Journal of Alloys and Compounds 1010 (2025) 177691

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Journal of Alloys and Compounds

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Review

High entropy alloys: A review of preparation techniques, properties and

industry applications
Yi-Fei Yang a,b , Feng Hu a,b,* , Ting Xia a,b, Rui-Han Li a,b, Jun-Yu Bai a,b, Jia-Qi Zhu a,b ,
Jian-Yi Xu a,b , Guo-Fang Zhang a,b
a
School of Materials Science and Engineering, Inner Mongolia University of Science and Technology, Baotou 014000, PR China
b
Inner Mongolia Key Laboratory of New Metal Material, Inner Mongolia University of Science and Technology, 014010, Baotou, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: High entropy alloys (HEAs) represent a novel class of multi-component materials characterized by a paradigm-
High Entropy Alloys shifting design that incorporates five or more principal elements in nearly equal proportions. This configuration
Preparation Techniques results in high configurational entropy and the formation of solid solutions. This review succinctly outlines the
First-Principles Calculations
theoretical foundations of HEAs, including the entropy of the alloy and its thermodynamic stability, following a
Hydrogen Storage Materials
discussion of design principles and first-principles calculations that are crucial for alloy optimization, we provide
a comprehensive review of various preparation techniques, such as mechanical alloying, magnetron sputtering,
vacuum smelting, and additive manufacturing, emphasizing their influence on the properties of HEAs. The paper
meticulously examines the core effects of these alloys—high entropy, lattice distortion, slow diffusion, and
cocktail effects—which contribute to their unique attributes. Additionally, the review explores the promising
applications of HEAs in sectors such as aerospace, energy, chemical industries, hydrogen storage, and ocean
engineering, highlighting the increasing demand for advanced materials. Looking ahead, we propose future
research directions that focus on the interplay between multi-scale structures and properties, interdisciplinary
preparation technologies, and sustainable alloy recovery and reuse strategies. This review aims to provide both
theoretical insights and practical guidelines for the rapidly evolving field of high entropy alloys.

1. Introduction Consequently, the formation of complex phases, such as ordered inter­

metallic compounds is impeded, allowing the alloy to transcend the
With the rapid advancement of contemporary industrial technology, limitations defined by traditional phase diagrams and adopt a simpler
there is an increasing demand for high-performance alloys. Traditional structure [6]. The collaboration of multiple elements generates a high
alloys typically consist of one or two primary elements, supplemented by mixing entropy within the alloy [7], facilitating the formation of simple
a few additional elements to enhance their properties. In contrast, high solid solution structures such as face-centered cubic (FCC),
entropy alloys (HEAs) challenge conventional alloy design principles body-centered cubic (BCC), or close-packed hexagonal (HCP) structures
and represent a novel class of multi-component alloys that comprise five [8]. The presence of a phase within the alloy is also influenced by
or more principal elements, each present in mole fractions ranging from various factors, including element composition and content, preparation
5 % to 35 % [1]. Since their inception, various terminologies have been method, and formation temperature. HEAs with a single-phase FCC
utilized to describe these materials, including multi-component alloys structure exhibit enhanced ductility but lower tensile strength at room
[2], compositive complex alloys [3], multi-principal element alloys [4], temperature. Conversely, BCC HEAs, despite their high strength, are
and complex concentrated alloys [5]. Unlike traditional alloys, which prone to premature cracking and other phenomena that compromise
generally contain one or several dominant elements, HEAs do not their ductility [9,10]. Achieving a balance between the strength and
possess dominant elements. This characteristic implies that the contri­ ductility of HEAs remains a focal point of research for scientists. Fig. 1
butions of each element in HEAs are approximately equal, leading to a illustrates the elemental distribution in various types of HEAs the unique
significant introduction of disorder during the design process. structure of these alloys ensures their stability within multi-element

* Corresponding author at: School of Materials Science and Engineering, Inner Mongolia University of Science and Technology, Baotou 014000, PR China.
E-mail address: [email protected] (F. Hu).

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Received 10 October 2024; Received in revised form 18 November 2024; Accepted 19 November 2024
Available online 22 November 2024
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Y.-F. Yang et al. Journal of Alloys and Compounds 1010 (2025) 177691

systems, allowing for precise adjustments of element types and pro­ concept in order to enhance the overall entropy of the system by
portions to meet diverse requirements. The comparison of size, struc­ increasing both the quantity and proportion of principal elements within
ture, and chemical complexity between HEAs and the reference the alloy [27].This approach facilitates the formation of solid solution
materials is depicted in the Fig. 2.As illustrated, the structural structures and enables the exploration of new alloy designs, as well as
complexity of HEAs is intermediate between binary compounds and the optimization of their performance.
quasicrystals, while exhibiting small particle sizes ranging from 1 to 100
μm. Due to their distinctive design concept and remarkable attributes, 2.2. Theoretical analysis of configurational entropy in HEA
which include high strength, exceptional hardness, superior oxidation
resistance, and corrosion resistance [12–14], HEAs have garnered sig­ The configurational entropy quantifies the degree of disorder among
nificant attention across various fields, including aerospace [15], the multiple elemental atoms in an alloy that are randomly arranged within
chemical industry [16], ocean engineering [17], nuclear engineering the lattice structure. When the atoms in the alloy are distributed
[18,19], and biomedicine [20]. Despite the considerable advancements randomly throughout the lattice, an approximation for the configura­
made in the research of HEAs, several unresolved issues continue to tional entropy can be derived as follows:
exist. The optimization of their properties, the precise control of their
structures, and the achievement of large-scale production remain central ΔSconf =kB ln(Ω)
challenges in ongoing investigations. This paper offers a thorough re­ The configurational entropy, ΔSconf, is defined by the number of
view of recent scholarly developments in the preparation of HEAs, possible atomic arrangements, Ω, which plays a crucial role in the for­
covering fundamental theories, preparation methods, performance mation capacity of solid solutions. Furthermore, it is important to
characteristics, and application areas. Furthermore, potential future acknowledge that kB=1.380649×10− 23J/K represents the Boltzmann
research directions are outlined and anticipated. constant. [28–30].
The aforementioned formula suggests that the incorporation of
2. The theoretical basis of HEAs diverse elements into the alloy fosters a random atomic distribution,
which in turn hinders the separation and ordering of seed phases within
2.1. Concept of alloy entropy the alloy. This phenomenon results in an increase in configurational
entropy, thereby promoting the establishment of a singular solid solu­
Entropy is a physical quantity that quantifies the degree of disorder tion phase and ultimately improving the alloy’s properties. As illustrated
within a system, as articulated by the second law of thermodynamics. In in Fig. 3, an alloy is typically classified as a HEA when the condition
the context of HEAs, a greater degree of disorder correlates with an ΔSconf ≥1.5 R is satisfied.
increased level of entropy. Specifically, a high entropy in HEAs suggests
that the system is more likely to maintain a solid solution state char­ 2.3. The thermodynamic stability of HEA
acterized by a mixture of multiple elements rather than undergoing
traditional phase separations or forming distinct compounds. The mix­ The stability of HEAs is primarily reflected in the changes in Gibbs
ing entropy in HEAs is typically augmented by the incorporation of free energy during their formation, which determines the extent to
additional principal elements. This mixing entropy is primarily which the feasibility of alloy formation and serves as an indicator of
composed of configurational entropy [21], vibrational entropy [22], whether the alloy is likely to form a solid solution or segregate into
magnetic dipole entropy [23], and electronic entropy [24]. Among these distinct phases. Under ideal conditions, a stable alloy system is expected
components, configurational entropy constitutes the largest proportion to exhibit low Gibbs free energy. A negative Gibbs free energy during
and thus serves as a significant indicator of the total mixing entropy of alloy formation signifies that the process is spontaneous, indicating that
an alloy [25]. Configurational entropy is defined as the statistical weight the system tends to minimize its free energy to achieve enhanced sta­
of various atomic arrangements within an alloy system at a specified bility. Conversely, an increase in Gibbs free energy during this process
temperature and pressure, and it is directly related to the number of suggests that alloy formation is non-spontaneous, leading the system to
microscopic states available to the system. In the context of free energy favor decomposition into separate phases. According to the Gibbs free
reduction, the impact of configurational entropy is grounded in the energy equation (ΔG =ΔH - TΔS), it can be inferred that an increase in
irreversible processes described by the second law of thermodynamics mixing entropy (ΔS) contributes to the reduction of Gibbs free energy in
[26]. The design of HEAs seeks to leverage the concept of mixed entropy HEAs, thereby facilitating the formation of solid solutions.

Fig. 1. Possible crystal structures of different elements in HEAs.

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Y.-F. Yang et al. Journal of Alloys and Compounds 1010 (2025) 177691

The thermodynamic stability of HEAs is predominantly governed by

the interplay between mixing entropy and mixing enthalpy. An
increased mixing entropy promotes the establishment of a stable solid
solution phase, whereas the magnitude and sign of the mixing enthalpy
dictate the energy variation associated with alloy formation. Table 1
illustrates the microstructure of a representative multi-principal
component HEA that has been documented in the literature.

2.4. Dynamic stability of HEA

The dynamic stability of HEAs pertains to their capacity to preserve

structural integrity and inherent properties throughout various dynamic
processes, which are influenced by a multitude of factors. In the context
of multicomponent alloy systems, the diffusion rate of atoms in HEAs is
typically low, which contributes to the maintenance of a stable structure
at elevated temperatures to a certain degree. HEAs may experience
phase experience during thermal cycling, and their microstructural Fig. 3. Relation between alloy classification and ΔSconf.
characteristics can be enhanced through processes such as annealing or
quenching, thereby improving dynamic stability. When subjected to among different elements. Consequently, the overall disorder within the
external mechanical stress, these alloys demonstrate significant resis­ alloy is enhanced, leading to a reduction in free energy and an
tance to deformation and fracture, exhibiting exceptional creep resis­ improvement in thermodynamic stability [37,38]. Due to this high
tance [36] while maintaining structural stability under conditions of mixing entropy effect, these alloys tend to form solid solution structures
high stress and temperature. During the design and fabrication of HEAs, with FCC phase, BCC phase, HCP phase or simple mixed phases. As a
it is imperative to concurrently consider both thermodynamic and ki­ result, the likelihood of element separation decreases significantly, and
netic factors to select an appropriate preparation method that ensures the observed phase types are fewer than those permitted by Gibbs’ phase
the stability and applicability of the alloy. rule [39].
Different elements exhibit varying valence states, ionic radii, elec­
tron configurations, electronegativity. and polarizability. By leveraging
2.5. Core effect of HEA the concept of high entropy, a diverse range of elements (such as Ni2+,
Mg2+, Sc3+, etc.) can simultaneously occupy equivalent lattice sites
Compared to traditional alloys, the exceptional properties of HEAs within the crystal structure, thereby, enhancing local polarization fluc­
stem from their unique inherent effects. The four fundamental effects tuations and increasing entropy. Zhang [40] discusses how a
that collectively define their distinctive characteristics and advantages high-entropy design strategy can improve the piezoelectric and dielec­
are the high entropy effect, lattice distortion effect, slow diffusion effect, tric energy storage properties of perovskite oxides by increasing system
and cocktail effect. Fig. 4 illustrates the correlation among these four disorder and adjusting the polarization configuration. The unique po­
core effects in HEAs. larization configuration resulting from the high-entropy design enables
The high entropy effect is the most prominent characteristic of HEAs, multi-component perovskite ceramics to achieve exceptionally high
and serves as the basis for their nomenclature. The presence of multiple piezoelectric coefficients. Nakamura et al. investigated the effects of
principal elements in these alloys results in a high mixing entropy, high entropy conditions at rare earth sites on the structural properties
which increases the configurational entropy and promotes miscibility

Fig. 2. [11] Comparison of HEA with other materials in size, structure and chemical complexity.

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Y.-F. Yang et al. Journal of Alloys and Compounds 1010 (2025) 177691

Table 1
[31–35] The microstructure of typical multi-principal component HEA that has been reported.
Alloy Phase structure Alloy Phase structure Alloy Phase structure

CoCrFeNiAl BCC WNbMoTa BCC TiCrFeNiCuAl BCC+FCC

CoCrFeNiCu FCC WNbMoTaV BCC TiCoCrFeNiAl BCC+FCC
CoCrFeNiTiAl BCC+FCC MoCrFeNiCu FCC TiCr0.5FeNiCuAl BCC+FCC
CoCrFeNiTiAl0.5 BCC+FCC MnCrFeNiCu BCC+FCC Ti0.5CoCrFeNiCu FCC
CoCrFeNiTiAl2.0 BCC Mn2Cr2FeNi2Cu2 BCC+FCC TiCoCrFeNiCuAlV BCC+FCC
CoCrFeNiCuAlSi BCC+FCC MnCrFeNiCuAl BCC Ti0.5CoCrFeNiAl BCC1+FCC2
CoCrFeNiCuAlMo BCC+ alpha phase MnCrFe2Ni2Cu2 BCC+FCC TiCoCrFeNiCuWMn BCC+FCC+ alpha phase

Fig. 4. The relationship between the four core effects of HEA.

and magnetic ordering temperature of DyCo2Si2. By systematically indicated that the self-diffusion rate of HEA grain boundaries is slower
substituting the Dy element in DyCo2Si2, samples with varying config­ than that of average atomic materials, suggesting presence of a slow
urational entropy were prepared. It was found that lattice parameters diffusion effect. This effect is particularly pronounced at low tempera­
are not significantly affected by the increase in configurational entropy; tures, but diminishes at high temperatures, implying that the slow
however, the antiferromagnetic order is suppressed in the high-entropy diffusion of grain boundaries may be temperature-dependent. Addi­
state. This suggests that competitive magnetic interactions in tionally, the study identified that the capture effect resulting from the
high-entropy alloys may disrupt the antiferromagnetic ordering [41]. compositional complexity in HEAs, along with the restricted
Due to the variation in atomic radii within the HEAs, lattice distor­ two-dimensional diffusion pathways in the grain boundaries, may be
tion [42–44] occurs, leading to a collective lattice distortion effect contribute to the observed slow diffusion behavior of these boundaries.
throughout the material. This effect impedes dislocation movement, The refers to the synergistic interaction among multiple principal
resulting in solid solution strengthening and enhancing the overall elements in HEAs, which leads to unexpected enhancements in perfor­
strength and hardness of the alloys [45]. Additionally, it influences the mance and imparts unique properties that cannot be achieved by any
diffusion rate and the tendency for phase separation within the alloy. Hu single element alone. These properties include increased strength and
et al. [46] investigated lattice distortion in the refractory HEA hardness, improved ductility and thermal stability, as well as excep­
HfNbTaTiZr and found that severe local lattice distortions (LLDs) is a tional corrosion and wear resistance [50–53]. Liu [54] investigated the
key factor affecting the mechanical properties and phase stability of the FeCoNiCr0.4CuXHEA and demonstrated that the appropriate addition of
material. They discovered that LLDs play a significant role in simulating Cu can significantly enhance the performance of HEAs by leveraging the
dynamic thermal vibrations in the high-temperature stable BCC phase, cocktail effect. The study found that the incorporation of Cu increases
effectively stabilizing the material’s structure. Roy et al. [47] examined the length-to-diameter ratio of the alloy powder and enhances the
the effects of lattice distortion in HEAs and its impact on solution shape-dependent anisotropy field, thereby improving the material’s
strengthening. They found that lattice distortion is crucial for enhancing permeability. The FeCoNiCr0.4Cu0.2HEA exhibits remarkable electro­
the hardness and elastic modulus of the alloys. Their experimental re­ magnetic wave absorption capabilities, which are closely linked to the
sults indicate a linear correlation between lattice distortion and alloy morphology and microstructure modifications induced by the cocktail
hardness, with alloys exhibiting higher cohesion energy demonstrating effect. In addition to Cu, the inclusion of Cr element can further enhance
superior structural properties. the overall mechanical properties and corrosion resistance of the alloy.
The reduced diffusion rate is attributed to both lattice distortion and The addition of Cu also optimizes the alloy’s high-temperature resis­
the complex distribution of elements within the alloy, which impede tance and corrosion resistance. Cao [55] discusses the cocktail effect in
atomic diffusion dynamics during phase transitions [48]. This phe­ HEAs and elucidates its impact on material stability and properties at
nomenon plays a crucial role in maintaining microstructural stability in both room and low temperatures through a multi-component alloying
high-temperature alloys, thereby enhancing their performance at strategy. The findings indicate that this effect significantly enhances the
elevated temperatures. Seoane [49] conducted a study on the gap strengthening mechanism of the material by introducing a meta­
self-diffusion behavior of grain boundaries in an equiatomic FeNiCr­ stable crystal structure, facilitating thermodynamic transformations,
CoCu HEA using molecular dynamics simulations. The findings and creating a severely distorted lattice. Cocktail alloying can induce

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Y.-F. Yang et al. Journal of Alloys and Compounds 1010 (2025) 177691

non-isothermal transformations in HEAs, such as plastic deformation, techniques to ascertain electron wave functions and energies. This
fatigue loading, and high-pressure phase transitions, resulting in the methodology facilitates the prediction of the physical and chemical
development of dual microstructures, martensitic transformations, and properties of materials. I In the context of designing HEAs, first princi­
mechanical twins. Furthermore, cocktail alloying provides a driving ples calculations can be employed to predict and analyze their stability,
force for thermodynamic transformations, promotes the formation of mechanical properties, and thermodynamic characteristics. The phase
multicomponent intermetallic phases, and enhances material properties stability of these alloys can be assessed by evaluating the mixing entropy
through precipitation strengthening and associated stacking fault and and formation energy associated with various alloying elements.
microstrip-induced plasticity. The HEAs demonstrates a diverse array of
properties that surpass those of conventional materials, attributable to 3.2. Application of first principles calculation
the interplay of multiple effects. This results in exceptional mechanical
properties across a range of temperatures, including low temperature The specific calculation process can generally be delineated into the
[56,57], room temperature [58,59], and high temperature [60,61]. The following steps: 1.Establishing a suitable crystal model based on the
performance characteristics of the HEAs are significantly influenced by chemical composition of the alloy; 2.Selecting an appropriate exchange-
their composition and phase distribution, which exhibit considerable correlation functional (such as the Generalized Gradient Approximation
variability. Additionally, the size, distribution, and morphology of each (GGA) or meta-GGA) and basis set; 3.Iteratively optimizing atomic po­
constituent phase, along with their synergistic interactions, play a crit­ sitions and lattice constants until the system’s energy is minimized; 4.
ical role in determining overall performance. Table 2 presents a Calculating the electronic structure, band structure, Density of States
comprehensive overview of the combined effects that can be achieved (DOS), and other properties of the optimized alloy system using density
through the incorporation of various chemical elements. functional theory. Tong [63] employed CASTEP software to conduct
first-principles calculations, utilizing the Perdew-Burke-Ernzerhof (PBE)
3. Design and calculation of HEAs GGA for the exchange-correlation functional. Additionally, Special
Quasi-Random Supercell (SQS) method was implemented to establish a
3.1. Introduction to first principles calculation 1×1×5 supercell model for each alloy, as illustrated in Fig. 5, wherein
five types of atoms were randomly distributed. The canonical conserved
In the preparation of HEAs, the investigation of the influence of each pseudopotential was employed to simulate the interaction between
constituent element on the properties of the alloy necessitates consid­ electrons and ions. The Broyden-Fletcher-Goldfarb-Shanno (BFGS) al­
erable human and material resources. Consequently, a hybrid approach gorithm was utilized to solve the Schrödinger equation, ensuring the
that integrates both experimental and computational methods is advis­ convergence and accuracy of the calculations. The tolerances for energy,
able. The first-principles approach, which employs electronic parame­ maximum force, maximum stress, and maximum displacement were set
ters to forecast the performance of the entire system, will be succinctly at 1×10− 5 eV/atom, 0.03 eV/ Å, 0.05 GPa, and 0.001 Å respectively.
introduced in the following section. Based on the aforementioned model and parameters, the lattice constant
First principles calculations represent a computational approach of the NbMoTaW HEA was determined to be 3.195 Å with a density of
grounded in the fundamental tenets of quantum mechanics, predomi­ 14.099 g/cm3.The simulated data closely align with subsequent exper­
nantly utilizing the Schrodinger equation and various numerical imental results (3.213 Å and 13.75 g/cm3), thereby validating the
appropriateness of the parameters employed. Yang et al. [64] utilized
the Exact Muffin-Tin Orbitals (EMTO) method within the framework of
Table 2
[62]The addition of different kinds of elements may produce the effect of HEAs.
pan-density functional theory to calculate the total energy. This method
is nearly as accurate as the full-potential method while maintaining
Element Possible effects
computational efficiency, and it solved the Kohn-Sham equation under
Fe Produces ferromagnetism and has basically no effect on organizational
structure. scalar relativistic and soft-core approximations to address the electronic
Cu It is conducive to the formation of FCC phase, which is polarized in the structure of the alloy. The PBE GGA was also employed for the
intergranular region, and may precipitate spherical Cu-rich nanophases, exchange-correlation functional, facilitating the design and perfor­
so that HEA has excellent overall mechanical properties. mance prediction of refractory HEAs containing Ti. It was observed that
Al With the increase of Al content, the phase structure of HEA changes from
FCC to BCC, the microstructure tends to be simple, the crystal structure
various properties of HEA can be tailored by adjusting their valence
changes from cellular to dendrite, and the microhardness and wear
resistance are improved.

Element Possible effects

Ti The large atomic radius promotes lattice distortion, improves hardness
and strength, and is conducive to the generation of BCC phase.
Ni It is conducive to the generation of FCC phase and makes the alloy exhibit
typical paramagnetism.
Au Can be combined with Cr, Co, Fe, Ni, Cu as binding intermediates.
Mn Reduce the antioxidant properties of HEA.
Zr May produce intermetallic compounds that reduce the strength and
plasticity of HEA.
V Reduce the oxidation resistance, resulting in the formation of uniformly
dispersed nanoparticles in the dendrite zone, making the alloy
microstructure fine, hardness and strength increased, but will reduce
plasticity.
Mo The addition of Mo makes the lattice constant of BCC phase gradually
increase, the structure is obviously refined, and the strength, hardness
and plasticity are improved.
Ag May result in the formation of silver-copper subeutectic phase layers.
Nb May lead to the formation of intermetallic compounds, reduce strength
and shape, appropriate addition of Nb can improve corrosion resistance.
B Can improve the high temperature compression performance and wear
resistance of HEA. Fig. 5. [63] BCC structure of (a)NbMoTaWx(X=Cr,Zr,V,Hf,Re) supercell
Si It can improve the compressive strength and shaping of HEA and reduce
membrane type, (b)FCC structure, (c)HCP structure, and (d) BCC structure of
the density of HEA.
NbMoTaW HEA.

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electron concentration (VEC). For instance, enhancements can be ach­ resources. The alignment between computed results and experimental
ieved in terms of elastic modulus, Vickers hardness, and yield strength. data serves to further validate the reliability and efficacy of first-
The VEC is expressed as follows: principles calculation methods in the design of HEAs.
n
∑
VEC = VECi 4. Preparation method of HEAs
i=1

In the presented formula, VEC denotes the valence electron con­ 4.1. Mechanical alloying
centration. When the valences of principal elements are comparable, the
solid solubility of these elements is enhanced, leading to a more stable Mechanical alloying (MA) is widely utilized technique for the pro­
solid solution within the alloy. An increase in VEC correlates with duction of HEA powders, wherein the ball milling process facilitates
improved elastic stability of the alloy, which in turn results in an in­ effective powder mixing and alloy formation through high-velocity
crease in the elastic constant C′ for BCC structures. Guo et al. [65] impacts. The overall procedure can be delineated into several distinct
examined the relationship between stability and FCC/BCC solid solu­ stages including ball milling, alloying, and subsequent treatment. Dur­
tions in HEAs and concluded that when VEC is greater than or equal to 8, ing the extended duration of ball milling, the constituent powders
the alloy exhibits an FCC structure; when VEC is between 6.87 and 8, it experience repeated impacts and collisions, leading to elemental
has a mixed FCC and BCC structure is observed; and when s less than or consolidation. However, the presence of impurities on the tank walls and
equal to 6.84, the alloy adopts a BCC structure. The increase in VEC the occurrence of high-temperature oxidation reactions during the ball
induces alterations in the lattice constant and electronic structure of the milling process often result in the production of alloy powders with
alloy, resulting in denser lattice packing and enhanced bond strength suboptimal purity. This challenge can be mitigated by employing Ar gas
between atoms, which restricts dislocation movement and improves [72] for protection or by conducting the process in a reducing atmo­
both the elastic modulus and Vickers hardness of the alloy. The observed sphere. Furthermore, sintering is typically performed following ball
increase in yield strength can be attributed to solution strengthening milling to ensure the integrity and stability of the powder.
effects [66]. As VEC increases, the disparity in size and shear modulus The preparation of HEAs through MA typically necessitates subse­
among the various elements within the alloy becomes more pronounced, quent treatment of the alloy powder to enhance consolidation. Common
leading to greater lattice distortion. This alteration subsequently affects post-processing techniques include spark plasma sintering(SPS) [73],
the microstructure, mechanical properties, and deformation mecha­ hot pressing sintering(HP) [74], and hot isostatic pressing (HIP) [75],
nisms of the alloy [67,68]. Zener anisotropy (AZ), which serves as a The selection of an appropriate consolidation method is crucial for
measure of lattice distortion, is defined as the ratio of C_44 to C′. As VEC optimizing the performance of HEAs. Each technique possesses distinct
increases, C′ rises while C_44 remains relatively stable or experiences advantages and limitations, which must be s evaluated in relation to the
only slight growth. This results in reduced AZ values, indicating specific application and performance criteria of the alloy. For instance,
diminished anisotropy within the alloy, and implies lesser disparities in SPS is particularly advantageous for applications that demand rapid
properties across different directions. Liu’s research demonstrates that densification while preserving an ultra-fine grain structure, whereas HIP
the variation of equivalent VEC is an effective parameter for controlling is more suitable for the fabrication of large, high-density, defect-free
the properties of HEAs, thereby facilitating the design of HEAs that meet components. H. Ahmadian et al. [76]developed a dynamic conceptual
specific performance criteria. model that effectively predicts particle size in hybrid composite powders
Utilizing first principles and the Monte Carlo method, Cai et al. [69] during MA. This model incorporates various factors, including the ki­
investigated the effects of Cu addition on the structure and stability of netic energy generated by collisions within the milling system, milling
the CoCrNiFe alloy. Their calculations indicated the formation of a duration, and powder mass. The total kinetic energy per unit mass of
short-range ordered structure on the surface of the HEAs, with a satu­ powder is denoted as KET, while K′E represents the cumulative kinetic
ration magnetic induction intensity of 52.2 emu/g, a value that is energy resulting from collisions within the system. Additional variables
comparable to the experimental measurement of 53.4 emu/g. In a considered in the model include collision frequency (f), milling time (t),
separate study, Li et al. [70] employed the VCA method based on density powder mass (mp), the Rittinger coefficient approximated by the
functional theory to develop a model for examining the effects of V grinding coefficient (C_r), the initial diameter of powder particles (di),
element addition on the structural properties of the Al0.4Co0.5VxFeNi and the final diameter of powder particles (df). By accounting for the
HEA. The calculations demonstrated that the Al0.4Co0.5VxFeNi series diverse physical changes that occur during milling, this model facilitates
HEA can adopt a BCC+FCC structure, with enhanced mechanical sta­ accurate predictions of particle size evolution, thereby enabling
bility observed in the FCC configuration. Furthermore, as the V content improved control over particle size refinement in mechanical alloying.
increases, both the bulk modulus and shear modulus exhibit a gradual KʹE × f × t
(
1 1
)
decrease, suggesting a reduction in plastic strain capacity and an in­ KET = = Cr −
mp df d i
crease in the brittleness of the alloy. These experimental findings align
with the predictions made through first principles calculations. The FeNiMnCuX (X: Co, Cr, Mo, Ti, W) HEA was synthesized through
Wang et al. [71], employed first principles calculations to investigate MA and SPS, as documented by N. Jahani et al. [77] stearic acid was
the shear modulus and formation energy of the CoCrFeNiTi HEA solid incorporated to mitigate the agglomeration of the raw materials.
solution phase as a function of Ti element content. The results indicated Following 15 hours of ball milling, a dense alloy powder was produced,
that both the shear modulus and formation energy exhibited a pro­ which was subsequently subjected to heating and compaction at a
gressive increase with higher Ti content, implying an enhancement in constant pressure of 30 MPa and a temperature of 1000℃ with a heating
hardness that intensifies with the incorporation of additional Ti into the rate of 20℃/min. XRD characterization indicated that the alloy
alloy composition. Experimental characterization corroborated that an exhibited a single-phase FCC structure, alongside the coexistence of
increase in Ti content leads to enhanced lattice distortion within the FCC1 and FCC2 phases, an FCC solid solution, orthogonal intermetallic
alloy, a reduction in dendrite spacing, optimization of the structural compounds, and other multi-phase configurations. The sintering process
configuration, a decrease in wear area, and an overall improvement in resulted in an increase in grain size for all constituent metals while
wear resistance. simultaneously reducing lattice strain, thereby enhancing the morpho­
Computational simulations facilitate the prediction of alloy proper­ logical and thermal stability of the alloy.
ties before conducting experimental investigations, thereby optimizing Burcak Boztemur et al. [78] synthesized a refractory HEA,
design parameters in an efficient manner that conserves both time and WNbMoVTa, utilizing MA and SPS. The WNbMoVTa powder underwent

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Y.-F. Yang et al. Journal of Alloys and Compounds 1010 (2025) 177691

MA for durations of 2, 4, 6, and 8 hours respectively, leading to the exclusively of FCC solid solution phase. Following heat treatment du­
formation of a BCC phase after 2 hours. Following structural analysis of rations ranging from 2 hours to 6 hours, it was observed that micro­
the powder, the sample subjected to MA for 6 hours was selected for hardness increased while the wear rate decreased with extended
further testing. The average grain size, lattice strain, and particle size treatment times. This improvement was attributed to the higher pro­
were measured to be approximately 8.1 nm, 2.5 %, and 400 nm portions and content of the MoO3 self-lubricating phase present in films
respectively. The subsequent addition of Cr and Al powders at concen­ treated for 2 hours which contributed to overall lubrication. Zhang et al.
trations of 0.05 w.t% and 1.0 w.t% significantly enhanced the micro­ [86] employed the magnetron sputtering technique to fabricate a
hardness of the sample by approximately 2.54 GPa, while concurrently high-entropy nitriding alloy film (HEAN) on a 304-steel substrate under
reducing the volume wear loss by about 1.05×10− 4 mm3 after SPS Ar conditions at a pressure of 4.1 Pa and a voltage of 920 V. The influ­
treatment at a temperature of 1500℃ under an applied pressure of ence of nitrogen flow fraction on the microstructure and properties of
30 MPa for a duration of 10 minutes. Therefore, the incorporation of Al HEAN films was investigated. The resulting film demonstrated excellent
and Cr effectively improved both the mechanical and thermal properties adhesion to the substrate, and with the incorporation of nitrogen, the
of the WNbMoVTa sample. Similarly, Hana Thurlova etal. [79] fabri­ phase structure gradually transitioned from a biphase FCC+BCC struc­
cated a (CoCrFeNiMn)100-xAlx HEA through a combination of mechani­ ture to a nano-phase FCC + amorphous composite structure. The
cal alloying and spark plasma sintering. Based on SEM and EDS maximum values of hardness and elastic modulus were recorded at the
observations, the addition of Al resulted in a FCC phase content and an proportion of nitrogen gas flow relative to the total gas flow (RN) of
increase in the Primitive Cubic lattice structure (PC) phase content in 23 %, measuring 14.42 GPa and 212 GPa, respectively. These findings
CoCrFeNiMnAl10. As the Al content increased, the proportion of the PC indicate that the incorporation of nitrogen positively influences the
phase in the alloy also increased. The inclusion of Al enhanced the performance of the AlCoCrFeNi alloy.
proportion of medium-hard phases such as PC and BCC, thereby The utilization of magnetron sputtering as a method for HEA thin
improving both the compressive yield strength and ultimate compres­ films enables precise control over their composition and structure,
sive strength of the alloy. which in turn facilitates modifications to the properties and phase
HEA powder characterized by a uniform microstructure can be structures of the substrate materials. However, in comparison to alter­
synthesized through MA, which is frequently followed by SPS to facili­ native fabrication methods, the equipment and targets required for
tate the rapid densification of bulk materials derived from powders [80]. sputtering tend to incur relatively higher production costs. Conse­
The MA technique enables the preparation of HEAs without being quently, this technique is predominantly employed in the fabrication
adversely affected by variations in the melting points of the constituent processes of thin film materials, where the achievement of large-scale
elements; even in cases where there is a substantial difference in melting thick sputtering remains a significant challenge. Furthermore, the slow
points, uniform nano-sized or amorphous particles can still be achieved. deposition rates associated with this method may necessitate additional
However, during the milling process, powder agglomeration may steps to enhance the performance of the films.
readily occur, and contaminants from grinding balls and milling tanks
can influence the particle size distribution and overall uniformity of the 4.3. Vacuum smelting method
resultant product, thereby affecting its performance. Consequently, it is
imperative to meticulously select the appropriate milling duration, Vacuum melting represents the most conventional technique for the
rigorously control the milling environment and atmosphere, and pre­ preparation of HEAs, which includes both vacuum arc melting and
treat raw materials using techniques such as ultrasonic shock to enhance vacuum induction melting. The primary distinction between these
their uniformity to the greatest extent possible. methods lies in whether the molten material comes into direct contact
with the electrode. The vacuum arc melting technique is typically uti­
4.2. Magnetron sputtering method lized for metals with high melting points and those that are susceptible
to oxidation, which can lead to the introduction of impurities.
The magnetron sputtering technique employs a plasma controlled by Conversely, the vacuum induction melting method is more appropriate
a magnetic field to effectively sputter atoms or molecules from a HEA for active metals, as it allows for precise control over the melting process
target onto a substrate within a high vacuum environment. By meticu­ while minimizing the introduction of impurities. As illustrated in Fig. 6,
lously adjusting the sputtering parameters and optimizing the compo­ the vacuum arc melting process involves the application of direct cur­
sitional structure of the target, this method ensures film uniformity and rent to metal raw materials contained within a crucible, facilitated by an
achieves the desired material properties. This technique is predomi­ electrode under vacuum conditions. This process generates high tem­
nantly utilized for the fabrication of thin film materials composed of peratures through arcing, resulting in the fusion of metals, which are
HEAs, which exhibit distinctive surface characteristics and unique in­
teractions [81]. The properties of the films can be manipulated by
varying the combinations of different elements within the HEA [82,83].
The HEA FeNiCoCrAl [84] is employed as the target material, which is
prepared through vacuum smelting. Magnetron sputtering is then uti­
lized to deposit thin films onto single crystal Si substrates, with the
objective of investigating the effects of annealing time on the compo­
sition and properties of these films. Initially, all obtained films are
amorphous. The results indicate that under sputtering conditions of
120 W and a duration of 90 min, the films exhibit a uniform composition
with a thickness of 300 nm. Upon annealing at 1000◦ C, a crystallization
transformation occurs, resulting in the conversion of the film’s alloy
structure into either a simple FCC phase or BCC phase solid solution.
Furthermore, an increase in annealing time correlates with an
enhancement in the flatness of the film.
Wang [85] prepared (TiVCrAlMo)N HEA films using direct current
(DC) magnetron sputtering and conducted a comparative analysis of
their tribological properties and microhardness before and after heat
treatment at 300℃. Prior to heat treatment, the film was composed Fig. 6. [62] Schematic diagram of vacuum arc melting method.

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Y.-F. Yang et al. Journal of Alloys and Compounds 1010 (2025) 177691

subsequently poured into a pre-prepared mold after cooling to achieve was measured under a magnetic field of 300–500 K and 2 T, revealing
the desired alloy composition. Zhu [87] employed the vacuum arc that the incorporation of diamagnetism provided by Mn increased the
melting method to prepare MnFeCoNix alloys with varying Ni contents ferromagnetic interaction. Specifically, the addition of 4 % Mn resulted
using the vacuum arc melting method. As shown in Fig. 7, an increase in in an increase in the saturation magnetization of HEA from
Ni content corresponded with a gradual enhancement in the elongation 43.8 A⋅m2Kg− 1 to 56.7 A⋅m2Kg− 1. The magnetic interaction among the
at break of the alloy, indicating an improvement in its plasticity. magnetic atoms within the structure was enhanced, leading to an in­
Furthermore, at lower Ni concentrations, the tensile strength of the alloy crease in the Curie temperature of the alloy from 361 K to 387 K. In
increased due to interface strengthening between FCC1 and FCC2 pha­ summary, the HEA prepared through vacuum arc melting can be
ses. However, as the Ni content reached a threshold where the volume controlled by adjusting the arc parameters to regulate the melting pro­
fraction of Cu and Mn-rich FCC2 phase diminished, the interface cess. This method is particularly suitable for metals with high melting
strengthening effect weakened, leading to a reduction in tensile points; however, it may lack precise control over the alloy microstruc­
strength. ture and could result in component segregation [91] and uneven grain
The CoCrFeNiMn0.25 HEA was synthesized using the arc melting size distribution [92].
method, as documented by Liu et al. [88], This alloy exhibits a struc­ The Vacuum induction melting method is a process conducted under
turally stable FCC phase. The microstructural analysis reveals dendritic high vacuum conditions, utilizing electromagnetic induction heating
characteristics with an average grain size of 17.47μm, alongside evi­ technology to melt and blend various metallic elements into a homo­
dence of component segregation. It is noteworthy that the concentra­ geneous alloy melt. This melt is subsequently cooled and solidified
tions of Mn and Ni surpass the expected calibration levels, attributed to rapidly by pouring it into a mold, facilitating the preparation of HEAs
the significantly lower mixing enthalpy between Mn and Ni in com­ with specific properties. Enrico Gianfranco Campari et al. [93] fabri­
parison to the other constituent elements. This reduced enthalpy facil­ cated a CoCrFeMnNi alloy using vacuum induction melting and exam­
itates the formation of stable compounds, resulting in a solid solution ined the effects of Zr addition on its melting temperature. The study
that incorporates Mn and Ni during the solidification process inherent to revealed that the incorporation of 5 at% Zr led to a decrease in the
the via arc melting technique used for HEA preparation. Consequently, it melting temperature, an acceleration of the melting process, the for­
is imperative to consider both the mixing enthalpy and the melting mation of eutectic phases between Zr and the individual elements,
temperature of the primary elements when striving for uniformity in the enhanced element uniformity, significant refinement of FCC grain size
desired alloy composition. In a related study, Mpofu et al. [89] suc­ due to Zr modification in HEAs, improved microstructural precision,
cessfully prepared an AlCrFeNiMn HEA with a dendritic structure optimized crystal orientation, and enhanced mechanical properties of
through the arc melting method, incorporating Sn at concentrations of the grains.Fig. 8 illustrates the "base alloy", exhibiting low toughness but
1 at%, 3 at% and 5 at% as additives to investigate the influence of Sn on shows substantial enhancement upon the introduction of high-volume
the corrosion resistance of the alloy. The findings indicated revealed that precipitates. Although ductility may be somewhat compromised, it can
the introduction of Sn atoms during the cooling phase can lead to the be restored by adjusting the quantities of added elements while also
formation of fine intermetallic precipitates, which effectively impede promoting other deformation mechanisms, such as twinning and phase
boundary growth and refine the grains of the HEA. Furthermore, the transformation.
incorporation of Sn can generate a protective film on the surface of the Dong et al. [95] synthesized an Al0.6CoCrFeNi2Mo0.08V0.04 HEA
HEA, thereby preventing solution infiltration and significantly utilizing the vacuum induction melting technique. This alloy exhibits a
enhancing its corrosion resistance in highly acidic, alkaline, and other dendritic microstructure characterized by a combination of FCC and B2
challenging environments. phases at room temperature. The dendritic regions are predominantly
The metal raw materials with a purity of 99.99 % were selected by enriched with Co, Cr, Fe, and Ni in the FCC phase, whereas the inter­
Atakan Tekgul et al. [90], and the alloys Mn24Cr10Ni33Ge25Si88 were dendritic egions are enriched with Al and Ni in the B2 phase. This
synthesized using the arc melting method. Elemental modification was microstructural configuration can be attributed to solid solution
employed to enhance the magnetic properties of the MnCrNiGeSi alloys. strengthening resulting from the trace additions of Mo and V. Conse­
The magnetization of Mn20Cr14Ni33Ge25Si8 and Mn24Cr10Ni33Ge25Si8 quently, the alloy demonstrates a yield strength of 400 MPa at room
temperature, along with an elongation of 39 %. In conclusion, the vac­
uum induction melting method effectively regulates the content of
active elements content in the alloy, mitigates the presence of gas and
non-metallic inclusions, and enhances the overall purity of the alloy.
When compared to the vacuum arc melting method, it offers advantages
such as reduced melting time, improved energy efficiency, better control
of the atmospheric conditions during the melting process, and mini­
mized alloy burning loss. However, this method requires specialized
equipment with elevated technical specifications. Despite these advan­
tages, the potential for casting defects, including cracks and residual
stress, remains; therefore, additional heat treatment may be necessary
following the alloy melting process to optimize its microstructure and
mechanical properties [96–99].

4.4. Additive manufacturing method

Additive manufacturing techniques employed for the preparation of

HEAs encompass a variety of methods, including Power Bed Fusion
(PBF) [100] which consists of Selective Laser Melting (SLM) [101] and
Selective Electron Beam Melting (SEBM) [102]. In PBF technology, HEA
powder is uniformly distributed across the work table and subsequently
melted layer by layer using a high-energy laser beam or electron beam.
Fig. 7. [87] Stress-strain curves of MnFeCoCuNix HEA with different Ni con­ This technique is characterized by rapid cooling, minimal porosity, and
tent:(a) x=0; (b) x = 0.5; (c) x = 1.0; (d)x = 1.5. excellent sample uniformity. Moreover, the performance of the resulting

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Y.-F. Yang et al. Journal of Alloys and Compounds 1010 (2025) 177691

Fig. 8. [94] Schematic diagram of the best combination of synergistic effects of different strengthening deformation mechanisms in HEAs.

samples can be optimized through adjustments in equipment parameters fabricate a lightweight refractory HEA composed of VNbTiSi. Compared
as well as through subsequent sample treatments [103,104]. The to the as-cast alloy, LMD technology refines the spacing between
Directed Energy Deposition (DED) process includes Laser Melting eutectic structures while achieving superior compressive strength at
Deposition (LMD) and Wire Arc Additive Manufacture (WAAM), As elevated temperatures, thereby underscoring its advantages in extreme
illustrated in Fig. 9, DED utilizes a high-energy beam to create a molten service conditions.
pool along the printing path, facilitating the construction of components The CrMnFeCoNi HEA was synthesized by Tian et al. [115] using the
through the addition of powder and wire. This technology effectively LMD method, followed by Deep Cryogenic Treatment (DCT). Following
mitigates composition segregation within the alloy and significantly the preparation of the alloy, it was subjected to immersion in liquid
enhances its mechanical properties [105]. nitrogen at a temperature of 77 K for a duration of 12 hours, subse­
Diverging from traditional mass production-oriented casting quently undergoing rapid cooling in a water bath at room temperature
methods, additive manufacturing presents a substantial advantage by (293 K) for 2 hours. The mechanical properties of the alloy exhibited
minimizing mold operations and improving alloy forming efficiency. significant enhancement post-DCT. Specifically, the yield strength and
Due to its flexibility in material selection and adaptability in prepara­ tensile strength along the rolling direction of the alloy, fabricated with a
tion, additive manufacturing is particularly well-suited for the custom­ power output of 1400 W, were markedly improved after 12 cycles of
ization and fabrication of components with complex structures DCT, with increases of 175 % and 56 %, respectively. This enhancement
[106–108]. is attributed to the formation of grains induced by DCT, which serve as
The HEAs produced through casting demonstrates a relatively uni­ barriers to dislocation movement and facilitate twinning-induced plastic
form microstructure and isotropic mechanical properties, as illustrated deformation. Furthermore, this increase in strength does not compro­
in Fig. 10. In contrast, additive manufacturing techniques result in more mise the ductility of the alloy; even after DCT treatment, it retains
pronounced grain orientation due to the concentrated energy input approximately 20 % elongation, indicating excellent ductility. These
during the fabrication process, which induces a significant temperature findings offer valuable insights for subsequent treatments applied to
gradient. This phenomenon leads to increased residual and thermal HEAs produced via LMD. Additive manufacturing technology allows for
stresses, ultimately resulting in crack formation and a reduction in the precise control over the microstructure and properties of the alloy,
alloy’s properties [109–111]. This issue can be mitigated through sub­ promoting a uniform distribution of alloy components while minimizing
sequent heat treatment or mechanical processing [112]. Zhang et al. both macroscopic and microscopic segregation. This not only results in
[113] employed laser melting deposition LMD to fabricate AlxCoCrFeNi cost savings but also enhances production efficiency [116,117]. Conse­
HEA with reduced sensitivity to cracking, as depicted in Fig. 11 The quently, additive manufacturing is extensively utilized in the aerospace,
study investigated the influence of Al content on the microstructural medical, and automotive industries and is anticipated to play an
evolution and corrosion resistance of the alloy. It was found that an increasingly critical role in future material manufacturing initiatives.
increase in Al content transformed the LMD substrate from FCC to BCC The preceding sections provide a summary of the prevalent prepa­
structure, Notably, when the Al content reached 10 mol%, the alloy ration methods for HEAs. It is noteworthy that variations in preparation
exhibited optimal corrosion resistance. This enhancement can be techniques for the same alloy can significantly influence its overall
attributed to changes in the composition and depth of the passivation properties. For instance, the FeCoNiCrMn HEA has been synthesized
film on the alloy surface, which facilitated the continuous formation of using different methods, including MA+SPS, SLM and VAM as demon­
Cr2O3. Therefore, the incorporation appropriate amounts of Al element strated by Liu [118], Kim [119] and Li [120] respectively. Liu employed
during the LMD preparation process significantly improves the corrosion high-purity powders of Fe, Co, Ni, Cr, and Mn, which were mixed in
resistance of HEAs. Wang et al. [114] utilized LMD technology to equal atomic ratios. The mixture underwent ball milling with C7H16 as

Fig. 9. [103] Diagram of WAAM equipment.

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Y.-F. Yang et al. Journal of Alloys and Compounds 1010 (2025) 177691

Fig. 10. [109] IPF diagram of EBSD of FeCoCrNiMn HEA prepared by (a) casting method (b) directional deposition method (c) powder bed melting method.

Fig. 11. [110] Flowchart of preparation of LMD AlCoxCrFeNi HEA.

a process control agent (PCA), introducing 0.5 wt% carbon to form a The MA, Magnetron Sputtering Method, Vacuum Smelting Method
HEA containing in situ carbide (HECin). This powder was subsequently and Additive Manufacturing method examined in this discussion.
combined with an additional 5 wt% of TiC and TaC powders and milled Following the analysis of these four techniques for the preparation of
for an additional five hours, resulting in a HEA (HECex) that contains HEAs, we provide a summary of their respective advantages and dis­
external carbides, which was then sintered using SPS technology. In advantages. To facilitate a more intuitive comparison of these ap­
contrast, Kim utilized pre-alloyed CoCrFeMnNi powder to fabricate the proaches, the benefits and limitations of each method are presented in
HEA via SLM. A laser scanning speed of 600 mm/s was employed to Table 3, so allowing for a quick understanding of the core characteristics
produce a strip specimen measuring 85 mm×10 mm, with a volumetric and application scenarios associated with each technique.
energy density (VED) of 75 J/mm3. Li prepared FeCoNiCrMnTix(x=0, 2,
4, 6 wt%) through vacuum arc melting, utilizing high-purity metal 5. Outstanding properties of HEAs
particles of Fe, Co, Ni, Cr, Mn and Ti. A comparative analysis of the three
distinct preparation methods revealed significant differences in the 5.1. Mechanical properties of HEAs
microstructure and properties of the FeCoNiCrMn HEA. The introduc­
tion of in situ and external carbides in the alloys produced via MA + SPS 5.1.1. Mechanical characteristics
led to the formation of M23C6 and M7C3 carbides within the micro­ HEAs, characterized by their multi-principal component structure,
structure, which markedly enhanced the hardness and strength of the introduce a significant degree of disorder by incorporating multiple el­
alloys. The alloys fabricated through SLM exhibited FCC single-phase ements in nearly equal proportions. This approach substantially en­
random solid solution structure, demonstrating excellent mechanical hances the material’s strength and hardness while preserving its
properties at both room and elevated temperatures, with a compressive plasticity. For example, the distinctive lattice distortion effect observed
yield strength reaching 778.4 MPa. Furthermore, the VAM-prepared in HEAs can influence their strength, hardness, and other mechanical
alloy facilitated the formation of BCC phase due to the addition of Ti, properties. The distribution of various elements within the HEA gener­
resulting in increased hardness and strength; notably, the hardness of ates a synergistic effect that may lead to a range of unexpected out­
the FeCoNiCrMnTi6 alloy reached 293 HV, indicating exceptional wear comes, further improving the material’s characteristics. Wang et al.
resistance. These findings underscore the critical influence of different [121] conducted an investigation into the impact of Nb on both the
preparation methods on the microstructure and properties of HEAs. microstructure and mechanical properties of HEA coatings. The CoCr­
Moreover, the properties of these alloys can be optimized by adjusting FeNiTi0.8Nby (y=0.25, 0.5, 0.75, 1) series coatings were fabricated on
the preparation parameters to fulfill specific application requirements. the Q235 substrate using a laser cladding technique (as illustrated in

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Y.-F. Yang et al. Journal of Alloys and Compounds 1010 (2025) 177691

Table 3 significant amount of laser power and prolonged processing times,

Comparison of different preparation methods of HEAs. which ultimately results in low efficiency [124,125]. An analysis of the
Methods for Advantages Disadvantages coating’s microstructure was conducted, and its wear resistance was
Producing HEAs evaluated. It was found that the incorporation of Nb led to a reduction in
Mechanical 1. Nanocrystalline and 1. Powder purity problem, the size of the coating’s microstructure, which exhibited a crystal
alloying amorphous particles, can be may introduce impurities. structure consisting of BCC, FCC, and (Ti, Nb) Laves phases. The addi­
prepared by breaking the 2. The long reaction time, the tion of Nb facilitated both fine crystal strengthening and solid solution
melting point difference limit. realization of alloy element strengthening throughout the coating. Furthermore, the formation of a
2.simple operation is simple, mix and alloying take a long
easy to control. time.
secondary phase contributed to an increase in the coating’s hardness,
3.The alloy has excellent thereby enhancing its wear resistance. Notably, optimal results were
mechanical properties such as observed when the Nb content reached 0.75 %, yielding a hardness
high strength and high value as high of 710HV—four times that of the substrate—along with
hardness.
minimal wear volume and relatively smooth wear marks [126].
Magnetron 1. Easy to get with the 1. Gas flow slight change
sputtering stoichiometric of target could significantly change The CoCrFeNiMn HEA with varying concentrations of Y2O3 nano­
similar film. the HEA thin film of. particles was synthesized using powder plasma additive manufacturing
2. Rapid quenching rate. 2. The entire process takes technology (PPA-AM) as reported by Tian et al. Fig. 13 presents the
3. Easy to manufacture longer. tensile properties of the HEA at 300◦ C. The incorporation of 0.5 at%
superior mechanical
properties and corrosion
Y2O3 resulted in an increase in yield strength and ultimate tensile
resistance of HEA coating. strength by 8.92 % and 19.07 %, respectively, while elongation
Vacuum melting 1.To provide accurate 1. The composition of low improved by 48.19 %. Fig. 14 illustrates the electron backscattering
composition and purity of boiling point may be in the diffraction (EBSD) pattern and grain size distribution for both
control. process of preparing alloy
CoCrFeNiMn-0 and CoCrFeNiMn-0.5 samples. The addition of 0.5at%
2.High vacuum environment evaporation.
to minimize the reaction gas 2. Rapid solidification leads Y2O3 significantly reduced the grain size of the HEA, leading to a more
pollution. to the change from the pronounced orientation effect on the refinement of the HEA micro­
3.Rapid solidification surface to the center of structure. This microstructure refinement is attributed to the impedi­
promotes the formation of microstructure ment of dislocation movement caused by the presence of fine grains, as
solid solution phase. characteristics.
well as the pinning effects on grain boundary migration due to the dis­
Additive 1. Higher accuracy, and rapid 1.The production cost is
manufacturing solidification characteristics higher. tribution of Y2O3 along the grain boundaries, which hindered grain
are more conducive to the 2.On the material itself is growth.
uniformity of the alloy. limited, not all materials are Zhang et al. [127] successfully synthesized a fine-grained CoCrFe­
2. The waste of raw materials applicable.
NiMn HEA utilizing underwater stirring processing (UFSP), This method
is reduced to a greater extent,
especially in high-precision resulted in significant grain refinement and the formation of numerous
complex parts. twin structures, as well as BCC phases that precipitated along the grain
3. It can realize the rapid boundaries. The optimization of the microstructure contributed to a
melting and solidification of substantial enhancement in the mechanical properties of the alloy,
high entropy alloy with
evidenced by a 206 % increase in microhardness and a 269 % increase in
complex structure and larger
size. tensile strength compared to the original material. The presence of twin
structures facilitated the distribution of stress distribution during tensile
deformation, effectively reducing stress concentration phenomena and
promoting excellent elongation behavior in the alloy.

5.1.2. Plasticity and toughness

The ductility and toughness of an alloy are essential parameters that
influence its capacity to preserve structural integrity under stress. Alloy
plasticity pertains to the material’s ability to endure deformation
without fracturing, whereas toughness serves as a vital metric for

Fig. 12. [122] Schematic diagram of HEA prepared by laser cladding method.

Fig. 12). This method provides advantages such as enhanced bonding

strength and complete formation [123].
Achieving complete melting of metal powders necessitates a
Fig. 13. [126] Tensile structure of HEA at 300℃.

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Y.-F. Yang et al. Journal of Alloys and Compounds 1010 (2025) 177691

Fig. 14. [126] EBSD patterns and grain size distribution of HEA with different Y2O3 contents: (a, b) CoCrFeNiMn-0; (c, d) CoCrFeNiMn-0.5.

assessing the alloy’s resistance to impact and crack propagation. The substantially enhance its capacity for plastic deformation. Furthermore,
elevated mixing entropy characteristic of HEAs fosters the development the Ta0.75 alloy displays remarkable strength and plasticity at high strain
of a homogeneous solid solution structure, effectively mitigating phase rates, a phenomenon that may be linked to the interactions between
separation and the emergence of brittle phases typically associated with primary adiabatic shear bands and cracks within the microstructure. The
conventional alloys. This phenomenon ensures a concurrent enhance­ formation of adiabatic shear bands leads to localized deformation con­
ment in material strength while preserving excellent plasticity and centration within the alloy, resulting in fracture initiation. Additionally,
toughness, thereby enabling HEAs to perform exceptionally well under it is observed that the adiabatic shear sensitivity of the alloy varies with
extreme conditions, such as impact loads, thermal cycling, and highly increasing Ta content.
corrosive environments. Li et al. [128] conducted an investigation into
the performance variations of HEAs at extremely low temperatures,
5.2. Physical properties of HEA
revealing that, in contrast to traditional alloys, HEAs do not exhibit a
reduction in plasticity at low temperatures. Rather, they are capable of
5.2.1. wear resistance
maintaining or even augmenting their plasticity and toughness due to
Wear resistance serves as a critical parameter for assessing the
the occurrence of twin phenomena within the material. At lower tem­
durability of HEAs under frictional conditions. The superior wear
peratures, the rate of twin formation is accelerated, which significantly
resistance exhibited by HEAs can be attributed primarily to the high
contrasts with the sluggish expansion of dislocation motion observed in
entropy effect and lattice distortion, which facilitate the formation of a
conventional alloys. These twins facilitate plastic deformation of the
single crystal structure, thereby enhancing wear resistance. Notably,
alloy at reduced temperatures while simultaneously refining the grain
certain HEAs retain their wear resistance even at elevated temperatures,
structure and enhancing material toughness.
which is essential for various industrial applications. The predominant
Zhang et al. [129] synthesized a HfZrTiTax HEA using vacuum arc
strategy for augmenting the wear resistance of HEAs involves the
melting and conducted a comprehensive analysis of its plasticity and
incorporation of diverse alloying elements and catalysts, alongside
toughness. Their findings indicate that the microstructure of the alloy is
modifications to the hardness and phase composition of the alloy. For
significantly affected by variations in Ta content, which in turn modifies
instance, Li [130] synthesized an Al0.8TiVNbNi0.2(SiC)0.2 refractory HEA
its mechanical properties. Alloys with compositions of Ta0.16 and Ta0.53
composite using SPS technology. The coefficient of friction (COF) and
demonstrate favorable plasticity and strength, primarily due to mecha­
wear rate of the composite were evaluated across a temperature spec­
nisms such as solid solution strengthening, dislocation entanglement,
trum from room temperature to 800℃. The introduction of SiC signifi­
and subgrain boundary coordination deformation. Notably, the Ta0.53
cantly enhanced the wear resistance of the composite over a broad
alloy exhibits a considerable number of subgrain boundaries, which
temperature range; particularly, at 500◦ C, the wear rate decreased by

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 Y.-F. Yang et al. Journal of Alloys and Compounds 1010 (2025) 177691

more than an order of magnitude. The incorporation of SiC nano­ conducted near the crystallization temperature, the wear resistance of
particles not only improved the tribological properties of the alloy by the alloy is significantly improved due to effective co-deformation be­
altering its phase composition and enhancing softening resistance but tween the amorphous matrix and the precipitated crystalline phase. This
also contributed to the continuity and compactness of the friction layer alteration in the wear mechanism shifts to slight abrasive wear and
at elevated temperatures through the formation of SiO2 oxides, thereby oxidation wear, thereby optimizing wear resistance.
bolstering the high-temperature wear resistance of the alloy. Medium-entropy alloys (MEAs) have garnered significant attention
You [131] developed two variants of TiCrNbTaWx (x=0, 0.5) HEAs as wear-resistant materials due to their flexible compositional design. By
via SPS technology and discovered that the addition of W significantly retaining the advantages associated with multi-principal component
enhanced the hardness and deformation resistance of the alloys. This alloys, MEAs enable precise control over alloy properties through the
improvement is primarily attributed to the solid solution strengthening adjustment of elemental proportions. Notably, advancements in wear
effect induced by W, as well as the formation of a high-hardness oxidized resistance and self-lubrication properties have been remarkable. For
amorphous layer during the friction process. Collectively, these factors instance, in the case of CoCrNi-basedMEAs, researchers have demon­
led to a substantial enhancement in the wear resistance of the TiCrNb­ strated that the wear resistance of the alloy can be enhanced by the
TaW0.5 alloy, resulting in a wear rate that is 67 % lower than that of the introduction of new elements or structural modifications. [136] Utiliz­
original TiCrNbTa alloy. Furthermore, You [132] conducted subsequent ing powder metallurgy and reaction sintering techniques, CoCrNi-based
research to fabricate TixCrNbTaW (x=1and1.5) HEAs, incorporating Ti self-lubricating composites containing in-situ graphite have been suc­
to promote complete alloying of the matrix and facilitate the in-situ cessfully synthesized. These composites not only exhibit increased
formation of a high-hardness Ti-enriched phase, This approach also hardness and strength but also demonstrate exceptional frictional
improved the uniformity and toughness of the matrix, effectively miti­ properties, with a coefficient of friction (COF) as low as 0.23 and a wear
gating wear and fracture behavior. Notably, the friction-induced dense rate of 8.1×10− 6 mm3N− 1m− 1, which is approximately one-thirtieth
oxide amorphous layer exhibited a higher hardness than the matrix, lower than that of CoCrNi MEAs. This improvement is attributed to
providing additional load-bearing capacity for the Ti1.5 alloy, which the strengthening effect of the hard silicide/carbide phases within the
achieved a remarkably low wear rate of 2.9 × 10− 5 mm3/(N⋅m), rep­ composite, as well as the self-lubricating properties conferred by the
resenting a 58 % reduction compared to the Ti1 alloy, thereby demon­ in-situ graphite. Furthermore, the mechanical properties and wear
strating exceptional wear resistance. resistance of CoCrNi MEAs have been enhanced through the incorpo­
HEA matrix composites have demonstrated the potential to enhance ration of Hf into a layered eutectic structure [137]. By controlling the
wear resistance. For instance, HEA-based ceramic composites and HEA- quantity of Hf added, it is possible to optimize both the hardness and
based bulk metallic glass，(HE-BMG) exhibit superior properties. plasticity of the alloy, thereby improving the ductility of the material
Composite materials typically possess improved plasticity and toughness while maintaining high strength. The introduction of this structural
compared to their ceramic or metallic counterparts, enabling them to modification not only increases the hardness of the material but also
endure impact and complex loading conditions while maintaining effectively enhances its wear resistance by dispersing stress
commendable wear resistance. Pei [133] synthesized NbMoWTa concentrations.
(h-BN)x(x = 0, 2.5, and 5 wt%) HEA-based ceramic composites by SPS Du [138] has developed a novel CoCrNi MEA-based self-lubricating
method. The incorporation of hexagonal boron nitride (h-BN) facilitates composite through powder metallurgy and reaction sintering, which
the in-situ formation of (Nb,Ta)N and (Nb,Ta)B2 ceramic phases, which incorporates in-situ graphite along with high-hardness silicide/carbide
possess significantly higher hardness than the matrix, thereby enhancing as reinforcement phases. The pyrolysis reaction between the CoCrNi
the overall hardness and wear resistance of the composite. The wear rate alloy matrix and added SiC ceramic particles at elevated temperatures
of the NbMoWTa(h-BN)0.5 composite is measured at an exceptionally results in the simultaneous precipitation of in-situ graphite,
low value of 1.32 × 10− 8 mm3/Nm, which is four orders of magnitude high-hardness silicides, and carbides within the composite. The volume
lower than that of the original refractory HEA. By introducing TiZrHfNb fraction of these phases can be controlled by varying the amount of SiC
high entropy crystal phase into TiZrHf CuBe high entropy amorphous ceramic particles added. Owing to the superior mechanical properties of
alloy matrix, Du [134] prepared TiZrHfNb0.5Cu0.5Be0.5HE-BMG. this material and the uniform distribution of a high-volume fraction of
Through microstructure and thermal stability characterization, it is in-situ graphite, the Gr@CoCrNi-SiC composite, with a volume fraction
found that the introduction of high entropy amorphous phase did not of 20.6 %, exhibits outstanding performance, characterized by a friction
adversely affect the glass-forming ability or thermal stability of the coefficient of 0.19 and a wear rate of 2.95×10− 6 mm3/Nm.
amorphous matrix; rather, it increased the free volume within the
amorphous matrix. Mechanical testing indicated that the composite 5.2.2. Magnetic properties
exhibited a distinctive combination of strength and plasticity, surpassing The presence of multiple components and solid solution structures in
that of traditional amorphous alloy composites. The high strength is HEAs can disrupt conventional magnetic ordering, leading to uncon­
attributed to the solid solution strengthening resulting from significant ventional magnetic behaviors such as ferromagnetism or antiferromag­
lattice distortion within the phase, coupled with a slight strength netic properties. These alloys are capable of maintaining their solid
mismatch between the HEA phase and the amorphous matrix. The solution structure at both room temperature and elevated temperatures,
enhanced plasticity is ascribed to the favorable plastic deformation thereby preserving their magnetic properties even under high-
characteristics of the HEA phase, which effectively inhibits the rapid temperature conditions. Additionally, the slow diffusivity character­
initiation and propagation of shear bands within the amorphous matrix. istic of these alloys contributes to the stability of their microstructure
In contrast to the non-uniform wear behavior observed in the HE-BMG, and overall properties. Furthermore, the magnetic properties of HEAs
which is influenced by the formation and failure of an oxidized amor­ exhibit excellent temperature stability and adjustability; by modifying
phous layer, the improved mechanical properties of the composite the alloy composition, one can regulate its saturation magnetization,
confer excellent wear resistance under varying normal loads or coercivity, and magnetic anisotropy. Moreover, the introduction of
frequencies. nanoscale precipitated phases or grain boundaries can enhance the
Liu [135] modified the internal microstructure and free volume of motion of magnetic domain walls and improve permeability.
the alloy through isothermal annealing of Ti20Zr20Cu20Hf20Be20 K.X Zhou et al. [139] synthesized a HEA composed of FeCONiAlSi
HE-BMG, resulting in enhanced strength and hardness. However, while through the process of arc melting. This alloy exhibits a BCC structure
the annealing treatment prior to crystallization increases hardness, it and demonstrates remarkable magnetic properties. Fig. 15 presents the
does not effectively enhance wear resistance due to a reduction in plastic coercivity Hc and saturation magnetization Ms of the high- entropy
deformation capability. Conversely, when isothermal annealing is magnetic alloy, alongside the (Co30Fe45Ni30)1-x(Al40Si60)x compositions

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Y.-F. Yang et al. Journal of Alloys and Compounds 1010 (2025) 177691

Fig. 15. [139] The Hx and Mcs diagrams of high entropy magnetic alloys and (Co30Fe45Ni30)1-x(Al40Si60)x studied by predecessors.

investigated by prior researchers. When the Al and Si content is set at 0.8 transformation of an alloy during the mechanical alloying process from
and 0.2, respectively, the resulting alloys exhibit a favorable combina­ FCC to the BCC phase. By monitoring XRD data at various alloying time
tion of high saturation magnetization (133 emu/g) and low coercivity intervals, the researchers were able to ascertain the relative content of
(59.7 A/m). This advantageous combination is particularly beneficial different phases and calculate the conversion fraction. Utilizing this
for applications in energy storage and conversion, as a higher saturation data, the researchers fitted the JMA equation, from which the reaction
magnetization contributes to a reduction in device volume, while lower rate constant k and the Avrami index n were derived. These parameters
coercivity minimizes energy losses. In the study conducted by Malihe offer valuable insights into the mechanisms underlying the phase tran­
Zeraati [140], the preparation and properties of CuCrFeTiNi HEAs were sition; for instance, the value of n can indicate whether the phase
thoroughly examined. Utilizing MA and SPS techniques, the researchers transition process is predominantly governed by continuous growth or
successfully produced CuCrFeTiNi alloys with varying microstructures. dispersed nucleation. The parameters derived from the JMA model
During the MA process, the grain size of the alloy progressively elucidate the dynamic characteristics of the alloy throughout the MA
decreased, resulting in a microstructure with dimensions less than process. Specifically, the trend in the k value may reflect the acceleration
48 nm. After 60 hours of MA, the alloy predominantly consisted of FCC or deceleration of the phase transition rate during MA, while the n value
and BCC phases, with the FCC phase comprising for 91 % and the BCC provides nuanced information regarding the phase transition mecha­
phase accounting for 8 %. nism. This information is essential for comprehending the microstruc­
The vibration sample magnetic (VSM) analysis of the sample indi­ tural evolution of alloys and can inform future alloy design and process
cated that, following 60 hours of MA, the sample exhibited a saturation optimization efforts.
magnetization of 19.12 emu/g and a coercivity of 13.4 Oe. In contrast, Jung et al. [141] prepared a novel type of HEA superconducting
the sample sintered sample via SPS demonstrated a significantly higher wire, specifically Ta1/6Nb2/6Hf1/6Zr1/6Ti1/6, utilizing powder filled tube
saturation magnetization of 64.38 emu/g and a lower coercivity of (PIT) technology. The wire exhibited remarkable superconductivity
4.63 Oe. Mechanical property assessments revealed that the alloy sin­ following sintering at 700℃ for one hour, with a critical current density
tered by SPS achieved a Vickers hardness of 725 Hv, a compressive (Jc) surpassing 100KA/cm2 and a significant increase in the super­
strength of 2466 MPa and a yield stress of 1525 MPa, These superior conducting transition temperature (Tc) from 5.10 K to 7.76 K. This
excellent mechanical properties are attributed to the fine grain structure investigation highlights the critical role of normal point pinning in the
and the solid solution strengthening effect inherent in the alloy. The HEA superconducting wire in achieving elevated Jc under high magnetic
findings suggest that the microstructure and magnetic properties of the fields, thereby underscoring the substantial potential of this material for
alloy can be effectively controlled by adjusting the MA duration and the applications in high-field superconducting magnets. Furthermore, by
parameters of the SPS process. In the research conducted by Malihe manipulating the sintering temperature and duration, the super­
Zeraati, the Johnson-Mehl-Avrami (JMA) kinetic model was employed conducting properties of the wire can be optimized. The unique
to analyze the phase transition behavior of the CuCrFeTiNi HEA during multi-component structure of the wire also offers a promising avenue for
MA. Utilizing the JMA model, the researchers were able to quantita­ the exploration of novel flux pinning mechanisms and the enhancement
tively characterize the formation and transition processes of the FCC and of superconducting properties.
BCC phases within the alloy. The JMA model is predicated on the In a pioneering study conducted by Zhou [142], the effects of Ge
nucleation and growth mechanism, positing that the phase transition additions on the structural and magnetic properties of the HEA (CoCr­
process comprises two distinct steps: the initial nucleation of a new FeNi)100-xGex were examined. The findings indicated that as the Ge
phase, followed by the subsequent growth of these nuclei. The model content increased, the alloys underwent a transition from a FCC struc­
assumes that nucleation occurs instantaneously and that each particle ture to a BCC structure, ultimately resulting in the formation of a hex­
surface is enveloped by a new phase layer. Under this framework, the agonal intermetallic compound at elevated Ge concentrations.
phase transition process can be articulated through the following Significantly, the magnetic properties of the alloys transitioned from
mathematical relations: paramagnetic to ferromagnetic at room temperature, which corre­
sponded with the observed structural transformations. The Ge-doped
α(t) = 1 − exp(﹣ktn)
HEAs demonstrated improved strength and a substantial increase in
α(t) represents the conversion fraction, which denotes the proportion hardness, positioning them as promising candidates for applications in
of the new phase at a given time t, The variable k signifies the reaction the aerospace and energy sectors, where magnetic properties are of
rate constant, t denotes time, and n is the Avrami exponent, which is paramount importance. This study offers critical insights into the po­
associated with the nucleation and growth mechanisms as well as the tential of Ge doping to modify the magnetic characteristics of HEAs for
geometric characteristics of the phase transition. In the research con­ advanced technological applications.
ducted by Zeraati, JMA model was employed to analyze the

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Y.-F. Yang et al. Journal of Alloys and Compounds 1010 (2025) 177691

5.3. Chemical properties of HEA in number and smaller in size, indicating that this alloy is more effective
in resisting swelling caused by the accumulation of helium bubbles in
5.3.1. Oxidation resistance and radiation resistance irradiated environments. In comparison to pure Ni, CoCrFeNiMn
Oxidation resistance and radiation resistance are critical parameters exhibited enhanced irradiation resistance, which may be attributed to
for evaluating the properties of HEAs. These characteristics are partic­ lattice distortion, reduced defect mobility, and diminished helium
ularly important for applications in extreme environments, such as bubble formation. Given their stability under irradiation, HEAs present
aerospace, the nuclear energy sector, and advanced manufacturing. The significant potential as novel radiation-resistant structural materials for
oxidation resistance of HEAs pertains to their capacity to withstand advanced nuclear reactor systems. Future research should further
oxidation at elevated temperatures. For instance, the TiZrV0.5Nb0.5Al0.75 investigate the effects of various elemental combinations and processing
alloy demonstrates [143] exceptional oxidation resistance at 1000◦ C, as techniques on the radiation resistance of HEAs, as well as their appli­
evidenced by its ability to effectively inhibit the internal diffusion of cability in specialized irradiation environments.
oxygen through the formation of a dense Al2O3 protective layer, thereby
reducing the oxidation rate. Furthermore, the incorporation of Si has 5.3.2. Corrosion resistance
been shown to enhance the spalling resistance of the alloy by facilitating The corrosion resistance of alloys serves as a critical parameter for
the formation of a continuous Nb oxide protective layer, which mitigates assessing their performance and structural integrity across various
the delamination of the oxide layer and the development of internal chemical environments. In the domains of marine engineering, chemical
cracks through a pinning effect. processing, and the energy sector, there is an increasing demand for
Palcut [144] conducted a study on the oxidation behavior of the enhanced corrosion resistance in alloys. HEAs, characterized by their
AlCoFeNiCux (x = 0.6–3.0) HEA through isothermal annealing in syn­ multi-principal solid solution structure, elevated mixing entropy, and
thetic air at 1000◦ C. The findings indicate that an increase in copper slow diffusion kinetics, demonstrate improved chemical stability and
concentration correlates with a rise in the oxidation rate constant of the resistance to the penetration of corrosive media, thereby outperforming
alloy, leading to the detachment of the oxide layer. This phenomenon conventional alloys in terms of corrosion resistance. Zheng et al. [149]
may be attributed to the mismatch in the coefficients of thermal fabricated a (Fe33Cr16Co15Ni15Ti1) 96Al4 alloy using vacuum induction
expansion between the oxide layer and the substrate. The results suggest melting. As illustrated in Fig. 16, the open circuit potential (OCP) of the
that the oxidation resistance of the alloy can be significantly influenced HEA consistently exceeded that of 304 stainless steels (304SS) at room
by adjusting the Al-to-Cu ratio; specifically, an increase in Al content temperature. It is well-established that a higher OCP value correlates
contributes to the formation of a more continuous and thicker Al2O3 with lower alloy activity and enhanced corrosion resistance. The Table 4
protective layer, thereby improving the oxidation resistance of the alloy presents electrochemical parameters derived from the potentiodynamic
at high temperature. Moghaddam [145] prepared several polarization curve analysis of both the HEA and 304SS in a 3.5 wt%
tungsten-containing HEAs via arc melting and evaluated their oxidation NaCl solution. The results indicate that the HEA exhibited lower I_corr
behavior at 1000◦ C. The results indicate that the oxidation resistance of and higher E_corr values, with an E_pit value of 846 mV in the NaCl
tungsten-containing alloys is generally low, primarily due to the solution, approximately three times greater than that of 304SS. This
oxidation of tungsten, which hinders the formation of a protective oxide finding underscores the superior corrosion resistance of the HEA. The
layer. Notably, the WMoTaAlCr alloy exhibits commendable oxidation enhanced corrosion resistance can be attributed to the formation of a
resistance, attributed to the development of a relatively continuous (Al, protective passivation film on the alloy’s surface, which is particularly
Cr)TaO4 oxide layer. Future research endeavors should focus on further pronounced when exposed to NaCl solutions that simulate marine en­
reducing the tungsten oxide content in tungsten alloys and compen­ vironments, in contrast to traditional 304 SS.
sating for the loss of Mo in the oxide layer. By optimizing alloy design, it In Wang’s study [150], varying concentrations of Mo were incor­
is possible to significantly enhance the oxidation resistance of HEAs. porated into the HEA Co1.5CrFeNi1.5Ta0.1Mox (x = 0, 0.1, 0.3, 0.5) to
The multi-principal component effect of HEAs may facilitate the investigate its effects on the alloy’s corrosion resistance. The alloy
hysteretic diffusion of internal point defects, thereby increasing the samples were synthesized through vacuum arc melting, and their
defect recombination rate. These alloys exhibit low defect accumulation corrosion resistance was evaluated in simulated seawater, as well as in
and enhanced phase stability in t radiation environments. El-Atwani both alkaline and acidic environments. The results indicate that the
[146] synthesized a W-Ta-V-Cr HEA thin film based on tungsten through
magnetron sputtering deposition. Under an irradiation dose of 8dPa, the
alloy demonstrated no irradiation-induced dislocation rings, indicating
a high level of radiation tolerance. Furthermore, the alloy possesses a
hardness of up to 14 GPa in its deposited state, with only a minimal
increase in hardness following irradiation, which suggests exceptional
resistance to radiation hardening. These advantageous properties are
attributed to the formation of Cr - and V- enriched second-phase parti­
cles within the alloy, as well as the equivalent mobility of point defects,
which maximizes the probability of defect recombination, thereby
reducing the defect concentration and the kinetics of precipitation and
growth of second-phase particles. Deluigi [147] investigated the
response of the FeNiCrCoCu HEA to radiation damage during the pri­
mary damage stage using molecular dynamics simulations. The study
simulated the radiation damage effects of primary breakdown atoms at
energies of 10 keV, 20 keV, and 40 keV on an idealized FCC structure of
FeNiCrCoCu and pure Ni at room temperature. The findings revealed
that, in all scenarios, the average number of defects in HEAs was lower
than that in pure Ni, thereby supporting the notion that HEAs exhibit
radiation resistance. Amanzhulov [148] prepared CoCrFeNi and CoCr­
FeNiMn HEAs via arc melting and examined the compositional and
structural changes following sequential irradiation with Kr and He ions. Fig. 16. [149] Open-circuit potential and potentiodynamic polarization curves
The study observed that the surface bubbles in CoCrFeNiMn were fewer of (Fe33Cr16Co15Ni15Ti1) 96Al4 and 304SS in 3.5 wt%NaCl solution.

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Y.-F. Yang et al. Journal of Alloys and Compounds 1010 (2025) 177691

Table 4 are expected to be utilized find applications in jet nozzles and various
[149] Electrochemical parameters were derived from potentiodynamic polari­ components of aircraft engines due to their superior resistance to high
zation curves of (Fe33Cr16Co15Ni15Ti1) 96Al4 alloy and 304SS in a 3.5 wt% NaCl temperatures. Additionally, given its outstanding heat resistance prop­
solution. erties, this alloy may also be considered for applications in thermal
Alloy Ecorr/(mVSCE) Icorr/(μA⋅cm− 2) Epit/(mVSCE) Epit-Ecorr/(mVSCE) protection systems. Zhang’s research findings indicate that the
HEA − 172 0.12 846 1018 AlMo0.5NbTa0.5TiZr alloy demonstrates minimal oxidation gain during
304SS − 209.5 0.24 285 494.5 oxidation tests conducted at temperatures of 900℃ and 1000℃, in
contrast to the AlMo0.5NbTa0.5TiZr alloy, which exhibits a greater
oxidation gain due to the presence of Mo and Ta elements. This obser­
Mo0.3 alloy exhibits superior corrosion resistance in a 3.5 wt% NaCl vation suggests that Mo and Ta significantly influence the oxidation
solution, while the Mo0.1 alloy demonstrates optimal passivation resistance of the alloy. Consequently, it is feasible to substantially
behavior in 1 mol NaOH solution. These findings suggest that the enhance the high-temperature oxidation resistance capabilities of this
corrosion resistance of the CoCrFeNiTa HEA can be significantly specific alloy type, rendering it suitable for consideration in spacecraft
enhanced through the judicious addition of Mo, particularly in simu­ thermal protection systems designed to mitigate high-temperature
lated seawater and alkaline conditions. Conversely, in acidic environ­ ablation during re-entry.
ments, an excessive concentration of Mo may diminish the alloy’s Zhang et al. [156] employed laser direct energy deposition (L-DED)
corrosion resistance. This research provides a critical experimental technology to combine TA15 alloy with AlNbTiVZr HEA resulting in the
foundation for the design of HEAs with exceptional corrosion resistance. creation of a multi-principal element alloy characterized by high
strength and toughness. Fig. 17 illustrates the equipment utilized in the
6. Applications of HEA L-DED process and outlines the preparation method for the alloy. The
L-DED technology facilitates the direct transport of powder to the
6.1. Aerospace field deposition area, where it is rapidly melted and formed into a sedimen­
tary layer using a high-energy laser beam. This technique is particularly
The aerospace sector is characterized by a unique service environ­ advantageous for the fabrication of large components. Notably, the
ment and stringent performance requirements, which impose excep­ tensile strength of 70 wt%AlNbTiVZrHEA/Ti multi-major element alloy
tionally rigorous demands on materials. These materials must is 18 % greater than that of the TA15 alloy, achieving a value of1068.0
demonstrate reliability and safety under extreme operating conditions. ±2.1 MPa. This enhancement in tensile strength can be attributed to the
Since 2010, Senkov [151] has proposed refractory HEA WNbMoTa and formation of fine equiaxed grains and the development of a robust and
WNbMoTaV for potential applications in aerospace, thereby garnering ductile BCC phase within the alloy matrix. The increased tensile strength
increasing attention from scientific researchers in this domain. As the significantly augments its potential as a load-bearing structural
global aerospace industry continues to evolve, there is an escalating component in aerospace applications.
demand for materials that are lighter, stronger, and exhibit enhanced Satish Dixit [157] conducted an investigation into refractory HEA
resistance to high temperatures and corrosion. Refractory HEAs typi­ coatings intended for high-temperature applications in the aerospace
cally possess a BCC structure with melting points exceeding 3000℃. and energy sectors. These coatings are engineered to enhance erosion
These alloys demonstrate remarkable wear resistance, corrosion resis­ and corrosion resistance in high-temperature components, thereby of­
tance, and mechanical properties at elevated temperatures. Given fering a viable and cost-effective solution to the requirements of both
exceptional structural characteristics and attributes, refractory HEAs industries. The study examined two nearly equiatomic compositions of
shows significant promise for application in the aerospace sector refractory HEAs, specifically HfNbTaZr and MoNbTaVW. A compre­
[152–154]. hensive methodology for the selection of refractory HEA coating com­
Zhang et al. [155] successfully fabricated refractory HEAs with positions, as well as their manufacturing and characterization, was
exceptional mechanical properties at elevated temperatures were suc­ presented. The findings indicated that HfNbTaZr is suitable for use in
cessfully fabricated using laser additive manufacturing technology. harsh environments devoid of nuclear reactor radiation, whereas
These alloys predominantly comprise metals with melting points MoNbTaVW is appropriate for environments that include radiation
exceeding 1650℃, such as W, Ta, Mo, Nb, Hf, Zr, and V. Notably, the exposure. The coatings were deposited onto stainless steel (SS) 321 and
AlMo0.5NbTa0.5TiZr alloy has exhibited remarkable performance in Inconel 718 substrates using air plasma spray (APS) and high-velocity
high-temperature service environments, achieving strength of oxygen-fuel (HVOF) thermal spray coating processes, resulting in
1600 MPa at 800℃ and 745 MPa at 1000℃. Consequently, these alloys

Fig. 17. [156] L-DED process equipment diagram and preparation method of the alloy.

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Y.-F. Yang et al. Journal of Alloys and Compounds 1010 (2025) 177691

functional coatings with thicknesses ranging from 50 to 200-microme­ The effective storage and transportation of hydrogen are critical for its
ters.and wear rates, which were dependent on contact force, along practical utilization. Hydrogen storage methods can be classified into
with hardness measurements that varied with depth and strain rate, three categories: gaseous [161], liquid [162], and solid forms [163].The
were obtained through spheroconical scratch-based and nano­ first two methods present various challenges, such as the requirement
indentation techniques. The data demonstrated excellent adhesive for high pressure and low temperature conditions, which lead to
properties, high strength, and satisfactory homogeneity. increased energy consumption and heightened safety risks [164,165].
HEAs exhibit significant potential as effective hydrogen storage mate­
6.2. Energy and chemical industry rials due to their high hydrogen storage capacity, exceptional cycle
stability, and favorable kinetic properties [166,167]. Notable examples
The energy and chemical industries exhibit a distinct demand for of HEAs include TiZrVCrNi [168], MgVAlCrNi [169], TiZrNbCrFe [170],
materials characterized by stringent requirements for resistance and TiZrNbMoV [171] among others. The complex crystal structures and
reliability. This is particularly pertinent in scenarios involving frequent multi-component nature of HEAs provide numerous adsorption sites for
exposure to corrosive chemicals, high-temperature operating condi­ hydrogen atoms. Additionally, the lattice distortion and multi-scale
tions, and substantial mechanical stress. Alloys must be capable of structure of these materials facilitate diverse pathways for the efficient
withstanding extreme conditions, including chemical corrosion, diffusion of hydrogen atoms, enabling rapid absorption and emission
elevated temperatures, and high pressures. As the energy and chemical kinetics without the need for high-temperature activation [172–174].
sectors continue to evolve, the demand for enhanced material perfor­ The slow diffusion effect observed in HEAs also aids in retaining va­
mance is correspondingly increasing. The synergistic application of the cancies generated during hydrogen absorption, thereby enhancing
multifaceted effects of HEAs, along with their superior properties, en­ subsequent hydrogen absorption kinetics during the desorption process.
ables these materials to adapt effectively to specific harsh environments. In BCC structured HEAs, hydrogen atoms typically occupy tetrahedral
Furthermore, the long-term stability of these alloys is essential for sites [175]. However, in the case of the TiVZrNbHf HEA, which also
ensuring the safe operation of equipment over extended durations. possesses a BCC structure, hydrides occupy both tetrahedral and octa­
Chen et al. [158] synthesized a Ti0.3(CoCrFeNi)0.7 HEA through hedral sites simultaneously. While the hydrogen storage capacity of BCC
vacuum arc melting (VAM) and examined its corrosion resistance in structured HEAs can be improved, the slow kinetics associated with
energy and chemical industries, including petroleum and natural gas these materials remains a significant challenge [176].
sectors. The Cr and Ti components within the alloy react with oxygen to Long et al. [177]fabricated a refractory HEA composed of TiVNbTa
form an oxide layer that offers effective protection. In comparison to utilizing the vacuum induction melting method. They investigated the
conventional 316 L, this alloy demonstrates enhanced corrosion resis­ kinetics of hydrogen absorption and desorption in this alloy. During the
tance in simulated H2S-HCl-H2O environments, particularly at 120℃ hydrogen absorption process, the formation of three novel oxide phases
where it exhibits excellent localized corrosion resistance, evidenced by was observed. The alloy exhibited reversible characteristics concerning
the lowest observed corrosion rate. Electrochemical assessments and hydrogen absorption and desorption, as it reverted to a single-phase BCC
high-temperature/high-pressure simulation experiments provide structure following dehydrogenation. Within the temperature range of
empirical support for the application of this HEA in harsh environments 423–723 K, the alloy demonstrated significant rates for both hydrogen
containing H2S, such as in the pipelines utilized for oil and gas explo­ uptake and desorption, indicating its excellent performance in hydrogen
ration, transportation, and refining processes. Yu et al. [159] success­ storage within this temperature range. Furthermore, the kinetics of
fully developed a Si-Cr-Ti silicide coating on the surface of a hydrogen uptake and desorption were found to conform to both JMA
NbMoTaWTi refractory HEA using the slurry melting technique, which equation and the second-order rate equation. The apparent activation
significantly improved the high-temperature oxidation resistance of the energies for hydrogen absorption and desorption were determined to be
alloy. An optimized secondary melting process was employed to form 21.87 J/mol and 8.67 J/mol respectively, thereby providing a scientific
silicide coating, which exhibited exceptional oxidation resistance even basis for the future application of the TiVNbTa HEA in solid-state
at 1300℃. After 50 hours of oxidation, a minimal weight gain of hydrogen storage.
8.12 mg/cm2 was recorded per unit area. This phenomenon can be Gao et al. [178]. fabricated a HEA composed of MgTiV2Cr0.2 through
attributed to the formation of a continuous and dense SiO2 film on the the method of high energy ball milling technique. They investigated the
surface of the coating, which effectively hinders oxygen penetration. impact of milling duration on the microstructure and hydrogen storage
Additionally, the incorporation of YSZ ceramic powder as a modifier in properties of the alloy. XRD analysis indicated that as the milling time
the coating composition resulted in further enhancement of oxidation increased, the alloying elements gradually dissolved into a solid solu­
resistance at 1500℃. Notably, with a YSZ content maintained at 15 %, tion, culminating in the formation of a single BCC phase after 20 hours
the coated alloy demonstrated favorable oxidation resistance after of milling. However, extending the milling time beyond this point
45 hours under oxidizing conditions, with a weight gain limited to resulted in the oxidation of Mg. Scanning Electron Microscopy (SEM)
7.83 mg/cm2; this primarily consisting of ZrO2 and TiO2 metal oxides and Transmission Electron Microscopy (TEM) results revealed that with
along with glassy SiO2 components. The application of surface coating prolonged ball milling, there was an enhancement in the uniformity of
technology imparts remarkable stability to this type of refractory HEA in the alloying elements on the surface, achieving optimal microstructural
extreme high temperature, oxygen-rich environments. Consequently, uniformity after 20 hours of milling. Under conditions of 6 MPa and
these alloys are extensively applicable not only in chemical industries, 573 K, the alloy subjected to 20 hours’ ball milling demonstrated a su­
including chemical reactors and heat exchangers, but also in other sec­ perior hydrogen absorption capacity of 1.17 %, accompanied by
tors such as petroleum refining and energy power generation, which significantly improved kinetic properties. These findings underscore the
involve elevated temperatures and pressures. importance of selecting an appropriate milling duration to optimize
hydrogen storage properties in HEAs. The Ti25V30Nb10Cr35-xMox HEA
6.3. Hydrogen storage materials with varying Mo contents were prepared by CALPHAD design and arc
melting method, as reported by Cheng et al. [179] Through adjustments
The global energy landscape is currently undergoing significant in atomic radius and VEC, a uniform single-phase BCC structure was
transformation, driven by an increasing demand for clean energy solu­ successfully achieved. Experimental results indicate that the
tions. In this context, hydrogen energy has emerged as a prominent area Ti25V30Nb10Cr31Mo4 alloy exhibits an unprecedented reversible
of research among scholars worldwide. Nevertheless, the commercial hydrogen storage capacity of 2.24 wt% at 323 K, representing a signif­
application of hydrogen faces numerous challenges, including low icant advancement in the field of BCC high-entropy hydrogen storage
storage efficiency, safety concerns, and transportation difficulties [160]. alloys. It is hypothesized that a larger atomic radius increases the

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number of gap sites within the alloy, thereby providing more attachment microstructure and macroscopic properties of the alloy by modulating
sites for hydrogen molecules. However, contrary to previous observa­ the cooling rate and atomic arrangement, thereby affecting the
tions, an increase in Mo content results in a decrease in the maximum hydrogen storage capabilities of the material. HEAs synthesized via
hydrogen storage capacity due to significantly prolonged hydrogen ab­ conventional melting and casting methods, exemplified by the Ti-Zr-V-
sorption times and a potential weakening of the alloy’s hydrogen ab­ Cr-Ni system, typically form C14-type Laves phases characterized by
sorption capability. Consequently, the introduction of Mo reduces the micron-sized grains [182], this alloy demonstrates favorable hydrogen
alloy’s affinity for hydrogen. Furthermore, it is noteworthy that higher storage properties attributed to its larger grain size and reduced defect
bulk modulus values are associated with poorer hydrogen affinity density. The hydrogen atoms within the grains experience extended
among these alloys, indicating that not only atomic radius but also diffusion pathways, which facilitate the adsorption and desorption
electronic structure and other thermodynamic properties play critical processes of hydrogen. However, the increased grain size may impede
roles in determining the hydrogen storage characteristics of HEAs. the rate of hydrogen absorption, as hydrogen atoms must diffuse over
Wu al. [180] synthesized a HEA composed of Mg10Ti30V25Zr10Nb25 greater distances. In contrast, the nanocrystalline Laves phase is
utilizing the MA and examined its effects on the hydrogen storage ca­ generated in HEAs synthesized through rapid solidification techniques,
pacity of the Mg/Mg hydride system. The unactivated alloy demon­ such as melt spinning, as observed in the Ti-Zr-V-Cr-Ni alloys discussed
strated favorable kinetics for hydrogen absorption at room temperature, in the same study. This nanostructure significantly enhances the
achieving a hydrogen absorption capacity of approximately 1.196 wt%. hydrogen storage performance of the alloy, as the smaller grain size
The introduction of the HEA significantly improved both the hydrogen provides a greater number of grain boundaries and defects, thereby of­
absorption and dehydrogenation kinetics of Mg at lower temperatures, fering more adsorption sites and shorter diffusion pathways for
while concurrently decreasing the activation energy required for dehy­ hydrogen atoms. The study [183] indicates that this alloy exhibits a high
drogenation. As illustrated in Fig. 18, the Mg-15wt% HEA composite hydrogen storage capacity and rapid hydrogen absorption/desorption
exhibited enhanced performance in hydrogen storage, with initial hy­ kinetics. Furthermore, through MA followed by heat treatment, [184]
drogenation and dehydrogenation temperatures that were lower than amorphous or nanocrystalline HEAs with excellent hydrogen storage
those of pure Mg by 78 K and 47 K, respectively. Although the HEA itself properties can be formed. A large number of structural defects and re­
has a higher dehydrogenation temperature, it demonstrates consider­ sidual stresses were introduced in the rapid solidification process of this
able potential for improving the overall performance of Mg-based alloy, which further enhanced the adsorption capacity of hydrogen
hydrogen storage materials. atoms and improved the kinetic properties. Alloys with amorphous or
Yin et al. [181] developed a Zr-based HEA catalyst that significantly nanocrystalline structures typically exhibit faster hydrogen diffusion
improved the hydrogen storage performance of MgH2 by modifying its rates and increased hydrogen storage capacities, rendering them
Laves phase structure. Among the various Laves phases, the C15 type potentially advantageous for dynamic hydrogen storage applications. In
HEA demonstrated superior catalytic activity, facilitating the trans­ conclusion, the different synthesis methods employed have a profound
formation of the rate-limiting step in hydrogen desorption from impact on the hydrogen storage properties of HEAs. Conventional
two-dimensional nucleation growth to two-dimensional phase boundary melting techniques tend to yield larger grains and lower defect densities,
migration. This transformation resulted in a notable enhancement in while rapid solidification methods facilitate the formation of nano­
hydrogen desorption kinetics. As illustrated in Fig. 19, the capacity structures, thereby enhancing hydrogen storage performance. Future
retention rate remained at an impressive 92 % even after 30 cycles, research should further investigate the regulatory mechanisms by which
indicating excellent cycle stability. The incorporation of the HEA not synthesis methods influence the hydrogen storage properties of these
only reduced the hydrogen desorption temperature of MgH2 but also alloys and explore strategies for designing more efficient hydrogen
improved the overall efficiency of hydrogen adsorption and desorption storage materials through the optimization of synthesis parameters.
through its "hydrogen pump" effect and the synergistic interactions
among multiple elements. These findings highlight the potential of HEA
6.4. Marine engineering
catalysts in enhancing the hydrogen storage performance of MgH2.
Different types of HEAs exhibit varying hydrogen storage properties
The ocean, recognized as the largest unexplored territory on Earth,
when utilized as catalysts or primary components. The HEA prepared
plays a crucial role in the sustainable development of the global econ­
through traditional methods, such as vacuum melting, induction
omy through the exploitation and utilization of its resources. However,
melting, and rapid solidification techniques, can influence both the
the complex and extreme environmental conditions present significant

Fig. 18. [180] Hydrogen absorption and release curve of Mg-x wt% HEA composite at temperature rise rate of 5k/min: (a) hydrogen absorption curve (b) hydrogen
emission curve.

18
Y.-F. Yang et al. Journal of Alloys and Compounds 1010 (2025) 177691

Fig. 19. [181] Isothermal hydrogen desorption curves of (a) the pure MgH2, (b) MgH2-HEA1 and (c) MgH2-HEA2 composite at 300℃ for different hydrogen ab­
sorption desorption cycles.

challenges, necessitating stringent material requirements. Offshore potentiostatic measurements, and electrochemical impedance spectros­
platforms, subsea facilities, and various marine installations must copy (EIS), were performed to evaluate the corrosion performance of
maintain stability in the face of challenges such as seawater erosion, alloys with varying grain sizes. The results demonstrated that a reduc­
deep-sea pressure, and extreme temperatures. HEAs present a viable tion in grain size markedly improved the material’s resistance to local­
solution due to their capacity to tailor alloy distribution according to ized corrosion. The alloy that underwent a 3-minute annealing
specific requirements, thereby enhancing oxidation and corrosion treatment demonstrated improved corrosion resistance in both 0.1 times
resistance. Furthermore, their high strength and exceptional toughness and 1 time the concentration of seawater solutions. This treatment
render them ideal materials for the construction of offshore platforms resulted in more favorable corrosion potential and current density when
and vessels. In deep-sea operations, the application of specialized HEAs compared to other treatment conditions. Furthermore, the chemical
as surface coatings can significantly improve resistance to oxygen brit­ composition of the passive layer on the alloy surface was analyzed using
tleness and sulfide stress corrosion cracking (SCC). Yang et al. [185], X-ray photoelectron spectroscopy (XPS) and secondary ion mass spec­
employed a laser cladding method to prepare a CoCrNiNb0.1+B4C HEA trometry (SIMS), which further substantiated that refined grains
coating on the surface of A100 ultra-high strength steel. This coating contribute to the formation of a more stable and compact protective
predominantly consists of FCC phase with the ceramic phase increasing passive layer. These findings offer significant theoretical insights for the
in proportion to higher B4C content. The observed increase in micro­ advancement of new HEAs resistant to corrosion in marine
hardness can be described by the Hall-Petch equation. [186]: environments.
( ) Sunbul [188] employed the vacuum arc smelting process to inves­
1 1 tigate the wear and corrosion resistance properties of atomic HEAs such
HvH− P = KH− P √̅̅̅̅ − √̅̅̅̅̅
di d0 as CoCuFeNiMo alloys. The positive mixing enthalpy, which leads to Cu
segregation, results in an increase in the friction coefficient with the
The material constant KH-P, in conjunction with the average grain
increment of load. Under a load of 50 N, the wear rate was measured at
sizes prior to (di) and subsequent to (d0) the application of the coating,
1.211×10− 4 mm3/N.m. The CoCuFeNiMo HEA exhibited pitting corro­
plays a critical role in determining the microhardness of the coating.
sion when exposed to a 3.5 wt% NaCl solution, with a recorded corro­
Empirical evidence indicates that an increase in B4C content correlates
sion potential (Ecorr) value at − 0.616 V and a corrosion current density
with an enhancement in microhardness. When the B4C content is 5 %,
of 2.22×10− 5A/cm2. These findings indicate that the CoCuFeNiMo HEA
the Vickers hardness value of the coating is 1090HV under a load of
possesses exceptional wear and corrosion resistance characteristics,
0.2 kg force, which exceeds the microhardness of both conventional Ni-
rendering it highly promising for various applications in marine engi­
based alloy coatings and CoCrNi HEA coatings devoid of a ceramic phase
neering, including ship propellers and protective coatings for submarine
by approximately fivefold when compared to coatings with 0 % B4C
pipelines and cables.
content. The predominant mechanism for strengthening is attributed to
second phase strengthening. However, it is important to acknowledge
7. Summary and prospect
that an increase in BC content is associated with a decline in corrosion
resistance, which can be ascribed to diminished arc resistance, reduced
The present paper offers a thorough review of the theoretical foun­
impedance mode values, and lower overpassivation potential. Electro­
dations, design principles, preparation techniques, properties, and po­
chemical assessments and immersion experiments indicate that galvanic
tential applications of HEAs. Due to their unique multi-element solid
corrosion constitutes the primary corrosion mechanism within this
solution structure and high mixing entropy, HEAs demonstrate
coating system, wherein the ceramic phase functions as the cathodic
remarkable mechanical properties, corrosion resistance, magnetic
phase and the FCC phase serves as the anodic phase. This investigation
characteristics, and stability in specific environments. Utilizing first-
offers significant insights into the application of A100 ultra-high
principles calculations and various fabrication methods, including me­
strength steel in marine environments and lays a theoretical ground­
chanical alloying, magnetron sputtering, vacuum smelting, and additive
work for the future utilization of HEAs as protective coatings.
manufacturing techniques, researchers have effectively predicted and
Researchers L. Xue [187] synthesized Al2Cr5Cu5Fe53Ni35 HEA uti­
optimized the properties of HEAs while achieving precise control over
lizing cold rolling and annealing processes, with a focus on examining
their composition and structure.
the influence of grain size on corrosion properties in marine environ­
Through the sustained efforts of scholars globally, considerable ad­
ments. The study revealed that the grain size, which was significantly
vancements have been achieved in the research on HEAs. The focus of
altered following the cold rolling and annealing treatments, played a
this research has evolved from the initial exploration of simple BCC or
pivotal role in the corrosion behavior of the alloy in seawater. A series of
FCC structure to the development of a diverse array of alloys charac­
electrochemical experiments, including potentiodynamic polarization,
terized by more intricate structures. HEAs exhibit several advantages,

19
Y.-F. Yang et al. Journal of Alloys and Compounds 1010 (2025) 177691

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tion. Yi-Fei Yang: Writing – original draft, Formal analysis, Data cura­ alloys: defect physics and radiation performance, Chem. Rev. 122 (1) (2021)
789–829, https://doi.org/10.1021/acs.chemrev.1c00387.
tion, Conceptualization. Ting Xia: Project administration. Jian-Yi Xu:
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Declaration of Competing Interest [21] Wenqian Wu, et al., Amorphization at twin-twin intersected region in FeCoCrNi
high-entropy alloy subjected to high-pressure torsion, Mater. Charact. 127 (2017)
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interests or personal relationships that could have appeared to influence properties, Mater. Lett. 169 (2016) 62–64, https://doi.org/10.1016/j.
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