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H.Z. Ye, R. Liu, D.Y. Li and R. Eadie
Department of Chemical and Materials Engineering, University of Alberta,
Edmonton, T6G 2G6, Canada
(Received April 30, 1999)
(Accepted in revised form August 3, 1999)
Keywords: TiC; TiNi; Composite; Pseudoelasticity; Wear
Recent studies [1–15] have demonstrated that equiatomic TiNi alloy exhibits high wear resistance.
Richman et al. [7] demonstrated superior cavitation resistance of TiNi alloy, compared to a number of
standard and wear-resistant materials commonly used in hydraulic machinery. Jin and Wang [8] showed
that TiNi alloy is more resistant than commercial wear-resistant Co45 alloy and nitrogenized 38Cr-
MoAlA steel during dry sliding. J. Singh and A.T. Alpas [9] compared Ti50Ni47Fe3 to SAE 52100
bearing steel and demonstrated that the former has significantly higher wear resistance than the latter.
The high wear resistance of TiNi alloy greatly benefits from its pseudoelasticity, resulting from a
reversible martensitic transformation. This special property makes the alloy exhibit rubber-like behavior
with a relatively large recoverable strain [10,11]. Shida and Sugimoto [12] observed a remarkable
resistance of TiNi alloy to water-jet erosion. They found that the erosion resistance of TiNi alloy
strongly depends on its chemical composition and microstructure. The optimal composition is from
Ti-55wt%Ni to Ti-56.5wt%Ni, where the reversible martensitic transformation occurs. Liang et al. [13]
investigated the wear behavior of TiNi alloy during sliding wear, impact abrasion and sandblasting
erosion. They noticed a strong correspondence between the wear resistance and the recoverable strain
resulting from the pseudoelasticity. Recent studies, combining wear tests and finite element analysis
[14], further demonstrate the beneficial effect of pseudoelasticity on wear. It was also noticed that the
high wear resistance of TiNi alloy is not only attributable to its pseudoelasticity but also to other
properties such as the strain-hardening capability. Clayton [15] investigated wear and rolling fatigue of
TiNi alloy having a composition beyond the range in which the martensitic transformation can occur.
He correlated good cyclic hardening capability of TiNi alloy to its high resistance to rolling fatigue.
Other studies have also confirmed the good fatigue resistance of TiNi alloys [16].
In this work, an attempt was made to develop a novel type of wear-resistant composite employing
a TiNi alloy matrix reinforced by hard particles. Titanium carbide was chosen as the reinforcing phase
because of its high hardness and TiNi alloy as the matrix due to its pseudoelasticity and good toughness.
TiC particles may sustain external load, while the TiNi matrix may accommodate deformation, absorb
impact energy and retain the hard particles. Such a combination is expected to lead to an enhanced wear
resistance, compared to TiNi alloy. As a matter of fact, some efforts were previously made to develop
TiNi-matrix composite reinforced by ceramic particles [17–20]. However, the emphasis of those studies
Scripta Materialia, Vol. 41, No. 10, pp. 1039–1045, 1999
Elsevier Science Ltd
Copyright © 1999 Acta Metallurgica Inc.
Printed in the USA. All rights reserved.
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was put on effects of the reinforcing particles on the phase transformation behavior, shape memory
effect and some mechanical properties of the composite; no attempt was made to explore the potential
benefit of the material for wear application.
Experimental Procedure
TiC/TiNi composite was fabricated by a sintering process. Ti, Ni and TiC powders having a size of
mesh Ϫ325 were mixed in air using a ceramic ball mill apparatus for 2 hours. The mixed powder was
then pressed into pin specimens under a pressure of 787 MPa for 30 seconds. The cylindrical specimens
were 8 mm long with a diameter of 6 mm. The specimens were sintered in a vacuum of about 5.0ϫ10
torr. The nominal composition of the matrix was Ti-51at%Ni (Ti-56wt%Ni). In order to identify the
optimal sintering condition at the range of temperature up to 1800°C, different sintering temperatures
and times were tried. The sintered TiC/TiNi specimens were examined by x-ray diffraction to check
whether the Ti and Ni powders were alloyed. Microstructure of the composite was examined by optical
and scanning electron microscopy. Wear behavior of the TiC/TiNi composite was evaluated using a
pin-on-disc tribometer, respectively under loads of 0.050, 0.133, 0.167 kN, at a sliding speed of 60
m/min. A copper tube was attached to the stainless steel disc through which cooling water could pass
to reduce the friction heat. Volume loss of each specimen was measured after sliding over 600 meters.
Wear resistance of the TiC/TiNi composite was compared to those of 304 stainless steel, Ti-51at%Ni
alloy and a WC/NiCrBSi hardfacing overlay.
Results and Discussion
1. Composition and Microstructure
TiC/TiNi specimen containing 20%TiC, 40%TiC, 60%TiC and 80%TiC particles were sintered at
various temperatures from 900°C to 1500°C for 6 hours, respectively. The specimen sintered at 1500°C
exhibited the best wear performance, as shown later. Fig. 1 illustrates an SEM microstructure image of
a 60%TiC/TiNi composite specimen sintered at 1500°C for 6 hours. One may see that TiC particles
were distributed homogeneously. However, in some areas many voids, especially in the central region
of the TiC/TiNi specimen, were found, forming nets along grain boundaries. In order to make sure that
the matrix was a TiNi alloy rather than a mixture of Ti and Ni powders, the specimen was examined
by X-ray diffraction. Fig. 2 illustrates the X-ray pattern of the specimen, which indicates that the matrix
Figure 1. Microstructure of 60%TiC/TiNi composite (ϫ300).
is in an alloy state.
The composition of the matrix was also analyzed by EDX. The results show that the matrix is still
not very uniform in composition. Therefore, the sintering process needs further improvement, although
such a specimen has already shown very good wear resistance as demonstrated later. It should be
pointed out that the powders may have oxide scales and oxidation might also occur during the vacuum
sintering process, which may make it harder for the stress-induced martensitic transformation to take
place. However, the potential oxides were not detected by the XRD and EDX and the sintered
composite possessed a reasonably good pseudoelasticity as demonstrated later using an indentation
technique. Therefore, the potential oxides, if existed, may not be enough to cause significant deterio-
ration in pseudoelasticity and thus the wear performance of the material.
2. Wear Behavior
a) Effect of TiC Content on the Wear Behavior
Volume losses of TiC/TiNi specimens with 20%, 40% and 60% TiC under loads of 0.05, 0.133 and
0.167 kN were evaluated respectively and the results are illustrated in Fig 3. The volume loss decreased
with the increase in TiC content up to 60%. The 80%TiC/TiNi specimens, however, were too brittle and
showed a lot of voids visible to the naked eye. They were worn out quickly during the wear test even
under a low load. It turned out that the best fraction of TiC particles was 60%. Surfaces of 60%
TiC/TiNi specimens worn under 0.05 and 0.167 kN were examined and are illustrated in Fig. 4 and Fig.
5 respectively. Under the low load, the worn surface shows sliding wear characteristic. Under the high
Figure 2. (Co-K␣1) X-ray pattern of 60%TiC/TiNi composite sintered at 1500°C for 6 hours.
Figure 3. Wear losses of samples with different TiC contents.
load, the wear was more severe and the specimen was stripped and TiC particles were torn out (see the
left-hand side of Fig. 5.)
b) Effect of the Sintering Condition on the Wear Performance
Since 60%TiC/TiNi composite showed the highest wear resistance, attention was then paid to this
composition. In order to identify the optimal processing parameters, 60%TiC/TiNi specimens were
sintered at 1300°C, 1500°C, 1600°C, 1700°C and 1800°C for 6 hours respectively. Different sintering
periods of time were also chosen. For instance, some 60%TiC/TiNi specimens were sintered at 1300°C
for 6, 12 and 18 hours and at 1500°C for 6 and 14 hours, respectively. Fig. 6 illustrates the wear
performance of the specimens prepared at different sintering temperatures for 6 hours. 1500°C appears
to be the best sintering temperature of those tested. As for the sintering time, the wear resistance of the
60%TiC/TiNi was improved by prolonging the sintering time when prepared at 1300°C while for those
specimens sintered at 1500°C, the wear resistance was not markedly influenced when the sintering time
was longer than 6 hours.
Figure 4. Worn surface of 60% TiC/TiNi under 0.05 kN (ϫ200).
Figure 5. Worn surface of 60% TiC/TiNi under 0.167 kN (ϫ200).
c) Comparison with Ti-51at%Ni Alloy, 304 Stainless Steel and WC/NiCrBSi Hardfacing Overlay
In order to evaluate the TiC/TiNi composite as a wear-resistant material, wear resistance of 60%TiC/
TiNi composite sintered at 1500°C for 6 hours was compared to several standard materials, including
Ti-51at%Ni alloy, 304 stainless steel, and WC/NiCrBSi hardfacing overlay. The comparison with the
Ti-51at%Ni alloy may provide the information about the efficiency of TiC particles in improving the
wear resistance. It is also worth comparing the TiC/TiNi composite to 304 steel and WC/NiCrBSi
hardfacing overlay. 304 stainless steel is a widely used industrial material and substantial information
about this steel is available. WC/NiCrBSi overlay is a specially designed hardfacing material widely
used in the mining and oilsand industries. The comparison of the TiC/TiNi composite with these two
standard materials provides evidence that this type composite is a promising wear-resistant material.
Volume losses of the above materials were measured and results are illustrated in Fig. 7. Clearly the
60%TiC/TiNi composite has significantly improved wear resistance, compared to Ti-51at%Ni alloy.
TiNi alloy specimens used for this testing were divided into two groups. One group was kept in the
as-received state and the other was aged at 500°C for 5 minutes followed by water quench. The second
group of specimens has better pseudoelasticity with the recoverable strain equal to 4%, compared to the
first group, whose recoverable strain is about 3% [14]. Under low loads, the second group of TiNi alloy
specimens had considerably better wear resistance than the first group due to their better pseudoelas-
ticity [14]. However, under higher loads this difference diminished. This happened because the
pseudoelasticity may not accommodate the large deformations introduced by higher loads. As a result,
the as-received and heat-treated TiNi alloy specimens behaved similarly. In addition, under the higher
Figure 6. Wear losses under different sintering temperatures.
Figure 7. Wear losses of different materials against the applied loads.
loads the increased friction heat may pull the material away from the temperature range for the
martensitic transformation to occur and this further decrease the difference between these two groups
of TiNi alloy. It was observed that the wear resistance of 60%TiC/TiNi composite was on more than
one order of magnitude higher than the wear resistance of the as-received TiNi alloy in the entire
loading range. Compared to the heat-treated TiNi alloy, the TiC/TiNi composite also showed consid-
erably higher wear resistance under high loads. However, under low loads this difference in wear
resistance decreased as Fig. 7 illustrates. This could be due to the superior pseudoelasticity of the
heat-treated TiNi alloy, which made this TiNi alloy extremely resistant to wear under low loads.
Compared to the volume loss ϳload curves of the as-received and the heat-treated TiNi alloys, it seems
that the TiNi matrix of the TiC/TiNi composite did not possess a high degree of pseudoelasticity. This
may be seen from the trend of the composite’s volume loss with respect to load, which is closer to the
trend of the as-received TiNi alloy. In order to determine whether or not the TiNi matrix of the TiC/TiNi
composite possessed good pseudoelasticity, a load ϳ depth curve of the TiNi matrix was determined
and compared to those of the as-received alloy, heat-treated Ti-51at%Ni alloy and 304 stainless steel,
using a nano-indentation apparatus. Fig. 8 demonstrates that the 304 steel had little recoverable
displacement, where the ratio of the recoverable deformation work to the total deformation work, ␩, is
11%. While the heat-treated TiNi alloy had a considerably larger recoverable displacement with a ␩ of
47% due to its pseudoelasticity. Compared to the TiNi alloy, the matrix of the TiC/TiNi composite
showed medium pseudoelasticity, corresponding to a smaller recoverable displacement with a ␩ of
33%. It is thus expected that an improvement in the matrix’s pseudoelasticity will enhance the wear
resistance of the material. In addition, it was noticed that the deformation of TiC/TiNi composite matrix
is the lowest and this is obviously due to the particle strengthening by TiC.
The 60%TiC/TiNi composite had a significantly higher wear resistance than 304 steel. This
difference was on three orders of magnitude as Fig. 7 shows. Compared to the high-performance
WC/NiCrBSi hardfacing overlay, TiC/TiNi composite showed superior wear resistance under low
loads. While under high loads, the latter had a better performance. The superior wear resistance under
low loads could result from the pseudoelastic effect of the TiNi matrix, which became less functional
as the load was increased. It should be noted that the TiC/TiNi composite is still under development and
there is great space for further improvement. Possible approaches may include, for instance, reducing
voids, homogenizing the matrix composition or using TiNi alloy powder, improving the matrix
pseudoelasticity and using better performing reinforcing phases.
Figure 8. The Load-depth curves during indentation under a maximum load of 20 mN.
Wear behavior of a novel wear-resistant material, TiC/TiNi composite, was investigated. It was
demonstrated that TiC particles significantly enhanced the wear resistance of TiNi alloy. The wear
resistance increased with an increase in the content of TiC particles, and among the TiC/TiNi specimens
tested, the optimal fraction of TiC particles was 60%. Wear performance of the TiC/TiNi composite was
compared to those of 304 stainless steel, TiNi alloys, and WC/NiCrBSi overlay. It was shown that the
wear resistance of 60%TiC/TiNi composite was on three orders of magnitude higher than that of the 304
steel; and on one order of magnitude higher than that of the TiNi alloys. Compared to high-performance
WC/NiCrBSi hardfacing overlay, TiC/TiNi composite showed superior performance under low loads.
The great potential of this new wear-resistant material has been demonstrated by this preliminary study
and further research is under way.
The authors are grateful for financial supports from the Natural Science & Engineering Research
Council of Canada (NSERC) and Syncrude Canada Ltd and some preliminary work by Mark Haldane.
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