Manufacturing Letters 36 (2023) 46–51

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Manufacturing Letters
journal homepage: www.elsevier.com/locate/mfglet

Letters

Multi principal element alloy particle reinforced metal matrix

composites: Synthesis, microstructure, and mechanical aspects
Nadeem Fayaz Lone a, Dhruv Bajaj a, Namrata Gangil b, Touseef Khan a, Mustufa Haider Abidi c,⇑,
Abdulrahman Al-Ahmari c, Arshad Noor Siddiquee a,⇑
a
Department of Mechanical Engineering, Jamia Millia Islamia, New Delhi 110025, India
b
Department of Mechanical Engineering, Ajay Kumar Garg Engineering College, Ghaziabad, Uttar Pradesh 201009, India
c
Raytheon Chair for Systems Engineering, Advanced Manufacturing Institute, King Saud University, Riyadh 11421, Saudi Arabia

a r t i c l e i n f o a b s t r a c t

Article history: The industrial usage of multi principal element alloys (MPEAs) is rare due to manufacturing constraints.
Received 4 November 2022 This gap was bridged by manufacturing single-step MPEA particles reinforced composite via friction stir
Received in revised form 29 December 2022 processing (FSP) of NiTi and Fe powders with Cu base metal, using WC tool at rotational and traverse
Accepted 12 February 2023
speeds of 560 rpm and 16 mm/min, respectively. Ultra-refined Cu matrix, having average grain size
Available online 13 March 2023
of
2.7 lm, containing uniformly decorated MPEAs was obtained. Microhardness of composite was
175HV, marking enhancement of 59% from base metal. The application of FSP for formation of MPEA par-
Keywords:
ticles having configurational entropy of medium entropy alloys (1R < DSmix < 1:5R) is novel.
Metal matrix composites
Multi principal element alloys
Ó 2023 Society of Manufacturing Engineers (SME). Published by Elsevier Ltd. All rights reserved.
Friction stir processing
Medium entropy alloys

1. Introduction
The industrial production of Medium and High Entropy Alloys
(MEAs/HEAs) remains dependent on casting, powder metallurgy,
and laser/wire arc additive manufacturing. Intricacies of the cast-
ing route involve macro-segregation and micro-segregation which
necessitate several rounds of homogenization treatment [1]. Since
industrial cooling rates are higher than those required for equilib-
rium solidification, segregation escalates during bulk production.
Moreover, even if heat treatment processes are necessary to elim-
inate micro-segregation, high solidification process control is
required to curtail macro-segregation [2]. Alternatively, powder
metallurgy is susceptible to media/atmospheric contamination,
microstructural alterations due to sintering temperatures, and con-
sumes enormous energy [3]. Mechanical alloying often produces
metastable alloys, which require annealing for long durations to
confirm that equilibrium states have been reached.
To provide mechanically superior materials in sustainable man-
ner, a conjoined effort is needed from the manufacturing and
materials engineers. This is necessary amidst the rising heat waves
and energy crisis across the globe. The aforementioned production
routes for multi-principal element materials have only been suit-
⇑ Corresponding authors.
E-mail addresses: mabidi@ksu.edu.sa (M.H. Abidi), arshadnsiddiqui@gmail.com
(A.N. Siddiquee).
able for research purposes since the corresponding power intake
is humongous. The synthesis of MEA and HEA particles reinforced
metal matrix composites can perhaps suffice the need for large-
scale production of MEAs and HEAs. Further, the utilization of
energy efficient technologies such as Friction Stir Processing
(FSP) to do so can serve tremendously towards the design of next
generation composites in an ecological fashion. The advancements
in friction stir welding and processing have enabled the processing
of more than 14 mm thick sections of base materials [4], which can
be innovatively combined with multi pass FSP for fabrication of
relatively large solids of MEA/HEA reinforced metal matrix com-
posites [5].
FSP has proven effective to reengineer the microstructure of
HEAs. For instance, Nene et al. [6] decreased the grain size and
increased the volume fraction of FCC phase in Fe50Mn30Co10Cr10
alloy through FSP. Such ‘Friction Stir Engineering’ (FSE) allows vast
compositional heterogeneity to append the functional behaviour,
simultaneously providing steep plastic strain gradient to actualize
grain size, morphological and phase heterogeneities. Wang et al.
[7] added Al powders to Al0.1CoCrFeNi through FSE to synthesize
a novel bimodal heterogenous HEA. Friction stir gradient additions
of Cu [8], Ti [9] and V [10] have also been reported to tune the HEA
microstructures for phase transformation and deformation mecha-
nisms. The addition of HEA particles via FSP is also observed to ran-
domize grain orientation and induce particle simulated nucleation
in AA5083 alloy [11]. The HEA particle reinforced Al matrix

https://doi.org/10.1016/j.mfglet.2023.02.001
2213-8463/Ó 2023 Society of Manufacturing Engineers (SME). Published by Elsevier Ltd. All rights reserved.
N.F. Lone, D. Bajaj, N. Gangil et al.
composite exhibited a yield strength improvement of 25.1 %. Li
et al. [12] also incorporated AlCoCrFeNi powders into AA5083 alloy
matrix and reported interfacial diffusion along with 56 % enhance-
ment in hardness. Pertinently, Al3CoCrFeNi was found on the inter-
facial region, rather than the intermetallic phases. Crucially, FSE
temperatures are intermediate between casting and mechanical
alloying, which obviates the micro-segregation and macro-
segregation predominant through casting; simultaneously elimi-
nating the need for assessing high temperature stability, as
required through powder metallurgy.
Although few studies have reported FSE of pre-existing MEAs/
HEAs, their in-situ formation through this route by using pure met-
als or binary alloys has not yet been witnessed. The in-situ synthe-
sis/formation of the multi principal element particles obviates the
need for any separate process such as mechanical alloying. There-
fore, in this study, the authors have fabricated non-equiatomic
CuNiTiFe MEA particle reinforced Cu-matrix composite by the
addition of Fe and NiTi shape memory alloy via FSE. Moreover,
the use of a smart material to obtain MEA particles is novel, such
incorporation of functional behaviour can further their industrial
applications.
2. Materials and methods
In this study, rolled commercially pure Cu plate (5 mm thick)
was milled to introduce a rectangular slot of 3 mm width and
2.5 mm depth. A vertical milling machine (make: BFW, Bangalore,
India; model: VF 3.5) was retrofitted for performing FSP. An
equimolar mixture of NiTi and Fe powders having an average par-
ticle size of 10 lm and 65 nm, respectively, was packed in the slot
and processed by a WC tool with tapered cylindrical pin profile.
The shoulder diameter, pin length, pin tip and root diameters were
22 mm, 3.4 mm, 5.8 mm and 6.2 mm, respectively. The tool rota-
tional and traverse speeds were kept at 560 rpm and 16 mm/
Fig. 1. Stepwise schematic depiction of FSP experimentation.
47
Manufacturing Letters 36 (2023) 46–51
min, respectively, to avert defects in the stirred region. A stepwise
schematic representation of the FSP experimentation is depicted in
Fig. 1. The advancing side (AS) and retreating side (RS) refer to the
sides of the tool (on the transverse cross section) where the tan-
gential velocity of the rotating tool is in the similar and opposing
direction of its traverse, respectively, with respect to the base
metal.
Standard metallographic procedure was followed on samples
cut using wire electric discharge machining to examine the trans-
verse processed sections. Polished samples were etched with 1:1
mixture of HNO3 and H2O for 30 s followed by rinsing with distilled
water. Scanning Electron Microscopy (SEM), Energy Dispersive
Spectroscopy (EDS) and X-ray Diffraction (XRD) were employed
to analyse the evolved microstructure. Corelation to mechanical
behaviour was drawn through Vickers micro-hardness indents at
100 g test force with a dwell time of 15 s.
3. Results and discussion
A myriad of Secondary Phase Alloyed Locales (SPALs) with vary-
ing shapes and sizes is revealed through SEM (Fig. 2a). Length of
these locales along the metal flow intercalations establishes their
formation during stirring. The refined equiaxed grains having an
average size of 2.7 lm are evident from Fig. 2b. The EDS maps
(Fig. 2a1-4) corresponding to Fig. 2a show the high concentration
of Ni in the matrix, and that of Ti in the SPALs. Whereas, Fe is rel-
atively balanced between the matrix and SPALs. Also, the EDS maps
corresponding to Fig. 2(c,d) show the localization of Fe and Ti at the
same locations (Fig. 2(c2,c4) and Fig. 2(d2,d4)). The localization at
the same locations is not apparent for Cu and Ni, as observable
from Fig. 2(c1,c3) and Fig. 2(d1,d3). This indicates the substitution
of Ni by Fe in NiTi particles. Markedly, the formation of SPALs
occurs across all scales, starting from a size of
60 nm to
3 lm,
up to
60 lm (Fig. 2(c,d,e)). Further, the site of maximum hardness
N.F. Lone, D. Bajaj, N. Gangil et al.
Fig. 2. (a) SEM of alloyed locales within FSP intercalations (a1-4) EDS map (b) Ultra-refined grains (c) SPAL of
3 lm size (c1-4) EDS map (d) SPAL of
60 nm size (d1-4) EDS
map (e) Stir Zone/Thermo-Mechanically Affected Zone Interface (f) Site of maximum micro-hardness.
(Fig. 2f) comprises SPALs of size 1–10 lm that are rich in Ti
(Fig. 3a). The decrease in interparticle spacing increases the
strengthening effect of the particles in MMCs. The least interparti-
cle spacing of the sub-micron scale can be seen from Fig. 2d. The
ultra-refinement of grains is likely to decrease the interparticle
spacing. Moreover, the inter-particle spacing during FSP can be
decreased further via multiple passes [13] and alteration of process
parameters [14].
Apart from their size, the strengthening effect of the reinforcing
particles is also dependent upon the shape of the particles. Fig. 2a
shows several needle/plate shaped SPALs, whereas, relatively
rounded/ellipsoidal/spherical particles can be observed in Fig. 2
(c,d,e,f). The high aspect ratio particles such as cylindrical, plate
or needle shaped particles tend to provide more strengthening
than the rounded or spheroidal particles [15]. However, the spher-
ical particles are known to impart more ductility than the angular
shaped particles [16]. Moreover, the spherical shape also dis-
tributes the stress uniformly which decreases the notch effect
[17]. A combination of strain gradient and high temperature during
FSP leads to manifold particle shapes in the same Cu matrix, which
can be challenging to obtain via conventional methods of MMC
fabrication.
The EDS map sum spectrums for Fig. 2(a,c,d) as shown in Fig. 3a,
vary marginally, inferring that the collective elemental homogene-
ity of matrix and SPALs is maintained. The EDS analysis for point
48
Manufacturing Letters 36 (2023) 46–51
spectrums 1–16 indicated in Fig. 2(a,d,f) and Fig. 3(b,c,d,e) taken
at different alloyed locales is also shown in Fig. 3a.
Generally, the configurational entropy ðDSmix Þ is used to classify
the low (DSmix < 1R), medium (1R < DSmix < 1:5R) or high entropy
alloys (DSmix > 1:5R) [18]. For an n-element multicomponent alloy
at a random state, DSmix is calculated by Boltzmann’s hypothesis
(Eqn-1):
X
n
DSmix ¼ R xi ln xi ð1Þ
i¼1
where xi is the concentration of element i and R is the Gas Constant
(8.314 JK-1mol1). The particles pertaining to Point Spectrums 1, 2,
11, 12, 13, 14, 15, and 16 have DSmix values of 1.29 R, 1.19R, 1.03R,
1R, 1.01R, 1.3R, 1.24R and 1.35R, respectively, satisfying the MEA
criterion. For Spectrums 1–5, the Cu content varies from 36.6 to
94.4 at. % within 50 lm (Fig. 2a), indicating that alloyed phases/lo-
cales are solid solutions having wide solubility limits. On comparing
EDS results of spectrums 6 and 7, it is apparent that similar compo-
sitional heterogeneity is maintained at the nanoscale.
Cu content for SPALs across the processed region shows a falling
trendline from advancing side to retreating side (Fig. 3f) due to
decreasing shear strain. The trendline was obtained through linear
regression. Also, the SPALs exhibit higher copper content in the
upper, shoulder stirred region (Fig. 3g) due to greater frictional
N.F. Lone, D. Bajaj, N. Gangil et al.
Fig. 3. (a) EDS results (b-e) SEM images of different alloyed locales (f) Cu content vs. distance from processed zone centre (g) Cu content vs. distance from top of processed
zone.
heat. For Fe and Ti, the SPALs are uniformly populated between 0
and 100 at. %, however, majority of spectrums contain less than
30 at. % Ni (Fig. 4a). This emboldens the inference that migration
of Ni into the matrix and that of Fe to NiTi has contributed to for-
mation of SPALs.
XRD results of the NiTi powder, Fe powder and the fabricated
MMC are shown in Fig. 4b. The Fe powder exhibit peaks at 44.8⁰,
65.2⁰, and 82.5⁰ which correspond to (1 1 0), (2 0 0), and (2 1 1)
planes, respectively, in the BCC Fe. The XRD pattern of NiTi powder
reflects the dominating monoclinic structure. The MMC exhibited
peaks at 38.47⁰ and 44.72⁰ corresponding to planes (1 1 1) and
(2 0 0) in FCC phase due to the presence of Cu and Ni. The peak at
52.25⁰ might have occurred due to the cubic to monoclinic trans-
formation of Ti-Ni-Cu alloys, possibly caused by the substitution
of Ni with Fe [19,20]. Further, presence of b-Ti and Fe rich SPALs
is reflected by the peak at 82.43⁰, which corresponds to (2 2 0)
plane in the BCC phase.
Balogh et al. [21] formulated that, if h + k + l – 3 m (m 2 Z), the
stacking faults affect peak broadening, shape, and induce peak pro-
file asymmetry. The above condition is satisfied by the peaks at
44.72⁰, 52.25⁰, 82.43⁰, and their profile asymmetry is apparent
(Fig. 4b). This may be due to the presence of stacking faults in
the stirred region. Also, stacking fault energy decreases due to
the severe plastic deformation [22]. The lattice parameter and lat-
tice strain were calculated as 3.605 Å and 1.62  10-3, respectively.
Importantly, the formation of intermetallic compounds seems
improbable since the formation of micro-locales of identical stoi-
chiometric compositions is highly unlikely during stirring. From
49
Manufacturing Letters 36 (2023) 46–51
the XRD data, the crystallite size (D) can be estimated from the
Scherrer’s formula, as follows [23]:
kk
D¼ ð2Þ
bcosh
where k is Scherrer’s constant (taken as 0.9), k is the X-ray wave-
length used (1.54 Å), b is the angular line width at half the maxi-
mum intensity, and h is the Bragg’s diffraction angle. Thereby, the
dislocation density (q) can be estimated as [24]:
1
q¼ ð3Þ
D2
Using the XRD data, the dislocation density was calculated as
1:1  1015 m2, which belongs to a relatively higher range. The
SPALs and dislocation density play crucial and interdependent
roles in strengthening of the Cu matrix composite. Based on their
size, the SPALs can obstruct the motion of the dislocations. Since
the size of the SPALs is seen to vary tremendously from 60 nm to
60 lm, it is likely that a section of simultaneously formed SPALs
lead to the retaining of high dislocation density in the Cu matrix,
thus contributing further to the strengthening of the fabricated
composite. A tremendous augmentation of average micro-
hardness in processed zone, from 110 HV (base metal hardness)
to 175 HV is observed (Fig. 4(c,d)). The hard and brittle nature of
Ti-Ni-Cu alloys with Cu content >10 at. % [25], affirms significant
alloying in the micro-locales. The frequency distribution of
micro-hardness values (Fig. 4e) shows an initial spike (70–90
N.F. Lone, D. Bajaj, N. Gangil et al. Manufacturing Letters 36 (2023) 46–51

Fig. 4. (a) Fe, Ni and Ti content of SPALs (b) XRD results for the NiTi powder, Fe powder, and processed sample (c) Macrostructure of fabricated MMC (d) Micro-hardness
contour map (e) Micro-hardness frequency plot (f) Grain size distribution for Fig. 2b and base metal with its inset microstructure.

HV) due to measurements from heat affected zones. Second spike Fig. 2b shows unimodality in the equiaxed grains. Average grain
occurs from 110 HV to 130 HV, due to recrystallization and grain size decreases from
79 lm (base metal) to
2.7 lm, as evident
boundary strengthening. The grain size distribution (Fig. 4f) for from Fig. 4f. Since the formed SPALs are likely to be solid solutions

50
N.F. Lone, D. Bajaj, N. Gangil et al.
occupying wide compositional space, the micro-hardness fre-
quency curve is similar to a normal distribution beyond 130 HV.
The variation in particle density across different regions can be
observed through a comparison of Figs. 2(a,e,f) and 3(b,c,e). The
variation in particle density contributed towards differing micro-
hardness in these domains, leading to the normal distribution of
the micro-hardness frequency curve beyond 130 HV. Upon plastic
deformation, the softer regions can accommodate the strain
whereas the harder regions can bear the stress. The existence of
such mechanically diverse microstructure can improve both the
strength and ductility of the fabricated composites.
4. Conclusions
In summary, FSE of Cu with NiTi and Fe results in the formation
of MEA particles during FSP. The Cu base metal reinforced by the
multi principal element alloy particles showed improved micro-
hardness values. The compositionally diverse non-equiatomic
CuNiTiFe MEAs appear to be formed as secondary phase alloyed
locales (SPALs) of size 60 nm to 60 lm. Owing to greater plastic
strain and frictional heat, SPALs show relatively high Cu content
in the advancing side and upper section of processed region. The
BCC phase is observed due to b-Ti and Fe rich SPALs. The substitu-
tion of Ni by Fe in Ti-Ni-Cu locales seemingly caused cubic to mon-
oclinic transformation. A micro-hardness enhancement of 59% is
observed in the stirred region. Since the formation of stoichiomet-
rically congruous locales is unlikely during FSE, formation of inter-
metallic compounds appears to be less probable. The simultaneous
formation of SPALs during severe plastic deformation also leads to
retainment of high dislocation density in the fabricated composite.
Data availability
The raw/processed data required to reproduce these findings
cannot be shared at this time as the data also forms part of an ongo-
ing study.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
The authors are grateful to Raytheon Chair for Systems Engi-
neering for funding this research.
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