Materials Characterization 187 (2022) 111856

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Materials Characterization
journal homepage: www.elsevier.com/locate/matchar

Review

Microstructure and properties of high entropy alloy reinforced titanium

matrix composites
Zhanwei Yuan a, *, Huan Liu a, Zhe Ma a, Xinkai Ma b, Kai Wang a, Xuemin Zhang a
a
School of Materials Science and Engineering, Chang'an University, Xi'an, Shaanxi 710064, China
b
Key Laboratory of Advanced Technologies of Materials, Ministry of Education China Southwest Jiaotong University, Chengdu 610031, China

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

Keywords: In this paper, CoCrFeNiMo0.2 high entropy alloy (HEA) particles reinforced titanium matrix composites were
Hot pressing sintering prepared by hot pressing sintering in the vacuum. The microstructure and composition of the composites at
Interface layer 700 ◦ C ~ 900 ◦ C were studied through X-ray diffraction (XRD), scanning electron microscopy (SEM), and
Titanium matrix composites
electron probe microanalysis (EPMA). Also, the mechanical properties of the composites were studied by
Mechanical properties
microhardness tester, nano-indentation and uniaxial compression experiment. The results show that the interface
layer of different thicknesses is formed between the particles and the matrix in the composites under different
sintering temperatures. At 700 ◦ C ~ 850 ◦ C, the mechanical properties of the composites increase with the in­
crease of temperature, which is related to the diffusion of HEA particles and the formation of the interface layer.
When the sintering temperature is 850 ◦ C, the hardness is 402.6 HV, the yield strength is 928.2 MPa, and the
compressive strength is 2032.6 MPa. However, the high entropy alloy particles have a greater degree of disso­
lution and diffusion at 900 ◦ C, the strengthening effect of the particles is weakened, so the mechanical properties
of the composites are correspondingly reduced.

1. Introduction
Based on the wear resistance and corrosion resistance of the original
titanium alloy, titanium matrix composites have the higher specific
strength, specific stiffness, and high-temperature resistance, so they
have an extensive application prospect in aerospace manufacturing,
vehicle engineering and other fields [1–5]. Particle reinforcement and
fiber reinforcement are common reinforcement methods of titanium
matrix composites. Compared with fiber reinforced titanium matrix
composites, particle reinforced titanium matrix composites have the
characteristics of material homogeneity, multiple synthesis methods,
and accessible processing technology [6,7]. The commonly used rein­
forcement particles are ceramic particles, such as SiC, TiB, TiC and
Si3N4, etc. Ceramic particle reinforced titanium matrix composites are
difficult to meet the service requirements of modern parts due to the
significant thermal expansion coefficient difference and weak interface
bonding ability between the particle and the matrix [8,9].
HEA, composed of five or more metal elements in approximately
equal atomic ratios, has become a hot spot in the field of materials sci­
ence research because of its excellent strength and plasticity [10,11].
Ceramic particles, metallic glass, and high entropy alloys are several
commonly used reinforcing particles. Compared with ceramic particles,
high entropy alloys have high strength and good plasticity, and the co­
efficient of thermal expansion between high entropy alloys and the
matrix is similar [12,13]. The metallurgical combination between the
high entropy alloy and the metal matrix forms the composites with the
core-shell structure, which is stronger than the composites reinforced by
ceramic particles [14]. Compared with metallic glass particles, high
entropy alloys have better thermal stability and will not change the
properties of the composites as the increase of preparation temperature
[15]. At present, some progress has been made in the research of high
entropy alloy reinforced metal matrix composites. Chen et al. [16] chose
AlCoNiCrFe particles with high strength and good plasticity as the
reinforcement particles, the yield strength of the composites increased
by more than 160%, and the elongation was up to 15%. Lu et al. [17]
prepared nanocrystalline CoNiFeAl0.4Ti0.6Cr0.5 into SiCp/7075Al com­
posites, the strength and plasticity of the composite were improved and
the grain of the matrix was refined. Tun et al. [18] used microwave
sintering and hot extrusion to prepare AlMgLiCuZn particles reinforced
magnesium matrix composites, the addition of HEA significantly

* Corresponding author.
E-mail address: yuanyekingfly@163.com (Z. Yuan).

https://doi.org/10.1016/j.matchar.2022.111856
Received 8 January 2022; Received in revised form 15 March 2022; Accepted 16 March 2022
Available online 21 March 2022
1044-5803/© 2022 Elsevier Inc. All rights reserved.
Z. Yuan et al.
improved the tensile and compressive strength of the composites and
slightly improved the compressive plasticity. Rahul et al. [19] studied
the effect of heat treatment temperature on Al0.5Si0.5FeCoNi particle
reinforced titanium matrix composites, new phases were generated in
the composites at 900 ◦ C, and it was speculated that the high entropy
alloy diffusion occurred in the titanium matrix due to the high heat
treatment temperature. The metallic glass reinforced aluminum matrix
composites with core-shell structure prepared by Guan et al. [20]
showed the strong interface bonding state during the stretching process,
and its tensile strength is higher than that of the same type of composite
made by other scholars. It can be seen that the transformation of the
combination of the strengthening phase and the matrix to form the
composite with the core-shell structure has a specific promoting effect
on the improvement of its mechanical properties. However, there are
few reports on using high entropy alloy particles as reinforcements to
manufacture titanium matrix composites.
According to the research on CoCrFeNiMo0.2 high entropy alloy by
related scholars [21,22], CoCrFeNiMo0.2 high entropy alloy is FCC
structure with high strength and good plasticity. In this paper, CoCr­
FeNiMo0.2 high entropy alloys are used as reinforcing particles, and pure
titanium as the matrix. The composites are prepared by hot pressing
sintering in the vacuum. The interface characteristics of composites at
different sintering temperatures are studied, and the influence of the
mechanical properties of composites at different sintering temperatures
is discussed.
2. Experimental
2.1. Samples preparation
There are using CoCrFeNiMo0.2 particles (20–45 μm) as the rein­
forcement and pure titanium powder (100 μm) as the matrix to prepare
CoCrFeNiMo0.2 HEA particles reinforced titanium matrix composites.
The CoCrFeNiMo0.2 HEA particles and pure titanium powder are placed
in a QM-3SP4 planetary ball mill and mixed until uniform under vac­
uum. The volume ratio of the high-entropy alloy powder and pure ti­
tanium is 7:93. The ball-to-mass ratio is 10:1, and the speed is 200 rpm.
The mixed powder was hot pressing sintering in vacuum at 700 ◦ C,
800 ◦ C, 850 ◦ C and 900 ◦ C respectively. The maximum pressure in the
sintering process was 140 MPa, the holding time was 1 h, and the vac­
uum degree is 2 × 10− 2 Pa.
2.2. Characterization of microstructure and mechanical properties
The microstructure of CoCrFeNiMo0.2 particles reinforced titanium
matrix composites observed by optical microscope (OM). The samples
prepared at different sintering temperatures were analyzed by X-ray
diffractometer (XRD). The element distribution results of high entropy
alloy particles and surrounding matrix were characterized by electron
probe microanalysis (EPMA).
The microhardness of CoCrFeNiMo0.2 particles reinforced titanium
matrix composites at different sintering temperatures was measured by
the HV-1000A microhardness tester. The experimental load is 500 g and
the pressure holding time is 10s. Select the sample surface center area
for multiple measurements (5 times), then analyze the hardness of the
composites. Nano-indentation technology was used to characterize the
mechanical properties of CoCrFeNiMo0.2 particle and titanium matrix in
the composites. The test is carried out at equal intervals step by step
along the direction of the reinforced particles to the matrix with a
spacing of 2 μm, and the load is 5000 μN. Uniaxial compression exper­
iments were carried out on CoCrFeNiMo0.2 particles reinforced titanium
matrix composites at room temperature. The size of the compressed
sample was the cylinder with a diameter of 5 mm and a height of 10 mm,
and the compression rate was 0.5 mm/min.
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Materials Characterization 187 (2022) 111856
3. Results and discussions
3.1. Microstructure
Fig. 1 shows the metallographic structure of CoCrFeNiMo0.2 particles
reinforced titanium matrix composites at different sintering tempera­
tures. Fig. 1 shows that the white CoCrFeNiMo0.2 particles are dispersed
in the composites, and the interface between the particles and the matrix
is well bonded without obvious pores and defects. Fig. 1(a) shows the
morphology of the composites at 700 ◦ C, the CoCrFeNiMo0.2 particles
are spherical. There is a straightforward interface between the particles
and the matrix, indicating that the particles do not diffuse significantly
during the sintering process. When the sintering temperature rises to
800 ◦ C, a thick diffusion layer is formed between the CoCrFeNiMo0.2
particles and the titanium matrix, and the particle shape becomes
irregular due to the diffusion of elements in CoCrFeNiMo0.2 particles at
high temperature. According to Fig. 1 (b) ~ (c), the thickness of the
diffusion layer gradually increases with the increase of sintering tem­
perature, and it is also found that the surface of CoCrFeNiMo0.2 particles
becomes uneven, This maybe related to the diffusion of CoCrFeNiMo0.2
particles when the sintering temperature is 900 ◦ C, as shown in Fig. 1(d),
the morphology of the CoCrFeNiMo0.2 particles in the composites is
quite different from the CoCrFeNiMo0.2 particles in the composites at
700 ◦ C, 800 ◦ C, and 850 ◦ C, the reason is that the higher temperature
causes severe dissolution and diffusion of HEA particles. The thickness of
the approximately circular particle interface in the composites were
measured at different temperatures. The thickness of the interface layer
at different sintering temperatures were 1.3 ± 0.1 μm (700 ◦ C), 4.5 ±
0.5 μm (800 ◦ C), 6.8 ± 0.8 μm (850 ◦ C) and 14.5 ± 0.2 μm (900 ◦ C),
respectively. The higher the temperature, the greater the interface
thickness. When the sintering temperature exceeds the α-β transition
point (882 ◦ C), the β‑titanium of the composites is transformed into
flake-shaped α‑titanium during the furnace cooling process, which can
be seen from the grain morphology of the titanium matrix in Fig. 1(d).
Fig. 2 shows the XRD patterns of pure titanium powders, mixed
powders and CoCrFeNiMo0.2 reinforced titanium matrix composites
under different sintering temperatures. It can be seen from Fig. 2(a) that
there are Ti phase and CoCrFeNiMo0.2 phase in the mixed powders. The
angle of the diffraction peak of the HEA is around 76◦ , and it has an FCC
structure. Compared with the XRD pattern of the mixed powder, the
composite material sintered at 700 ◦ C has new diffraction peaks at the
scanning angles of 43◦ and 50◦ , which is CoCrFeNiMo0.2. It can be seen
from Fig. 2(b) that the TiCr2 phase and the CrMo phase are present when
the CoCrFeNiMo0.2 reinforced titanium matrix composites are prepared
at high temperatures. The TiCr2 phase is obvious at 800 ◦ C and 850 ◦ C. It
is guessed that the formation of the TiCr2 phase is related to the diffusion
of CoCrFeNiMo0.2 HEA into the titanium and the construction of a
diffusion layer with a certain thickness. The diffraction peak of the phase
in the composites has a slight amplitude shift with the increase of
temperature, which may be caused by the lattice distortion of CoCrFe­
NiMo0.2 HEA particles diffusing into the titanium during the hot pressing
sintering process.
There are significant differences in the morphology of the composites
under different sintering temperatures. The CoCrFeNiMo0.2 HEA parti­
cles and surrounding matrix regions in the composites at different sin­
tering temperatures are selected for electron probe microanalysis. Fig. 3
shows the element distribution results of the composites at sintering
temperatures of 700 ◦ C, 800 ◦ C and 850 ◦ C. From the backscatter dia­
gram in Fig. 3(a), it can be seen that there are three phases in the
structure, the white ones are CoCrFeNiMo0.2 HEA particles, the gray
ones are the matrix, and the bright gray ones are the diffusion layer with
a certain thickness. The diffusion layer is composed of HEA elements and
titanium elements. The content of different CoCrFeNiMo0.2 HEA alloy
elements in the diffusion layer has certain differences, which is related
to the delayed diffusion effect of HEA and the different diffusion rates of
different elements. The three elements of Co, Fe, and Ni have diffused to
Z. Yuan et al. Materials Characterization 187 (2022) 111856

Fig. 1. Microstructure of composites at different sintering temperatures (a)700 ◦ C, (b)800 ◦ C, (c)850 ◦ C, (d)900 ◦ C.

Fig. 2. XRD patterns of Initial powder and composites.

a certain extent in the titanium matrix outside the area of the interface
layer. It is guessed that an intermetallic compound composed of Co, Fe,
and Ni is formed at the edge of the particle. Fig. 3(b) and (c) shows the
backscattering images and element distribution results of the composites
at the sintering temperature of 800 ◦ C and 850 ◦ C, it is found that the
thickness of the diffusion layer increases to a certain extent, and the
diffusion layer becomes an inner and outer layer. The inner layer of the
diffusion is composed of a large number of five elements of HEA and a
small amount of titanium. In contrast, the outer layer of the diffusion is
formed of a small amount of Cr, Mo and a large amount Ti. Compared
with the high-entropy alloy element distribution results at 700 ◦ C, the Cr
and Mo elements diffuse fully. When the temperature is above 800 ◦ C,
the content of Cr and Mo elements in the center of the particle is lower
than that near the diffusion layer, and the distribution of the other three
elements is exactly the opposite. Comparing the element distribution
results of the composite at different sintering temperatures, there is no
titanium element in the high-entropy alloy particle area, so the forma­
tion of the diffusion layer is due to a certain degree of unidirectional
diffusion of the CoCrFeNiMo0.2 HEA particles.
In order to analyze the specific composition of the diffusion layer at
different sintering temperatures, using the electron probe test the
chemical composition of the labeled points in Fig. 3, and the results are
shown in Table 1. At the sintering temperature of 700 ◦ C, it can be seen
from the distribution of elements at point A that the distribution of
CoCrFeNiMo0.2 elements in the particles is basically the same as before
sintering state. The content of Co, Fe and Ni at point B is higher than that

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Z. Yuan et al. Materials Characterization 187 (2022) 111856

Fig. 3. Element distribution of composites at different sintering temperatures (a)700 ◦ C, (b)800 ◦ C, (c)850 ◦ C.

of Cr and Mo, mainly because Co, Fe and Ni can stabilize FCC structure
in the solidification process of composites as FCC stabilizers [23].
Compared with the content of C, D, E and F, the content of high entropy
alloying elements decreases gradually near the matrix region. The
content of Cr and Mo in the diffusion layer is higher than that of Co, Fe,
and Ni. According to reference [22], with the heat treatment tempera­
ture increases from 700 ◦ C to 1000 ◦ C, compounds of Cr and Mo ele­
ments precipitate at the grain boundaries of CoCrFeNiMo0.2 particles,
and the content increases with the rises of heat treatment temperature,
which is at the interface layer in this article. The distribution results of
the elements are corroborated. According to the electron hole theory of
the alloy [24], Co and Mo are the key elements of the σ phase, because
they have a larger number of electrons and holes (Nv = 4.66) than most
transition elements, it is believed that the σ phase is generated in the
diffusion layer, so the content of Cr and Mo is higher.

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Z. Yuan et al. Materials Characterization 187 (2022) 111856

Fig. 3. (continued).

with the composites at the sintering temperature of 700 ◦ C, the hardness

Table 1
of the composites at 850 ◦ C is increased by 40%. It can be seen that the
Chemical composition of the composites (at.%).
production of the diffusion layer has a significant effect on the hardness
Regions Ti Co Cr Fe Ni Mo of the composites. Due to the severe element diffusion and interface
A 0.69 23.63 26.75 23.64 20.81 4.58 reaction between the HEA and the matrix in the diffusion layer, the hard
B 62.86 11.64 3.86 8.97 12.22 0.44 phase and solid solution generated in the diffusion layer increase the
C 35.71 5.60 38.89 11.70 2.56 5.51
hardness of the composites. As the thickness of the diffusion layer in­
D 46.98 4.04 34.74 8.39 2.19 3.66
E 24.79 9.46 38.39 15.73 4.82 6.81 creases, the hardness of the composites also increases. When the tem­
F 38.99 7.93 31.71 13.22 3.88 4.26 perature is 900 ◦ C, the hardness of the composites is significantly
reduced. It is guessed that the strengthening effect of CoCrFeNiMo0.2
particles at high temperature is weakened because of the greater degree
3.2. Analysis of mechanical properties of dissolution and diffusion, so the hardness of the composites is
reduced.
Fig. 4 shows the hardness distribution of the composites at different The nano-indentation test method is to apply a certain load on the
sintering temperatures. From Fig. 4 we can see that the hardness value of sample surface, then unload, and calculate the Young's modulus and
the composites at 850 ◦ C is the largest, which is 402.4 HV. Compared hardness of the material according to the load-indentation depth curve,
which is proposed by Oliver and Pharr [25], specifically:

(π)1/2 S 1 1 − v2 1 − v2i
Er = 1/2
, = + (1)
2β A Er E Ei

where S is the contact stiffness, S = dP dh∣h = hmax , Er is the equivalent

modulus of elasticity, Ei is the elastic modulus of the indenter, E is the
elastic modulus of the sample, vi is the Poisson's ratio of the indenter,
and v is the Poisson's ratio of the sample, β is the shape parameter of the
indenter. A is the contact area. The parameters of the intermediate head
in this paper are as follows: β=1.034，Ei=1141GPa and vi=0.07.
The contact depth is related to the maximum indentation depth. It
defined as:
Pmax
hc = hmax − hd = hmax − ε , A = 24.56h2C (2)
S

where hd is the elastic recovery depth, ε is the geometry parameter of the

indenter, Pmax is the maximum press-in load.
The ratio of the maximum indentation load to the contact area is
used to calculate the hardness:
Fig. 4. The microhardness of composites at different sintering temperatures.

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Z. Yuan et al. Materials Characterization 187 (2022) 111856

Pmax hardness of the CoCrFeNiMo0.2 particles. The outer composition of the

H= (3)
A diffusion layer is mostly Ti element and the closer to the matrix, the
Integrate Eqs. (1), (2) and (3) into formula (4), as follows: Young's modulus in the diffusion layer is reduced accordingly. With the
increase of temperature, the Young's modulus of the titanium matrix and
1 − v2 1 − v2 the CoCrFeNiMo0.2 particles in the composites is the same. Hence, the
E= ( )=( ) ( ) (4)
1− vi2 √̅̅̅̅̅̅̅
2 24.56
̅ 1− v2i increase of temperature only has an obvious effect on the Young's
(1 − Ei ) − √̅̅ hC −
Ei S π E
i modulus of the diffusion layer.
Fig. 7 shows calculation of the hardness of the composites according
The nano-indentation experiments were performed on areas with
to the p-h indentation curve, the hardness value of CoCrFeNiMo0.2
obvious interface characteristics between the particles and the matrix in
particles is close to matrix. The diffusion layer has the relatively highest
the composites at 700 ◦ C, 800 ◦ C, and 850 ◦ C respectively. The test load
hardness. The increase in the hardness of the diffusion layer may be
is 5000μN, and the indentation test is performed at equal intervals along
related to the following two aspects: (1) A large number of hard phases
the direction of the particle to the matrix with a test interval of 2 μm. The
rich in Cr and Mo elements are precipitated in the diffusion layer area. In
p-h curve obtained from the nano-indentation experiment is shown in
the analysis of the interface layer, it is believed that the σ phase is
Fig. 5. The indentation curve is relatively smooth at the sintering tem­
generated in the interface layer, which makes the content of Cr and Mo
perature of 700 ◦ C. When the sintering temperature is 800 ◦ C and 850 ◦ C,
elements higher. According to reference [21], the hardness of the σ
there is a displacement explosion in the indentation loading curve of the
phase is significantly higher than that of the FCC structure HEA. High
particle and the interface layer, and the indentation loading curve of the
mixing entropy can significantly reduce free energy, so random solid
matrix is relatively smooth. This is related to the existence of defects in
solutions are easier to form than intermetallic compounds or other or­
the particles caused by the inconsistent diffusion rate of the CoCrFe­
dered phases in the cooling and solidification process of multi-principal
NiMo0.2 elements and the certain roughness of the formed interface
alloys. The researchers added Ti to the high entropy alloy to creat
layer. It can be seen from Fig. 1 that the surface of the CoCrFeNiMo0.2
AlCoCrFeNiTix [26], CoCrFeMnNiTix [27], (CoCrFeMnNi)85Ti15 [28],
particles when the sintering temperature is 700 ◦ C is relatively smooth,
they found that the addition of Ti dramatically improves the hardness of
and the surface of the CoCrFeNiMo0.2 particles when the sintering
the composites. The reason is that Ti with a larger atomic radius oc­
temperature is 800 ◦ C and 850 ◦ C is relatively rough.
cupies the lattice position, the effect of solid solution strengthening in­
Fig. 6 shows the calculation of the Young's modulus of the compos­
creases significantly with the increase of lattice distortion energy.
ites according to the p-h indentation curves. The Young's modulus of
Fig. 8 shows the stress-strain curves of CoCrFeNiMo0.2 particles
CoCrFeNiMo0.2 particles is about 208 GPa. In Fig. 6(c), the Young's
reinforced titanium matrix composites under uniaxial compression at
modulus in the central area of the particle is 185 GPa. The Young's
700 ◦ C–900 ◦ C. As can be seen from the figure, the yield strength and
modulus near the edge of the particles are consistent with the Young's
compressive strength of the composite tend to rise first and then
modulus of the particles at 700 ◦ C. This may be related to the occurrence
decrease, and the plasticity decreases. The yield strength, tensile
of defects under the CoCrFeNiMo0.2 particles caused by the inconsistent
strength and maximum strain of the composites at different tempera­
diffusion rate of elements of CoCrFeNiMo0.2 when the sintering tem­
tures are shown in Table 2. The maximum yield strength and compres­
perature is 850 ◦ C. When the indentation moves to the interface, the
sive strength of the composites sintered at 850 ◦ C are 928.2 MPa and
inner composition of the diffusion layer is mainly composed of elements
2032.6 MPa. Compared with the composites prepared at 700 ◦ C, the
of CoCrFeNiMo0.2, and the Young's modulus is roughly the same as the

Fig. 5. The p-h curves of composites at different sintering temperatures (a)700 ◦ C, (b)800 ◦ C, (c)850 ◦ C.

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Z. Yuan et al. Materials Characterization 187 (2022) 111856

Fig. 6. Young's modulus of composites by indentation test at different sintering temperatures (a)700 ◦ C, (b)800 ◦ C, (c)850 ◦ C.

Fig. 7. Hardness of composites by indentation test at different sintering temperatures (a) 700 ◦ C, (b) 800 ◦ C, (c) 850 ◦ C.

yield strength and compressive strength of the composites at 800 ◦ C are matrix. The production of the diffusion layer makes the bonding mode
increased by 38.5% and 20.6%, respectively. This is mainly due to the between CoCrFeNiMo0.2 particles and titanium matrix in the composites
formation of the diffusion layer between the HEA particles and the changed from the bonding mode mainly based on weak mechanical

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Z. Yuan et al. Materials Characterization 187 (2022) 111856

motion. (5) Compared with the composites formed by mechanical

bonding between the particles and the matrix, the formation of the hard
diffusion layer between the high entropy alloy and the matrix signifi­
cantly improves the mechanical properties of the composites with the
core-shell structure.
Fig. 9 is schematic diagram of the formation process of the com­
posites from 700 ◦ C to 850 ◦ C. Compared with the composites at 700 ◦ C,
the composites at 850 ◦ C have a thinner inner interface layer and a
thicker outer interface layer. According to the results of elemental
analysis of the composites by electron microprobe, the inner interface
layer is mainly composed of HEA elements, and the outer interface layer
is mainly Ti element. The Cr and Mo elements diffuse sufficiently when
the temperature is above 800 ◦ C. The content of Cr and Mo appears to be
lower in the center of the particle than in the area near the diffusion
layer, which is exactly the opposite of the distribution of Co, Fe, and Ni.
According to the reference [20], the element distribution of Cr and Mo
are the same due to the same BCC crystal structure and similar electronic
configuration; the element distribution of Co, Fe and Ni are consistent
Fig. 8. Compressive stress-strain curves of composites at different sintering with their electronegativity similarity.
temperature. In addition, the bonding state between the CoCrFeNiMo0.2 particles
and the titanium matrix has changed at high temperatures. As shown in
Fig. 9, the interface between the CoCrFeNiMo0.2 particles and the tita­
Table 2
nium in the composites changes from a weak mechanical bond to a
Compressive mechanical properties of composites at different sintering
strong diffusion bond due to the formation of the diffusion layer. The
temperature.
strong bonding interface makes the interface of the composites have
Temperature Young's Yield Compressive Maximum good performance during the deformation process, to avoid damage and
(◦ C) modulus strength strength (MPa) strain (%)
(MPa) (MPa)
failure at the interface in advance. According to the results of the nano-
indentation experiment, the hardness and yield strength of the interface
700 C 16,630 670.1 1684.6 37.5
layer area have been significantly improved with the increase of the
◦

800 ◦
C 17,140 730.1 1864.1 37.2
850 ◦
C 22,270 928.2 2032.6 34.4
900 ◦
C 18,380 901.3 1845.1 29.7
bonding to the bonding mode mainly based on diffusion bonding. The
change of the bonding method can improve the bonding ability between
the CoCrFeNiMo0.2 particles and the titanium matrix, thus the strength
of composites is improved. The composites have higher density and
minimal porosity with the increase of temperature, and the strength of
the composites can be improved. When the temperature is 900 ◦ C, the
high sintering temperature causes CoCrFeNiMo0.2 particles to dissolve
and diffuse to a greater extent, which weakens the particle enhancement
effect and reduces the mechanical properties of the composites.
3.3. Discussion
According to the reference [29], the compressive strength of pure
titanium at room temperature is 880 MPa. Comparing the compressive
strength of the composites in Table 2, the addition of CoCrFeNiMo0.2
particles improves the mechanical properties of the composites. Com­
bined with the research of related scholars on the same type of high
entropy alloy reinforced metal matrix composites [30–32], the rein­
forcement mechanism of the composites in this paper is mainly reflected
in the following five aspects: (1) Fine grain strengthening. The grain size
of the composites is smaller than that of the matrix material without
CoCrFeNiMo0.2. The grain-refined composites can generate more grain
boundaries to accommodate plastic deformation. (2) Load transfer. High
entropy alloys have higher stiffness than titanium. When the load is
transferred from the matrix to the CoCrFeNiMo0.2, the load-bearing
capacity of the matrix is enhanced. (3) Orowan strengthening. The
presence of hard reinforcing particles (such as hard phases rich in Cr and
Mo elements) hinders dislocations, thereby greatly improving the
deformation resistance of the composites. (4) Solid solution strength­
ening. During the sintering process of the composites, high entropy el­
ements diffuse into the titanium matrix and distribute in the titanium
lattice, resulting in point defects. The interaction between solute ele­
ments and dislocations leads to a pinning effect that hinders dislocation
thickness of the diffusion layer. Comparing the mechanical properties of
the composites under the uniaxial compression experiment, it can be
seen that the performance of the interface layer affects the mechanical
properties of the composites.
To explore the relationship between the macroscopic and micro­
scopic properties of the composites, the Voigt model, Paul model, Reuss
model, Maxwell method, and P.G.klemens method are used to calculate
mechanical properties of the composites [33]. The mechanical proper­
ties of CoCrFeNiMo0.2 particles and titanium come from nano-
indentation experiments, and the mechanical parameters of the parti­
cles and the matrix are averaged. Fig. 10(a) shows the hardness of
composites calculated according to different mixing models. Except that
the hardness calculated by the Maxwell method decreases at 850 ◦ C, the
hardness of the composite materials calculated by the other four models
all increase with the increase of temperature. The hardness calculated by
Paul model and P.G.klemens method are almost the same. Compared
with the hardness measured by the microhardness tester in Fig. 4, the
hardness of composites calculated by the Reuss model is closer at
different temperatures. Fig. 10(b) shows the Young's modulus of com­
posites calculated according to different mixing models. The Young's
modulus under the above-mentioned different mixing models has a
maximum value at 700 ◦ C, and the relatively minimum value at 800 ◦ C.
This is inconsistent with the Young's modulus change rule at different
sintering temperatures obtained in Table 2. It may be because the
Young's modulus of the interface and the particle is averaged as the
Young's modulus of the particle in the calculation process, which un­
derestimates the ratio of the interface performance to the Young's
modulus of the composites. This may also be related to the fact that the
elastic modulus of the matrix is mainly the value close to the particles in
the nano-indentation experiment.
4. Conclusions
In this paper, CoCrFeNiMo0.2 particle reinforced titanium matrix
composites were prepared by hot pressing sintering in the vacuum,
drawing the following conclusion:

8
Z. Yuan et al. Materials Characterization 187 (2022) 111856

Fig. 9. Schematic diagram of the formation process of composites.

Fig. 10. Mechanical properties of composites based on hybrid calculation model at different sintering temperatures (a) Hardness, (b) Young's modulus.

(1) When the sintering temperature is 700 ◦ C, the CoCrFeNiMo0.2 Declaration of Competing Interest
particles are spherical. There is a clear interface between the
particles and the matrix, indicating that the particles do not The authors declare that they have no known competing financial
diffuse significantly during the sintering process. When the sin­ interests or personal relationships that will affect the reporting in this
tering temperature is 800 ◦ C and above, The CoCrFeNiMo0.2 article.
particles in the composites have evident diffusion phenomenon,
and the thickness of the diffusion layer increases with the rises of
Acknowledgement
the sintering temperature.
(2) With the increase of the sintering temperature from 700 ◦ C to
The authors are very grateful for the support received from Nature
850 ◦ C, the hardness and strength of the composite show a trend
Science Foundation of Shaanxi (No. 2021JQ-286), Key Research and
of first increasing and then decreasing. The composite has the
Development Plan in Shaanxi Province of China (No.2021GY-211), and
best mechanical properties when the sintering temperature is
Fundamental Research Funds for the Central Universities, CHD
850 ◦ C, the hardness is 402.6 HV, and the yield strength is 928.2
(No.300102311403). The authors acknowledge the financial support
MPa, the compressive strength is 2032.6 MPa.
from the 2020 Open Projects (No: KLATM202007) of Key Laboratory of
(3) The sintering temperature of the composite should not be too
Advanced Technologies of Materials, Ministry of Education China,
high. When the sintering temperature reaches 900 ◦ C, the CoCr­
Southwest Jiaotong University.
FeNiMo0.2 high entropy alloy has a greater degree of dissolution
and diffusion, which weakens the strengthening effect of the
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