Accepted Manuscript

Preparation and properties of medium entropy CoCrNi/boride metal matrix composite

Igor Moravcik, Larissa Gouvea, Jan Cupera, Ivo Dlouhy

PII: S0925-8388(18)31074-0
DOI: 10.1016/j.jallcom.2018.03.204
Reference: JALCOM 45434

To appear in: Journal of Alloys and Compounds

Received Date: 20 November 2017

Revised Date: 14 March 2018
Accepted Date: 15 March 2018

Please cite this article as: I. Moravcik, L. Gouvea, J. Cupera, I. Dlouhy, Preparation and properties of
medium entropy CoCrNi/boride metal matrix composite, Journal of Alloys and Compounds (2018), doi:
10.1016/j.jallcom.2018.03.204.

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Preparation and properties of medium entropy CoCrNi/boride metal matrix composite

Igor Moravcik, Larissa Gouvea, Jan Cupera, Ivo Dlouhy

Institute of Materials Science and Engineering, NETME Centre, Brno University of Technology,
Technicka 2896/2 Brno, Czech Republic

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Corresponding author: Igor Moravcik, Tel: +420 541 143 100; E-mail: moravcik@fme.vutbr.cz

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Abstract
The present work deals with synthesis, microstructural and mechanical properties’ evaluation of
a metal matrix composite, produced by a combination of mechanical alloying and spark plasma

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sintering utilizing FCC CoCrNi medium entropy alloy as the matrix phase, with dispersion of
Cr5B3 particles. Cr5B3 was formed in-situ, by the reaction of B4C, which was added to the
powders prior to mechanical alloying, during sintering with Cr element present in the powders.

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The composite exhibited excellent tensile strength level with Rm of 1432 MPa, tensile elongation
to fracture of 1.83 %, and elastic modulus of 226 GPa. Very fine dimple-like fracture morphology
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has been observed, despite the composite`s high strength properties.

Keywords: powder metallurgy, mechanical alloying, entropy, mechanical properties, metal

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matrix composites
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1 Introduction
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The class of metallic materials, possessing near equi-atomic compositions, designated as high
entropy alloys (HEA), has recently drawn significant attention of materials scientific community
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[1, 2]. These alloys became of great interest as a consequence of the novelty of their basic design
concept. They are composed of at least five elements with very close atomic proportions,
differentiating them from the traditional alloys, which usually comprise of single base element
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[3]. Apart only from fuelling the pure scientific curiosity to explore previously unanalysed
compositions, HEAs demonstrated a significant application’s potential as they exhibited a
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number of extraordinary features. Some of the most intriguing properties are (but are not limited
to): high fracture resistance at cryogenic temperatures [4], high tensile strength and ductility
combinations [5-8], good thermal stability [9, 10], high temperature strength [11, 12] etc.
A similar design approach of equi-atomic elemental proportions has been successfully applied to
the alloys containing only three to four elements that were named correspondingly as medium
entropy alloys (MEAs) [13-15].
Among the vast group of HEAs and MEAs bearing FCC microstructures, the single particular
alloy with CoCrNi composition is standing out, owing to the remarkable combination of fracture

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resistance and strength, both being positively increased with negative increase in temperature
[16]. The properties of this alloy surpassed that of extensively studied CoCrFeMnNi alloy [16].
In the last few years, the mechanistic aspects underlying the extraordinary performance of
CoCrNi alloy have been extensively studied [17-20]. It has been shown that the mechanical
properties are mostly governed by the formation of stress induced nano-twins (twinning induced
plasticity effect - TWIP) which increase the ability of the material to accommodate plastic strain,

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and thus delays the onset of plastic instability and postpones catastrophic failure [7, 21].
Recently, it has been demonstrated that deformation induced, displacive transformation of FCC
to HCP phase in CoCrNi alloy may take place as well, in addition to twinning [22].

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In our previous research, it has been demonstrated that the CoCrNi medium entropy alloy is
suitable as a matrix phase for metal matrix composites (MMC) [23], as well as its production
feasibility by powder metallurgy processes. The powder metallurgy processes possess certain

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advantages over the casting route, seen in the simplicity of composite materials manufacturing
and reduced grain sizes [23-25]. The idea of preparation of MMC based on CoCrNi composition
is associated to the attempt to improve high temperature strength properties, as well as wear

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resistance, of this alloy by the introduction of stable ceramic reinforcement.
In the light of previously mentioned evaluation, the presented work’s objective is the preparation
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of MMC with CoCrNi matrix and in-situ formed boride reinforcement, with the prospective use
of mechanical alloying (MA) and Spark Plasma Sintering (SPS) densification processes.
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2 Materials and methods

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Elemental powders of Co, Cr and Ni (composition of CoCrNi expressed in atomic ratio) with 7.5
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volume % of B4C were introduced into a, in-house made, tool steel milling bowl together with
mixture of 15 mm and 20 mm bearing steel milling balls with 10:1 total ball to powder weight
ratio. Elemental powders possessed industrial purity over 99 weight %. The most noticeable
impurity is recognized to be Al element, present in Cr elemental powder due to manufacturing
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procedure. The use of powders with higher purity was intentionally avoided to simulate more
accurately the conditions used in potential commercial applications. The 7.5 volume % of
ceramic reinforcement was chosen to obtain reasonable trade-off between increased strength
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properties and reasonable ductility, based on the previous authors experience with MMC. The
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properties of B4C, very low density of 2.52 g cm-3, high hardness of 3800 HV and elastic
modulus of 441 GPa predetermine it for the use as a reinforcement phase in MMCs, especially
considering its low CTE of 4.5 ×10-6 K-1 [26]. Upon introduction into metallic matrix of CoCrNi
(CTE of 17.4 ×10-6 K-1) it should produce significant strengthening upon cooling from processing
temperature due to stresses arising from high CTE mismatch. The milling was performed by
Pulverisette 6 planetary ball mill (Fritsch), into which the sealed milling bowl filled with a high
purity nitrogen atmosphere (6.0 – 99.9999%) for powder protection was inserted; speed of
250 revolutions per minute and milling time of 35 hours was applied. To remove the powder
stuck to the milling balls surfaces, toluene was further added and such wet milling has been

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performed for additional 15 minutes. The mechanically alloyed powders were, then, removed
from the milling bowl and dried in air. The consecutive densification has been performed in
Sumitomo Coal Mining, Dr. Sinter SPS machine in Central European Institute of Technology
(CEITEC). Graphite die with 30 mm inner diameter has been used. For an easy removal, graphite
foils were placed between the powders and die walls. The temperature of 950 ºC with 60 MPa
pressure and 10 minutes soaking time were used for the densification. Heating rate of 50 ºC min-1

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has been utilized. The resulting bulk specimen was approximately 6 mm high cylinder with 30
mm diameter.
Preparation of powder and bulk samples for microstructural observations was carried out by hot

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mounting in a polymeric resin. The samples were then mechanically ground with SiC emery
papers of different particles sizes down to 1200 grit size. Subsequently, the samples were
polished using diamond paste with 3 µm and 1 µm particle size. The last step of sample

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preparation was performed by mechano-chemical polishing, using Struers OPS suspension, to
obtain perfectly flat, scratch free surfaces.
X-ray diffraction analysis (XRD) of the materials phase composition was carried out using

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diffractometer Philips X´Pert Pro operated at 40 kV with Cu Kα. XRD patterns analysis was
performed in X´Pert High Score Plus software. The scanning electron microscope (SEM)
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characterization of whole set of materials was performed with Carl Zeiss Ultra Plus microscope
in secondary (SE) and backscattered electrons (BSE) mode respectively. Electron backscattered
diffraction (EBSD) mode and energy dispersive X-ray analysis (EDS) was used for the evaluation
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of grain lattices and chemical composition, respectively. For EBSD measurements, the reference
direction for inverse pole figures (IPF) is perpendicular to the pressing direction during SPS
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densification (as the texture was most likely to be formed in this direction). The same direction
corresponds to X0 axis in pole figures of Fig. 5b, with X0 and Y0 axis pointing perpendicular and
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parallel with respect to SPS pressing direction, respectively. Both axis perpendicular to pressing
direction (X0 and Z0) of Cartesian standard frame are equivalent, due to the spherical symmetry
of the produced cylindrical sample. The grain boundaries have been denoted for grain
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misorientation angles higher than 10°. The presented values of mean grain sizes and volume
fractions of respective phases have been taken as an average of measurement on three random
places. Image J software has been used for image analysis of residual porosity.
Measurement of Vickers hardness was carried out according to ISO 6507-1:2005, with LECO
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LM 274 AT hardness tester, with 0.3 kg load. The selected load was observed to be appropriate
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to measure the average mechanical properties of bulk with present phases within the fine grained
microstructure (average diagonal of the imprint 35 µm for determined hardness level). The
presented values are an average of at least 7 measurements. The tensile strength test was
performed using cylindrical 28 mm long sample having a gauge length of 12.5 mm, 3.5 mm in
diameter, tested with cross-head speed of 0.2 mm min-1 (i.e. strain rate of 0.25×10-4 according to
EN ISO 6892) on Instron 8801 testing machine at room temperature. The elongation was
measured directly on sample gauge length with clip-on extensometer. The sample was
manufactured by fine turning from rectangular block with dimensions of 6 × 6 × 28 mm cut from

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SPSed cylinder by electric discharge machining (EDM). The value of elastic modulus has been
calculated from the slope of elastic part of tensile curve.

3 Results

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3.1 CoCrNi / B4C composite powders
Powder particles morphology and microstructures used for bulk material preparation, in the state
after MA process, are presented in Fig. 1. Despite the use of elemental powders of Co, Cr and Ni,

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the MA powder particles exhibit good chemical homogeneity, as there is no visible black and
white contrast in the BSE SEM mode. In addition to this, there is no evidence of layered

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microstructure of present element in observed as well, due to perfect elements mixing during MA
processing.
The dispersion of B4C has been detected by the EDS measurement in the milled powder cross
section as well as small volume fraction of Cr oxides, denoted in Fig 1c, d by yellow and blue

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arrows. As compared to the original B4C powder (bearing of average particle size of 2 µm), the
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particle size after mechanical alloying has been severely reduced by the constant crushing of
powder particles by milling balls during MA. This is also visible from Fig. 2 b.
The XRD patterns presented in Fig. 2 a, b corresponds to blended and milled CoCrNi / B4C
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composite powder. While the pure elements and B4C are clearly distinguishable in the blended
powder, after the MA process, only broad peaks of FCC solid solution are visible. The same
phenomenon of FCC phase formation by element dissolution has been observed previously in the
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literature, with the peak broadening phenomena pertaining to decrease in size of crystallites by
plastic deformation during MA process [8, 27]. There may be other peaks present in the milled
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powder pattern, however, due to extreme deformation induced to the powders, the corresponding
phases are not recognizable as the background noise is significant. The peak-like formation at
approximately 33° of 2 theta angle may correspond to the peak of phase with extremely reduced
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crystallite size, but at the same time may be just a part of the background noise.
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Fig. 1 SEM micrographs CoCrNi / B4C mechanically alloyed powders a) powder morphology; b)
powder cross-section; c), d) powder cross-section details with denoted B4C and Cr-oxide particle
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by yellow and blue arrows, respectively.

3.2 CoCrNi / boride composite bulk

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The XRD pattern analysis of the CoCrNi / B4C alloy mechanically alloyed powder and bulk
SPSed material produced from the same powder are provided in Fig. 2 c. After the SPS
densification, the major FCC solid solution phase with lattice parameter of 3.57 Å was formed.
The peaks of the FCC phase are slightly shifted towards higher angles and much sharper than
peaks of FCC in the milled powder. This fact contemplates to slight change in FCC phase lattice
parameter and increased average crystallite size respectively, after SPS densification as compared
to FCC phase detected in milled powders. Surprisingly, no traces of added B4C phase, that was
observed in the milled powders prior to SPS densification, were detected in the pattern of bulk
materials (Fig. 2c). Instead, the peaks of second most dominant phase were attributed to
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tetragonal Cr5B3 boride phase with lattice parameter a = 5.39 Å and c = 10.17 Å. It seems that the
thermodynamic stability of B4C phase in CoCrNi matrix was not sufficient, as upon high
temperature sintering, boron reacted with Chromium to form previously mentioned boride. As
B4C transformed to Cr5B3, these materials will be further referred to as CoCrNi / boride
composite. The volume fractions of FCC and Cr5B3 boride phase calculated from diffraction
pattern are 83 % and 12.4 %, respectively. There are additional peaks in the pattern conforming

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to the rest 4 % fraction of the microstructure, that correspond mostly to chromium carbides of
Cr7C3 and Cr3C2 stoichiometry and chromium oxide phases. However, as they were impossible to
precisely characterize due to their complexity and relatively small fraction on the interstice of

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detectability by XRD, they will be referred to as carbide and oxide phases.

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Fig. 2 XRD pattern of a) CoCrNi / B4C blended powder; b) CoCrNi / B4C mechanically alloyed
powder; c) sintered bulk composite.

The chemical composition of the alloy is presented in Fig.3. The ratio of the elements of Co, Cr
and Ni is very close to 1:1:1, as desired. It can be seen on the obtained EDS pattern that the bulk
material also contains significant amounts of C and B. However, due to the very problematic
determination of true C and B concentration given by the nature of the EDS method, the
presented results should be taken only as a proof of B and C presence. The presence of hard

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ceramic particles of B4C most probably induced wear of steel milling media and milling bowl –
hence the reason why elevated concentration of Fe was detected, even though it was not
intentionally added to the milling bowl, prior to start of MA. The Al peaks and its concentration
present in the EDS spectra originate from a trace amount of Al present in used Cr elemental
powder. However, due to its significantly low concentration, no significant phase changes should
be imposed to the microstructure.

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Fig. 3 Chemical composition of CoCrNi / boride bulk alloy measured by SEM EDS. Due to the
nature of the method, the amounts of B and C are only for reference.
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Fig. 4 depicts the representative microstructures of the CoCrNi / boride composite. The
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microstructure is not completely porous free. However, the size of the pores is rather small and
their volume very low; less than 1 volume % was measured by image analysis. In addition to that,
pore shape is rounded, therefore the pores should not present a sites of high stress concentration,
i.e. they should not impede the material`s ductility decidedly. The microstructure is composed of
FCC phase grains, with dispersed Cr5B3 boride. Additionally, the black dots (denoted by green
arrow) located on the grain boundaries of all phases were determined to be carbides and oxides.
The results correlate perfectly with previously presented XRD patterns results. Oxides containing
mostly Cr element (as presented by EDS measurement of such particle in Fig. 5d) have been

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formed as a consequence of powder contamination by oxygen – a phenomenon common to PM

production methods.
The carbides appear in the microstructure due to the reaction of remaining C from B4C with
chromium, i.e. the free C atoms previously contained within B4C also reacted with Cr, forming a
Cr carbide phase, as a consequence of Cr is the strongest carbide former among the present
elements. However, as the amount of C in B4C is 4 times lower compared to B, the amount of

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formed carbides is relatively smaller, especially considering that the available carbon for carbide
forming reaction may have been also reduced due to dissolution of carbon in FCC and Cr5B3
phases. The presence of additional nitrides, that may have formed as a consequence of the

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utilization of nitrogen as a protective atmosphere has not been detected i.e. the atmosphere was
inert. The grain size of the major phases present in the microstructure is extremely small, as seen
from Fig. 4 c. For quantitative evaluation of the microstructure, EBSD measurement has been

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performed with results concerning the phase distribution, orientation and grain sizes, which are
presented together in Fig. 5. Average grain size of FCC phase and Cr5B3 phase is 0.77 and 0.46
µm in diameter respectively, as measured by EBSD. It is undoubtedly a consequence of the

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utilized rapid densification by SPS of the severely plastically deformed mechanically alloyed
powders. The grain growth of FCC phase was additionally significantly impeded by present
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dispersed borides as well as carbides and oxides, by pinning of the traveling grain boundaries.
The grains of both phases do not exhibit any type of preferential crystallographic orientation (as
seen from Fig. 5a and b) in spite of the uniaxial nature of applied pressure during SPS. The grains
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of the Cr5B3 are located on the boundaries of the FCC grains and compose approximately 11 % of
the microstructure (area fraction of Cr5B3 as measured by EBSD). Even though only 7.5 volume
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% of B4C was added, the reaction with Cr caused the total volume of formed Cr5B3 to be higher
than 7.5 %. Due to the resolution constraints of SEM EBSD measurement, the carbides and oxide
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phases are not present in Fig. 5.

The comprehensive analysis of boride phase by SEM, presented in Fig. 6, reveals the boride
phase perfectly matches the Cr5B3 phase that was already observed in XRD patterns. The Kikuchi
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diffraction patterns measured from the particle in Fig. 6b closely matches the pattern of tetragonal
Cr5B3 from the database, while the chemical compositions measured by point EDS and the
calculated one in Fig. 6c, are almost identical. It seems some amount of Co and Ni elements is
also dissolved in Cr5B3 phase, or the volume of the particle was too small for the resolution of
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EDS method, which caused the signal pick up from surrounding FCC grains.
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Fig. 4 a), b), c) SEM micrographs in BSE mode of CoCrNi/boride bulk composite showing FCC
grains denoted by yellow arrow, Cr5B3 boride particles denoted by red arrow and oxides by green
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arrow respectively d) EDS pattern of the oxide particle denoted by green arrow revealing high O
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and Cr concentration.

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Fig. 5 Representative SEM EBSD measurement results a) inverse pole figure

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orientation map, with X axis as reference direction, perpendicular to SPS pressing direction -
FCC grain boundaries denoted by black lines; b) pole figures of FCC and Cr5B3 phases; c) phase
map showing distribution of Cr5B3 boride particles in FCC matrix; d) grain size distribution of
respective phases with average grain size and volume fraction.

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Fig. 6 analysis of Cr5B3 particle a) SEM micrographs with particle denoted by yellow arrow; b)
corresponding electron diffraction pattern matching tetragonal Cr5B3 reflections; c) EDS point
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microanalysis (B content only for reference).

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3.3 Mechanical properties of CoCrNi / boride composite

The hardness value obtained by Vickers test was found to be 467 ± 21 HV0.3. The ultimate
tensile strength (Rm) of the composite was measured at room temperature on one sample, due to
the relatively limited volume of the produced material. The evaluation of results is presented in
Table 1 and Fig. 7, respectively, and are also compared to previous results [18,23] of CoCrNi

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alloy produced by same route (combination of MA and SPS) with average grain size of 4 µm and
cast alloy after high pressure torsion (HPT) and annealing with average grain size of 0.29 µm.
The presence of refined grain size and ceramic particles dispersion resulted in the dramatic

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increase of tensile strength properties, as compared to pure powder metallurgy CoCrNi alloy
from [23], as the values of both yield strength Rp0.2 and ultimate tensile strength Rm are surpassing

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1400 MPa, while the ductility is severely reduced. However, very low strain hardening is also
observed with the difference in the measured values of Rp0.2 and Rm reaches 7 MPa only. The
values of the tensile stress are decreasing after they reach the Rm value – which may look like the

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presented Rm is only distinguishable yield point. However, this yield point effect occurred
probably due the onset of cracking instantly after Rm as consequence of crack initiation and its
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rapid propagation. The total elongation value reached 1.86 % as a consequence of the pronounced
strengthening by the present boride phase, as well as carbides and oxides.
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Fig. 7 Stress – strain curves from tensile test of CoCrNi / boride composite and pure CoCrNi
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alloys at room temperature.

Table 1 Tensile properties of CoCrNi / boride composite in comparison with pure CrCrNi alloys.
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Elastic
Rp0.2 Rm Elongation to Reduction in
modulus E Ref.
(MPa) (MPa) fracture At (%) area Z (%)
(GPa)
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1425 1432 226 1.86 3.9 This study

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993 1100 - 20 - [18]

652 1024 222 26 22 [23]

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The results of fractographic analysis of the broken tensile test specimen are presented in Fig. 8.
Fracture was initiated on the relatively large, brittle particle (as compared to the rest of
microstructural features). The EDS analysis revealed that the particle is composed almost solely
of pure Cr element. Most probably, some small amount of Cr particles have not been milled, thus
remaining in the microstructure, despite the fact that powders were controlled for sufficient
homogeneity. Such unfractured particle was not observed previously in the milled powders

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microstructure prior to SPS densification, as the area controlled by SEM was relatively small
compared to the bulk sample volume. It is presumable that the absence of this inclusion could
slightly increase the ductility of the composite. To prevent appearance of such inclusions, the

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milling time of the MA process will be increased in future investigation. Apart from the crack
initiating inclusion, the morphology of the fracture surface is a mixture of ductile and brittle
fracture behaviour. The surface is composed of very fine ductile dimples, formed by adjacent

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microvoids’ coalescence, but without visible inclusions and/or other particles present at the
dimple bottoms. However, the fracture surface contains ridges retracting towards the fracture
initiation site, i.e. morphology typical for brittle fracture behaviour. In general, considering the

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low value of ductility at tensile loading, the fracture should be referred to as generally brittle,
with transgranular nature, often called low energy tearing.
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Fig. 8 SEM micrographs of fracture surfaces of CoCrNi / boride composite tensile specimen a)
fracture surface overview with crack initiation site denoted by yellow arrow; b) image of
initiation site; c) image of area denoted by yellow rectangle of initiation particle interface; d)
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typical fracture surface morphology with fine ductile dimples.

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4 Discussion

The use of MA process, coupled with rapid densification by SPS, yielded powder and bulk
materials respectively, with severely reduced grain sizes. The grain size reduction is attributed to
the plastic deformation of the powder during the MA process, imposed by the repeated impacts of
the steel milling balls [28]. In this manner, the mechanical milling presents one of the most

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promising severe plastic deformation (SPD) technologies for the production of advanced
materials with reduced grain size, especially regarded for its simplicity [29]. It should be noted

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that, the B4C particle size was also decreased by powder crushing during high energy milling
process – during preparation of the CoCrNi/B4C composite powder.
Severely reduced crystallite size of the powders resulted in the formation of extremely grain

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refined microstructure after SPS densification, which were enabled by the relatively low selected
sintering temperature of 950 ºC, as compared to traditional sintering [35][23][30]. The lower
processing temperature and introduction of boride and oxide particles resulted in decrease of FCC

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phase grain size, as compared to pure CoCrNi alloy produced by the same route in last research
report of the authors [23]. However, it is worth noting that the direct comparison of sintering
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temperature for SPS process between different studies may be sometimes slightly misleading.
The methodology of the temperature measurement may be changing with different SPS machine
manufacturer, and it is largely dependent also on factor such as die dimension and geometry, the
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type of used thermocouple, etc.

The B4C particles introduced to the milling bowl with elemental powders have remained stable
during the MA process. However, the presence of B4C particles in the CoCrNi alloy resulted in
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an in-situ reaction during sintering process, forming Cr5B3 boride phase due to increased
diffusion kinetics at high temperature exposure. This phenomenon seems interesting, since one
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would expect B4C ceramic phase to be very stable in the metallic matrixes. The result can be
explained by the calculation of enthalpy of formation change ∆Hf (calculated by Miedema`s
thermodynamic model from [31, 32]). The ∆Hf for B4C is 46.5 kJ mol-1 while the value for Cr5B3
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is 186.3 kJ mol-1. Since in general, more negative value of ∆Hf corresponds to higher phase
stability by decreasing free energy of the system [33], the formation of Cr5B3 is evidently more
thermodynamically favourable. The reaction in the solid state was additionally supported by the
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preceding severe mechanical activation of the powder blends during mechanical alloying process,
which severely suppresses the activation energy needed for the start of boride forming reaction.
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During sintering process, the original B4C completely reacted as its traces have not been found in
bulk materials. Considering the later preposition, it is possible to calculate the upper volume
fraction of formed Cr5B3. The calculation was performed with consideration of retaining the same
amounts of the present elements, with B being completely bonded to Cr, and tabulated density of
Cr5B3 - 9.93 g.cm3.The rest of the microstructure was assumed to be base FCC phase partially
depleted by Cr (as part of Cr atoms was partially bonded to B) and enriched by C, with density
approximated by the rule of mixture to be 8.41 g.cm3. The calculated fraction is 14.6%, which
correlates relatively well with the determined fraction of 11 volume % by EBSD and 12.4 % by

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XRD. The slight discrepancy is most probably associated with the fact that part of present boron
may be dissolved in the FCC phase (as B and C atoms possess relatively small atomic sizes, some
extent of solubility in solid solution phase is expected). The remaining C atoms of original B4C
additionally formed chromium carbide phase. The oxide phases present in the milled powders
due to oxygen contamination remained in the bulk material accordingly, pertaining to their high
characteristically thermal stability.

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The presence of hard particles of in-situ formed Cr5B3 boride as well as carbides and oxides
caused significant increase in the ultimate tensile strength and hardness of PM CoCrNi / boride
composite, as compared to previous studies [16, 23, 34]. However, the increase in strength has

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been accompanied by notably decreased total tensile elongation to 1.86 %. Nevertheless, the
mechanical performance of presented composite is still imposing, especially compared to
comparable materials produced by combination of MA and SPS, which, on occasion, does not

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even possess sufficient ductility to perform credible tensile test [27, 35, 36]. It may be theorized
that a higher level of strength of composite microstructure should be maintained also in the
elevated and high temperature range, due to dislocation and grain boundary pinning by

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precipitated stable ceramic particles, i.e. similar as in boride reinforced, titanium matrix
composites, exhibiting increased creep resistance [12, 37, 38]. This assumption is seen as the
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main advantage of the CoCrNi/Boride composite as compared to highly ductile pure CoCrNi
single phase alloys, and it became a central part of our future investigation on this system. The
high strength of presented composite is generated by the concurrent manifestation of several
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strengthening phenomena. The extremely reduced average grain size of the composite, inherited
from the severely plastically deformed MA powders, have caused pronounced effect of grain
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boundary strengthening [39]. The presence of hard borides and carbides resulted directly in the
increase of strength by dislocation motion suppression (as they represent formidable obstacles for
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dislocation glide), by introduction of residual stresses due to CTE and elastic moduli (EM)
mismatch and indirectly by grain boundary pinning effect, i.e. Zener strengthening induced by
grain growth decrease during sintering [10]. As the interface between boride particles and FCC
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phase seems to be strong (as explained later in discussion), the contribution of load-transfer
strengthening should be considered as well [41, 42].
The analysis of fracture surfaces of broken tensile test specimen demonstrated that the interface
between the boride reinforcement and the matrix FCC phase exhibited very high bonding
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strength, as no direct interfacial decohesion has been observed in fracture surfaces.

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This explanation is supported by the absence of hard boride particles or other ceramic particles in
the bottoms of the fracture dimples. The presumed void fracture mechanism in the composite is
depicted in Fig. 9. The dimples formed predominantly at places possessing the highest stress
triaxiality (grain boundaries, intersection of slip systems, etc.) by ductile tearing of FCC phase,
i.e. not by FCC / boride interphase boundary decohesion. Presumably, the dimples had nucleated
and subsequently grew between narrowly spaced angular boride particles by matrix voiding
microprocess (displayed in inset of Fig. 9), same as previously observed in [43]. At such
locations, the local stress raised by the angular edges of boride particles, acting as stress
concentrators, prevails over the cohesive strength of the FCC phase and new free surface, in the
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form of void, is created. In this manner, transgranular fracture occurred throughout fine FCC
grains. Therefore, it is interesting to note that despite relatively high ceramic loading, the fracture
process is governed by the plastic deformation of the matrix (CoCrNi) FCC phase.
The strength of the plastic FCC phase appears to be lower than cohesive strength of the
interphase boundary between boride and FCC phase. Therefore, the interphase boundary between
in-situ formed Cr5B3 borides must be inherently strong, which is one of the basic requirements for

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ductile composites with high ceramic loadings [44]. It should be noted that, in the present study,
the fracture process was initiated on brittle Cr inclusion particle. To avoid such inclusions and
further improve properties, a simple increase in the milling time could be applied in the future

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preparation.

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Fig. 9 Mechanism of transgranular crack formation in CoCrNi / boride composite by adjacent

microvoids coalescence on the crack tip in FCC matrix phase induced by stress concentration
between rounded boride corners.
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The presented results raise the question concerning the effectivity of production of the medium
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entropy alloy / boride in-situ composite. It has been widely accepted that HEAs and MEAs are
promising materials for the employment as matrix phase [44-46]. However, the formation of in-
situ boride phase by reaction of Cr with B4C is more disputable. It may seem that, it would be
more efficient to produce boride reinforced composite by conventional, ex-situ route, i.e. by the
boride reinforcement phase directly introduced to melted metal matrix and it would not transform
during manufacturing process. However, in-situ composites can be more cost effective and
deliver higher mechanical strength, particularly at relatively higher operating temperature [47].

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This is usually attributed to better mechanical bonding between matrix and reinforcement. The
presented results from this contribution are in good agreement with this claim.
Another aspect is the use of B4C phase as a precursor phase for boride formation. It is more usual
to either use precursor pure elements, or oxides, to fuel reinforcement forming reactions [46]. The
utilization of pure B as a precursor for boride formation is however limited by its extremely high
price, while the use of cheap boron oxide (e.g. B2O3) is associated with appearance of significant

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amount of undesirable oxide phases [47, 48], sometimes surpassing the total volume of boride
reinforcement (given by stoichiometry of boron oxide ).
B4C is relatively cheap and it has been already successfully utilized as a precursor phase for the

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production of TiB2/TiC HEA coatings [49] as well as bulk materials [48, 50]. Therefore, its use
as a raw material is sufficiently justified. As such, the production of boride reinforcement by
decomposition of B4C should be in theory achievable in any metallic matrix containing

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corresponding fraction of element with high boron chemical affinity.

5 Conclusions
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The preparation of in-situ CoCrNi / boride composite by a combination of mechanical alloying
and spark plasma sintering has been carried out, with subsequent microstructural and mechanical
properties’ characterization. The conclusions are drawn as follows:
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• Metal matrix composites with extremely fine grain size may be readily prepared by the
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combination of mechanical alloying and spark plasma sintering;

• B4C ceramic phase exhibited significant instability during high temperature sintering in
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Cr- rich metal matrix;

• The introduction of B4C resulted in the in-situ solid state reaction during sintering,
producing 11 volume % of Cr5B3 boride phase;
•
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The CoCrNi/boride in-situ composite possessed high strength values, surpassing ultimate
tensile strength Rm of 1400 MPa and tensile elongation of 1.86 %;
• Ductile dimples have been observed on fracture surfaces;
•
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Cr5B3 boride reinforcement and FCC CoCrNi matrix phase exhibited especially high
interfacial strength.
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Acknowledgments
The research was co-funded by the Ministry of Education, Youth and Sports within the „National
Sustainability Programme I” (NETME CENTRE PLUS - LO1202). Authors would also like to
thank Dr. David Salomon and Hua Tan, MSc. from CEITEC for their help with the SPS sample’s
densification experiments. The presented results have been obtained within the PhD. thesis
project of the corresponding author [51].

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Research highlights

Preparation and properties of medium entropy CoCrNi/boride metal matrix composite

• CoCrNi medium entropy alloy metal matrix composite has been produced for the first
time

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• Valid tensile test has been performed on material produced by mechanical alloying and
spark plasma sintering
• the composite exhibited excellent tensile strength over 1400MPa with 1.86 % total

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elongation
• ductile fracture mode with dimple morphology has been observed on fracture surfaces

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