MOL 92236 Special Treatise on Materials Science

High Entropy Alloys

Zhao Fu (245014)

Tampere University of Technology

25/2/2016

Table of Contents
1

Introduction ........................................................................................................................... 1

Basics of High Entropy Alloy ............................................................................................... 2

2.1

2.1.1

Entropy ................................................................................................................... 2

2.1.2

High-Entropy Alloy ............................................................................................... 2

2.1.3

Four Core Effects of High-Entropy Alloys ............................................................ 3

2.2

Thermodynamics ........................................................................................................... 4

2.3

Properties of High Entropy Alloys ................................................................................ 6

2.3.1

Mechanical Properties ............................................................................................ 6

2.3.2

Corrosion Resistance.............................................................................................. 8

2.3.3

Magnetic Properties ............................................................................................... 8

2.3.4

Other Properties ..................................................................................................... 9

Synthesis Methods of High Entropy Alloys ....................................................................... 10

3.1

Entropy and High-entropy Alloy ................................................................................... 2

Vacuum Melting .......................................................................................................... 10

3.1.1

Vacuum Arc Melting............................................................................................ 10

3.1.2

Vacuum Induction Melting .................................................................................. 10

3.2

Powder Metallurgy ...................................................................................................... 11

3.3

Mechanical Alloying ................................................................................................... 11

3.4

Casting and Forging..................................................................................................... 12

3.5

Other Techniques ......................................................................................................... 12

Synthesis of High Entropy Alloy Coatings ......................................................................... 13

4.1

Laser Cladding ............................................................................................................. 13

4.1.1

Laser Cladding Profile ......................................................................................... 13

4.1.2

Case Study of HEA Coated by Laser Cladding ................................................... 14

4.1.3

Methods of Manufacturing HEA Coating with Laser Cladding .......................... 16

4.2

Thermal Spraying ........................................................................................................ 17

4.2.1

Thermal Spraying Coating Processes................................................................... 17

4.2.2

Plasma Spray Manufacturing HEA Coatings ....................................................... 18

4.2.3

HVOF (High Velocity Oxygen Fuel Thermal Spray) .......................................... 19

4.2.4

Arc Spray Manufacturing HEA Coatings ............................................................ 20

4.2.5
4.3

Research of the HEA Film Synthesis by Electrochemical Deposition ................ 21

4.3.2

Experiment of HEA Film Synthesis by Electrochemical Deposition .................. 21

4.3.3

Characterization of HEA Film Synthesis by Electrochemical Deposition........... 22

Magnetron Sputtering .................................................................................................. 22

4.4.1

Research of the HEA Film Synthesis by Magnetron Sputtering .......................... 22

4.4.2

Experiment of HEA Film Synthesis by Magnetron Sputtering ............................ 23

4.4.3

Characterization of HEA Film Synthesis by Magnetron Sputtering .................... 24

Properties of High Entropy Alloy Coatings ........................................................................ 25

5.1

Metallic HEA Coatings................................................................................................ 25

5.2

Compound HEA Coatings ........................................................................................... 26

5.3

Composite HEA Coatings............................................................................................ 26

Applications and Outlook of High Entropy Alloys............................................................. 28

6.1

High-Speed Cutting Tools ........................................................................................... 28

6.2

Corrosion-resistant High-Strength Parts ...................................................................... 29

6.3

Airplane Engine Turbine Blades.................................................................................. 29

6.4

Refractory Skeleton of Skyscrapers ............................................................................. 30

6.5

Other Applications ....................................................................................................... 30

Current Research of High Entropy Alloys .......................................................................... 31

7.1

Electrochemical Deposition ......................................................................................... 20

4.3.1

4.4

Other Thermal Spray Techniques Manufacturing HEA Coatings ....................... 20

Researchers and Universities ....................................................................................... 31

7.1.1

Jien-Wei Yeh........................................................................................................ 31

7.1.2

Yong Zhang.......................................................................................................... 32

7.1.3

B. S. Murty ........................................................................................................... 34

7.1.4

Sheng Guo ............................................................................................................ 35

7.1.5

Other Researchers ................................................................................................ 37

7.2

Companies ................................................................................................................... 38

7.3

Current Research Outlook ........................................................................................... 38

Conclusions ......................................................................................................................... 40

References ................................................................................................................................... 42

1 Introduction

The alloys which humans have developed so far include the iron-oriented steel,
aluminum alloys, the intermetallic compounds in the Ti-Al alloy system and other
alloying systems. All these alloys were designed based on certain main properties
demand, meaning they were synthesized by selecting one or two dominant elements
mixed with some trace alloying elements to meet the property demands. The formation,
structures and properties of the crystalline phases are basically all based on these. [1]
It was not until the 1990s that people start thinking to make some breakthroughs in alloy
synthesis concept. The concept of high-entropy alloys (HEAs) was brought up in 1996,
while the first real development came in 2004 when Jien-Wei Yeh and Brian Cantor
published the first relevant paper. Yeh created the term high-entropy alloy when he
found the high configuration entropy causing the stabilization of the solid solution
phase [2].
High-entropy alloys (HEAs) have attracted increasing attention because of their unique
composition, microstructures, and great properties, like the high strength, high hardness,
good corrosion resistance, high thermal resistance and electric resistance. Great
potential can be from these, for example [2], small-scale HEA samples (e.g. NbTaMoW
micro-pillars) exhibit extraordinarily high yield strengths of 4-10 GPa one order of
magnitude higher than that of its bulk form. Some researchers also predict that in the
following few decades, bulk amorphous, composites and high-entropy alloys would
become three most potential research fields [3].
High-entropy alloys bring a revolutionary new concept of alloy design, which worth
further exploration. It would create a new world of materials synthesis, processing,
analysis and applications, it can also bring great commercial profits to the industry.
In this paper, the basic information related to high entropy alloys are introduced, the
manufacturing methods of HEAs are discussed, the coating process is also discussed
with examples. The paper focuses on the coating-use high entropy alloys, the properties
of which are explained. HEAs applications are discussed with examples. The paper also
gives introduction and analysis of the current research on HEAs and its future prospects.

2 Basics of High Entropy Alloy

2.1 Entropy and High-entropy Alloy

2.1.1

Entropy

In thermodynamics, entropy is a measure of disorder of a system. Disorder refers to

the number of different microscopic states a system contain, given that the system has a
given fixed composition, volume, energy, pressure, and temperature. [4] It is notated as
S, the change in entropy (S) of a system was originally defined with macroscopic
definition for a thermodynamically reversible process as: [2]

Where, T is the absolute temperature of the system. dQ is the heat energy of the added
substances during the increase of entropy.
The entropy of a system contains the atomic arrangement entropy, atomic vibration
entropy, magnetic moment configuration entropy, etc. But for alloys, the entropy of
mixing mainly depends on the mixing entropy of the atomic arrangements [1].
According to the second law of thermodynamics, the entropy of an isolated system
would never decrease. Since, in physics, any chemical reaction would more or less
make the system more disordered, hence, entropy would be increased.
2.1.2

High-Entropy Alloy

High-entropy alloys, which is a term from multi-principal-element alloys, was brought

up in 1996. It emphasizes their inherent high mixing entropies. High-entropy alloys
(HEAs) are a class of multi-component alloys composed at least 5 principal constituent
elements, each with a concentration between 5 and 35 atomic%. [5] The constituent
elements of HEAs are alloyed with the equi-atomic or equi-molar ratio, their entropy of
mixing exceeds the entropy of alloy melting, and they form the alloy with high-entropy
solid solution phases. Generally, in the five-principal component alloys, there is a solid
solution phase region in the intermediate area, the solid solution phases in which are
regarded to have stable mixing entropy. [3] The typical feature of HEAs over other
alloys is that they consist entirely or primarily of a simple solid solution phase, thus,
having high entropy of mixing. HEAs generally have better strength-to-weight ratios,
fracture toughness, tensile strength, high-temperature strength, and corrosion resistance
2

than similar conventional alloys. [5] The representative HEAs have CoCrCuFeNi,
which is an alloy with fcc solid solution discovered by WeijunYe; AlCoCrFeNi, which
is an alloy with bcc solid solution discovered by Yong Zhang [3]. The Figure 1 presents
the atomic arrangement of graphene.

Fig. 1: Illustration of atomic arrangement of graphene [6].

2.1.3

Four Core Effects of High-Entropy Alloys

According to the properties and characteristics of high entropy alloys, four effects
related to the high entropy effects can be summarized as below. [1]
(1) High Entropy Effect: In thermodynamics, the entropy of mixing of the alloy melt is
0.69R when the alloy is composed of the equi-atomic ratio of two constituent elements,
while this mixing entropy of the alloy melt can reach 1.61R when the alloy is composed
of equi-atomic ratio of five constituent elements. While the entropy of melting of
ordinary metallic alloys is around 1R. Therefore, it can be seen that, the entropy of
mixing of the high entropy alloys is obviously higher than the conventional metallic
alloys [1]. The figure below presents the relationship of the mixing entropy of the alloys
with the configuration number of elements N.

Figure 2. Entropy of mixing of alloys as a function of the number of configuration

constituent elements N [1].

Figure 2 demonstrates that the entropy of mixing of the alloys increases with the
increase of the number of configuration constituent elements, but when the number of
configuration elements exceeds 13, the entropy of mixing of the alloy melt would be
slowed and till almost stable.
(2) Lattice Distortion Effect: In structure, high-entropy alloys have serious lattice
distortion, because all atoms are solute atoms and their atomic sizes are all different
from each other. This would reduce the thermal conductivity and electrical conductivity,
and the temperature effect would be reduced too, while it enhances the solid solution
hardening; XRD scattering and intensity are all effected.
(3) Sluggish Diffusion Effect: In dynamics, the phase transformation depends on the
atomic diffusion, which needs the joint diffusion of elements to reach the balanced
separation of different phases. Such joint diffusion and the lattice distortion which
prevent the atomic movement, would limit the effective diffusion rate in the high
entropy alloys. In the foundry, the phases separated in the high temperature region in
the cooling would be inhibited to be delayed to the low temperature region.
(4) Cocktail Effect: The cocktail effect of the high entropy alloys refers to the
complicated effect of the intrinsic properties of the various elements and their
interactions. For example, more light elements are used, the overall density will be
reduced. If more oxidation-resistant elements are used, such as Al, Cr and Si, the
oxidation resistance at high temperatures can be improved. If an element such as Al is
added, which has strong binding force and large different atomic size with the other
elements present, such as Co, Cr, Cu, Fe and Ni, and promotes the formation of a BCC
phase, the strength will be increased.

2.2 Thermodynamics
The statistical-mechanics definition of entropy was developed by Ludwing Boltzmann
in the 1870s and by analyzing the statistical behavior of the microscopic components of
the system. Boltzmann states that the entropy of a system is linearly related to the
logarithm of the frequency of occurrence of a macro-state or the number, W, of the
possible micro-states corresponding to the macroscopic state of a system: [7]
S = kLnW
Where k = 1.3810-23J/K is Boltzmanns constant.

For the alloy system, the Gibbs free energy of mixing can be expressed as:
Gmix = Hmix TSmix
Where, Gmix is the Gibbs free energy of mixing, Hmix is the enthalpy of mixing,
Smix is the entropy of mixing, and T is the absolute temperature. The equation presents
that, if the Hmix is kept constant, the increase of mixing entropy would lead to the
decrease of Gibbs free energy, and make the alloy system more stable.
For a random solid solution with N components, the entropy of mixing is expressed as:
Smix = -R*cilnci
Where R =8.31J/K-mol is the gas constant, ci is the molar content of the ith component.
For the equi-atomic or equi-molar ratio alloys, the entropy of mixing can reach its
maximum. In this case, the entropy of mixing can be expressed as: [7]
Smix = RlnN
Figure 3 presents the entropy of mixing as a function of composition in a ternary alloy
system. For the equi-molar ration ternary alloy, Smix =1.1R, reaching the maximum for
the ternary alloy system.

Fig.3. Illustration of Smix for ternary alloy system with the composition change [7].

2.3 Properties of High Entropy Alloys

High entropy alloys (HEAs) have some unique and excellent properties due to its
special configuration. The properties of HEAs are still in the study, here is the
discussion of its properties which have been known.
2.3.1

Mechanical Properties

Table 1 displays the mechanical properties of TiCrFeCoNiAl HEAs, it can be seen that
HEAs

have

excellent

compressive

mechanical

properties.

For

example,

Ti0.5CrFeCoNiAl HEA (marked as Ti0.5 in the table), the yield strength is up to 2.26
GPa and compressive plasticity is 23.3%.
Table 1: Room-temperature compressive mechanical properties for the
TiCrFeCoNiAl series alloys (BMG: bulk metallic glasses; LOS: long-period order
structure). Youngs modulus (E), yield stress (y), fracture strength (max), elastic
strain (e), and plastic strain (p) [8].

Table 2: Casting hardness of 3 coating-used high entropy alloys [9]

Alloy Notation
B8
C1
C3

Composition
NiCoFeCrSiAlTi 1
NiCoFeCrSiAlTi 2
NiCoFeCrSiAlTi 3

Hardness (HV)
880
888
1045

Table 2 presents the casting hardness of the three coating-used HEAs. The high
hardness can be seen, besides, three HEAs show high-temperature precipitation
hardening at around 800 after coating, and they didnt become soft even after
annealing [1], as like the Figure 4 shows.

Fig. 4: Hardness of three coating-used HEAs over time [9].

As-cast HEAs own hardness ranging from 130 to 1100 HV depending on the alloying
elements [10]. Table 3 shows some typical HEAs with hardness higher than 590HV and
several other alloys for comparison. The HEAs exhibit very high hardness and excellent
resistance to the anneal softening at 1000 for 12h [10].
Table 3: Hardness of as-cast and fully annealed high-entropy alloys and
commercial alloys [10].

2.3.2

Corrosion Resistance

Table 4 presents some HEAs resistance to the corrosive solution, it indicates the HEAs
can even resist the very corrosive H2SO4, HCl, and HNO3 solution.
Table 4: Corrosion resistance of high entropy alloys ( indicates resistance) [1]

2.3.3

Magnetic Properties

The Figure5 shows the magnetization curve of the TixCoCrCuFeNi alloy series,
CoCrCuFeNi and CoCrCuFeNiTi0.5 both exhibit typical paramagnetism, the saturation
magnetizations for them are 1.5 emu/g and 0.33 emu/g, respectively, under 20000 Oe
magnetic field. While, Ti0.8CoCrCuFeNi and CoCrCuFeNiTi alloys show the curve like
the superparamagnetic one, the saturation magnetization are around 1.4 emu/g and 1.5
emu/g, respectively.

Fig.5: Magnetization curves of TixCoCrCuFeNi alloys (x=0, 0.5, 0.8, 1) [11].

Figure 6 below is the curve of magnetization (M(T)) over time, it proves the magnetic
transition. CoCrCuFeNi and CoCrCuFeNiTi0.5 only experience Curie temperatures (Tc),
8

which are shown on the curves, while the CoCrCuFeNiTi0.8 and CoCrCuFeNiTi have
extra blocking temperature (TB) besides Tc when temperature is at 19-23K [11].
Although TB is so low that it limits those two HEAs to be superparamagnetic alloys,
there is a trend that TB increases with the addition of Ti, this can be the clue for
improving the magnetic property for further research.

Fig.6: The temperature dependence of magnetization (M(T)) curves while cooling of

CoCrCuFeNiTix (x=0, 0.5, 0.8, 1) [11].
HEAs also own anisotropy soft magnetic property and high electric resistance, which
can be seen from Table 5 below.
Table 5: Magnetic and electrical properties of three sputtering deposited high
entropy alloy coatings (Bs is the saturation magnetization, Hk is the anisotropy
magnetization, Hc is coercivity) [9]
HEAs
FeCoNiAlB
S
FeCoNiAlCrSi
FeCoNiAlCrSi

2.3.4

Energy/W
40
40
53

Annealing
300, 1h
300, 1h
300, 1h

Bs/T
1.3
0.9
1.3

Hk/Oe
25
20
20

He/Oe
5
5
1.7

/*cm
420
830
290

Other Properties

Apart from the properties discussed above, HEAs also own very good wear resistance,
oxidation resistance, and heat resistance or high temperature stability. Whats more,
these properties can usually be controlled and changed by adjusting the alloying
elements and synthesis operation parameters.

3 Synthesis Methods of High Entropy Alloys

High entropy alloys (HEAs) is still a new field, many researchers are exploring its
manufacturing methods. There isnt a perfect synthesis method for HEAs that can be
suitable for various HEAs and for different requirements, while some good techniques
have been explored. The common synthesis methods include vacuum melting, which
consists of arc melting and induction melting. Mechanical alloying is widely accepted
for processing solid state HEAs [12]. In addition, the coating techniques like CVD,
PVD and sputtering, thermal spray, laser cladding, electrodeposition, are also widely
used for synthesizing HEAs [13].

3.1 Vacuum Melting

Vacuum melting is the most commonly used technology for manufacturing high entropy
alloys (HEAs). The technology procedure is, firstly, placing certain amount pure metal
in the crucible; then vacuum the furnace, and fill the furnace with argon gas for
shielding; when the metal is fully melted, conduct slip casting in the water-cooled
copper module [12]. Vacuum melting consists of vacuum arc melting and vacuum
induction melting.
3.1.1

Vacuum Arc Melting

Vacuum arc melting (VAM) is a technology operated in vacuum furnace. The arc is
generated between the electrode and crucible, which subsequently generate high
temperature to melt the metal. Then the alloy can be gained in crucible through
condensing formation [12]. VAM is operated under high temperature, therefore, it can
be used to melt the metal with high melting temperature. Meanwhile, the vacuum
environment and shielding argon gas can prevent the entry of impurities. High-energy
plasma arc is also often implemented with VAM for melting the metals with melting
points up to 2200 [13]. Ti-Al, Ti-Zr, Ti-V, Ni-Ti alloys are the examples for being
synthesized by VAM [13].
3.1.2

Vacuum Induction Melting

Vacuum induction melting (VIM) is a technique which uses the theory of

electromagnetic induction to melt the metal in a vacuum environment. The skin effect
occurs in the electromagnetic induction, and it generates eddy current, which is
10

transferred into induction heat through the electric resistance of the raw materials in the
furnace, and this induction heat is used to melt the metal [12]. Such vacuum induction
melting is advantageous for melting many alloys simultaneously, but it cannot melt the
metals with high melting temperature. Since high entropy alloys contain one or more
elements which have high melting point, this technology is not so widely used.

3.2 Powder Metallurgy

Powder metallurgy is a technology which uses metal or non-metal powder as raw
materials, and manufacture the powder metallurgy products through compacting and
sintering. The process starts with powder production and powder mixing, alloying
addition can be involved in this step. Then compact the mixed power and sinter the
compact to enhance the integrity and strength [14]. The mechanical engagement, plastic
deformation, working hardening happen among powder particles when compacted
under room temperature, there generates the mechanical engagement force and Vander
waals force among atoms, which increase the interacting size and surface activity. When
it comes to sintering, the powder particles diffuse, weld, combine, dissolve and
recrystallize to change the particles. Thus, the metallurgical combination among the
alloying particles replaces the mechanical combination, making the billet a solid
integrity with the metals properties [12].
Powder metallurgy is advantageous in manufacturing the special materials which cannot
by manufactured by other normal techniques, and its sintering temperature is relatively
low compared with other technique, segregation is also avoided [12]. In addition, it can
make full use of the raw material and reduces waste.

3.3 Mechanical Alloying

Mechanical alloying is a dry powder processing technique which is used to synthesize
equilibrium and metastable phases of materials [15]. Its also the most commonly used
technique for processing solid-state high entropy alloys. The alloying elements firstly
are mixed in the ball mill and be ground into powder. The powder particles collide with
the ball mill strongly and constantly, the powder particles experience cold welding and
fracture, which lead to the atoms diffusion in the powder particles, this is the process to
achieve the solid alloying [15, 12]. In this process, the alloying powder is rolled,
laminated, crushed, and re-rolled, re-crushed again and again, which makes nanocrystals
or amorphous particles with uniformly distributed components and microstructures.
11

Since mechanical alloying can gain nanocrystal and amorphous structure, it is widely
applied in the manufacturing of some special materials like the nano-crystalline and
amorphous alloying powder, nanocomposite powder, and etc [12]. The high entropy
alloys manufactured by mechanical alloying generally own better mechanical properties
than the HEAs fabricated with melting techniques. They generally have stable
microstructure and good processing properties. Mechanical alloying also avoids
segregation, and can also manage the metals which have very different melting points
[12]. However, since its product is powder, which needs post-treatment to become bulk
material. This is the drawback that prevent mechanical alloying being widely used.
Mechanical alloying is carried out mostly with mills, SPEX mills [16], and Fritsch
Pulverisette mills [17] are commonly used. Mechanical alloying can be utilized to
synthesize nanocrystalline and amorphous materials as well [18].

3.4 Casting and Forging

Casting is a manufacturing technique in which the liquid metal is poured into a prepared
mold, there is a hollow cavity with the ideal shape in the mold, in this way, the liquid
metal can solidify and cool to be solid product. Its very traditional technique which is
useful for making complicated-shape products. Its very well used for the metals like
copper.
Forging applies local compressive force with the hammer to shape the metals. Its also a
traditional technique for making strong piece of the parts. Some metals are forged cold,
while the steel and iron are hot forged [19]
Casting and forging can also be applied in the HEAs manufacturing process, while they
are usually used with other techniques like arc melting or mechanical alloying as a
pre-treatment process.

3.5 Other Techniques

Apart from the methods discussed above, laser cladding and thermal spray are very
useful techniques for manufacturing high entropy alloys, which will be discussed in
detail in the Chapter 4. The traditional casting, forging and magnetron sputtering can
also be applied to manufacture the high entropy alloys bulk, coatings or films.

12

4 Synthesis of High Entropy Alloy Coatings

Coating is a process of covering the substrate (for example nylon, cotton, wool, or
sheets) with a coating material to enhance the substrate materials properties and
appearance. Coating, as a surface treatment technology, plays an important role for
changing the properties of the material, and it is also applied to high entropy alloys.
Apart from the synthesized methods introduced in Chapter 3, coating is another main
series of techniques used for HEAs.
Coating methods covers a wide range, which includes some commonly used ones like
laser cladding, thermal spry, chemical and physical vapor deposition (CVD, PVD), high
velocity oxygen fuel thermal spray (HVOF), plasma spraying, and also some less
widely used ones like hot melt coating, roller coating, dip coating, etc [20]. In this
chapter, several coating methods are discussed with some HEAs research cases and
results and HEAs coatings properties are also covered.

4.1 Laser Cladding

4.1.1

Laser Cladding Profile

Laser Cladding, or laser deposition, is metal-bonding technique which add one material
to the surface of another material in a controlled manner. In laser cladding, a laser steam
in defocused on the desired spot area of the workpiece surface, the powder coating
material is carried by an inert gas through the powder nozzle to melting pool, the laser
and powder nozzle move across the workpiece surface to deposit the coating material
(shown as the figure below). [21-22]

Fig 7. Schematic of laser cladding process [22].

13

4.1.2

Case Study of HEA Coated by Laser Cladding

The current research papers show that HEAs coating is widely manufactured by laser
cladding, since laser cladding can heat the material dramatically and also cool very soon
(104 ~ 106 /s), and it can manufacture the coating in the nanometer scale, which can
apply the HEAs properties to the largest extend [23-24].
Manufacturing HEAs coatings with laser cladding is an effective way to modify the
substrate materials structures and properties. Such a typical operation often needs a
laser machine to provide the laser. The base metal is usually cut in suitable size, be
polished by sandpaper, and cleaned by acetone or ethanol. The elements of the
researched high entropy alloy are mixed by the weight fraction, the mixed coating
material is then compacted on the substrate. Then the uniformly mixed alloys is spread
on the substrate surface [23-25]. Sometimes, to prevent the powder moving, a small
amount of glue can be mixed with acetone as well [26]. During the laser cladding, argon
gas with purity of 99.9% is used as shielding gas [23-24].
Based on the available literature, the specific laser cladding technologies play a critical
role in such coating. First of all, the selection of substrate material is critical, the
common substrate material for laser cladding HEAs can be Q235 steel and 45 steel, they
are carbon structural steels and mainly consist of iron, since the melting point of iron is
not so different from other elements melting points, the operation of present powder
cladding is easy to be controlled, which is the reason that they are widely used as
substrate materials [26]. AISI 1045 steel is also used as substrate material in some
research [27-28]. The researches on the HEAs coating by laser cladding mainly apply
the preset powder cladding method, which better the cladding layers quality by
adjusting the spot diameter, value of laser power, scanning speed. The overall
parameters and critical technologies applied are displayed as the following table.
However, they are just for reference, some researchers also applied larger diameters, for
example, scanning speed of 30mm/s to study the influence on the and properties of the
coatings [28]. Some greater and smaller parameters can also be applied.
Table 6: Substrate Material and Technology Parameters in HEAs coating by Laser
Cladding [23-28].

Values

Substrate

Spot

Material

Diameter

Q235, 45 steels

3 ~ 5 (mm)

Laser Power
1.2 ~ 2 kW

Scanning

Pre-coating

Speed

Thickness

3 ~ 8 mm/s

0.5-1.5 mm

14

Apart from the technology parameters, the research equipment should be carefully
selected. After laser cladding, the sample is usually sectioned perpendicular to the
scanning track with a wire-EDM (Electrical Discharge Machining) machine. Therefore,
a wire DEM is needed. Meanwhile, a laser machine is needed to produce laser. X-ray
diffraction analysis system (XRD) is used to analyze the phases and structure of the
coating, optical microscope is often used to observe the macro-structure and surface
condition of the cladding layer, and a further microstructure observation is done with
scanning electron microscope (SEM). Transmission electron microscope (TEM) is
sometimes used to study the crystal structure of the cladding layer. Energy dispersive
X-ray (EDX) microanalysis system is often used with SEM to study the chemical
composition of the cladding. The property study involves the testing of hardness,
high-temperature hardness and wear resistance of the cladding layer. Therefore, Vickers
Hardness Tester, High-Temperature Micro-hardness Tester, and the friction and wear
tester are applied. Some recommendations are shown as below. [23-28]
Table 7: Recommended Equipment for Studying the HEAs coating with Laser
Cladding [23-31].
Equipment Needed

Equipment Recommended

Wire EDM Machine

SLN6000G, SL400G, SL400Q, VL600Q, AG600L

Laser Machine

HUST-500, DL-HL-T500B Transverse Flow CO2 Laser,

LDF3000-60 VG Semiconductor Fiber-coupled Laser

XRD

TF-5500 XRD, D/Max Ultima XRD, XRD-7000, D8

Advanced XRD

Optical Microscope

XJP-6A, Zeiss series

SEM

S3400 , KYKY-3800B, JSM-6460LV, JSM-6700F

SEM, JEOL series SEM, Zeiss series SEM

EDX

Oxford INCA X-sight 7573 EDX

TEM

JEOL-JEM-2010, JEOL-JEM-200CX TEM

Vickers Hardness Tester

HX-200, DHV-1000, HVT-1000, TUKON2000

High-Temperature

AKASHI AVK-A

Micro-hardness Tester
Friction and Wear Tester

MMW-1 Universal, UMT-3, ML-10

15

Laser cladding can generally produce HEAs coatings with much better properties than
the substrate material. The researches [23-28, 32] show that the structure of the cladded
layer consists of mainly FCC and BCC solutions, sometimes Laves phases and other
phases also occur in small amount. Elements relative amounts can change the phases
and structure of the cladding coating, among these, Cr, Al, Co, Ni, Fe are important
elements, Ni and Co are quite expensive, which increase the manufacturing cost a lot,
thats also a reason why manufacturing HEAs coating is effective [24]. The well-made
cladding coating usually have very good high-temperature stability, high surface
hardness and toughness, especially high hardness in high temperature, good wear
resistance and corrosion resistance. The specific values of the hardness depends on the
substrate material, elements, heat treatment, and etc. For example, Hui Zhang found that
[33], the FeCoNiCrCu HEA coating consists of only FCC solution phase no matter the
elements Si, Mn and Mo are added or not, but before addition, the microstructures
consist of columnar grains and equiaxed grains, various alloying elements are uniformly
distributed and the hardness reached 375HV0.5. While after adding Si, Mn and Mo, the
coating hardness reached 450HV0.5 and the microstructure transited from disorder to be
in order. Generally, the micro-hardness of the cladded coatings ranges from 300HV to
1000HV [23-28, 32].
4.1.3

Methods of Manufacturing HEA Coating with Laser Cladding

Another research trend related to HEA coating is the study of the effects of alloying
elements on the microstructures and properties of the coatings, as mentioned above.
Currently, the manufacturing mainly relays on the preset powder method, but the study
is still limited to Fe, Cr, Mo whose melting points are close to the substrate materials
melting point. For the elements of Al, Mg, Ti, whose melting points are very different
from the substrate Q235 and 45 steels melting points, the study is still lacked [26].
While the preset powder method is not perfect. Ziqing Weng [34] applied gas
atomization to fabricate FeCrNiCoMn HEA powder, which was deposited on medium
carbon steel substrate by laser cladding. He got evenly distributed coating with single
FCC phase, and maximum micro-hardness was 500HV0.2. He compared the preset
powder method with coaxial powder sending method, finding that preset powder
technology is hard to control for getting good coatings, since the small laser power
cannot make the coating dissolve into the substrate, while large laser power would
damage the coating.

16

Can Tang [35] applied coaxial powder sending method for manufacturing TiCrAlSi
series HEAs. He preheated the substrate material to reduce the temperature gradient and
thus reducing the stress induced by expansion, and he got TiCrAlSi-Ni alloy coatings
with average hardness of 1000HV0.2, and the hardness increased after 24h annealing.
Xiubing Liang [36] applied arc spraying to manufacture FeCrNiCoCu HEA coating,
and gained the coating with BCC and FCC crystals and hardness of 400HV0.2. While
this technologys application on manufacturing HEA coating has not been reported in
laser cladding [26]. Its similar to arc hybrid welding in theory, it can be potential if the
technology can be controlled well.
Since the research on the HEA coating is still new, many researchers are just exploring
different methods, some can be potential in the future, while currently, the commonly
used method for manufacturing HEA coatings is still preset powder method, but its still
not perfect method. More efficient and convenient technologies need further research.

4.2 Thermal Spraying

Thermal spraying is a coating technique which sprays the melted materials onto the
surface of another material. It can provide thick coatings ranging from 20m to few mm
over a large area under high deposition rate. Metals, alloys, ceramics and composites are
all potential coating materials. In the thermal spraying, they are heated to molten state
and sprayed to the substrate material in the micrometer-size particle form. It includes
plasma spraying, wire arc spraying, flame spraying, high velocity oxy-fuel coating
spraying, cold spraying and warm spraying [37]. While, thermal spray has not been
widely applied into HEAs coating manufacturing like laser cladding.
4.2.1

Thermal Spraying Coating Processes

Different kinds of thermal spraying have different specific coating procedures, while a
common general process is shown as the figure below.

Fig.8: Processes of thermal spraying [38].

17

Before starting the spraying, the powder feedstock, which is the mixture of spraying
materials, should be prepared. The powder should be small and light enough. Next, the
powder particle is melted, the energy of which is provided by the gas or electric heating.
This accelerates the particle towards the substrate material. After cooling, the substrate
is coated with the spraying materials.
4.2.2

Plasma Spray Manufacturing HEA Coatings

Among several thermal spray techniques, plasma spray is relatively most popular
technique applied to the manufacturing of high entropy alloy coatings, while its still a
new field worth further exploration. The current research in this field is mainly the
study of the microstructure and properties of the plasma sprayed HEA coatings [39-40].
The plasma spray is usually not used individually, its a part of the whole manufacturing
process. The sample preparation is usually done with ball milling (mechanically
alloying) or arc melting, the elements are mixed and grinded into very small particles,
which are melted and then be sprayed on the substrates [39-40]. Heat treatment is often
necessary after the spraying. In the operation, the specific coating parameters like
current, voltage, gas flow, powder feed speed, spray nozzle dimension and the distance
of the spray nozzle to the substrates, should be carefully controlled. While due to the
lack of the previous research in this field, the standards for these parameters have not
been available yet, it mainly depends on the experience and the coating requirements.
Below is an example of the plasma spray coating parameters, which is from Andrews
study [39] of plasma sprayed HEA AlCoCrFeNi and MnCoCrFeNi.
Table 8: An Example of Plasma Spray Operation Parameters [39]

Post heat treatment is important for the HEA coatings manufactured by plasma spray.
Wang studied the effect of the heat treatment on the HEA coatings microstructure and
hardness, finding that even the plasma spraying significantly decreases the samples
mechanical properties, the post heat treatment increases its hardness a lot. Besides,

18

within the elevated temperature, the sample hardness increases with the increase of the
heat treatment temperature, meanwhile, the coarsening resistance is also enhanced [40].
4.2.3

HVOF (High Velocity Oxygen Fuel Thermal Spray)

High velocity oxygen fuel thermal spray (HVOF) is a very advanced thermal spray
technology. Its basic principle is not so different from plasma spray, while the
difference from other thermal spraying techniques is that HVOF uses the highly
exothermic materials as spraying material, and enables the materials synthesis and
deposition during the spraying through the SHS (selfpropagation hightemperature
synthesis) reaction, thus obtaining the ceramic coatings with high melting point [41].
For HVOF, the parameters of fuel amount, oxygen flow amount and rate, distance of the
spraying nozzle to the substrate, spraying guns length, and jet velocity are very critical.
With HVOF, Gao [42] studied the influence of the spraying distance on the structure
and properties of the coating, finding that, at different distance, the coatings density,
voids, hardness can be very different.
The temperature of the fuel jet can reach 3200, and the velocity can be up to 1500m/s
[41]. HVOF just uses such high temperature and velocity of the fuel jet to produce the
molten particles and enables them to hit the deposition on the substrate surface, making
coating. Since the spraying particles moves with great velocity and energy, the coating
formed in this way would have very strength, hardness and density. Such high velocity
also enables it to manufacture thick coatings. As a spraying technology, HVOF can
almost spray all kinds of materials, while only the carbide cermet powder can benefit
most from it since HVOF can reduces its decomposition and fabricate coating with high
hardness and wear resistance [41, 43]. Therefore, HVOFs application is still quite
limited by the materials. Another serious drawback of HVOF is that, when the particles
hit the substrate, part of the particle form the coating on the substrate, while part of
particle would rebound and loss. At the initial period, deposition is easy to happen,
while when the hard coating has been formed, more particles are rebounded, which
reduces the deposition. Meanwhile, when the particles are accelerated in the gun tube,
part of the particles would get stick to the gun tube, which would accumulate and affect
the guns normal function.
Because of these, HVOF hasnt been well applied in manufacturing high entropy alloy
coatings, meanwhile, there are more effective techniques like laser cladding for
manufacturing for the coatings of HEAs. The research of HVOFs application in
fabricating the coatings of HEAs are very rare seen.

19

4.2.4

Arc Spray Manufacturing HEA Coatings

Arc spray is a thermal spray technique which uses electric-arc generated between two
charged wires as the energy for spraying. Compared with plasma spray and flame spray,
arc spray has only little heat transferred to the area being coated [44]. Because of the
electric arc, arc spray is almost limited to the electrically conductive materials and be
made into wire form. Its mostly applied to fabricate the coatings for the zinc wire and
aluminum wire.
Similar to HVOF, the research of arc spray manufacturing HEA coatings is rare, and
there isnt standards for the parameters and operation either. Guo used inductrial AZ91
magnesium alloy as the substrate material to manufacture FeCrNiCoCu and
FeCrNiCoCuB HEA coatings with arc spraying, finding that the two coatings contain
only simple FCC crystal structure and in lamination structure, and the coatings have
good mechanical properties [45].
4.2.5

Other Thermal Spray Techniques Manufacturing HEA Coatings

High entropy alloys (HEAs) is still quite new field for the researchers, the
understanding of HEAs is still limited and many standards are lacked. The research on
the HEAs are mainly about its properties and microstructure, which is the fundamental
for manufacturing. As for the HEA coating manufacturing, only laser cladding has been
well used [26], among the thermal spray techniques, plasma spray is preferred, while arc
spray, flame spray, and other techniques are very rarely used in researching the HEA
coating manufacturing.

4.3 Electrochemical Deposition

Electrochemical deposition is a technique which deposits thin films of materials on
wafers or other substrates. The source gases are introduced into the reaction chamber,
high voltage or heat supply the energy to decomposit the source gas, the chemicals react
to form the film. In the deposition, the power source and the two electrodes are
connected into a circuit in the water or organic soluble electrolyte, and they react under
the effect of the electric field, ions react with redox reaction on the substrate material,
which make the segregation of dense pure metal or alloys, and this creates the film [12].
Electrochemical deposition is easy to operate, and the operator can control the
technology parameters of current, pH, deposition time, temperature, concentration, etc.
to get the deposition layer with the ideal chemical composition, structure and thickness
20

[12]. This also enables it to fabricate multi-functional films. But it fails to control the
crystal growth and the growth rate on the substrate surface, the fabricated compound
films are in polycrystalline or amorphous state, which dont have good properties.
4.3.1

Research of the HEA Film Synthesis by Electrochemical Deposition

The application of the electrochemical deposition in high entropy alloys (HEAs) is still
quite limited. Yao manufacture the Fe13.8Co28.7Ni4.0Mn22.1Bi14.9Tm16.5 amorphous HEA
films with constant potential electrochemical deposition, finding that the film is in
granular structure and has soft magnetic property, and when applied crystallization
treatment with the shielding argon gaseous, the alloy got single cubic crystal structure
[46]. With the same method, he also synthesized the Nd-Fe-Co-Ni-Mn HEA film, and
he found that the electrodeposition parameters like the deposition potential and time can
affect the formation of the nanostructure and surface morphologies of the film. While he
found the deposited HEA film was amorphous, and in this synthesis, he also found the
deposited HEA film have soft magnetic properties [47], his previous research had
already had the same finding, and found that, after crystallization, the coercivity is
increased and obtain hard magnetic properties [48]
4.3.2

Experiment of HEA Film Synthesis by Electrochemical Deposition

For synthesis of HEA film or coating with electrochemical deposition, a working

electrode (WE), a counter electrode (CE), and a reference electrode (RE) are the basic
elements needed. Metals are usually selected as WE, graphite is the most common CE,
double salt bridge saturated calomel electrode (SCE) is very good RE. An example of
the apparatus is shown as below. The WE metal usually needs to be polished to be flat
on the surface by sandpaper and then be immersed in the mixed solution of HCl and
H2O2, and then be rinsed in the distilled water, which is followed by ultrasonic cleaning
in the acetone and dry [46-47].

Fig. 9: Apparatus of the electrochemical deposition [49].

21

In the deposition operation, the electrolytic solution should be carefully selected, same
for the WE material and CE material. Besides, the WE treatment process should be
carefully performed, for example the polishing, immersion time, etc. In addition, the
deposition potential, deposition time and rate are all important parameters which can
affect the synthesized HEA coatings or films.
4.3.3

Characterization of HEA Film Synthesis by Electrochemical Deposition

When the HEA film is synthesized, the characterization is usually followed to study its
properties and microstructures. Field emission scanning electron microscope (FE-SEM)
can be applied to observe the microstructure, XRD is used to study the synthesized
films morphologies and structure. The researches had a common finding that the
synthesized films have soft magnetic properties, this is measured and characterized by
magnetic measuring instrument, which is to measure the magnetic saturation intensity,
residual magnetization, coercivity, and other magnetic properties [46-47].

4.4 Magnetron Sputtering

Magnetron sputtering is a plasma vapor deposition process in which the plasma is
created, ions are positively charged and be accelerated by electrical field which is
superimposed on the negatively charged electrode. Accelerated by the potential, the
positive ions hit the negative electrode to eject atoms from the target. These atoms are
ejected from the target and condense on the surfaces that are placed close to the
magnetron sputtering cathode. Magnetron sputtering uses a closed magnetic field to trap
electrons to enhance the initial ionization process and make the plasma to be generated
at lower pressure which reduces energy loss in the sputtered atom [50].
4.4.1

Research of the HEA Film Synthesis by Magnetron Sputtering

Magnetron sputtering is an effective method for synthesizing very thin HEA films, and
it can control the chemical composition easily by adjusting the magnetron powder and
the relative surface of each elements [51]. Overall, the study of the HEA films deposited
by magnetron sputtering mainly covers the synthesized HEA films structure, phases
and mechanical properties, and the effect of some elements or operation condition on
the structure and properties of the deposited HEA films.
Braeckman synthesized AlCoCrFeNi HEA thin films with magnetron sputtering
deposition of the homemade pressed powder targets, which was made as the figure
shown below. With characterization, he found observed the occurrence of the crystalline
22

and amorphous phase depending on the composition. Meanwhile, he found the

crystallographic structure can transit from FCC to BCC with the increase of the Al
fraction, and mixed crystalline structure also occurred [52]. Dolique deposited
AlCoCrCuFeNi HEA thin films on Si substrate with magnetron sputtering with three
mosaic targets, and found that the morphology and the crystalline phases of the
deposited HEA films depend on the chemical composition [51]. Li deposited
AlFeCoNiCuZrV HEA film with magnetron sputtering, finding it all has amorphous
structure. While his research used the mixture of argon and oxygen as shielding gas, and
found that the chemical composition, microstructure, and the mechanical properties of
the HEA films depend on the concentration and flow rate of the oxygen, by adjusting
the concentration and flow of oxygen, the smallest and biggest film thickness, ideal
roughness of the film surface can be achieved [53].
There are also researchers investigating the effect of the elements on the structure and
properties of the synthesized HEA film, for example, Cheng studied the how Si affect
the structure and the mechanical properties of HEA coatings with magnetron sputtering,
finding that Si improves the oxidation resistance of (AlCrTaTiZr)N films and the
hardness and oxidation resistance can achieve best combination when Si content is 7.9%
[54]. There is also investigation of how nitrogen flow affect the properties of the
deposited HEA film, finding that the flow rate of nitrogen influences the film structures,
hardness and Youngs module coefficients increase with the increase of the nitrogen
flow. The research also found the substrates significance on the synthesized HEA films
[55]. Cheng also found potential of the nitrogen system on the rigid HEA film [56].

Fig. 10: Process of homemaking of the powder target [52]

4.4.2

Experiment of HEA Film Synthesis by Magnetron Sputtering

The preparation of the HEA films with magnetron sputtering usually starts with
homemade powder target, in which the different elements are mixed by the fraction
ratio and weight, and then press to form the round shape targets. Powder targets are best
suited to deposit HEA films as well, and sputtering powder targets is an efficient and
23

easy method to deposit many different alloys [48]. In making the target, the amount of
each element should be carefully decided. Meanwhile, how many targets to make
depends on the elements involved and the research objectives, and the thin thickness of
the target is critical issue, it can be, for example, 1mm [51].
In the experiment operation, some parameters can be very important. For example, the
target power, which determines the argon ion sputtering energy can range from 200V to
500V for instance. The substrate bias is also critical. Depending on the research, the
targets diameter can be several centimeters and thickness can be few mm. Another
critical issue is the distance between the substrate and the target, which can be some
centimeters. Besides, the shielding gas is usually argon gas, oxygen is sometimes also
used, but when applied, the gas flow rate is very important for determining the
deposited HEA film thickness and quality [51-53].
4.4.3

Characterization of HEA Film Synthesis by Magnetron Sputtering

After obtaining the deposited HEA film, the characterization is usually followed for
studying its phases, microstructure, and properties. SEM-EDX or field-emission SEM is
applied to observe the surface morphology and thickness of the deposited HEA film, the
EDS can be applied with SEM to analyze the composition, and XRD is applied to study
the structure. Some researchers may also study the Youngs modulus, which can be
measured by nanoindenter [51-53].
There are some common findings from the research of synthesizing HEA films with
magnetron sputtering. For the structure, BCC and FCC are the main structures and there
can be transition from FCC to BCC when the elements changes, and therefore, there is
also mixed crystalline structure to occur. Besides, many researches found the soft
magnetic properties of the deposited films. In addition, the chemical composition can
affect the surface morphology, structure, phase formation and mechanical properties of
the synthesized HEA films [51-56].
The technique is easy to perform, and it enables the researcher to modify the elements
and chemical composition to get the HEA films with the needed morphology, thickness
and mechanical properties. However, the research on the effect of the addition or
amount of the elements on the synthesized films structure and properties is still limited.

24

5 Properties of High Entropy Alloy Coatings

The synthesized high entropy alloys (HEAs) usually contain only FCC or BCC crystal
structure or the mixed crystalline structure of them, some even have amorphous
structure. The as-cast and fully tempered HEAs have nanophase structure, and show
very rare high-temperature precipitation hardening phenomenon [57-58]. The large
amount of relevant research suggest that, HEA coatings own high strength and hardness,
excellent corrosion resistance, wear resistance and oxidation resistance.
Based on the literature, by the coated materials, the HEA coatings can be classified into
metallic coatings, compound coatings, and composite coatings [59].

5.1 Metallic HEA Coatings

High entropy alloys (HEAs) coatings are mainly synthesized by laser cladding, which
has been well used. Zhang applied laser cladding to manufacture FeCoNiCrCu and
6FeNiCoSiCrAlTi HEA coatings with steel Q235, finding that the hardness of
FeCoNiCrCu achieved 375HV0.5 and the microstructures are columnar crystal and
equiaxed crystal, while the hardness increased to 450 HV0.5 when small amount of Si,
Mn and Mo are added [33]. The 6FeNiCoSiCrAlTi HEA coating was found to have
simple BCC structure, and the microstructure consists of equiaxed polygon grains,
discontinuous dendrite area and precipitates [60]. The rapid cooling of the laser
cladding eliminates the precipitation among the elements and enhances the hardness of
the coating by grain refinement and solid solution strengthening mechanisms [33, 60].
Lin manufactured NiCrAlCoMo, NiCrAlCoW [57] and NiCrAlCoSi [62] HEA coatings
on the medium carbon steel surface by tungsten electrode gas shielding welding. The
research suggested large amount of intermetallic compound in NiCrAlCoMo and
hardness 1000HV0.5. NiCrAlCoSi HEA coating also shows excellent wear resistance in
the sliding friction experiment [62]. The high hardness of NiCrAlCoW and NiCrAlCoSi
HEA coatings can both be attributed to the precipitation hardening [61-62].
Some metallic HEA coatings also show high entropy effect and slow diffusion effect,
and present stable amorphous structure, for example AlMoNbSiTaToVZr coating [63],
which can effectively prevent formation of the coppers silicide.

25

5.2 Compound HEA Coatings

Compound coating generally can enhance the hard wear resistance, Yeh firstly studied
the HEA nitride film mainly by magnetron sputtering with his group [59]. There have
been some studies of the effects of the magnetron sputtering parameters on the HEA
films. The literally reported such compound HEA films include for example,
(AlCrTaTiZr)Nx [64], (AlCrSiTiV)Nx [65], (AlCrMoSiTi)Nx [66], and etc. They
generally posses high hardness ranging from 16 to 37 GPa, good high-temperature
stability and chemical inert [67]. A typical example is (AlCrNbSiTiV)N film, the
hardness of which reaches 41 GPa, and its crystal structure, lattice parameters and
hardness dont change even when it is annealed at 900 for 5h [68].
Cheng synthesized (AlCrMoTaTiZr)Nx HEA film with magnetron sputtering method,
the HEA films thickness is 1.2-1.5m, hardness reaches 40.2GPa, and the film kept
stable even when annealed at 1000 for 10h, which shows excellent high temperature
stability, and the film shows excellent wear resistance in the sliding wear test with
100Gr6 steel ball [69]. The films are strengthened through grain refinement and solid
solution hardening.
Some studies also revealed the transition of the crystal structure and the effect of the
elements on the properties of the HEA coatings. Ta-kun Chen found that for high
entropy alloy AlxCoCrCuFeNi (x=0.5, 1, 2), the metallic coating consists of simple
solid solution phase, while the structure transit from BCC to FCC with the increase of
the value of x. Its oxide has similar solid solution phase, and the hardness increases to
22.6 GPa with the addition of aluminum and oxygen [70]. Miao-I. Lin found the
amorphous structure of the (AlCrTaTiZr)Ox film, and the amorphous structure was kept
even after annealing at 800 for 1h, but it shows excellent precipitation hardening after
annealing at 900 for 5h, which enhances the films hardness to 20GPa and enhances
Youngs modulus to 260GPa [71].

5.3 Composite HEA Coatings

As it known, synthesizing nanocomposite films is a way to achieve super-hardness.
Inspired by this idea, some researchers are also exploring the synthesis of HEA
nanocomposite film by adding the elements C, B, Si into the HEA nitrides, to form the
bonding similar to the covalent [59].

26

Cheng synthesized (AlCrTaTiZr)-Six-N film with magnetron sputtering and studied the
effect of silicon on the morphology, structure, and mechanical properties of the film. He
found that, the nitride film has BCC structure when the content of silicon is low, while
when the silicon content reaches 7.9%, the thermodynamics drives the BCC structure to
segregate and SiNx phase is separated, strengthening the film. In this condition, the film
consists of BCC nitride solid solution and amorphous SiNx, and the films hardness
achieves 34 GPa. The film only formed oxide layer with thickness of 330nm after
annealing at 1000 for 2h, which shows excellent oxidation resistance [54].
Chang deposited (AlCrTaTiZr)NxCy film by sputtering on the AlCrTaTiZr target and
carbon target, finding that (AlCrTaTiZr)N0.6 film consists of loose columnar and
face-centered solid solution structures, its hardness was 20 GPa and its steady-state
creep rate was 1.5*10-4/s, while with the addition of carbon, the hardness of
(AlCrTaTiZr)N0.6C0.2 film was increased to 32 GPa and the steady-state creep rate
slowed to 1.1*10-4/s. These property variations are attribute to the formation of covalent
when carbon was added, which refined the grains and made the columnar structure
closer to each other, forming the nanocomposite structure [72].

27

6 Applications and Outlook of High Entropy Alloys

The multi-component high entropy alloys (HEAs) have simplified crystal structures,
intermetallic compounds are not easily generated, while the nano-precipitates and
amorphous structures occur in HEAs. Meanwhile, HEAs generally own high strength
and hardness, good resistance to the temper softening, excellent wear resistance, high
temperature stability and etc. The combination of such properties becomes HEAs
dominant advantage over the conventional alloys. The research on HEA is still at its
early period, and the research are mainly investigating its properties and structures, and
the effects of different elements on the HEA and HEA coatings properties. Due to the
lack of the understanding of the processing and manufacturing technologies, HEAs have
not been widely put into applications. However, based on their outstanding properties
known by now, many researchers keep very positive for its potential applications.
Below is the discussion of HEAs potential application outlook.

6.1 High-Speed Cutting Tools

HEAs own very excellent wear resistance and high hardness, many HEAs as-cast
structure have hardness of 600-900HV [73], or even higher than the hardness of carbon
steels after complete quenching hardening, and its hardness can be furtherly enhanced
by changing the amount of the alloying elements. Meanwhile, HEAs usually show very
excellent heat resistance and high temperature stability.
The normal high speed steels (HSS), for example W18Cr4V and W6Mo5Cr4V2, can only
perform cutting at the temperature below 600, above which the material experiences
passivation [74]. Besides, the HSS tool needs to lose some plasticity and toughness for
gaining high hardness and wear resistance. Because of this, when the normal HSS tool
needs high hardness and wear resistance for good cutting function, fracture happens a
lot to it. Differently, HEA can obtain high hardness and good plasticity and toughness
simultaneously. For example, FeCoNiCrCuAl0.5 didnt show any cracking after cold
compacting during which the plastic deformation reached 50%, on the contrary, some
nanocrystals grew during the plastic deformation and compacting, enhancing the
hardness furtherly [9]. Many HEAs also show good ductility during the compacting.
There together make the HEAs perfect material for high speed cutting tools. In addition,

28

the magnetron sputtering can synthesize the HEA film, one can deposit such HEA
coating on the normal steel tool to improve the cutting performance and save the cost.

6.2 Corrosion-resistant High-Strength Parts

HEAs own excellent corrosion resistance. The HEA coating Al0.5FeCoCrNiCu shows
very good corrosion resistance and Cl- ions resistance in the 0.5mol/L H2SO4 and
1mol/L NaCl solution [76]. AlxFeCoCrNiCu coating shows better corrosion resistance
than 304 stainless steel in the 0.5mol/L H2SO4 solution and 1mol/L solution [76].
Therefore, HEA has potential for the application in the high-pressure resistant,
corrosion resistant container or the high-strength corrosion resistant parts on the boats.

6.3 Airplane Engine Turbine Blades

The good plasticity enables it to be manufactured for turbine blades of the airplane
engine. The current difficulty for the turbine blade is to keep the blade stable under high
temperature and excellent wear resistance and corrosion resistance during the fast
spinning, while HEAs show good wear resistance, high temperature stability and high
work hardening rate, these enable it to work stably for long time in the turbine blades.
Especially the sluggish diffusion effect for HEAs enable them to work well at elevated
temperature even [77]. In addition, compared with the conventional superalloys, HEAs
can reduce the weight for the blade, which lowers the engine weight and thus reduces
the demands on the wings carrying the engine [77]. A diagram of the typical turbine
engine is shown as the figure below.

Fig. 11: Diagram of Turbine Blades of Aircraft Engine [78].

29

6.4 Refractory Skeleton of Skyscrapers

The skyscrapers are supported by concrete iron, also, the breakdown of the high
buildings is due to the plastic deformation of the concrete iron, which is induced by the
dramatic strength decrease when heated. HEA has extremely high compression strength
[8] and excellent high temperature resistance and high-temperature stability [79], which
enable HEAs to keep the shape when the fire disaster happens, for example.

6.5 Other Applications

The soft magnetic property and high electric resistance give HEA potential for the
application in the high-frequency communication parts, for example, high-frequency
transformer, the magnetic CD, core head of the motor, speaker. Some researchers and
companies have manufactured some products with HEA, which are shown as the
pictures below.

Fig.12: Some Applications of High Entropy Alloys: various cutting tools; Bearing;
Head of the Golf club [80-82].
High entropy alloy is a brand new concept for alloy design, which breaks the
conventional alloy synthesis limits, it creates a new field for the researchers to explore.
Researchers keep positive attitude towards to HEAs that with more understanding on its
properties, processing and manufacturing, etc., more HEA products would come into
being in the future.

30

7 Current Research of High Entropy Alloys

High entropy alloys (HEAs) is a relatively new field, the concept of which was brought
up in middle 1990s, and it attracted attention from 2004 when professor Jien-Wei Yeh
published the first relevant paper of HEAs in Taiwan [2]. Since then, some researchers
and companies, institutions have been doing research on it. Below is an introduction and
summary of the key researchers, companies, institutions which are leading the HEAs
research in the world.

7.1 Researchers and Universities

The research of high entropy alloys is mainly led by the research group of professor
Jien-Wei Yeh [83] in National Tsing Hua University in Taiwan and the group of
professor Yong Zhang [84] of University of Science and Technology Beijing, China.
B.S Murty [85] of Indian Institute of Technology Madras, Chennai, India and S.
Ranganathan [86] of Indian Institute of Science, Bangalore, India also contribute a lot to
the research of HEAs. Besides, some other universities, for example High-entropy
Alloy Group of Chalmers University of Technology, Sweden [87], are also active in the
research of HEAs.
7.1.1

Jien-Wei Yeh

Jien-Wei Yeh is a professor of Department of Materials Science and Engineering at

National Tsing Hua University. He is the first person who brought high-entropy alloys
into peoples view and established it as a field within materials science, for this, he was
titled Father of high-entropy alloys. He pioneered HEAs research when he coauthored
the book High Entropy Alloys with B.S. Murty and S. Ranganathan in 2014, the book
has become a standard textbook for high-entropy alloys since Elsevier published it since
it is the first book introducing high-entropy alloys thoroughly in the world [83, 88].
Also in 2014, he published the paper High-Entropy Alloys: A Critical View with
Ming-Huang Tsai through Journal Materials Research Letters, which gave an in-depth
introduction to the critical aspects of HEAs [89]. Before that in 2013, his published
paper Alloy Design Strategies and Future Trends in High-Entropy Alloys. He
emphasized four core effects and clarified several misconceptions on HEAs, and also
claimed that even there were over 400 HEA papers, the understanding of HEA is still at
infant stage, many new HEAs would come to peoples eyes, HEAs would have potential
31

in many fields and will replace traditional materials in some aspects [90]. Later in 2015,
Yeh did some research of the metallurgy of HEAs, an example is his paper Physical
Metallurgy of High-Entropy Alloys. Apart from the conventional thermodynamics,
kinetics, structures, properties of HEAs, his research also found the lattice distortion
effect, which is particularly important since it influence the microstructures and
properties a lot. Yeh also gave brief orientation for the future research, claiming that
suitable mechanism and theories related to the composition, microstructure and
properties for HEAs should be built to complete the physical metallurgy [91].
Since his first paper on HEAs in 2004, Yeh did lots of research and published
productive papers related to the metallurgy, treatment, microstructures, properties,
behaviors, etc. of high-entropy alloys in the past decade [92].
Yeh is highly concentrated on the research of several aspects of HEAs, and he also leads
a research group of HEAs at the Laboratory of High-performance Metals of National
Tsing Hua University, Taiwan. He leads the group doing groundbreaking research of
high entropy alloys. He proposes that the future research of HEAs would lie in the fields
of enhancing alloy design, microstructure and properties discussion, including high
toughness HEAs, refractory HEAs, cemented carbide, hard-surface HEAs, functional
high entropy film, etc [93].
7.1.2

Yong Zhang

Yong Zhang is a professor of State Key Laboratory for Advanced Metals and Materials,
University of Science and Technology, Beijing, China [84]. Zhang started studying
HEAs quite early since Jien-wei Yeh brought this field, and in the first few years, he
had some collaboration with Yeh in the research of HEAs, he also coauthored Yeh for
the book Recent Advances in High-Entropy Alloys (ISBN2743009578) in 2006, which
updated the breakthroughs of HEAs research findings at that time, and the book was
published by France Lavoisier Paris Press [84].
In 2007, Zhangs group firstly manufactured body-centered cubic-structure high entropy
solid solution alloys AlCoCrFeNiTix which have excellent mechanical properties under
room temperature and equivalent properties as bulk amorphous alloys [94]. In 2008,
based on the rules of phase formation in the alloys, Zhang proposed the enthalpy of
mixing of the high-entropy alloys solid solution formation and atomic size difference
criterion [95]. This laid good foundation for the further research on HEAs. In 2012,
based on the equilibrium relation of entropy of mixing and the enthalpy of mixing,

32

Zhang proposed parameter w, which firstly predicted the phase structures of HEAs in
the scientific way, and became the important criteria of HEAs structure design [96-97].
Apart from these, Zhang also devoted to the research of amorphous materials, and also
studied the relationship of amorphous and high-entropy alloys. These research led to the
publishing of book Amorphous and High-Entropy Alloys (ISBN 97870302642-1)
(Chinese version) in 2010. The book introduced the thermodynamics and kinetics of the
formation of amorphous, vitrification formation ability, properties and technologies of
amorphous alloys, and also the development of high-entropy alloys based on amorphous
[98]. The book mainly focused on the amorphous, but also gave an idea for the future
research of the relationship of HEAs and amorphous.
Afterwards, Zhang did some work on the microstructure control and properties
optimization of HEAs. In 2011 Chinese Materials Conference, he shared his paper
Microstructural Control and Properties Optimization of High-Entropy Alloys, in which
the properties of CoCeFeNiCu HEAs can be optimized by several processing and the
soft magnetic alloy CoFeNiAlxSix was developed [99]. He also studied the effects of
some metallic elements on the microstructure and properties of HEAs. In the study of
Nb addition on the microstructure and properties of AlCoCrFeNi HEA, he found two
phases, BCC and Laves Phase, exist, more surprisingly, he found the factor can
predict the phase formation for the multi-components alloys [100]. Therefore, based on
this finding, and consider that HEAs contains at least 5 elements and the phase diagram
of is often not available for designing alloys, in 2012, he proposed that the parameters
and can predict the phase formation, he conducted research to test this, and got
surprising finding that no ductile-to-brittle transition was shown in the CoCrFeNiAl
HEAs even at low temperature ranging from 298K to 77K [96]. This research led to the
paper Alloy Design and Properties Optimization of High-entropy Alloys. With these, he
did a further investigation, and found that the high-entropy stabilized solid-solution is
located at > 1.1 and < 6.6% [97].
Based on the research findings in the microstructures, properties, phases, alloying, two
important factors and , Zhang published the literature review of Microstructures and
properties of high-entropy alloys on the Journal Progress in Materials Science, which
gives thoroughly introduction to the basics of HEAs, including its thermodynamics,
kinetics, various properties, deformation, glass formation behavior, modeling, and also
gives orientation for the future development and research [7]. This is also a very
valuable reference in the field of high-entropy alloys currently, Zhang also became a
noted figure in this field after this publication.
33

7.1.3

B. S. Murty

Professor B. S. Murty leads his Advanced Materials Research Group at Indian Institute
of Technology Madras, Chennai, India. High entropy alloy is one of his four interested
fields [85]. His group studies many aspects of high-entropy alloys, including phase
prediction, properties, magnetism, application in the high-temperature coating,
oxidation and corrosion behavior as well [101]. He was well-known in HEAs field after
coauthored with Jien-wei Yeh and S. Ranganathan for the book High Entropy Alloy in
2014. Different from Jien-wei Yeh and Yong Zhang, Murtys research on HEAs is very
partial to the mechanical alloying, and the experimental HEAs are quite similar, the
research scope is not as wide as Yong Zhang and Jien-wei Yeh, while he has some
unique contribution in the world of HEAs.
Murtys research papers on the high entropy alloys started from around 2009 [102]. In
2009, he processed the nanocrystalline equiatomic CuNiCoZnAlTi HEA by mechanical
alloying, and found the mechanically alloyed CuNiCoZnAlTi HEA has very high
hardness of 7.55GPa and compressive strength of 2.36GPa, he thought that its the solid
solution strengthening and the nanocrystalline nature that caused high strength [103].
He also studied decomposition of HEA, in which he produced the decomposition by
splat quenching and casting, respectively. It was found that the splat-quenched alloy
contained an imperfectly ordered BCC phase, while the as-cast alloy contained several
BCC and a FCC phases within the dendrites. He also found the composition fluctuation
and segregation in the dentrite, and if the HEA consists of the elements with very
different enthalpy of mixing, the HEA is very likely to show segregation during
solidification [104]. In the study of the alloying behavior of HEAs, he found out that
simple FCC and BCC phases appeared after mechanical alloying, while Cu-rich FCC
and phase appeared after spark plasma sintering (SPS). The phase increases the
hardness of HEA, and therefore he proposed the solid solution criteria for HEAs needs
to be changed with consideration of enthalpy of mixing between elements in the alloy
system [105]. Also, in studying the phase formation in mechanically alloyed HEAs, he
got same result that the criteria of the solid solution formation for HEAs in the literature
cannot explain the phase formation of HEAs in the real practice, those criteria only
work for very specific condition. Moreover, his research indicated that the composition
limit for HEAs components proposed by Jien-wei Yeh is not s compulsory condition,
and he suggested that the range of parameter to form ordered solid solutions proposed
by Y. Zhang can be extended to higher value [106]. In addition, in 2012, Murty applied
CALPHAD approach to study the BCC and FCC phases formation in HEAs, finding
that the solid solution in HEAs in favored when the ratio of Sconfig / Sconfig is over 1
34

for equitatomic alloys and 1.2 for non-equitatomic alloys. The research also found that
with the increase of the atomic size difference of the alloying elements in the HEAs,
BCC phase is more likely to be formed, BCC phase formation is governed by S /k
while FCC phase formation is controlled by Hmix [107].
7.1.4

Sheng Guo

The High-Entropy Alloys Group at Chalmers University of Technology is under the

lead of Dr. Sheng Guo. One of their main interests is to achieve both high strength and
high tensile ductility in HEAs simultaneously. Their target is to develop HEAs as new
structural materials for high-temperature applications [108].
S. Guo started research on HEAs from 2009 when he took the research project Phase
Stability in High-Entropy Alloys (equiatomic or close-to-equiatomic multi-component
alloys) in Hong Kong, and his research focuses on the phase stability in HEAs [109]. In
this research, he found that the solid solution formation can only happen when the
mixing enthalpy (Hmix), atomic size difference (), and mixing entropy (Smix) satisfy
-22 Hmix 7kJ/mol, 0 8.5, and 11 Smix 19.5J/(K.mol) simultaneously, and
the stomic size difference plays the most critical role in the solid solution formation
[110]. Guo also found that the mixing enthalpy is the key factor controlling the
formation of solid solution or compounds, and valence electron concentration controls
the phase stability of FCC and BCC solid solution [111]. Later in the further study with
Al0.5CoCrCuFeNi HEA, Guo found that solid solution phases were stable at high
temperature of above 850 and low temperature below 300, while the intermetallic
-phase co-existed with the solid solution phases at intermediate temperatures. The
reasons behind this is that when at room temperature, the phases in as-cast HEAs are
not at equilibrium status, the sluggish diffusion kinetics slows down the phase
transformation while the high entropy favors the stability of solid solutions at very high
temperature [112]. The Al0.5CoCrCuFeNi2 HEA also showed very stable mechanical
properties and microstructures even under high temperature of 1100. Meanwhile, the
solid solution phases are also found to be metastable in nature [113].
Based on the valence electron concentration rule, in 2013, he found that the submicron
rob-like microstructure existed in eutectic the fcc/B2 alloys and sunflower-like
microstructures existed in the hyper-eutectic alloys [114]. Afterwards, in the further
study of sunflower-like microstructure, he found that in the solidification process, the
Ni-Al-rich B2 phase was firstly formed with spherical or ellipsoidal morphology, then
Ni-Al-rich B2/Cr-rich A2 eutectics grew, and finally the B2 phase decomposed to be
nearly cubic particles when temperature got down [115].
35

S. Guo also conducted research of phase selection in HEAs. He revealed that (1)
topology, mainly the atomic size, (2) chemistry, which includes electronegativity,
electron concentration or the mixing enthalpy, and (3) complexity of the constitution
elements are the three factors governing the phase selection, meanwhile, the phase
selection in HEAs with equiatomic or nearly-equiatomic compositions, can be predicted
by parametric approach with atomic size polydispersity parameter () and the mixing
enthalpy (Hmix) [116]. They are also most important factors affecting the phase
selection [117]. Another important factor governing the phase selection in HEAs is
valence electron concentration (VEC), which is also a factor for verifying the solid
solution structure. FCC structure exist when VEC > 7.84 while BCC structure exist
when VEC < 6.87, they coexist when VEC is between 6.87 and 7.84; VEC can also
verify the intermetallic compounds, which occur when VEC is in its medium range, fcc
solid solution phases are stable at VEC > 7.8 and bcc solid solution phases are stable at
VEC < 6.0 [117]. Taking the kinetic and thermodynamic factors into account, the phase
selection among different phases is determined by the competition of mixing enthalpy
Hmix and TSmix [118]. For studying the phase selection rule in HEAs, Yang and
Zhang also proposed a new parameter which is defined by [119]:

, where Tm is determined by
and (Tm)i is the melting point
of the ith component of the alloy. By this, the phase selection rule for the solid solution
then becomes 1.1 and 0.066, the specific rule is demonstrated in the following
figure 12 [118]. The mixing enthalpy Hmix and also work together in governing the
solid solution types, as shown in the figure 13. The plot presents that fcc-structured
solid solutions form when is small and Hmix is lea negative, while bcc-structured
solid solutions form at greater and more negative Hmix [118].

Fig. 12: An - plot showing phase selection in HEAs and BMGs [119].
Fig. 13: Dependence of solid solution types on and Hmix [120].
36

One tough challenge in HEA research is to achieve high strength and high ductility
simultaneously, while this is exactly the interest of his research group at Chalmers
University of Technology [121, 108]. For this goal, Sheng Guo tried to design the HEA
with microstructure containing alternating soft fcc and hard bcc phases, that is eutectic
HEAs. While surprisingly, the AlCoCrFeNi2.1 eutectic HEA he synthesized showed
great combination of high tensile ductility and high fracture strength at room
temperature [121]. This also gave him hint that eutectic HEAs would be a promising
new high-temperature alloys.
7.1.5

Other Researchers

High entropy alloys (HEAs) is still a relatively new research field since Jien-wei Yeh
started research on HEAs in 2004. There are currently over 400 research papers related
to HEAs around the world. The book High Entropy Alloys, which was coauthored by
Jien-wei Yeh, B. S. Murty, and S. Ranganathan, is the only book which thoroughly
introduces HEAs, much of Jien-wei Yehs research results on HEAs are included in the
book. Yeh also became the most pioneering person in the field of HEAs, B. S. Murty
also did much research on HEAs and became well-known because of this book. Apart
from them, Yong Zhang is another pioneering researcher on HEAs, Zhang was
productive in HEAs field and after ten years research, he summarized his research
results, including the development of HEAs in his special literature review paper
Microstructures and Properties of High-entropy Alloys, this paper also serves as
standard reference for HEAs, especially HEAs fundamental information.
Sheng Guo is very active in the research of phase stability, mechanical properties of
HEAs and HEAs design. Most of his work in these fields are done in cooperation with
U. T. Liu. Professor U. T. Lius research in the HEAs field is quite similar to Sheng
Guos [122]. Globally, the researches on HEAs are mainly in China, USA, India, UK,
Germany, Sweden [123]. Besides, there is also a high entropy alloy research group in
Rolls-Royce UTC, University of Cambridge, their research focuses on phase metallurgy
of near equiatomic HEAs and HEAs applications at elevated temperature [124].
Professor T.G. Nieh of University of Tennessee, USA, also shows interest in the research
of HEAs, most of his such research were done in collaboration with Y. Zhang, Jieh-wei
Yeh, C. T. Liu [125]. After the international workshop on the microstructures and
mechanical behavior of HEAs in Guiyang, China in December 2014, T.G. Nieh
summarized the the valuable research results on HEAs and gave guidance on the future
development of HEAs [126]. In addition, there is also a group of Indian researchers
active in HEAs field [127]. Their first workshop on HEAs were held in IT Madras in
37

March 2015, and some valuable results were achieved [128]. K.G. Pradeep, who works
at RWTH Aachen University, has close cooperation with this group in the research of
HEAs [129-130].
Since HEAs is still a new field in the research, in the past few years, many updates on the
progress of HEAs were shown. Some critical review articles also occurred among them
[131]. Y. Zhangs paper Microstructures and properties of High-entropy Alloys was the
most typical one. Gaos review paper Progress in High Entropy Alloys briefly
summarized the advanced updates on HEAs and collected some very valuable references
[132]. Huang also summarized the patterns in HEAs field till 2009 [133]. In addition to
the progress updates, there are also some papers giving outlook for the future
development and research on HEAs [134-136].

7.2 Companies
High entropy alloys (HEAs) is still in its initial research stage, many issues of which have
not been well understood. Therefore, there is still a long way to go before HEAs products
can be massively manufactured. Some companies in Taiwan show some have some
exploration for HEAs products, like Bewise Inc. [137], but HEA has not been massively
put into application and industry.

7.3 Current Research Outlook

Since Yeh proposed the concept of high entropy alloys (HEAs), he has been dedicated
into the research for it. In the earlier years, he studied a lot about the microstructures and
properties of the HEAs, while he now takes his group to study the HEA films synthesis
with magnetron sputtering and electrochemical sputtering, and study the effect of the
operation parameters and the chemical elements on the microstructure and properties of
the HEA films.
The research of HEA is mainly led by Yeh and Yong Zhang, and some other Chinese
researchers. Overall, the research on HEA is focusing on the synthesis technologies and
the effects of the chemical elements on the microstructures and properties of the HEA.
The elements involved are mainly Al, Ti, V, Co, Cr, Cu, Ni, Mn, Fe, and Zr, the
properties studied are mainly mechanical properties like hardness, compression strength,
wear resistance, corrosion resistance, some physical properties, especially magnetic
properties have been studied, other properties have rare seen being studied. Lots of
38

micro-mechanisms of HEAs have not been revealed thoroughly [74], Yong Zhangs
group from University of Science and Technology is pioneering in this field. Sheng Guo
studies a lot about the phase selection, phase stability and mechanical properties of
HEAs. There are also many studies of property optimization of HEAs.
HEAs research is still at the initial stage, the understanding for it is still not sufficient,
most of the relevant data and information are still being experimented, thus, the
standards for HEA are still lacked. Because of this, HEA has not been put into industrial
production.
The synthesis methods for HEA is also explored. Laser cladding has been widely used
by Chinese researchers for depositing HEA coatings, laser cladding is also almost the
only technology that has been well applied in manufacturing HEA and HEA coatings.
Electrochemical sputtering and magnetron sputtering is also studied, especially in
Taiwan, Jien-wei Yeh is doing this research with his group. Plasma spraying is also
used, but not as common as laser cladding and sputtering. For other materials which
have been known well, the coating methods can be many, for example, arc spraying,
high velocity of fuel spraying, flame spraying, plating, etc. While they have not been
well applied to the manufacturing of HEA coatings, only few researchers are trying with
them basically.

39

8 Conclusions

The new concept of high entropy alloy (HEA) was proposed by Jien-Wei Yeh in 2004,
and the research for HEA is led by him and Yong Zhang. The main difference of HEA
from other conventional alloys is its components, which contains at least 5 constituent
elements, each with a concentration between 5 and 35 atomic%. Such configuration
brings HEA four dominant effects of high entropy, lattice distortion, sluggish diffusion,
and cocktail effect. These also create some unique properties like high hardness and
strength, excellent wear resistance and corrosion resistance, good high temperature
stability and soft magnetic properties, and etc. HEA usually contains simple FCC and
BCC crystal structures, phase transition happens to HEA when the alloying elements
and relative amount is changed, and amorphous structure sometimes also occurs.
Since the concept of HEA being proposed, there have been lots of studies about its
microstructure and properties, mechanical properties and some physical properties are
the focus, some other properties still worth further research. There are also intensive
studies of the effect of the alloying elements on the microstructure, phases and
properties of HEAs, and the exploration of phase stability and phase selection rules.
Property optimization is also explored by alloying elements control and synthesis
operation control.
The researchers are also exploring the manufacturing methods for HEA, vacuum arc
melting, powder metallurgy, mechanical alloying, sputtering are the very commonly
used techniques for manufacturing HEAs, some other techniques like vacuum induction
melting, and conventional forging and casting are also used sometimes. For the
synthesis of HEA coatings, laser cladding is the most and only widely applied method,
there are also some data reference for it due to the numerous studies. Electrochemical
sputtering is now intensively studied by Jien-Wei Yeh and other researcher for
depositing HEA films and optimizing the HEA film properties. Magnetron sputtering is
also very convenient and effective method for HEA coating synthesis. Meanwhile,
plasma spraying, arc spraying, high velocity of fuel thermal spraying, chemical vapor
deposition, physical vapor deposition, plating may also be applied, but they are still
experimented and worth further exploration. The HEA coatings can be classified into
metallic coating, compound coating and composite coating, each has its own unique
properties and limitations.

40

Due to the lack of thorough understanding of the properties, synthesis technologies, and
etc, the authorized and reliable data for HEA is still lacked, thus HEA has not been
massively applied in the industry. But regarding its unique and excellent known
properties, HEA can be well applied in cutting tools, high-strength corrosion resistant
parts of the boat and chemical engineering. It also has potential for being applied to the
turbine engine blades of the aircrafts. In addition, some HEA products like Golf club
head and bearing have been made in Taiwan.
The research for the properties, phases, synthesis methods of HEA is still at its early
stage, and lots of reliable data and references are lacked, but the current understanding
of HEA enables people to predict its great potential applications in the future.

41

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