Tribology International 44 (2011) 18001809

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Tribology International
journal homepage: www.elsevier.com/locate/triboint

Effect of particle size on tribological behavior of Ni3Al matrix high

temperature self-lubricating composites
Shengyu Zhu a,b, Qinling Bi a,n, Jun Yang a, Weimin Liu a,n, Qunji Xue a
a
b

State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, PR China
Graduate University of Chinese Academy of Sciences, Beijing 100039, PR China

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 22 October 2010
Received in revised form
3 July 2011
Accepted 13 July 2011
Available online 23 July 2011

The Ni3Al matrix high temperature self-lubricating composites with different particle size were
fabricated by the powder metallurgy technique. The effect of particle size on the mechanical and
tribological properties of the composites was investigated in this paper. The results showed that the
coarse particle composite exhibited the lowest friction coefcient and wear rate compared to the ne
particle ones at a wide temperature range from room temperature to 1000 1C. The reason for the low
wear rate was that the coarse bulk phase could provide better deformation resistance and higher load
bearing capacity than the ne microstructure.
& 2011 Elsevier Ltd. All rights reserved.

Keywords:
Ni3Al matrix
Self-lubricating
High temperature
Particle size

1. Introduction
The composite fabricated via powder metallurgy technique has
many advantages, such as composition precise controlling and also
easy to realize a special function property [1]. The sintering process
and variables involved in sintering, such as temperature, time,
atmosphere, pressure, heating rate and cooling rate, as well as
variables related to raw materials including the size of powder
particles, shape and agglomeration of particles, had been studied
extensively. Some important conclusions were obtained. One of
them is that ne particle size can improve the mechanical property
apart from the sintering ability and the uniformity of material [2].
According to the traditional sintering theory, it is reasonable that
ner powders always make a denser, harder and higher strength
composite because smaller particles produce a larger driving force
for sintering and promote the diffusion process of grain boundary.
However, it is not always the case for some functional materials,
especially for self-lubricating materials.
The effect of particle or grain size on the tribological behavior
of materials is an important topic that has received much attention
[39]. In general, ner size materials have better wear resistance
owing to the improved mechanical properties [35]. But there have
been few reports, where the opposite is found [69]. The reason is
that larger particles carried greater load, as well as protected other
smaller particles from being gouged out during the wear process [8].

Corresponding authors. Tel.: 86 931 4968193; fax: 86 931 8277088.

E-mail address: qlbi@lzb.ac.cn (Q. Bi).

0301-679X/$ - see front matter & 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.triboint.2011.07.002

Recently, a high temperature self-lubricating Ni3AlBaF2

CaF2AgMo composite was developed in the authors laboratory
[10]. The composite is comprised of Ni3Al matrix phase, Ag and
BaF2/CaF2 as solid lubricants and Mo as reinforcement phase. Fine
raw particle in sintering can make the lubricating phase to
distribute uniformly in the bulk phase. Meanwhile, the mechanical property also changes with microstructure of material. Thus
the study of the effect of particle size on the mechanical property
and tribological behavior is important.
High-energy ball milling is an effective technique to improve
the powder homogeneity and rene powders for intermetallic
matrix composites [1113]. Therefore, in our study, it is employed
to prepare the raw powder mixture with different particle size by
adjusting the milling conditions (grinding medium, grinding
vessel, time of milling, intensity of milling, etc.).
The objective of this paper is to design and fabricate high
temperature self-lubricating composite with excellent tribological
properties from room temperature to 1000 1C, as well as to
explore the friction and wear mechanisms at high temperatures.
Aimed at this purpose, the effect of particle size on the mechanical and tribological properties of Ni3Al matrix composites at a
wide temperature range was investigated.

2. Experimental procedure
The Ni3Al matrix high temperature self-lubricating composites
with different particle size were fabricated by the powder metallurgy technique. Commercially available Ag, Mo, BaF2, CaF2

S. Zhu et al. / Tribology International 44 (2011) 18001809

powders and Ni3Al (produced by self-propagating high temperature synthesis in our laboratory) powders with mean particle size
of 3070 mm were used as the starting materials. The nominal
composition in mass of the composite is: Ni3Al, BaF2/CaF2
(520%), Ag (015%) and Mo (515%). The milling operation was
carried out in a Fritsch Pulverisette 5 planetary high-energy ball
milling system in argon at room temperature. A 250-ml tungsten
carbide vial and tungsten carbide balls were used in milling. Three
kinds of powders with an average particle size of 20, 10 and 5 mm
(denoted as AC, BM and CF) were obtained by adjusting mill
variables, which is listed in Table 1. The as-milled powders were
put into an hBN-coated graphite die, and then heated at a rate of
10 1C/min in a hot-press-sintering furnace at a dynamic vacuum of
Table 1
Milling variables of the three kinds of powders produced by high-energy ball
milling.
Sample Milling time
(h)

Ball-to-powder ratio (in

weight)

Milling speed
(rpm)

AC
BM
CF

2.5:1
10:1
10:1

300
300
300

8
8
16

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about 10  2 Pa. The powders were pressed at 900 1C for 15 min

under 35 MPa, and then heated to 980 1C and held for 20 min.
The size and the morphology of the three kinds of powder
particles were examined using a scanning electron microscopy
(SEM, JSM-5600LV). The densities of the hot-pressed samples
were measured using Archimedes method. The details on the
mechanical properties and tribological tests were described elsewhere [14]. The tribological tests were conducted on an HT-1000
ball-on-disk high temperature tribometer. Before test, the surfaces of the disk were cleaned with acetone and then dried in hot
air. The counterpart ball was the commercial Si3N4 ceramic ball
with a diameter of 6 mm (about HV 15 GPa). The selected test
temperatures were 20, 200, 400, 600, 800 and 1000 1C. The sliding
speed was 0.188 m/s, the applied load was 10 N and the testing
time was 20 min.
Microstructures of the sintered composites, phase compositions and morphologies of the worn surfaces at different wear
condition were examined using scanning electron microscopy
(SEM, JSM-5600LV), energy dispersive spectroscopy (EDS, Kevex,
USA) and X-ray Diffraction (XRD, Philips X Pert-MRD X-ray
diffractometer, 40 kV, 30 mA, Cu Ka radiation). Samples for SEM
observations were polished using colloidal alumina (0.05 mm) and
chemical etch with aqua regia solution.

Fig. 1. SEM morphology of the milled powders and XRD results of the milled powders: AC, BM and CF.

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S. Zhu et al. / Tribology International 44 (2011) 18001809

3. Results
3.1. Microstructural and mechanical properties
Three kinds of powder mixtures (AC, BM and CF) are used in
our experiments. It can be found from Fig. 1 that most of the AC
particles (mainly Ni3Al) are coarse particles with an average
particle size of about 20 mm, the mean particle size of BM is about
10 mm and that of CF is about 5 mm. Meanwhile, it can be also
observed that particle shape of AC is aky and irregular, whereas
CF turns round after the milling process. XRD results of the milled
powders indicate that the peaks of Ni3Al and Mo become broader
and the intensity get weaker with reducing particle size, which

can be attributed to the renement of the grain size and the

increase of atomic level strain. In addition, few peaks of Ag can be
found and peaks of uorides disappear. One reason for this is that
uorides grains easily crack during mechanical alloying and
undergo deformation and/or fracture processes. The other reason
is that the decomposition of uorides could happen. The amorphization and internal stress of these phases during mechanical
milling can make their peaks to become weaker, broader or
disappear [1113].
The microstructures of AC, BM and CF composites are shown in
Figs. 24. EDS analysis indicates that the gray area is the
continuous bulk Ni3Al phase with uniformly dispersed Mo element; the white phase is Ag-rich phase and the deep gray area is

Fig. 2. Microstructure and elemental distribution of AC,  1000.

S. Zhu et al. / Tribology International 44 (2011) 18001809

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Fig. 3. Microstructure and elemental distribution of BM,  1000.

uoride-rich phase. It can be observed that the isolated Ag phase

and uorides phase are surrounded by the continuous bulk Ni3Al
phase. The AC Ni3Al phase forms coarser continuous phase
compared to BM and CF, while CF provides ner microstructure
than AC. In other words, the second-phase of CF distribute more
uniformly in Ni3Al matrix phase.
Table 2 shows densities and mechanical properties of the
sintered Ni3Al matrix composites. AC has the lowest density,
and its microhardness (3.60 GPa) is signicantly lower than
microhardness of BM (4.40 GPa) and CF (4.90 GPa). However, AC
possesses the highest yield stress (1220 MPa) while CF has the
lowest (790 MPa). In addition, AC (1390 MPa) and BM (1400 MPa)
have high compressive strength. It suggests that with decreasing

particle size, the density and microhardness increase but the yield
stress and compressive strength decrease.
The variation of the above mechanical properties is related to
the microstructure of the composites. It can be found from Figs.
24 that element Mo as the hard phase uniformly disperses into
Ni3Al phase, while lubricants as the soft phase locate at the grain
boundary. It is well known from the sintering theory that small
particles possess larger driving force of sintering. The ner the
particles, the easier the solid solution and dispersion process, and
also the denser and harder the sintered materials. Furthermore,
the ner the particles, the more volume percent of the low load
bearing lubricant phase and the less the continuous load bearing
phase is, correspondingly, the lower the strength is.

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S. Zhu et al. / Tribology International 44 (2011) 18001809

Fig. 4. Microstructure and elemental distribution of CF,  1000.

Table 2
Densities and mechanical properties of the sintered Ni3Al matrix composites.
Samples

r (g/cm3)

Hardness (GPa)

Yield stress (MPa)

Compressive
strength (MPa)

AC
BM
CF

7.020
7.060
7.070

3.707 0.50
4.407 0.15
4.907 0.10

12207 5
1135 7 5
7907 5

1390 75
1400 75
1140 75

In the case of AC, the lubricants are enclosed by the coarse Ni3Al
bulk phase. As for CF, with the ner microstructure, the lubricants
have the larger contact area with the Ni3Al bulk phase. This lead to

weakness in boundary strength of CF compared to that of AC.

Furthermore, it should be noted that the volume fraction of soft
lubricants is larger than that of Mo. In the compressive test, yield
stress determines the deformation resistance of material. Therefore, AC with the coarse Ni3Al bulk phase has a better yield stress
and compressive resistance than CF with the ne one.
For BM and CF, since the lubricants (Ag and uorides) and
reinforcement phase (Mo) can be distributed uniformly in the
Ni3Al matrix, the hardness has small error. However, for the
hardness of AC, indentation contacts with an inhomogeneous
microstructure. Namely, there is more hard phase like Mo or soft
phase like Ag at the contact region. Therefore, a large test error is
obtained.

S. Zhu et al. / Tribology International 44 (2011) 18001809

3.2. Tribological properties

Fig. 5 shows the variations in friction coefcients of the
sintered Ni3Al matrix composites with different particle size after
tests. It can be found that the friction coefcient of the three
composites is in the window from 0.3 to 0.4 at a wide temperature range from room temperature to 1000 1C. Additionally, the
friction coefcient of the coarse particle AC is the lowest, ranged
from 0.3 to 0.35. And the friction coefcient of BM is slightly
lower than that of CF.
Variations in wear rates of the sintered Ni3Al matrix composites
with different particle size after tests are presented in Fig. 6. From
room temperature to 1000 1C, it can be noted that the wear rate
increases with decreasing particle size. AC has the lowest wear
rate. At room temperature, the low wear rate is about 4 
10  6 mm3 N  1 m  1. With increasing temperature, the wear rate
tends to increase and rises to the peak point at 600 1C, AC to
4.11  10  4 mm3 N  1 m  1, BM to 4.47  10  4 mm3 N  1 m  1 and
CF to 4.92  10  4 mm3 N  1 m  1. And then the wear rate remarkably

Fig. 5. Variation of friction coefcients of the sintered Ni3Al matrix composites

with different particle size.

Fig. 6. Variation of wear rates of the sintered Ni3Al matrix composites with
different particle size.

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decreases to the low point about 1  10  4 mm3 N  1 m  1 at

800 1C. As the temperature further rises to 1000 1C, the wear rate
of AC increases to 3.02  10  4 mm3 N  1 m  1, BM to 4.93 
10  4 mm3 N  1 m  1 and CF to 8.02  10  4 mm3 N  1 m  1. Still, AC
is the lowest.
XRD results in Fig. 7 show that the peaks of the sintered AC
sample are stronger than those of the milled powders, suggesting
that the soluble Ag and embedded uorides precipitate from
Ni3Al matrix. At 600 1C, the peaks of a new phase BaMoO4 occur in
XRD results. With increasing temperature, the peaks of BaF2 and
CaF2 disappear, but the peaks of BaMoO4 and CaMoO4 get
stronger. The presence of BaMoO4 and CaMoO4 on the worn
surface is attributed to the complex reaction, including high
temperature and tribo-chemical reaction.
At room temperature, some plastic deformed debris, which is the
Ag-rich phase by EDS analysis, is attached on the worn surface
together with some ne grooves, as shown in Fig. 8. It suggests that
the discontinuously lubricating Ag lm develops on the worn surface.
In addition, the patch of Ag-rich phase is present on the AC worn
surface, whereas the stripe of Ag-rich phase takes place on the BM
and CF worn surface. The wear mechanism is mainly microploughing.
The worn surfaces appear to be alike when the test temperatures are 200 and 400 1C. The typical morphologies of the worn
surfaces of the three samples tested at 200 1C are shown in Fig. 9.
Signicant differences in the wear behavior are found. For AC, it
can be observed from Fig. 9(a) that cracks and ake of debris take
place at some regions, which are the Ni3Al-rich and Mo-rich phase
by EDS analysis, as well as the discontinuous grooves. The
discontinuous grooves and delaminated debris reveal that there
exists interaction between this area and the coupled Si3N4 ball
during sliding. Therefore, it is proposed that the area containing
Ni3Al and Mo should be the wear resistant area. The wear resistant
area is also found on the worn surface of BM. However, for the ne
particle CF, it is clear that some ne grooves are present on the
worn surface, the wear resistant area like those of AC and BM
cannot be found. Additionally, the discontinuously deformed Ag
lm on the worn surface at room temperature does not occur. It
indicates that the wear mechanism is transformed from delamination to microploughing with decreasing particle size.
At 600 1C, it is similar to the characteristic of worn surface at
200 1C that some delaminated layers occur on the worn surface of

Fig. 7. XRD patterns of the sintered sample (a); and worn surfaces of AC after
sliding for 20 min at an applied 10 N loads and different temperatures: 600 1C (b);
800 1C (c); 1000 1C (d).

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S. Zhu et al. / Tribology International 44 (2011) 18001809

Fig. 8. Worn surfaces at room temperature: AC (a); BM (b); CF (c).

Fig. 9. Worn surfaces at 200 1C: AC (a); BM (b); CF (c).

AC, while ne grooves appear on the worn surfaces of BM and CF,

as shown in Fig. 10. Furthermore, few wear debris remains on the
worn surface. The wear mechanisms are delamination for AC and
microploughing for BM and CF.

As the temperature rises to 800 1C, the deformed surface and

grooves are present on the worn surface in all the three samples
(shown in Fig. 11). Compared to BM and CF, AC provides a
relatively smooth surface and glaze lm, which is composed of

S. Zhu et al. / Tribology International 44 (2011) 18001809

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Fig. 10. Worn surfaces at 600 1C: AC (a); BM (b); CF (c).

Fig. 11. Worn surfaces at 800 1C: AC (a); BM (b); CF (c).

NiO, BaMoO4 and CaMoO4 by XRD analysis. The wear mechanism

is dominant surface deformation.
When the temperature increases up to 1000 1C, the coarse
grooves break down the smooth surface of AC (see Fig. 12a),

whereas severe plow grooves and the delaminated pits are found
on the worn surfaces of BM and CF (see Fig. 12b, c). XRD results
show that large numbers of oxides, which consist of BaMoO4,
CaMoO4 and NiO, develop on the worn surface. Moreover, the

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S. Zhu et al. / Tribology International 44 (2011) 18001809

4. Discussion

Fig. 12. Worn surfaces at 1000 1C: AC (a); BM (b); CF (c).

worn track of AC is found to be much smoother compared to

those of BM and CF. The wear mechanism is mainly microploughing and oxidative wear.

In general, the tribological property of material is closely

related to its microstructure and mechanical properties. Although
a higher hardness of the ne particle size composite always
implies a higher wear resistance, this rule seems not to be
completely suitable for the high temperature self-lubricating
composite.
From the tribology principle point of view, the ideal composition of a high temperature self-lubricating composite should
be composed of high temperature oxidation resistant and
high strength matrix, favorable solid lubricant, as well as wear
resistant phase. Solid lubricant plays a dominant role in friction
behavior, and wear behavior is determined considerably by the
wear resistant phase. In the case of Ni3AlBaF2CaF2AgMo
composite, Ni3Al acts as a high strength matrix, Ag and uorides
act as solid lubricants and Mo acts as reinforcement. Therefore,
Ag and uorides in the composite provide a lubricity, while
Ni3Al and Mo are the wear resistant phase and the load-carried
phase.
The three composites show good lubricating property at a
wide temperature range from room temperature to 1000 1C. It
could be attributed to Ni3Al matrix with favorable high temperature combined properties and the coaction of Ag (as a lubricant at
relatively low temperatures below 450 1C), uorides (act above
400 1C) and molybdates formed by the complex reaction (as high
temperature solid lubricants) [1517]. In addition, AC exhibits
better frictional performance compared to BM and CF. The reason
is briey explained as following.
During mechanical milling, with increasing milling time and
enhanced milling intensity, decomposition of uorides and solid
solubility of Ag in BM and CF decrease the lubricity (seen in
Fig. 1). Therefore, AC provides more effective lubricity.
At low temperatures, the soft and coarse Ag particles on the
sliding surface of AC were scratched and squeezed gradually by
the Si3N4 ball, and then spread on the sliding surface and formed a
Ag-rich lm on the worn circle. Therefore, the Ag-rich lm of AC
expressed more effective lubricating ability than those of BM and
CF. At high temperatures (above 600 1C), the higher load-carried
capacity and the lubricity of uorides and molybdates formed
during the sliding process allow AC to provide lower friction
coefcient.
With respect to wear behavior, the following explanations are
given to clarify obtained results. The coarse bulk phase can
provide better deformation resistance and higher load bearing
capacity than the ner microstructure and the presence of the
lubricating lm on the worn surface also plays an important role
in wear of the three composites. At low temperatures, the low
wear rate is obtained, which is due to the discontinued Ag lm on
the worn tracks, as shown in Fig. 8. Although strength of the
monolithic Ni3Al increases with temperature, the presence of the
soft lubricants make the strength to decrease a lot. Therefore, it
results in decrease in the combined strength of the composite.
With the rise of temperature, the absence of the lubricating lm
leads to a higher wear rate (seen in Figs. 9 and 10) as a result of
decrease in strength. However, at 800 1C, the formation of the
glaze lm effectively reduces wear rate, as shown in Fig. 11. As
the temperature rises to 1000 1C, the decrease in strength
degrades wear resistance (see Fig. 12).
At low temperatures, the presence of the more effective Agrich lm on the worn track allows AC to obtain the lower wear
rate. In the temperature range from 200 to 600 1C, there is the
absence of the lubricating lm on the worn surface. The Si3N4
ceramic ball directly contact with the asperities on the worn
surface. Meanwhile, the area containing Ni3Al and Mo can be the
wear resistant area. The coarse microstructure possesses the high

S. Zhu et al. / Tribology International 44 (2011) 18001809

deformation resistance and protects the worn surface from being

gouged out during the sliding process (Figs. 10 and 11). Above
800 1C, the higher strength of the coarse Ni3Al and Mo phases
can ensure the formation of the smooth surface lm (seen in
Figs. 10 and 11), which is accounted for the improved anti-wear
performance of AC.

5. Conclusions
(1) The Ni3Al matrix high temperature self-lubricating composites with different particle size (about 20, 10 and 5 mm) were
fabricated by the powder metallurgy technique.
(2) At a wide temperature range from room temperature to
1000 1C, the three composites provide good lubricating properties, which can be attributed to the coaction of Ag, uorides
and molybdates formed by the complex reaction.
(3) The coarse particle AC exhibits excellent frictional property
compared to BM and CF because AC provides more effective
lubricity and higher load-carried capacity.
(4) In the case of the coarse particle AC, the low wear rate is
obtained. The reason is that the coarse bulk phase can provide
better deformation resistance and higher load bearing capacity than the ne microstructure.

Acknowledgments
The authors are grateful to the National Natural Science Foundation of China (51075383), the Innovation Group Foundation from
NSFC (50721062), and the National 973 Project (2007CB607601) for
nancial support.

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