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Article
Characterization of In-Situ CuTiH2C and CuTiC
Nanocomposites Produced by Mechanical Milling
and Spark Plasma Sintering
Nguyen Thi Hoang Oanh 1, *, Nguyen Hoang Viet 1 , Ji-Soon Kim 2 and
Alberto Moreira Jorge Junior 3,4,5,6,7
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 Department of Materials Science and Engineering, Federal University of So Carlos, Via Washington Luiz,
km 235, So Carlos, SP 13565-905, Brazil; Jorge.Moreira@simap.grenoble-inp.fr
4 University of Grenoble Alpes, Science et Ingnierie des Matriaux et Procds (SIMAP),
F-38000 Grenoble, France
5 Centre National de la Recherche Scientifique (CNRS), Science et Ingnierie des Matriaux et
Procds (SIMAP), F-38000 Grenoble, France
6 University of Grenoble Alpes, Laboratoire dElectrochimie et de Physico-chimie des Matriaux et des
Interfaces (LEPMI), F-38000 Grenoble, France
7 Centre National de la Recherche Scientifique (CNRS), Laboratoire dElectrochimie et de Physico-chimie des
Matriaux et des Interfaces (LEPMI), F-38000 Grenoble, France
* Correspondence: oanh.nguyenthihoang@hust.edu.vn; Tel.: +84-4-3868-0409

Academic Editor: Manoj Gupta


Received: 5 February 2017; Accepted: 27 March 2017; Published: 29 March 2017

Abstract: This study focuses on the fabrication and microstructural investigation of CuTiH2C and
CuTiC nanocomposites with different volume fractions (10% and 20%) of TiC. Two mixtures of
powders were ball milled for 10 h, consequently consolidated by spark plasma sintering (SPS) at 900
and 1000 C producing bulk materials with relative densities of 9597%. The evolution process of TiC
formation during sintering process was studied by using X-ray diffraction (XRD), scanning electron
microscopy (SEM), and high resolution transmission electron microscopy (HRTEM). XRD patterns
of composites present only Cu and TiC phases, no residual Ti phase can be detected. TEM images
of composites with (10 vol % TiC) sintered at 900 C show TiC nanoparticles about 1030 nm
precipitated in copper matrix, most of Ti and C dissolved in the composite matrix. At the higher
sintering temperature of 1000 C, more TiC precipitates from CuTiH2C than those of CuTiC
composite, particle size ranges from 10 to 20 nm. The hardness of both nanocomposites also increased
with increasing sintering temperature. The highest hardness values of CuTiH2C and CuTiC
nanocomposites sintered at 1000 C are 314 and 306 HV, respectively.

Keywords: spark plasma sintering; CuTiC; in-situ composites; mechanical milling

1. Introduction
Metal matrix composites (MMCs) are advanced materials which combine ductility and toughness
of metal and high strength and modulus of ceramic particles. The unique properties of MMCs are
high specific strength, specific modulus, and good wear resistance compare to unreinforced metal [1].
In many type of MMCs, copper matrix composites (CMCs) have received a lot of interest because of
super toughness and wear resistance which are used for structural application in wear industry [2].

Metals 2017, 7, 117; doi:10.3390/met7040117 www.mdpi.com/journal/metals


Metals 2017, 7, 117 2 of 12

Generally, there are two routes to produce particulate-reinforced CMCs, which are ex-situ and in-situ.
In the ex-situ method, ceramic particles such as TiB2, TiC, and oxide are introduced into the metal
matrix via powder metallurgy or conventional casting methods [3,4]. However, the CMCs fabricated
by these methods revealed a drawback because of poor interfacial bonding between reinforcement
particles and copper matrix [5]. In order to improve the wettability of the Cu matrix and reinforcement
phase, nano-ceramic particles were used [6]. Nevertheless, ceramic nanoparticles have tendency to
segregate into clusters in milling process leading decrease strength of composite. The distribution of
reinforced particles are non-uniform in the copper matrix, the mechanical and electrical features of
the composite will be affected negatively [7]. On the contrary, ceramic particles synthesized by the
in-situ method were dispersed more homogeneously in the copper matrix. The interfaces between
reinforcement particles and matrix are clean, and very fine reinforcement particles are formed. Among
CMCs, CuTiC system is attracted more attention due to their potential applications as electrical
sliding contacts, resistance welding electrodes [8]. In the in-situ method, TiC nanoparticles were
produced by the reaction between Ti and C during sintering process. In order to prevent grain growth
of reinforcement and copper particles occur at high sintering temperature a fast sintering process need
to be carried out. Spark plasma sintering (SPS) has some advantages such as rapid sintering, uniform
sintering, low running cost, easy operation proves a suitable sintering technique for consolidation
nano-structure, nanocomposite, and amorphous materials. In SPS, very high temperature over melting
temperature may be attained in the contact area of powder particles which enhances interparticle
bonding without considerable grain growth occurring [913].
The replacement of Ti powder in CuTiC composite by another powder such as TiH2 is
considerable because of high price of Ti powder. In addition to, dehydrogenation of TiH2 occurs during
sintering process is always accompanied by formation of high concentration of lattice defects and the
highly activated Ti atoms. Released hydrogen from TiH2 will react with oxygen on the surface of TiH2
powders in the form of H2O which affect positively on the electrical conductivity of the composite [14].
The objectives of the present work are to explore the possibility of synthesizing CuTiC in-situ
composites made from CuTiH2C and CuTiC powder mixtures by mechanical milling and SPS.
The effect of reinforcement content and sintering temperature on microstructure and hardness
properties of composites was investigated.

2. Experimental Procedure
The copper (with average particle size of 75 m), titanium (average particle size of 45 m), TiH2
(average particle size of 40 m) and graphite (average particle size of 5 m) powder (99% purity, from
HIGH PURITY CHEMICALS Co., Ltd., Chiyoda, Japan) were used as starting materials. The powder
mixtures of two composites CuTiH2C and CuTiC with mixing ratio of 10 and 20 vol % TiC were
mechanically milled in a high-energy planetary ball mill (P100-Korea). Milling was operated for 10 h at
the rotational speed of 500 rpm and 0.5 wt % stearic acid was used as the milling process control agent.
Balls and vials are made of stainless steel, the diameter of the balls was 5 mm and the powder-to-ball
ratio was 1:10. The vial was evacuated and subsequently filled with argon up to 0.3 MPa.
A 1.5 g amount of as-milled powder was loaded into a cylindrical graphite die with 10 mm-inner
and was subjected to a pulsed current using a spark plasma sintering equipment, (SPS-515 apparatus
Sumitomo Coal Mining, Tokyo, Japan). The chamber was pumped to low vacuum (<5 Pa).
The composite powders were spark plasma sintered at 900 and 1000 C under a pressure of 50 MPa for
5 min with a heating rate of 50 C/min.
X-ray diffraction patterns of the composites were recorded by a SIEMENS D5000 diffractometer
(Siemens Industry Inc., Karlsruhe, Germany) using Cu K radiation ( = 1.5418 ). Microstructural
analysis of powders and composite samples was carried out by using Scanning Electron Microscopy
(SEM/EDX-JEOL JSM-7600F, JEOL Ltd., Tokyo, Japan) and Transmission Electron Microscopy
(TEM-JEOL JEM-2100, JEOL Ltd., Tokyo, Japan). Relative densities of bulk composites were determined
Metals
Metals2017, 7, 7,
2017, 117117 3 of 1212
3 of

Archimedes method. The indexation of such selected area electron diffraction (SAED) patterns was
by Archimedes method. The indexation of such selected area electron diffraction (SAED) patterns was
performed using JEMS software [15].
performed using JEMS software [15].
Microhardness measurements were performed using a Vickers hardness instrument (Mitutoyo
Microhardness measurements were performed using a Vickers hardness instrument (Mitutoyo
MVK-H1 Hardness Testing Machine, Mitutoyo, Japan) under a load of 100 g.
MVK-H1 Hardness Testing Machine, Mitutoyo, Japan) under a load of 100 g.
To analyze the surface of fracture, samples were simply fractured by gripping the halves of the
To analyze the surface of fracture, samples were simply fractured by gripping the halves of the
composite with pliers and bending them apart.
composite with pliers and bending them apart.

3.3.Results
Resultsand
andDiscussion
Discussion

3.1.Characterization
3.1. Characterizationofofthe
thePowders
Powders
Figure1a,b
Figure 1a,bshows
showsSEMSEMimages
imagesofofstarting
startingpowders,
powders,respectively
respectivelyfor forTiH
TiH andcopper
2 2and copperpowders.
powders.
TiH particles have an irregular shape while Cu powder particles have a dendritic
TiH2 particles have an irregular shape while Cu powder particles have a dendritic shape. Figure 1cf
2 shape. Figure 1c
f show
show SEM SEM images
images of of composite
composite powders
powders formed
formed after
after 1010
h ofh of milling
milling ofofCuTiH2C
CuTiH2Cand andCuTiC
CuTiC
mixtures,
mixtures, with
with different
different amounts
amounts of of reinforcement
reinforcement particle
particle content.
content. As As
oneonecancan observe,
observe, the increase
the increase of
of the reinforcement particle content the particle size of milled powders decreases
the reinforcement particle content the particle size of milled powders decreases for both composites. for both composites.
CuTiC
CuTiC composite
composite presented
presented finer
finer particles
particles thanthose
than thosefor
forthe
theCuTiH2C
CuTiH2Ccomposite,
composite,withwiththethesame
same
reinforcement particle content. As can be seen from SEM images shown
reinforcement particle content. As can be seen from SEM images shown in Figure 1g,h. Some large in Figure 1g,h. Some large
particles
particles werewere formed
formed duedue to agglomeration
to agglomeration of particles
of small small particles
reachingreaching
a size ofa1030
size m.
of 1030 m. EDS
EDS analyses
analyses
(Figure (Figure
2) were 2) were performed
performed on particles onsuch
particles
as in such
Figureas 1g,h
in Figure
which 1g,h whichspectra
presents presentsrelative
spectratorelative
such
to such analyses, of which it is worth noting that there was no contamination
analyses, of which it is worth noting that there was no contamination of Fe either from the milling of Fe either from the
milling
tools (Tabletools
1). (Table
However,1). However, such contamination
such contamination was alreadywas alreadyeven
observed observed even inmethod
in the ex-situ the ex-situ
as
methodin
reported as[16].
reported in [16].

Figure 1. Cont.
Metals 2017, 7, 117 4 of 12
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Metals 2017, 7, 117 4 of 12

Figure
Figure 1.1. SEM
SEM of starting powders
of starting powders in in (a)
(a) TiH
TiH22 and
and (b)
(b) copper
copper powders.
powders. SEM images of
SEM images of composite
composite
powders milled
powders milled for
for1010h,h,with
with1010vol %%
vol TiCTiCin in
(c)(c)
CuTiH2C
CuTiH2C andand
(d) (d)
CuTiC;
CuTiC; andand
withwith
20 vol
20 % TiC
vol %
in (e) Figure 1. SEM of starting powders in (a) TiH2 and (b) copperSEM
powders. SEM images ofrectangles
composite
TiC in CuTiH2C
(e) CuTiH2C and (f) (f)
and CuTiC.
CuTiC. Higher-magnification
Higher-magnification SEMimages;
images;the the rectanglesmarkmark areas;
areas;
powders milled for 10 h, with 10 vol % TiC in (c) CuTiH2C and (d) CuTiC; and with 20 vol % TiC
from which EDS
from which EDSinspectra
spectra wereand
were
(e) CuTiH2C taken
taken (g) CuTiH2C
(g) CuTiH2C
(f) CuTiC. and (h)
and
Higher-magnification (h)
SEMCuTiC.
CuTiC.
images; the rectangles mark areas;
from which EDS spectra were taken (g) CuTiH2C and (h) CuTiC.

Figure 2. Typical EDS analyses acquired from particles presented in Figure 1e (CuTiC) in (a) and 1f
Figure 2. Typical EDS analyses
(CuTiH2C) acquired
in (b), both with 20 vol from
% TiC. particles presented in Figure 1e (CuTiC) in (a) and
Figure 1f (CuTiH2C) in (b), both with 20 vol % TiC.
Table 1. EDS analysis of the ball milled powders with 20 vol % of TiC reinforcement particles.

Concentration, wt %
Table
Figure 1. EDS analysis
2. Typical EDS analyses of theacquired
ball milled
Composite frompowders Ti
with
Cu particles
20 volC%inofFigure
presented TiC reinforcement particles.
O1e (CuTiC) in (a) and 1f
(CuTiH2C) in (b), both with 20 vol % TiC.
CuTiH2C 73.78 8.75 13.42 4.05
CuTiC 70.73 7.89
Concentration, 16.49
wt % 4.89
Composite
Table 1. 3.2.
EDS analysis ofofthe
Characterization ball milled
Compacts powders with
after SPSCu Ti 20 volC% of TiCOreinforcement particles.
X-ray diffraction patterns of as-sintered
CuTiH2C 73.78nanocomposites
8.75 are illustrated 4.05
13.42 in Figure 3. After SPS at
900 Composite
C (Figure 3a), CuTiC
XRD patterns presents
Concentration,
only diffraction
wt %
70.73 7.89 peaks related to 4.89
16.49 pure copper. There is a
Cu Ti C O
CuTiH2C 73.78 8.75 13.42 4.05
3.2. Characterization CuTiC
of Compacts after SPS
70.73 7.89 16.49 4.89
X-ray diffraction patterns of as-sintered nanocomposites are illustrated in Figure 3. After SPS
3.2.
at 900 C (Figure 3a),
Characterization of Compacts after SPS
XRD patterns presents only diffraction peaks related to pure copper. There
X-ray diffraction patterns of as-sintered nanocomposites are illustrated in Figure 3. After SPS at
900 C (Figure 3a), XRD patterns presents only diffraction peaks related to pure copper. There is a
Metals 2017, 7, 117 5 of 12

Metals 2017, 7, 117 5 of 12


is a shift peak of copper in sintered composite compare to starting Cu powder. This fact clearly
shift peak
evidences thatofmost
copperof in
thesintered
Ti and composite comparein
C have dissolved to the
starting Cu powder.
copper matrix and Thisalso
fact that
clearly
theevidences
sintering
that most of the Ti and C have dissolved in the copper matrix and also that
temperature was not high enough to precipitate the TiC phase. Conversely, by increasing the sinteringthe sintering temperature
was not to
temperature high
1000enough to precipitate
C, Ti reacts with C, andthe TiC
TiC precipitates,
phase. Conversely, by increasing
as it is clearly noticeable theinsintering
the XRD
temperature to 1000 C, Ti reacts with C, and TiC precipitates, as it is clearly noticeable in the XRD
patterns of Figure 3b for mixtures with 20 vol % TiC. However, there is reason to believe that the
patterns of Figure 3b for mixtures with 20 vol % TiC. However, there is reason to believe that the
same has occurred for mixtures with 10 vol % of TiC because this is a thermodynamical condition.
same has occurred for mixtures with 10 vol % of TiC because this is a thermodynamical condition.
TiC weight percentages in bulk composites sintered at 1000 C produced from starting powders was
TiC weight percentages in bulk composites sintered at 1000 C produced from starting powders was
calculated by Rietveld refinement method as shown in Table 2. The weight percentages of in-situ
calculated by Rietveld refinement method as shown in Table 2. The weight percentages of in-situ TiC
TiC nanoparticles with 10 vol % reinforcement particles for CuTiH2C and Cu-TiC composites are
nanoparticles with 10 vol % reinforcement particles for CuTiH2C and Cu-TiC composites are 1.43
1.43 and
and 2.86%,
2.86%, respectively.
respectively. Furthermore,
Furthermore,asasitit will will be
be under
under mentioned,
mentioned, TEM TEM analyses
analysesconfirm
confirmthe the
presence of TiC
presence nanoparticles
of TiC nanoparticles in mixtures
in mixtures with
with 1010vol
vol%%ofofTiC.TiC.At
Athigher
higherreinforcement particlesof
reinforcement particles of
20 vol %, the amount of TiC precipitated from CuTiH2C and Cu-TiC composites
20 vol %, the amount of TiC precipitated from CuTiH2C and Cu-TiC composites also increases to also increases to
6.9 and 6.45 wt %, respectively. Additionally, it is important to observe that there was
6.9 and 6.45 wt %, respectively. Additionally, it is important to observe that there was no precipitation no precipitation
of intermetallic
of intermetallicphases during
phases during sintering
sinteringprocess
process atatany
anyofofthe
thesintering
sinteringtemperatures.
temperatures. If If one
one considers
considers
the CuTiC system, normally Cu, Ti, and C may interact to form several products
the CuTiC system, normally Cu, Ti, and C may interact to form several products through chemical through chemical
reactions [17].[17].
reactions However,
However, thetheGibbs
Gibbsfree energy
free energy ofof
TiC formation
TiC formationatatthe thetemperature
temperature of 1273 K K isisabout
about
84.4 84.4 kJ/mol,
kJ/mol, which which is much
is much lower
lower than
than thosetotoform
those formother
otherintermetallic
intermetallic phases
phases of Ti and
and Cu,
Cu,implying
implying
that that the precipitation
the precipitation of TiC
of TiC is thermodynamically
is thermodynamically preferredrelative
preferred relativetotoother
otherpossible
possible reactions.
reactions.

1000 oC

Cu
900 oC

Cu
TiC
Intensity (a.u)
Intensity (a.u.)




Cu-TiH2-C 20 %-TiC
Cu-TiH2-C 20%-TiC
Cu-Ti-C 20 %-TiC
Cu-Ti-C 20%-TiC
Cu-TiH2-C 10 %-TiC

10 %-TiC
Cu-TiH2-C 10%-TiC
Cu-Ti-C

Cu-Ti-C 10%-TiC
0

Cu
30 40 50 60 70 80
30 40 50 60 70 80
(a) 2 Theta (deg.) (b) 2 Theta (deg.)

Figure 3. XRD patterns of nanocomposites (a) Spark Plasma Sintered at 900 C; (b) Spark Plasma
Figure 3. XRD patterns of nanocomposites (a) Spark Plasma Sintered at 900 C; (b) Spark Plasma
Sintered at 1000 C.
Sintered at 1000 C.

Table 2. Fraction of phases of CuTiH2C and CuTiC composites sintered at 1000 C calculated by
Table 2. Fraction of phases of CuTiH2C and CuTiC composites sintered at 1000 C calculated by
Rietveld refinement.
Rietveld refinement.
Fraction of Phases (%)
Phase CuTiH2CFraction of Phases (%) CuTiC
Phase 10 vol %CuTiH2C
TiC 20 vol % TiC 10 vol % TiC
CuTiC 20 vol % TiC
TiC 2.86
10 vol % TiC 6.9
20 vol % TiC 1.43
10 vol % TiC 6.45
20 vol % TiC
Cu 97.14 97.14 98.57 93.55
TiC 2.86 6.9 1.43 6.45
Cu 97.14 97.14 98.57 93.55
Figure 4ad present backscattered electron (BSE) SEM images of CuTiH2C and CuTiC
nanocomposites sintered at 1000 C, showing details of the surface of samples. From these images,
Figure
one 4ad present
can observe backscattered
the presence electron
of three gray tones,(BSE)
whereSEMblackimages
regionsof CuTiH2C
indicate and CuTiC
the presence of some
nanocomposites sintered
closed porosity on theat 1000 C,
surface, showing
dark-gray detailscorrespond
regions of the surface of solid
to the samples. From
solution theseC),
Cu(Ti, images,
and,
one finally,
can observe
whitethe presence
regions of threetogray
correspond tones, regions.
Cu-richer where black regions indicate
It is interesting to notethe presence
that of some
the porosity is
closed porosity on the surface, dark-gray regions correspond to the solid solution
minimal for CuTiH2C nanocomposites for any amount of TiC. The porosity increases for CuTiC Cu(Ti, C), and,
finally, white regionsbut
nanocomposites correspond
reduces by to increasing
Cu-richer the
regions.
amountIt isofinteresting to note
TiC. However, that the porosity
apparently, Cu-richeris
regions
minimal forare thinner and
CuTiH2C better distributed
nanocomposites for CuTiC
for any amount nanocomposites
of TiC. The porosity than increases
for CuTiH2C ones,
for CuTiC
diminishing with
nanocomposites the amount
but reduces of TiC. Conversely,
by increasing the amountthe of
thicker and worse apparently,
TiC. However, distributed Cu-richer
Cu-richerregions
regions
in CuTiH2C
are thinner nanocomposites
and better distributed foraugment
CuTiCwith the amount of than
nanocomposites TiC. for CuTiH2C ones, diminishing
Metals 2017, 7, 117 6 of 12

with the amount of TiC. Conversely, the thicker and worse distributed Cu-richer regions in CuTiH2C
nanocomposites augment with the amount of TiC.
Metals 2017, 7, 117 6 of 12
Relative density measurements, presented in Table 3, confirm the above results regarding porosity.
The relative Relative
density density measurements,
of the CuTiH2Cpresented
and CuTiCin Table 3, confirm the above
nanocomposites increasesresults
as regarding
the sintering
porosity. The relative density of the CuTiH2C and CuTiC nanocomposites increases as the
temperature increases from 900 to 1000 C. Therefore, one could infer that this fact may be due to the
sintering temperature increases from 900 to 1000 C. Therefore, one could infer that this fact may be
enhanced viscosity of Cu/Cu(Ti, C) matrix at the higher sintering temperature, which results in an
due to the enhanced viscosity of Cu/Cu(Ti, C) matrix at the higher sintering temperature, which
efficient filling
results in anof efficient
pores due to high
filling diffusion
of pores due to rates. In composites
high diffusion rates. Inproduced
composites in-situ,
producedthe interfacial
in-situ, the area
is higher compared
interfacial area isto ex-situ
higher composites,
compared detrimental
to ex-situ composites,effects of interfacial
detrimental effects of phenomena (decohesion,
interfacial phenomena
void formation)
(decohesion,are voidmore likely to
formation) areprevail at high
more likely sintering
to prevail temperatures
at high compared compared
sintering temperatures to low sintering
to
temperatures.
low sinteringIslaktemperatures.
et al. [7] reported
Islak etthat
al. in
[7]hot-pressed
reported thatCuTiC nanocomposites,
in hot-pressed with 10 vol % TiC,
CuTiC nanocomposites,
with 10relative
the highest vol % TiC, the highest
density obtained relative
was density obtained
about 86.4%, wasin
while about
our 86.4%, while
samples, within our
the samples,
same TiCwithcontent,
it is, on average, around 96.8 either for CuTiH2C or CuTiC nanocomposites sintered at 1000 C.
the same TiC content, it is, on average, around 96.8 either for CuTiH2C or CuTiC nanocomposites
sintered atof1000
The presence C. Theon
porosity presence of porosity
the surface on the surface ofisnanocomposites
of nanocomposites a natural result is aofnatural result of
the consolidation
the consolidation process. The relative density of CuTiH2C has higher than that of CuTiC
process. The relative density of CuTiH2C has higher than that of CuTiC composite that why the
composite that why the amount of porosity can be seen in Figure 4b,d is more than in Figure 4a,c,
amount of porosity can be seen in Figure 4b,d is more than in Figure 4a,c, respectively. The maximum
respectively. The maximum relative density values were measured for CuTiH2C and CuTiC
relative density values
nanocomposites at were measured
the sintering for CuTiH2C
temperature of 1000 and CuTiC
C with 10 vol nanocomposites
% TiC, which were at 97%
the sintering
and
temperature of 1000 C with 10 vol % TiC, which were 97% and 96.6%, respectively.
96.6%, respectively.

(a) (b)

10m 10m

(c) (d)

10m 10m

Figure 4. SEM images of CuTiH2C and CuTiC nanocomposites Spark Plasma Sintered at 1000 C:
Figure 4. SEM images of CuTiH2C and CuTiC nanocomposites Spark Plasma Sintered at 1000 C:
(a) 10 vol % TiC, CuTiH2C nanocomposite; (b) 10 vol % TiC, CuTiC nanocomposite; (c) 20 vol %
(a) 10 vol % TiC, CuTiH2C nanocomposite; (b) 10 vol % TiC, CuTiC nanocomposite; (c) 20 vol %
TiC, CuTiH2C nanocomposite; (d) 20 vol % TiC, CuTiC nanocomposite.
TiC, CuTiH2C nanocomposite; (d) 20 vol % TiC, CuTiC nanocomposite.
Table 3. Relative density of Spark plasma sintered CuTiH2C and CuTiC nanocomposites.

Table Relative
3. Relative density of Spark plasma sintered Density
CuTiH2C and (%)
CuTiC nanocomposites.
Sintering
CuTiH2C CuTiC
Temperature (C)
10 vol % TiC 20 volRelative
% TiC Density
10 vol
(%)% TiC 20 vol % TiC
Sintering
900 95.8 95.3 95.4 95.2
Temperature ( C) CuTiH2C CuTiC
1000 97.0 96.4 96.6 96.2
10 vol % TiC 20 vol % TiC 10 vol % TiC 20 vol % TiC
Figure900
5 displays TEM images
95.8 of CuTiH2C95.3nanocomposites with
95.4 10 vol % TiC and
95.2sintered at
900 C. As1000
one can observe, Ti97.0
still continues in 96.4
the matrix, having96.6
a particle size of about
96.2 50 nm.
Metals 2017, 7, 117 7 of 12

Figure 5 displays TEM images of CuTiH2C nanocomposites with 10 vol % TiC and sintered
at 900 C. As one can observe, Ti still continues in the matrix, having a particle size of about 50 nm.
Figure 5a2017,
Metals shows
7, 117some TiC nanograins of about 1020 nm precipitated near Ti particles. 7As stated
of 12
before, the reaction between Ti and C is not complete because the sintering temperature is not high
Figure 5a shows some TiC nanograins of about 1020 nm precipitated near Ti particles. As stated
enough to enhance the diffusion of C into Ti. Thus most of Ti and C remains in the composite matrix.
before, the reaction between Ti and C is not complete because the sintering temperature is not high
Figure 5ce presents examples of selected area electron diffraction (SAED) patterns of CuTiH2C
enough to enhance the diffusion of C into Ti. Thus most of Ti and C remains in the composite matrix.
nanocomposite showing diffraction patterns for Cu, Ti, and TiC particles. There is a small misfit in
Figure 5ce presents examples of selected area electron diffraction (SAED) patterns of CuTiH2C
the indexation
nanocomposite of Cu due to diffraction
showing the presence of Ti for
patterns andCu,C inTi,solution
and TiC into the copper.
particles. There isIn addition,
a small misfitthere
in are
extrathe
spots in SAEDs
indexation because
of Cu due toof theparticle
presencesizes.
of TiAs
andthe
C particles
in solutionare smaller
into than In
the copper. theaddition,
smallestthere
aperture,
the diffraction will in
are extra spots beSAEDs
taken because
from theofparticle
particle and
sizes.regions
As the around.
particles areAt the sintering
smaller than thetemperature
smallest of

1000 aperture, the diffraction
C, TiC particles will be
precipitate taken from
copiously the nanocomposite
on the particle and regionsmatrix around. At the sintering
with particles size ranging
temperature
between 10 and 30 of nm
1000asC,
shownTiC inparticles
Figure precipitate copiously
6a,b. No other phaseon the nanocomposite
containing Ti could bematrix withunder
detected
particles
the TEM size ranging between 10 and 30 nm as shown in Figure 6a,b. No other phase containing Ti
resolution.
could be detected under the TEM resolution.
Figure 6c,d present TEM images of CuTiC nanocomposites, with 10 vol % TiC, and sintered
Figure 6c,d present TEM images of CuTiC nanocomposites, with 10 vol % TiC, and sintered
at 900 C, showing few TiC nanoparticles with sizes ranging between 10 to 30 nm. As it occurred for
at 900 C, showing few TiC nanoparticles with sizes ranging between 10 to 30 nm. As it occurred for
CuTiH2C nanocomposites, at the low sintering temperature of 900 C, only a small fraction of Ti
CuTiH2C nanocomposites, at the low sintering temperature of 900 C, only a small fraction of Ti
will react withwith
will react C, and most
C, and mostofof TiTi
and
andCCcontinue
continue dissolving
dissolving ininthe
the composite
composite matrix.
matrix. At theAtsintering
the sintering
temperature of 1000 C (Figure 6e,f), more TiC precipitates, whose particle size ranges from 10 to
temperature of 1000 C (Figure 6e,f), more TiC precipitates, whose particle size ranges from 10 to 20
20 nm.
nm.Nevertheless,
Nevertheless, Ti is is still
stillobserved
observed inin
thethe HRTEM
HRTEM image
image presented
presented in Figure
in Figure 6f. 6f.
The The presence
presence of TiC,
of TiC, eveneven ininmixtures
mixtureswith
with 10
10 vol
vol%%ofofTiC
TiCatat
high
high sintering temperature
sintering during
temperature during
XRD analyses (Figure 3), is confirmed by the observation that TiC precipitates
XRD analyses (Figure 3), is confirmed by the observation that TiC precipitates in the TEM analysis. in the TEM analysis.

Figure
Figure 5. TEM
5. TEM images
images andand SAEDofofCuTiH2C
SAED CuTiH2C nanocomposites
nanocomposites of of
10 10
volvol
% TiC sintered
% TiC 900 C:
at 900atC:
sintered
(a) bright-field image; (b) HR-TEM image of TiC crystal on copper matrix; (c) SAED of Ti; (d)
(a) bright-field image; (b) HR-TEM image of TiC crystal on copper matrix; (c) SAED of Ti; (d) SAED of SAED
of TiC; and (e) SAED of copper.
TiC; and (e) SAED of copper.

As it can be observed in Figures 5 and 6, the amount of TiC precipitated in the CuTiH2C
As it can be observed
nanocomposite is higher in
thanFigures 5 and
that for 6, the
CuTiC amount
after of TiC
sintering precipitated
at 1000 in al.
C. Yang et the[14]
CuTiH2C
also
nanocomposite is higher than that for CuTiC after sintering at 1000 C. Yang et al. [14] also prepared
prepared bulk TiC from TiH2C and TiC by self-propagation high-temperature synthesis method.
bulk By
TiCXRD
fromand
TiHDSC
2 C and TiC
results, by self-propagation
they found that for TiHhigh-temperature synthesis
2C, Ti and C reacted method.
to produce TiCByinXRD
the and
Metals 2017, 7, 117 8 of 12

DSCMetals 2017, 7, 117


results, they found that for TiH2 C, Ti and C reacted to produce TiC in the temperature8range of 12
of

1130 to 1300 C, very small amount of Ti remained after SHS process. For TiC, only an endothermic
temperature range of 1130 to 1300 C, very small amount of Ti remained after SHS process. For TiC,
peakonly
appears at 880 C because
an endothermic of the
peak appears at -Ti transformation
880 C to -Ti
because of the -Ti and a lot ofto
transformation Ti-Ti
andand
C remain. Little
a lot of Ti
TiC is detected, but the amount is much smaller than TiH
and C remain. Little TiC is detected, but the amount is much C.
2 smaller than TiH2C.

Figure 6. TEM images of: CuTiH2C nanocomposite10 vol %TiC and sintered at 1000 C, bright-
Figure 6. TEM images of: CuTiH2C nanocomposite10 vol %TiC and sintered at 1000 C, bright-field
field image in (a) and HR-TEM image in (b); CuTiC nanocomposite10 vol %TiC and sintered at
image
900inC,
(a)bright-field
and HR-TEM image image
in (c) in
and(b); CuTiC
HRTEM nanocomposite10
image vol %TiC and sintered
in (d); CuTiC nanocomposite10 vol %TiC 900 C,
atand
bright-field
sintered image
at 1000in
C,(c)bright-field
and HRTEM image
image in (e)inand
(d);HRTEM
CuTiC nanocomposite10
image vol
in (f), SAEDs refer to%TiC and sintered
TiC particles.
at 1000 C, bright-field image in (e) and HRTEM image in (f), SAEDs refer to TiC particles.
3.3. Hardness Results of Compacts
3.3. Hardness Results of Compacts
The hardness of a composite is an important parameter that determines their wear resistance for
sliding contact applications.
The hardness In this
of a composite sense,
is an hard TiC
important particles play
parameter thatan important role
determines theirwhen
wearreinforcing
resistance for
the soft Cu matrix. These particles lead to a higher hardness of the composite.
sliding contact applications. In this sense, hard TiC particles play an important role whenTable 4 summarizes
reinforcing
hardness
the soft values for
Cu matrix. all conditions
These particles studied
lead to in this work.
a higher From this
hardness table,
of the it is possible
composite. to observe
Table that,
4 summarizes
hardness values for all conditions studied in this work. From this table, it is possible to observe that,
Metals 2017, 7, 117 9 of 12

at the sintering temperature of 900 C, hardness values of CuTiC nanocomposites are lower than
those for CuTiH2C nanocomposites, for any addition of TiC. The formation of Cu(Ti, C) solid solution
Metals 2017, 7, 117 9 of 12
enhances the hardness of the composites. As the sintering temperature increases, there is a significant
increase in the
at the hardness
sintering values because
temperature more
of 900 C, TiC particles
hardness values ofprecipitate after the reaction
CuTiC nanocomposites are between
lower than Ti and
C. Thethose
highest hardness value
for CuTiH2C of an ex-situfor
nanocomposites, CuTiC composite
any addition of TiC.with
The10 vol % ofofTiC
formation wasC)
Cu(Ti, found
solidto be
aboutsolution
86.4 HVenhances
[7], much thelower
hardness
thanofthose
the composites. As the
found for the sintering
in-situ temperature
produced increases, there
nanocomposites is awork,
of this
significant increase in the hardness values because more TiC particles precipitate
which were 295 and 290 HV respectively for CuTiH2C and CuTiC nanocomposites with the same after the reaction
between Ti and C. The highest hardness value of an ex-situ CuTiC composite with 10 vol % of TiC
TiC content and sintered at 900 C. By increasing the volume of TiC, the hardness of nanocomposites
was found to be about 86.4 HV [7], much lower than those found for the in-situ produced
also increases to 314 and 306 HV correspondingly for CuTiH2C and CuTiC nanocomposites when
nanocomposites of this work, which were 295 and 290 HV respectively for CuTiH2C and CuTiC
sintered at 1000 C.
nanocomposites with the same TiC content and sintered at 900 C. By increasing the volume of TiC,
the hardness of nanocomposites also increases to 314 and 306 HV correspondingly for CuTiH2C
Table 4. Hardness values of nanocomposites sintered at 900 and 1000 C.
and CuTiC nanocomposites when sintered at 1000 C.
Hardness Value, HV
Table 4. Hardness values of nanocomposites sintered at 900 and 1000 C.
Sintering
Temperature ( C) CuTiH2C CuTiC
Hardness Value, HV
Sintering 10 vol % TiC 20 vol % TiC 10 vol % TiC 20 vol % TiC
CuTiH2C CuTiC
Temperature
900 (C) 250TiC
10 vol % 20 vol245
% TiC 242% TiC
10 vol 20244
vol % TiC
1000 295 314 290 306
900 250 245 242 244
1000 295 314 290 306
3.4. Fracture Analysis
3.4. Fracture Analysis
Figure 7 presents fracture morphologies of nanocomposites with 10 vol % TiC. The presence of
dimples onFigure 7 presents
the fracture fracture
surface morphologies
suggests of nanocomposites
a ductile fracture mode with 10 vol
in both % TiC. The presence
nanocomposites of
CuTiH2C
dimples on the fracture surface suggests a ductile fracture mode in both nanocomposites CuTiH2
and CuTiC. Fracture surface of the composites exhibits nano-void and micro-void coalescence in the
C and CuTiC. Fracture surface of the composites exhibits nano-void and micro-void coalescence in
matrix. Gray ultrafine particles are embedded in the copper matrix, which are fracture paths along
the matrix. Gray ultrafine particles are embedded in the copper matrix, which are fracture paths along
grain boundaries of the matrix.
grain boundaries of the matrix.

(a) (b)

100nm 100nm

(c) (d)

100nm 100nm

Figure 7. Fracture surfaces of 10 vol. %TiC (a) CuTiH2C nanocomposite sintered at 900 C; (b) Cu
Figure 7. Fracture surfaces of 10 vol. %TiC (a) CuTiH2C nanocomposite sintered at 900 C;
TiC nanocomposite sintered at 900 C; (c) CuTiH2C nanocomposite sintered at 1000 C; and (d)
(b) CuTiC nanocomposite sintered at 900 C; (c) CuTiH2C nanocomposite sintered at 1000 C;
CuTiC nanocomposite sintered at 1000 C.
and (d) CuTiC nanocomposite sintered at 1000 C.
Metals 2017, 7, 117 10 of 12
Metals 2017, 7, 117 10 of 12

At the highest sintering temperature of 1000 C, one can observe a better contact between
Metals 2017, 7,
reinforcement 117
particles and matrix, as presented in Figure 7c,d. The dimple size decreases 10 of 12 an
with
At the highest sintering temperature of 1000 C, one can observe a better contact between
increase in TiC content from 10 to 20 vol % as seen in Figure 8. The presence of more reinforcement
reinforcement
At theparticles and matrix,
highest sintering as presented
temperature of 1000inC,
Figure
one can 7c,d. The dimple
observe a better size decreases
contact between with
particle content
reinforcement in the copper
particlesfrom matrix
and matrix, prevents dimple growth. The fracture behaviorwithofanthese
an increase in TiC content 10 to 20asvol
presented
% as seenin Figure 7c,d.8.The
in Figure Thedimple sizeof
presence decreases
more reinforcement
nanocomposites
increase in TiCalso depicts a mixed mode, %with theinbrittle mode
8. Theof fractureofbeing the predominant
particle content incontent from
the copper 10matrix
to 20 vol as seen
prevents Figure
dimple growth. presence
The fracturemorebehavior
reinforcement
of these
one. The fracture
particle content surface of both composites indicate nearly flat surface, minimal plastic deformation
nanocomposites alsoin the copper
depicts a mixedmatrix
mode,prevents
with thedimple growth.
brittle mode The fracturebeing
of fracture behavior of these
the predominant
preceding the fracture
nanocomposites occurs. mixed
also depicts The mode,
microscopic characteristics include faceted surface and
one. The fracture surface of botha composites with the brittle
indicate nearlymode of fracture
flat surface, being
minimal the predominant
plastic deformation
one. The fracture
transgranular fracturesurface
of Cuofgrains
both composites indicate nearly flat surface, minimal plastic deformation
in the composites.
preceding the fracture occurs. The microscopic characteristics include faceted surface and transgranular
preceding the fracture occurs. The microscopic characteristics include faceted surface and
fracture of Cu grains in the composites.
transgranular fracture of Cu grains in the composites.
(a) (b)
(a) (b)

100nm 100nm
100nm 100nm
(c) (c) (d)
(d)

100nm 100nm
100nm 100nm
Figure 8. Fracture surfaces of 20 vol % TiC (a) CuTiH2C nanocomposite sintered at 900 C; (b) Cu
Figure 8. Fracture surfaces of 20 vol % TiC (a) CuTiH2C nanocomposite sintered at 900 C;
FigureTiC
8. Fracture surfaces
nanocomposite of 20 vol
sintered % TiC
at 900 (a)CuTiH2C
C; (c) CuTiH2C nanocomposite
nanocomposite sintered
sintered at 900
at 1000 C; (b)
C; and (d) Cu
(b) CuTiC nanocomposite sintered at 900 C; (c) CuTiH2C nanocomposite sintered at 1000 C;
TiC nanocomposite
CuTiC nanocompositesintered at 900atC;
sintered (c)C.
1000 CuTiH2C nanocomposite sintered at 1000 C; and (d)
and (d) CuTiC nanocomposite sintered at 1000 C.
CuTiC nanocomposite sintered at 1000 C.
In order to investigate the distribution of reinforcing particulates in copper matrix, EDS analyses
In ordercomposite
for
In the
order sintered
to investigate
to investigate theat
the 1000 C with
distribution
distribution of10
of vol % TiC,particulates
reinforcing
reinforcing is presentedin
particulates inincopper
Figure matrix,
copper 9. The size
matrix, EDS
EDS ofanalyses
the
analyses
for the waves
the composite on the Ti
composite sintered and
sintered atC at 1000 C
concentration
C with profiles
with 10 10 vol along
vol % the
% TiC, x-axis (distance) corresponds
TiC, is presented in Figure 9. The well to
The size the
size of
of the
the
for
waves sizeon
of the
the TiC
Ti nanoparticles
and C introduced
concentration into the
profiles copper
along the matrix
x-axis through ballcorresponds
(distance) milling. The distribution
well to the size
on the Ti and C concentration profiles along the x-axis (distance) corresponds well to the
of the Ti and C through copper matrix in CuTiH2C is better than of CuTiC. The content of oxygen
of the
size of TiC nanoparticles
the TiC nanoparticles introduced
introduced intointo
the the
copper
copper matrix
matrixthrough
throughballball
milling. The
milling. Thedistribution
distribution of
in CuTiH2C is lower than CuTiC composite which means that the effect of hydrogen release
thethe
of Ti Ti
andandCC through
through copper
copper matrix
matrix ininCuTiH2C
CuTiH2C isisbetter
better than
than of
of CuTiC.
CuTiC. The
The content of oxygen
oxygen
from TiH2 reacts with the oxygen lead to reduce the oxygen content in the composite after sintering.
in CuTiH2C
in CuTiH2C is lower
is
No contamination
lowersuch
than
than CuTiC composite
as Fe from thecomposite
which
balls and jarwhich
means
can be means
that
detectedthat
the effect
the
for both
effect of
of hydrogen
composites.
hydrogen release
release
from TiH
from TiH22 reacts
reacts with
with the
the oxygen
oxygen lead
lead to
to reduce
reduce the
the oxygen
oxygen content
contentin
inthe
thecomposite
compositeafter
aftersintering.
sintering.
No contamination
No contamination such as Fe from the balls and jar can be detected for both composites.

Figure 9. Cont.
Metals
Metals 2017,2017, 7, 117
7, 117 11 of1112of 12

(a) (b)
120 120
Cu L 12 Cu L 12
90 90

60 60

30 30

0 0
Ti L 12 Ti L 12
11.4 11.4

7.6 7.6
Intensity (cps)

Intensity (cps)
3.8 3.8

0.0 0.0
20 C K 12 20 C K 12
15 15
10 10
5 5
0 0
O K 1 O K 1
30 30

20 20

10 10

0 0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0

Distance (m) Distance (m)

Figure
Figure 9. SEM
9. SEM images
images andand
EDSEDS profiles
profiles for CuTiH2C
for (a) (a) CuTiH2C
andand (b) CuTiC
(b) CuTiC composites
composites sintered
sintered at at
C with
10001000 C with 10 vol
10 vol % reinforcement
% reinforcement particles.
particles.

4. Conclusions
4. Conclusions
In-situ
In-situ copper
copper matrix
matrix composites
composites strengthened
strengthened with with
(10 (10
andand 20 vol
20 vol %) %)TiCTiC
werewere prepared
prepared by SPS
by SPS
of ball
of ball milled
milled mixtures
mixtures of CuTiH2C
of CuTiH2C andand CuTiC
CuTiC powders.
powders. TheThe relative
relative densities
densities of composites
of composites
sintered at 900 and 1000
C are in the range of 95%97%. The XRD of composites
sintered at 900 and 1000 C are in the range of 95%97%. The XRD of composites sintered at 900 sintered at 900
C C
showed
showed onlyonly
Cu(Ti,Cu(Ti,
C) solidC)solution,
solid solution, noTiC
no trace of trace of TiC
or oxide or oxide
phases. phases.
Increasing Increasing
sintering sintering
temperature
temperature
to 1000 C, diffraction peaks of TiC and pure Cu phases can be seen
to 1000 C, diffraction peaks of TiC and pure Cu phases can be seen from XRD patterns for composites from XRD patterns
for composites reinforced with 20 vol % TiC, while for composite with 10 vol
reinforced with 20 vol % TiC, while for composite with 10 vol % TiC reinforcement no diffraction % TiC reinforcement
no diffraction
peaks of TiC phase peaks
can of
beTiC phase can
detected. Theberesults
detected. The results
of TEM analysisoffor
TEM analysis
these for these
composites composites
confirmed
confirmed the presence of nanoparticle TiC about 10 to 20 nm disperse on Cu
the presence of nanoparticle TiC about 10 to 20 nm disperse on Cu matrix near residual Ti particlesmatrix near residual Ti
particles whereas, under XRD resolution, it cannot detected. A larger amount
whereas, under XRD resolution, it cannot detected. A larger amount of TiC nanoparticles precipitated of TiC nanoparticles
precipitated
in the CuTiH2C in the CuTiH2C
composite composite
is observed thanis for
observed
that ofthan for that
CuTiC fromof CuTiC
TEM images.from These
TEM images.
TiC
nanoparticles enhance the hardness of composites prepared from the former. With the increasing the the
These TiC nanoparticles enhance the hardness of composites prepared from the former. With
increasing the
reinforcement reinforcement
particles particles
content from 10 to content
20 vol %from 10 to 20 vol
the hardness % the
values of hardness
composites values of composites
increased while
increased while relative density slightly decreased. The hardness of composites also
relative density slightly decreased. The hardness of composites also increased with increasing sintering increased with
increasing sintering temperature with any reinforcement particles addition.
temperature with any reinforcement particles addition. The highest hardness values of CuTiH2C The highest hardness
andvalues
CuTiCof CuTiH2C
composites and CuTiC
sintered at 1000composites
C are 314sintered
and 306atHV,1000 C are 314 and 306 HV, respectively.
respectively.

Acknowledgments:
Acknowledgments: ThisThis research
research waswas funded
funded by the
by the Vietnam
Vietnam National
National Foundation
Foundation for Science
for Science andand Technology
Technology
Development (NAFOSTED),
Development (NAFOSTED),grant number
grant 103.02-2011.49.
number 103.02-2011.49.
Author Contributions:
Author Nguyen
Contributions: NguyenThi Thi
Hoang Oanh
Hoang andand
Oanh Nguyen
NguyenHoang VietViet
Hoang designed the the
designed research, conducted
research, the the
conducted
experiments, and wrote the paper. Ji-Soon Kim supervised the project and Alberto Moreira Jorge Junior revised
the experiments, andauthors
manuscript. All wrote the paper.the
reviewed Ji-Soon Kim supervised the project and Alberto Moreira Jorge Junior revised
manuscript.
the manuscript. All authors reviewed the manuscript.
Conflicts of Interest: The authors declare no conflict of interest.
Conflicts of Interest: The authors declare no conflict of interest.
Metals 2017, 7, 117 12 of 12

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