Wei-Hong WU, Chih-Chao YANG, and Jien-Wei YEH, INDUSTRIAL DEVELOPMENT

OF HIGH-ENTROPY ALLOYS, Annales De Chimie Science des Materiaux, 31(2006),

pp. 737-747.

INDUSTRIAL DEVELOPMENT OF HIGH-ENTROPY ALLOYS

Wei-Hong WUa, Chih-Chao YANGa, and Jien-Wei YEHb

Nano-Powder and Thin Film Technology Center, Industrial Technology Research Institute,
Tainan 70955, Taiwan
b
Department of Materials Science and Engineering, National Tsing Hua University, Hsinchu 300,
Taiwan

Abstract- High-entropy alloys (HE alloys) are composed of at least five major metal elements,
as opposed to traditional alloy systems that are typically based on only one or two major
elements. Dependent upon their composition and/or processing route, HE alloys have been
found to possess a wide range of microstructures and properties. Some of them exhibit
promising properties such as high hardness, wear resistance, chemical inertness and
high-temperature softening resistance. By exploiting their merits, properly-designed HE alloys
are developed with an aim to replace traditional alloys in specific applications. This paper
describes the current status of several industrial applications of HE alloys.

Rsum Dveloppements industriels dalliages haute entropie. Les alliages haute

entropie (AHE) sont composs dau moins cinq lments mtalliques majeurs, par opposition
aux systmes dalliages classiques qui sont typiquement bass sur seulement un ou deux
lments majeurs. En fonction de leur composition et du procd dlaboration, il sest avr
que les AHE pouvaient avoir un large spectre de microstructures et de proprits. Certains
_______________________________________________________________________
Reprints: C.C. Yang, Nano-Powder and Thin Film Technology Center, Industrial Technology
Research Institute, Tainan 70955, Taiwan
dentre eux prsentent des proprits prometteuses telles que duret leve, rsistance lusure,
rsistance aux agents chiques et rsistance ladoucissement haute temprature. En exploitant

W. H. Wu

ces avantages, des AHE convenablement conus sont en cours de dveloppement en vue de
remplacer des alliages classiques dans des applications spcifiques. Cet article dcrit ltat
actuel de plusieurs applications industrielles dAHE.

1. INTRODUCTION
There are about thirty traditional alloy systems used in practical applications. They are
typically based on one principal element, as in the iron-based, aluminum-based,
magnesium-based, and titanium-based alloys [1, 2]. High-entropy alloys (HE alloys) are a novel
alloy concept beyond the realm of traditional alloys that consist of at least five major metallic
elements and therefore have a huge number of possible compositions [3-11]. After a decades
research, HE alloys have been developed from various alloy compositions to give them
combinations of functional properties such as high hardness [7], work hardening capacity, wear
resistance [8], high-temperature softening resistance, anti-oxidation [9], anti-corrosion [10, 11],
and electrical resistance. These merits are found to originate from the tendency of HE alloys to
form simple nanostructured solid-solutions and the cocktail effect of these multi-element
mixtures [3, 12]. The special features of HE alloys could be listed as follows:
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.

The tendency to form simple FCC and BCC solid-solution phases with nanoscale or
even amorphous structures.
Hardnesses that range from 100 to 1100 Hv.
Deformation in FCC phases by a nano-twining mechanism.
Thermally stable microstructures.
Excellent resistance to temper softening.
High-temperature precipitation hardening between 600 and 1000 oC.
A positive temperature coefficient of strength, and hence maintain a high strength
level at elevated temperatures.
Can possess excellent corrosion resistance, wear resistance and oxidation resistance.
Can have a high electrical resistivity with a low or negative temperature coefficient.
Can have good high-frequency soft magnetic properties.
Potential of good thermoelectric properties.

By exploiting the special features listed above, HE alloys have been developed for numerous
industrial applications, which will now be reviewed.
2. THERMAL BARRIER COATINGS OF HIGH-ENTROPY ALLOYS

W. H. Wu

Nano-precipitated structures are rarely observed in conventional castings of traditional

alloys. A rapid solidification process or precipitation treatment is required to form
nanostructures in specific traditional alloys. On the contrary, HE alloys readily form
nano-precipitated structures, even in the as-cast state, due to the sluggish elemental diffusion [2,
5, 7]. During thermal spray deposition, the higher cooling rate allows HE alloys to easily form
supersaturated states [9]. For some thermally sprayed HE alloy coatings (table I), 5-20 nm
precipitates and structures with 50-100 nm grains were produced. It is noted from table I that the
thermal conductivities (K) of the HE alloy coatings, measured by the hot disk method, are 3.24
W/mK and 3.14W/mK, which are much lower than those of their as-cast bulk states. Since
phonons and electrons are the carriers in solid-state thermal conduction, their scattering by point
defects and boundaries are the main causes for a reduction in thermal conductivity. For HE
alloys, large mass and size differences are easy to obtain among the different atoms, and these
induce large phonon- and electron-point defect scattering. This results in HE alloys with low
thermal conductivities. Furthermore, the nano-sized grains and precipitates inside HE alloy
coatings provide a large amount of boundaries and interfaces that further retard the movement of
the heat-transferring phonons and electrons. Scattering by these different interactions is shown
schematically in figure 1. From table I, it can also be seen that the measured thermal
conductivity of commercial hot-mold steel SKD61, in its wrought form, is far higher than that of
the HE alloys. This suggests that HE alloy coatings are good candidates for the thermal
management of casting molds.
Table I. Thermal conductivities of HE alloys and SKD61 steel measured by the hot disk
method.
Material
Thermal conductivity (W/mK)

Bulk
Coating

HE alloy A
7.94
3.24

HE alloy B
6.69
3.14

SKD61
28

The casting of thin-gage and large-area castings requires molds of low thermal conduction to
keep the liquid hot and slow down solidification. Steel molds are thus limited in producing very
thin-gage and large-area castings, such as notebook and mobile-phone cases made of Al or Mg
alloys. Although this might be solved by high-speed injection, additional drawbacks arise, such
as more turbulence, more pores, and heavier erosion of the gating system. These defects might
result in a rejection rate of 50%. Thus, low-K HE alloy coatings present a potential solution to
this problem by reducing the overall heat transfer rate at the cavity surfaces of the molds.

W. H. Wu

.
Figure 1. Schematic diagram depicting the mechanisms that reduce thermal conductivity in HE
alloy coatings.
Table II reveals the results of die-casting tests under various press rates. It can be seen that
low-K HE alloy coatings significantly improve the filling ratio of magnesium alloy plates and
can improve the yield. By combining the low-K, good high-temperature hardness, wear
resistance and oxidation resistance of HE alloys, they appear to have potential use for other
high-temperature applications, such as turbines, burners, and reactors.
Table II. Filling tests of molds with and without HE alloy coatings
Mold condition
Without HE alloy coating
With HE alloys coating

Pressing rate

0.1 m/s

0.2 m/s

0.3 m/s

Plates (kg)

0.185

0.207

0.26

Filling ratio

70%

76%

95%

Plates (kg)
Filling ratio

0.265
96%

0.27
98%

0.275
100%

3. HARDFACING APPLICATIONS OF HIGH-ENTROPY ALLOYS

In order to protect the surface of machine components and tools, hardfacing technology can
be employed. In hardfacing a thick layer of wear and/or corrosion resistant material is welded,
thermal spray welded, or plasma arc welded to the surface. HE alloys are very suitable
candidates for hardfacing because of their high hardness, wear resistance, high-temperature
softening resistance, anti-corrosion, and combinations of the aforementioned properties. Some
HE alloys are now fabricated into rods and powders and then welded or thermally-sprayed onto
the surface of tools and other components. Additional high-temperature aging can be used to

W. H. Wu

enhance the hardness and wear resistance of the layers.

As well as the above, high-temperature age-hardening of AlCrX HE alloys can be exploited
to produce graded materials for surface protection, as illustrated in figure 2. This is
accomplished by heating the required area to a suitable temperature for an appropriate time. The
surface hardness (from Hv350 to Hv850) and the thickness can be controlled by the temperature
gradient and time period. As shown in figure 3, the wear resistances of two AlCrX HE alloys
that have undergone various treatments are better than the base line connected by several
conventional alloys. Oxidizing and nitriding treatments can further increase the wear resistance
by more than 100 times. Moreover, these alloys have better hot hardnesses than those of

Hardfacing
hardening,
Hardfaced layer
layer after
after aging
age hardening,
nitridizing
,
or
oxidizing
treatment:
>Hv800
nitriding or oxidizing
Base: Hv300~400

Figure 2. Schematic diagram showing a HE alloy graded mold with a hardfaced layer on the
mold-cavity surface.

Traditional alloys

Wear Rate (mm3/N.m)

1E-4

1E-5

AlCrX HE alloys
1E-6

Oxidation at high temperature

1E-7
200

300

400

500

600

Al-0.3 Casting, Homogenization, Quenching

Al-0.3 Casting, Homogenization, Air-cooling
Al-0.3 Casting, Homogenization, Furnace-cooling
Al-0.3 Forging, Homogenization, Air-cooling
Al-0.3 Forging, Homogenization, Furnace-cooling
Al-0.5 Casting
Al-0.3 600oC 50h Aging
Al-0.3 1100oC 2h Furnace-cooling, Oxidation
316 Stainless Steel
SKD61
SUJ2
SKH51

700

800

900

1000

Hardness (HV)
Figure 3. The comparison of wear-resistance and hardness of several HE alloys and traditional
alloys.

W. H. Wu

high-carbon steels and high speed steels. Through different combinations of process and surface
treatments, AlCrX alloys could be made more versatile in tool and mold applications.
Figure 4 is an example showing a cast-mold of AlCrX alloy that had been treated by age
hardening and oxidizing to give it a graded hardness. In a real forging test, it was found that the
mold showed negligible wear after forging 300 pieces of low-carbon steel rods at 1000oC. These
different hardfacing techniques using HE alloy may be applied to a wide range of components,
including golf club heads, walls of steel tubes, roller surfaces, knives, shafts, molds.

Figure 4. HE alloy graded mold (right side) and forgings (left side) of the forging test. No tear
cracks or wear were observed after forging 300 low-carbon steel rods at 1000oC.

4. HARD METALS USING HIGH-ENTROPY-ALLOY BINDERS

Hard metals, because of their excellent combinations of high hardness, wear-resistance,
toughness, and high-temperature stability [13], have been widely used in a lot of industrial
products, such as molds, tools and nozzles. Hard metals are classed as composites comprising of
binder metals, such as Fe, Co and Ni, and ceramic particles such as WC and TiC. For WC, Co is
the most common binder metal, whereas for TiC, Ni and Ni13Mo7 are the common binders.
Grain refiners such as VC, TaC are usually added to improve the strength and toughness of the
sintered hard metal by preventing coarsening of the carbide grains. Numerous compositions of
binder metals have been investigated and developed for grain refinement and to reduce costs.
HE alloys, designated as AlCoX and CoCrX, have potential to replace the conventional binders
in hard metals as they have low contents of the expensive cobalt and are composed of an FCC
phase that exhibits a better high-temperature strength than Co, Ni, or Ni13Mo7. It has been found
that the grain size of WC and TiC can be effectively reduced in the HE alloy binders after
liquid-phase sintering, even without the presence of grain refiners. Furthermore, the effective
grain refinement was found to lead to improvements in the hardness and wear resistance.
Figure 5 shows the comparison of the hot hardness between sintered WC-10%AlCoX,
WC-25%AlCoX, WC(2.5 m)-20%Co and WC(0.5 m)-9.5%Co. The 25%-AlCoX, alloy is

W. H. Wu

seen to have a higher hot hardness than that of 20%Co. This is attributed to the greater grain
refinement in the HE alloy binder and its higher hot hardness compared to Co. The higher
hardness at lower temperatures for WC(0.5 m)-9.5%Co alloy is through the use of smaller WC
grains, however, the difference in its hot hardness with the WC-10%AlCoX alloy at higher
temperatures is small, reflecting the higher hot hardness of the AlCoX HE alloy binder.

WC-25AlCoX
WC-10AlCoX
WC(2.5mm)-20% Co
WC(0.5mm)-9.5% Co

2000
1800
1600

Hardness HV30

1400
1200
1000
800
600
400
200
0
0

200

400

600

800

1000

Temperature( C)

Figure 5. Hot hardness as a function of temperature for WC-AlCoX and WC-Co hard metals
Table III displays the combination of superior hardness and fracture toughness of
WC-AlCoX compared to the other WC-Co hard metals which contain modifiers [14, 15].
Table III. Hardness and toughness of WC-AlCoX and WC-Co hard metals.
Composition

Hardness (Hv)

K1C (MNm-1.5)

Total crack length (m)

WC+10%AlCoX

1446

11.89

230

WC+10 (TiC,TaC,NbC)+11.5Co

1380

10.9

261

WC+31(TiC,TaC,NbC)+9Co

1560

8.1

535

Cermets employing AlCoX and CoCrX binders have also been found to exhibit superior
combinations of hardness and toughness to those of other cermets [16, 17], as shown in table IV.
In figure 6, the high-temperature softening resistances of TiC-AlCoX and TiC-CoCrX cermets
can also be seen to be better than the other TiC or WC hard metals [18, 19]. This is attributed to
the fact that HE alloy binders significantly inhibit TiC grain growth and inherently provide

W. H. Wu

better elevated-temperature strength. In summary, HE alloy binders have several advantages

over conventional binders in terms of low Co contents, lower cost, higher hardness, increased
toughness and improved high-temperature softening resistance. They therefore have potential to
be used commercially in components such as cutting knives, tools, press dies etc.

Table IV. Hardness and toughness of TiC-AlCoX, TiC-CoCrX and other non-HE alloy cermets.

composition
TiC+20%AlCoX
TiC+20%CoCrX
TiC+20%Ni
TiC+20%Ni
TiC+20%Ni13Mo7
TiC+20%Ni13Mo7
Commercial TiC-based cermet

Hardness (Hv)
193719
1876
137231
~1300
163918
~1430
168511

K1C (MNm-1.5)
8.80.1
9.0
11.80.3
~11.1
8.50.2
~11.8
9.10.1

TiC + 20% CoCrX

TiC + 20% AlCoX
TiC + 20% Ni
TiC + 20% (Ni,Mo)
WC + 9.5% Co
WC + 9.5% (60Co/20Ni/20Fe)
WC-based submicron hardmetal (0.5-0.83) mm
WC-based fine grain hardmetal (0.8-1.3) mm
WC + Co + 1.0% Ru

High-temperautre hardness of hardmetals

2000
1800
1600

Hardness (HV)

Total crack length (m)

562
518
222
237
510
231
458

1400
1200
1000
800
600
400
200
0

200

400

600

800

1000

Temperature ( C)

Figure 6. Hot hardness as a function of temperature for TiC-HE alloy, TiC non-HE alloy and
WC non-HE alloy hard metals.

W. H. Wu

5. ANTIBACTERIAL
COATINGS

AND

ELECTROMAGNETIC

INTERFERENCE

SHIELDING

Other functional characteristics of HE alloys that have been studied include their
electromagnetic and biochemistry properties. Table V illustrates the results of 4 different
bacteria antimicrobial tests on the surfaces of HE alloy coatings. Colony-forming units on HE
alloy coatings are seen to be considerably inhibited, and the antibacterial rates for all 4 different
bacteria exceed 99.999%. This indicates that the HE alloy coatings have efficient antibacterial
abilities. Thus, HE alloy coatings have potential to be applied to various daily appliances like
tableware, kitchenware etc. Accompanied with high hardness, wear-resistance, anti-oxidation,
and anti-corrosion, multifunctional HE alloy coatings will turn daily appliances into durable,
stable and germless products.
Table V. Antibacterial analyses of HE alloys.

Colony-forming
Colony-forming
Antimicrobial Antibacterial
unit of
Bacterium name
unit of sample
activity
rate (%)
comparison group
group after 24h
after 24h

S. aureus

2.1 x 106

< 10

5.32

>99.999

Escherichia coli

1.1 x 106

< 10

5.04

>99.999

Klebsiella
pneumoniae
Pseudomonas
aeruginosa

1.6 x 106

< 10

5.20

>99.999

1.9 x 107

< 10

6.28

>99.9999

How to efficiently suppress electromagnetic interference (EMI) has became a very important
issue in the rapidly developing field of electronics. It has been found that HE alloy coatings can
efficiently suppress electromagnetic interference (EMI), as shown in figure 7. The EMI
shielding efficiency of HE alloy coatings increases with the frequency of the electromagnetic
wave. Moreover, thicker HE alloy coatings have higher EMI shielding efficiency. At high
frequencies, above 1300MHz, the EMI shielding efficiency of 1 m-thick HE alloy coatings
meets the standard required for commercial applications. Therefore, through careful alloy design
and selected coating processes, HE alloys used to coat electronic products may have multiple
functions, such as, wear-resistance, anti-oxidation, anti-bacteria and EMI shielding.

W. H. Wu 10

Shielding Effectiveness (db)

35

EMI Analyses of HEA thin films

30

Qualified
25

~1 mm
100 nm
20

15

10
-200

200

400

600

800 1000 1200 1400 1600 1800 2000

Frequency (MHz)

Figure 7. EMI shielding efficiency as a function of frequency for HE alloy coatings of different
thicknesses.

6. CONCLUSIONS
By exploiting the special features of HE alloys, they can be designed and developed for
numerous commercial applications, including low-K thermal barriers, hardfacings, graded
materials, hard metals, antibacterial coatings, and EMI coatings. HE alloys exhibit a high
potential for huge commercial and industrial usage. For certain through future research and
development, HE alloys will find even more commercial applications.

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