PROCESSING AND MECHANICAL BEHAVIOR OF

POWDER METALLURGY (PM) TI-6AL-4V

ALLOY MADE FROM TIH2

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by

Pankaj Kumar
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A dissertation submitted to the faculty of

The University of Utah
in partial fulfillment of the requirements for the degree of
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Doctor of Philosophy

Department of Metallurgical Engineering

The University of Utah

December 2016




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 The University of Utah Graduate School

STATEMENT OF DISSERTATION APPROVAL

The dissertation of Pankaj Kumar

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has been approved by the following supervisory committee members:

Ravi Chandran
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Date Approved

Zhigang Zak Fang , Member 8/16/2016

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Date Approved

Sivaraman Guruswamy , Member 8/16/2016

Date Approved
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Dinesh K. Shetty , Member 8/16/2016

Date Approved

Ashley Spear , Member 8/22/2016

Date Approved

and by Manoranjan Misra , Chair/Dean of

the Department/College/School of Metallurgical Engineering

and by David B. Kieda, Dean of The Graduate School.

 ABSTRACT

Powder metallurgy (PM) offers a cost-effective approach to produce titanium alloys

in near net shape. Conventionally, two general processes have been followed to produce

PM titanium alloys: Blended Elements (BE) and the Pre-Alloyed (PA) methods. Cost

considerations, however, favor BE over the PA method. BE titanium alloy products are

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typically characterized by a significant amount of residual porosity. In general, porosity

adversely affects the mechanical properties in PM titanium. Porosity acts as stress

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concentration sites and, at the same time, reduces the load bearing area, which leads to
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decrease in both the tensile strength and ductility of the material. Pores also have a

greater effect in reducing the fatigue life of PM titanium. In order to improve the

mechanical properties, porosity needs to be reduced or eliminated. It has been shown that
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effective densification and therefore improvement in mechanical properties of titanium

alloys can be achieved through the use of TiH2 powder.

In the first part of the present work, the effects of powder processing and sintering on

tensile properties of PM Ti-6Al-4V alloy processes by a newly developed PM process

based on TiH2, called “hydrogen sintering and phase transformation (HSPT)”, have been

examined. The investigation is aimed at the effect of TiH2 particle size and sintering time

on the tensile properties of HSPT-processed Ti-6Al-4V. Very fine powder particles lead

to enhance densification but increase the interstitial element, leading to reduced ductility

of the PM alloy. An increase in sintering time improves the tensile ductility

by reducing the pore size, without affecting the strength of the alloy. In the second part of

the present work, the effect of residual pores on the tensile properties of PM Ti-6Al-4V

alloys processed by HSPT has been examined. The primary objective is to establish a

relation between tensile ductility of the HSPT-processed Ti-6Al-4V and the extreme-

sized pores present as a part of the low-volume-fraction porosity in the material. Even

though each sample is similar to the other in terms of average volume-fraction porosity,

there was unusually large variation in ductility from sample to sample. It is observed that

the extreme-sized pores actually control the ductility of the PM Ti-6Al-4V alloy. A

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strong correlation has been found between the extreme pore size and tensile ductility. A

mathematical model is developed to predict the influence of the extreme-sized pores on

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the tensile ductility based on the assumption that the pore-containing area yields, causing

strain concentration and early crack initiation.

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A new sintering approach to enhance densification of PM Ti-6Al-4V alloy is

investigated in the last part of this work. The hypothesis of the approach is that the
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continuous phase transition (between α and β) leads to strain due to volume change

during phase transformation in addition to the enhanced self-diffusivity of titanium,

thereby accelerating the sintering kinetics. A phase reversal experiment was performed

by cyclic sintering across the phase transition temperature (1010°C) of Ti-6Al-4V alloy.

It was found that thermal cyclic across alpha (α)-beta (β) transition temperature led to a

reduction in residual porosity. A mechanical properties evaluation of Ti-6Al-4V alloy

indicated an improved mechanical properties (tensile and fatigue) compared to the

conventional vacuum-sintered Ti-6Al-4V alloy.

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 TABLE OF CONTENTS

ABSTRACT ....................................................................................................................... iii

LIST OF TABLES ........................................................................................................... viii

ACKNOWLEDGEMENTS ............................................................................................... ix

Chapters

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1. INTRODUCTION .........................................................................................................1

1.1 Background ........................................................................................................2

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1.2 Objectives of the Present Research ....................................................................5
1.3 References ..........................................................................................................5
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2. LITERATURE REVIEW ..............................................................................................8

2.1 Introduction ........................................................................................................9

2.1.1 The Blended-Element Method ..............................................................10
2.1.2 Pre-alloyed Powder Method ..................................................................11
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2.1.3 PM Methods Based on Titanium Hydride Powder................................13

2.2 Relative Merits of Processing Approaches for PM Ti-6Al-4V Alloy .............14
2.3 Microstructure of PM Ti-6Al-4V Alloys .........................................................17
2.4 Tensile Properties of PM Ti-6Al-4V Alloy .....................................................20
2.4.1 Strength-Ductility Map of PM Ti-6Al-4VAlloy ...................................20
2.4.2 Factors Affecting Strength-Ductility of BE PM Ti-6Al-4V Alloy .......21
[Link] Effect of Density and Purity ...................................................22
[Link] Effect of Post Sintering Treatment .........................................23
2.4.3 Factors Affecting Strength-Ductility of PA PM Ti-6Al-4V Alloy .......24
[Link] The Role of Microstructure and Heat Treatment ...................25
2.5 The Specific Effects of Porosity on Tensile Properties of PM Ti-6Al-4V ......27
2.5.1 Effect on Tensile Strength .....................................................................27
2.5.2 Effect on Tensile Ductility ....................................................................29
2.5.3 Strength-Ductility Maps at Constant Microstructure ............................32
2.6 Microstructure Factors Affecting Tensile Properties .......................................33
2.7 Effect of Manufacturing Process on the Tensile Properties.............................36
2.8 Summary ..........................................................................................................40
2.9 Acknowledgement ...........................................................................................42
 2.10 References ......................................................................................................52

3. MATERIALS AND EXPERIMENTAL PROCEDURE.............................................63

3.1 Starting Powder Preparation ............................................................................64

3.2 Powder Compaction .........................................................................................64
3.3 Sintering ...........................................................................................................65
3.3.1 Hydrogen Sintering and Phase Transformation (HSPT) Processing.....65
3.3.2 Thermal Cyclic Sintering ......................................................................66
3.3.3 Isothermal Vacuum Sintering ................................................................66
3.4 Density and Chemical Analysis .......................................................................66
3.5 Microstructure Analysis ...................................................................................67
3.6 Mechanical Testing and Fractography .............................................................67

4. EFFECTS OF POWDER PROCESSING AND SINTERING ON TENSILE

DUCTILTIY OF PM TI-6AL-4V ALLOY MADE BY HYDROGEN SINTERING

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OF TITANIUM HYDRIDE POWDERS.....................................................................71

4.1 Introduction ......................................................................................................72

4.2 Experimental Procedure ...................................................................................72
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4.3 Results and Discussion ....................................................................................73
4.4 Conclusions ......................................................................................................75
4.5 References ........................................................................................................75
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5. THE NATURE OF TENSILE DUCTILITY AS CONTROLLED BY EXTREME-
SIZED PORES IN POWDER METALLURGY TI-6AL-4V ALLOY .......................77

5.1 Introduction ......................................................................................................78

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5.2 Experimental Procedures .................................................................................79

5.3 Results .............................................................................................................80
5.3.1 Microstructure .......................................................................................80
5.3.2 Tensile Properties ..................................................................................81
5.4 Discussion ........................................................................................................83
5.4.1 Effect of Porosity on Strength ...............................................................83
5.4.2 Effect of Porosity on Tensile Ductility ..................................................85
5.4.3 Mechanism of Pore Size Effect on Ductility .........................................87
5.5 Conclusions ......................................................................................................89
5.6 References ........................................................................................................89

6. A CONSTITUTIVE EQUATION TO PREDICT THE PORE SIZE EFFECT ON

TENSILE DUCTILTIY OF LOW POROSITY MATERIALS ..................................90

6.1 Introduction ......................................................................................................91

6.2 Mechanism of Fracture Due to Presence of a Large Pore ...............................93
6.3 Analytical Model .............................................................................................95
6.3.1 Case I: Material Containing Uniformly Distributed Small Pores .........96

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 6.3.2 Case II: Material Containing Extreme Size Pore ..................................97
6.3.3 Fracture Conditions ...............................................................................98
6.4 Stress Concentration Factor .............................................................................99
6.5 Comparison with Experimental Data .............................................................100
6.6 Effect of Strain Hardening on Prediction of Tensile Ductility ......................102
6.7 Conclusions ....................................................................................................104
6.8 References ......................................................................................................110

7. ACCELERATED SINTERING OF POWDER METALLURGY TI-6AL-4V

ALLOY BY REPEATED PHASE TRANSFORMATION INDUCED BY
THERMAL CYCLING .......................................................................................112

7.1 Introduction ....................................................................................................113

7.2 Experimental Procedure .................................................................................115
7.3 Results and Discussion ..................................................................................117
7.3.1 Thermal Cycling and Isothermal Densification ..................................117

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7.3.2 Microstructure .....................................................................................121
7.3.3 Tensile Properties ................................................................................123
7.3.4 Fatigue Performance ............................................................................126
7.4 Conclusions ....................................................................................................128
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7.5 References ......................................................................................................146

8. CONCLUSIONS..................................................................................................150
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 LIST OF TABLES

2.1 Room-temperature tensile properties of lamellar PM Ti-6Al-4V alloy at various

density levels.............................................................................................................43

2.2 Room-temperature tensile properties of lamellar PM Ti-6Al-4V alloy at specific

microstructure conditions..........................................................................................44

2.3 Room-temperature tensile properties of lamellar PM Ti-6Al-4V alloy made from

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different initial powders ............................................................................................45

4.1 Chemical composition of HSPT Ti-6Al-4V alloys ...................................................73

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4.2 Effect of TiH2 particle size on the density and oxygen content of HSPT processed
Ti-6Al-4V .................................................................................................................73
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4.3 Tensile properties of HSPT Ti-6Al-4V samples .......................................................74

5.1 Chemical composition of HSPT-Processed Ti-6Al-4V ............................................79

5.2 Tensile Properties of HSPT-Processed Ti-6Al-4V samples .....................................83

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6.1 Parameters used for the prediction of pore size effect on the tensile ductility of cast
and PM alloys .........................................................................................................105

7.1 Chemical composition of vacuum-sintered PM Ti-6Al-4V....................................130

7.2 Density of PM Ti-6Al-4V alloy obtained in three different conditions .................130

7.3 Summary of tensile properties obtained for isothermal sintered compared with
cyclic sintered PM Ti-6Al-4V ................................................................................131
 ACKNOWLEDGEMENTS

I take this opportunity to express my sincere graduate to my advisor, Prof. K.S. Ravi

Chandran, for providing me an opportunity to work on this project. His constant guidance

and encouragement, and easily approachable personality made my project work

experience really enjoyable.

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I would like to thank, Prof. Z. Zak Fang for allowing me his facilities to carry out my

experiments, and serving on my supervisory committee. I am also thankful to Dr.

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Sivaraman Guruswamy, Dr. Ashley Spear, and Dr. Dinesh K. Shetty for serving on my
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supervisory committee. I extend my unlimited thanks to Pei, James, Mark, Matt, Lu, and

my lab mates Fei, Yuxuan, Bhaskar, and Madhusudan for their constant support in

carrying out my project work and taking their time to help me in getting things done. I
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express my sincere thanks to James Paramore for his help in setting up the furnace

facility. I am also thankful to Kay, Evelyn, and Sara Wilson for administrative support.

Last but not least, I need to thank my parents and sisters for their continued faith in

my abilities, their support, and their love, of which I have been the fortunate recipient

throughout my life.

Finally, I would like to acknowledge the financial grant from the U.S. Department of

Energy, Innovative Manufacturing Office and the Office of Energy Efficiency and

Renewable Energy, which made this project possible. The initial raw titanium hydride

and aluminum-vanadium powders were supplied by Reading Alloys (AMETEK), USA.

 CHAPTER 1

INTRODUCTION

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1.1 Background

Titanium materials are important engineering materials for structural applications.

Despite its excellent structural properties, use of titanium is restricted to a few

engineering applications such as aerospace and chemical and medical devices. The

common reason for its limited application is its cost. It was pointed out that most of the

cost of titanium comes from the cost of manufacturing processing [1]. The raw material

cost accounts only for 4% of the total cost of titanium [2]. Since the production and

manufacturing of titanium is expensive, its use is limited to high-end engineering

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applications. Powder metallurgy (PM) processing method, on the other hand, proved to

be cost effective, and has been used as an alternative to the conventional processing for

titanium [3].
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Conventionally, PM titanium and its alloy product follow two general processing
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methods: Blended Elements (BE) and the Pre-Alloyed (PA) methods [4]. In BE method,

the raw powders are blended, compressed, and then sintered. The amount of residual
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porosity in the final product, however, is large, which ultimately dictates the poor

mechanical properties. On the other hand, the PA process uses the pre-alloyed powder to

sinter. Though the properties of the final product of the PA process are better than the

BE-processed materials, the processing is not cost effective. Therefore, the BE method is

preferred over the PA method.

Different alternatives have been tried and applied to reduce the residual porosity in

BE product. In recent years, vacuum sintering of TiH2 powder emerged as a prevailing

technique to produce near porosity-free titanium and its alloy. People have shown the

improved sinterability, low residual porosity, and better mechanical properties in titanium
 3

processed by vacuum sintering of TiH2 powders [5]. The improved porosity level in the

final product has been attributed partially to the hydrogen cleaning of the surfaces during

sintering. In addition, hydrogen refines and thus modifies the microstructure of the

material, therefore improving the properties. By taking advantage of hydrogen as a

temporary alloying element, a new method has been recently introduced to produce fully

densified BE product [6]. This process uses a controlled hydrogen atmosphere to sinter

the TiH2 powder instead of using vacuum sintering. This process is thus called the

Hydrogen Sintering and Phase Transformation (HSPT) process. This process is able to

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produce fully densified and fine microstructure of Ti and its alloys.

Though we can produce high-density PM product, the residual porosity has always
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been a concern in PM materials. It is well known that the PM-processed components may

exhibit different mechanical properties (fracture-related properties) despite having the

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same processing conditions, average microstructure, and alloy chemistry. The variability

can be attributed to the defects present in the materials. As we know in PM materials,

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porosity contributes the major part of the defect and thus controls the properties of the

materials. Several studies have related the effect of porosity on the mechanical properties

in various material systems [7–13]. Porosity in materials greatly affects the ductility of

the materials. Similar processed components exhibit different ductility levels. Caceres et

al. [14] describe a relationship between the ductility and area fraction of porosity. Power-

law-type expression is proposed by Gokhale et al. [8] to correlate the tensile ductility and

area fraction of porosity in cast Al alloys. Note that all the studies above are focused on

the effect of total area fraction of defects on the fracture surface on the tensile ductility.

But as we know, the fracture is a highly localized phenomenon, i.e., a crack tends to form
 4

in the weakest cross-section from a large pore. Strain localization at pores leads to early

crack initiation, thus limiting the plastic deformation, i.e., the ductility of the materials

and the fatigue life. There are pores that are big enough to act as fracture initiation sites

during applications. These pores are not part of the average microstructure but occur due

to rare events during processing.

Also, processing variables such as initial particle size, impurities, sintering

temperature, and time have significant effect on the amount of residual porosity, and

consequently the tensile properties of PM titanium change. It would be interesting to

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study how raw particle size and sintering parameter affect the tensile properties of a PM

titanium alloy.
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One of the objectives of this research is to systematically study of how the residual

pores at low-volume fraction affect the tensile properties of HSPT-processed PM Ti-6Al-

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4V alloy. The pore size distribution and pore morphology are also investigated as part of

the study. A theoretical model based on the local strain concentration needs to be
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developed to quantitatively illustrate the effect of residual pore on the tensile properties.

In addition, effects of powder process and sintering on tensile properties of PM Ti-6Al-

4V alloy processes by HSPT are studied.

A unique characteristic of HCP transition metals like titanium is that they show

anomalous diffusion behavior at phase transition temperature. In these metals, the self-

diffusivities are anomalous higher than at other temperatures, and thus do not follow the

Arrhenius law of diffusion [15]. On this basis, one of the hypotheses of this work is that

that diffusivity enhancement at phase transition temperature should cause rapid

densification at this temperature. The various sintering conditions near phase transition
 5

temperature and their effectiveness in accelerating the densification are investigated in

this research.

1.2 Objectives of the Present Research

The general objective of this research is to investigate the processing effects on the

microstructure and, consequently, the mechanical properties of PM Ti-6Al-4V alloy. The

key objectives are the following:

1. Establish relationship between powder processing, sintering and tensile properties

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of PM Ti-6Al-4V alloy made by HSPT process.

2. Determine the process variables and the microstructural constituents affecting the
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tensile properties of PM Ti-6Al-4V alloy. The possible mechanisms responsible for the

varying tensile properties are also to be determined.

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3. Develop a quantitative model that can explain the tensile behavior with the

microstructural discontinuities such as porosity in PM Ti-6Al-4V alloy.

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4. Investigate the process that can enhance the sintering kinetics and therefore

improve the mechanical properties, including the mechanisms responsible for the

sintering kinetics caused during the sintering, and its effect on densification of the PM Ti-

6Al-4V alloy.

1.3 References

[1] V.C. Petersen, V.K. Chandhok, C.A. Kelto, Hot isostatic pressing of large
titanium shapes, in: F.H. Froes, J.E. Smugeresky (Eds.), Powder Metall. Titan.
Alloy., A.I.M.E, Warrendale, PA, USA, 1980: pp. 243–254.

[2] A.D. Hartman, S.J. Gerdemann, J.S. Hansen, Producing lower-cost titanium for
automotive applications, Jom. 50 (1998) 16–19. doi:10.1007/s11837-998-0408-1.
 6

[3] I.S. Polkin, V.N. Samarov, Advances in Powder Metallurgy of Titanium, in: Ti-
2011, Beijing, China, 2011: pp. 1817–1820.

[4] F.H. Froes, D. Eylon, Powder metallurgy of titanium alloys, Int. Mater. Rev. 35
(1990) 162–184. doi:10.1179/095066090790323984.

[5] O.M. Ivasishin, D.G. Savvakin, F.H. Froes, V.S. Mokson, K. Bondareva,
Synthesis of the Ti-6 Al-4 V alloy having low residual porosity by powder
metallurgy method, Poroshkovaya Metall. 7 (2002) 54–64.

[6] Z.Z. Fang, P. Sun, H. Wang, Hydrogen Sintering of Titanium to Produce High
Density Fine Grain Titanium Alloys, Adv. Eng. Mater. 14 (2012) 383–387.
doi:10.1002/adem.201100269.

[7] G.W. Mugica, D.O. Tovio, J.C. Cuyas, A.C. González, Effect of porosity on the
tensile properties of low ductility aluminum alloys, Mater. Res. 7 (2004) 221–
229. doi:10.1590/S1516-14392004000200002.

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[8] A.M. Gokhale, G.R. Patel, Origins of variability in the fracture-related
mechanical properties of a tilt-pour-permanent-mold cast Al-alloy, Scr. Mater.
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52 (2005) 237–241. doi:10.1016/[Link].2004.09.011.

[9] H. Mae, X. Teng, Y. Bai, T. Wierzbicki, Relationships between Material

Ductility and Characteristic Size of Porosity Correlated before/after Testing of a
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Cast Aluminum Alloy, J. Solid Mech. Mater. Eng. 2 (2008) 924–942.
doi:10.1299/jmmp.2.924.

[10] R. Haynes, A study of the effect of porosity content on the ductility of sintered
metals, Powder Metall. 20 (1977) 17–20.
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[11] Y. Yan, G.L. Nash, P. Nash, Effect of density and pore morphology on fatigue
properties of sintered Ti–6Al–4V, Int. J. Fatigue. 55 (2013) 81–91.
doi:10.1016/[Link].2013.05.015.

[12] P. Kumar, K.S. Ravichandran, F. Cao, P. Sun, M. Koopman, Z.Z. Fang, Effects
of Powder Processing and Sintering on Tensile Ductility of Pm Ti-6Al-4V Alloy
Made by Hydrogen Sintering of Titanium Hydride Powders, in: Ti-2015 Sci.
Technol., The Minerals, Metals and Materials Society, 2015: pp. 1355–1359.

[13] M. Hagiwara, Y. Kaieda, Y. Kawabe, S. Miura, Fatigue Property Enhancement

of .ALPHA.-.BETA. Titanium Alloys by Blended Elemental P/M Approach.,
ISIJ Int. 31 (1991) 922–930. doi:10.2355/isijinternational.31.922.

[14] C.H. Cáceres, B.I. Selling, Casting defects and the tensile properties of an
AlSiMg alloy, Mater. Sci. Eng. A. 220 (1996) 109–116. doi:10.1016/S0921-
5093(96)10433-0.

[15] B. Sarma, Accelarated Kinetics and Mechanics of Growth of Boride layers on

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Titanium unider Isothermal and Cyclic Diffusion, PhD Thesis, University of

Utah, 2011.

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 CHAPTER 2

LITERATURE REVIEW

Submitted for publication as:

P. Kumar and K.S. Ravi Chandran

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Strength-Ductility Property Maps of Powder Metallurgy (PM) Ti-6Al-4V Alloy: A

Critical Review of Processing-Structure-Property Relationships

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Metallurgical and Materials Transaction A, 2016
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.
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2.1 Introduction

Titanium alloys are attractive for light-weight structural applications due to their

relatively high specific stiffness and strength properties, good creep resistance, and

excellent corrosion resistance [1,2]. Despite the excellent combination of physical and

mechanical properties both at ambient and elevated temperature, extensive usage of

titanium is limited to high-value aerospace and chemical industry applications. This is

largely due to the relatively high costs of the finished titanium products. While the raw

material cost is relatively high, a large portion of the total cost of manufacturing titanium

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components is actually associated with the machining of wrought material into the

finished components [3]. A study [4] indicates that about 30% of the total cost of titanium
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is spent in machining rough-forged titanium components to final product forms. This

figure, put in perspective, is notably higher than the cost of metal charge and casting
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combined (26%). In addition, the total utilization factor (defined as the weight percentage

of raw material that becomes the final component) for machining rough-forged
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components to finish product is about 17% [5]. The combined material loss and

fabrication costs inevitably increase the total cost of titanium components. Therefore,

production of near net-shape (NNS) titanium components is a very attractive option to

reduce the overall cost of the titanium product, especially if the material loss in

machining can be largely minimized.

Powder metallurgy (PM) is the principal NNS manufacturing process that has the

potential to reduce the material loss, processing steps, and fabrication costs associated

with the wrought forms. The PM approach to making sintered titanium compacts was

first reported by Kroll [6] in the late 1940s. However, the presence of residual impurities,
 10

especially magnesium chloride in the alloy, severely degraded the mechanical properties

and the weldability of titanium alloy [7,8]. Abkowitz et al. [8] studied the effect of

chlorine on the mechanical properties of PM Ti-6Al-4V alloy. A significant improvement

in density and mechanical properties, especially fatigue strength, was shown when the

chloride content was decreased from 0.16 wt.% to 0.016 wt.%. However, the titanium

PM route was not pursued widely due to the lack of approaches to produce high-purity

titanium powder at that time.

Since Kroll’s work, several studies have focused on developing further the PM

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approach for titanium. The primary goal is to reduce cost and material loss in

manufacturing, with the need to improve mechanical properties playing a secondary role.
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If a commercial NNS-processed PM Ti-6Al-4V alloy could be made at a much-reduced

cost, with properties roughly equivalent to the wrought forms, then the hurdles to
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practical applications will be minimal. With this broader objective, various techniques

were developed, first, for the production of high purity titanium alloy powder in 1980s.
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Secondly, two manufacturing approaches were pursued in order to establish PM of

titanium alloys as a low-cost manufacturing technique. One is the blended elemental (BE)

method and the other is the pre-alloyed (PA) powder method [9–11]. Prototype

components of titanium were made using PM and cost minimization strategies have been

demonstrated [12,13].

2.1.1 The Blended-Element Method

The BE method refers to the process of cold pressing of blended elemental powders

followed by sintering at a temperature higher than the beta-transus temperature. The

 11

desired alloy composition is attained by mechanically blending the elemental titanium

powder and the powders of alloy elements. The blended powder is then pressed into

desired shapes and then pressure-less sintered at high temperature, usually in the beta-

phase field, in order to homogenize the microstructure with respect to the high-melting-

point alloying elements such as V, Mo, Cr, etc. A titanium component produced by the

BE method generally tends to have poor mechanical properties, primarily due to a

significant residual porosity (94% relative density), coarse microstructure (lamellar

colonies with large prior-beta grains), and impurities from the initial powders [7,14]. A

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major disadvantage of this approach is that the microstructure of the BE PM titanium

alloy cannot be refined further without any additional mechanical working, which would
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very likely increase the cost of the final PM product. In general, the BE PM Ti-6Al-4V

alloys have subpar mechanical properties compared to wrought Ti-6Al-4V, especially

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fatigue strength.
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2.1.2 Pre-alloyed Powder Method

The PA method, on the other hand, has been found to produce components with

mechanical properties comparable to those of wrought Ti alloys. It was pursued

extensively in the 1980s for the production of Ti-alloy components with superior

mechanical properties, especially fatigue strength, the levels of which were often targeted

to rival those of the wrought titanium and with an intention of introduction into aerospace

applications. This method also uses sintering of pre-alloyed powders in the beta-phase

field. This process uses very high-purity pre-alloyed powders made by, for example, the

rotating electrode (PREP-plasma rotating electrode process) process [15]. Additionally,

 12

gas-atomization (GA) and electrode-induction-gas-atomization (EIGA) are some of the

techniques that have been used to produce spherical pre-alloyed titanium powder [15].

However, the pre-alloyed powders showed poor pressability or deformation

characteristics. Hence, they had to be consolidated using pressure-assisted consolidation

techniques such as hot iso-static pressing (HIP), to achieve nearly 100% density [16–19].

There is no doubt that the PA method can produce titanium components with

properties comparable to those of wrought materials, but the energy consumed in both the

powder production and the HIPing steps makes the PA method significantly more

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expensive than the BE method. Cost consideration therefore strongly favors the BE

method over the PA method. Therefore, substantial research efforts, from powder
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production to postsintering treatments, have been directed to improve the properties of

BE titanium. An example is the advancement of the BE approach by the use of low-

EV
chlorine titanium powder [20–28]. It is known that a chlorine content of > 0.2 wt%

adversely affects the densification process during sintering [8,29,30]. Nearly 100%
PR

density in PM compacts was achieved in the BE Ti-6Al-4V alloy using titanium powders

with a chlorine content less than 10 ppm [31]. Additionally, several studies have used

postsintering thermo-mechanical processing steps, such as hot forging and heat treatment,

in an effort to close the residual pores and to increase the levels of mechanical properties

[31–34]. It is therefore evident that some form of mechanical working is necessary to

bring up the properties of BE PM titanium to the levels of wrought forms—it is the

postsintering mechanical working step to close the pores in BE method and it is the

HIPing step to consolidate the poorly deformable alloy powders in the PA method. There

is no doubt, however, that the postsintering treatments, which are energy intensive,
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largely contribute to the increased cost and the complexity of processing steps in PM

titanium manufacturing.

2.1.3 PM Methods Based on Titanium Hydride Powder

In this approach, hydrogenated titanium (titanium hydride, TiH2) powder is used as

feedstock to make PM titanium alloy components. In general, hydrogen is considered an

unwanted element in titanium alloy, due to the hydrogen embrittlement of titanium at

hydrogen concentrations in excess of about 100 ppm. However, due to the high

W
diffusivity of H in Ti and the reversible nature of the hydrogenation reaction, hydrogen

can be easily incorporated or removed from a titanium matrix at high temperature. The
IE
use of hydrogenated titanium for sintering a niobium-based superconductor alloy was

first reported by Gregory in 1969 [35]. Subsequently, a process to make titanium alloy
EV
and titanium metal matrix composites using TiH2 powder, by hot pressing, was reported

and was named, “decomposition sintering” [36]. Obara et al. in 1976 [37] showed that
PR

TiH2, blended with alloying elements, can be pressed and sintered between 1273K

(1000°C) and 1773K (1500°C) to make PM titanium alloys. Since 2000, significant

progress on PM processes based on titanium hydride powder has been made [38–42]. In

general, in these studies, an increase in the green density and the green strength of PM

compact as well as a significant increase in sintered density, relative to that of

conventional PM methods, are often quoted as major advantages [22,43]. Several studies

[44–47] have shown that a relatively high-density (>98%) alloy with a highly refined

microstructure can be achieved using TiH2 powder as feedstock, without using any

additional mechanical or heat treatment steps after sintering. Consequently, a significant