Journal of Materials Processing Technology 122 (2002) 301–304

In situ reacted titanium nitride-reinforced aluminum alloy composite

R.F. Shyua, F.T. Wenga, C.T. Hob,*
a
Department of Mechanical Manufacturing Engineering, National Huwei Institute of Technology, Huwei, China
b
Department of Mechanical Design Engineering, National Huwei Institute of Technology, Huwei, China
Received 18 November 2001

Abstract

In this paper, an aluminum matrix containing titanium nitride particles was fabricated by an in situ process in which nitrogen gas reacts with
titanium in the liquid melt to form TiN. The tensile and yield strength increased by up to 20% after the formation of TiN particles in the Al
alloy matrix, whilst the hardness increased by up to 27%. The abrasive and sliding-wear resistance increased with the in situ formation of the
TiN particles. # 2002 Elsevier Science B.V. All rights reserved.

Keywords: Wear; Composites; Aluminum alloy; Titanium nitride

1. Introduction tion [10]. A Al–Si–graphite piston cylinder used in a Ferrari

Leaded-tin bronzes have been used in many tribological
applications, including plain bearings, and, even now, they
are amongst the universally accepted materials for such
applications. However, the high density of bronzes, asso-
ciated with problems such as health hazards caused by the
toxic properties of lead that are effective during melting, and
the use of the costly and scarce element tin, has led to the
searching for alternative materials for possible applications.
In many tribological applications, aluminum alloys are
desirable because of their low densities, but they are not used
because of their extremely poor wear resistance. Therefore,
the development of aluminum matrix composites is receiv-
ing considerable emphasis in meeting the requirements of
various industries. In previous work, it was shown that the
incorporation of both hard ceramic particles (e.g. alumina
[1–3], silicon carbide [4–6], silica [7] or zircon [8,9]) and a
soft solid lubricant (e.g. graphite [10–12] or mica [13]) into
an aluminum alloy increased the wear resistance.
Considerable progress has been made in the application of
particle-reinforced metals, most notably for engine compo-
nents. Alumina particle-reinforced aluminum alloy pistons
have performed well, the power output increasing with a
remarkably low wear rate of the composite piston [14]. The
use of a Al–Si–graphite particle composite piston resulted in
a 9% reduction in the frictional horsepower losses of the
engine and up to 3% reduction in the specific fuel consump-
*
Corresponding author.
E-mail address: hoct@ms25.hinet.net (C.T. Ho).
Formula One world-championship-winning engine provided
increased and consistent output and reduced the fuel con-
sumption [15,16]. Particle-reinforced metals are so promis-
ing that metal-matrix composites may gradually replace
most unreinforced metals [17].
The present study utilizes an in situ process in which a
nitrogen gas reacts with titanium in the liquid melt to form
TiN, Al-MðliquidÞ þ 1=2 N2 ¼ MNðsolidÞ þ AlðliquidÞ
[18]. From a processing view-point, the advantages of the
in situ process via conventional powder metallurgy or the
casting-particulate approach include: (1) a single step, cost-
effective reaction and casting approach; (2) finer particulates
(0.1–0.2 mm) with a more homogeneous distribution; and (3)
improved wettability between the particulate and the matrix.
One of the limitations of the current technique is the
relatively high temperature (1300–1600 K) necessary for
processing the material. A secondary limit is the high
apparent viscosity of the melt that precludes the use of high
percentages of reinforcement [18].
In this paper, the mechanical properties and the wear
behavior of an in situ TiN particle-reinforced aluminum
alloy were investigated.
2. Experimental procedure
Al–5.1%Cu–6.2%Ti was used as the matrix material. The
in situ reaction was carried out in a vacuum induction
furnace. Melting of the Al–5.1%Cu–6.2%Ti was achieved
under vacuum and subsequently the chamber was back-filled

0924-0136/02/$ – see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 4 - 0 1 3 6 ( 0 2 ) 0 0 0 7 2 - 9
302 R.F. Shyu et al. / Journal of Materials Processing Technology 122 (2002) 301–304
with purified argon gas, which was also the carrier gas. Upon
reaching the appropriate processing temperature, the nitride
carrying gas was introduced into the melt via a gas diffuser
system. The reaction was carried out at a constant tempera-
ture 1400 K for 4 h to ensure complete the conversion of
titanium nitride. After the completion of the reaction the
melt was solidified using a mould cavity of 6 cm length and
1.3 cm width for tensile testing samples, or using a mould
cavity of 14 mm diameter for wear-testing samples. The
mould material is SKD4. After pouring the liquid samples
into the mould, pressure ranging from 30 to 50 MPa was
applied immediately through a piston at the top of the mould.
The pressure was maintained for 2 min, then the samples
were cooled to room temperature [18]. The composites was
examined by optical microscopy and scanning electron
microscopy (SEM) with link electron energy dispersive
analysis (EDX), after polishing. Verification of the particu-
lates in titanium nitride was carried out by EDX.
Dog-bone samples with a gauge length of 25 mm and a
cross-sectional area of 48 mm2 was machined from the cast
samples. The tensile tests were performed on these samples
using a hydraulic material testing system (MTS) machine.
The strain was measured using a strain gauge. Hardness
testing was also performed on these samples.
Fig. 1. Abrasive wear and sliding wear test geometry.
Abrasive tests were carried out using a Teledyne Taber
Model 503 standard abrasive tester. Three cylindrical sam-
ples, of 14 mm diameter, were positioned at three points
along a circle, in a disc-like sample holder (Fig. 1(a)). Two
crystalon (a clay composite impregnated with 180 grit SiC
particles) grinding wheels, of 10 mm thickness, were loaded
by weights in a perpendicular direction onto the samples and
rotated with the sample holder in a horizontal plane. The
samples were abraded by the grinding wheels twice each
cycle because of the use of two wheels. The load was
adjusted by changing the weights. The rotational speed of
the sample holder was constant at 72 rpm corresponding to a
linear speed of 0.3 m/s.
Sliding wear tests were conducted on a Denison wear-
testing machine using a pin-on-disc type tester at a sliding
speed of 0.3 m/s under dry conditions. A sample of 6 mm in
diameter and 12 mm in length was pressed against a rotating
horizontal steel disc (hardness 60 HRC) under a 1 kg applied
load (Fig. 1(b)). The coefficient of friction was obtained by
measuring the side-force on the specimen produced by the
rotation of the disc at a linear speed of 0.3 m/s. The weight
loss due to wear was measured, the wear rate of the samples
being calculated from the weight loss and the volume loss.
3. Results and discussion
Fig. 2 shows a scanning electron micrograph of the TiN
particles distributed in the aluminum matrix. Verification of
the particulates to be titanium nitride was carried out by
ESCA analysis.
The titanium nitride particle size is estimated from 0.1 to
1.5 mm upwards, which is much smaller than that of the
commercially available TiN powder, as expected. The
volume fraction of TiN in the composite was about 6%,
which was determined from the theoretical densities of the
phases.
The tensile properties and the hardness data of the sam-
ples are listed in Table 1, each item of data being the average
of at least five tests. The tensile and yield strength increased
by up to 20% after the formation of TiN in the Al alloy
Fig. 2. Composite containing TiN particles formed in situ.
 R.F. Shyu et al. / Journal of Materials Processing Technology 122 (2002) 301–304
Table 1
Tensile strength and hardness data of samples
Sample UTS YS Hardness Modulus
(MPa) (MPa) (GPa)
Al–5.1Cu–6.2Ti 330  12 262  6 94  4 HB 78  4
(Al alloy)
Compositea 397  15 314  8 121  5 HB 89  5 (94)b
a a
Al alloy containing in situ formation of TiN.
b
Rule of mixture, based on the assumption that the modulus of the
matrix is 78.
matrix, whilst the hardness increased by up to 27%. Com-
paring the value of the modulus of the composite from
Table 1, there appears to be close agreement between the
measured value and the predicted value using the rule of
mixtures. This strongly suggests that the bonding between
the TiN particles and the aluminum matrix is strong, so the
dispersoid TiN particles could accommodate the majority of
the applied force and strength the Al alloy [19,20]. Further-
more, if the thermal expansion coefficient of the dispersoid
is lower than that of the matrix, a compressive stress and
dislocation field would be generated around the dispersoid
and would strengthen the composite. In the present study, the
coefficient of thermal expansion of TiN is less than that of
the matrix and hence the mechanical properties of the
composite are superior to those of the Al alloy without
TiN. In addition, dislocation can be deflected and twisted by
dispersed particle in the inter-grain or intra-grain of the
matrix, acting as dislocation resistant obstacles, which is
often used to explain the higher yield strength values
obtained in some composites [21]. Hence, the results of
the present study show that the composite has higher tensile
properties and hardness than those of the Al-based alloy.
Fig. 3. Abrasive wear rate versus load plots for: (*) Al–5.1Cu–6.2Ti, (~) Al alloy containing TiN formed in situ.
303
Table 2
Pin and disc test results under 1 kg applied load with a rotational speed of
72 rpm
Pin material Pin wear Plate wear Friction
(108 cm3 cm1) (108 cm3 cm1) coefficient
Al–5.1Cu–6.2Ti 34 4.7 0.8
Compositea 4.0 14.2 0.94
Al alloy containing in situ formation of TiN.
The effect of the titanium nitride on the wear rate is shown
in Fig. 3. Each item of data was the average of at least five
tests. The wear rate dropped abruptly after the incorporation
of the TiN into the matrix alloy. At loads of up to 1 kg, the
Al-based alloy wore severely, while the wear rate of the
composite still increased gradually. Further, the wear rate
had a higher slope initially, which was followed by a reduced
slope at larger loads. This tendency was more clearly visible
in the matrix alloy. Comparison of the curves in Fig. 3
indicates that the presence of titanium nitride helps the
matrix alloy to sustain different wear loads. The result of
the sliding-wear tests indicates that the formation of titanium
nitride reduced the wear rate by a factor of 8 compared to
that of the Al-based alloys (Table 2). However, the wear on
the plate was considerably higher in the case of the compo-
site.
It is well known that the mechanical and wear properties
of a material play an important role in controlling its wear
behavior. One of the reasons for the improved wear resis-
tance of the composite as compared to that of the Al-based
alloy could be the decreasing cutting efficiency of the grits.
The abrasive particles would become blunted, fragmented
and removed from their position during abrasion, if hard
304 R.F. Shyu et al. / Journal of Materials Processing Technology 122 (2002) 301–304
dispersoid phases were encounted on the specimen surface
[22]. Increasing wear rate with load could be attributed to the
grits ploughing more deeply into the specimen surface. The
presence of the hard TiN reinforcement in the matrix could
lead to a reduced depth of penetration of the grits (abrasive
particles) and protect the softer matrix [23]. As a result, the
abrasive wear resistance of the composite became greater
than that of the matrix alloy.
A reduction in the slope of the wear rate versus load
curves at higher applied loads in the case of the matrix alloy
(Fig. 3) could be attributed to the increased work-hardening
of the matrix taking place due to abrasion-induced deforma-
tion of subsurface regions, the ductile debris of particles also
tending to become entrapped in the inter-particles spacing
due to the larger depth of penetration [22,26]. In the case of
the composite, a similar effect was noticed despite there
being less work hardening in the sub-surface regions and a
decreasing amount of the entrapment of the relatively brittle
debris in the inter-particle spacing. The reason could be the
decreasing cutting efficiency of the abrasive (grits) due to
the blunting effect on the grits produced by the TiN particles
[22,26], which results in less penetration depth by the grits
on the specimen surface.
The wear surface of the abrasive or the sliding-wear
surface was observed by SEM. No cracks existed in the
interface between the particles and the matrix nor within
the particles, which further confirms the strong bonding
between the TiN and the alloy matrix: this made a more-
effective load transfer between the softer matrix and the hard
TiN phase, and enabled the TiN particles to provide protec-
tion to the softer matrix [24,25]. As a result, the composite
exhibited better wear resistance (sliding and abrasive wear)
than the aluminum matrix. The wear on the plate was higher
in the case of composite. The possible explanation for this
observation could be that the dispersed hard particles, which
have a higher friction coefficient, scratched the steel disc and
resulted in increased wear of the disc.
4. Conclusion
In conclusions, an aluminum alloy matrix containing
titanium nitride particles can be fabricated successfully
by an in situ process in which nitrogen gas reacts with
titanium in the liquid melt to form TiN. The tensile and yield
strength were found to increased substantially after the
formation of TiN particles in the aluminum alloy matrix.
Also, the abrasive and sliding-wear resistance increased with
the in situ formation of TiN particles. The composite
produced thus has potential for industrial application where
high strength and high wear resistance are required.
Acknowledgements
The authors thank the National Council, Taiwan, for
financial support, under contract No. NSC88-2216-E-150-
002.
References
[1] A. Sato, R. Mehrabian, Metall. Trans. B 7 (1976) 443.
[2] F.M. Hosking, F.F. Portillo, W. Wunderlin, R. Mehrabian, J. Mater.
Sci. 17 (1982) 477.
[3] M.K. Surappa, P.K. Rohatgi, J. Mater. Sci. 16 (1981) 983.
[4] D.M. Schuster, M. Skibo, F. Yep, J. Met. 39 (1987) 60.
[5] R. Mehrabian, R.G. Riek, M.C. Flemings, Metall. Trans. 5 (1974)
1899.
[6] Light Met. Age 44 (5–6) (1986) 7.
[7] P.K. Rohatgi, B.C. Pai, S.C. Panda, J. Mater. Sci. 14 (1979) 2277.
[8] S. Banerji, M.K. Surappa, P.K. Rohatgi, Metall. Trans. B 14 (1983)
273.
[9] A. Banerji, S.V. Prasad, M.K. Surappa, P.K. Rohatgi, Wear 82 (1982)
141.
[10] B.P. Krishnan, N. Raman, K. Narayanaswamy, P.K. Rohatgi, Wear 80
(1980) 205.
[11] P.K. Rohatgi, B.C. Pai, Wear 59 (1980) 323–332.
[12] P.R. Gibson, A.J. Clegg, A.A. Das, Wear 95 (1984) 193.
[13] Deonath, R.T. Bhat, P.K. Rohatgi, J. Mater. Sci. 15 (1980) 1241.
[14] Automob. Ind. 5 (1984) 33 (in Russian).
[15] L. Bruni, P. Ignera, Automot. Eng. 3 (1978) 29.
[16] R.C. Cornell, Proceedings of the 10th Sdce International Die Casting
Exposition and Congress, St. Louis, MO, 1979, Paper G-179-071,
p. 1.
[17] C.F. Lewis, Mater. Eng. 103 (1986) 33.
[18] L.E. Toth, Transitional Metal Carbides, Nitrides, Academic Press,
New York, 1971, p. 1.
[19] M.E. Fine, Scripta Met. 15 (1981) 523.
[20] M.S. Zedalis, D.J. Skinner, in: E.W. Lee, E.H. Chia, N.J. Kim (Eds.),
Light-weight Alloys for Aerospace Applications, TMS/AIME,
Warrendale, PA, 1989 p. 335.
[21] P. Sahoo, M.J. Koczak, J. Mater. Sci. Eng. 36 (1990).
[22] B.K. Prasad, S. Das, A.K. Jha, O.P. Modi, A.H. Yegneswaran, Mater.
Trans. JIM 36 (1995) 1048.
[23] B.K. Prasad, S.V. Prasad, A.A. Das, J. Mater. Sci. 27 (1992) 213.
[24] B.K. Prasad, O.P. Modi, A.K. Jha, Tribol. Int. 27 (1994) 153.
[25] B.K. Prasad, A.K. Patwardhan, A.H. Yegneswaran, Metall. Mater.
Trans. A 27 (1996) 3513.
[26] T. Kulik, T.H. Kosel, Y. Nu, in: K.C. Ludema (Ed.), Proceedings of
the International Conference on Wear in Materials, Vol. 1, April 9–
13, 1989, Denver, CO, ASME, New York, p. 23.