coatings

Article
Addition of Si3N4 Strengthens SiC Coatings via Heat
Treatment with Nitrogen Gas onto
Carbon/Carbon Composites
Zuli Mao 1,2 and Li Yang 3, *
1 Research Institute of Automobile Parts Technology, Hunan Institute of Technology, Hengyang 421000, China;
maomao5657@yeah.net
2 National Joint Engineering Laboratory of Automobile Pump Parts Design and Manufacturing,
Hengyang 421000, China
3 School of Safety and Environmental Engineering, Hunan Institute of Technology, Hengyang 421000, China
* Correspondence: yangch_1234@sina.com




Received: 3 July 2020; Accepted: 11 August 2020; Published: 13 August 2020


Abstract: We report the synthesis of SiC/Si3 N4 coatings on carbon/carbon composites via pack
cementation and heat treatment with nitrogen gas, the latter of which improves the coating wear
resistance. X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray
spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) are used to analyse the microstructure,
surface morphology, chemical states and elemental distribution, respectively, of SiC and SiC/Si3 N4
coatings. In addition, we analyse the tribological behaviour of the SiC and SiC/Si3 N4 coatings and the
related microstructure and wear mechanisms. The results show that SiC/Si3 N4 coatings are compact
and contain the three phases: Si3 N4 , SiC and C. Additionally, specimens with the SiC/Si3 N4 coating
have smaller, more stable friction coefficients and less weight loss than specimens with only the SiC
coating. Adhesive wear and abrasive wear are the main wear mechanisms contributing to the higher
friction coefficient of the SiC coating. Furthermore, with the SiC/Si3 N4 coating, adhesive wear is the
main wear mechanism causing a high friction coefficient at the initial stage of frictional wear. In the
subsequent stages of frictional wear, the graphite in the SiC/Si3 N4 coating generates a thin lubricating
film that decreases the friction coefficient.

Keywords: carbon/carbon composites; SiC/Si3 N4 coating; microstructure; tribological behaviour;

wear mechanism

1. Introduction
Mechanical seals are extensively used in industry to prevent losses of lubricant or gases and to
prevent the entry of contaminants into hydraulic or lubrication circuits. A mechanical seal comprises
two parts: a static seal ring and a rotating ring. Many situations employing seals require frequent
seal replacement because of wear and surface damage caused by external contaminants in the system.
The replacement of seals requires stopping of rotating equipment, which can incur losses to productivity.
To address these concerns and to improve the life and energy efficiency of seals, many approaches have
been explored worldwide [1]. Carbon/carbon composite (C/C composites) have drawn great interest
owing to their excellent mechanical properties such as light weight, high module, high specific strength,
low thermal expansion, high temperature resistance, outstanding corrosion resistance and low friction
coefficient [2–5]. However, for conventional C/C composite-based sealing materials, the stability of
the friction coefficient is relatively low and the wear resistance is poor when applied as mechanical
seals. Therefore, there is an urgent need to modify conventional C/C composites to improve their
tribological properties.

Coatings 2020, 10, 787; doi:10.3390/coatings10080787 www.mdpi.com/journal/coatings

Coatings 2020, 10, 787 2 of 10

To address this issue, conventional C/C composites may be coated with wear-resistant materials
to improve their tribological properties. Silicon carbide (SiC) exhibits several excellent properties such
as a high melting point, high stiffness, good chemical resistance, good electrical conductivity and
remarkable wear resistance [6–8]. Studies have also shown that the SiC coating on C/C composites
improves their tribological properties [9–13].
Several methods are used to prepare SiC coatings. Pack cementation is cheap, simple, and it has
no sample shape requirements [14–18]. Through the use of this technique, all layers of a surface can be
coated using a single process. However, SiC coatings prepared through pack cementation exhibit poor
performance. Some researchers have attempted to address this shortcoming. Pourasad reported that
SiC/ZrO2 coatings can be prepared in two steps. The first step involves the preparation of a functionally
graded SiC layer via through the pack cementation process. The second step involves the formation
of SiC/ZrO2 coating through pack cementation at 1873 K [19]. Huang stated that SiC coatings were
strengthened when doped with Al synthesised on C/C composites through pack cementation [20].
Liu reported that the SiC and ZrSi2 coatings were prepared in two steps: pack cementation and
supersonic atmospheric plasma spraying, respectively. In the first step, the SiC coating was prepared
via the pack cementation process. In the second step, the outer ZrSi2 coating was deposited via
supersonic atmospheric plasma spraying [21].
Silicon nitride (Si3 N4 ), a typical non-oxide ceramic material, has been used in applications
requiring high tribological performance owing to its low chemical activity, high wear resistance and
satisfactory mechanical properties [22,23]. In a previous study [24], SiC coatings have been prepared
through the use of a low-temperature embedding method to remove any loosely embedded material.
However, SiC coatings suffer from defects that reduce the adhesion between the SiC coating and
substrate. To address these problems, we applied nitriding and low-temperature packing cementation
to form SiC/Si3 N4 recombination coatings on C/C composites. The resulting Si3 N4 strengthens the
SiC coating.

2. Experiment

2.1. Sample Preparation

Bulk two-dimensional C/C composites with a density of 1.2–1.4 g/cm3 were produced through
chemical vapour deposition. Substrate specimens (7 mm × 7 mm × 30 mm) were cut from the bulk
material and hand-polished using 600-grit SiC paper. Prior to pack cementation, the C/C substrates
were cleaned ultrasonically in acetone, then rinsed with distilled water and dried in a drying oven at
100 ◦ C for 2 h, followed by immersion in peroxide for 1 h and drying again in a drying oven at 100 ◦ C
for 2 h.
The packing powder materials were composed of 300 mesh Si powder, 325 mesh graphite powder
and 300 mesh MgO powder. The MgO served to increase the diffusing reaction rate at high temperature.
All powders were of analytical grade and were cleaned ultrasonically in ethanol for 30 min, dried at
70 ◦ C for 24 h and then mixed in a powder-mixing machine for 12 h.
After treatment, the C/C composite specimens were packed with the as-prepared powder mixture
and then placed in a crucible. The entire crucible was placed in a tube furnace, and SiC was formed
upon heating the impregnated specimens under argon gas at 1100 ◦ C for 8 h. The specimens were then
allowed to cool passively in the furnace.
Following pack cementation, all specimens were removed from the crucible, and the embedded
materials were cleaned off with a brush. The specimens were again placed in the crucible, heated under
nitrogen to 1300 ◦ C for 2 h and allowed to cool passively in the furnace. The specimens were then
taken out and cleaned ultrasonically in distilled water for 5 min and finally dried at 100 ◦ C for 2 h.
Figure 1 shows the preparation process of the specimens.
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Figure
Figure1.1.
Figure Flow
1.Flow chart
Flowchart describing
chartdescribing the
describingthe specimen
thespecimen preparation
specimenpreparation process.
preparationprocess.
process.

2.2.Friction
2.2. Frictionand
Friction andWear
and WearTests
Wear Tests
Thewear-resistance
The wear-resistanceproperties
propertieswere wereinvestigated
investigatedvia viaring-block
ring-blockcontact
contactwear
weartests
tests(see
(seeFigure
(see Figure2)
Figure 2)
2)
withaasliding-wear
with sliding-weartester testerserving
servingfor forthethefriction
frictionandandwearweartests
tests(Model
(ModelMM-P2MM-P2Screen
Screendisplay
displaywear
wear
tester, Jinan Times Gold Assay Testing
Testing Machine
Machine Co.,
Co., Ltd.,
Ltd., Jinan,
Jinan, China).
China).
tester, Jinan Times Gold Assay Testing Machine Co., Ltd., Jinan, China). The test ring was 23.38 mm The test ring was 23.38 mm
in diameter and made of #45
in diameter and made of #45 steel. For steel. For
Forwearwear testing,
weartesting,
testing,thethe test
thetest load was 100 N, the test ring
testload was 100 N, the test ring speed was speed was
constant 200
aa constant 200 rpm
rpm and
and the
the testing
testing time
time waswas
was 30 30 min.
30 min.
min. The experimentalresults
The experimental results were digitised and
were digitised and
recorded by
by the
the integrated
integrated computer
computer system.
system.Before each
Before test,
each the samples
test,
recorded by the integrated computer system. Before each test, the samples and test ring were the and
samples test ring
and were
test carefully
ring were
hand-polished
carefully
carefully using 3000
hand-polished
hand-polished grit SiC
using
using 3000
3000 paper, followed
grit SiC
grit SiC paper,by
paper, ultrasonic
followed
followed bycleaning
by ultrasonic
ultrasonic in cleaning
anhydrous
cleaning in inethanol
anhydrous
anhydrous and
acetone and and acetone
drying ◦
ethanol
ethanol acetoneatand100drying
and C for 2at
drying ath.100
These
100 °C tests
°C for 22were
for carried
h. These
h. These outwere
tests
tests under
were a relative
carried
carried out humidity
out level of
under aa relative
under relative
50–70% and
humiditylevel
humidity room
levelof temperature.
of50%–70%
50%–70%and androomPrior to each
roomtemperature. test,
temperature.Prior the test
Priorto ring
toeach was
eachtest, hand-polished
test,the
thetest
testring
ringwas with 3000 grit
washand-polished
hand-polished SiC
paper.
with
with For grit
3000
3000 each
grit SiCsample
SiC type,
paper.
paper. four
For
For samples
each
each sample
sample were tested,
type,
type, fourwith
four each were
samples
samples individual
were tested, sample
tested, with tested
with four times.
each individual
each individual
The
samplefinal mass
tested loss
four was
times.theTheaverage
final of
mass these
loss 16 measurements.
was the average
sample tested four times. The final mass loss was the average of these 16 measurements. TheThe
of mass
these 16 loss W of the
measurements. samples was
The mass
mass
calculated
lossW
loss Wof oftheby using:
thesamples
sampleswas wascalculated
calculatedby byusing:
using:
W = [(m0 − m)/m0 ] × 100% (1)
WW==[(m[(m00−−m)/m
m)/m00]]××100%
100% (1)
(1)
where m0 and m are the mass of the samples before and after wear testing, respectively.
wherem
where m00and
andm marearethe
themass
massof ofthe
thesamples
samplesbeforebeforeand andafter
afterwearweartesting,
testing,respectively.
respectively.

Figure2.2.Schematic
Figure Schematic describingfriction
friction andwear
wear tests.
Figure 2. Schematicdescribing
describing frictionand
and weartests.
tests.

2.3. SpecimenCharacterisation
2.3.Specimen
Specimen Characterisation
Characterisation
The crystalline
The crystalline structure
structure ofof the
the coatings
coatings was
was analysed
analysed byby x-ray
X-ray
x-ray diffractometry
diffractometry (XRD, SmartLab
(XRD, SmartLab
Studio ll,
ll, Rigaku,
Rigaku, Tokyo,
Tokyo, Japan).
Japan). The The
XRD XRD
patterns patterns
were were
collected collected
by using
Studio ll, Rigaku, Tokyo, Japan). The XRD patterns were collected by using a Bruker D8 a by using
Bruker D8 a Bruker D8
diffractometer
with ◦ to 80◦ . The chemical states of the samples were
diffractometerwith
Cu Kα
diffractometer withCuCuKα
irradiation Kαirradiation
irradiationover
over a 2θ overaa2θ
range of 2θrange
10rangeofof10°
10°to
to80°.
80°.The
Thechemical
chemicalstates
statesof
ofthe
thesamples
samples
were investigated
investigated by X-rayby x-ray photoelectron
photoelectron spectroscopy
spectroscopy (XPS; (XPS;
Thermo Thermo
Fisher—VG
were investigated by x-ray photoelectron spectroscopy (XPS; Thermo Fisher—VG Scientific, Fisher—VG
Scientific, Scientific,
ESCALAB
ESCALAB250Xi,
ESCALAB 250Xi,Waltham,
Waltham,MA, MA,USA)USA)with
withan
anAlAlKαKαsource
sourcegungunoperating
operatingatat1486.6
1486.6eV.
eV.The
Thechamber
chamber
pressurewas
pressure wasfixed
fixedatat11××10
10−7 mbar,
−7 mbar,andandthe
thebeam
beampower
powerwaswas200
200W.
W.The
Thesurface
surfacemorphology
morphologyof ofboth
both
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250Xi, Waltham, MA, USA) with an Al Kα source gun operating at 1486.6 eV. The chamber pressure
was fixed at 1 × 10−7 mbar, and the beam power was 200 W. The surface morphology of both the initial
the initial surface and of typical worn surfaces were analysed by scanning electron microscopy (SEM,
surface and of typical worn surfaces were analysed by scanning electron microscopy (SEM, Hitachi
Hitachi S-3400 and Hitachi S-4800, Hitachi, Ltd., Tokyo, Japan).
S-3400 and Hitachi S-4800, Hitachi, Ltd., Tokyo, Japan).
3. Results and Discussion
3. Results and Discussion

3.1.
3.1. Characterisation
Characterisation of
of SiC
SiC and
and SiC/Si
SiC/Si33N
N44Coatings
Coatings
Figure
Figure 33 shows
shows the
the XRD
XRD patterns
patterns ofof the
the SiC and SiC/Si
SiC and SiC/Si33N
N44 coatings,
coatings, which
which reveal
reveal that
that the
the SiC,
SiC,
Si
Si3 N4 and carbon phases are all present in the SiC/Si3 N4 coating on the C/C composite surface and and
3N 4 and carbon phases are all present in the SiC/Si 3 N 4 coating on the C/C composite surface that
that the Si
the SiC, SiC,
andSicarbon
and carbon
phasesphases
are all are all present
present in coating.
in the SiC the SiC coating.
SiC formsSiC formsduring
mainly mainlytheduring
processtheof
process of embedding. At temperatures below
◦ 1400 °C, the following solid-state
embedding. At temperatures below 1400 C, the following solid-state reaction occurs: reaction occurs:

(s)++ C
SiSi(s) (s)→
C (s) →SiC
SiC(s)(s) (2)

Figure
Figure 3.
3. X-ray
X-ray diffractometry
diffractometry (XRD)
(XRD) patterns
patterns of
of coated
coated specimens.
specimens.

The reaction
The reactionbetween
betweenthe thetwo
twosolid
solid phases
phases proceeds
proceeds at aatlower
a lower
raterate
thanthan
thatthat between
between solidsolid
and
liquid phases.
and liquid Therefore,
phases. some some
Therefore, reactions do not
reactions do complete
not complete at temperatures
at temperatures below
below °C, ◦as
14001400 C,
demonstrated
as demonstrated in our previous
in our previous work
work[24]. Thus,
[24]. at temperatures
Thus, at temperatures below
below1400
1400 ◦
°C, Si
C, phases remain
Si phases remainin
the SiCSiC
in the coating
coatingafter embedding,
after embedding, which degrades
which the the
degrades friction andand
friction wear properties
wear of the
properties coatings.
of the To
coatings.
remove
To removethisthis
residual
residualSi Si
phase,
phase, thethe
specimens
specimens were
wereheated
heatedtoto1300
1300°C◦ Cunder
undernitrogen
nitrogen after
after pack
pack
cementation.
cementation. Upon
Upon injecting
injecting nitrogen,
nitrogen, the
the residual
residual Si reacts with nitrogen gas as follows:
3Si (s) + 2N2 (g) → Si3N4 (s)
3Si (s) + 2N2 (g) → Si3 N4 (s) (3)
The nitrogen converts all residual Si to Si3N4 in the SiC/Si3N4 coatings, as indicated in Figure 3.
The nitrogen
The carbon converts the
phase includes all residual Si to Si
matrix phase 3 Nresidual
and 4 in the SiC/Si 3 N4 coatings, as indicated in Figure 3.
graphite.
The carbon
An XPSphase includes
survey showsthe thematrix phase
chemical and residual
states of Si, N,graphite.
C and O on the surface of the SiC/Si3N4
coatings (Figure 4a). Figure 4b shows the deconvolution ofOthe
An XPS survey shows the chemical states of Si, N, C and on Sithe2psurface of theinto
spectrum SiC/Si 3 N4 coatings
sub-peaks that
(Figure 4a). Figure 4b shows the deconvolution of the Si 2p spectrum into sub-peaks
indicate binding energies of 101.8 and 102.9 eV, which are attributed to Si-C and Si-N, respectively. that indicate
binding
This energies
finding of 101.8 and
is consistent with102.9 eV, which are
the coexistence attributed
of SiC and Si3to
N4Si-C and Si-N,
evinced by XRDrespectively.
(Figure 3) This finding
[25,26]. The
is consistent with the coexistence of SiC and
peaks at 284.7 and 285.7 eV in the high-resolution Si N evinced by XRD (Figure 3) [25,26]. The
3 4spectra of Figure 4c are assigned to C 1s, and the peaks at
284.7 and
peak 285.7 eV
at 285.7 eV in the high-resolution
confirms the presence spectra of Figure
of SiC. 4c are assigned
The other deconvolvedto C 1s, and the peak
sub-peak at 285.7
at 284.7 eV
eV confirms the presence of SiC. The other deconvolved sub-peak at 284.7 eV corresponds
corresponds to C=C, which is attributed to graphite in the coatings [25–27]. In Figure 4d, the peak at to C=C,
whicheV
397.3 is confirms
attributedthe
to graphite
presence inofthe
Si3Ncoatings
4 [26,28].[25–27]. In Figure 4d, the peak at 397.3 eV confirms the
presence of Si3 N4 [26,28].
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Figure 4. X-ray photoelectron spectroscopy (XPS) patterns of SiC/Si N4 -coated specimens. (a) spectrum
Figure 4. X-ray photoelectron spectroscopy (XPS) patterns of3 SiC/Si 3N4-coated specimens. (a)
and high resolution spectra of (b) Si2p, (c) C1s, and (d) N1s.
spectrum and high resolution spectra of (b) Si2p, (c) C1s, and (d) N1s.
Figure 5 shows the surface morphology of C/C composites, revealing numerous large holes in the
Figure 5 shows the surface morphology of C/C composites, revealing numerous large holes in
matrix. Some fibres appear in Figure 5, and the specimen surface is uneven. During the preparation
the matrix. Some fibres appear in Figure 5, and the specimen surface is uneven. During the
of the coating, SiC and Si3 N4 penetrate through the pores in the C/C composite, which improves
preparation of the coating, SiC and Si3N4 penetrate through the pores in the C/C composite, which
the bonding strength between the coating and the matrix. Thus, the C/C composite microstructure
improves the bonding strength between the coating and the matrix. Thus, the C/C composite
facilitates the bonding between coating and matrix.
microstructure facilitates the bonding between coating and matrix.

Figure 5. Scanning electron microscopy (SEM) image showing surface morphology of carbon/carbon
Figure 5. Scanning electron microscopy (SEM) image showing surface morphology of
composites.
carbon/carbon composites.

Figure
Figure 66 shows
shows the
the surface
surface morphology
morphology of the SiC
of the SiC and
and SiC/Si
SiC/Si3N 4 coatings on C/C composites.
3 N4 coatings on C/C composites.
Figure
Figure 6a reveals various defects, such as cracks and loose structures, in the
6a reveals various defects, such as cracks and loose structures, in the SiC
SiC coating,
coating, which
which affect
affect
the friction and wear characteristics of the coating. Conversely, the specimen coated by SiC/Si
the friction and wear characteristics of the coating. Conversely, the specimen coated by SiC/Si3 N4 3N4 has

fewer defects, as shown in Figure 6b. The cracks in the SiC/Si3N4 coating can be attributed to the
coefficients of thermal expansion. The lower defect density in the SiC/Si3N4 coating reduces the
friction coefficient and the wear of the coating.
Coatings 2020, 10, 787 6 of 10

has fewer defects, as shown in Figure 6b. The cracks in the SiC/Si3 N4 coating can be attributed to
the coefficients of thermal expansion. The lower defect density in the SiC/Si3 N4 coating reduces the
friction coefficient and the wear of the coating.
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Figure 6. SEM images showing surface morphology of (a) SiC and (b) SiC/Si3N4 coatings on
Figure 6. SEM images showing surface morphology of (a) SiC and (b) SiC/Si3 N4 coatings on
Figure 6. SEMcomposites.
carbon/carbon images showing surface morphology of (a) SiC and (b) SiC/Si3N4 coatings on
carbon/carbon composites.
carbon/carbon composites.
Figure
Figure 77 shows
shows the cross-section of
the cross-section of aa SiC/Si
SiC/Si3N N4 coating and its energy dispersive x-ray spectrum
3 4 coating and its energy dispersive X-ray spectrum
(EDS).Figure
The 7 shows
coating the
is cross-section
determined to of
be a SiC/Si
8.25 µm
(EDS). The coating is determined to be 8.25 µm thick. 3N 4 coating
thick. Si and its
Si atoms
atoms energy
that
that dispersive
diffuse
diffuse into the x-ray
into the C/C spectrum
composite
C/C composite
(EDS).
react The coating is determined to be 8.25 µm thick. Si atoms that diffuse into the C/C
react with the matrix, which increases the adhesion between these materials. In addition, the coating
with the matrix, which increases the adhesion between these materials. In addition, composite
the coating
react with
penetrates the matrix, which increases the adhesion between these materials. In addition,
penetrates into the C/C composite, which also increases the adhesion between the materials. The EDS
into the C/C composite, which also increases the adhesion between the the
materials. coating
The EDS
penetrates
analysis
analysis into the
reveals
reveals theC/C
the composite,
presence
presence thewhich
in the
in SiC/Sialso
SiC/Si increases
3N4 coating of the adhesion
elemental Si, between
C and N,the
butmaterials.
no MgO. The EDS
3 N4 coating of elemental Si, C and N, but no MgO.
analysis reveals the presence in the SiC/Si3N4 coating of elemental Si, C and N, but no MgO.

Figure 7. The cross-section morphology and energy dispersive x-ray spectrum (EDS) of SiC/Si3N4
Figure 7.7. TheThe
coating.
Figure cross-section morphology
cross-section and energy
morphology dispersive
and energy x-ray spectrum
dispersive (EDS) of (EDS)
X-ray spectrum SiC/Si3N
of4
coating.
SiC/Si N coating.
3 4
3.2. Tribological Performance
3.2. Tribological Performance
Figure 8 shows the friction coefficient µ as a function of time from the onset of wear testing for
Figure 8 shows
C/C composites with the friction
different coefficient
coatings. µ asspecimens
For the a functionwith
of time from
the SiC the onset
coating, theof testing for
wear coefficient
friction
composites
C/C composites
increases different
with different
at the outset, and then coatings.
coatings. theaspecimens
For In
decreases. follow-up with the SiC(i.e.,
experiment coating,
withthe
thefriction
friction coefficient
coefficient
same specimen),
increases at the outset, and then decreases. In a follow-up experiment (i.e., with
with the
the same
same specimen),
specimen),
the friction coefficient likewise decreases after small increase. Finally, the friction coefficient for SiC
the friction
coatings coefficient
stabilises likewise
around decreases
0.2 after s. a small increase. Finally,
ca. 103after Finally, the friction coefficient for SiC
coatings stabilises around 0.2 after ca. 1033 s.s.
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Figure 8. Friction coefficients for C/C composites with different coatings as a function of time from
Figure
Figure 8. Friction
8.
the onset Friction coefficientsfor
of wear coefficients
testing. forC/C
C/Ccomposites
compositeswith
withdifferent
different coatings
coatings as as a function
a function of time
of time from
from the
the onset
onset of wear
of wear testing.
testing.
For specimens with the SiC/Si3N4 coating, the friction coefficient (µ) decreases immediately from
For specimens
the outset to rapidlywith (ca. the
102 SiC/Si 33N44 coating,
s) approach coating, the
a constantthefriction
friction
value of coefficient
less than (µ)
coefficient (µ) decreases
0.1, decreases
which is less immediately
immediately
than the stable from
the outset to friction
rapidly coefficient
(ca. 10 s)2 s) approach aa constant value
value of of less than
than 0.1,
0.1, which is lessof than
the the stable
2 approach constant less which
value of the of the SiC-coated specimens. Microstructural analysis SiC/Si 3N4
value of the friction coefficient
coefficient of
of the
the SiC-coated
SiC-coated specimens.
specimens.
coating indicates that the Si and graphite powder do not react completely so that a significant Microstructural
Microstructural analysis
analysis of
of the
the SiC/Si
SiC/Si N44
33N
coating indicates
indicates that
that thetheSi Si
and and graphite
graphite powderpowder do notdo not
react
quantity of graphite powder remains after processing at 1100 °C. This remaining graphite powder is react
completelycompletely
so that so
a that
significanta significant
quantity
quantity
of graphite
consumed ofasgraphite
powder powder
remains
the residual remains
after
Si proceeds after the
processing
with 1100 ◦ C.atdecreasing
processing
atreaction, 1100remaining
This °C. This remaining
graphite
the friction graphite
powder
coefficient. powder
isInconsumed
addition, is
consumed
as the residualas the
Si residual
proceeds Si proceeds
with the with
reaction, the reaction,
decreasing decreasing
the friction
as shown in Figure 7, the defect density in the SiC/Si3N4 coating is much less than in the SiC coating. the friction
coefficient. coefficient.
In addition, In addition,
as shown
as
in shown the in
Figure
Thus, 7, Figure
the
SiC/Si 7, the
defect defectindensity
density the SiC/Si in theNSiC/Sicoating3N4 coating
is muchisless much than
3N4-coated specimens yield3 a 4relatively small friction coefficient (less than 0.1; see
lessinthan
the SiCin the SiC coating.
coating. Thus,
Thus,
the the
SiC/Si 3SiC/Si
N 4 3N4-coated
-coated specimens specimens
yield a yield a
relatively relatively
small small
friction
Figure 8). The rather large (about 0.2–0.4) and unstable friction coefficient for SiC-coated specimensfriction
coefficient coefficient
(less than (less
0.1; than
see 0.1;
Figure see
8).
Figure
The 8).
rather The
large rather
(about large (about
0.2–0.4) and 0.2–0.4)
unstable and unstable
friction
is attributed to the loose structure and the type of wear in the SiC coatings. friction
coefficient coefficient
for SiC-coated for SiC-coated
specimens is specimens
attributed
is
to attributed
theFigure 9toshows
loose structurethe loose andstructure
the the typeweight
average and
of weartheloss
type
in theofofSiC
wear inspecimens,
the SiC coatings.
coatings.
several which is directly related to the
Figure 99 shows
shows thethe average
average weight
weight lossloss
friction coefficient. As shown in Figure 8, the friction coefficient of of several
several specimens,
specimens, of which
which is directly
is directly
SiC coatings related related to
so the
to the friction
is unstable, the
friction coefficient.
coefficient. As shown As shown
in Figure in
8, Figure
the 8,
friction the friction
coefficient coefficient
of SiC
weight loss is significant. The opposite is true for the SiC/Si3N4-coated specimens: the friction of
coatings SiC is coatings
unstable, is
so unstable,
the weight so the
loss
weight
is
coefficientlossis is
significant. Thesignificant.
lower opposite
and more isThe
true opposite
stable,forresulting is true
the SiC/Si in3 N 4for the
-coated
much SiC/Si
less specimens:
weight 3N4-coated
loss.the specimens:
friction
Furthermore, the the
coefficient Si3Nisfriction
lower
4 in the
coefficient
and more is lower
stable, and
resulting morein stable,
much resulting
less weight in
SiC/Si3N4 coatings is more resistant to wear than Si in the SiC coating, so much
loss. less
Furthermore,weight loss.
the Si Furthermore,
N
3 the4 in the SiC/Si the
SiC/Si3N4 coating N
3 4Si 3N in
coatings
4 the
loses
SiC/Si
is more
less 3N
mass coatings
resistant
4
than the is
to SiC more
wearcoating,resistant
than Si which to
in the SiC wear than
alsocoating, Si
contributes in the SiC
so toSiC/Si coating,
the more so
3 N4 coating the SiC/Si
loses less
stable friction 3 N 4 coating
mass than
coefficient loses
of the
the
less
SiC mass
coating, than
SiC/Si3N4 coating. the
which SiC
also coating,
contributes which to also
the morecontributes
stable to
frictionthe more stable
coefficient of friction
the SiC/Si coefficient
3 N 4 coating. of the
SiC/Si3N4 coating.

Figure
Figure 9. Average weight
9. Average weight loss
loss of
of different
different coatings.
coatings.
Figure 9. Average weight loss of different coatings.
3.3. Analysis of Worn Surface
3.3. Analysis of Worn Surface
Figure 10a,b shows SEM images that reveal the morphology of the worn surface of specimens
withFigure
the SiC10a,b shows
coating and SEM
with images that
the SiC/Si reveal the morphology of the worn surface of specimens
3N4 coating, respectively. These images show different levels
with the SiC coating and with the SiC/Si3N4 coating, respectively. These images show different levels
Coatings 2020, 10, 787 8 of 10

3.3. Analysis of Worn Surface

Figure 10a,b shows SEM images that reveal the morphology of the worn surface of specimens
Coatings 2020, 10, x FOR PEER REVIEW 8 of 10
with the SiC coating and with the SiC/Si3 N4 coating, respectively. These images show different levels
of
of deterioration
deterioration of of the
the worn
worn surfaces
surfaces of
of the
the two
two specimens. Moreover, the
specimens. Moreover, the typical
typical debris
debris and
and the
the
characteristics of the worn surface are closely linked with the wear process, which helps
characteristics of the worn surface are closely linked with the wear process, which helps to to understand
the wear mechanisms.
understand the wear mechanisms.

Figure 10. SEM images showing surface morphology of worn surfaces of (a) SiC and (b) SiC/Si3N4
Figure 10. SEM images showing surface morphology of worn surfaces of (a) SiC and (b) SiC/Si3 N4
coatings on carbon/carbon composites.
coatings on carbon/carbon composites.

Figure 10a
Figure 10a shows
shows the the surface
surface of of aa SiC
SiC coating
coating worn
worn at at room
room temperature.
temperature. The The wear
wear track
track is is very
very
deep, and debris is apparent along with some degree of exfoliation.
deep, and debris is apparent along with some degree of exfoliation. However, a smooth, worn surfaceHowever, a smooth, worn surface
is also
is also apparent.
apparent. Additionally,
Additionally, severalseveral furrows
furrows appear
appear on on the
the worn
worn surface.
surface. These
These results
results imply
imply thatthat
the worn surface contributes to abrasive and adhesive wear. Initially,
the worn surface contributes to abrasive and adhesive wear. Initially, adhesive wear proceeds easily adhesive wear proceeds easily
because of
because ofthe
theeffect
effectofof polishing
polishing of the
of the specimens.
specimens. Moreover,
Moreover, becausebecause
of theofbrittle
the brittle
fracturefracture of SiC
of SiC grains,
grains,debris
some someformsdebris forms
easily duringeasily
wear during
[29,30],wearwhich [29,30],
means which means wear
that adhesive that isadhesive
accompanied wear by is
accompanied by abrasive wear. In the first stage of the dynamics of the
abrasive wear. In the first stage of the dynamics of the friction coefficient of SiC coatings (see Figure 8),friction coefficient of SiC
coatings
the (see Figure
large friction 8), themay
coefficient large friction coefficient
contribute to adhesivemay contribute
and abrasive to adhesive
wear. Along with andtheabrasive
development wear.
Along with the development of friction and wear, a thin film forms on
of friction and wear, a thin film forms on the coating surface, which decreases the friction coefficient ofthe coating surface, which
decreases
the coating. theInfriction
turn, this coefficient
decreases ofthe
thefriction
coating.coefficient
In turn, thisin the decreases
subsequent the friction
stage ofcoefficient
the dynamics in theof
subsequent stage of the dynamics
the friction coefficient of SiC coatings. of the friction coefficient of SiC coatings.
Figure 10b
Figure 10b shows
shows the the SEM
SEM image
image of of the
the surface
surface ofof aa SiC/Si
SiC/Si33N N44coating
coatingworn
wornat atroom
roomtemperature.
temperature.
The image reveals a shallow wear track, some smooth worn regions and several non-worn regions.
The image reveals a shallow wear track, some smooth worn regions and several non-worn regions.
The deformation and fracture of the SiC/Si 3N4 coating are mainly due to the friction process. Because
The deformation and fracture of the SiC/Si3 N4 coating are mainly due to the friction process. Because the
the coating
coating waswas polished
polished beforehand,
beforehand, the the surface
surface of the
of the coating
coating is smooth
is smooth andand clean.
clean. Adhesive
Adhesive wearwear is
is facilitated on such smooth and clean surfaces, especially if the surfaces
facilitated on such smooth and clean surfaces, especially if the surfaces are dense and resistant to are dense and resistant to
moisture or
moisture or other
other hydrated
hydrated contaminations
contaminations [12,31]. [31,32]. Thus,
Thus, wewe deduce
deduce thatthat the
the smooth
smooth andand clean
clean worn
worn
surface contributes to the adhesive wear. Meanwhile, a small quantity
surface contributes to the adhesive wear. Meanwhile, a small quantity of debris appears on the of debris appears on the worn
worn
surface, which
surface, which leads
leads to to mild
mild abrasive
abrasive wear.wear. Adhesive
Adhesive wear wear combined
combined with with mild
mild abrasive
abrasive wear
wear could
could
lead to a large friction coefficient [30], which can explain the large initial friction coefficient in the first
lead to a large friction coefficient [30], which can explain the large initial friction coefficient in the first
stage of
stage of the
the dynamics
dynamics of of the
the friction
friction coefficient
coefficient (Figure
(Figure 8). 8). In
In addition
addition to to the
the development
development of of friction
friction
and wear,
and wear, aa layer
layer of of thin
thin film
film forms
forms on on the
the coating
coating surface,
surface, which
which decreases
decreases the
the friction
friction coefficient
coefficient of of
the coating. As a result, the friction coefficient of SiC/Si 3N4 coatings decreases in the latter stage of the
the coating. As a result, the friction coefficient of SiC/Si3 N4 coatings decreases in the latter stage of the
friction coefficient
friction coefficient dynamics
dynamics (Figure
(Figure 8). 8). Compared
Compared with with SiC
SiC coatings,
coatings, SiC/Si
SiC/Si3NN4 coatings has a lower
3 4 coatings has a lower
friction coefficient
friction coefficient and and less
less abrasion
abrasion loss,loss, which
which is is attributed
attributed mainly
mainly to to the
the compact
compact coating
coating structure
structure
and the different forms
and the different forms of wear. of wear.

4. Conclusions
4. Conclusions
To improve
To improve wear
wear resistance,
resistance, SiC
SiC andand SiC/Si
SiC/Si33N44 coatings were synthesised on C/C composites via
pack cementation
pack cementationand,
and,for
forthe
theSiC/Si
SiC/Si
3 N3N 4 coatings,
4 coatings, heat
heat treatment
treatment with
with nitrogen
nitrogen gas.gas.
XRD,XRD,
XPS,XPS,
EDSEDS
and
and SEM analyses reveal differences between the SiC and SiC/Si3N4 coatings in terms of
microstructure, surface morphology and tribological behaviour. The SiC coatings synthesised
through pack cementation at 1100 °C are loose and contain large pores, whereas the SiC/Si3N4
coatings similarly synthesised but with a subsequent nitrogen-gas heat treatment are more compact.
The SiC coating has a relatively large friction coefficient, which is caused mainly by adhesive and
Coatings 2020, 10, 787 9 of 10

SEM analyses reveal differences between the SiC and SiC/Si3 N4 coatings in terms of microstructure,
surface morphology and tribological behaviour. The SiC coatings synthesised through pack cementation
at 1100 ◦ C are loose and contain large pores, whereas the SiC/Si3 N4 coatings similarly synthesised but
with a subsequent nitrogen-gas heat treatment are more compact. The SiC coating has a relatively large
friction coefficient, which is caused mainly by adhesive and abrasive wear. The SiC/Si3 N4 coating
yields a smaller, more stable friction coefficient and less weight loss than the SiC coating. At the onset
of frictional wear of the SiC/Si3 N4 coating, the friction coefficient is relatively large (although not as
large as that of the SiC coating) and is due mainly to adhesive wear. Graphite in both the SiC/Si3 N4 and
the SiC coatings produces a thin lubricating film that subsequently decreases the friction coefficient
after certain duration (102 to 103 s, respectively) of frictional wear. Thus, compared with SiC coating,
SiC/Si3 N4 coating offers a lower friction coefficient and better wear performance.

Author Contributions: Z.M. is responsible for organizing and writing the whole article. L.Y. is responsible for
data collection and collation. All authors have read and agreed to the published version of the manuscript.
Funding: This work was supported by the Science Foundation of Hunan Province in China (No. 2016JJ6032)
and by the National College Students Innovation and Entrepreneurship Training Program of Local Universities
(No. 201711528009).
Conflicts of Interest: There is no conflict of interest in this article.

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