Article

Compositional Design, Microstructure, and Thermal Processing

of Aluminum-Based Complex Concentrated Alloys
Spyridon Chaskis 1,2, * , Constantinos Tiktopoulos 1 , Evangelos Gavalas 3 , Marianthi Bouzouni 3 , Fotis Tsiolis 3
and Spyros Papaefthymiou 1, *

1 Laboratory of Physical Metallurgy, Division of Metallurgy and Materials, School of Mining and Metallurgical
Engineering, National Technical University of Athens, 9, Heroon Polytechniou Street, 15780 Athens, Greece;
[email protected] or [email protected]
2 Technology and R&D Department of HALCOR, Copper Tubes and Alloys Extrusion Division,
ELVALHALCOR S.A., 62nd km Athens-Lamia National Road, 32011 Oinofyta, Greece
3 Department of Physical Metallurgy and Forming, Hellenic Research Centre for Metals (ELKEME S.A.),
61st km Athens-Lamia National Road, 32011 Oinofyta, Greece; [email protected] (E.G.);
[email protected] (M.B.); [email protected] (F.T.)
* Correspondence: [email protected] or [email protected] (S.C.); [email protected] (S.P.);
Tel.: +30-69-7958-7537 (S.C.)

Abstract: Three lightweight aluminum-based complex concentrated alloys with chemi-

cal compositions that have not been previously studied were manufactured and studied:
Al52 Mg9.6 Zn16 Cu15.5 Si6.9 w.t.% or Al63 Mg13 Zn8 Cu8 Si8 a.t.% (alloy A), Al44 Mg18 Zn19 Cu19
w.t.% or Al55 Mg25 Zn10 Cu10 a.t.% (alloy B), and Al47 Mg21.4 Zn12 Cu9.7 Si9.7 w.t.% or
Al52.7 Mg26.6 Zn5.6 Cu4.6 Si10.4 a.t.% (alloy AM), with low densities of 3.15 g/cm3 , 3.18 g/cm3
and 2.73 g/cm3 , respectively. During alloy design, the CALPHAD method was used to
calculate a variety of phase diagrams for the various chemical compositions and to predict
possible phases that may form in the alloy. The CALPHAD methodology results showed
good agreement with the experimental results. The potential of the designed alloys to be
used in some industrial applications was examined by manufacturing them using standard
industrial techniques, something that is a rarity in this field. The alloys were produced
using an induction furnace and pour mold casting process, while industrial-grade raw
materials were utilized. Heat treatments with different soaking times were performed
Academic Editor: Yuying Wu in order to evaluate the possibility of improving the mechanical properties of the alloys.
Received: 19 December 2024 Alloys A and AM were characterized by a multiphase microstructure with a dendritic
Revised: 7 January 2025 FCC-Al matrix phase and various secondary phases (Q-AlCuMgSi, Al2 Cu and Mg2 Si),
Accepted: 11 January 2025
while alloy B consisted of a parent phase T-Mg32 (Al,Zn)49 and the secondary phases α-Al
Published: 17 January 2025
and Mg2 Si. The microstructure of the cast alloys did not appear to be affected by the
Citation: Chaskis, S.; Tiktopoulos, C.;
heat treatments compared to the corresponding as-cast specimens. However, alterations
Gavalas, E.; Bouzouni, M.; Tsiolis, F.;
Papaefthymiou, S. Compositional
were observed in terms of the elemental composition of the phases in alloy A. In order to
Design, Microstructure, and Thermal investigate and evaluate the mechanical properties of the as-cast and heat-treated alloys,
Processing of Aluminum-Based hardness testing along with electrical conductivity measurements were conducted at room
Complex Concentrated Alloys. temperature. Among the as-cast samples, alloy AM had the highest hardness (246 HV4 ),
Crystals 2025, 15, 88. https://doi.org/ while among the heat-treated ones, alloy A showed the highest value (256 HV4 ). The
10.3390/cryst15010088
electrical conductivity of all the alloys increased after the heat treatment, with the highest
Copyright: © 2025 by the authors. increase occurring during the first 4 h of the heat treatment.
Licensee MDPI, Basel, Switzerland.
This article is an open access article Keywords: complex concentrated alloys; aluminum-based alloys; lightweight high-entropy
distributed under the terms and
alloys; CALPHAD; mechanical properties; heat treatment; application-based design
conditions of the Creative Commons
Attribution (CC BY) license
(https://creativecommons.org/
licenses/by/4.0/).

Crystals 2025, 15, 88 https://doi.org/10.3390/cryst15010088

Crystals 2025, 15, 88 2 of 26

1. Introduction
In the automotive industry, reducing the vehicle’s weight is the primary goal in order
to lower fuel consumption and CO2 emissions. Aluminum, with its low specific weight
and excellent mechanical properties, plays a key role in achieving this objective [1]. An
average car (1300–1400 kg) contains approximately 180 kg of aluminum, of which, 65%
(117 kg) is cast aluminum—about 10% of the vehicle’s total weight [2,3]. Notably, reducing
a vehicle’s weight by 1 kg can prevent 20 kg of CO2 emissions over its lifecycle [4].
The key cast aluminum components include cylinder heads, engine blocks, pistons,
brake calipers, rims, and crankcases. Pistons, subjected to high mechanical and thermal
loads, require alloys with high strength, hardness, and thermal stability [5]. Cylinder
heads and engine blocks prioritize strength, thermal conductivity, and recyclability, with
recycled aluminum gaining importance over primary aluminum as a raw material [5].
Common alloys such as AlCu4 MgSi (A206), AlSi10 Mg (A360), and AlSi9 Cu3 (A380) are
widely used, though the adoption of cast aluminum in automotive applications is expected
to decline [2]. Therefore, continuous research is being carried out to develop novel low-
density alloys, which will have the required properties at a reasonable cost in order to
replace Al cast components.
Aluminum alloys are essential in internal combustion engine (ICE) applications, where
they must exhibit high strength, fatigue resistance, and thermal stability [6]. While tra-
ditional Al-Si alloys have dominated due to their casting properties and mechanical per-
formance [6], sustainability goals have prompted exploration of complex concentrated
alloys (CCAs). These CCAs can incorporate recycled aluminum scrap with a high alloying
element content, transforming post-consumer waste into valuable raw materials. This
approach conserves natural resources, while reducing energy consumption and the carbon
footprint of aluminum production. The innovative use of “dirty” alloys, as highlighted by
Raabe et al., enables the development of advanced aluminum alloys that meet stringent
mechanical requirements while promoting a circular economy by leveraging sustainable
raw materials [7].
In this direction, along with the CCAs, the Lightweight High-Entropy Alloys
(LWHEAs) could offer an alternative. In general, High-Entropy Alloys (HEAs) consti-
tute a relatively new field of research that is trying to subvert and revitalize the materials
science sector’s way of thinking about alloying design strategies. Lightweight High Entropy
Alloys (LWHEAs) are defined as alloys with a density less than or equal to that of commer-
cial titanium alloys (4.51 g/cm3 ) [8]. In other publications, alloys with a density lower than
the density of an alloy used for a particular application are considered LWHEAs [9].
By definition, HEAs or equiatomic multicomponent alloys are composed of at least
five metallic elements in equimolar or near-equimolar ratios [10]. Yeh et al. proposed
a classification of the alloys based on their configurational entropy (∆Sconf). The alloys
were classified as HEAs if their ∆Sconf in a random state is greater than 1.5 R (R being
the gas constant); as Medium-Entropy Alloys (MEAs) when the value of their ∆Sconf is in
the range of 1R-1.5 R; and finally, traditional alloys are classified as Low-Entropy Alloys,
with a ∆Sconf less than 1R. The concept of HEAs was initially based on the theory that
an increase in the number of alloying elements would result in an increase in the ∆Sconf
of such systems and it would promote solid-solution (SS) structures, such as FCC and
BCC structures [10]. However, now that this field is more scientifically mature, this effect
is not considered to be as great as was initially believed [11], since the addition of more
components has been proven to lead to the formation of second phases [12]. Therefore,
since the limitation of single-phase SS microstructures was surpassed, the term CCAs [8]
was introduced, which enables a greater degree of freedom in the design and development
of novel compositions with a more complex microstructure, which could provide broader
Crystals 2025, 15, 88 3 of 26

potential comparing to HEAs. Multiphase HEAs, known as CCAs [13], are now mainly
composed of two or more phases, sharing similar core effects with HEAs and are a unique
subject of research [14]. High-Entropy Aluminum Alloys (HEAls), a promising derivative
of HEAs, were recently introduced by Asadikiya et al. as a novel category of aluminum
alloys [15]. Although, their entropy is lower than that of traditional HEAs, HEAls still take
advantage of it to achieve enhanced properties [16]. The formation of intermetallics (ICs) in
HEAls is inevitable due to the high negative enthalpy of mixing (∆Hmix) between Al and
most of the commonly employed alloying elements [4]. As a result, HEAls generally feature
multiphase microstructures with α-Al solid-solution phases reinforced by multicomponent
ICs. Mundrha et al. proposed this novel approach as robust design direction to create
high-performance Al alloys strengthened with multicomponent ICs [9].
HEAs, MEAs, and CCAs are usually manufactured using expensive high-purity raw
materials and vacuum arc melting and vacuum induction melting techniques, in an Ar
or N2 protective atmosphere, and cast in water-cooled copper molds [15]. However, in
order to scale up the production of these alloys, a more industrially applicable approach
is necessary [9,16]. In the industry, instead of high-purity raw materials, industrial-grade
raw materials are used, making the large-scale production of metals sustainable [14,17].
Thus, the concept of a circular economy is capitalized on and added value is created for
lower-purity materials [18–20]. The aim of the current project was to design alloys using
standard industrial techniques and economically viable raw materials.
Barnett et al. introduced a scrap-tolerant alloying concept based on HEAs, highlighting
compositional flexibility as a pathway to create value from waste alloys [18]. HEAls are
promising for high-wear, high-temperature applications, and as candidate materials for
circular product design. Their multicomponent, multiphase compositions also render them
suitable for manufacturing using recycled scrap materials.
There have been several studies of promising Lightweight HEAs (LWHEAs) using Al
as the principal element. Lei Shao et al. developed a series of low-density alloys with Al
and Mg as the main components, accounting for 90 at.% of the alloy, with the remaining
components consisting of Cu, Zn, and Si [21]. These alloys were prepared using pure raw
materials in an Ar protective atmosphere and they presented densities ranging from 2.64 to
2.75 g/cm3 and compression strengths of up to 814 MPa. Their microstructure consisted of
various large intermetallic phases such as Mg2 Si and Mg32 (AlZn)49 within an aluminum
matrix. Using the same components, Sanchez et al, through Thermocalc software (TCAL5
database), designed two systems, Al65 Cu5 Mg5 Si15 Zn5 X5 and Al70 Cr5 Cu5 Mg5 Si10 Zn5 X5 ,
where the elements Fe, Ni, Cr, Mn, and Zr were introduced in place of X. The best results
were from the Al70 Cr5 Cu5 Mg5 Si10 Zn5 at.% alloy, which consisted of Al2 Cu, Mg2 Si, and
Al13 Cr4 Si4 intermetallic phases in an aluminum matrix with compressive strength of
490 MPa, plastic deformation of 6%, and microhardness of 200HV0.1 . The rest of the
alloys demonstrated slightly higher strengths and hardnesses, but the majority exhibited
embrittlement behaviors [13]. Following his original research, Sanchez designed a number
of LWHEAs by testing various combinations of compositions with the primary elements
Al, Mg, Cu, Zn, and Si and additional elements Ca, Ti, Sn, Mn, Ni, and Fe [8,22,23].
The results of his work revealed that with the HEA design strategy, hardness values
ranging from 437 HV to 916 HV with densities in the range of 3.15–5.10 g/cm3 could be
achieved. In further continuation of this design strategy, Sanchez et al. designed two
scrap-tolerant LWHEAs, Al65 Cu10 Mg10 Si10 Zn5 and Al80 Cu5 Mg5 Si5 Zn5 at.%, with high
compressive strengths of 696 and 722 MPa, respectively, due to the formation of ICs [24]. In
an attempt to produce alloys with even lower densities, Tun et al. used Li in the composition
of their alloys. As a result, they successfully manufactured Al70 Li10 Mg10 Cu5 Zn5 and
Al75 Li10 Mg5 Cu5 Zn5 a.t% systems, with densities of 2.76 g/cm3 and 2.7 g/cm3 , respectively.
Crystals 2025, 15, 88 4 of 26

The alloys were prepared using disintegrated melt deposition and ultra-pure raw materials
in a protective Ar atmosphere [25] [21]. In fact, the latter alloy, which presented the highest
compressive strength (533 MPa), was also examined for its anti-corrosion behavior, with
encouraging results [26]. However, Li is a scarce and expensive raw material. More
generally, the density found in the LWHEA literature varies between 2.67 g/cm3 and
5.20 g/cm3 [12]. The largest high-entropy alloy reported in the literature is approximately
10 kg with a density of 3.08 g/cm3 and it is the only Al-based CCA, which was prepared
by electromagnetic stirring casting. Using this method, a microhardness of 177 HV and
compressive strength of 554 MPa were achieved. The most important finding of this
work, however, was that the electromagnetic frequency influenced the morphology and
distribution of the Mg2 Si phase, whose average particle size decreased from 40.0 to 17.7 mm.
The research on the Al-Mg-Zn-Cu-Si system is limited to few alloys [27]. Recently, Chaskis
et al. designed an Al58 Mg18 Zn12 Cu5 Si7 at.% (Al47.4 Mg13 Zn23 Cu9 Si6 wt.%) alloy, which
displayed a multiphase microstructure consisting of an Al matrix reinforced with various
secondary phases, such as Mg2 Si and MgZn2 . In terms of mechanical properties, the
developed alloy exhibited a high hardness value of 249 Vickers and compressive strength
of 588 MPa. In this work, it was proven that, if the Mg2 Si phase is present in large
amounts, it leads to embrittlement of the alloy [28,29]. Nonetheless, the importance of
controlling Mg2 Si- and Mg-bearing eutectic phases was underlined, since plasticity can be
compromised [30]. Therefore, a way to reduce the size and the percentage of this phase is
deemed important.
However, most studies on these alloys have focused solely on hardness and compres-
sive strength, with limited investigation into other mechanical properties. Additionally,
alloy designs often lack application-specific targets, complicating the assessment of their
potential to replace existing commercial materials. Moreover, the reliance on protective at-
mospheres and high-purity raw materials in HEA production significantly increases costs.
The motor contributes slightly to the overall vehicle weight, but sustainability de-
mands innovative solutions to repurpose cast aluminum alloys from machine parts and
utilize them as raw materials. These alloys, with their high alloying content, are unsuitable
for malleable products and require alternatives for use in next-generation internal com-
bustion engines (ICEs) or other cast aluminum components. For example, Tesla utilizes
two die-cast aluminum parts for the chassis of its models, highlighting opportunities for
aluminum-based CCAs in a circular product design approach.
To evaluate their industrial potential, the alloys in this study were manufactured
in a standard induction furnace without a protective atmosphere, using industrial pu-
rity raw materials from the Greek metallurgical industry. Developed for cast aluminum
automotive components, the alloys were compared with 3xx and 7xx series casting al-
loys since they combine elements from these groupings. This research aimed to develop
lightweight aluminum-based alloys in the Al-Mg-Cu-Zn-Si and Al-Mg-Cu-Zn systems
using an industry-relevant approach.
In this work, the term HEAs is used for single-phase alloys with a ∆Sconf greater than
1.5 R. The term CCAs is used for multiphase alloys with a ∆Sconf greater than 1.5 R. Finally,
MEAs have a ∆Sconf that lies between 1 R and 1.5 R. Since MEAs can also be multiphase
alloys, in order to better describe the manufactured alloys under investigation, the term
CCAs was adopted. The developed alloys could offer a lightweight alternative to some
other aluminum alloys, while promoting a sustainable alloy design approach utilizing
raw materials commonly used in industry practices. Moreover, the compositional design
focuses on controlling the size and the percentage of specific phases found in earlier studies.
This work provides valuable information for researchers aiming to design and produce
industry-like aluminum-based CCAs with an industrially relevant approach.
Crystals 2025, 15, 88 5 of 26

2. Materials and Methods

In this work, the Al-Mg-Cu-Zn-Si and Al-Mg-Cu-Zn systems were selected for study.
Aluminum was chosen to be the main component of the alloy due to its low specific weight,
combined with its excellent mechanical properties and recyclability [1]. The remaining
components were selected based on certain criteria, such as
• Widely available components in the Greek metallurgical industry.
• Does not significantly increase the specific weight of the alloy.
• Provides positive properties to the alloy for its final application.
The components Mg, Zn, Cu, and Si satisfy most of the requirements and were there-
fore considered the most suitable. The design of the first system was based on the restriction
of the Mg2 Si phase in a controlled quantity. Although this phase is known to enhance the
hardness of commercial aluminum alloys [31], when present in large amounts, it has been
proven to lead to embrittlement of the alloy [28,29] due to its high hardness in contrast to
the neighboring phases. It is also known that Al-Cu alloys exhibit deteriorated casting prop-
erties, which significantly limits the production of these alloys. Additionally, they do not
respond to aging heat treatments, preventing the achievement of higher levels of strength-
ening [30]. Thus, the chemical composition of the first alloy (alloy A—Al63 Mg13 Zn8 Cu8 Si8
a.t.%) was chosen with the aim of having a very low percentage of the Mg2 Si phase ac-
cording to the Thermocalc software’s calculations (TCAL7 database). The design of the
second system (alloy B—Al55 Mg25 Zn10 Cu10 a.t.%) was based on the complete absence of
the Mg2 Si phase, so that the properties of an Al-based HEA without its presence could be
examined. Finally, the purpose of the third alloy (alloy AM—Al52.7 Mg26.6 Zn5.6 Cu4.6 Si10.4
a.t.%) design was to test the limits of adding Mg to an HEA without ignition occurring in
the melt pool.
For the purpose of designing HEAs and CCAs, some thermo-physical parameters,
based on Hume–Rothery rules and thermodynamic parameters, were taken into ac-
count [32]. These criteria consist of parameters such as the enthalpy of mixing in the
liquid phase (∆Hmix), atomic size difference (r), Pauling electronegativity difference (∆χ),
and Ω parameter. In the current study, the artificial neural network software pyMPEALab
Toolkit (Upadesh Subedi et al.) was used for the thermodynamic calculations, as a means
of calculating the thermo-physical parameters of the chosen alloys [33].
Thermocalc® software (Version 2022a, Thermo-Calc Software AB, Stockholm, Sweden)
in conjunction with the TCAL7 [34] thermodynamic database was used to calculate a variety
of phase diagrams for various chemical compositions with the selected components during
the alloy development process. ThermoCalc® software utilizes the CALPHAD (CALcu-
lation of PHAse Diagrams) method which has been extensively used in the prediction of
the thermodynamic equilibrium of multicomponent systems. In the CALPHAD method,
the thermodynamic equilibrium is predicted by minimizing the total ∆G for a certain
temperature, pressure, and chemical composition. The TCAL7 database is commonly used
for commercial Al alloys and according to previous works, the use of this database for
Al-based HEAs shows good agreement with experimental results [8,29]. This tool shows
the equilibrium phases as a function of temperature in order to provide an approximate
idea of the type of phases that would form in the selected alloy [35].
The experimental alloys were melted in an electrical resistance N 41/H Nabertherm
furnace under atmospheric conditions and casted into conventional cast iron ingot molds.
The raw materials used to produce the alloys consisted of master alloys of industrial purity
(such as Al65 Cu35 , Al50 Si50 , and Al95 Mg5 , supporting the approach of scrap-based alloy
design), sheets of pure zinc, and tablets of cast bars of pure magnesium. These master
alloys are commercially available and their physical characteristics are listed in Table 1. To
prevent the oxidation of the elements, casting flux was used to protect the melt pool surface
Crystals 2025, 15, 88 6 of 26

and prior to casting the molten metal, it was skimmed (after each of the alloying additions,
the melt was thoroughly stirred with a graphite rod to ensure a homogenous melt without
disturbing the metal/flux interface). The ingot was manufactured using a typical furnace
pour mold casting method similar to industry practices.

Table 1. Physical information about the utilized alloying elements and master alloys [29,36–45].

Crystal Lattice
Alloying Melting Boiling Atomic Radius Electronegativity
Density (g/cm3 ) Type/Lattice
Element Temperature (◦ C) Temperature (◦ C) (pm) (Pauling Scale)
Constant (nm)
Al 660.3 2450 2.70 FCC/0.4 143 1.61
Mg 650.0 1005 1.74 HCP/0.32 141 1.31
Cu 1085.0 2570 8.96 FCC/0.36 128 1.90
Zn 419.5 907 7.13 HCP/0.1 122 1.65
Si 1410.0 3280 2.33 FCC/0.543 111 1.90

For alloys A and AM, master alloys Al65Cu35, Al50Si50 and Al95.5Mg4.5 were added
to a steel mold, which was placed in the furnace at 1100 ◦ C. After melting, a bath base
at 800 ◦ C was guaranteed. Subsequently, Mg and Zn were added to the molten pool and
soaked for 1 h. The reason the direct addition of magnesium and zinc was avoided is
because they have a boiling point lower than the initial bath temperature and they would
volatilize (see Table 1). Finally, the melt was cooled down to 700 ◦ C and manually poured
into a steel mold (pouring temperature of melting: +50 ◦ C superheat).
For alloy B, master alloys Al65Cu35 and Al95.5Mg4.5 were added to the mold together
with the pieces of pure magnesium and Zn sheets and placed in the furnace at 700 ◦ C. After
melting, the melt was manually poured into a steel mold. For all 3 alloys, before casting,
the melt was stirred for at least for 15 min in order to achieve a fully homogenous bath.
Ingots with dimensions of 35 mm × 35 mm × 40 mm were obtained for each alloy,
as shown below (Figure 1). Following this, the microstructures of the as-cast and heat-
treated alloys at room temperature were studied to evaluate the suitability and behavior
of the developed CCAs. The alloys’ density was determined experimentally using the
Archimedes Principle [46].
The X-ray diffraction (XRD) equipment used to characterize the crystal structures of
the alloys was a Phillips Xpert diffractometer with a long fine focus copper anode X-ray
source and the diffraction diagrams were measured at a diffraction angle of 2θ, in the range
from 10◦ to 110◦ , with a step size of 0.02◦ /sec.
Samples were sectioned from the center of the ingot, parallel to the casting direc-
tion. Metallographic preparation of the samples was conducted with the appropriate
techniques and microscopic observation was performed on as-polished condition, without
prior etching using a Nikon Epiphot 300 inverted metallographic microscope.
Specimens AH4, BH4, and AMH4 underwent a solid-solution heat treatment at 400 ◦ C
for 4 h, followed by water cooling, while AH24, BH24, and AMH24 were subjected to a
heat treatment at 400 ◦ C for 24 h, followed again by water cooling, with the purpose of
examining the effect of soaking time. For the heat treatment of the samples, an N 60/85HA
Nabertherm furnace was used.
The different regions, the average overall chemical composition of each sample and of
the phases in it were investigated using a JEOL JSM-IT800 scanning electron microscope
(SEM) equipped with an energy-dispersive X-ray spectrometer (EDS).
A Vickers hardness Duramin-40 M1 model (Struers, Copenhagen, Denmark) measurer
was employed on the polished sample surface using a 4 kg load, which was applied for
10 s. At least 10 random individual measurements were made for each test. At least five
specimens were recorded to ensure repeatability. To measure the electrical conductivity,
Crystals 2025, 15, 88 7 of 26

a SIGMATEST
Crystals 2025, 15, x FOR PEER REVIEW D-2.068 (FOERSTER Instruments Inc., Pittsburgh, PA, USA) device
7 of 28 was
utilized and at least 5 random individual measurements were made for each specimen.

Figure 1.
Figure 1. Specimens
Specimens before
beforeandand
afterafter
sectioning (1 box(1isbox
sectioning equal
is to 1cm):to(a,b)
equal as-cast
1cm): (a,b)sample A,sample
as-cast (c,d) A,
as-cast
(c,d) sample
as-cast B, (e,f)
sample as-cast
B, (e,f) sample
as-cast AM, AM,
sample (g,h) (g,h)
heat-treated sample
heat-treated A, (i) A,
sample heat-treated sample
(i) heat-treated B,
sample B,
and
and (j)
(j) heat-treated sampleAM.
heat-treated sample AM.

3. Results
Samples were sectioned from the center of the ingot, parallel to the casting direction.
Metallographic
3.1. preparation
Thermo-Physical of the
Parameters samples
for Phase was conducted
Formation with the appropriate tech-
in HEAs/CCAs
niques and microscopic observation was performed on as-polished condition, without
After the preliminary study of the thermo-physical parameters for phase formation in
prior etching using a Nikon Epiphot 300 inverted metallographic microscope.
the HEAs and of various equilibrium phase diagrams for the different chemical composi-
Specimens AH4, BH4, and AMH4 underwent a solid-solution heat treatment at 400
tions, the systems that were finally selected were the following: Al52 Mg9.6 Zn16 Cu15.5 Si6.9
°C for 4 h, followed by water cooling, while AH24, BH24, and AMH24 were subjected to
w.t.%
a heatortreatment
Al63 Mg13atZn 4008 Cu
°C8 Si
for8 a.t.%
24 h, (alloy
followedA), again
Al44 Mg Zn19 Cu
by18water 19 w.t.%
cooling, or Al
with Mg25 Znof
the55purpose 10 Cu10
a.t.% (alloy B), and
examining the effect of47 Al Mg Zn
21.4 time.
soaking Cu
12 For Si
9.7the9.7 w.t.% or Al
heat treatment52.7 Mg
of the 26.6 Zn Cu
5.6 an4.6
samples, Si10.4 a.t.%
N 60/85HA (al-
loy AM) (Table
Nabertherm 2). was used.
furnace
The different regions, the average overall chemical composition of each sample and
Table Chemical
of the2.phases in it compositions
were investigated of alloys in wt.%
using a JEOLand at.% in this
JSM-IT800 work. electron microscope
scanning
(SEM) equipped with an energy-dispersive X-ray spectrometer (EDS).
Al Cu Mg Si Zn Al Cu Mg Si Zn
Alloy A Vickers hardness
(w.t.%) (w.t.%) (w.t.%) (w.t.%) Duramin-40
(w.t.%) M1 model (Struers,
(a.t.%) (a.t.%) Copenhagen,
(a.t.%) Denmark)
(a.t.%) meas- (a.t.%)
urer was employed on the polished sample surface using a 4 kg load, which was applied
A 52 15.5 9.6 6.9 16 63 8 13 8 8
B 44 19 for 10 s.18At least 10- random individual 19 measurements
55 10 were made 25 for each test.
- At least10
AM 47 9.7 five specimens
21.4 were9.7 recorded12 to ensure 52.7
repeatability.
4.6To measure26.6 the electrical
10.4 conduc- 5.6
tivity, a SIGMATEST D-2.068 (FOERSTER Instruments Inc., Pittsburgh, PA, USA) device
was utilized and at least 5 random individual measurements were made for each speci-
men.In Table 3, the calculated thermo-physical parameters of the defined systems are
summarized. The ∆Hmix of this system was in the range of −8 to −1 kJ/mole, which
is
3.outside
Resultsthe limits required for the formation of SS structures [23]. Additional criteria
3.1. Thermo-Physical Parameters for Phase Formation in HEAs/CCAs
Crystals 2025, 15, 88 8 of 26

related to the formation of SS structures in alloys containing low-density elements are

δ values below 4.5%, a ∆χ equal or below 0.175, and an Ω higher than 10 [23,47]. It is
expected that multiphase alloys were obtained regardless of the ∆Smix value, since the
∆Hmix i–j between Al and other elements is highly negative [12]. Thus, based the alloy
design approach of other studies [13,23,29,48–50], the parameters were kept as close as
possible to the threshold parameters for SS formation, in order to restrain the formation of
excessive amounts of ICs. Following the standard classification of HEAs, all three alloys
were categorized as Medium-Entropy Alloys. Nonetheless, maximizing the ∆Smix was
not necessary in the developed alloys. In contrast to the main goal of classic HEA design
approaches, which is to promote the formation of SS phases, in this study, the formation
of multiphase microstructures was promoted to enhance the mechanical properties of the
aluminum alloys. To obtain a microstructure composed of a mix of SS structures and
ICs, the ∆Hmix was kept between −8 kJ/mol and −4 kJ/mol, avoiding excessively high
negative values. A decrease in the Al content and absence of Si increased the value of
∆Hmix, whereas increases in the Mg and Si contents further decreased the value of ∆Hmix.
The increased δ in all three alloys highlights the tendency to form intermetallics. On the
other hand, in alloy A, the ∆χ value indicates that SS structures can be formed, but it
is well known that satisfying only one parameter does not promote the formation of SS
structures [51,52]. The calculated Ω parameters (ratio between the ∆Hmix and the ∆Smix
in the liquid state of the alloy) were very far away from the literature’s proposed value
of Ω > ~10 for the formation of SS structures in low-density multiprincipal-component
alloys [48]. A higher Ω is related to a lower tendency to form complex phases in Al-
based multicomponent alloys [53]. In contrast, the Ω value in all three alloys indicated
a tendency of promoting intermetallics according to the threshold value proposed for
traditional HEAs [12]. Lastly, the ∆χ was within the recommended values (under 0.175) for
forming SS structures in HEAs for alloys A and B and above that limit for alloy AM [12].
Therefore, mixed microstructures consisting of SS structures and ICs were expected to form
based on the known thermo-physical parameters. This was found to be consistent with the
CALPHAD calculations for these alloys. The theoretical density of the alloys was calculated
using the rule of mixtures.

Table 3. Thermo-physical parameters and the theoretical density of the developed alloys.

∆Hmix ∆Smix ρtheoretical

Alloy δ (%) Ω ∆χ VEC Tm (K)
(kJ/mol) (J/K/mol) (g/cm3 )
A −5.63 7.64 9.66 (1.16R) 1.73 0.16 4.31 1006.5 3.15
B −1.76 6.57 9.44 (1.14R) 5.09 0.17 4.45 948.8 3.18
AM −7.04 9.03 10.21 (1.22R) 1.47 0.19 3.71 1014.4 2.73

In these systems, a microstructure consisting mainly of an Al-based face-centered

cubic (FCC) matrix phase along with other intermetallic compounds was expected to be
stable at room temperature.

3.2. CALPHAD Methodology and Equilibrium Phase Diagrams

The equilibrium phase diagrams of the developed alloys are shown in Figure 2. Alloy
A was expected to be composed of a mixture of five different phases at equilibrium, namely
Al2 Cu, α (Al-FCC), C14_Laves (MgZn2 ), Q (Al4 Cu2 Mg8 Si7 ), and V (AlCuMgZn), while
alloy B was expected to be composed of just three phases, namely α (Al), C14_Laves
(MgZn2 ), and και T (Al2 Mg3 Zn3 or Mg32 (Al,Zn)49 ). As for alloy AM, it was expected to
consist of Al2 Cu, α (Al-FCC), C14_Laves (MgZn2 ), Mg2 Si, and T (Mg32 (Al,Zn)49 ).
2025, 15, xCrystals
FOR PEER 2025,REVIEW
15, 88 10 of 28 9 of 26

Figure 2. Cont.
25, 15, x FOR PEER REVIEW 11 of 28
Crystals 2025, 15, 88 10 of 26

Figure 2. Al-Zn isopleth

Figure 2.pseudo-binary
Al-Zn isoplethphase diagram for
pseudo-binary (a) diagram
phase alloy A and (c) alloy
for (a) alloy A
AMandand Al-CuAM and Al-Cu
(c) alloy
isopleth
isopleth pseudo-binary pseudo-binary
phase diagram forphase diagram
(b) alloy for arrows
B. The (b) alloyrepresent
B. The arrows represent
the areas the areas of thermody-
of thermody-
namic stability for the various phases. The red circle represents the heat-treatment
namic stability for the various phases. The red circle represents the heat-treatment temperature and temperature and
the blue circle the room temperature.
the blue circle the room temperature.

A brief description of the aforementioned phases is provided below. The θ (Al2 Cu)
In Table 4, the volume fraction of the formed phases was estimated for the thermo-
phase is widely known to enhance the strength of Al-Cu alloys after aging [54] and to
dynamic equilibrium conditions.
form during solidification as well along the grain boundaries in the form of veins or
skeletal shapes and after metallic mold casting, they can only be revealed after detailed and
Table 4. Volume fraction of phases in the developed alloys at room temperature.
meticulous microanalysis [30]. Precipitation of the Q-Al4 Cu2 Mg8 Si7 phase (also known
y as the Al5 Cu2 Mg
FCC_A1 Q_AlCuMgSi Al2Cu_C16 V8 Si6 orC14_Laves
Al3 Cu2 Mg9 Si7Mg2Si
phase) in Al-Cu-Mg-Si
T quaternary
S alloys has been
45 30 demonstrated
14 to6improve creep
5 resistance -and tensile strength,
- both at
- room temperature
22 - and- at higher temperatures
- 17[55]. It was reported
- that 61
the addition of- copper, even with
39 - impurities,
17 will promote
- the
10formation of38the Q phase,16 which appears - as inclusions with
sharp and irregularly shaped edges [30]. The C_14 Laves (MgZn2 ) phase is the most
commonly
3.3. Microstructural encountered intermetallic phase in all HEAs [56]. It plays an important role in
Characterization
the excellent mechanical properties of the precipitation-hardenable 7xxx series [57]. The
3.3.1. Microstructural Characterization of As-Cast Alloys
Mg2 Si phase, as mentioned previously, is a desirable phase in various Al-based alloys to
By studying the as-cast sample A, its dendritic morphology and intense porosity was
improve the mechanical properties through the formation of intermetallic compounds. It is
distinguished (Figure
usually3), which
found in was
platemore
shapes obvious
[58], asinoctahedron
the upper [59]
partor
oftruncated
the ingot octahedron
(part that blocks [60],
was in contact with
and asthe atmospheric [57].
nano-particles air). Finally,
Nevertheless,
the S (AltheCuMg)
existence
and of minor(Al,Zn)
T (Mg shrinkage
2 32 49 or Al2 Mg3 Zn3 )
porosity did not influence the outcome of the present study, since it
phases in the 7XXX series are responsible for the increased hardness can be easily
afterad-
aging [61]. The
dressed at the industrial scale.phase has been reported to provide a strong increase in the hardness of
S (Al2 CuMg)
The microstructure
mold-castedof the
alloysalloy
[30].revealed four distinct phases: a white-colored den-
dritic phase, which is probably the aluminum base phase (A), a dark grey phase (B), a
light grey phase (C), and large dark intermetallic phases (D).
Crystals 2025, 15, 88 11 of 26

In Table 4, the volume fraction of the formed phases was estimated for the thermody-
namic equilibrium conditions.

Table 4. Volume fraction of phases in the developed alloys at room temperature.

Alloy FCC_A1 Q_AlCuMgSi Al2Cu_C16 V C14_Laves Mg2Si T S

A 45 30 14 6 5 - - -
B 22 - - - 17 - 61 -
AM 39 - 17 - 10 38 16 -

3.3. Microstructural Characterization

3.3.1. Microstructural Characterization of As-Cast Alloys
By studying the as-cast sample A, its dendritic morphology and intense porosity was
distinguished (Figure 3), which was more obvious in the upper part of the ingot (part that
was in contact with the atmospheric air). Nevertheless, the existence of minor shrinkage
porosity did not influence the outcome of the present study, since it can be easily
Crystals 2025, 15, x FOR PEER REVIEW addressed
12 of 28

at the industrial scale.

Opticalmicrographs
Figure3.3.Optical
Figure micrographsofofspecimen
specimenAAatat(a)(a)center
centerofofthe
themiddle
middlepart
partofofthe
theingot
ingotand
and(b)
(b) edge
of the
edge of middle partpart
the middle of the ingot.
of the A,A,
ingot. B, B,
C,C,
D.D.

Themicrostructure
The microstructure ofof the Balloy
alloy revealed
revealed four distinct
a dendritic phases:and
morphology a white-colored
shrinkage poros- dendritic
phase,
ity, which
mainly is probably
in the upper parttheofaluminum base phase
the cast (Figure 4). At (A), a dark grey phase
low magnification, it was(B),easy
a light
to grey
distinguish
phase (C), two
andphases: a polygonal
large dark phasephases
intermetallic (A) and(D).
a eutectic structure. The eutectic struc-
ture consisted of a light-colored
The microstructure of alloydendritic phase
B revealed (B) and phase
a dendritic (A). The and
morphology thickness of theporosity,
shrinkage B
phase was greater than that of A, but the B phase was present in a smaller
mainly in the upper part of the cast (Figure 4). At low magnification, it was easy tovolume fraction
indistinguish
the microstructure. At higher
two phases: magnification,
a polygonal phasea(A) darkand
angular phase structure.
a eutectic (C) and gray Theden-
eutectic
dritic phase were evident.
structure consisted of a light-colored dendritic phase (B) and phase (A). The thickness of
the An interesting
B phase observation
was greater than was
thatthat thebut
of A, A phases appeared
the B phase wastopresent
be larger
in in the center
a smaller volume
of the ingot than at the edge. Τhis phenomenon can be attributed to temperature gradients
fraction in the microstructure. At higher magnification, a dark angular phase (C) and gray
and the cooling rate. At the edge of the mold, the cooling rate is faster than in the center;
dendritic phase were evident.
thus, there is limited time for the phases to grow.
An interesting observation was that the A phases appeared to be larger in the center
of the ingot than at the edge. This phenomenon can be attributed to temperature gradients
and the cooling rate. At the edge of the mold, the cooling rate is faster than in the center;
thus, there is limited time for the phases to grow.
Similar to all the previous castings, alloy AM was characterized by a noticeable
dendritic morphology and porosity (greater in the upper part of the ingot) (Figure 5).
The microstructure of this alloy revealed three distinct phases: a white-colored dendritic
phase, which is probably the aluminum base phase (A); a large dark angular phase (B);
and a eutectic structure. At higher magnification, it can be seen that the eutectic structure
consisted of small dendrites of phase (A) and a small ecru phase, designated as (C). It is
 ture consisted of a light-colored dendritic phase (B) and phase (A). The thickness of the B
phase was greater than that of A, but the B phase was present in a smaller volume fraction
in the microstructure. At higher magnification, a dark angular phase (C) and gray den-
Crystals 2025, 15, 88 dritic phase were evident. 12 of 26
An interesting observation was that the A phases appeared to be larger in the center
of the ingot than at the edge. Τhis phenomenon can be attributed to temperature gradients
worth
and thementioning
cooling rate.that theedge
At the darkofphases (B) the
the mold, were slightly
cooling ratelarger in than
is faster the center
in the of the ingot
center;
thus, there
than at theisedge.
limited time for the phases to grow.

Crystals 2025, 15, x FOR PEER REVIEW 13 of 28

phase, which is probably the aluminum base phase (A); a large dark angular phase (B);
and a eutectic structure. At higher magnification, it can be seen that the eutectic structure
consisted of small dendrites of phase (A) and a small ecru phase, designated as (C). It is
Figure
worth 4. Opticalmicrographs
Figure mentioning
4. Optical micrographs ofofspecimen
that the dark specimen Batat(a)
phasesB(B) (a)
were edge
edge of of
thethe
slightly bottom
bottom
larger of of
in thethe
the ingot
ingot and
center and
of the(b,c)
(b,c) center of
center
ingot
thethe
of
thanbottom
atbottomofofthe
the edge. theingot.
ingot.

Similar to all the previous castings, alloy AM was characterized by a noticeable den-
dritic morphology and porosity (greater in the upper part of the ingot) (Figure 5). The
microstructure of this alloy revealed three distinct phases: a white-colored dendritic

Figure
Figure5.5.Optical
Opticalmicrographs
micrographsof of
specimen AMAM
specimen from (a) center
from of the
(a) center ofupper part of
the upper theof
part ingot and and
the ingot
(b,c)
(b,c)edge
edgeofofthe
theupper
upperpart
partofof
thethe
ingot.
ingot.

In
Inall
allthe
theheat-treated
heat-treated samples
samples (Α4, A24,
(A4, B4, B4,
A24, B24,B24,
AM4 and and
AM4 AM24), no substantial
AM24), no substantial
structure
structure alteration perceived compared
alteration was perceived comparedtotothe
thecorresponding
correspondingas-cast
as-cast specimens.Hence,
specimens.
Hence,
the samethemain
samephases
main phases
as theas the as-cast
as-cast samples
samples werewere identified.
identified.
The
Theoverall
overallcomposition
composition of the
of alloys was estimated
the alloys using scanning
was estimated electron micros-
using scanning electron mi-
copy (S.E.M.) and energy-dispersive X-ray spectrometry (E.D.S.) on
croscopy (S.E.M.) and energy-dispersive X-ray spectrometry (E.D.S.) on largelarge areas.areas.
At least
At least
three random measurements were made, and the overall values are presented in Table 5.
The obtained results showed good approximations to the target compositions of the alloys
(Table 2). Any deviations could be attributed to (i) partial oxidation of the components
during the melting due to the absence of a protective atmosphere and (ii) E.D.S. analyses
only providing semi-quantitative information. Therefore, the manufacturing process that
Crystals 2025, 15, 88 13 of 26

three random measurements were made, and the overall values are presented in Table 5.
The obtained results showed good approximations to the target compositions of the alloys
(Table 2). Any deviations could be attributed to (i) partial oxidation of the components
during the melting due to the absence of a protective atmosphere and (ii) E.D.S. analyses
only providing semi-quantitative information. Therefore, the manufacturing process that
was followed, in order to achieve the target compositions, was considered successful.

Table 5. Indicative chemical composition in wt.% and at.% of the manufactured alloys obtained
by EDS.

Al Cu Mg Si Zn Al Cu Mg Si Zn
Alloy
(w.t.%) (w.t.%) (w.t.%) (w.t.%) (w.t.%) (a.t.%) (a.t.%) (a.t.%) (a.t.%) (a.t.%)
A 51.2 11.8 12.4 10.6 13.4 59.8 5.8 16 11.9 6.4
B 49 15.5 16.4 - 18.6 60.2 8.1 22.4 - 9.4
AM 51.6 9.5 19.3 8.3 11.4 57.5 4.5 24.9 8.8 5.2

Table 6 summarizes the phases in alloy A and their chemical compositions, as mea-
sured by the EDS analyses. For alloy A, the EDS analysis at spot 1 indicated that this
phase is a primary Mg2 Si intermetallic compound. Based on the analysis of spot 2, the
light white phase in Figure 6 is an Al2 Cu phase. Both phases were in good agreement with
the Thermocalc predictions at room temperature (RT). The analysis of spot 3 verified the
formation of an Al-rich solid-solution matrix with a small amount of Zn. It is interesting to
note that there was very good agreement between the composition of this phase and the
Al-FCC phase predicted by Thermocalc near the solidus temperature of the alloy, although
the composition of the Al-FCC phase at room temperature was significantly different from
the one predicted by the EDS analysis. The composition was predicted by Thermocalc
under thermodynamic equilibrium conditions, whereas in reality, the cooling rates were
faster. This phenomenon needs further investigation and it is worth studying whether it
appears in the remaining phases. The analysis of spot 4 showed that this phase consisted of
all the components in similar quantities. The composition of this phase was consistent with
what Thermocalc predicted as the Q-Al4 Cu2 Mg8 Si7 phase at room temperature and near
the solidus temperature. Finally, the analysis performed on spot 5 detected a high content
of Fe (11 w.t.%). As can be seen, the main impurity was Fe, which is commonly found in
secondary aluminum alloys [62]. The presence of Fe was probably due to impurities, which
were included in the industrial purity raw materials. This phase was not predicted during
the alloy design and it an AlFeSi-type phase, which is well known in 3xx series alloys with
a low Mg content such as Al5 FeSi [30]. It is known that all industrial aluminum alloys
contain iron-bearing constituents. Such iron-bearing phases tend to not undergo significant
changes during heat treatments prior to quenching [30].

Table 6. Elemental composition of the manufactured alloy in sample A obtained by EDS.

Spot 1 Spot 1 Spot 2 Spot 2 Spot 3 Spot 3 Spot 4 Spot 4 Spot 5 Spot 5
Element
(w.t.%) (a.t.%) (w.t.%) (a.t.%) (w.t.%) (a.t.%) (w.t.%) (a.t.%) (w.t.%) (a.t.%)
Al 1.0 1.0 45.4 64.8 81.0 89.4 18.0 22.0 72.3 77.2
Mg 52.7 56.9 1.3 2.1 1.6 2.0 24.1 32.6 0.3 0.3
Cu 0.7 0.3 48.9 29.7 3.5 1.6 21.2 11.7 0 0
Zn 1.4 0.6 3.3 1.9 12.8 5.8 14.1 7.1 0 0
Si 44.2 41.3 1.1 1.5 1.1 1.2 22.7 26.6 16.2 16.7
Fe - - - - - - - - 11.1 5.7
 rities, which were included in the industrial purity raw materials. This phase was not pre-
dicted during the alloy design and it an AlFeSi-type phase, which is well known in 3xx
series alloys with a low Mg content such as Al5FeSi [30]. It is known that all industrial
Crystals 2025, 15, 88
aluminum alloys contain iron-bearing constituents. Such iron-bearing phases tend to not14 of 26
undergo significant changes during heat treatments prior to quenching [30].

Figure
Figure6.6.FESEM
Crystals 2025, 15, x FOR PEER REVIEW backscatter
FESEM electron
backscatter microstructure
electron with EDS
microstructure analysis
with EDS of selectedofphases
analysis in
15speci-
selected phases
of 28 in
men A. A.
specimen

TableQualitative elemental mapping

6. Elemental composition was conducted
of the manufactured alloy in using
sampleEDS to identify
A obtained the distribution
by EDS.
Qualitative elemental mapping was conducted using EDS to identify the distribution
Ele- Spot 1 Spot 1
of Spot
elements in the2observed
2 inSpot
regions
Spotregions
3 Spot
(Figure 7). For
3 7). Spot
a better understanding of the maps,
of elements the observed (Figure For a4 betterSpot 4 Spot 5 of the
understanding Spot 5
maps,
ment (w.t.%) (a.t.%) oxygen
(w.t.%)was ignored due to
(a.t.%) due(w.t.%) its insignificant amount
(a.t.%) amount(w.t.%) in the composition of the alloys. The
oxygen was ignored to its insignificant in the (a.t.%)
composition (w.t.%) (a.t.%)
of the alloys. The
Al 1.0 1.0 microstructure
45.4
microstructure
showed a 81.0
64.8 matrixcomposed
showed a matrix
composed
89.4 ofofanan Al-rich area.
18.0
Al-rich area.
This
22.0This region corresponded
72.3 corresponded
region 77.2 to
Mg 52.7 56.9 the phase
to the1.3 predicted
2.1
phase predicted by Thermocalc
1.6
by Thermocalc asas Al-FCC.
2.0Al-FCC. 24.1 The elements
The elements Mg and
32.6Mg and 0.3 Si were located
0.3 in
Si were located in
Cu 0.7 0.3 the sameareas
48.9
the same areas29.7
andininplaces
and places where
3.5where thetheMgMg
1.6 Si 21.2
phases
2Si2phases werewere11.7found.
found. Si,
0 however,
Si, however, 0 appeared
appeared
Zn 1.4 0.6 to 3.3
found in 1.9
small 12.8
amounts in other5.8 areas of14.1
the cast, 7.1
possibly in 0
to be found in small amounts in other areas of the cast, possibly in phase C. Finally, Cu Cu
be phase C. 0
Finally,
Si 44.2 41.3 1.1 to
appeared
appeared be1.5
tobe located 1.1
locatedininplaces
places where
where 1.2
thethe light
light 22.7
graygray phase
phase B26.6B appeared
appeared 16.2 the16.7
inOM,
in the OM,
whichwhich
Fe - - -
was designated
designatedas -asAl
Al2Cu,
Cu, -
while
while Zn Zn
waswas - dispersed
dispersed - throughout
throughout - the the
ingot. 11.1
ingot. 5.7
2

Figure 7.
Figure 7.EDS
EDSmap
mapofofspecimen
specimenA.A.

Regardingalloy
Regarding alloyB,B,the
theEDS
EDS analysis
analysis at area
at area 1 showed
1 showed thatthat
this this
phasephase consisted
consisted of all of all
the components
componentsthat thatconstitute
constitute thethe
alloy in in
alloy relatively equal
relatively amounts
equal amounts(Figure 8). Table
(Figure 7
8). Table 7
summarizes the
summarizes thephases
phasesininalloy
alloyBB and
andtheir chemical
their chemicalcompositions,
compositions, as measured by the
as measured by the
EDS analyses.
EDS analyses.The
Thecomposition
composition of of
this phase
this phasewaswas
highly consistent
highly withwith
consistent that of theofphase
that the phase
calculated by
calculated byThermocalc
Thermocalcnear near
thethe solidus
solidus temperature
temperature and reported
and reported as the(Al,Zn)
as the T-Mg T-
32 49
Mg 32(Al,Zn)49 phase. However, the composition calculated by the software at room tem-
phase. However, the composition calculated by the software at room temperature deviated
perature deviated
significantly fromsignificantly from theresults.
the point analysis point analysis results. This phenomenon
This phenomenon was alsoin the
was also observed
observed in the Al-FCC phase of alloy A. The analysis of spot 1 found that it was enriched
Al-FCC phase of alloy A. The analysis of spot 1 found that it was enriched in Mg and Si.
in Mg and Si. For alloy B, silicon was not included in the alloy design and it may have
derived from the industrial-grade raw materials. It appears that its minimal presence in
the melt led to the formation of several Mg2Si phases, much smaller in size than those in
alloy A. As for spot 2, it corresponded to an Al-rich phase. This phase is the Al-FCC phase
since the Al-FCC composition predicted by Thermocalc near the solidus temperature was
Crystals 2025, 15, 88 15 of 26

For alloy B, silicon was not included in the alloy design and it may have derived from the
industrial-grade raw materials. It appears that its minimal presence in the melt led to the
formation of several Mg2 Si phases, much smaller in size than those in alloy A. As for spot
2, it corresponded to an Al-rich phase. This phase is the Al-FCC phase since the Al-FCC
composition predicted by Thermocalc near the solidus temperature was predominantly
in agreement with that of the spot analysis. In the OM, this phase was visualized as a
white color and was designated as phase B (Figure 4). The analysis carried out in the
neighboring phase of α (Al-FCC) in the eutectic area showed a composition close to that of
the Q-Al4 Cu2 Mg8 Si7 phase. However, due to the relatively small lamellae of the eutectic
phase, which were less than 0.5 µm, the measured phase was probably influenced by
the neighboring phase so the displayed percentages may deviate from the actual values.
Crystals 2025, 15, x FOR PEER REVIEW
Neither the C14 Laves (MgZn2 ) phase that was predicted at room temperature 16 of or
28 the S

phase near the solidus temperature were observed.

Figure
Figure8.8.FESEM backscatter
FESEM electron
backscatter microstructure
electron with EDS
microstructure analysis
with EDS of selectedof
analysis phases in speci-
selected phases in
men B.
specimen B.

Table 7. Elemental composition of the manufactured alloy in sample B obtained by EDS.

Table 7. Elemental composition of the manufactured alloy in sample B obtained by EDS.
Ele- Area 1 Area 1 Spot 1 Spot 1 Spot 2 Spot 2 Area 2 Area 2 Spot 3 Spot 3
ment Area 1
(w.t.%) Area 1 (w.t.%)
(a.t.%) Spot 1 (a.t.%)
Spot 1 (w.t.%)
Spot 2 (a.t.%)
Spot 2 (w.t.%)
Area 2 (a.t.%)
Area 2(w.t.%)
Spot 3(a.t.%)Spot 3
Element
(w.t.%) (a.t.%) (w.t.%)
Al 30.3 40.4 2.0 2.0(a.t.%) 87.3
(w.t.%) (a.t.%)
90.4 (w.t.%)
54.4 64.7(a.t.%) 36.4(w.t.%) 46.4 (a.t.%)
Al
Mg 30.3
22.3 33.040.4 43.42.0 47.7 2.0 5.887.3 6.790.4 15.354.4 20.2 64.7 22.4 36.4 31.7 46.4
Mg
Cu 22.3
23.4 13.333.0 1.443.4 0.6 47.7 2.0 5.8 0.9 6.7 12.915.3 6.5 20.2 14.8 22.4 8.0 31.7
Cu 23.4 13.3 1.4 0.6 2.0 0.9 12.9 6.5 14.8 8.0
Zn 24.0 13.3 1.8 0.8 4.9 2.1 17.5 8.6 26.4 13.9
Zn 24.0 13.3 1.8 0.8 4.9 2.1 17.5 8.6 26.4 13.9
Si
Si - - 51.451.4 49.049.0 - - - - - - - - - - - -

Qualitative elemental mapping was conducted using EDS to identify the distribution
Qualitative
of elements in theelemental mapping
observed regions was conducted
(Figure 9). It can beusing
seen EDS to was
that Al identify thedistrib-
mainly distribution
of elements
uted in the B in the observed
phases, identifiedregions (Figurein
as α (Al-FCC) 9).the
It can
EDSbe seen that
analysis, andAl waswas
there mainly distributed
a stronger
enrichment
in the B phases, T phase’s grain
in the identified as α boundaries.
(Al-FCC) inMg theseemed to be more
EDS analysis, andconcentrated
there was in the
a stronger
places where there was a presence of Si, which was probably trapped in the
enrichment in the T phase’s grain boundaries. Mg seemed to be more concentrated in the melt from the
industrial
places where purity rawwas
there materials and lead
a presence towhich
of Si, the formation of Mg2Si
was probably phases.inAsthe
trapped formelt
Cu and
from the
Zn, there seems to be a greater concentration of them in the T phase, but in
industrial purity raw materials and lead to the formation of Mg2 Si phases. As for Cu andgeneral, they
were distributed
Zn, there seems throughout the cast.
to be a greater concentration of them in the T phase, but in general, they
were distributed throughout the cast.
 enrichment in the T phase’s grain boundaries. Mg seemed to be more concentrated in the
places where there was a presence of Si, which was probably trapped in the melt from the
industrial purity raw materials and lead to the formation of Mg2Si phases. As for Cu and
Crystals 2025, 15, 88 Zn, there seems to be a greater concentration of them in the T phase, but in general, they16 of 26
were distributed throughout the cast.

Figure 9.
Figure EDSmap
9.EDS mapofofspecimen
specimenB. B.

For alloy AM, Table 8 summarizes the phases and their chemical compositions, as
measured by the EDS analyses. The analysis at spot 1 (EDS Spot 1) proved that the dark
angular phases were Mg2 Si phases, as they were overwhelmingly composed of Mg and Si
as shown in Figure 10. This confirmed that this was an Mg2 Si phase. An expected alteration
resulting from the further addition of Mg to the composition of alloy A was the formation
of more Mg2 Si phases, which were much bigger and angular than those in alloy A. The
results from the analysis at spot 2 revealed that the dendrites of phase A were an Al-FCC
phase since its composition was in close agreement with that predicted by Thermocalc as
an Al-FCC phase near the solidus temperature of the alloy. The analysis at spot 3 indicated
that this phase, located in the grain boundaries of the Al-FCC dendrites, showed very high
percentages of Al and Cu and a small percentage of Zn. This composition is consistent
with the phase predicted by Thermocalc at room temperature as Al2 Cu, though it was
not detected during the OM observations. Finally, the EDS analysis in the eutectic area
(Selected Area 1) where phases A (FCC) and B alternated showed a high percentage of
Al and a significant proportion of Cu, Zn, and Mg. The identification of the B phase was
difficult due to its very small size (less than 0.5 µm) and therefore the analysis was probably
influenced by the neighboring Al-FCC phase. It is not clear whether the phase identified as
Al2 Cu, based on the analysis of spot 3, corresponded to the B phases alternating with the
Al-FCC phases. However, it can be assumed that it was a phase of the T-Mg32 (Al,Zn)49 or
Q-Al4 Cu2 Mg8 Si7 form, in which all the components that constitute the alloy were present.

Table 8. Elemental composition of the manufactured alloy in sample AM obtained by EDS.

Area 1 Area 1 Spot 1 Spot 1 Spot 2 Spot 2 Spot 3 Spot 3

Element
(w.t.%) (a.t.%) (w.t.%) (a.t.%) (w.t.%) (a.t.%) (w.t.%) (a.t.%)
Al 50.0 63.7 0.9 0.9 86.2 91.0 47.2 2.5
Mg 10.5 14.9 61.0 64.9 3.6 4.3 1.6 66.4
Cu 18.0 9.8 0.5 0.2 2.3 1.1 47.5 28.4
Zn 20.9 11.0 0.9 0.3 7.3 3.2 3.1 1.8
Si 0.6 0.7 36.7 32.7 0.5 0.5 0.7 0.9

By studying the qualitative elemental map from the EDS analysis in Figure 11, it can be
seen that Al was mainly found in the large dendrites of the A phase, identified as Al-FCC,
and to a lesser extent in the smaller dendrites throughout the cast. The elements Mg and Si
were located in the same areas where the presence of Mg2 Si phases was evident. Zn and
 eutectic area (Selected Area 1) where phases A (FCC) and B alternated showed a high
percentage of Al and a significant proportion of Cu, Zn, and Mg. The identification of the
B phase was difficult due to its very small size (less than 0.5 µm) and therefore the analysis
Crystals 2025, 15, 88 was probably influenced by the neighboring Al-FCC phase. It is not clear whether the17 of 26
phase identified as Al2Cu, based on the analysis of spot 3, corresponded to the B phases
alternating with the Al-FCC phases. However, it can be assumed that it was a phase of the
Cu appeared
T-Mg 32(Al,Zn)to beQ-Al
49 or uniformly
4Cu2Mgdistributed throughout
8Si7 form, in thecomponents
which all the ingot, in places
that far from the
constitute theMg2 Si
and Al-FCC phases.
alloy were present.

Crystals 2025, 15, x FOR PEER REVIEW 18 of 28

FCC, and to a lesser extent in the smaller dendrites throughout the cast. The elements Mg
and Si were located in the same areas where the presence of Mg2Si phases was evident.
Figure
Figure
Zn and10.
10.
CuFESEM backscatter
FESEM
appeared to beelectron
backscatter microstructure
electron
uniformly distributedwith
microstructure EDS analysis
with
throughoutEDS of selected
theanalysis
ingot, phases
inofplaces in spec-
selected
far phases in
from
imen AM.
specimen AM.
the Mg2Si and Al-FCC phases.

Table 8. Elemental composition of the manufactured alloy in sample AM obtained by EDS.

Ele- Area 1 Area 1 Spot 1 Spot 1 Spot 2 Spot 2 Spot 3 Spot 3

ment (w.t.%) (a.t.%) (w.t.%) (a.t.%) (w.t.%) (a.t.%) (w.t.%) (a.t.%)
Al 50.0 63.7 0.9 0.9 86.2 91.0 47.2 2.5
Mg 10.5 14.9 61.0 64.9 3.6 4.3 1.6 66.4
Cu 18.0 9.8 0.5 0.2 2.3 1.1 47.5 28.4
Zn 20.9 11.0 0.9 0.3 7.3 3.2 3.1 1.8
Si 0.6 0.7 36.7 32.7 0.5 0.5 0.7 0.9

By studying the qualitative elemental map from the EDS analysis in Figure 11, it can
be seen that Al was mainly found in the large dendrites of the A phase, identified as Al-

Figure 11.
Figure 11. EDS map
map of
ofspecimen
specimenAM.
AM.

3.3.2.
3.3.2. Microstructural CharacterizationofofHeat-Treated
Microstructural Characterization Heat-Treated Alloys
Alloys
Despite
Despite the
the fact
fact that
thatnonomorphological
morphological changes
changes were
were observed
observed after
after the
theheat
heattreatments
treat-
in alloyinA,
ments there
alloy A, were
there changes
were changesin thein compositions
the compositions of its phases,
of its according
phases, accordingtotothe
the spot
analyses which
spot analyses are are
which summarized
summarized in in
Table
Table9.9.In
Inparticular, theAl-FCC
particular, the Al-FCCphase
phase displayed a
displayed
significant decreasein
a significantdecrease inAl
Al (10%),
(10%), while
whileititwas
wassignificantly
significantlyenriched
enrichedin Zn (13%)
in Zn as shown
(13%) as shown
inFigure
in Figure 12. Comparing
Comparingthe thespot
spotanalysis
analysis ofof
thetheQ phase
Q phasein the as-cast
in the andand
as-cast the heat-treated
the heat-treated
samples, aamajor
samples, major reduction
reduction in in Zn
Zn (by
(by 11%)
11%) was
was observed.
observed. Therefore,
Therefore, it can be
it can be assumed
assumed that
that this is where the enrichment of Zn in the Al-FCC phase was
this is where the enrichment of Zn in the Al-FCC phase was derived from. There wasderived from. There wasalso a
also a small drop in the percentages of Al and Cu (2% and 3%, respectively),
small drop in the percentages of Al and Cu (2% and 3%, respectively), while significant while signif-
icant increases
increases in MginandMg Si and Si (8%
(8% each)each)
were were observed.
observed. MgMgand andSiSiprobably
probably diffused
diffused into
into the
the Q phase from the interface of the Mg2Si phases or from the Mg2Si into the matrix phase
Q phase from the interface of the Mg2 Si phases or from the Mg2 Si into the matrix phase
and then to the Q phase, as observed by the small reduction (2%) in these percentages
and then to the Q phase, as observed by the small reduction (2%) in these percentages
(EDS Spot 1). Nonetheless, distortions in the analysis from the neighboring phases should
(EDS Spot 1). Nonetheless, distortions in the analysis from the neighboring phases should
always be taken into consideration. As for the Al2Cu phase (EDS Spot 3), its composition
always be taken into consideration. As for the Al2 Cu phase (EDS Spot 3), its composition
remained stable after the heat treatment. Regarding the remaining heat-treated samples
remained stableand
(B4, B24, AM4, after the heat
AM24), treatment.inRegarding
no alterations the remaining
the compositions heat-treated
of their phases samples
were noted
in comparison with the corresponding as-cast specimens.
Crystals 2025, 15, 88 18 of 26

(B4, B24, AM4, and AM24), no alterations in the compositions of their phases were noted in
comparison with the corresponding as-cast specimens.

Table 9. Elemental composition of the manufactured alloy in heat-treated sample A4 obtained

by EDS.

Spot 1 Spot 1 Spot 2 Spot 2 Spot 3 Spot 3 Spot 4 Spot 4

Element
(w.t.%) (a.t.%) (w.t.%) (a.t.%) (w.t.%) (a.t.%) (w.t.%) (a.t.%)
Al 0.9 0.8 16.0 17.7 47.7 67.3 69.5 83.6
Mg 50.5 54.6 32.7 40.1 0.8 1.3 1.0 1.4
Cu 0.6 0.2 17.7 8.3 47.6 28.5 3.3 1.7
Zn2025, 15, x FOR1.3
Crystals PEER REVIEW 0.5 3.1 1.4 2.9 1.7 25.5 19 of12.6
28
Si 46.8 43.8 30.5 32.4 0.9 1.2 0.6 0.8

Figure
Figure12.
12.FESEM backscatter
FESEM electron
backscatter microstructure
electron with EDS
microstructure analysis
with of selected
EDS analysis ofphases in heat-
selected phases in
treated specimen
heat-treated A4. A4.
specimen

3.4. X-Ray
Table Diffraction
9. Elemental Analysis
composition of the manufactured alloy in heat-treated sample A4 obtained by
EDS. In addition, diffraction analysis was used to evaluate the produced alloys in order to

Spot 1 verify
Spot 1 the phases
Spot 2 that were
Spotidentified.
2 In Figure
Spot 3 13,Spot
the XRD
3 analysis
Spot 4 resultsSpot
for samples
4 A,
Element B, and AM(w.t.%)
are presented.
(w.t.%) (a.t.%) (a.t.%) (w.t.%) (a.t.%) (w.t.%) (a.t.%)
Al 0.9 0.8 In alloy16.0
A, the parent17.7
Al-base phase with an FCC
47.7 structure can
67.3 69.5be observed.
83.6 Moreover,
Mg 50.5 the
54.6 intermetallic
32.7 phases of Mg
40.1 2 Si (FCC), Al
0.8 2 Cu (Tetragonal),
1.3 and Al
1.01.9 CuMg Si3.3 (Hexag-
4.11.4
Cu 0.6 0.2
onal), which17.7 8.3
is the stoichiometric 47.6
equivalent of the28.5
Al4 Cu2 Mg83.3
Si7 –Q phase,1.7 were noted.
Zn 1.3 0.5
The Al9 Fe0.843.1 1.4
Mn2.16 Si (Hexagonal) 2.9 phase that
is the 1.7 appeared25.5 12.6
due to the impurities in-
Si 46.8 43.8 30.5 32.4 0.9 1.2 0.6
cluded in the industrial purity raw materials. As for alloy B, the primary Mg (Al,Zn) 0.8 T
32 49—
phase (Bergman Cubic) was recognized. Additionally, the Al-base phase (FCC) and Mg2 Si
3.4. X-Ray Diffraction Analysis
phase (FCC) were observed. For alloy AM, the XRD analysis identified the Al-base ma-
In addition,
trix phase (FCC),diffraction analysis
along with was intermetallic
various used to evaluate the produced
phases, such as alloys
Mg2 Siin(FCC),
order to
Al2 Cu
verify the phases that were identified. In Figure 13, the XRD analysis results for
(Tetragonal), Al1.9 CuMg4.1 Si3.3 —Q (Hexagonal) and MgZn2 (Hexagonal) phases. Thanks samples
A, B, and AM are presented.
to the XRD analysis, it was obvious that the eutectic lamellae that were not identified in the
In alloy A, the parent Al-base phase with an FCC structure can be observed. Moreo-
EDS analysis was the Q phase. Thus, the XRD analysis confirmed the results from the EDS
ver, the intermetallic phases of Mg2Si (FCC), Al2Cu (Tetragonal), and Al1.9CuMg4.1Si3.3
analyses and all the phases were accurately identified.
(Hexagonal), which is the stoichiometric equivalent of the Al4Cu2Mg8Si7–Q phase, were
Regarding the heat-treated samples, only alloy B showed alterations. It was interesting
noted. The Al9Fe0.84Mn2.16Si (Hexagonal) is the phase that appeared due to the impurities
to note that, in the case of the heat-treated B4 alloy, the XRD analysis identified a MgZn2
included in the industrial purity raw materials. As for alloy B, the primary Mg32(Al,Zn)49—
phase.
T phaseThis could mean
(Bergman Cubic)that
wasthis phase precipitated
recognized. following
Additionally, the thermal
the Al-base phase treatment
(FCC) andat the
nanometer scale. It would be intriguing to use TEM to verify this hypothesis.
Mg2Si phase (FCC) were observed. For alloy AM, the XRD analysis identified the Al-base
matrix phase (FCC), along with various intermetallic phases, such as Mg2Si (FCC), Al2Cu
(Tetragonal), Al1.9CuMg4.1Si3.3—Q (Hexagonal) and MgZn2 (Hexagonal) phases. Thanks to
the XRD analysis, it was obvious that the eutectic lamellae that were not identified in the
EDS analysis was the Q phase. Thus, the XRD analysis confirmed the results from the EDS
analyses and all the phases were accurately identified.
Regarding the heat-treated samples, only alloy B showed alterations. It was interest-
Crystals 2025,
Crystals 15,15,
2025, 88x FOR PEER REVIEW 20 of 28
19 of 26

Figure X-raydiffraction
13. X-ray
Figure 13. diffraction patterns
patterns of specimen
of (a) (a) specimen
A, (b)A,specimen
(b) specimen
AM, (c)AM, (c) specimen
specimen B, and
B, and (d)
(d) heat-treated
heat-treated specimen
specimen B4. B4.

3.5. Mechanical and Physical Properties

3.5. Mechanical and Physical Properties
The
The hardness
hardness ofofthe
theas-cast
as-castand
andheat-treated
heat-treated alloys
alloys at room
at room temperature
temperature is shown
is shown in in
Figure
Figure 14. Additionally, a hardness/density ratio diagram is presented, with the purpose of
14. Additionally, a hardness/density ratio diagram is presented, with the purpose
evaluating their
of evaluating performance
their performance ininrelation
relationtotothat
thatof
ofcommercial
commercial aluminum alloys(Figure
aluminum alloys (Figure 15).
15). The hardness of the as-cast and heat-treated alloys was measured at room temperature
and the results are shown in Table 10. In addition, the hardness to density ratio is depicted
as well.

Table 10. Average hardness values of as-cast and heat-treated samples of manufactured alloys.

Specimen Hardness (HV4) Density (g/cm3 ) Specific Hardness

A 236 3.15 74.9
A4 256 3.15 81.3
A24 241 3.15 76.5
B 245 3.18 77
B4 245 3.18 77
B24 251 3.18 78.9
AM 246 2.73 90.1
AM4 229 2.73 83.9
AM24 219 2.73 80.2

Figure 14. Hardness values of as-cast and heat-treated samples of manufactured alloys.
According to hardness measurements, alloy AM had the highest hardness (246 HV4 )
among the as-cast samples, while from the heat-treated ones, alloy A showed the highest
value (256 HV4 ). In alloy A, the hardness increased by 8.5% in the first 4 h of the heat
treatment, followed by a 6% decrease. In alloy B, the hardness remained constant in the
first 4 h of the heat treatment, followed by a small increase (2.5%), while in alloy AM, a
reduction of 7% in hardness was observed after 4 h of soaking, followed by a reduction
of 4% after 24 h of soaking in the furnace. However, comparing the hardness to density
ratios, alloy AM showed the highest value both in the as-cast and heat-treated samples.
The increase in hardness after the heat treatment for alloys A and B indicates that the
most prominent strengthening mechanism was precipitation hardening due to the natural
aging effect, while in the case of alloy AM, the decrease in hardness indicates that the main
strengthening mechanism was probably solid-solution hardening.
 3.5. Mechanical and Physical Properties
The hardness of the as-cast and heat-treated alloys at room temperature is shown in
Figure 14. Additionally, a hardness/density ratio diagram is presented, with the purpose
Crystals 2025, 15, 88 of evaluating their performance in relation to that of commercial aluminum alloys (Figure
20 of 26
15).

Crystals 2025, 15, x FOR PEER REVIEW 21 of 28

Figure 14.Hardness
Figure14. Hardnessvalues
valuesof
ofas-cast
as-castand
andheat-treated
heat-treatedsamples
samples of
ofmanufactured
manufactured alloys.
alloys.

Figure15.
Figure 15.Hardness/density
Hardness/density ratio
ratiovalues
valuesofofas-cast
as-castand
andheat-treated
heat-treated samples
samples of of manufactured
manufactured al-
alloys.
loys.
Furthermore, electrical conductivity measurements were conducted in order to es-
timateThe
thehardness
amount of of the as-castelements
alloying and heat-treated
that werealloys wasin
trapped measured
the solidatsolution
room tempera-
and dif-
ture and the resultsduring
fused/precipitated are shown in Table
the heat 10. In stage,
treatment addition, the hardness
as shown in Figure to 16.
density ratio is
It is evident
depicted
that after as
thewell.
heat treatment, the electrical conductivity of all the alloys increased, with
the highest percentage increase occurring in the first 4 h of the heat treatment. Alloy A
Table 10. Average
presented hardness
the highest values of as-cast
conductivity valuesandinheat-treated samples(as-cast
both conditions of manufactured alloys.
and heat-treated).
Alloy BSpecimen
showed the lowest values,
Hardness although
(HV4)after a Density
4 h heat (g/cm
treatment,
3) it demonstrated
Specific Hardness the
largest percentage
A increase (36%) compared
236 to alloys A and3.15AM, with percentage 74.9increases
of 7% and 13%,
A4 respectively. The fact
256 that the electrical conductivity
3.15 increased in all three
81.3
alloys afterA24
the heat treatment indicates241 that the alloying3.15 elements diffused from 76.5 the solid
solution, which
B were trapped during
245 casting and solidification
3.18 due to the limited
77 time
for diffusion,
B4 as described as the sluggish
245 diffusion principle
3.18 that defines HEAs. 77 More
importantly,B24since the greatest percentage
251 increase in conductivity
3.18 occurred in78.9
the first 4 h
of the heatAMtreatment, it demonstrates 246 that for sufficient2.73precipitation of the 90.1components
trapped inAM4
the solid solution, 4 h of229 2.73
heat treatment is adequate. 83.9
AM24 219 2.73 80.2

According to hardness measurements, alloy AM had the highest hardness (246 HV4)
among the as-cast samples, while from the heat-treated ones, alloy A showed the highest
value (256 HV4). In alloy A, the hardness increased by 8.5% in the first 4 h of the heat
treatment, followed by a 6% decrease. In alloy B, the hardness remained constant in the
first 4 h of the heat treatment, followed by a small increase (2.5%), while in alloy AM, a
reduction of 7% in hardness was observed after 4 h of soaking, followed by a reduction of
4% after 24 h of soaking in the furnace. However, comparing the hardness to density ra-
tios, alloy AM showed the highest value both in the as-cast and heat-treated samples. The
 the solid solution, which were trapped during casting and solidification due to the limited
time for diffusion, as described as the sluggish diffusion principle that defines HEAs.
More importantly, since the greatest percentage increase in conductivity occurred in the
Crystals 2025, 15, 88 21 of 26
first 4 h of the heat treatment, it demonstrates that for sufficient precipitation of the com-
ponents trapped in the solid solution, 4 h of heat treatment is adequate.

Figure 16.
Figure 16. Conductivity
Conductivity measurements
measurementsofofas-cast and
as-cast heat-treated
and specimens.
heat-treated specimens.

4.4. Discussion
Discussion
4.1.
4.1. Better UnderstandingofofAl-Based
Better Understanding Al-BasedCCA
CCA Phase
Phase Diagrams
Diagrams Calculated
Calculated by Thermocalc
by Thermocalc
The
The order
order inin which
whichthe thephases
phasessolidified
solidified in in each
each of of
thethe manufactured
manufactured alloys
alloys will will
be be
mentioned bellow,
mentioned bellow, sincesincethese
thesewere
werethethephases
phases that
thatappeared
appeared in the final
in the microstructure
final microstructure
atatRT.
RT.
Based on
Based on the
the phase
phase diagram
diagram corresponding
correspondingto toalloy
alloyA,A,when
whenreducing
reducingthethetempera-
temperature
ture
in thein the the
melt, melt, thephase
first first phase
formed formed
was Mg wasSiMgat 2Si at about 610 °C. As the temperature
about 610 ◦ C. As the temperature decreased
2
decreased
◦ to 480 °C, the Al-FCC, Q (Al 4Cu2Mg8Si7), Al2Cu, and V (AlCuMgZn) phases
to 480 C, the Al-FCC, Q (Al4 Cu2 Mg8 Si7 ), Al2 Cu, and V (AlCuMgZn) phases began to
began tountil
nucleate nucleate until completely
the melt the melt completely
solidifiedsolidified
at 380 ◦ C. atThe
380 only
°C. The onlythat
phase phase
wasthat
notwas
present
not present in the final microstructure of the alloy was the V phase.
in the final microstructure of the alloy was the V phase.
For alloy B, by studying its phase diagram, it was clear that the first phases formed
For alloy B, by studying its phase diagram, it was clear that the first phases formed
were T (Mg32(Al,Zn)49) and S (Al2CuMg) at about 520 °C.◦At 480 °C, ◦the eutectic reaction
were T (Mg32 (Al,Zn)49 ) and S (Al2 CuMg) at about 520 C. At 480 C, the eutectic reaction
of L = Al-FCC + T (Mg32(Al,Zn)49) was taking place until the melt completely solidified. It
of L = Al-FCC + T (Mg32 (Al,Zn)49 ) was taking place until the melt completely solidified. It
should be noted that the S phase was not observed in the final microstructure.
should be noted
Finally, that AM,
in alloy the Satphase was700
around not°C,
observed in the forming.
Mg2Si started final microstructure.
As the temperature
Finally, in alloy AM, at around 700 ◦ C, Mg Si started forming. As the temperature
decreased to 550 °C, Al-FCC (pro-eutectic) began to 2 nucleate, while below 40 °C, the eu-
decreased to 550 ◦ C, Al-FCC (pro-eutectic) began to nucleate, while below 40 ◦ C, the
tectic reaction L = Al-FCC + Q (Al4Cu2Mg8Si7) started taking place until the melt com-
eutectic reaction L = Al-FCC
pletely solidified. The solidification + Qprocess
(Al4 Cu 2 Mg
was 8 Si7 ) started
completed before taking
the C14place
Lavesuntil
(MgZnthe2)melt
completely solidified.
and V (AlCuMgZn) Thestarted
phases solidification process
to nucleate, since was
they completed
were not observedbefore in
thetheC14 Laves
final
(MgZn ) and
microstructure.
2 V (AlCuMgZn) phases started to nucleate, since they were not observed in
the final microstructure.
This new knowledge and better interpretation of the Al-based CCA phase diagrams
will help future research to be more accurate in predicting the final microstructure and
consequently will considerably improve CALPHAD alloy design strategies.

4.2. Alloy Design Outcome

The design strategy for alloy A was based on the restriction of the Mg2 Si phase to
a controlled quantity. Nevertheless, this phase formed to a large extent. Thanks to a
better understanding of the phase diagrams due to this research, it was concluded that
it is challenging to limit this phase to a controlled quantity, since, according to the phase
diagrams (Figure 2), the Mg2 Si phase was the first to form and it was found that it remained
stable until room temperature was reached.
Crystals 2025, 15, 88 22 of 26

Therefore, one approach to reduce the percentage of this phase, as demonstrated in

the case of alloy B, is to minimize the percentage of Si. However, it was found that even the
minimum amount of Si led to a few small-sized Mg2 Si phases with a particularly angular
morphology, the edges of which may generate crack initiation points and thus make the
material brittle [29]. Such an approach did not result in the expected improvement in
mechanical properties and brittleness. Another intriguing design direction would be to
add an appropriate modifier to the melt in order to convert the angular morphology of the
brittle Mg2 Si phases into a more spherical one [28]. Lastly, the addition of industrial grain
refining, e.g., Ti-B, could be considered as an alternative to controlling the brittle Mg2 Si
phases. As for alloy AM, it was successfully designed with a major Mg addition, without
ignition occurring in the melt pool, and thus a lightweight HEA with a very low density of
2.73 g/cm3 was produced. Nonetheless, Mg2 Si is an intermetallic compound, which results
in high-hardness alloys and since it has a high melting point, its formation has potential in
automotive components where thermal loads are a challenge.
It is important to highlight that the presence of impurities is very likely to lead to the
appearance of unexpected phases, which are not predicted by Thermocalc. Therefore, any
research intended to produce industry-like Al-based CCAs with a more industrially applicable
approach should expect that the utilization of industrial-grade raw materials will create
unanticipated phases, which must be taken into account during the alloying design.
For thermal stability, composition design should incorporate an element that will
provide coherent precipitates that do not dissolve or coarsen at the operating temperature,
e.g., something like Al3 X where X = Sc, Zr, Ti, V, etc.
It is evident that the proposed alloys showed high hardness–density ratios, specifically
when compared to other cast aluminum alloys, as shown in Figure 17. These results
are very promising, since the newly manufactured alloys have been shown to be an
appealing alternative for applications where commercial cast aluminum alloys are used,
since the hardness-to-density ratios are higher. Furthermore, this new system can be
directly compared with some major LWHEAs from the literature. From an economic point
of view, taking into consideration production and cost limitations, all three alloys offer a
friendly alternative since they were manufactured with industrial purity raw materials
using a common furnace. Although there is still a lot of room for exploration in the field of
CCAs, the microstructures and the superior strength-to-density ratios of the investigated
alloys in combination with the manufacturing method that focuses on industrial practices
can broaden the horizon for various applications in the structural, automotive and energy
industries. The assessment of particular properties based on the exact needs
Crystals 2025, 15, x FOR PEER REVIEW 24 of 28can confirm

the suitability of alloys for each specific application.

Figure
Figure17.
17.Comparative
Comparativediagram of compressive
diagram strength
of compressive hardnesses
strength and density
hardnesses ratios from
and density cur-from current
ratios
rent
studystudy
andand
of of variousalloys
various alloys found
found in
incommercial
commercialapplications and in
applications andthein
literature [13,24,29,63–
the literature [13,24,29,63–65].
65].

5. Conclusions
In this work, three new lightweight aluminum-based CCAs were successfully pro-
duced using an industrially relevant approach: Al52Mg9.6Zn16Cu15.5Si6.9 w.t.% or
Crystals 2025, 15, 88 23 of 26

5. Conclusions
In this work, three new lightweight aluminum-based CCAs were successfully
produced using an industrially relevant approach: Al52 Mg9.6 Zn16 Cu15.5 Si6.9 w.t.% or
Al63 Mg13 Zn8 Cu8 Si8 a.t.% (alloy A), Al44 Mg18 Zn19 Cu19 w.t.% or Al55 Mg25 Zn10 Cu10 a.t.%
(alloy B), and Al47 Mg21.4 Zn12 Cu9.7 Si9.7 w.t.% or Al52.7 Mg26.6 Zn5.6 Cu4.6 Si10.4 a.t.% (alloy
AM), with low densities of 3.15 g/cm3 , 3.18 g/cm3 , and 2.73 g/cm3 , respectively. They
were manufactured using industrial-grade raw materials, a standard furnace, and a pour
mold casting process.
• The Thermocalc software predictions showed good agreement with the experimental
results as it successfully predicted the majority of phases that appeared in the alloys.
Therefore, Thermocalc can be a useful tool to guide alloy design.
• During the alloy design process, the presence of impurities in industrial-grade raw
materials should be taken into consideration since it could lead to the formation of
unforeseen phases, though such phases do not undermine the alloy’s properties.
• Alloy AM had the highest hardness (246 HV4) from among the as-cast samples, while
from the heat-treated ones, alloy A showed the highest value (256 HV4). By comparing
the hardness/density ratios of the alloys of this work with other alloys in the HEA
literature and commercial cast Al alloys that are used for automotive pistons, it was
evident that they could offer alternatives with a high hardness strength for automotive
Al cast pistons.
• Heat treatment was found to induce alterations in the elemental composition of the
constitutional phases along with changes in hardness. It was found that natural aging
can be used in these alloys to improve their hardness. Alloy A underwent an 8%
increase in hardness.

Author Contributions: Conceptualization, S.C., E.G. and S.P.; methodology, S.C., C.T. and E.G.;
software, S.C., C.T., M.B. and F.T.; resources, E.G., M.B. and F.T.; writing—original draft preparation,
S.C., C.T., M.B. and F.T.; writing—review and editing, S.C., C.T., E.G., M.B., F.T. and S.P.; visualization,
S.C.; supervision, S.C. and S.P.; project administration, S.P. All authors have read and agreed to the
published version of the manuscript.

Funding: This research received no external funding.

Data Availability Statement: Data are contained within the article.

Acknowledgments: The authors express their gratitude to the Hellenic Research Centre for Metals
ELKEME S.A. for supporting this research. We thank E. Stachouli for contributing to the metallogra-
phy and electron microscopy analyses and A. Flampouri for the design and realization of the casting
trials on behalf of ELKEME S.A., V. Loukadakis on behalf of National Technical University of Athens.

Conflicts of Interest: Author Spyridon Chaskis was employed by the company ELVALHALCOR
S.A. and authors Dr. Evangelos Gavalas, Dr. Marianthi Bouzouni, Fotis Tsiolis were employed by
the company ELKEME S.A. The remaining authors declare that the research was conducted in the
absence of any commercial or financial relationships that could be construed as a potential conflict
of interest.

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