Vous êtes sur la page 1sur 11

metals

Article
Structural Investigations of TiCCu Nanocomposites
Prepared by Ball Milling and Spark Plasma Sintering
Oanh Nguyen Thi Hoang 1, *, Viet Nguyen Hoang 1 , Ji-Soon Kim 2 and Dina V. Dudina 3,4
1 School of Materials Science and Engineering, Hanoi University of Science and Technology, No 1 Dai Co Viet,
Hanoi 100000, Vietnam; viet.nguyenhoang@hust.edu.vn
2 School of Materials Science and Engineering, University of Ulsan, San-29, Mugeo-2 Dong, Nam-Gu,
Ulsan 680-749, Korea; jskim@ulsan.ac.kr
3 Lavrentyev Institute of Hydrodynamics, Siberian Branch of the Russian Academy of Sciences,
Lavrentyev Ave. 15, Novosibirsk 630090, Russia; dina1807@gmail.com
4 Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch of the Russian Academy of
Sciences, Kutateladze str. 18, Novosibirsk 630128, Russia
* Correspondence: oanh.nguyenthihoang@hust.edu.vn; Tel.: +84-4-3868-0409

Academic Editors: Mieczyslaw Jurczyk and Manoj Gupta


Received: 17 January 2017; Accepted: 31 March 2017; Published: 3 April 2017

Abstract: In this work, TiCCu composites containing 20 and 30 vol % of nano-sized titanium carbide
(TiC) particles were prepared by powder metallurgy using copper powders with micrometer-sized
and nanometer-sized particles. Mixtures of TiC and Cu powders were ball milled for 10 h and spark
plasma sintered at 800900 C under an applied pressure of 50 MPa. The relative density of the
sintered composites was 95.0%96.5%. The composites fractured in a ductile mode. The crystallite
size of the copper matrix in the composites prepared using the nanometer-sized copper powder was
smaller than that in composites prepared using the micrometer-sized copper powder, which was
confirmed by transmission electron microscopy (TEM). The hardness of the composites increased
as the sintering temperature was increased from 800 to 900 C. When the TiC content increased
from 20 to 30 vol %, the hardness of the composites obtained from the micrometer-sized copper
powder and sintered at 900 C increased from 284 to 315 HV, while in composites obtained from the
nanometer-sized copper, the hardness decreased from 347 to 337 HV.

Keywords: spark plasma sintering; titanium carbide; copper; ball milling; hardness

1. Introduction
Copper is widely used as a material for electrical contacts due to its high electrical and thermal
conductivities, low cost, and good corrosion resistance. However, the poor mechanical properties
of copperlow hardness and strengthnarrow the range of its possible applications. Inherent
limitations of copper stimulate the development of copper matrix composites reinforced with ceramic
particles [16]. To maintain high electrical conductivity, reinforcements that are thermodynamically
stable in copper should be used. This avoids the dissolution of other elements in copper and maintains
its high electrical conductivity. Titanium carbide (TiC) can be used as a reinforcing phase in copper
matrix composites due to its high modulus, high hardness, and high melting temperature. In addition,
TiC has negligible solubility in copper such that the TiC/Cu interface remains free from intermetallic
compounds or solid solutions [7,8].
Discontinuously reinforced metal matrix composites can be produced by powder metallurgy,
casting, self-propagating high-temperature synthesis, and other techniques [4,5,911]. All of these
techniques are based on the addition of ceramic reinforcements to the matrix materials, which are in
the liquid or solid (powder) state. In practice, it is rather difficult to distribute reinforcing nanoparticles

Metals 2017, 7, 123; doi:10.3390/met7040123 www.mdpi.com/journal/metals


Metals 2017, 7, 123 2 of 11

in metallic melts [12,13]. Therefore, in order to improve the dispersion of TiC in the Cu matrix,
high-energy ball milling is used to produce composite powders. Until now, most studies have focused
on the possibilities of reducing the size of the reinforcing particles down to the nanoscale. The main
issue in the synthesis of TiCCu composites is low wettability of the reinforcing particles by the matrix.
It is generally accepted that a finer size of the reinforcing particles is desirable for improving the
mechanical properties of the metal matrix composites.
Another possibility to achieve a better mechanical performance of TiCCu is to use copper
powders with different particle sizes. It should be noted that the effect of reducing the particle size
of the copper powders down to the nanoscale on the microstructure and mechanical properties of
TiCCu composites has been much less investigated.
In this work, TiCCu composites were prepared by high-energy ball milling and spark plasma
sintering (SPS). This sintering technique has gained a reputation of a versatile method of fast
consolidation of powder materials [1418]. The SPS method proves effective for consolidating
composite powders. This works is aimed at investigating the influence of the size of the starting
copper powders on the microstructure and hardness of the spark plasma sintered TiCCu composites.

2. Experimental Procedures
Two copper powders with average particle sizes of 75 m and 40 nm (US1090, US Research
Nanomaterials, Inc., Houston, TX, USA) were used as the staring materials. Titanium carbide TiC
powder (US2052, US Research Nanomaterials, Inc.) with particles in the 4060 nm range was used as a
reinforcement. The TiCCu powder mixtures containing 20 and 30 vol % of TiC were mechanically
milled in a high-energy planetary ball mill (P100, Taemyong Scientific Co., Ltd., Seoul, South Korea) for
10 h under an argon atmosphere. The ball-to-powder weight ratio was 10:1, and the ball diameter was
5 mm. To disperse the nanometer-sized TiC particles in the copper matrix homogeneously, the milling
conditions (vial rotation speed and milling time) were optimized. At a rotation speed of 500 rpm, sticking
of the powder to the milling vials and balls prevailed, and the iron contamination of the powder mixture
was significant. At 300 rpm, mixing of the Cu and TiC powders was poor, which resulted in low hardness
of the sintered materials. Conditions of milling established at 400 rpm were found to be optimal for the
selected powder mixtures. A milling time of 10 h was determined to be sufficient for achieving a uniform
distribution of TiC nanoparticles in the copper matrix. Composites obtained from the 75-m copper
powder are designated as nanocomposite A, while those obtained from the 40-nm copper powder are
designated as nanocomposite B. The ball-milled powders were placed into a graphite die with an inner
diameter of 10 mm. Before sintering, the SPS chamber was pumped to a pressure below 5 Pa.
The sintering experiments were conducted using a spark plasma sintering facility (DR. SINTER
LAB Model: SPS-515S, Sumitomo Coal Mining, Tokyo, Japan). The samples were heated from room
temperature to 800900 C by pulsed DC current passing through the graphite die, punches, and
the sample itself. The samples were held at the maximum temperature for 5 min. A pressure of
50 MPa was applied through the sintering cycle. The microstructure of the composites was studied by
scanning electron microcopy and energy-dispersive spectroscopy (SEM/EDS) using a field-emission
JEOL JSM-7600F microscope (JEOL Ltd., Tokyo, Japan) and transmission electron microscopy (TEM)
using a JEOL JEM-2100 microscope (JEOL Ltd., Tokyo, Japan). The phase composition of the sintered
samples was studied by means of X-ray diffraction (XRD) using a RIGAKU RINT-2000 diffractometer
with Cu K radiation (Rigaku Corporation, Tokyo, Japan). The relative density of the composites was
determined by Archimedes method. The hardness of the sintered TiCCu composites was measured
using a Vickers hardness instrument (Mitutoyo MVK-H1 Hardness Testing Machine, Mitutoyo, Japan)
under a load of 100 g.

3. Results and Discussion


Mechanical milling of the TiCCu powder mixtures resulted in the formation of composite
agglomerates. The SEM images showing the morphology of the agglomerates of nanocomposites A
Metals 2017, 7, 123 3 of 11

and B containing 20 and 30 vol % of TiC are presented in Figure 1. With increasing TiC content from
Metals 2017, 7, 123 3 of 11
20 to 30 vol %, the size of the agglomerates decreased in both nanocomposites. The agglomerates
of nanocomposite
nanocomposite B were finer than those of nanocomposite A at the same TiC content. Most of the
Metals 2017, 7, 123 B were finer than those of nanocomposite A at the same TiC content. Most 3 ofof11the
particles
particles of nanocomposite B were smaller than 10 m, as can be seen from the SEM images shown in
of nanocomposite B were smaller than 10 m, as can be seen from the SEM images shown
Figure 2. Some
in nanocomposite
Figure largeBlarge
2. Some particles were
wereparticles
finer formed
were
than ofdue
formed
those to agglomeration
due to agglomeration
nanocomposite of of
A at the small
same particles,
small
TiC content.reaching
particles, Most of athe
reaching asize
sizeof
1030 m. m.
of particles
1030 of nanocomposite B were smaller than 10 m, as can be seen from the SEM images shown
in Figure 2. Some large particles were formed due to agglomeration of small particles, reaching a size
of 1030 m.

Figure
Figure 1. Morphology
1. Morphology ofofthe
themilled
milledTiCCu
TiCCupowders
powders (a)
(a) 20 vol
vol %
% TiC,
TiC,nanocomposite
nanocompositeA;A;(b) 2020
(b) vol %%
vol
Figure 1. Morphology of the milled TiCCu powders (a) 20 vol % TiC, nanocomposite A; (b) 20 vol %
TiC,TiC, nanocomposite
nanocomposite B;B;
(c)(c)3030vol
vol%%TiC,
TiC,nanocomposite
nanocomposite A;
A; and
and (d)
(d) 30
30 vol
vol %
% TiC,
TiC,nanocomposite
nanocomposite
TiC, nanocomposite B; (c) 30 vol % TiC, nanocomposite A; and (d) 30 vol % TiC, nanocomposite B
BB
(SEM
(SEM(SEM images).
images).
images).

Figure 2. Morphology of the milled powders (a) 30 vol % TiC, nanocomposite A; and (b) 30 vol % TiC,
Figure
Figure 2. 2. Morphologyof
Morphology of the
the milled
milledpowders
powders(a)(a)
3030
volvol
% TiC, nanocomposite
% TiC, A; and
nanocomposite A;(b)
and30 (b)
vol %
30TiC,
vol %
nanocomposite B (higher-magnification SEM images; the rectangles mark areas from which energy-
TiC,nanocomposite
nanocomposite B (higher-magnification
B (higher-magnificationSEM images;
SEM
dispersive spectroscopy (EDS) spectra were taken).
the rectangles
images; the mark areas
rectangles markfrom which
areas fromenergy-
which
dispersive spectroscopy
energy-dispersive (EDS) (EDS)
spectroscopy spectraspectra
were taken).
were taken).
In the ball-milled powders, iron was detected by the EDS analysis (Table 1). The rectangles in
In the ball-milled powders, iron was detected by the EDS analysis (Table 1). The rectangles in
thethe
In micrographs shown
ball-milled in Figure
powders, iron2 mark the areas by
was detected analyzed
the EDS by the EDS. The
analysis presence
(Table of rectangles
1). The iron was in
thedue
micrographs
to shownofinthe
contamination Figure 2 mark
powders fromthe
the areas analyzed
milling vials andbyballs.
the EDS.
The The presence
measured of iron was
concentrations
thedue
micrographs shownofinthe
to contamination Figure 2 mark
powders the
from theareas analyzed
milling byballs.
vials and the EDS. The presence
The measured of iron was
concentrations
Metals 2017, 7, 123 4 of 11
Metals 2017, 7, 123 4 of 11
of iron were much smaller than those detected in the powders subjected to treatment in a horizontal
miller [19].
due to contamination of the powders from the milling vials and balls. The measured concentrations
of iron were much smaller than those detected in the powders subjected to treatment in a horizontal
Table 1. EDS analysis of the ball milled TiCCu powders, nanocomposites A and B containing
miller [19].
30 vol % TiC.
Table 1. EDS analysis of the ball milled TiCCu powders, nanocomposites A and B containing 30 vol
Concentration, wt %
% TiC. Composite
Cu Ti C O Fe
Nanocomposite A 63.83 11.32 18.26wt %
Concentration, 5.75 0.83
Composite
Nanocomposite B 64.23
Cu 11.32
Ti C14.04 O 7.78 Fe 2.63
Nanocomposite A 63.83 11.32 18.26 5.75 0.83
Figure 3 shows the XRDBpatterns
Nanocomposite 64.23of nanocomposites
11.32 A and B7.78
14.04 containing2.63
20 vol % TiC spark
plasma sintered at 800 and 900 C. After sintering, the nanocomposites retained the phase
composition
Figure 3 of the the
shows ball-milled powder
XRD patterns mixtures and consisted
of nanocomposites of two phases,
A and B containing CuTiC
20 vol % and TiC,plasma
spark as no
chemical reaction took place between Cu and TiC. No copper oxides were found in
sintered at 800 and 900 C. After sintering, the nanocomposites retained the phase composition of thethe sintered
nanocomposites.
ball-milled powder Themixtures
values ofand
theconsisted
lattice parameters of TiCCu
of two phases, and CuTiC,
and are as
presented in Tables
no chemical 25.took
reaction The
lattice parameter
place between Cuvalues
and TiC. obtained fromoxides
No copper each crystallographic
were found in the plane werenanocomposites.
sintered plotted against the Nelson
The values
Riley function f() [20]:
of the lattice parameters of TiC and Cu are presented in Tables 25. The lattice parameter values
obtained from each crystallographic plane were
cplotted against the NelsonRiley function f () [20]:
os2 cos2
f ()
 2 sin 
cos cos2
f () = +
where is Braggs angle. In this manner, a straight sin was obtained. The value of the lattice
line
parameter was estimated by extrapolating the straight line to f() = 0. The obtained values of the
where is Braggs angle. In this manner, a straight line was obtained. The value of the lattice parameter
lattice parameter of TiC were 4.312 and 4.306 for nanocomposites A and B, respectively. These
was estimated by extrapolating the straight line to f () = 0. The obtained values of the lattice parameter
values are only slightly smaller than the value reported in the Joint Committee on Powder Diffraction
of TiC were 4.312 and 4.306 for nanocomposites A and B, respectively. These values are only
Standards file (JCPDS 311400)4.33 . The values of the lattice parameter of Cu in nanocomposites
slightly smaller than the value reported in the Joint Committee on Powder Diffraction Standards file
A and B were 3.613 and 3.616 , respectively. These values agree with that reported in JCPDS
(JCPDS 311400)4.33 . The values of the lattice parameter of Cu in nanocomposites A and B were
040836 file (3.615 ). Good agreement of the calculated lattice parameters with those of pure TiC and
3.613 and 3.616 , respectively. These values agree with that reported in JCPDS 040836 file (3.615 ).
Cu phases indicate the absence of any chemical interactions or compositional changes in the phases
Good agreement of the calculated lattice parameters with those of pure TiC and Cu phases indicate the
during sintering.
absence of any chemical interactions or compositional changes in the phases during sintering.

Cu composite B, 900C
TiC Composite A, 900C
composite B, 800C
Composite A, 800C
Intensity (a.u.)

30 40 50 60 70 80
2 theta (deg.)
Figure 3. XRD
Figure 3. patterns of
XRD patterns of nanocomposite
nanocompositeAAand
andnanocomposite
nanocompositeBBcontaining
containing2020vol
vol%% TiC
TiC sintered
sintered at
at 800 and 900

800 and 900 C. C.
Metals 2017, 7, 123 5 of 11

Table 2. Structural parameters of TiC in nanocomposite A with 20 vol % TiC sintered at 900 C.

a () from the
(hkl) h2 + k2 + l2 2 Sin a () f()
NelsonRiley Plot
(111) 3 36.088 0.309 4.312 2.970
(200) 4 41.88 0.357 4.316 2.483 4.312
(220) 8 60.77 0.505 4.312 1.496

Table 3. Structural parameters of TiC in nanocomposite B with 20 vol % TiC sintered at 900 C.

a () from the
(hkl) h2 + k2 + l2 2 Sin a () f()
NelsonRiley Plot
(111) 3 36.091 0.309 4.312 2.970
(200) 4 41.885 0.357 4.315 2.483 4.306
(220) 8 60.868 0.506 4.306 1.493

Table 4. Structural parameters of Cu in nanocomposite A with 20 vol % of TiC sintered at 900 C.

a () from the
(hkl) h2 + k2 + l2 2 (deg.) a () f()
NelsonRiley Plot
(111) 3 43.2 3.628 2.389
(200) 4 50.4 3.622 1.956 3.613
(220) 8 74.1 3.620 1.075

Table 5. Structural parameters of Cu in nanocomposite B with 20 vol % of TiC sintered at 900 C

a () from the
(hkl) h2 + k2 + l2 2 (deg.) a () f()
NelsonRiley Plot
(111) 3 43.309 3.620 2.382
(200) 4 50.41 3.622 1.956 3.616
(220) 8 74.139 3.618 1.074

The fracture surfaces of nanocomposites A and B sintered at 800 C and 900 C are shown in
Figures 4 and 5. The sintered nanocomposites fractured in a ductile mode. The relative densities of
nanocomposites A and B increase slightly with an increase in the sintering temperature from 800 to
900 C (Table 6). As the concentration of TiC increased from 20 to 30 vol %, the relative densities of the
nanocomposites decreased. A similar effect was reported by Reddy et al. for the TiCCu composites
produced by microwave processing [21].

Table 6. Relative densities of the spark plasma sintered (SPS) TiCCu nanocomposites.

Relative Density, %
SPS Temperature, C A B A B
20 vol % TiCCu 20 vol % TiCCu 30 vol % TiCCu 30 vol % TiCCu
800 96.4 96.2 95.2 95.8
900 96.5 96.4 95.5 96.0

The hardness values of nanocomposites A and B are presented in Table 7. For all concentrations of
TiC and sintering temperatures studied, nanocomposite B showed higher hardness than nanocomposite
A. An increase in the content of TiC from 20 to 30 vol % in nanocomposite A sintered at 900 C resulted
in an increase in the hardness from 284 to 315 HV. Such an increase can be expected because hard
particulate reinforcements act as barriers to the dislocation movement within the copper matrix. In the
case of nanocomposite B, an increase in the TiC content led to a slight decrease in the hardness. Indeed,
Metals 2017, 7, 123 6 of 11

TiC particles can easily agglomerate to form clusters [22]. The agglomeration phenomena can cause
deterioration of the mechanical properties of the metal matrix composites. The actual inter-particles
distances become larger than the distances expected without the particle agglomeration. As a result,
Metals 2017, 7, 123 6 of 11
Metals 2017, 7, 123
the contribution of the Orowan mechanism to the total strengthening decreases. The hardness 6 of 11values

of composites
decreases.B Thesintered at 900
hardness C decreased
values from
of composites 347 to 337
B sintered HV
at 900 oCas the TiC from
decreased content
347 increased
to 337 HV as from 20
decreases. The hardness values of composites B sintered at 900 oC decreased from 347 to 337 HV as
the
to 30 vol TiC content increased from 20 to 30 vol %.
the %.
TiC content increased from 20 to 30 vol %.

Figure 4. Fracture
4. Fracture surfaces
surfaces of the
of the TiCCu nanocomposites spark
TiCCu plasma sintered at 800 20(a)
C: (a) vol % vol %
FigureFigure 4. Fracture surfaces of the TiCCunanocomposites sparkplasma
nanocomposites spark plasma sintered
sintered at 800
at 800 C: (a)C:
20 vol20
%
TiC, nanocomposite
TiC, nanocomposite A;
A; (b) (b) 20
20 20 vol
volvol
%% % TiC,
TiC, nanocomposite B; (c) 30 vol % TiC, nanocomposite A; and
TiC, nanocomposite A; (b) TiC,nanocomposite
nanocomposite B;B;(c)
(c)3030 vol
vol %% TiC,
TiC, nanocomposite
nanocomposite A; andA; and
(d) 30 vol % TiC, nanocomposite B.
(d) 30 (d)
vol30%vol
TiC,% nanocomposite
TiC, nanocomposite B. B.

Figure 5. Fracture surfaces of the TiCCu nanocomposites spark plasma sintered at 900 C:
C:900
FigureFigure 5. Fracture
5. Fracture surfaces
surfaces of the of the TiCCu
TiCCu nanocomposites
nanocomposites spark spark
plasmaplasma sintered
sintered at 900at (a) C:
20 vol %
(a) 20 vol % TiC, nanocomposite A; (b) 20 vol % TiC, nanocomposite B; (c) 30 vol % TiC,
(a) 20 vol
TiC, nanocomposite% TiC, nanocomposite A; (b) 20 vol % TiC, nanocomposite B; (c) 30 vol %
A; (b) 20 vol % TiC, nanocomposite B; (c) 30 vol % TiC, nanocomposite A; and TiC,
nanocomposite A; and (d) 30 vol % TiC, nanocomposite B.
(d) 30 nanocomposite A; and (d) 30 vol
vol % TiC, nanocomposite B. % TiC, nanocomposite B.
Metals 2017, 7, 123 7 of 11

Metals 2017, 7, 123 7 of 11

Table 7. Vickers Hardness of the spark plasma sintered TiCCu nanocomposites.


Table 7. Vickers Hardness of the spark plasma sintered TiCCu nanocomposites.
Hardness,
Hardness,HV
HV
C
SPSSPS Temperature,C
Temperature, AA BB AA B B
20 vol % TiCCu
20 vol % TiCCu 20
20 vol %TiCCu
vol % TiCCu 3030
vol % TiCCu
vol % TiCCu 30 vol
30 volTiCCu
% % TiCCu
800800 280
280 337
337 300300 332 332
900 284 347 315 337
900 284 347 315 337

The microstructure
The microstructureofofthe thenanocomposites
nanocompositesobserved observed bybyTEMTEM is is presented
presented in Figures
in Figures 69.69. Figure
Figure 6a
6a shows
shows a bright-field
a bright-field TEM TEM micrograph
micrograph of nanocomposite
of nanocomposite A sintered
A sintered at 900
at 900 C.
C. It canIt be
canseen
be seen
that that
TiC
TiC nanoparticles
nanoparticles are dispersed
are dispersed in the
in the copper
copper matrix.
matrix. TheThe average
average crystallitesize
crystallite sizeofofcopper
copperwas was about
about
15 nm,
15 nm,as ascan
canbe beobserved
observedfrom from a high-resolution
a high-resolution TEMTEM (HRTEM)
(HRTEM) imageimage in Figure
in Figure 6b. The
6b. The selected-
selected-area
area diffraction
diffraction patternpattern
(SADP)(SADP)
insertedinserted
in Figurein 6a Figure 6a corresponds
corresponds to the TiC phase. to theA TiCsimilar phase. A similar
microstructure
microstructure
can can be seen in B,
be seen in nanocomposite nanocomposite
having the same B, having the same
TiC content (Figure TiC8a,b).
contentThe(Figure
crystallite8a,b).
sizeThe
of
crystallite
copper size of copper in
in nanocomposite B ofnanocomposite
the 20 vol % TiCCu B of thecomposition
20 vol % TiCCu was about composition
10 nm. Inwas about 10 nm.
nanocomposites
In nanocomposites
containing 30 vol % containing 30 vol %
of TiC (Figure 7a,bof TiC
and(Figure
Figure 7a,b and
9a,b), Figure
the 9a,b), the
crystallite sizecrystallite
of Cu was size10ofnm
Cu
was 10 nm (nanocomposite
(nanocomposite A) and 5 nmA) and 5 nm (nanocomposite
(nanocomposite B). So,inan
B). So, an increase theincrease
contentin ofthe
thecontent of the TiC
TiC nanoparticles
nanoparticles
in the copper in the copper
matrix matrix
resulted in aresulted
decreaseinin a decrease
the size of in the
the size
copper of the copper crystallites
crystallites in the
in the sintered
sintered composites.
composites. Indeed, TiC Indeed, TiC nanoparticles
nanoparticles have been shownhave been shown
to restrict to restrict
grain growth grain of the growth of the
copper matrix
copper sintering
during matrix during[23]. Ansintering
additional[23]. confirmation
An additional of confirmation
good dispersion of good
of thedispersion of the TiC
TiC nanoparticles in
nanoparticles
the copper matrix in thein copper matrix
the sintered in the sintered is
nanocomposites nanocomposites
presented in Figure is presented
10, which in Figure
shows 10, which
scanning
shows
TEM scanning
images andTEM images and the
the corresponding corresponding
EDS EDS profiles of A
profiles of nanocomposites nanocomposites
and B of the 20 A and
vol B of the
% TiCCu
20 vol % TiCCu
composition: the composition: the size on
size of the waves of the
the waves on the Tiprofiles
Ti concentration concentration
along the profiles
x-axisalong the x-
(distance)
axis (distance)well
corresponds corresponds
to the size well
of tothethe sizenanoparticles
TiC of the TiC nanoparticles
introducedintroduced
into the copper into the copper
matrix matrix
through
through
ball ball milling.
milling.
As the
As therelative
relativedensities
densitiesofofthethenanocomposites
nanocomposites obtained
obtained fromfromtwotwo kindskinds of the
of the coppercopper powder
powder did
did show
not not show significant
significant differences,
differences, it can be it concluded
can be concluded
that the that
reason theforreason for the nanocomposites
the nanocomposites produced
produced
using using the
the copper copper nanopowder
nanopowder being harderbeing harder
is a lower is a lower
crystallite crystallite
size of the coppersize ofmatrix
the copper matrix
preserved in
preserved
the sinteredinstate
the sintered
compared state
withcompared with the nanocomposites
the nanocomposites obtained using obtained using the micrometer-
the micrometer-sized copper
sized copper
powder, as waspowder,
confirmedas was
by confirmed
TEM. by TEM.

Figure 6.
Figure 6. TEM
TEM images
images and
and selected-area
selected-area diffraction
diffraction pattern (SADP) of nanocomposite A of 20 vol %
TiCCu composition
TiCCu composition sintered
sintered at
at 900 C: (a) bright-field image (inset: SADP corresponding to a TiC
900C: TiC
crystallite); (b) High-resolution TEM (HRTEM) of the Cu
crystallite); (b) High-resolution TEM (HRTEM) of the Cu matrix.matrix.
Metals 2017, 7, 123 8 of 11
Metals 2017, 7, 123 8 of 11
Metals 2017, 7, 123 8 of 11
Metals 2017, 7, 123 8 of 11

Figure 7.
TEMTEM imagesand and SADPofofnanocomposite
nanocomposite A of 30 vol % TiCCu composition sintered at
Figure
Figure7. 7. TEMimages
images andSADP
SADP of nanocomposite A A of
of 30
30 vol
vol%%TiCCu
TiCCucomposition
composition sintered
sintered at at
900C:

900Figure (a)
C: (a) bright-field
7. bright-field image
image (inset:
(inset:SADP
SADP corresponding
correspondingto a
30atoTiC
a% crystallite);
TiC (b)
crystallite); HRTEM of
(b) HRTEM the Cu
900C: (a) TEM images image
bright-field and SADP ofSADP
(inset: nanocomposite A of to
corresponding vol
TiC TiCCu composition
crystallite); (b) HRTEM of theof
sintered atthe
Cu
matrix.
Cu900C:
matrix.(a) bright-field image (inset: SADP corresponding to a TiC crystallite); (b) HRTEM of the Cu
matrix.
matrix.

Figure 8. TEM images and SADP of nanocomposite B of 20 vol % TiCCu composition sintered at
Figure 8. TEM images and SADP of nanocomposite B of 20 vol % TiCCu composition sintered at
Figure
900C: TEM
8. (a) images and
bright-field SADP
image of SADP
(inset: nanocomposite B ofto
corresponding 20 vol
TiC% TiCCu composition sintered at
Figure
900C:

8. TEM
(a) imagesimage
bright-field and SADP
(inset:ofSADP
nanocomposite 20 aavol
B of to
corresponding
crystallite);
TiC%crystallite);
(b) HRTEM of
TiCCu composition the Cu
(b) HRTEMsintered at
of the Cu
900matrix.
C: (a) bright-field image (inset: SADP corresponding to a TiC crystallite); (b) HRTEM of the
900C:
matrix.(a) bright-field image (inset: SADP corresponding to a TiC crystallite); (b) HRTEM of the Cu
Cu matrix.
matrix.

Figure 9. TEM images and SADP of nanocomposite B of 30 vol % TiCCu composition sintered at
Figure 9. TEM images and SADP of nanocomposite B of 30 vol % TiCCu composition sintered at
900C: 9.
Figure (a)TEM
bright-field
imagesandimage (inset:ofSADP
andSADP
SADP corresponding
nanocomposite BB of to
30 a TiC%crystallite); (b) HRTEM of the Cu
Figure
900C: TEM
9. (a) images
bright-field image ofSADP
(inset: nanocomposite
correspondingofto 30avol
vol
TiC %TiCCu
TiCCucomposition
crystallite); (b) HRTEMsintered
composition at at
sintered
of the Cu
matrix.

900C: (a) bright-field image (inset: SADP corresponding to a TiC crystallite); (b) HRTEM of the Cu
900matrix.
C: (a) bright-field image (inset: SADP corresponding to a TiC crystallite); (b) HRTEM of the
Cumatrix.
matrix.
Metals 2017, 7, 123 9 of 11
Metals 2017, 7, 123 9 of 11

Cu K series
40 (a) Cu K series
30
80 (b)
20 60
10 40
0
Ti K series 20
150
0
100 80 Ti K series
50 60
Intensity (Cps)
0
Intensity (cps)

C
O K series 40
45
20
30
0
15
20 C K series
0
40 O K series 15
30 10
20
5
10
0
0
Fe K series 20 O K series
15
15
10
10
5
0 5
0.00 0.03 0.06 0.09 0.12 0.15 0.18 0
0.00 0.03 0.06 0.09 0.12 0.15 0.18
Distance (m)
Distance (m)

Figure 10. Scanning TEM images and EDS profiles of the 20 vol % TiCCu: (a) nanocomposite A; and
(b) nanocomposite B sintered at 900 C.
Figure 10. Scanning TEM images and EDS profiles of the 20 vol % TiCCu: (a) nanocomposite A; and
(b) nanocomposite B sintered at 900C.
4. Conclusions
In this study, TiCCu nanocomposites containing 20 and 30 vol % of titanium carbide were
4. Conclusions
obtained by ball milling and SPS using two copper powders with different particle sizes (75 m
In this study, TiCCu nanocomposites containing 20 and 30 vol % of titanium carbide were
and 40 nm) and a TiC nanopowder. In the compacts sintered at 800900 C, relative densities of
obtained by ball milling and SPS using two copper powders with different particle sizes (75 m and
95.0%96.5% were achieved. The presence of Cu and TiC as the only phases in the composites was
40 nm) and a TiC nanopowder. In the compacts sintered at 800900 C, relative densities of 95.0%
confirmed by the XRD phase analysis. No copper oxides were found in the sintered nanocomposites.
96.5% were achieved. The presence of Cu and TiC as the only phases in the composites was confirmed
The microstructure and hardness of the nanocomposites were investigated depending on the sintering
by the XRD phase analysis. No copper oxides were found in the sintered nanocomposites. The
temperature, TiC content, and the particle size of the starting copper powder. Nanocomposites
microstructure and hardness of the nanocomposites were investigated depending on the sintering
obtained using the 40-nm copper powder showed higher hardness than those obtained using the
temperature, TiC content, and the particle size of the starting copper powder. Nanocomposites
75-m copper powder. The reason for a higher hardness of the TiCCu nanocomposites produced
obtained using the 40-nm copper powder showed higher hardness than those obtained using the 75-
using the copper nanopowder was a lower crystallite size of the copper matrix in these composites
m copper powder. The reason for a higher hardness of the TiCCu nanocomposites produced using
compared with those obtained from the micrometer-sized copper powder.
the copper nanopowder was a lower crystallite size of the copper matrix in these composites
compared with those
Acknowledgments: obtained
This researchfrom the micrometer-sized
was funded copper
by Vietnam National powder. for Science and Technology
Foundation
Development (NAFOSTED), grant number 103.02-2011.49.
Acknowledgments: This research was funded by Vietnam National Foundation for Science and Technology
Development (NAFOSTED), grant number 103.02-2011.49.
Metals 2017, 7, 123 10 of 11

Author Contributions: Oanh Nguyen Thi Hoang and Viet Nguyen Hoang designed the research, conducted the
experiments, and prepared the draft manuscript, Ji-Soon Kim and Dina V. Dudina supervised the project and
participated in the discussions, all authors reviewed the manuscript.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Rathod, S.; Modi, O.P.; Prasad, B.K.; Chrysanthou, A.; Vallauri, D.; Deshmukh, V.P.; Shah, A.K. Cast in
situ CuTiC composites: Synthesis by SHS route and characterization. Mater. Sci. Eng. A 2009, 502, 9198.
[CrossRef]
2. Palma, R.H.; Seplveda, A.O. Creep behavior of two Cu-2 vol % TiC alloys obtained by reaction milling and
extrusion. Mater. Sci. Eng. A 2013, 588, 8285. [CrossRef]
3. Nemati, N.; Khosroshahi, R.; Emamy, M.; Zolriasatein, A. Investigation of microstructure, hardness and
wear properties of Al4.5 wt % CuTiC nanocomposites produced by mechanical milling. Mater. Des. 2011,
32, 37183729. [CrossRef]
4. Akhtar, F.; Askari, S.J.; Shah, K.A.; Du, X.; Guo, S. Microstructure, mechanical properties, electrical
conductivity and wear behavior of high volume tic reinforced cu-matrix composites. Mater. Charact.
2009, 60, 327336. [CrossRef]
5. Kim, J.S.; Dudina, D.V.; Kim, J.C.; Kwon, Y.S.; Park, J.J.; Rhee, C.K. Properties of Cu-based nanocomposites
produced by mechanically-activated self-propagating high-temperature synthesis and spark-plasma
sintering. J. Nanosci. Nanotechnol. 2010, 10, 252257. [CrossRef] [PubMed]
6. Mula, S.; Panigrahi, J.; Kang, P.C.; Koch, C.C. Effect of microwave sintering over vacuum and conventional
sintering of Cu based nanocomposites. J. Alloys Compd. 2014, 588, 710715. [CrossRef]
7. Jarfors, A.E.W. Solubility of copper in titanium carbide. Mater. Sci. Technol. 1996, 12, 990994. [CrossRef]
8. Ni, S.; Jiang, J.; Chen, J.; Song, D.; Ma, A. Microstructure and properties of in-situ synthesized Cu-1 wt % TiC
alloy followed by ECAP and post-annealing. Prog. Nat. Sci. Mater. Int. 2016, 26, 643649. [CrossRef]
9. Liang, Y.H.; Wang, H.Y.; Yang, Y.F.; Wang, Y.Y.; Jiang, Q.C. Evolution process of the synthesis of TiC in the
CuTiC system. J. Alloys Compd. 2008, 452, 298303. [CrossRef]
10. Karbalaei Akbari, M.; Rajabi, S.; Shirvanimoghaddam, K.; Baharvandi, H.R. Wear and friction behavior of
nanosized TiB2 and TiO2 particle-reinforced casting A356 aluminum nanocomposites: A comparative study
focusing on particle capture in matrix. J. Compos. Mater. 2015, 49, 36653681. [CrossRef]
11. Shirvanimoghaddam, K.; Hamim, S.U.; Karbalaei Akbari, M.; Fakhrhoseini, S.M.; Khayyam, H.;
Pakseresht, A.H.; Ghasali, E.; Zabet, M.; Munir, K.S.; Jia, S.; et al. Carbon fiber reinforced metal matrix
composites: Fabrication processes and properties. Compos. Part A Appl. Sci. Manuf. 2017, 92, 7096. [CrossRef]
12. Casati, R.; Vedani, M. Metal matrix composites reinforced by nano-particlesA review. Metals 2014, 4, 6583.
[CrossRef]
13. Akbari, M.K.; Shirvanimoghaddam, K.; Hai, Z.; Zhuiykov, S.; Khayyam, H. Al-TiB2 micro/nanocomposites:
Particle capture investigations, strengthening mechanisms and mathematical modelling of mechanical
properties. Mater. Sci. Eng. A 2017, 682, 98106. [CrossRef]
14. Munir, Z.A.; Quach, D.V.; Ohyanagi, M. Electric current activation of sintering: A review of the pulsed
electric current sintering process. J. Am. Ceram. Soc. 2011, 94, 119. [CrossRef]
15. Tokita, M. CHAPTER 11.2.3Spark plasma sintering (SPS) method, systems, and applications A2Somiya,
shigeyuki. In Handbook of Advanced Ceramics, 2nd ed.; Academic Press: Oxford, UK, 2013; pp. 11491177.
16. Dudina, D.V.; Mukherjee, A.K. Reactive spark plasma sintering: Successes and challenges of nanomaterial
synthesis. J. Nanomater. 2013, 2013, 12. [CrossRef]
17. Dudina, D.V.; Mali, V.I.; Anisimov, A.G.; Bulina, N.V.; Korchagin, M.A.; Lomovsky, O.I.; Bataev, I.A.;
Bataev, V.A. Ti3SiC2-Cu composites by mechanical milling and spark plasma sintering: Possible
microstructure formation scenarios. Met. Mater. Int. 2013, 19, 12351241. [CrossRef]
18. Ghasali, E.; Pakseresht, A.H.; Alizadeh, M.; Shirvanimoghaddam, K.; Ebadzadeh, T. Vanadium carbide
reinforced aluminum matrix composite prepared by conventional, microwave and spark plasma sintering.
J. Alloys Compd. 2016, 688, 527533. [CrossRef]
19. Zhuang, J.; Liu, Y.; Cao, Z.; Li, Y. The influence of technological process on dry sliding wear behaviour of
titanium carbide reinforcement copper matrix composites. Mater. Trans. 2010, 51, 23112317. [CrossRef]
Metals 2017, 7, 123 11 of 11

20. Lemine, O.M. Effect of milling conditions on the formation of ZnFe2 O4 nanocrystalline. Int. J. Phys. Sci.
2013, 8, 380387.
21. Chandrakanth, R.G.; Rajkumar, K.; Aravindan, S. Fabrication of copperTiCgraphite hybrid metal matrix
composites through microwave processing. Int. J. Adv. Manuf. Technol. 2010, 48, 645653. [CrossRef]
22. Maity, P.C.; Panigrahi, S.K. Metal and intermetallic matrix in-situ particle composites. Key Eng. Mater. 1995,
104, 313328. [CrossRef]
23. Panda, S.; Dash, K.; Ray, B.C. Processing and properties of Cu based micro- and nano-composites.
Bull. Mater. Sci. 2014, 37, 227238. [CrossRef]

2017 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).