Int.

Journal of Refractory Metals and Hard Materials 54 (2016) 1926

Contents lists available at ScienceDirect

Int. Journal of Refractory Metals and Hard Materials

journal homepage: www.elsevier.com/locate/IJRMHM

The applicability of WC10Co4Cr/Si3N4 tribopair to the different

natural waters
Defa Wu, Yinshui Liu , Donglin Li, Xufeng Zhao, Xiaojun Ren
School of Mechanical Science and Engineering, Huazhong University of Science and Technology, No. 1037 Luoyu Road, Wuhan, Hubei 430074, China

a r t i c l e

i n f o

Article history:
Received 13 May 2015
Received in revised form 20 June 2015
Accepted 22 June 2015
Available online 24 June 2015
Keyword:
Friction coefcient
Wear resistance
Abrasive wear
Cemented carbide
Silicon nitride

a b s t r a c t
Natural water is widely used as working or lubricating medium instead of the traditional oil. Hard materials have
potential application to solve the abrasive wear caused by the silt suspending in natural water and poor lubrication of water. As the candidate materials can worked in water, the tribological characteristics of the tribological
properties of high velocity oxy-fuel (HVOF) spraying WC10Co4Cr coating combined with sintered Si3N4
were investigated under different natural water lubrication, including natural silt-laden and ltered water
from sea and river. In addition, distilled water was used as typical water lubricants to study the effect on the tribological behaviours. The tribological results of the tribopair exhibit excellent friction and wear resistance behaviours under the natural waters. The average steady-state friction coefcients of the tribopair under natural water
are below 0.009, whilst the average wear rates under all natural waters are below 9 1012 cm3/(Nm) for both
materials. The results indicate that the WC10Co4Cr/Si3N4 tribopair owns wider applicability to different natural waters. The water hydraulic components with this tribopair can work in different water areas in word, even
unltered natural waters as pressure medium.
2015 Elsevier Ltd. All rights reserved.

1. Introduction
Water hydraulics using natural water (tap water, river water, seawater, etc.) as a pressure medium instead of traditional mineral oil have
found more applications as environmental awareness and the development of underwater engineering continue to increase [1]. For underwater apparatus, there are many other especial advantages as follows:
1) avoiding water pollution due to medium leakage; 2) less pressure
loss due to less viscosity of water than mineral oil; and 3) simplifying
the hydraulics system by utilizing surrounding water freely and
discharging drainages to open surrounding without return lines, reservoirs, and storage of working medium if work as an open-circuit system.
Consequently, water hydraulics variable ballast system is almost instead
of all mineral oil variable buoyancy system in deep-sea submersible,
such as New ALVIN and JIAOLONG submersibles [2,3].
However, many challenges are involved in developing water hydraulic components, particularly for open-circuit systems, due to the
poor lubrication properties, corrosiveness of the water and the silt
suspending in natural water. Therefore, most of the metallic materials
used in traditional oil hydraulic components cannot be utilised in
water hydraulic components. The tribopairs consisting of polymers
and stainless steels have applied in piston pump to solve the poor lubrication of water [4]. However, this scheme is limited to low contamination level and moderate pressure water due to the soft surface of the
Corresponding author.
E-mail address: liuwater@hust.edu.cn (Y. Liu).

http://dx.doi.org/10.1016/j.ijrmhm.2015.06.016
0263-4368/ 2015 Elsevier Ltd. All rights reserved.

stainless steel and low modulus elasticity of polymers. Engineering ceramics and ceramic-based composite materials have showed greater
potential for application in water hydraulic components, especially
under silt-laden water, because they have good corrosion resistance,
low friction coefcients and abrasion resistance [58].
The primary forming processes used for engineering ceramics are
thermal spraying and sintering. The thermal spraying is one of the surface engineering solutions used to obtain a composite surface, in which
the hard phases are on the surface to resist wear and a soft but more
ductile and tough metallic binder is the substrate to prove the structural
functionality rather than wear resistance [9]. High velocity oxy-fuel
(HVOF) spraying coating technique utilises higher particle velocities
and relatively low temperatures, thus minimising the degradation of
both the coating and the substrate [10]. WC-based HVOF-spraying coatings on steel are popular in the gas and oil industries because of their superior wear resistance [11]. M.R. Thakare et al. found that the WC
10Co4Cr coating, one of WC-based coatings, exhibits better corrosion
resistance compared to WC6Co [12]. H.J.C. Voorwald et al. compared
the abrasive wear resistance of the WC10Co4Cr and WC17Co coatings; the former has better behaviour [13,14]. The WC10Co4Cr coating exhibits better corrosion and abrasion resistance compared to the
WCCo coating, probably because the Cr provides better corrosion resistance than the Co matrixes do.
However, it is difcult to utilize a thermal sprayed coating for the interior surface of a long bore with a small diameter, such as the small cylinder of a piston pump. Furthermore, some materials with good wear
and corrosion resistance, such as Si3N4 and SiC, are not suitable for

20

D. Wu et al. / Int. Journal of Refractory Metals and Hard Materials 54 (2016) 1926

thermal spraying [1518]. Although pure a Si3N4 ceramic has a low

toughness, some research indicates that silicon nitride ceramics with
whisker additives have increased fracture toughness and wear properties compared to monolithic Si3N4 under both dry and lubricated conditions [19,20]. The lower wear rate is probably related to improving the
fracture toughness or pullout of the whiskers [21].
Therefore, a tribopair consisting of different materials and forming
processes based on the structural properties of the components and materials sometimes is essential to design machines. According to a lot of
screening tests, the WC10Co4Cr/Si3N4 tribopair exhibits excellent tribological properties [22]. Its minimum friction coefcients reach at
0.0023 under tap water lubrication.
However, the properties of waters from different regions are diverse,
including contamination level of particle, and the electrical conductivity. Therefore, it is important to study the effect of different waters on
the friction and wear behaviours of the tribopair before application in
components. Consequently, the tribological behaviours of the tribopair
were researched under different natural waters, including natural siltladen sea and river water, as well as ltered natural sea and river waters
in this study. In addition, distilled water was used as typical water lubricants to study the effect of the contamination levels on the tribological
behaviours and to study the applicability to different waters.

Speed sensor Test

Driving
system

Synchronous
belt

system
Speed test

Drive shaft
Frequency
converter Electric
motor
Upper
specimen
Bottom
specimen

Hydarulic
power unit

Water tank

Loading
cylinder

Temperature
test
Temperature
sensor
Friction
test
Force sensor
Loading force
test

Pressure sensor

Loading system

a)

2. Experimental
2.1. Principle and procedure
The tribological experiments of the WC10Co4Cr/Si3N4 tribopair
were conducted on an MMU-10F type disc/disc tribological test rig produced by Jinan Shidai Shijin Testing Machine Group Co., Ltd., China.
Fig. 1a) shows the principles of the tribological test rig, which consists
of a loading system, driven system and test system. The loading system
includes two parts, a hydraulic power unit and a loading cylinder. The
loading force can be regulated by adjusting the output pressure of the
hydraulic power unit. The driven system includes a frequency converter, an electric motor, a synchronous belt, a drive shaft and upper and
lower ring specimens. The rotational speed can be controlled by regulating the output frequency of the frequency converter in the experiment.
The test system can measure the loading force, friction, temperature and
speed [22]. The upper specimen rotates with a shaft driven by an electric
motor. Because a spherical joint is used to connect the upper specimen
and driving shaft, the upper and bottom specimens can maintain
uniform contact.
However, the standard tribological test rig cannot be used to study
electrochemical corrosion. An electrochemical testing set with three
electrodes was designed to study the tribocorrosion behaviours of the
tribopair. Fig. 1b) shows the principles of the electrochemical test set.
This test set is one part of the adapted tribological test rig that connects
with a standard CS310 electrochemical workstation made by Wuhan
CorrTest Instrument Co. Ltd. The electrochemical workstation was
used to measure the potentiodynamic polarisation curves of WC
10Co4Cr coating before and after tribological test and open potentials
during the test. In addition, the workstation was utilised to provide electrochemical protection. A saturated calomel reference electrode (SCE)
and a platinum counter electrode were used under both potentiodynamic and potentio-static conditions.
Before testing, the contact surfaces of the upper and bottom
specimens were polished using 1500# diamond anti-scufng paste
(ISO6106-79), and the specimens were then immersed in water for
more than 64 h to allow the ceramics to absorb water thoroughly. The
mass of the specimens was measured before and after the test with an
MS105 type electronic balance able to provide measurements within
0.01 mg. Before measuring the mass, the specimens were cleaned
with a brush under owing tap water, ultrasonically cleaned in industrial alcohol for 3 min, dried by a blower for 3 min and cooled in a drying
cabinet for 5 min.

b)
Fig. 1. The principles of the experimental rig: a) MMU-10F type disc/disc tribological test
rig; b) the electrochemical test set with three electrodes.

In the study, the loading forces were 200 N, 500 N and 1000 N, and
the sliding velocities were 500 and 1000 r/min. Under one operating
condition, tribological testing is conducted three times, and the mass
of the WC10Co4Cr and Si3N4 was measured three times before and
after every experiment.

2.2. Specimens
The bottom specimens are WC10Co4Cr coatings sprayed on a
316 L stainless steel substrate using HVOF thermal spraying technology.
The upper specimens are sintered Si3N4 with 5% SiC whisker added to
increase the toughness. The inner and outer diameters of the specimens
are 16 mm and 30 mm, respectively. The surface hardness of the specimens was measured with a DHT-1000 type digital microhardness tester. The roughness of the contacting surfaces was measured with a
Talysurf PGI 830 surface prole general measuring instrument. The
properties of the composite surface coating and the sintered ceramics
are listed in Tables 1 and 2, respectively.

D. Wu et al. / Int. Journal of Refractory Metals and Hard Materials 54 (2016) 1926
Table 1
The properties of WC10Co4Cr coating.
Composition

WC10Co4Cr

Coating technique
Coating thickness (mm)
Hardness (HV0.3)
Porosity (%)
Density (g/cm3)
Initial roughness

HVOF
0.3
1213 200
b0.9
14.7
b0.15

21

exceeding the allowable contamination level of a traditional hydraulic

system using mineral oil as the working medium. The particle size distribution of the different silt-laden waters is shown in Fig. 2. The particle
size distribution for the ltered water and distilled water is shown in
Fig. 3. Obviously, most silt particles are smaller than 15 m. And the particles less than this size usually induce the abrasive wear on the
matching pair of the water hydraulic pump, because this particle size
is similar to the clearance of the typical tribopairs of pump.

3. Results and discussions

Table 2
The properties of silicon nitride.
Composition

Si3N4 + 5% SiC

Manufacturing technique
Hardness (HV0.3)
Density (g/cm3)
Initial roughness

Sintering
1628 100
3.2
b0.06

2.3. Lubricant
To study the tribological behaviours of the WC10Co4Cr/Si3N4
tribopair under different natural water lubricants, natural seawater
and river water were tested. The natural seawater was from the Pacic
Ocean and the river water was from the Yangtze River. The unltered
natural water from the sea or river was called natural silt-laden sea or
river water. The water ltered through a lter paper was called natural
ltered sea or river water. In addition, distilled water was also used as a
typical water lubricant in this study.
The contamination levels of the different water samples were measured with a KT-1-type particle counter produced by Tianjin Logan
Science&Technology Co. Ltd. The conductivity of the different water
samples was measured with a DDS-11A type electrical conductivity
meter produced by Shanghai Shenchi Co. Ltd., China. The element of
natural seawater and river water was measured by inductively coupled
plasma mass spectrometry (ICP-MS) produced by PerkinElmer Inc. The
contamination levels and conductivity data are shown in Table 3. The
concentration of the main element of the natural river water and sea
water is shown in Table 4.
The contamination levels adhere to the ISO4406 standard, which
was dened by three numbers divided by slashes. The numbers correspond to 4, 6 and 14 micron particle. The contamination levels of natural
silt-laden river water and seawater are 25/23/20 and 25/23/18,

3.1. The tribological performances under different natural waters from sea
and river
The average steady-state friction coefcients in different natural waters including both ltered and unltered sea and river waters are
shown in Fig. 4. The average wear rates for the WC10Co4Cr coating
and Si3N4 ceramics with different natural silt-laden water and ltered
water lubricants are shown in Figs. 5 and 6, respectively.
The coefcient often can reach a steady value after a running-in period when the applied loads are below the limited values. The limited
values under different operating conditions and lubricants are different.
In this study, the experiment in silt-laden natural seawater could not be
completed due to impetuous vibration at the highest applied load
(1000 N) and lowest rotary speed (500 r/min), but the tribological
tests under the other lubricants and operating conditions could operate
steadily without impetuous vibration.
As shown in Figs. 46, the effects of the different natural waters on
the steady-state friction coefcients and wear rates are obvious. The
steady-state friction coefcients under silt-laden river water are smaller
than those under silt-laden seawater, whilst the coefcients under ltered river water are also smaller than ltered seawater. The wear
rates of the coating and Si3N4 under natural river water are lower than
those under seawater.

Table 3
The contamination levels and conductivity of the different waters.
Different waters

Contamination levels
(ISO4406)

Conductivity
(mS/m)

Natural silt-laden river water

Natural silt-laden seawater
Sand-laden river water
Natural ltered river water
Natural ltered seawater
Distilled water

25/23/20
25/23/18
25/23/16
18/17/12
18/15/13
10/08/05

40.5
4560
40.2
40.4
4480
0.67

Fig. 2. Particle size distribution of the three different silt-laden waters.

Table 4
Concentration of the main element of the different waters (ppm).
Element

River water

Seawater

Cl
Na
Mg
Ca
K

44.1
7.0
4.0
12.6
0.8

19,100
10,705
1280
420
380

Fig. 3. Particle size distribution of the ltered water and distilled water.

22

D. Wu et al. / Int. Journal of Refractory Metals and Hard Materials 54 (2016) 1926

Fig. 4. The steady-state friction coefcients under different natural waters.

Fig. 5. The wear rates of WC10Co4Cr coating under different natural waters.

In general, the results exhibit that the ltering process improves the
tribological behaviours under most operating conditions. The wear rates
in ltered natural water are lower than those in natural silt-laden water,
regardless of whether the water came from the sea or the river. The
steady-state friction coefcients under ltered river water less than

Fig. 6. The wear rates of Si3N4 under different natural waters.

silt-laden river water, although the results do not display the clear relationship with contamination levels in natural sea water.
However, obtaining clean natural waters is difcult for an opencircuit water hydraulic system in engineering application. In a traditional hydraulic system, the micron rating of the inlet lter is usually 100 m
for avoiding suction problem. But the 100 m lter (even 40 m) is ineffective for removing the silt suspended in natural water. Because the
most silt suspended in natural water is smaller than 15 m, as shown
in Fig. 2. Therefore, ne ltration is difcult for the open-circuit water
hydraulic system.
Fortunately, the tribopair in this study exhibits excellent friction and
wear resistance behaviours, even in silt-laden natural water no matter
from sea or river. The maximum average steady-state friction coefcients under natural silt-laden seawater, silt-laden river water, ltered
seawater and ltered river water are 0.0087, 0.0065, 0.0078 and
0.0039, respectively, and the minimum friction coefcients are 0.0052,
0.0043, 0.0039 and 0.0026, respectively. The average wear rates under
the different natural waters are all below 9 10 12 cm3/(Nm). Although the tribological properties are improved by ltration, the differences under the same operating conditions are not enormous. The
friction coefcients and wear rates under natural silt-laden water are
still small relative to most couple-pairs. The friction coefcient of the
WC12Co/Ti alloy tribo-couple under deionised water lubrication is
0.3 [23]. J.K. Robert found that the friction coefcient of the self-mated
WC10Co4Cr under distilled water is 0.26, whilst the wear rate is
5 1011 cm3/(Nm) [24]. C. Ming found that the steady-state friction
coefcient of self-mated Si3N4 is 0.0035, whilst the coefcient of selfmated SiC is 0.01 under the 5 N and 120 mm/s test conditions in fresh
water [25]. The steady-state friction coefcients of a tribopair consisting
of a CrN coating and Si3N4 are approximately 0.30.5 under distilled
water lubrication, whilst their wear rates are approximately
5 109 cm3/Nm and 3 109 cm3/(Nm) [26].
Although the tribological behaviours under natural silt-laden sea
and river water are excellent, there are a few differences between seawater and river water, as well as differences between ltered water
and non-ltered water. Therefore, studying the effects of different properties in the natural water on the on tribological behaviours may be important for understanding the failure mechanism and for improving the
service life.
3.2. The effect of chemical properties of different waters on tribological
behaviours
The friction coefcient of the tribopair under different natural waters is less than 0.009. According to the published Stribeck curves, the
lubrication mode should be full lm lubrication. Because published
Stribeck often suggest values of 0.2 or more when the lubrication
mode is mixed and boundary, but this is largely speculation [27]. Actually, mixed and boundary lubrication would be the main lubrication
mode in this study. As showed in Figs. 1314, the mechanical wear
marks appear on the worn surfaces. Because the two plane surface of
the samples contact directly, with no the full hydraulic supporting by
the pressure water.
The excellent tribological behaviours of the WC10Co4Cr/Si3N4
tribopair under river or sea water lubrication should benet from the
tribochemical reaction of Si3N4 with water. Si3N4 reacts rapidly with
water to produce a lm that is easily sheared. The reaction process
can be described as follows: Si3N4 + 6H2O 3SiO2 + 4NH3;
SiO2 + 2H2O Si(OH)4 [16,17]. Because the SiO2 and Si(OH)4 lms
are easily sheared, the friction coefcient of the tribopair under water
is lower than the friction coefcient of the self-mated WC10Co4Cr
[24].
However, the differences in friction and wear properties of the
tribopair under the sea and river water lubrication indicate that the
tribological behaviours are affected by the chemical properties of the
water. Because the contamination levels of silt-laden water or ltered

D. Wu et al. / Int. Journal of Refractory Metals and Hard Materials 54 (2016) 1926

23

Fig. 7. The coefcients of friction varying with test duration under free corrosion and electrochemical protection when lubricant is natural silt-laden seawater (1000 r/min & 500 N).

Fig. 8. Wear rates of WC10Co4Cr coating and Si3N4 under free corrosion and electrochemical protection when lubricant is natural silt-laden seawater (1000 r/min & 500 N).

water for seawater and river water are similar. The ISO4406 contamination levels of the silt-laden natural seawater and river water are 25/23/
18 and 25/23/20, whilst the contamination levels of ltered natural seawater and river water are 18/15/13 and 18/17/12, respectively. In this
study, the friction coefcients under river water are lower than in seawater, and the wear rates of the WC10Co4Cr coating and Si3N4 in
river water are lower than in seawater.

The results for the wear rates of the coating are easy to understand
due to the electrochemical corrosion of the coating in water. Seawater
is more corrosive than river water. The conductivities of seawater and
river water in this study are 4560 and 40.5 ms/m. However, it is necessary to study further about the reason why wear rates of the insulated
Si3N4 ceramics under seawater are also larger than in river water. To
study the effect of tribocorrosion of coating on tribological behaviours,

Fig. 9. The effect of contamination levels on the friction coefcients under fresh water.

Fig. 10. The wear rates of WC10Co4Cr coating under different contamination levels of
water.

24

D. Wu et al. / Int. Journal of Refractory Metals and Hard Materials 54 (2016) 1926

Fig. 11. The wear rates of Si3N4 under different contamination levels of water.

the electrochemical protection technology was used to depart the effect

of tribocorrosion of the coating and tribochemical reaction of Si3N4. The
tribological tests were performed under free corrosion and electrochemical protection condition in natural silt-laden seawater. The
tribological test was carried out under electrochemical protection at
1000 r/min and 500 N. The protective potential was 0.38 V (SCE)
and was chosen based on the open potential measured under free corrosion conditions. Fig. 7 shows the variations in the coefcients of friction under both free corrosion and electrochemical protection
conditions. The wear rates affected by the tribocorrosion are shown in

Fig. 8. The friction coefcient under electrochemical protection is

lower than under free corrosion, and the wear rates of the WC10Co
4Cr coating and Si3N4 under electrochemical protection are both smaller
than under free corrosion conditions. The results indicate that the tribological performances of the WC10Co4Cr/Si3N4 tribopair are affected
by tribocorrosion of the coating.
Although tungsten carbide has a good corrosion resistance, the Co
metal matrix is easily corroded because Co does not easily form a passivated lm. The corrosion process proceeds as follows: the binder phase,
specically the interface between the WC particle and the binder matrix, is corroded rst. Subsequently, the WC particles are removed
from the matrix [28,29]. Consequently, the Cr is added to the WCCo
coating to improve corrosion resistance in this study because Cr easily
forms a passivated, protective oxide lm. However, the WC10Co4Cr
coating may still be corroded somewhat in electrolyte solutions [30].
The effect of tribocorrosion on the friction characteristics may be as follows: rst, the area rich in Co loses material due to corrosion. Subsequently, increasing amounts of hard and sharp tungsten carbide
particles are exposed on surface as the corrosion continues. The WC
10Co4Cr surface becomes rougher under seawater due to corrosion.
Afterward, the rougher surface causes more tribochemical reaction
lm to be destroyed by sliding, increasing the friction, tribochemical
and abrasive wear.
In addition, the friction coefcients and wear rates in seawater under
electrochemical protection are still bigger than in river water under free
corrosion conditions. This phenomenon indicates that the tribological
performances of the tribopair under natural waters are not only affected
by tribocorrosion of the coating but are also affected by the
tribochemical reaction of Si3N4. Mitsuo et al. have studied the tribological properties of self-mated SiC under different natural water samples

Fig. 12. The morphology and component of silt suspended in natural water: a) morphology; b) EDS analysis of sharp silt.

Fig. 13. The morphology of original and worn surface of WC10Co4Cr coating: a) original surface; b) worn surface.

D. Wu et al. / Int. Journal of Refractory Metals and Hard Materials 54 (2016) 1926

25

Fig. 14. The morphology of original and worn surface of Si3N4: a) original surface; b) worn surface.

and found that the friction coefcients in the river water are smaller
than in seawater [31].
3.3. The effect of contamination levels of silt on tribological behaviours
As shown in Figs. 46, there are some differences in the friction coefcients and wear rates between the natural silt-laden and ltered waters from both river and sea sources.
Therefore, natural silt-laden river water, ltered river water and distilled water are used as lubricants to study the effect of contamination
levels on the tribological behaviours of the WC10Co4Cr/Si3N4
tribopair and evaluate its applicability to different waters. The
ISO4406 contamination levels of the natural silt-laden and ltered
river waters are 25/23/20 and 18/17/12, respectively. The contamination level of the distilled water is 10/08/05 and is less than the minimum
contamination level of an aerospace hydraulic system (14/12/9). Distilled water has been chosen for comparison due to the following reasons: 1) the typical properties of all waters; 2) low contamination
level that is too difcult to obtain via ltration when using natural
river water; and 3) low conductivity, precluding the effect of the electrochemical corrosion of the coating on the tribological behaviours.
The steady-state friction coefcients under the three water lubricants
are shown in Fig. 9. The wear rates of the WC10Co4Cr coating and
the Si3N4 are shown in Figs. 10 and 11, respectively. The lowest friction
coefcient is not achieved under unltered natural river water nor distilled water. Instead, the best behaviours were exhibited in ltered river
water lubricant, which has intermediate contamination levels compared to the other two lubricants. The wear rates under natural siltladen water are larger than under the ltered and distilled waters. However, the wear rates under the ltered water and distilled water do not
display a clear relationship with contamination levels.
The best tribological behaviours are not obtained under the distilled
water possibly due to the tribochemical reactions of the silt. Quartz is
the main component of the silt-laden water. Quartz is composed of
SiO2 and can react with water to produce a Si(OH)4 lm that shears easily. In addition, the silt in the clearance between the contact surfaces
may work as rollers that bear thrust, decreasing the friction coefcient.
Although the tribological behaviours observed under different contamination levels are different, they remain excellent under the three
types of water. This tribopair displays excellent applicability to different
waters, including in natural silt-laden water. The good abrasion resistance to natural silt occurs because the two materials are much harder
than quartz, which is the hardest component of natural silt-laden
water. The micrographs of the silt particles before tribological test are
showed in Fig. 12a) and the component of the sharper silt suspended
in natural river water was analysed by EDS technology of the SEM, as
showed in Fig. 12b). It shows that the sharpest silt is quartz. The Mohs

hardness of quartz is 7, which is equivalent to Vickers micro-hardness

HV820 approximately, whilst the microhardness of the WC10Co4Cr
coating and Si3N4 is HV1213 and HV1628, respectively. The testing materials are harder than the natural suspending silt maybe one of factors
why the tribopair displayed the excellent tribological behaviours. When
the silt penetrated in the interface, the silt is pulverized by sliding motion of the harder contacting surfaces. Before and after the testing
(200 N and 1000 r/min), contamination level of the natural silt-laden
sea water lubricant is measured by laser particle number machine.
The results of level are shown in Table 5. From the results, it can be
seen that the number of big particles decreases whilst the number of
the small ones increases. It indicates that the abrasive particles are broken into pieces by the tribopairs due to their high hardness.
Although the two materials are harder than the abrasives and possess excellent abrasion resistance, they still become damaged. The mechanical wear process is similar to the corrosion process. The binder
phase is worn due to its lower hardness; the depletion of the binder
phase undermines the interface between the carbide particles and the
matrix, allowing them to be pulled out easily instead of becoming
worn, the original and worn surface as showed in Fig. 12. For the
Si3N4, tribochemical and mechanical wears are the main worn modes,
as indicated by the original and worn surface SEM images in Fig. 13.
In some study, the articial particles are usually used to examine
abrasion resistance and coarse abrasives (both N 200 m) are commonly
employed [32]. Al2O3 and SiC particles are often used to prepare siltladen water in most research [33,34]. However, the harder and more
angular articial particles would cause more wear. And wear mechanisms of coarser abrasives are expected to be very different to those observed with natural abrasives. Because the ne natural abrasives can
free path in cermet materials due to its size is of the same order of magnitude as the hard-phase particle size and binder [28]. Hence, the tribological behaviours in natural silt-laden water represented in this study
maybe different from the results in articial silt-laden water because
there are the many differences in size, hardness and morphology
between got-up particles and natural silt [35].
In a word, the tribological results of this study indicate the WC
10Co4Cr/Si3N4 tribopair possesses the wide applicability to different
water and excellent abrasion to silt laden in natural water. And the friction and wear characteristics of tribopair are affected by tribochemical
Table 5
The contamination level of original and wore natural sea lubricant (200 N & 1000 r/min).
Test condition

Original lubricant
Worn lubricant

Particle size number/1 mL

N4 m

N6 m

N14 m

190,444
204,960

61,686
56,628

1444
708

Contamination level
(ISO4406)
25/23/18
25/23/17

26

D. Wu et al. / Int. Journal of Refractory Metals and Hard Materials 54 (2016) 1926

Fig. 15. The WC10Co4Cr coating piston and Si3N4 cylinder.

reactions, tribocorrosion and mechanical abrasion, which is different

from the self WC10Co4Cr and Si3N4 couple.
3.4. Application of the tribopair
Nowadays, the WC10Co4Cr coating pistons and Si3N4 cylinders
(Fig. 15) have been used in a high pressure seawater pump. The pump
is the key component of a variable buoyancy water hydraulic system
of the high-depth submersible. Under the tap water, the mechanical efciencies of pump at 45 MPa and 80 MPa are 90.2% and 94.7%, respectively. And the volumetric efciencies are 91.8% and 85.8%. The
efciency does not descend after experiencing a 400 hour duration
test. The experimental results of the pump indicate that these tribopairs
are feasible in applying the components under water lubrication. In the
next work, the pump will be installed in large-depth manned submersible in 2015 and take sea test in 2016 following the submersible.
4. Conclusions
The tribological characteristics and inuence factors of the WC
10Co4Cr/Si3N4 tribopair in different water samples have been investigated. Its friction and wear behaviours are affected by tribochemical reactions, tribocorrosion, mechanical abrasion and effect of each other.
The tribological results indicate that the tribopair owns a wide applicability to different waters, ranging from natural seawater to distilled
water. In all the experimental water, the tribopair displays the excellent
tribological behaviours even in silt-laden natural sea and river water
due to its excellent abrasion resistance. The maximum steady-state friction coefcients under natural silt-laden seawater, silt-laden river
water, ltered seawater and river water are 0.0087, 0.0065, 0.0078
and 0.0039, respectively, and the minimum friction coefcients are
0.0052, 0.0043, 0.0039 and 0.0026, respectively. All of the average
wear rates under natural water are below 9 1012 cm3/Nm. Nowadays, the tribopair was used in a ultra-high seawater pump and the
pump displays the preeminent properties in efciency and duration.
Acknowledgement
The authors would like to thank the China Postdoctoral Science
Foundation (no. 2014M560609, no. 2015T80804), the National High
Technology Research and Development Program of China (no.
2009AA090100) and the Program for New Century Excellent Talents
in University of China (NCET-13-0231) for providing the funding for
this project. Thanks are also given to Master Zhen Yang, Tao Jiang,
Wudi Fang and Hui Tang for their contributions to this project. Additionally, we are grateful to the Huazhong University of Science and Technology Test Centre for offering necessary assistance.
References
[1] E. Trostmann, Water Hydraulics Control Technology, Marcel Derkker, Inc., New York
Basel, 1995.
[2] Z.L. Qiu, Design and research on a variable ballast system for deep-sea manned submersibles, J. Mar. Sci. Appl. 7 (2008) 225260.
[3] B.B. Walden, R.S. Brown, A replacement for the Alvin Submersible, Mar. Technol. Soc.
J. 38 (2004) 8591.
[4] Y.S. Liu, D.F. Wu, X.F. He, Materials screening of matching pairs in water hydraulic
pump, Ind. Lubr. Tribol. 61 (2009) 173178.

[5] K. Bonny, P. De Baets, W. Ost, S. Huang, J. Vleugels, W. Liu, B. Lauwers, Inuence of

electrical discharge machining on the reciprocating sliding friction and wear response of WCCo cemented carbides, Int. J. Refract. Met. Hard Mater. 27 (2009)
350359.
[6] Y.X. Wang, L.P. Wang, Q.J. Xue, Improvement in the tribological performances of
Si3N4, SiC and WC by graphite-like carbon lms under dry and water-lubricated
sliding conditions, Surf. Coat. Technol. 205 (2011) 27702776.
[7] M. Hadad, R. Hitzek, P. Buergler, L. Rohr, S. Siegmann, Wear performance of sandwich structured WCCoCr thermally sprayed coatings using different intermediate
layers, Wear 263 (2007) 691698.
[8] H. Engqvist, G.A. Botton, S. Ederyd, M. Phaneuf, J. Fondelius, N. Axn, Wear phenomena on WC-based face seal rings, Int. J. Refract. Met. Hard Mater. 18 (2000) 3946.
[9] M.R. Thakare, J.A. Wharton, R.J.K. Wood, C. Menger, Exposure effects of strong alkaline conditions on the microscale abrasion-corrosion of D-gun sprayed WC10Co
4Cr coating, Tribol. Int. 41 (2008) 629639.
[10] T. Sudaprasert, P.H. Shipway, D.G. McCartney, Sliding wear behavior of HVOF
sprayed WCCo coatings deposited with both gas-fuelled and liquid fuelled systems, Wear 255 (2003) 943951.
[11] U. Beste, T. Hartzell, H. Engqvist, N. Axen, Surface damage on cemented carbide
rock-drill buttons, Wear 249 (2001) 324342.
[12] M.R. Thakare, J.A. Wharton, R.J.K. Wood, Exposure effects of alkaline drilling uid on
the microscale abrasioncorrosion of WC-based hardmetals, Wear 263 (2007)
125136.
[13] H.J.C. Voorwald, R.C. Souza, W.L. Pigatinc, M.O.H. Ciofb, Evaluation of WC17Co and
WC10Co4Cr thermal spray coatings by HVOF on the fatigue and corrosion
strength of AISI 4340 steel, Surf. Coat. Technol. 190 (2005) 155164.
[14] J.G. Legoux, B. Arsenault, L. Leblanc, V. Bouyer, C. Moreau, Evaluation of four high velocity thermal spray guns using WC10%Co4%Cr cermets, J. Therm. Spray Technol.
11 (2002) 8694.
[15] D.A. Rani, Y. Yoshizawa, H. Hyuga, K. Hirao, Y. Yamauchi, Tribological behavior of ceramic materials (Si3N4, SiC and Al2O3) in aqueous medium, J. Eur. Ceram. Soc. 24
(2004) 32793284.
[16] M.C. Vera, J. Ramirez-Rico, J. Martinez-Fernandez, M. Singh, Sliding wear resistance
of biomorphic SiC ceramics, Int. J. Refract. Met. Hard Mater. 49 (2015) 327333.
[17] M. Chen, K. Kato, K. Adachi, The comparisons of sliding speed and normal load effect
on friction coefcients of self-mated Si3N4 and SiC under water lubrication, Tribol.
Int. 35 (2002) 129135.
[18] T. Saito, Y. Imada, F. Honda, An analytical observation of the tribochemical reaction
of silicon nitride sliding with low friction in aqueous solutions, Wear 205 (1997)
153159.
[19] G. Pezzotti, I. Tanaka, T. Okamoto, Si3N4/SiC-whisker composites without sintering
aids. I. Quantitative evaluation of microstructure, J. Am. Ceram. Soc. 73 (1990)
33033311.
[20] L.X. Tao, C.X. Jun, Q.J. Huang, X.F. Cheng, Preparation and thermal shock properties of
Si3N4 ceramic reinforced by orientation SiC whiskers, J. Inorg. Mater. 19 (2004)
553558.
[21] Y.N. Liang, S.W. Lee, D.S. Park, Effects of whisker distribution and sintering temperature on friction and wear of Si3N4-whisker-reinforced Si3N4-composites, Wear
225229 (1999) 132711337.
[22] D.F. Wu, Y.S. Liu, S.D. Yang, Z. Yang, H. Tang, Friction and wear characteristics of WC
10Co4Cr/Si3N4 tribopair lubricated under silt-laden water, Wear 294295 (2012)
370379.
[23] X.D. Wu, D.P. Wang, S.R. Yang, Q.J. Xue, Tribochemical investigation of tungsten carbide/titanium alloy tribo-couples under aqueous lubrication, Wear 237 (2000)
2832.
[24] R.J.K. Wood, Tribology of thermal sprayed WCCo coatings, Int. J. Refract. Met. Hard
Mater. 28 (2010) 8290.
[25] C. Ming, K. Kato, K. Adachi, The difference in running-in period and friction coefcient between self-mated Si3N4 and SiC under water lubrication, Tribol. Lett. 11
(2001) 2328.
[26] F. Zhou, K.M. Chen, M.L. Wang, X.J. Xu, Friction and wear properties of CrN coatings
sliding against Si3N4 balls in water and air, Wear 265 (2008) 10291037.
[27] B. Bhushan, Modern Tribology Handbook, Volume One, CRC press LLC, Florida, 2001.
[28] P.H. Shipway, L. Howell, Microscale abrasioncorrosion behaviour of WCCo hard
metals and HVOF sprayed coatings, Wear 258 (2005) 303312.
[29] M.M. Stack, T.M.A.E. Badia, Some comments on mapping the combined effects of
slurry concentration, impact velocity and electrochemical potential on the
erosioncorrosion of WC/CoCr coatings, Wear 264 (2008) 826837.
[30] L. Fedrizzi, L. Valentinelli, S. Rossi, S. Segna, Tribocorrosion behaviour of HVOF cermet coatings, Corros. Sci. 49 (2007) 27812799.
[31] M. Mitsuo, K. Koji, H. Atsushi, Friction and wear properties of silicon carbide in water
from different sources, Tribol. Lett. 43 (2011) 3341.
[32] Standard test method for abrasive wear resistance of cemented carbides, ASTM
standards: B611-85, West Conshohocken, PA, 2005.
[33] Q. Fang, P.S. Sidky, M.G. Hocking, The effect corrosion and erosion on ceramic materials, Corros. Sci. 39 (1997) 511527.
[34] G.C. Saha, T.I. Khan, G.A. Zhang, Erosioncorrosion resistance of microcrystalline and
near-nanocrystalline WC17Co high velocity oxy-fuel thermal spray coatings,
Corros. Sci. 53 (2011) 21062114.
[35] A.J. Gant, M.G. Gee, A review of micro-scale abrasion testing, J. Phys. D. Appl. Phys.
44 (2011) 115.