.; Constantin, L.R.; Braic, V.; Vladescu, A. In vitro evaluation
of Ag doped hydroxyapatite coatings in acellular media. Ceram. Int. 2019, 45, 11050–11061. [CrossRef]
74. Šupová, M. Substituted hydroxyapatites for biomedical applications: A review. Ceram. Int. 2015, 41, 9203–9231.
[CrossRef]
75. Popescu, A.C.; Sima, F.; Duta, L.; Popescu, C.; Mihailescu, I.N.; Capitanu, D.; Mustata, R.; Sima, L.E.;
Petrescu, S.M.; Janackovic, D. Biocompatible and bioactive nanostructured glass coatings synthesized by
pulsed laser deposition: In vitro biological tests. Appl. Surf. Sci. 2009, 255, 5486–5490. [CrossRef]
76. Tite, T.; Popa, A.C.; Balescu, L.M.; Bogdan, I.M.; Pasuk, I.; Ferreira, J.M.F.; Stan, G.E. Cationic substitutions in
hydroxyapatite: Current status of the derived biofunctional effects and their in vitro interrogation methods.
Materials 2018, 11, 2081. [CrossRef] [PubMed]
77. Wopenka, B.; Pasteris, J.D. A mineralogical perspective on the apatite in bone. Mater. Sci. Eng. C 2005, 25,
131–143. [CrossRef]
78. Mihailescu, N.; Stan, G.E.; Duta, L.; Chifiriuc, M.C.; Bleotu, C.; Sopronyi, M.; Luculescu, C.; Oktar, F.N.;
Mihailescu, I.N. Structural, compositional, mechanical characterization and biological assessment of
bovine-derived hydroxyapatite coatings reinforced with MgF2 or MgO for implants functionalization.
Mater. Sci. Eng. C 2016, 59, 863–874. [CrossRef] [PubMed]
79. Wang, Y.; Liu, X.; Fan, T.; Tan, Z.; Zhou, Z.; He, D. In vitro evaluation of hydroxyapatite coatings with
(002) crystallographic texture deposited by micro-plasma spraying. Mater. Sci. Eng. C. 2017, 75, 596–601.
[CrossRef] [PubMed]
80. Fu, J.; He, C.; Xia, B.; Li, Y.; Feng, Q.; Yin, Q.; Shi, X.; Feng, X.; Wang, H.; Yao, H. c-axis preferential orientation
of hydroxyapatite accounts for the high wear resistance of the teeth of black carp (Mylopharyngodon piceus).
Sci. Rep. 2019, 6, 23509. [CrossRef]
81. Kim, H.; Camata, R.P.; Chowdhury, S.; Vohra, Y.K. In vitro dissolution and mechanical behavior of c-axis
preferentially oriented hydroxyapatite thin films fabricated by pulsed laser deposition. Acta Biomater. 2010,
6, 3234–3241. [CrossRef]
82. Nordstrom, E.G.; Sanchez Munoz, O.L. Physics of bone bonding mechanism of different surface bioactive
ceramic materials in vitro and in vivo. Bio Med. Mater. Eng. 2011, 11, 221–231.
83. LeGeros, R.Z.; Daculsi, G. In vitro transformation of biphasic calcium phosphate ceramics: Ultrastructural
and physicochemical characterizations. In Handbook of Bioactive Ceramics, Vol. II. Calcium Phosphate Ceramics;
Yamamuro, T., Hench, L.L., Wilson, J., Eds.; CRC Press: Boca Raton, FL, USA, 1990; pp. 17–28.
84. Kokubo, T.; Takadama, H. How useful is SBF in predicting in vivo bone bioactivity? Biomaterials 2006, 27,
2907–2915. [CrossRef]

181
Metals 2019, 9, 1332

85. Daculsi, G.; LeGeros, R.Z.; Nery, E.; Lynch, K.; Kerebel, B. Transformation of biphasic calcium phosphate
ceramics in vivo: Ultrastructural and physicochemical characterization. J. Biomed. Mater. Res. 1989, 23,
883–894. [CrossRef]
86. Porter, A.E.; Patel, N.; Skepper, J.N.; Best, S.M.; Bonfield, W. Comparison of in vivo dissolution processes
in hydroxyapatite and silicon-substituted hydroxyapatite bioceramics. Biomaterials 2003, 24, 4609–4620.
[CrossRef]
87. Kattimani, V.S.; Kondaka, S.; Lingamaneni, K.P. Hydroxyapatite—Past, present, and future in bone
regeneration. Bone Tissue Regen. Insights 2016, 7, 9–19. [CrossRef]
88. Lim, J.; Lee, J.; Yun, H.-S.; Shin, H.-I.; Park, E.K. Comparison of bone regeneration rate in flat in long bone
defects: Calvarial and tibial bone. Tissue Eng. Regen. Med. 2013, 10, 336–340. [CrossRef]
89. Tavafoghi, M.; Cerruti, M. The role of amino acids in hydroxyapatite mineralization. J. R. Soc. Interface 2016,
13, 20160462. [CrossRef]
90. Wang, K.; Leng, Y.; Lu, X.; Ren, F.; Ge, X.; Ding, Y. Theoretical analysis of protein effects on calcium phosphate
precipitation in simulated body fluid. CrystEngComm 2012, 14, 5870–5878. [CrossRef]
91. Zareidoost, A.; Yousefpour, M.; Ghaseme, B.; Amanzadeh, A. The relationship of surface roughness and
cell response of chemical surface modification of titanium. J. Mater. Sci. Mater. Med. 2012, 23, 1479–1488.
[CrossRef]
92. Hatamleh, M.M.; Wu, X.; Alnazzawi, A.; Watson, J.; Watts, W. Surface characteristics and biocompatibility
of cranioplasty titanium implants following different surface treatments. Dent. Mater. 2018, 34, 676–683.
[CrossRef]

© 2019 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).

182
 metals
Article
Evaluation of Support Structure Removability for
Additively Manufactured Ti6Al4V Overhangs via
Electron Beam Melting
Wadea Ameen 1,2, * , Muneer Khan Mohammed 2 and Abdulrahman Al-Ahmari 1,2
1 Industrial Engineering Department, King Saud University, Riyadh P.O. Box 800-Riyadh 11421, Saudi Arabia;
[email protected]
2 Raytheon Chair for Systems Engineering (RCSE Chair), Advanced Manufacturing Institute,
King Saud University, Riyadh P.O. Box 800-Riyadh 11421, Saudi Arabia; [email protected]
* Correspondence: [email protected]; Tel.: +966114697372




Received: 22 October 2019; Accepted: 9 November 2019; Published: 11 November 2019


Abstract: The addition of support structures is essential for the successful fabrication of overhang
structures through additive manufacturing (AM). The support structures protect the overhang
portion from distortions. They are fabricated with the functional parts and are removed later after
the fabrication of the AM part. While structures bearing insufficient support result in defective
overhangs, structures with excessive support result in higher material consumption, time and
higher post-processing costs. The objective of this study is to investigate the effects of design and
process parameters of support structures on support removability during the electron beam melting
(EBM)-based additive manufacturing of the Ti6Al4V overhang part. The support design parameters
include tooth parameters, no support offset, fragmentation parameters and perforation parameters.
The EBM process parameters consist of beam current, beam scan speed and beam focus offset.
The results show that both support design and process parameters have a significant effect on support
removability. In addition, with the appropriate selection of design and process parameters, it is
possible to significantly reduce the support removal time and protect the surface quality of the part.

Keywords: additive manufacturing; support structures; electron beam melting; support

structure removability

1. Introduction and Literature Review

Additive manufacturing (AM) is a manufacturing technique used to fabricate three-dimensional
parts in a layer-by-layer manner directly from a computer-aided design (CAD) model.
In powder-bed-fusion (PBF) processes, such as electron beam melting (EBM), and in selective laser
sintering and melting, a thin powder layer is selectively melted using an electron or laser beam [1,2].
Once the powder layer is molten, a new powder layer is spread and melted based upon the CAD data,
the steps are repeated until the full component is fabricated. Although PBF technology can fabricate
complex geometries, it has some limitations in the fabrication of structures with overhang geometries.
The fabrication of structures with overhang geometries that do not contain support structures results
in warpage deformation due to the thermal gradient and residual stress.
Support structures are essential in the manufacturing of defect-free overhang structures through the
PBF process [3]. By facilitating the removal of heat from the structure, support structures prevent part
curling, distortion, sagging, cracks, shrinkage, and/or other deformations that result from thermal stresses.
They also serve to hold the fabricated part in the construction platform during the manufacturing process [4].
Current support generation methods usually involve the use of certain types of structures to cover the

Metals 2019, 9, 1211; doi:10.3390/met9111211 183 www.mdpi.com/journal/metals

Metals 2019, 9, 1211

overhang space. These methods may result in overestimation of the support volume or the placement
of a large number of supports, which may be unnecessary and increase the post-processing time [5].
Support structures have many design rules that are to be incorporated by the designers. For example,
the support structures should be designed to engage in minimal contact with the overhang surface parts [6].
The design of the support structure must also consider the post-processing costs. For instance, minimising
the number of supports, which leads to a minimal number of marks on the surface and reduces the amount
of part clean-up and post-processing [7]. Support structures are the non-functional part of the structure
and are removed after the construction process. Optimisation of the support structure is an important
consideration for the successful fabrication of parts. Accurate selection of support structure design is critical,
as it affects the production cost, time and quality of construction. For example, applying a large contact area
support to the overhang part would result in increased difficulty in support removal, and it might damage
the part surface during removal [8,9]. The support structures are used to build the overhanging geometries
and are later removed by breaking them away. Often, commercial software like Magics (Materialise, Leuven,
Belgium) is used to automatically generate support structures. After the parts are fabricated using AM
technology (EBM), the excess powder and support structures are removed. In PBF, the support structures
are mechanically removed by the application of force or cutting (often manually) [10]. In some cases,
the inability to remove the support structures leads to the inability to manufacture the desired structures.
Various methods are used to remove metal support structures, depending on the material and geometry.
Wire electrical discharge machining, saws [10,11], Dremel handheld power tools [12] and pliers [13] are
popular methods and tools for removing the support structures from PBF parts [14]. Sandpaper is a quick
tool that is used to remove the witness marks leftover by the supports on the bottom surface.
For metal supports, a wire EDM machine, milling equipment, and bandsaw may be required to
remove the part support from the baseplate and then remove the supports from the part [7]. Most of
the AM cost models consider support structures as main parts and as a factor in the estimate of the
total cost. Furthermore, some cost models consider the density of the support structure to estimate the
cost of AM [15,16]. Calignano et al. investigated the effect of block support structures fabricated by
selective laser melting of aluminium and titanium alloys. The results show that the removal of the
support structures from the titanium samples is an easier task as compared to the aluminium samples.
In addition, the support design has an effect on the removability of the applied support structures [17].
Kuo et al. used topology optimisation to design an easily removable support structure that minimises
support material and fabrication time, and results in the fewest artefacts on the surface of the specimen.
A cost-based formulation, comprising a simple and straightforward method, is employed to find a
compromise between the cost and surface profile error induced by specimen weight [18]. To select the
type of support structure design for optimal support removability and the surface quality of the parts,
Järvinen et al. compared the properties of two types of support structures (web and tube) during the
evaluation of removability. The results showed that the web supports provided superior removability
as compared to the tube supports [19]. All block support structure parameters (tooth, no support offset
parameters, fragmentation, and perforation parameters) are shown in Figure 1.

Figure 1. Design parameters: (a) tooth parameters, (b) fragmentation parameters, (c) perforation parameters.

184
Metals 2019, 9, 1211

In the EBM process, parameters such as beam current (I), beam scanning speed (V), line offset (LO)
and beam focus offset (FO) are the most relevant process parameters [20]. Line offset refers to the distance
between two hatch lines, and focus offset is the offset of the focal plane from its zero position. Increased line
offset results in lower energy densities, which forms voids in Ti-6Al-4V specimens. An increase in the focus
offset increases the beam diameter and reduces the energy density, which in turn, results in an increase in
the porosity [21]. From the above parameters, the energy density (J/mm2 ) can be calculated as follows [22]:

Π × Vacc × Iscan × γabs

Q = (1)
4 × Dbeam × Vscan

where Q is energy input/mm2 (J/mm2 ), Π = 3.14, Vacc is accelerating voltage (V) = 60,000 V (standard
accelerating voltage in Arcam EBM), Iscan is beam current (mA), Vscan is beam scan speed (mm/s), Dbeam
is beam spot diameter (mm) and P1 is focus offset (mA). Dbeam is calculated from the focus offset (P1)
by using quadratic nonlinear regression approximation (Source: Arcam AB):

Dbeam = 0.000102 (P1)2 + 0.00151 (P1) + 0.131, (2)

where γ is percentage of energy absorbed by the system, 1 − εback. Mahale [22] by Monte Carlo
simulation in CASINO software, obtaining a value of εback = 0.0025; thus, γabs = 0.9975.
EBM is a metal additive manufacturing process that utilises stiffness support structures for the
production of overhangs. In this study, the effect of support structure parameters (design and process)
is envisaged to develop the design rules for the support structure of Ti6Al4V parts fabricated by EBM.

2. Experimental Procedures
In the current study, ledge overhangs with an overhang portion length of 15 mm and a thickness of
5 mm were designed using block support structures in Magics software (Materialise, Leuven, Belgium).
ARCAM A2 (Arcam EBM, Mölnlycke, Gottenburg, Sweden) was used to construct the overhang
specimens. The support structure design and process parameters were varied to evaluate their effect
on support structure removability during the fabrication of the overhang structures. Table 1 lists the
design and process parameters, and their corresponding settings.
In the EBM process, after the completion of the build, the specimens were surrounded by sintered
powder within the build envelope, as shown in Figure 2a. The build envelope was subjected to a
powder recovery system (powder blasting process) to obtain parts free from sintered powder, as shown
in Figure 2b.

Figure 2. Fabricated specimens: (a) specimens on sintered powder; (b) specimens after sand blasting.

The fabricated specimens were then subjected to the support structure removal process. To evaluate
the effect of support structure design and process parameters on the removability of the support
structures, the support structures were removed manually using simple pliers, and the time consumed
in removing the support structures for each specimen was recorded. To maintain uniformity, the support

185
Metals 2019, 9, 1211

structure removal pattern was kept the same for all the specimens and rest time was given after each
specimen to avoid the fatigue. The support removal process was started by removing the support
tooth and then the support body to make the pliers accessible to the interior tooth. Finally, the supports
adhered to the body of the overhang part were removed.
Post processing such as powder and support removal as performed as a last step of the fabrication
stage. However, small support removal burrs remain on the supported part surface, which in turn effect
the surface quality of the produced part. To evaluate the effect of the addition of a support structure
and its parameters on surface quality, surface roughness analysis was carried out by utilizing the
Dektak XT surface profiler (Bruker, Germany), as shown in Figure 3. The support teeth, fragmentation
and process parameters were considered in this investigation. The surface profiles were measured
at three different locations on the supported surface with evaluation length of 10 mm, as shown in
Figure 3b, and then the averages were calculated.

Table 1. Support structure design and process parameters.

Support Structure Parameters Level 1 Level 2 Level 3 Level 4

Tooth height (mm) 1.2 1.80 2.4 3
Tooth top length (mm) 0.05 0.1 0.15 0.2
Tooth and No Tooth base length (mm) 0.5 0.7 0.90 1.1
Support Offset
Parameters Tooth base interval 0.5 1.50 2.5 3.5
Z offset (mm) 0 0.5 0.1 0.25
No support offset (mm) 0 2 4 6
X and Y hatching (mm) 3 6 12 15
Design Hatching and Fragmentation 0 1 - -
parameters Fragmentation
Parameters Fragmentation interval (mm) 2.5 5 10 -
Separation width (mm) 0.2 0.4 0.8 1.6
Perforation style 0 1 (Diam.) 1 (Rect.) -
Perforation beam (mm) 1.75 3.5 7 -
Perforation
Perforation angle 30 45 60 -
Parameters
Perforation height (mm) 1 2 4 -
Perforation solid height (mm) 1 2 4 -
Current (mA) 1.5 2.5 5 10
Process Processes Scan speed (mm/s) 1000 1400 1800 2200
parameters Parameters
Focus offset (mA) 1 2 4 4

Figure 3. Surface roughness measuring (a) Dektak XT surface profiler; (b) specimen measured surface.

186
Metals 2019, 9, 1211

3. Results Analysis

3.1. Effect of Design Parameters

During the support removal process, it was found that the time taken to remove the support
structure tooth is very small as compared to the time consumed in removing the support structure body,
particularly when some of the support body is adhered to the part surface. In addition, the supports,
which are very close to the part surface, affect the surface quality of the part, as shown in Figure 4.
Therefore, it is recommended to offset the side support body from the part surface, even by a small
distance (no support offset).

– – layers of support adhesion on the

Figure 4. Overhang side surface quality: (a) No support offset; (b–d)
overhang wall.

It was observed that the support structures with a hatching distance of 6 mm consumed more
time to remove than the supports with a hatching distance of 12 mm. This is because of the increase in
the number of the support teeth for the 6 mm hatching, which decreases the accessibility of the cutting
tool during the removal process. Therefore, the support structures with 6 mm hatching are removed
in smaller segments, which result in increased removal time. It was also observed that the sintered
powder behind the support walls act as an obstacle to support removability, as shown in Figure 5.
To remove the effect of the sintered powder on support structure removability, the powder-blasting
process is carried out as and when it is required.

Figure 5. Support tooth structures: (a) before powder removal; (b) after powder removal.

The influence of support structure teeth parameters, hatching, fragmentation parameters and
perforation parameters were evaluated in this section. To study the effect of the support tooth
parameters on support structure removability, overhangs with different support tooth parameters were
constructed and analysed. Teeth parameters after the removal of the sintered powder are presented in
Figure 6.

187
Metals 2019, 9, 1211

Figure 6. Support structure teeth parameters.

The effect of support design parameters on the support removal time for 6 and 12 mm hatching
distances supports is shown in Figure 7. Tooth height, tooth top length, tooth base interval, no support
offset and separation width were found to have significant effect on the support removal time.
Whereas the other factors had little or no effect on the removability. The support removal time
decreases with increase in the tooth height, this is because the increase in the tooth height increases
the accessibility of the cutting tool (pliers) and reduces the need to remove the support body to reach
all teeth. In addition, with increased tooth height, the non-melted powder around the tooth is easily
removed during powder blasting, thereby easing the support removal. Regarding the effect of the
tooth top and base length, the support removal time increases with increase in tooth top length. This is
because the tooth strength increases with increase in tooth top length. However, the tooth base length
did not have a significant effect on support removal time. The results also found that the support tooth
interval has a significant effect on the support removal time. As the tooth interval increases, the support
removal time decreases. This is because as the support tooth interval increases, the total number of
teeth decrease, and the removal tool accessibility increases, which results in easier support removal.
Reducing the support structure volume through the increase of no support offset has a significant
effect on the support removal time. As the no support offset increases, the support removal time
decreases significantly. This is due to the decrease in the supported area and increase in the accessibility
of the cutting tool during the support removal. In addition, the elimination of the contact between
the support structure wall and side surface of the part facilitates the support removal process, which
results in reduced support removal time.
The effect of the hatching distance in the x- and y-directions on support structure removability
is shown in Figure 8. It can be seen that at lower hatching distance, the support removal time is
significantly high. This is because the lower hatching distance results in greater support structure,
and the support-part contact area decreases the removability of the non-melted powder and accessibility
of the support removal tool (pliers).

188
Metals 2019, 9, 1211

Removal time (min)

Figure 7. Effect of support design parameters on support removability.

Figure 8. Effect of hatching distance on support removability.

Implementing the fragmentation design strategy results in subdivision of support structures and
slightly improves its removability. It can be seen in Figure 7 that the improvement is higher in the case
of the 6 mm hatching distance support, because without the fragmentation strategy, the support body
is solid; therefore, the addition of fragmentation strategy results in subdivided support blocks which
ease the support removal. Whereas in the case of the 12 mm hatching distance, the perforation strategy

189
Metals 2019, 9, 1211

is present by default even without the fragmentation strategy. The application of the fragmentation
strategy results in the elimination of the perforation strategy. Therefore, there is very little effect on
support removal time.
In addition, it was found that the fragmentation separation width has a significant effect on the
removability of support structures. As the fragmentation separation width increases, the support
removal time decreases. This is due to the decrease in the supported surface, increasing the accessibility
of the removal tool and separating the supports into contiguous blocks that are easy to remove,
as shown in Figure 9.

Figure 9. Support structures with various fragmentation separation widths.

Application of perforation strategy results in new support structure configurations, wherein

the supports have holes, which make them weaker as compared to the solid supports and they
consume less material. The effect of perforation style, beam, angle, height, and solid height on support
removability in the 6 and 12 mm hatching distance specimens is shown in Figure 7. The diamond-style
perforation had no effect on support removal time in the 6 mm hatching case, because there is no
change in the geometry of the support. However, in the case of the 12 mm hatching distance support,
the diamond-style perforation resulted in a decrease in the support removal time. Rectangular-style
perforation was found to have a negative effect on support removal time, owing to the disintegration
of the body of the built support into small pieces, which consumes more time.
Figure 7 shows the influence of the perforation beam on support removability. As the perforation
beam increases, the time required to remove the support increases. This is due to the reduction in the
perforation holes, which in turn results in the increase in support body strength. It was also found that
the default perforation angle of 45◦ performed better than other angles in terms of support removal
time. Regarding the effect of perforation height and perforation solid height, it is found that an increase
in the perforation height resulted in the slight decrease in support removal time, causing a decrease in
solid-wall support and an increase in hole size, and vice versa, for perforation solid height, as shown
in Figure 7.
An ANOVA test with 95% confidence was performed to determine the significance of the selected
parameters. Results of 6 and 12 mm hatching are presented in Tables 2 and 3, respectively.
In case of 6 mm hatching distance supports, most of the selected factors were found to have
significant effects (p < 0.05) on the support removal time. The factors such as tooth top length, tooth
base length, tooth top height and fragmentation interval were found to have no significant effect on the
support removal time, as shown in Table 2. However, in case of 12 mm hatching distance supports,
all the factors except the fragmentation interval were found to have significant effect on the support
removal time.

190
Metals 2019, 9, 1211

Table 2. ANOVA for support removability with respect to the support design parameter (hatching 6).

Source df Sum of Squares Mean Square F-Value p-Value Prob > F

Model 34 36.411 1.071 13.88 <0.0001
Linear 34 36.411 1.071 13.88 <0.0001
Tooth height 3 4.698 1.566 20.29 <0.0001
Tooth top length 3 0.613 0.204 2.65 0.093
Tooth base length 3 0.575 0.192 2.48 0.107
Tooth base interval 3 6.341 2.114 27.39 <0.0001
Tooth top height 3 0.022 0.007 0.09 0.962
No support offset 3 10.558 3.519 45.60 <0.0001
Fragmentation 1 2.255 2.255 29.23 <0.0001
Fragmentation interval 2 0.089 0.045 0.58 0.575
separation width 3 5.021 1.674 21.69 <0.0001
Style 2 0.837 0.419 5.42 0.019
Beam 2 0.753 0.377 4.88 0.026
Angle 2 0.592 0.296 3.84 0.049
Height 2 0.712 0.356 4.61 0.031
Solid height 2 1.368 0.684 8.86 0.004
Error 13 1.003 0.077 - -
Total 47 37.415 - - -

Table 3. ANOVA for support removability with respect to the support design parameter (hatching 12).

Source df Sum of Squares Mean Square F-Value p-Value Prob > F

Model 34 12.275 0.361 45.08 <0.0001
Linear 34 12.275 0.361 45.08 <0.0001
Tooth height 3 0.746 0.249 31.06 <0.0001
Tooth top length 3 0.250 0.083 10.42 0.001
Tooth base length 3 0.989 0.330 41.17 <0.0001
Tooth base interval 3 2.371 0.790 98.70 <0.0001
Tooth top height 3 0.141 0.047 5.85 0.009
No support offset 3 2.133 0.711 88.77 <0.0001
Fragmentation 1 0.469 0.469 58.52 <0.0001
Fragmentation interval 2 0.000 0.000 0.00 0.997
separation width 3 1.490 0.497 62.03 <0.0001
Style 2 0.310 0.155 19.38 <0.0001
Beam 2 0.293 0.147 18.31 <0.0001
Angle 2 0.061 0.031 3.82 0.049
Height 2 0.176 0.088 10.96 0.002
Solid height 2 0.284 0.142 17.71 <0.0001
Error 13 0.104 0.008 - -
Total 47 12.379 - - -

3.2. The Influence of Process Parameters

The effect of the EBM process parameters on support structure removability is shown in Figure 10.
It was found that as the beam current increases, the support removal time increases. This is due to
the fact that as the beam current increase, the input energy into the supports increase, which in turn,
increases the support strength, thereby increasing the support removal time. In case of scan speed,
it was found that as the scan speed increases the support removal time decreases. Focus offset was
found to have a little or no effect on the removal time, as shown in Figure 10.

191
Metals 2019, 9, 1211

Figure 10. Effect of EBM process parameters on support removability.

A beam current of 1.25 mA in the specimen labelled C1 resulted in supports wherein the supports
were broken during the powder-blasting process, as shown in Figure 11. The support remains were
easily removed by hand owing to the low strength of supports due to the low input energy. It was
observed that the increase in current from 1.25 to 2.5 mA resulted in supports that could withstand
powder blasting but were very easy to remove. A further increase in the beam current resulted in
supports with considerable strength and significantly higher support removal times.

Figure 11. Specimen C1 (current = 1.25 mA) (a) before powder-blasting process, and (b) after
powder-blasting process.

Regarding the effect of the scan speed as the scan speed increases, the energy flux decreases,
which reduces the support strength. The support structure of specimen S4 (speed = 2200 mm/s)
had the lowest strength and was most easy to remove. Some of its support was broken during the
powder-blasting process.
The results of ANOVA tests for the effect of the EBM process parameters on support removability
are shown in Table 4. It is clear that the beam current and scan speed have a significant effect on the
removal time. Whereas, focus offset was found to have no significant effect on support removal time.

Table 4. ANOVA for the effect of EBM process parameters on support removability.

Source df Sum of Squares Mean Square F-Value p-Value Prob > F

Model 9 3.691 0.410 109.84 0.009
Linear 9 3.691 0.410 109.84 0.009
Current 3 3.354 1.118 299.48 0.003
Scan speed 3 0.228 0.076 20.33 0.047
Focus offset 3 0.040 0.013 3.61 0.224
Error 2 0.007 0.004 - -
Total 11 3.698 - - -

192
Metals 2019, 9, 1211

3.3. Surface Roughness

Support structure parameters were found to have an effect on the surface roughness of the
overhangs. In general, 6 mm hatching support structures resulted in higher surface roughness,
as compared to 12 mm hatching support structures, as shown in Figure 12. This is because of the
presence of a greater number of support teeth with the 6 mm hatching supports, than with the 12 mm
hatching supports. Tooth top length, tooth base length and separation width were found to have
significant effect on the surface roughness. The surface roughness decreases with increases in tooth top
length and separation width. Whereas it increases with increases in tooth base length, as shown in
Figure 12.

Figure 12. Effect of support parameters on surface roughness.

The surface profiles of the samples with minimum support removal time (0.2 min) and maximum
support removal time (4.77 min) are shown in Figure 13a,b, respectively. The surface roughness results
showed the Ra of 21.9 µm for the sample with minimum support removal time, whereas the sample
with maximum support removal time resulted in Ra of 20.68 µm. It was found that the support
structure parameters that resulted in minimum support removal time did not have any adverse effect
on the surface quality of the overhangs and that the surface roughness was similar to the samples built
with other parameters.

193
Metals 2019, 9, 1211

Figure 13. Surface roughness profiles: (a) minimum support removal time; (b) maximum support
removal time.

4. Conclusions
In the current study, the effect of support design and process parameters on support structure
removability was evaluated during the additive manufacturing of Ti6Al4V overhangs via electron
beam melting. In general, the results show that the design and process parameters of the support
structures have a significant effect on support removability. It was found that with the appropriate
selection of design and process parameters for the support structures, it is possible to reduce the support
removal time and protect the part surface quality. The results show that support removability can be
improved significantly with help of proper support design parameters by reducing the supported area,
decreasing the strength of the part/support contact area, and decreasing the strength of the support
structure body. Process parameters, such as beam current and scan speed, were found to have a more
significant effect on support structure removability as compared with beam focus offset.
Based on the current study the following conclusions can be drawn:

1. As compared to the default support tooth parameters, 3 mm tooth height, 0.05 mm tooth top length
and 3.5 mm tooth base interval were found to significantly reduce the support removal time.
2. The fragmented support structure with separation width of 1.6 mm was found to decrease the
support removal time by about 80%.
3. The perforation parameters such as 1.75 mm perforation beam, 60◦ angle, 4 mm height, and 1 mm
solid height resulted in around 20% reduction in support removal time, as compared to the
default parameters.
4. In case of EBM process parameters, as compared to the default parameters, the beam current
of 1.25 mA and scan speed of 2200 mm/sec resulted in more than 80% reduction of support
removal time.

Author Contributions: W.A. and A.A.-A. conceived and designed the study. W.A. and M.K.M. conducted the
EBM experiments. W.A. conducted the measurements and analysed the results. W.A. and M.K.M. wrote the
manuscript and reviewed it. A.A.-A. supervised the work.

194
Metals 2019, 9, 1211

Funding: This study received funding from the Raytheon Chair for Systems Engineering. The authors are grateful
to the Raytheon Chair for Systems Engineering for funding.
Acknowledgments: The authors thank the Deanship of Scientific Research and RSSU at King Saud University for
their technical support.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Gu, D.; Meiners, W.; Wissenbach, K.; Poprawe, R. Laser additive manufacturing of metallic components:
Materials, processes and mechanisms. Int. Mater. Rev. 2012, 57, 133–164. [CrossRef]
2. Bobbio, L.D.; Qin, S.; Dunbar, A.; Michaleris, P.; Beese, A.M. Characterization of the strength of support
structures used in powder bed fusion additive manufacturing of Ti-6Al-4V. Addit. Manuf. 2017, 14, 60–68.
[CrossRef]
3. Umer, U.; Ameen, W.; Abidi, M.H.; Moiduddin, K.; Alkhalefah, H.; Alkahtani, M.; Al-Ahmari, A. Modeling the
Effect of Different Support Structures in Electron Beam Melting of Titanium Alloy Using Finite Element
Models. Metals 2019, 9, 806. [CrossRef]
4. Poyraz, Ö.; Yasa, E.; Akbulut, G.; Orhangul, A.; Pilatin, S. Investigation of Support. Structures for Direct Metal.
Laser Sintering (DMLS) of IN625 Parts; International Solid Freeform Fabrication Symposium: Austin, TX,
USA, 2015.
5. Cheng, B.; Chou, Y.K. Overhang Support Structure Design for Electron Beam Additive Manufacturing.
In Proceedings of the ASME 2017 12th International Manufacturing Science and Engineering Conference
Collocated with the JSME/ASME 2017 6th International Conference on Materials and Processing, Los Angeles,
CA, USA, 4–8 June 2017.
6. Jhabvala, J.; Boillat, E.; André, C.; Glardon, R. An innovative method to build support structures with a
pulsed laser in the selective laser melting process. Int. J. Adv. Manuf. Technol. 2012, 59, 137–142. [CrossRef]
7. Gibson, I.; Rosen, D.W.; Stucker, B. Additive Manufacturing Technologies; Springer: Berlin, Germany, 2010.
8. Thomas, D. The Development of Design Rules for Selective Laser Melting; University of Wales: Wales, UK, 2009.
9. Pullin, J.; Offen, A. Back to the Drawing Board-Addressing the design issues of RM. In Proceedings of the Time
Compression Technologies Rapid Manufacturing Conference 2008, Coventry, West Midlands, October 2008.
10. Sames, W.J.; List, F.; Pannala, S.; Dehoff, R.R.; Babu, S.S. The metallurgy and processing science of metal
additive manufacturing. Int. Mater. Rev. 2016, 61, 315–360. [CrossRef]
11. Das, P.; Mhapsekar, K.; Chowdhury, S.; Samant, R.; Anand, S. Selection of build orientation for optimal
support structures and minimum part errors in additive manufacturing. Comput. Aided Des. Appl. 2017, 14,
1–13. [CrossRef]
12. Bibb, R.; Eggbeer, D.; Williams, R. Rapid manufacture of removable partial denture frameworks.
Rapid Prototyp. J. 2006, 12, 95–99. [CrossRef]
13. Ameen, W.; Al-Ahmari, A.; Mohammed, M.K.; Mian, S.H. Manufacturability of Overhanging Holes Using
Electron Beam Melting. Metals 2018, 8, 397. [CrossRef]
14. Williams, R.E.; Melton, V.L. Abrasive flow finishing of stereolithography prototypes. Rapid Prototyp. J. 1998,
4, 56–67. [CrossRef]
15. Byun, H.-S.; Lee, K.H. Determination of the optimal part orientation in layered manufacturing using a genetic
algorithm. Int. J. Prod. Res. 2005, 43, 2709–2724. [CrossRef]
16. Piili, H.; Happonen, A.; Väistö, T.; Venkataramanan, V.; Partanen, J.; Salminen, A. Cost Estimation of Laser
Additive Manufacturing of Stainless Steel. Phys. Procedia 2015, 78, 388–396. [CrossRef]
17. Calignano, F. Design optimization of supports for overhanging structures in aluminum and titanium alloys
by selective laser melting. Mater. Des. 2014, 64, 203–213. [CrossRef]
18. Kuo, Y.-H.; Cheng, C.-C.; Lin, Y.-S.; San, C.-H. Support structure design in additive manufacturing based on
topology optimization. Struct. Multidiscip. Optim. 2017, 57, 1–13. [CrossRef]
19. Järvinen, J.P.; Matilainen, V.; Li, X.; Piili, H.; Salminen, A.; Mäkelä, I.; Nyrhilä, O. Characterization of effect of
support structures in laser additive manufacturing of stainless steel. Phys. Procedia 2014, 56, 72–81. [CrossRef]
20. Safdar, A.; He, H.; Wei, L.-Y.; Snis, A.; Chavez de Paz, L.E. Effect of process parameters settings and thickness
on surface roughness of EBM produced Ti-6Al-4V. Rapid Prototyp. J. 2012, 18, 401–408. [CrossRef]

195
Metals 2019, 9, 1211

21. Schwerdtfeger, J.; Singer, R.F.; Körner, C. In situ flaw detection by IR-imaging during electron beam melting.
Rapid Prototyp. J. 2012, 18, 259–263. [CrossRef]
22. Mahale, T.R. Electron Beam Melting of Advanced Materials and Structures, Mass Customization, Mass
Personalization. Ph.D. Thesis, North Carolina State University, Raleigh, CA, USA, 2009.

© 2019 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).

196
 MDPI
St. Alban-Anlage 66
4052 Basel
Switzerland
Tel. +41 61 683 77 34
Fax +41 61 302 89 18
www.mdpi.com

Metals Editorial Office

E-mail: [email protected]
www.mdpi.com/journal/metals
MDPI
St. Alban-Anlage 66
4052 Basel
Switzerland
Tel: +41 61 683 77 34
Fax: +41 61 302 89 18
www.mdpi.com ISBN 978-3-0365-1323-2