Q1/Scopus/JCR/ISI

IF (2019)=3.830
ISSN:0272-8842 5 ‫ ردﯾﻒ‬- 1 ‫ ﺑﻨﺪ‬-2 ‫ﺟﺪول‬
MIF (2019)=1.163 Ceramics International 42 (2016) 8895–8899

Contents lists available at ScienceDirect

Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Synthesis of Al/TiC–Al2O3 nanocomposite by mechanical alloying

and subsequent heat treatment
M. Zarezadeh Mehrizi n, R. Beygi, Gh. Eisaabadi
Department of Materials Science and Engineering, Faculty of Engineering, Arak University, Arak 38156-8-8349, Iran

art ic l e i nf o a b s t r a c t
1‫ﻒ‬ ‫ ردﯾ‬- 3 ‫ ﺑﻨﺪ‬-2 ‫ﺟﺪول‬
Article history: In this study, Al/TiC–Al2O3 nanocomposite was synthesized via mechanical alloying and heat treatment.
Received 3 February 2016 Phase development and structural changes were studied by X-ray diffraction technique and field-
Received in revised form emission gun scanning electron microscopy. The results showed that the phase evolutions during me-
21 February 2016
chanical alloying were strongly dependent on milling time until 20 h by formation of Al3Ti and Al2O3.
Accepted 23 February 2016
Available online 27 February 2016
After that, by increasing milling time, no new phases formed. Heat treatment of 60 h milled powder
showed that no new phases (especially TiC) were found after annealing at 500 °C. But increasing tem-
Keywords: perature to 1000 °C caused the Al3Ti and TiO2 peaks disappeared and TiC peaks emerged. These results
Al/TiC–Al2O3 confirmed that the formation of TiC is not feasible in an Al–TiO2–C system with excess Al by mechanical
Mechanical alloying
alloying.
Milling time
& 2016 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
Heat treatment

1. Introduction nanocrystalline alloys and intermetallic compounds. MA allows

Metal matrix composites (MMCs) reinforced with carbides,
nitrides, borides or oxides have been regarded as materials that
meet various modern engineering needs where a combination of
multiple/complex properties is required [1]. These composites
combine metallic properties (ductility and toughness) with cera-
mic characteristics (high-strength and modulus), leading to
greater strength in shear and compression and to higher service
temperature capabilities [2].
The high specific strength and stiffness, good toughness
and wear resistance of Al/TiC–Al2O3 composite have attracted
considerable attention in fields of aeronautics, astronautics,
automobile industries [3,4]. In some early reports, TiC and
Al2O3-reinforced Al composites with improved mechanical prop-
erties and wear resistance were manufactured by field-activated
combustion synthesis [3], microwave sintering [5] and spark
plasma sintering [6]. The improved mechanical properties can be
further obtained by decreasing the grain size of both the matrix
and the reinforced phase to nanometer scale [7].
The formation of alloys by solid state reaction that occurs
during ball milling of elemental powders is called mechanical al-
loying. This process is characterized by repeated welding and
fracturing of powder particles, and microstructural changes during
mechanical alloying are influenced by the mechanical behavior,
the powder components and process variables [8,9]. Mechanical
alloying (MA) is a solid state technique used for fabrication of
n
Corresponding author.
materials scientists to overcome material limitations and to
manufacture alloys that are difficult or impossible to be produced
by conventional melting and casting techniques. Through this
technique, the fine-grained powders can be formed [10–13].
Two kinds of reaction mechanism for MA have been proposed
[7,14]:
(1) gradual inter-diffusion of elements and formation of new
phases and products by prolonged milling time.
(2) Sudden formation of products in a short period of milling
time and, therefore, occurrence of mechanically alloyed
self-sustaining reaction (MSR) (the calculated adiabatic
temperature41800 K).
WC formation from W and C raw materials and TiC compound
from Ti and C are examples of the first and second mechanism,
respectively [7].
There have been some studies to synthesize TiC–Al2O3 nano-
composite by mechanical alloying. Razavi and coworkers used
impure Ti chips and elemental powders of Al and carbon black,
TiC–Al2O3 was formed during the annealing of milled powder [15].
Kumar et al. synthesized the Al2O3–TiC composite from a mixture
of graphite, Al2O3 and TiO2 powders by high energy ball milling
followed by spark plasma sintering (SPS) process [6]. Hajalilou
et al. synthesized TiC–Al2O3 nanocomposite from titanium dioxide
(rutile type), aluminum and graphite powders by mechanical al-
loying [7]. In these studies (TiC–Al2O3 formation), mechanically
alloyed self-sustaining reaction have been proposed as reaction
mechanism for MA because the calculated adiabatic temperature

http://dx.doi.org/10.1016/j.ceramint.2016.02.144
0272-8842/& 2016 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
8896 M.Z. Mehrizi et al. / Ceramics International 42 (2016) 8895–8899
were more than 1800 K. An excess amount of Al in Al–TiO2–C
system will decrease the adiabatic temperature below the
threshold value (1800 K) and the SHS reaction cannot take place or
self-sustain and reaction mechanism will change. For
(4 þx)Al–3TiO2–3C system, if the excess Al content, x, is more than
9 mol, it will be impossible to initiate reaction of the system be-
cause its adiabatic combustion temperature is below 1800 K.
To the authors' knowledge, no articles were found dealing with
the investigation of TiC formation mechanism in Al–TiO2–C system
with an excess amount of Al by mechanical alloying.
In this study, the 14Al–3TiO2–3C system was evaluated by
mechanical alloying and heat treatment and effect of excess Al on
TiC formation mechanism has been investigated. The phase
transformation, microstructure and morphological evolutions of
powders during mechanical alloying and heat treatment were also
investigated.
2. Experimental procedure
The Al/TiC–Al2O3 nanocomposite from starting powders of Al
(  50 mm, 99.2%), TiO2 ( 10 mm, 99.5%), and graphite (  10 mm,
99.9%) was prepared by reaction as:
3TiO2 + 3 C + (4 + x) Al=3TiC+2Al2 O3 + x Al (1)
The powders were mixed in the desired stoichiometry (Reac-
tion (1)) with excess Al content x ¼10 mol to produce Al/TiC–Al2O3
composite. Mechanical alloying of powder mixture was performed
in a planetary ball mill at room temperature. The milling media
consisted of balls with different diameters, confined in a 310 mL
volume vial. The ball and bowl materials were made of hardened
chromium steel. The ball to powder weight ratio was 20:1, and the
vial rotation speed was 350 rev min  1. A total amount of 10 g of
powder mixture was milled. No process control agent was added
to powder mixture. Isothermal annealing of the milled specimens
was carried out at 1000 °C for 1 h.
The phase changes that occurred during ball milling and heat
treatment were investigated by X-ray diffraction analysis using a
Philips X'PERT multipurpose X-ray diffractometer (Philips Analy-
tical BV, Almelo, The Netherlands) with Cu Kα radiation
(0.15405 nm). The crystallite size and internal strain of powders
were estimated using the Williamson–Hall method [16]:
0.91λ
β cos θ = + 2Aε sin θ
d (2)
where θ is the Bragg diffraction angle, d is the crystallite size, ε is
the average internal strain, λ is the wavelength of the radiation
used, β is the diffraction peak width at half-maximum intensity,
and A is the coefficient, which depends on the distribution of
strain. The average internal strain can be estimated from the linear
slope of β cos θ versus sin θ, and the average crystallite size can be
estimated from intersect of this line at sin θ ¼0.
The microstructure and morphology of powder particles were
analyzed using a field-emission gun scanning electron microscope
(MIRA3 TESCAN).
3. Results and discussion
3.1. Phase development
Fig. 1 showed XRD patterns of Al, TiO2 and C (graphite) powder
mixture as received and after different milling times. As seen,
diffraction patterns showed strong Al peaks because Al has a high-
mass percentage. Also, the intensity of Al and TiO2 diffraction
Fig. 1. X-ray diffraction results of powders milled for different durations.
peaks decreased during MA and their width increased progres-
sively with increasing milling time. With an increase in milling
time up to 5 h, the (002) reflections of graphite completely dis-
appeared indicating that graphite particles were heavily deformed
and fractured into fine slices. On the other hand, the intensities of
graphite peaks declined significantly while no new phase was
observed. This drop can be attributed to the mixing of powders at
the beginning of ball milling. The brittle behavior of graphite after
5 h of milling made the grain size to decrease significantly. In
addition with increasing milling time, the intensity of Al and TiO2
peaks decreased and their width increased as a result of refine-
ment of crystallite size and enhancement of lattice strain.
As milling continued to 10 h, the Al peaks slightly shifted to-
wards higher angles. Since graphite has smaller radii than Al, in-
stitutional dissolution of graphite into Al lattices decreased the
lattice parameter of Al. These changes suggest that a Al(C) solid
solution begins to form during this stage of the process. In this
pattern, it can see broad Al-based solid solution peaks and a small
broad halo. The peak broadening may be due to severe plastic
deformation or due to an amorphous component seeming to
overlap the most intense peak [11].
Further milling time (20 h), new peaks related to Al2O3 and
Al3Ti appeared, suggesting that the reactions in the as-milled
powders of 14Al þ3TiO2 þ 3C took place not according to Reaction
(1). This result has been reported previously by Kim and cow-
orkers in combustion reaction in Al–TiO2–C system with excess Al
[17]. By increasing the milling time from 20 h to 60 h, no structural
change was detected except peak broadening due to the crystallite
size reduction.
In an attempt to activate the un-reacted powders, 60 h milled
powders were annealed at different temperatures for 1 h (Fig. 2).
As shown in Fig. 2, no new phases (especially TiC) were found after
annealing at 500 °C. The width of XRD peaks decreased and their
intensity increased due to stress release as well as grain growth.
But phase identification after heat treatment at 1000 °C of 60 h
milled powder indicates that the Al3Ti and TiO2 peaks disappeared
and TiC peaks emerged. It can be seen that TiO2 and Al3Ti com-
pletely changed to new phases.
According to Fig. 2, after annealing of 60 h milled powder at
1000 °C, the average crystallite size of Al, TiC and Al2O3 were
∼43 nm, ∼28 nm and ∼31 nm, respectively. The mean lattice
strains for this sample, determined by the same formula, were
0.506%, 0.554% and 0.405% for Al, TiC and Al2O3, respectively.
 M.Z. Mehrizi et al. / Ceramics International 42 (2016) 8895–8899
Fig. 2. XRD patterns of powder mixture before and after annealing.
3.2. Mechanism of TiC formation
Previous studies showed that Al2O3–TiC nanocomposite was
synthesized by mechanical alloying according to Reaction (1) with
x ¼0 (without any Al in final product) which involved two reac-
tions: reduction of TiO2 by Al to form elemental Ti followed by the
reaction of Ti with C to form TiC. These two reactions can be re-
presented as a thermite reaction, Reaction (3), and a subsequent
synthesis reaction, Reaction (4):
4Al + 3TiO2 = 2Al2 O3 + 3Ti
ΔG°298K = − 500.2 kJ/mol, ΔH °298K = − 521.2 kJ/mol
Ti+C = TiC,
ΔG°298K 298 = −180 kJ/mol, ΔH °298K = −183.7 kJ/mol
Hu et al. [3] studied the formation mechanism of TiC in Al–TiO2
–C system containing an excess amount of Al (in comparison of
Reaction (1)) during combustion synthesis. They reported that TiC
was not produced by a single reaction as given by Eq. (1), but ra-
ther formed as a result of a series of reactions that occurred be-
tween the reactions products produced during the intermediate
stages. At first, Al tended to react with TiO2 due to its high affinity,
forming Al2O3 and Al3Ti, and Al4C3 was produced by the reaction
between Al and C. Subsequently, these intermittent reaction pro-
ducts, Al3Ti and Al4C3, reacted with each other to form TiC.
The mechanical alloying is a chemical solid state process, and
diffusion has an essential role on the formation of different phases
in solid state [10,11]. In this study, TiC was not formed during the
mechanical alloying. The XRD results confirmed that Reaction (5)
has been taken place during ball milling and Al3Ti formed. Heat
treatment of 60 h milled powder at 500 °C has no effect and no
new phases were formed. By increasing of annealing temperature
8897
to 1000 °C, molten Al reacted with remained TiO2 according to
Reaction (5) and Al3Ti/ Al2O3 formed. Also, the rest of molten Al
dissolved graphite particles and Al3C4 phase was formed (Reaction
(6)). Based on Hu et al. proposed mechanism, Al3C4 and Al3Ti re-
acted together and TiC was formed (Reaction (7)). The following
reactions are:
During mechanical alloying:
13Al + 3TiO2 → 2Al2 O3 + 3Al3 Ti
ΔG°298K = −1022.0 kJ mol−1, ΔH °298K = −960.4 kJ mol−1 (5)
During heat treatment at 1000 °C:
(3)
4Al + 3C → Al4 C3
ΔG°298K = −242.5 kJ mol−1, ΔH °298K = −215.7 kJ mol−1 (6)
(4)
3Al3 Ti + Al4 C3 → 3TiC + 13Al
ΔG°298K = −125.2 kJ mol−1, ΔH °298K = −116.7 kJ mol−1 (7)
This results showed that TiC was not formed in solid state in
Al–TiO2–C system with an excess amount of Al. During mechanical
alloying just one of the intermediate reaction products, Al3Ti and
Al2O3 were formed. The subsequent heat treatment must be done
at temperatures above Al melting point. In this temperatures,
molten Al reacted to graphite and Al4C3 intermediate product
formed. The reaction between Al3Ti and Al4C3 caused to TiC
formation.
4. Morphological changes
Fig. 3 showed the morphology of powder particles during ball
milling at various durations. As can be seen in Fig. 3a, after 5 h
milling, raw material powders in the form of big agglomerates and
8898 M.Z. Mehrizi et al. / Ceramics International 42 (2016) 8895–8899

Fig. 3. Cross-sectional SEM micrographs of powder mixture after (a) 5 h, (b) 20 h, (c) 40 h, (d) 60 h of milling times and (e), (f) high-magnification of 60 h milled powder at
two different zones.

fine particles with irregular morphologies and heterogeneous
distribution were observed. The formation of fine particles with
agglomerates could be attributed to cold welding and plastic de-
formation of powders.
The fine particles agglomerated beyond 20 h of milling due to
the occurrence of an exothermic reaction between the raw mate-
rials according to Reaction (3) and the formation of Al3Ti and
Al2O3, which increased the temperature locally (Fig. 3b). Also, the
existence of fine Al and C powders caused these particles to adhere
together, and further agglomerates were formed.
Increasing milling time to 40 h decreased the size of agglom-
erates again as a result of work hardening and the increasing
fracture rate of powders when compared to the cold welding rate
(Fig. 3c). In fact during MA, between 20 and 40 h, work hardening
of powder takes place and fracturing overcame cold welding and
the distribution of the powder particles became more homo-
genous. With increasing milling time from 40 h to 60 h, powder
particles adhered together and agglomeration process occurred.
The average powder particles size seems to be within 1–10 mm
(Fig. 3d). High-resolution SEM images for different powder parti-
cles milled after 60 h confirmed that the average particles size of
agglomerates is 25 nm (Fig. 3e and f).
5. Conclusion
The following conclusions can be made from the present
research:
 M.Z. Mehrizi et al. / Ceramics International 42 (2016) 8895–8899
 Al/TiC–Al2O3 nanocomposite was formed by mechanical alloy-
ing and subsequent heat treatment.
 During ball milling of Al–TiO2–C with excess Al, TiC was not
formed.
 During ball milling, Al3Ti and Al2O3 formed after 20 h and by
increasing milling time to 60 h, no new phases were formed.
 The annealing of 60 h milled powder showed that no new
phases (especially TiC) were found after annealing at 500 °C. But
increasing temperature to 1000 °C caused the Al3Ti and TiO2
peaks disappeared and TiC peaks emerged.
References
[1] S.G. Son, B.H. Lee, J.M. Lee, J.C. Lee, Low-temperature synthesis of (TiC þAl2O3)/
Al alloy composites based on dopant-assisted combustion, J. Alloy. Compd. 649
(2015) 409–416.
[2] G. Xiao, Q. Fan, M. Gu, Z. Jin, Microstructural evolution during the combustion
synthesis of TiC–Al cermet with larger metallic particles, Mater. Sci. Eng. A 425
(2006) 318–325.
[3] Q. Hu, P. Luo, Y. Yan, Microstructures, densification and mechanical properties
of TiC–Al2O3–Al composite by field-activated combustion synthesis, Mater. Sci.
Eng. A 486 (2008) 215–221.
[4] H. Zhu, Y. Jiang, Y. Yao, J. Song, J. Li, Z. Xie, Reaction pathways, activation en-
ergies and mechanical properties of hybrid composites synthesized in-situ
from Al–TiO2–C powder mixtures, Mater. Chem. Phys. 137 (2012) 532–542.
[5] Y. Cheng, S. Sun, H. Hu, Preparation of Al2O3/TiC micro-composite ceramic tool
materials by microwave sintering and their microstructure and properties,
8899
Ceram. Int. 40 (2014) 16761–16766.
[6] R. Kumar, A.K. Chaubey, S. Bathula, B.B. Jha, A. Dhar, Synthesis and char-
acterization of Al2O3–TiC nano-composite by spark plasma sintering, Int. J.
Refract. Met. Hard Mater. 54 (2016) 304–308.
[7] A. Hajalilou, M. Hashim, M. Nahavandi, I. Ismail, Mechanochemical carboalu-
minothermic reduction of rutile to produce TiC–Al2O3 nanocomposite, Adv.
Powder Technol. 25 (2014) 423–429.
[8] C. Suryanarayana, Mechanical alloying and milling, Prog. Mater. Sci. 46 (2001)
1–184.
[9] C. Suryanarayana, N. Al-Aqeeli, Mechanically alloyed nanocomposites, Prog.
Mater. Sci. 58 (2013) 383–502.
[10] M. Zarezadeh Mehrizi, M. Shamanian, A. Saidi, Synthesis of CoWSi–WSi2 na-
nocomposite by mechanical alloying and subsequent heat treatment, Ceram.
Int. 40 (2014) 9493–9498.
[11] B.S.B. Reddy, K. Das, S. Das, A review on the synthesis of in situ aluminum
based composites by thermal, mechanical and mechanical–thermal activation
of chemical reactions, J. Mater. Sci. 42 (2007) 9366–9378.
[12] C. Koch, Structural nanocrystalline materials: an overview, J. Mater. Sci. 42
(2007) 1403–1414.
[13] M.Z. Mehrizi, A. Saidi, M. Shamanian, Production of Fe3Al–TiC nanocomposite
by mechanical alloying of FeTi2–Al–C powders, Mater. Sci. Technol. 27 (2011)
1465–1468.
[14] C.J. Lu, Z.Q. Li, Structural evolution of the Ti–Si–C system during mechanical
alloying, J. Alloy. Compd. 395 (2005) 88–92.
[15] M. Razavi, M.R. Rahimipour, R. Mansoori, Synthesis of TiC–Al2O3 nano-
composite powder from impure Ti chips, Al and carbon black by mechanical
alloying, J. Alloy. Compd. 450 (2008) 463–467.
[16] G.K. Williamson, W.H. Hall, X-ray line broadening from filed aluminium and
wolfram, Acta Met. 1 (1953) 22–31.
[17] J.-W. Kim, J.-M. Lee, J.-H. Lee, J.-C. Lee, Role of excess Al on the combustion
reaction in the Al–TiO2–C system, Met. Mater. Int. 20 (2014) 1151–1156.