Accepted Manuscript

Multilayer graphene reinforced functionally graded tungsten

carbide nano-composites

Jialin Sun, Jun Zhao, Mengjie Chen, Yonghui Zhou, Xiuying Ni,
Zuoli Li, Feng Gong

PII: S0264-1275(17)30793-1
DOI: doi: 10.1016/j.matdes.2017.08.041
Reference: JMADE 3300
To appear in: Materials & Design
Received date: 11 May 2017
Revised date: 11 August 2017
Accepted date: 18 August 2017

Please cite this article as: Jialin Sun, Jun Zhao, Mengjie Chen, Yonghui Zhou, Xiuying Ni,
Zuoli Li, Feng Gong , Multilayer graphene reinforced functionally graded tungsten carbide
nano-composites, Materials & Design (2017), doi: 10.1016/j.matdes.2017.08.041

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 ACCEPTED MANUSCRIPT

Multilayer graphene reinforced functionally graded tungsten carbide

nano-composites
Jialin Suna, Jun Zhaoa*, Mengjie Chenb, Yonghui Zhoua, Xiuying Nia, Zuoli Lia, Feng
Gonga
a
Key Laboratory of High Efficiency and Clean Mechanical Manufacture of MOE,
School of Mechanical Engineering, Shandong University, Jinan 250061, PR China
b
School of Chinese Materia Medica, Beijing University of Chinese Medicine, Beijing

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100102, PR China
Abstract:

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Mechanical and tribological properties of functionally graded multilayer graphene

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(MLG) reinforced WC-TiC-Al2O3 ceramics prepared employing two-step sintering
(TSS) are determined in this paper. Results showed that MLG can act as not only an
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exceptional reinforcement phase, but also a superior lubricant phase. A 0.1wt% MLG
/WC-TiC-Al2O3 ceramics exhibits ～53.3% enhancement in fracture toughness, ～
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73.8% decrement in friction coefficient, ～82.65% improvement in wear resistance in

comparison with monolithic ceramics. MLG bending, wrapping, interface debonding,
MLG wall and network, MLG induced weak interface, grains bridging by MLG, MLG
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pullout, crack deflection, crack bridging and crack stopping are the major toughening
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mechanisms. The dramatic improvement in tribological performance is attributed to

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the self-lubrication of MLG and easily formed friction layer in the contact interface.
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Furthermore, the unrivalled thermal conductivity of MLG and its rather significant
effect in inhibiting the grain growth are the important contribution to the improved
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tribological performance. Therefore, the functionally graded MLG/WC-TiC-Al2O3

ceramics are conducive to be engineered as high-speed cutting tools.
Keywords: FGM; MLG; Microstructure; Mechanical properties; Tribological
properties
1. Introduction

* Corresponding author. Tel.: +86 053188399304; Fax: +86 053188399304.

E-mail address: zhaojun@sdu.edu.cn.(J. Zhao)

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Graphene has been widely applied as ideal mechanical reinforcement phase for
materials such as metals [1, 2], polymers [3, 4] and ceramics [5-7], due to its
unprecedented combination of extraordinary mechanical properties (e.g., breaking
strength 42 N·m-1, tensile strength 130 GPa, stiffness 300-400 N·m-1, thermal
conductivity 3000-5000 W·m-1·K-1, spring constant 1-5 N·m-1 and Young’s modulus
0.5-1 TPa) and unique two-dimensional sp2 structure with considerable theoretical
specific surface area (～2630 m2·g-1) [8-11]. Apart from the excellent intrinsic

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mechanical properties, graphene possesses good dispersion properties and can be

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homogeneously dispersed into a ceramic matrix, which is another rather advantageous
factor in improving the microstructure and mechanical properties of the ceramic

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composites [12, 13].
Comparing to TiN or TiC based composite tool materials, WC based composite
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tool materials normally possess higher hardness, strength, thermal conductivity,
chipping resistance and plastic deformation resistance and have been universally used
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in high speed cutting [14, 15]. Cobalt is usually employed as binder phase during the
conventional sintering process, owing to its favourable wettability on tungsten carbide,
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[16] whereas its addition brings about the deterioration in hardness, oxidation and
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corrosion resistance and elevated temperature properties. Albeit binderless WC

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composite may be a feasible approach to eliminating the negative influence with

metallic binder addition, it is difficult to consolidate pure WC free metallic binders to
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a full density through conventional sintering method. Besides, WC abnormal grain

growth and the formation of sub-carbide W2C are also unavoidable during the
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sintering process [17, 18]. Binderless WC-based composites usually have such
deficiencies as unsatisfactory flexural strength and fracture toughness [19]. Therefore,
particle toughening (Al2O3, MgO, Cr3C2, etc.), phase-transformation toughening
(ZrO2), whisker-toughening (Al2O3, Si3N4, SiC, etc.) and microcrack toughening have
been addressed to improve toughness of binderless WC material [20, 21].
In recent years, increasingly research has been focused on whisker-toughened
binderless WC. It is found that WC-whisker composite kept an increased toughness
compared with pure WC [22]. Whisker bridging, load transfer, whisker pulling-out,
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crack deflection and branching are the major mechanisms contributing to the
enhanced flexural strength and fracture toughness [23, 24]. However, degradation was
brought into hardness of WC-whisker composite [22]. Moreover, the effect of
whisker-toughening depends too much on the characteristics of whiskers and whiskers
tend to agglomerate in ceramic matrix [25]. Also, whiskers may be degraded into
particles under high sintering temperature and then discount the reinforcement effect

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[26]. Therefore, an ideal mechanical reinforcement phase for ceramic composites
should not only tremendously improve the toughness, but also enhance or maintain

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the hardness. Besides, for ceramic tool materials, it is perfect that the reinforcing
phase can simultaneously act as lubricant phase.

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High-aspect-ratio graphene sheets perform better in inducing crack deflection
compared with conventional reinforcements [27, 28]. It is reported that graphene
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showed remarkable effectiveness in improving the mechanical properties of
Al2O3-based ceramics [29], Si3N4-based ceramics [6], ZrB2-based ceramics [30],
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ZrO2-based ceramics [31], TaC-based ceramics [32]. On the other hand, graphene
may straightforwardly result in the enhancement in tribological properties of
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composites [33]. Consequently, graphene can not only act as an exceptional

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reinforcement phase, but also a superior lubricant phase. To the best of our knowledge,
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few literatures have been reported on the effects of graphene addition on the
mechanical and tribological properties of binderless WC-based advanced tool
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materials hitherto.
Two-step sintering (TSS), put forward by Chen and Wang [34] as a promising
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approach to obtain highly dense final sintered compact with nano-sized grains, has
been widely applied to plenty of materials such as nanoceramics. It is suggested that a
temperature interval exists between the start of grain boundary migration and the
occurrence of densification [35]. According to the TSS methodology, the green body
would be heated to a high temperature and then immediately cooled to a lower
temperature with a long soaking time. TSS may be a sensible sintering method to
avoid the possible damage of the featured structure of graphene. Besides, it is proved
that a little Al2O3 addition can suppress the formation of W2C and facilitate the
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sintering, which may help to lower the sintering temperature for binderless WC [36].
Functionally graded materials (FGMs) can be another innovative method to the
balance between the wear resistance and the fracture toughness [37]. Though the
production of graphene has been paid close attention, the price of defect-free
graphene is also higher compared to that of other carbide reinforcement as Cr3C2 and
VC [38]. Therefore, graded structure can be a reasonable approach to decreasing the

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graphene content and producing ceramic tool materials with tailored mechanical and
tribological properties at efficient cost.

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Based on the above discussion, WC-TiC-Al2O3 ceramics reinforced by MLG
were chosen for the study. TSS was adopted to avoid the possible damage of the

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featured structure of MLG. This research aims at investigating the effects of graphene
as reinforcement phase and lubricant phase on binderless WC-based ceramic tool
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materials. Functionally graded MLG-reinforced WC-TiC-Al2O3 ceramic tool
materials were fabricated employing two-step hot-pressing sintering. The mechanical
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and tribological properties of as-designed specimens were evaluated and the

toughening mechanisms were discussed. Furthermore, the influence of graded
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structure on the mechanical properties of so-designed samples was also analyzed.

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2. Experimental details
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2.1 Material preparation

Multilayer graphene (MLG) (thickness: 1～5 nm, diameter: 5 μm, Nangjing
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XFNANO Materials Tech Co. Ltd., China), powders of tungsten carbide (400nm,
99.9% purity, Shanghai Chaowei nanotechnology Co. Ltd., China), powders of
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titanium carbide (40nm, 99.8% purity, Shanghai Chaowei nanotechnology Co. Ltd.,
China), powders of vanadium carbide (80nm, 99.9% purity, Shanghai Chaowei
nanotechnology Co. Ltd., China), powders of chromic carbide (100nm, 99.9% purity,
Shanghai Chaowei nanotechnology Co. Ltd., China), powders of aluminum oxide
(80nm, 99.9% purity, Beijing Wangyong Technology Co. Ltd., China), powders of
Polyvinylpyrrolidone (PVP, 99.9% purity, Shanghai Gobekie new material technology
Co. Ltd., China) and powders of PEG (99.9% purity, Sinopharm Chemical Reagent
Co. Ltd., China) were utilized as starting materials. It is proved that by our previous
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study [39] that a little Al2O3 additive can suppress the formation of W2C and facilitate
the sintering, which is conductive to lowering the sintering temperature for binderless
WC. The addition of cubic phases as TiC can improve the hardness of WC based
composite. Besides, combined addition of VC and Cr3C2 with an Cr3C2/(Cr3C2+VC)
ratio 0.6 to WC-TiC-Al2O3 composite performed a more pronounced effectiveness on
inhibiting grain growth and improving the homogeneous dispersion of

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Al2O3 nano-particulates in WC matrix than single addition of VC or Cr3C2 did
[38]. Therefore, the compositions in Table 1 were chosen for the study.

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Table 1 - Compositions of powder mixtures for five designed samples (wt.%)
Composites WC Al2O3 TiC MLG Cr3C2 VC

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Ceramics ASL 95 3 2 0 0 0
Ceramics AIL 90 6 4 0 0 0
Ceramics ACL 84 9 6 0 0.6 0.4
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Ceramics BSL 94.8 3 2 0.05 0 0
Ceramics BIL 89.8 6 4 0.05 0 0
Ceramics BCL 84 9 6 0 0.6 0.4
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Ceramics CSL 94.6 3 2 0.1 0 0

Ceramics CIL 89.6 6 4 0.1 0 0
Ceramics CCL 84 9 6 0 0.6 0.4
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Ceramics DSL 94.4 3 2 0.15 0 0

Ceramics DIL 89.4 6 4 0.15 0 0
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Ceramics DCL 84 9 6 0 0.6 0.4

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Ceramics ESL 94.2 3 2 0.2 0 0

Ceramics EIL 89.2 6 4 0.2 0 0
Ceramics ECL 84 9 6 0 0.6 0.4
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SL: surface layer.

IL: interlayer.
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CL: core layer.

Nanostructured powders (TiC, Al2O3, Cr3C2, VC) were ultrasonically dispersed

by PFG in absolute alcohol maintaining the temperature at 78℃ for 1 h, and then
sub-microstructured WC powders were added into the nanopowder suspension
followed by another 1 h ultrasonically dispersion. MLGs were firstly ultrasonically
dispersed by PVP in absolute alcohol maintaining the temperature at 78 ℃ for 1 h.
Subsequently, MLG suspension was dropped into the micro-nanopowder suspension
with dropper pipette under strong agitation conditions followed by another 1 h
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ultrasonic dispersion. After dispersing, the mixed slurries were milled for 20 h in a
high energy attrition mill with cemented carbide milling ball (ball-to-powder mass
ratio is 25:1). Finally, the powder mixtures were dried at 116 °C in a vacuum oven
and sieved.
2.2 Two-step hot-pressing sintering
The powder mixtures were pressed into a circular die in the following order:

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surface layer mixture, interlayer mixture, core layer mixture, interlayer mixture and
then surface layer mixture. Finally, the composite powders were sintered by two-step

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hot-pressing in a hot-pressing vacuum furnace. Fig. 1 illustrates the two-step sintering
processes.

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Fig. 1 - Two-step hot-pressing sintering processes for functionally graded WC-TiC-Al2O3-MLG

composite.
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2.3 Microstructural characterization

The morphologies of the samples were observed by a scanning electron
microscope (SEM, QUANTAFEG 250, FEI Inc., USA) with the EBSD hardware
attached, Lasers Microscope (VK-X250) and white light interferometer (Wyko
NT9300, USA). The element distribution was investigated by energy dispersive
spectroscopy (EDS, X-MAX30, Oxford Instruments Inc., UK). X-ray diffraction
(XRD, D8ADVANCE, Bruker AXS Inc., Germany) and Raman spectroscopy
(LabRam HR Evolution, HORIBA JOBIN YVON S.A.S.) were determined to
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characterize the phase identification of the specimens.

2.4 Mechanical measurements
The flexural strength of the specimens was measured on a WDW-50E tester by
using a three-point bending method with a 0.5 mm/min loading rate and a 14.5 mm
span between the loading points. The surface residual stress was measured by X-stress
system (XSTRESS 3000X, G2R system, Stresstech Oy Inc., Finland). The principle
of X-ray measurement is based on Bragg’s law, the sine-square-psi (sin2Ψ) method.

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CrKα radiation and 138.5°diffraction angle were chosen. The residual stress was

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measured at five different locations in two perpendicular directions. The hardness
(HV10) was measured employing a Vickers indenter (Model: MHVD-30AP, China)

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with a load of 98N and a duration time of 15 s using a diamond frustum of rectangular
pyramid indenter with an opposite angle of 136°. The fracture toughness was
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determined by the crack length around the harness indent and the following equation
was adopted [14]:
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HV  P
K IC  0.0889 (1)
L
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where L is the length of crack (mm), HV is Vickers hardness (MPa), P is the load (N).
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2.5 Tribological test

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The tribological tests were performed in dry reciprocating sliding mode

employing a ball-on-disk tribometer (UMT-2, USA) at room temperature in ambient
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air. AISI 1045 steel (40-50 HRC) ball was chosen as the upper counterpart and the
lower specimen was so-designed MLG/WC-Al2O3-TiC material. The tests were
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conducted with a constant speed of 10mm/s, a normal load of 20N, a wear track of 6
mm and sliding distance of 6000mm. Wear rate was calculated by the following
equation:
V
W (2)
PS
where V is the wear volume in mm3, P is the imposed load in N and S is the total
sliding distance in mm.
V  AL (3)

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where A is the cross-section area of the worn scar in mm2, L is the perimeter of the
worn scar in mm.

3. Results and discussions

3.1. Phase constitutions and microstructures
Fig. 2(a) presents the XRD patterns of WC-TiC-Al2O3 composites with varied
MLG contents after two-step hot-pressing sintering (heated to 1800℃ and then

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immediately cooled to 1600℃ with a soaking time of 60min). No obvious differences
were identified among them. The patterns indicate that all specimens contain Al2O3

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and TiC as secondary phase particles regardless of the MLG contents. It is concluded

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that neither W2C nor graphite exists in the specimens, similarly to the reports by
Huang [36] that Al2O3 additive may well facilitate the sintering and suppress the
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formation of W2C. Furthermore, no newly generated phase was detected implying no
significant reaction between MLG and tungsten carbide. Raman spectra and EBSP
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were conducted to confirm the existence of MLG. Characteristic D (1350 cm-1), G

(1580 cm-1) and 2D (2700 cm-1) bands confirmed the survival of MLG after the
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so-designed two-step sintering [9]. It is suggested that D band is closely associated

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with the structural defects, G band is in relation to the C=C bond stretching and two
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phonon 2D band is the significant indication of graphene layers [40, 41]. The low
intensities ratio of D band and G band (ID/IG) suggested a fairly ordered and
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low-defect material [42].

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Fig. 2 - (a) X-ray diffraction patterns of polished surfaces of sintered ceramics with different MLG

contents, (b) Raman spectroscopy of MLG and sintered ceramics with 0.1wt% MLG and EBSP of
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WC (c), MLG (d), TiC (e) and Al2O3 (f).

Fig. 3 illustrates the cross-sectioned microstructure of ceramics D and EDS maps

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of distribution of Al, Ti, W elements on the line starting from core layer and ending at
the surface layer and surface residual stress of composites with different MLG
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contents. The thickness ratio of neighbouring layers is about 0.2 that has been
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suggested by Zhao [43] as the optimum layer thickness ratio. Based on the XRD
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patterns in Fig. 2(a), the content changes of Al, Ti and W elements from surface layer
to core layer as shown in Fig. 3 can reflect the content changes of Al2O3, TiC and WC,
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respectively. It is apparent that the contents of TiC and Al2O3 maintain an increase
from surface layer to core layer while the content of WC maintains a decrease from
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surface to core layer. It is noted that from Fig. 3(e) the surface residual stresses of all
specimens were compressive stress. As suggested by Zhao [44], the increased
coefficient from the surface layer to core layer can induce compressive residual stress
in the surface of FGM during the cooling process of the fabricating process. Because
the coefficient of thermal expansion of TiC (7.74x10-6/℃) and Al2O3 (8.8x10-6/℃) are
higher than that of WC (3.84x10-6/℃) and MLG has a negative thermal expansion, an
increase content of TiC and Al2O3 from surface layer to core layer and a decrease
content of WC from surface layer to core layer may generate significant compressive
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residual stress on the surface of material. N. Scuor et al. [45, 46] suggested that the
residual compressive stress on material surface can contribute to an improved
combination of fracture toughness and hardness.

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Fig. 3 - SEM micrographs (a) and EDS maps of the distribution of (b) Al (c) Ti (d) W elements on

the red line of functionally graded WC-TiC-Al2O3-0.1MLG ceramics polished cross-section

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surfaces and (e) surface residual stress of composites with different MLG contents.
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The distribution of MLG in the composite was evaluated by investigating the

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electropolished surface of ceramics with 0.1wt% MLG employing EBSD as presented

in Fig. 4(a) and the fracture surface of composites added 0.2wt% MLG by SEM as
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illustrated in Fig. 4(b). WC phase distribution was marked in blue, while MLG phase
distribution was marked in red. It is obvious that the MLG are homogeneously
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dispersed in the WC-based ceramic matrix containing low content MLG and MLG
tends to agglomerate and form clusters in composites reinforced by too much MLG.
The fracture surface of composites of monolithic ceramics is demonstrated in Fig.
4(c). Comparing with monolithic ceramics as shown in Fig. 4(c), the WC grains of
composites reinforced by MLG as exhibited in Fig. 4(b) kept a more narrow grain size
distribution and absenting abnormal growth implying that MLG had the effect of
refining ceramics grains in agreement with the study by Fang [5] and Ahmad [47].
Moreover, more intergranular fracture was observed in ceramics containing MLG
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than monolithic ceramics for the appearance of weaker interface induced by MLG
[41].

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Fig. 4 - (a) Te distribution of MLG (color in red) of composites reinforced by 0.1wt% MLG (by

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EBSD), (b) the fracture surface of composites added 0.2wt% MLG showing agglomeration of

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MLG (by SEM) and (c) the fracture surface of composites without MLG (by SEM).

The SEM image of fractured surface of WC-based ceramics containing 0.1wt%

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MLG depicted in Fig. 5 can be another evidence to support the uniform distribution of
MLG in ceramic matrix. The ab plane of MLG seemed to have a preferential
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orientation perpendicular to the direction of applied pressing similarly to that reported

by [41, 42]. It is suggested that the alignment of MLG played a very significant role
in improving the mechanical properties [41, 48], thermal [49] and electrical properties
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[6, 42, 50].

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Fig. 5 - Preferential orientation of graphene in ceramics matrix after two-step hot-pressing

sintering (0.1wt% MLG) (a) in low magnification and (b) in high magnification.

3.2. Densification and mechanical properties

As illustrated in Table 2, the samples developed in our study are dense, due to the
combination of high sintering temperature and external pressure applied for alloy
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consolidation. Ceramics E reinforced by 0.15wt% MLG reached highest densification

(99.5%), while ceramics A without MLG had only a relative density of 94.7%. It is
inferred MLG facilitated the sintering of so-designed WC-based materials for the
reason that MLGs acting as heat conducting plates had an unrivalled thermal
conductivity (6×103 W·m-1·K-1 [51, 52]) and electrical conductivity (106 S·m-1 [53,
54]) improving the distribution of the current and heat during the consolidation

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process [32]. Furthermore, it is suggested that the rearrangement of ceramic matrix
particles could be accelerated by MLG at early stage of sintering for its impressive

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self-lubricating effects [55]. However, the relative density decreased slightly at a
higher MLG content of 0.2wt%. As presented in Fig. 4(b), agglomeration of MLG

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resulted from too much added MLG and the MLG clusters deteriorated the
distribution of heat and current and then lower the densification. Though possessing
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higher densification and smaller grain size, the hardness of WC-based ceramics
containing MLG was not improved in comparison with monolithic ceramics as
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illustrated in Table 2. Actually, MLG is a soft phase and the hardness deterioration is
expected [7, 32].
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Table 2 - Physical and Mechanical properties of as-designed functionally graded WC-based materials reinforced by
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MLG.
Material MLG content Relative density SL-Hardness Flexural strength SL-Fracture toughness
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(wt.%) (%) (GPa) (MPa) (MPa·m1/2)

Ceramics A 0 95.3±0.6 24.2±1.3 962.6±28.9 9.2±1.7
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Ceramics B 0.05 97.6±0.4 23.6±0.9 978.5±20.6 12.2±1.3

Ceramics C 0.1 99.3±0.2 22.9±0.6 1021.9±15.1 14.1±1.1
Ceramics D 0.15 98.9±0.1 22.1±1.5 990.7±30.7 14.5±1.6
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Ceramics E 0.2 98.6±0.3 18.9±1.8 996.3±35.2 13.7±2.0

Only a certain improvement in flexural strength was noted from Table 2 for the
reason that MLG was added merely into the surface and interlayer of the as-designed
graded ceramics, whereas further addition of 0.2wt% MLG resulted in a slight
degeneration of flexural strength. Generally, the reinforcing efficiency of
reinforcement is mainly determined by three factors: the distribution lever of
reinforced phase, the interface bonding of reinforced phase to host matrix coupled
with the densification degree of reinforced materials [12]. Albeit homogeneous

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dispersion of MLG is preferable for composites reinforced by low-content MLG, it is

also the key impediment to realize the MLG uniform distribution for composites
added with high-content MLG. Furthermore, it is suggested by [56] that a finer grain
is also conducive to the enhancement of flexural strength. Because of its high thermal
conductivity, MLG acting as heat-sink plate boosts the cooling rate during the cooling
process and then plays the grain refinement effect as shown in Fig. 4. On the other

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hand, MLG agglomeration resulting from uneven distribution of MLG could play the
part as fracture origins and rigid inclusions and then increase the weak bonding

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interface impairing the flexural strength [24, 57].
The toughness increased from ~9.2 to ~14.5MPa·m1/2 with increasing MLG

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content as illustrated in Table 2 and the WC-based ceramics reinforced by MLG
underwent ~57.6% enhancement in comparison with monolithic ceramics. Fig. 6
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summarized the representative toughening mechanisms observed from the Vickers
indentation cracks and fracture surface resulting from graphene intrinsic toughening
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and the interactions of graphene and WC grains.

It is suggested by [58] graphene is endowed with energy dissipating mechanism
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by generating graphene bending and kinking shown in Fig. 6(a). The coordination
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deformation of graphene consumes strain energy and then reduces the crack extension
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energy. Graphene intrinsic toughening mechanism is a significant contribution to the

improvement of fracture toughness.
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Fig. 6 - Toughening mechanisms in WC-based ceramics reinforced by MLG: (a) graphene bending,
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(b) graphene wrapping, (c) graphene wall and network, (d) graphene interface debonding, (e)
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graphene intergranular bridging, (f) graphene pullout, (g) graphene deflection, (h) crack bridging

and (i) crack stopping.

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Another toughening mechanism is the result of the interactions of graphene with

WC grains such as graphene wrapping (Fig. 6(b)), graphene wall and network (Fig.
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6(c)), graphene interface debonding (Fig. 6(d)), grains bridging by graphene (Fig. 6(e))
and graphene pullout (Fig. 6(f)).
The graphene appeared to wrapping and trapping around the WC grains as
shown in Fig. 6(b) and formed a continuous graphene network as present in Fig. 6(c).
There is no doubt that the graphene wrapping may as well benefit WC grains resist
crack propagation when gains are wrapped together and form graphene network.
More intergranular fracture were found in ceramics containing MLG (Fig. 4(b))
than monolithic ceramics (Fig. 4(c)), implying the weaker interface bonding strength
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between MLG and ceramic grains than that between ceramics grains [41]. It is found
that the weak interface (Fig. 6(d)) can block the motion of the dislocations and
change the main crack propagation direction and result in forming lamella fracture
surface as demonstrated in Fig. 6(c) [59, 60]. As shown in Fig. 6(e), a MLG existing
between two adjacent ceramics grains play the role of bridge bonding two grains.
Generally, the toughness of ceramic grain boundary is much lower than that in

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ceramic grains [9]. It is undoubted the grain bridging can reinforce the toughness of
grain boundary, thereby resulting in the improvement of the toughness of ceramic

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composites.
The contributions of graphene pullout and graphene debonding interface on

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toughening can be estimated as follows [61, 62]:
1
 E C  A   i  2
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 
1
 2
K IC  E C  J     I  (4)
 r 
where A∞ is the area fraction of pulled out graphene and can be approximately
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represented by volume fraction V∞, I∞ is the length of pulled out graphene, r is the
radius of graphene, τi is the friction of debonding interface and EC is the Young’s
modulus of composites.
A∞ and I∞ were increased due to the pullout of graphene. As shown in Fig. 6(b)
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(c), MLG weave around ceramic grains with varied sizes and followed the grain
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boundaries, thus increased the MLG-ceramics contact area, providing a higher

interfacial friction impeding MLG pull out. The high specific surface area and layer
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2D structure of MLG can be another essential contribution to the increase of the

interfacial friction impeding MLG to pull out from ceramic matrix. Therefore, it
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consumed more energy to pull out a MLG than other conventional reinforced
materials, thus helping in the outstanding increment of toughness.
Both the graphene intrinsic toughening mechanism and graphene and ceramic
grains interactions resulted the generation of crack deflection, crack bridging and
crack stopping.
Because of the relative week interface between the graphene and the WC grains,
load is easily transferred from the WC ceramic matix to the graphene during the crack
propagation process. Once the crack reached MLG, the stress area beside the tip of
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main crack was disturbed, therefore crack altered the propagation direction and
advanced along the interface of MLG (i.e., a three-dimensional crack deflection) and
ceramic matrix, resulting in crack bridging (Fig. 6(h)) that consuming more external
energy to force the crack to propagate further and deflect (Fig. 6(g)), absorbing more
energy and retarding the crack propagation [48]. If the driving force transmits
insufficiently through the MLGs, crack would be arrested and stopped at the MLG as

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depicted in Fig. 6(i). The effect of graphene bridging on toughening can be evaluated
by the following equation [61]:

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1
  r 2 d w f r Ec  2
K IC   (5)
 24 E r  i

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

where σr is the tensile strength of the elongated grain, dw is the diameter of the
elongated grain, f is the volume fraction of the bridging grains, γi and γr are the
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interfacial debonding energy and fracture energy respectively. Ec and Er are the
Young’s moduli of the composite matrix and the reinforcing phase respectively.
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According to this equation, the graphene bridging toughening can be ascribed to

its unbeatable tensile strength (130 GPa) and larger dw in comparison with many other
toughening materials.
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All the above multiple toughening mechanisms are combined to yield a

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significant improvement in the toughness of MLG-reinforced materials. Also, the

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preferential orientation of MLG as shown in Fig. 5 and MLG intrinsic energy

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dissipating mechanisms as sheet kinking, bending and sliding play very significant
roles in contributing to the toughness enhancement of ceramics reinforced by MLG
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[32].
3.3. Tribological properties
Fig. 7 described the friction coefficient of sintered samples against AISI 1045
steel with the sliding time. It is evident that the friction coefficients of WC-based
ceramics reinforced by MLG were dramatically lower than that of monolithic
ceramics. The friction coefficient decreased by 73.8% from 0.42 to 0.11 because of
MLG addition. Furthermore, it is observed from Fig. 7 that the friction behavior of
MLG-reinforced ceramics was stable while that of monolithic was fluctuant. Wear
rate of sintered specimens against AISI 1045 steel was presented in Fig. 8. Obviously,
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the wear rates of composites containing MLG were much lower than that of
monolithic ceramic. An excessive graphene addition would result in aggregation,
which would deteriorate the friction and wear between counterparts. Ceramics
reinforced by 0.1 wt% MLG possessed a wear rate of 0.51×10-6mm3·N-1·m-1, 82.65%
lower than that of monolithic (2.94×10-6 mm3·N-1·m-1) ceramics. Therefore, it can be
concluded that MLG performed effectively in improving the tribological properties

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similarly to what is reported by some literatures [33, 63, 64].

0.6

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without MLG
with 0.05wt% MLG
with 0.1wt% MLG
0.5
with 0.15wt% MLG

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Friction coefficient μ

with 0.2wt% MLG

0.4

0.3
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0.2

0.1
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0.0
0 100 200 300 400 500 600
Time(s)
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Fig. 7 - Friction coefficient of AISI 1045 steel vs WC-based ceramics reinforced by different MLG
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contents.
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3.0

2.5
Wear rate, 10-6 mm3 N-1m-1
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2.0

1.5

1.0

0.5

0.0
0.00 0.05 0.10 0.15 0.20
Content of MLG (wt.%)

Fig. 8 - Wear rates of AISI 1045 steel vs WC-based ceramics reinforced by different MLG

contents.
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Fig. 9 demonstrated the three-dimensional surface topographies of the wear

tracks on monolithic ceramics and ceramics containing 0.1 wt% MLG by a white light
interferometer and lasers microscope, respectively. Both the depth and the width of
the wear track on ceramics containing 0.1 wt% MLG are smaller than that of
monolithic ceramics. Wear tracks of WC-based ceramics without MLG and
MLG-reinforced WC-based composites were analyzed to further determine the

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anti-friction and wear resistance mechanisms employing SEM and EDS as illustrated
in Fig. 10. Apparently, severe surface damage can be observed for monolithic

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ceramics in the form of many adhesions and ploughs on the worn surface as shown in
Fig. 10(a). The EDS analysis of point A confirms the presence of many adhesions of

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Fe and O, implying grievous adhesive wear and oxidation wear during the sliding
process. However, the worn surface of ceramics containing MLG was more smooth
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and with little adhesive abrasion and ploughs, suggesting MLG effectively enhanced
the adhesive and oxidation wear resistance of so-designed materials.
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Fig. 9 - Three-dimensional surface topographies of the wear tracks on (a) (a’) monolithic ceramics

and (b) (b’) ceramics containing 0.1 wt% MLG by a white lighe interferometer and lasers

microscope, respectively.

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Fig. 10 - SEM micrographs of worn surfaces of (a) monolithic ceramics, (b) ceramics containing

0.1wt% MLG and (c) EDS composition analyses of point A.

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As mentioned above, with an unrivalled thermal conductivity (6×103 W·m-1·K-1
[51, 52]), MLG can act as a heat cooling plate during the sliding process, which has a

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definite effect in lowering the temperature in the contact area. A lower temperature is
helping in reducing the adhesive and oxidation wear. Furthermore, it is
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demonstrated that fine-grained materials possessed better wear resistance in
comparison with coarse-grained materials [65, 66]. As stated above, MLG played a
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rather significant role in inhibiting the grain growth, thereby resulting in an improved
tribological performance.
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The effect mechanism of MLG on improving the tribological performance may

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be explained as illustrated in Fig. 11. The carbon atoms within monolayer

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are held together by strong chemical bonds, whereas those between layers are
combined by weak van der Waals forces. Therefore, the anti-shear ability of interlayer
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is lower and the friction decreased with the increasing layers [67] and MLG is born
with the function of self-lubrication. As demonstrated in Fig. 11(a), MLG are exposed
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to the contact surface acting as nanobearing and partially reduced the contact area of
steel to WC ceramics. With the friction proceeding, some ploughs are formed
resulting from the peeling of materials. A certain amount of MLGs appeared shear
slipping and moved along the sliding direction to fill the ploughs as shown in Fig.
11(b), which is helping in protecting the surface integrity. As the amount of MLG
undergoing shear slipping increases, a thick and complete friction layer is formed at
the interface as depicted in Fig. 11(c), which can dramatically improve the
tribological property [64, 68, 69]. When the protective friction layer was formed, it
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can effectively avoid the direct contact of steel to WC ceramics. The impact of
outstanding lubrication performance is advancing with the completeness of formed
friction layer. Furthermore, an enhanced toughness and strength resulting from MLG
addition is also an indispensable contribution to the improvement of tribological

properties [70].
(a) (b) (c)
AISI 1045 steel ball
Shearing slip

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Ploughs

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Friction layer
MLG
WC substrate

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Fig. 11 - Schematic of effect mechanism of MLG reinforced WC-based materials against AISI
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1045 steel.

4. Conclusions
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Functionally graded MLG/WC-TiC-Al2O3 ceramic composite tool materials are

successfully fabricated by employing two-step hot-pressing sintering (heated to
1800 °C and then immediately cooled to 1600 °C with a soaking time of 60min). It is
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indicated that MLG facilitated the sintering of so-designed WC-based materials for
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the reason that MLG acting as a heat conducting plate had an unrivalled thermal and
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electrical conductivity improving the distribution of the current and heat during the
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consolidation process. Results showed that MLG can act as not only an exceptional
reinforcement phase, but also a superior lubricant phase. MLG bending, wrapping,
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interface debonding, MLG wall and network, MLG induced weak interface, grains
bridging by MLG, MLG pullout, crack deflection, crack bridging and crack stopping
are the major toughening mechanisms. The dramatic improvement in tribological
performance is attributed to the self-lubrication of MLG and easily formed friction
layer in the contact interface. Furthermore, the unrivalled thermal conductivity of
MLG and its rather significant effect in inhibiting the grain growth are the
indispensable contribution to the improved tribological performance. Therefore, the
functionally graded MLG/WC-TiC-Al2O3 ceramics are conducive to be engineered as

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high-speed cutting tools.

Acknowledgements

This work is supported by the National Natural Science Foundation of China

(51475273).

Reference

[1] S. Bashirvand, A. Montazeri, New aspects on the metal reinforcement by carbon

PT
nanofillers: a molecular dynamics study, Mater. Des. 91 (2016) 306-313.
[2] H. Rhee, W.R. Whittington, A.L. Oppedal, A.R. Sherif, R.L. King, H.J. Kim, C.
Jee, Mechanical properties of novel aluminum metal matrix metallic composites:

RI
application to overhead conductors, Mater. Des. 88 (2015) 16-21.
[3] S. K umar, S. Raj, S. Jain, K. Chatterjee, Multifunctional biodegradable polymer

SC
nanocomposite incorporating graphene-silver hybrid for biomedical
applications, Mater. Des. 108 (2016) 319-332.
[4] Q. Jing, W. Liu, Y. Pan, V.V. Silberschmidt, L. Li, Z.L. Dong, Chemical
NU
functionalization of graphene oxide for improving mechanical and thermal
properties of polyurethane composites, Mater. Des. 85 (2015) 808-814.
[5] Y. Fan, L. Wang, J. Li, J. Li, S. Sun, F. Chen, L. Chen, W. Jiang, Preparation and
MA

electrical properties of graphene nanosheet/Al2O3, composites, Carbon 48 (2010)

1743-1749.
[6] C. Ramírez, S.M. Vega-Diaz, A. Morelos-Gómez, F.M. Figueiredo, M. Terrones,
D

M.I. Osendi, M. Belmonte, P. Miranzoa, Synthesis of conducting

graphene/Si3N4 , composites by spark plasma sintering, Carbon 57 (2013)
E

425-432.
PT

[7] L.S. Walker, V.R. Marotto, M.A. Rafiee, N. Koratkar, E.L. Corral, Toughening in
graphene ceramic composites, Acs Nano 5 (2011) 3182-90.
[8] T. Wejrzanowski, M. Grybczuk, M. Chmielewski, K. Pietrzak, K.J. Kurzydlowski,
CE

A. Strojny-Nedza, Thermal conductivity of metal-graphene composites, Mater.

Des. 99 (2016) 163-173.
[9] L. Zhang, W. Liu, C. Yue, T. Zhang, P. Li, Z. Xing, Y. Chen, A tough graphene
AC

nanosheet/hydroxyapatite composite with improved in vitro,

biocompatibility, Carbon 61 (2013) 105-115.
[10] A.K. Geim. Graphene: status and prospects, Science 324 (2009) 1530-1534.
[11] KS Novoselov, AK Geim, SV Morozov, D Jiang, MI Katsnelson, IV Grigorieva,
Two-dimensional gas of massless dirac fermions in graphene, Nature 438 (2005)
197.
[12] O. TapasztÓ, L. TapasztÓ, M. MarkÓ, F. Kern, R. Gadow, C. Balázsi, Dispersion
patterns of graphene and carbon nanotubes in ceramic matrix composites, Chem.
Phys. Lett. 511 (2011) 340-343.
[13] S. Stankovich, D.A. Dikin, G.H.B. Dommett, K.M. Kohlhaas, E.J. Zimney, E.A.
Stach, et al, Graphene-based composite materials, Nature 442 (2006) 282-286.

21
 ACCEPTED MANUSCRIPT

[14] J. Sun, J. Zhao, Z. Li, X. Ni, Y. Zhou, A. Li, Effects of initial particle size
distribution and sintering parameters on microstructure and mechanical
properties of functionally graded WC-TiC-VC-Cr3C2-Co hard alloys, Ceram. Int.
43 (2017) 2686-2696.
[15] J. Sun, Y. Zhou, J. Deng, J. Zhao, Effect of hybrid texture combining micro-pits
and micro-grooves on cutting performance of WC/Co-based tools, Int. J. Adv.
Manu. Tech. 86 (2016) 3383-3394.
[16] S.I. Cha, S.H. Hong, G.H. Ha, B.K. Kim, Microstructure and mechanical
properties of nanocrystalline WC-10Co cemented carbides, Scripta. Mater. 44
(2001) 1535-1539.

PT
[17] B. Huang, L.D. Chen, S.Q. Bai, Bulk ultrafine binderless WC prepared by spark
plasma sintering, Scripta. Mater. 54 (2006) 441-445.

RI
[18] J. Zhang, G. Zhang, S. Zhao, X. Song, Binder-free WC bulk synthesized by spark
plasma sintering, J. Alloy. Compd. 479 (2009) 427-431.

SC
[19] E. Håkan, G.A. Botton, A. Niklas, H. Sture, Microstructure and abrasive wear of
binderless carbides, J. Am. Ceram. Soc. 83 (2004) 2491-2496.
[20] D. Zheng, X. Li, Y. Li, S. Qu, C. Yang, In-situ elongated β-Si3N4, grains
NU
toughened WC composites prepared by one/two-step spark plasma sintering, Mat.
Sci. Eng. A 561 (2013) 445-451.
[21] O. Malek, B. Lauwers, Y. Perez, P.D. Baets, J. Vleugels, Processing of ultrafine
MA

zro2 toughened wc composites, J. Eur. Ceram. Soc. 29 (2009) 3371-3378.

[22] W. Dong, S. Zhu, T. Bai, Y. Luo, Influence of Al2O3, whisker concentration on
mechanical properties of WC-Al2O3, whisker composite, Ceram. Int. 41 (2015)
13685-13691.
D

[23] X.H. Zhang, Z. Wang, P. Hu, W.B. Han, C.Q. Hong, Mechanical properties and
thermal shock resistance of ZrB-SiC ceramic toughened with graphite flake and
E

sic whiskers, Scripta. Mater. 61 (2009) 809-812.

PT

[24] Y. Fu, Y.W. Gu, H. Du, Sic whisker toughened Al2O3-(Ti,W)C ceramic matrix
composites, Scripta. Mater. 44 (2001) 111-116.
[25] P.F. Becher, .CH. Hsueh, P. Angelini, T.N. Tiegs, Toughening behavior in whisker
CE

reinforced ceramic matrix composites, J. Am. Ceram. Soc. 71 (2005) 1050-1061.

[26] P. Zhang, P. Hu, X. Zhang, J. Han, S. Meng, Processing and characterization of
ZrB2-SiCw, ultra-high temperature ceramics, J. Alloy. Compd. 472 (2009)
AC

358-362.
[27] C. Ramirez, M.I. Osendi, P. Miranzo, M. Belmonte, F. Figueiredo, A.
Castro-Beltrán, M. Terrones, Graphene nanoribbon ceramic composites, Carbon
90 (2015) 207-214.
[28] M.A. Rafiee, J. Rafiee, I. Srivastava, Z. Wang, H. Song, Z.Z. Yu, N. Koratkar,
Fracture and fatigue in graphene nanocomposites, Small 6 (2010) 179-83.
[29] Z. Gao, L. Zhao, Effect of nano-fillers on the thermal conductivity of epoxy
composites with micro-Al2O3, particles, Mater. Des. 66 (2015) 176-182.
[30] Y. An, X. Xu, K. Gui, Effect of sic whiskers and graphene nanosheets on the
mechanical properties of ZrB2-SiCw-graphene ceramic composites, Ceram. Int.
42 (2016) 14066-14070.

22
 ACCEPTED MANUSCRIPT

[31] SM Kwon, SJ Lee, IJ Shon. Enhanced properties of nanostructured ZrO2

–graphene composites rapidly sintered via high-frequency induction
heating. Ceram Int 2015;41(1):835-842.
[32] A. Nieto, D. Lahiri, A. Agarwal, Graphene nanoplatelets reinforced tantalum
carbide consolidated by spark plasma sintering, Mat. Sci. Eng. A Struct 582
(2013) 338-346.
[33] Z. Xu, X. Shi, W. Zhai, J. Yao, S. Song, Q. Zhang, Preparation and tribological
properties of tial matrix composites reinforced by multilayer graphene, Carbon
67 (2014) 168-177.
[34] I.W. Chen, X.H. Wang, Sintering dense nanocrystalline ceramics without

PT
final-stage grain growth, Nature 404 (2000) 168-71.
[35] K. Bodišová, P. Šajgalík, D. Galusek, P. Švančárek, Two-Stage Sintering of

RI
Alumina with Submicrometer Grain Size, J. Am. Ceram. Soc. 90 (2007)
330-332.

SC
[36] S. Huang, K. Vanmeensel, O.V.D. Biest, J. Vleugels, Pulsed electric current
sintering and characterization of ultrafine Al2O3-WC composites, Mat. Sci. Eng.
A 527 (2010) 584-589.
NU
[37] J. Zhao, X. Ai, Y. Li, Y. Zhou, Thermal shock resistance of functionally gradient
solid cylinders, Mat. Sci. Eng. A 418 (2006) 99–110.
[38] J. Sun, J. Zhao, M. Chen, X. Ni, Z. Li, F. Gong, Determination of microstructure
MA

and mechanical properties of VC/Cr3C2, reinforced functionally graded

WC-TiC-Al2O3, micro-nano composite tool materials via two-step sintering, J.
Alloy. Compd. 709 (2017) 197-205.
[39] J. Sun, J. Zhao, M. Chen, X. Wang, X. Zhong, G. Hou, Determination of
D

microstructure and mechanical properties of functionally graded

WC-TiC-Al2O3-GNPs micro-nano composite tool materials via two-step
E

sintering, Ceram. Int. 43 (2017) 9276-9284.

PT

[40] Z.H. Ni, H.M. Wang, Y. Ma, J. Kasim, Y.H. Wu, Z.X. Shen, Tunable stress and
controlled thickness modification in graphene by annealing, Acs Nano 2 (2008)
1033-9.
CE

[41] H. Porwal, P. Tatarko, S. Grasso, J. Khaliq, I. Dlouhý, M.J. Reece, Graphene

reinforced alumina nano-composites, Carbon 64 (2013) 359.
[42] C. Ramirez, F.M. Figueiredo, P. Miranzo, P. Poza, M.I. Osendi, Graphene
AC

nanoplatelet/silicon nitride composites with high electrical conductivity, Carbon

50 (2012) 3607-3615.
[43] X.H. Tian, J. Zhao, Y.T. Wang, F. Gong, W.Z. Qin, H.L. Pan, Fabrication and
mechanical properties of Si3N4/(W, Ti) C/Co graded nano-composite ceramic
tool materials, Ceram. Int. 41 (2015) 3381-3389.
[44] G.M. Zheng, J. Zhao, Y.H. Zhou, Friction and wear behaviors of Sialon-Si3N4
graded nano-composite ceramic materials in sliding wear tests and in cutting
processes, Wear 41 (2012) 290-291.
[45] N. Scuor, E. Lucchini, S. Maschio, S.L. Casto, V. Sergo, Wear mechanisms and
residual stresses in alumina-based laminated cutting tools, Wear 258 (2005)
1372-1378.

23
 ACCEPTED MANUSCRIPT

[46] I. Konyashin, B. Ries, F. Lachmann, A.T. Fry, Gradient WC-Co hardmetals:

Theory and practice, Int. J. Refract. Met. Hard. Mater. 36 (2013) 10-21.
[47] I. Ahmad, M. Islam, H.S. Abdo, T. Subhani, K.A. Khalil, A.A. Almajid, B.
Yazdani, Y. Zhu, Toughening mechanisms and mechanical properties of graphene
nanosheet-reinforced alumina. Mater. Des. 88 (2015) 1234-1243.
[48] Y. Zhao, K.N. Sun, W.L. Wang, Y.X. Wang, X.L. Sun, Y.J. Liang, X.N. Sun, P.F.
Chui, Microstructure and anisotropic mechanical properties of graphene
nanoplatelet toughened biphasic calcium phosphate composite, Ceram. Int. 39
(2013) 7627-7634.
[49] P. Rutkowski, P. Klimczyk, L. Jaworska, L. Stobierski, A. Dubiel, Thermal

PT
properties of pressure sintered alumina–graphene composites, J. Therm. Anal.
Calorim. 122 (2015) 105-114.

RI
[50] C. Ramirez, L. Garzón, P. Miranzo, M.I. Osendi, C. Ocal, Electrical conductivity
maps in graphene nanoplatelet/silicon nitride composites using conducting

SC
scanning force microscopy, Carbon 49 (2011) 3873-3880.
[51] Y.H. Hu, H. Wang, B. Hu, Thinnest two-dimensional nanomaterial-graphene for
solar energy, Chemsuschem 3 (2010) 782-796.
NU
[52] Z. Sun, Q. Xing, E. Axinte, W. Ge, J. Leng, Y. Wang, Formation of highly
thermal stable Al88Ni6Y6, amorphous composite by graphene addition
design, Mater. Des. 81 (2015) 59-64.
MA

[53] M. Drozdova, I. Hussainova, D. Pérez-Coll, M. Aghayan, R. Ivanov, M.A.

Rodríguez, A novel approach to electroconductive ceramics filled by graphene
covered nanofibers, Mater. Des. 90 (2016) 291-298.
D

[54] R.T. Weitz, A. Yacoby, Nanomaterials: graphene rests easy, Nat. Nanotechnol. 5
(2010) 699-700.
E

[55] G.B. Yadhukulakrishnan, S. Karumuri, A. Rahman, R.P. Singh, A.K. Kalkan, S.P.
PT

Harimkar, Spark plasma sintering of graphene reinforced zirconium diboride

ultra-high temperature ceramic composites, Ceram. Int. 39 (2013) 6637-6646.
[56] L. Yu, J. Yang, T. Qiu, J. Zhang, L. Pan, Microstructure, mechanical, and thermal
CE

properties of (ZrB2 + ZrC)/Zr3[Al(Si)]4C6 composite, J. Am. Ceram. Soc. 97

(2014) 2950-2956.
[57] S. Yan, P. He, D. Jia, Z. Yang, X. Duan, S. Wang, Y. Zhou, Effect of reduced
AC

graphene oxide content on the microstructure and mechanical properties of

graphene-geopolymer nanocomposites, Ceram. Int. 42 (2015) 752-758.
[58] A. Nieto, D. Lahiri, A. Agarwal, Synthesis and properties of bulk graphene
nanoplatelets consolidated by spark plasma sintering, Carbon 50 (2012)
4068-4077.
[59] G.Y. Wei, J. Zhao, N. Yun, J.T. Fu, Z. Xing, W. Wei, Effect of weak interface on
tensile behavior of cold rolled q235 steel, Heat Treatment of Metals 28 (2003)
48-51.
[60] Y.F. Chen, J.Q. Bi, C.L. Yin, G.L.You, Microstructure and fracture toughness of
graphene nanosheets/alumina composites, Ceram. Int. 40 (2014) 13883-13889.
[61] Z. Krstic, Z. Yu, V.D. Krstic, Effect of grain width and aspect ratio on mechanical

24
 ACCEPTED MANUSCRIPT

properties of Si3N4, ceramics, J. Mater. Sci. 42 (2007) 5431-5436.

[62] M. Song, L.I. Shuang, Z.P. Xie, Microstructure and properties of graphene
nanoplate /3y-tzp composite prepared by spark plasma sintering, Transactions of
Materials & Heat Treatment, 36 (2015) 1-6.
[63] H.J. Kim, S.M. Lee, Y.S. Oh, Y.H. Yang, Y.S. Lim, D.H. Yoon, C. Lee, J.Y. Kim,
R.S. Ruoff, Unoxidized graphene/alumina nanocomposite: fracture- and
wear-resistance effects of graphene on alumina matrix, Sci. Rep. 4 (2014) 5176.
[64] M. Belmonte, C. Ramírez, J. González-Julián, J. Schneider, P. Miranzo, M.I.
Osendi, The beneficial effect of graphene nanofillers on the tribological
performance of ceramics, Carbon 61 (2013) 431.

PT
[65] X. Wang, N.P. Padture, H. Tanaka, A.L. Ortiz, Wear-resistant ultra-fine-grained
ceramics, Acta. Mater. 53 (2005) 271-277.

RI
[66] R.S. Roy, D. Basu, A. Chanda, M.K. Mitra, Distinct wear characteristics of
submicrometer-grained alumina in air and distilled water: a brief analysis on

SC
experimental observation, J. Am. Ceram. Soc. 90 (2007) 2987-2991.
[67] C. Lee, Q. Li, W. Kalb, X.Z. Liu, H. Berger, R.W. Carpick, J. Hone, Frictional
characteristics of atomically thin sheets, Science 328 (2010) 76-80.
NU
[68] D. Berman, A. Erdemir, A.V. Sumant, Few layer graphene to reduce wear and
friction on sliding steel surfaces, Carbon 54 (2013) 454-459.
[69] D. Berman, A. Erdemir, A.V. Sumant, Reduced wear and friction enabled by
MA

graphene layers on sliding steel surfaces in dry nitrogen, Carbon 59 (2013)

167-175.
[70] X.J. Shen, X.Q. Pei, S.Y. Fu, K. Friedrich, Significantly modified tribological
performance of epoxy nanocomposites at very low graphene oxide content,
D

Polymer 54(2013) 1234-1242.

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Graphical abstract
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Highlights
 Multilayer graphene (MLG)-reinforced functionally graded WC-based
nono-composites were prepared through two-step sintering (TSS).
 53.3% enhancement in fracture toughness was obtained by adding 0.1 wt.%
MLG.
 73.8% decrement in friction coefficient and 82.65% improvement in wear
resistance were obtained by adding 0.1 wt.% MLG.
 Toughening mechanisms and anti-friction and wear resistance mechanisms were
studied.

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