Ceramics International 45 (2019) 6858–6862

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

The effect of graphene nanoplatelet thickness on the fracture toughness of T

Si3N4 composites
Orsolya Tapasztóa, Viktor Puchyb, Zsolt E. Horvátha, Zsolt Fogarassya, Eszter Bódisc,
⁎
Zoltán Károlyc, Katalin Balázsia, Jan Duszab, Levente Tapasztóa,
a
Institute of Technical Physics and Materials Science, Centre for Energy Research, Hungarian Academy of Sciences, Konkoly Thege str. 29-33, 1121 Budapest, Hungary
b
Institute of Materials Research, Slovak Academy of Sciences, Watsonova 47, 040 01 Košice, Slovak Republic
c
Institute of Materials and Environmental Chemistry, Research Centre for Natural Sciences, Hungarian Academy of Sciences, Budapest, Hungary

A R T I C LE I N FO A B S T R A C T

Keywords: Si3N4 composites with 3 and 5 wt% of graphene nanoplatelet (GNP) additions were prepared by spark plasma
Silicon nitride sintering. We used both commercially available GNPs and thinner few-layer graphene nanoplatelets (FL-GNPs)
Composites prepared by further exfoliation through ball milling with melamine addition. We found that by employing
Graphene nanoplatelets thinner FL-GNPs as filler material a 100% increase in the fracture toughness of Si3N4/3 wt% FL-GNP composites
Toughening
(10.5 ± 0.2 MPa m1/2) can be achieved as compared to the monolithic Si3N4 samples (5.1 ± 0.3 MPa m1/2),
and 60% increase compared to conventional Si3N4/3 wt% GNP composites (6.6 ± 0.4 MPa m1/2). For 5 wt%
filler content the increase of the fracture toughness was near 50% for both GNP and FL-GNP fillers. The hardness
of the composites decreased with increasing GNP content. However, composites reinforced with 5 wt% of FL-
GNPs displayed 30% higher Vickers hardness (12.8 ± 0.2 GPa) than their counterparts comprising conventional
GNP fillers (9.8 ± 0.2 GPa). We attribute the enhanced mechanical properties obtained with thinner FL-GNPs to
their higher aspect ratio leading to a more homogeneous dispersion, higher interface area, as well as smaller
pores in the ceramic matrix.

1. Introduction
It has been demonstrated that the addition of graphene nanoplate-
lets to ceramic matrix composites can enhance their electrical con-
ductivity by orders of magnitudes [1,2], significantly increase the
flexural strength [3–5], as well as substantially improve tribological
properties [6–8]. Besides these beneficial effects, the addition of gra-
phene nanoplatelets has been found to be highly efficient in increasing
the fracture toughness of ceramic composites, in general [9–11], and
Si3N4 based composites, in particular [12–14]. The improvement
achieved in the fracture toughness of various Si3N4/GNP composites
strongly varied depending on several factors, such as: filler content,
preparation technique, as well as the properties of the GNPs. The
highest improvements in the fracture toughness have been achieved
when employing chemically derived graphene oxide (GO) as filler
material. For Si3N4 composites prepared by spark plasma sintering
(SPS) a large improvement (from 2.8 to 6.6 MPa m1/2) has been re-
ported upon addition of 1.5 vol% of graphene platelets obtained by the
rapid thermal expansion of graphite oxide [12]. In a similar manner, it
has been shown that upon the addition of 4.3 vol% of GO the toughness
of Si3N4 composites improved from 4.5 MPa m1/2 to 10.4 MPa m1/2 [4].
By direct comparison the same study showed that the addition of 4.3 vol
% of conventional unoxidized GNPs yielded a substantially lower
toughness value of about 6 MPa m1/2. By analyzing the existing litera-
ture, a recent review paper pointed out, that the improvement of the
fracture toughness is in general almost double when graphene oxide is
employed as filler material instead of unoxidized graphene nanoplate-
lets [15]. The higher efficiency of graphene oxide in the toughening of
composites is usually attributed to two factors: (1) their reduced
thickness, as the oxidation enables a more efficient exfoliation, which in
turn leads to a more homogeneous dispersion within the ceramic ma-
trix, and (2) the chemical functionalization of their surfaces, enhancing
the adhesion to the ceramic matrix, which plays an important role in
determining the efficiency of crack bridging. However, it has also been
shown that GO (even in reduced form) is far less efficient in improving
the tribological properties of the ceramic composite as compared to
unoxidized graphene platelets [6,16]. Therefore, to obtain Si3N4/gra-
phene composites that are outstanding in both tribological and me-
chanical applications, it is desirable to prepare composites with un-
oxidized graphene flakes that are also characterized by high toughness

⁎
Correspondig author.
E-mail address: tapaszto@mfa.kfki.hu (L. Tapasztó).

https://doi.org/10.1016/j.ceramint.2018.12.180
Received 8 October 2018; Received in revised form 13 December 2018; Accepted 24 December 2018
Available online 25 December 2018
0272-8842/ © 2019 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
O. Tapasztó et al.
values. A first step in this direction is to prepare thin unoxidized GNPs
with their thickness approaching that of graphene oxide flakes. Typi-
cally, the thickness of GNP fillers added to ceramic composites ranges
from a few nanometers to a several tens of nanometers, which can
further aggregate within the ceramic matrix. Reducing the thickness of
the GNPs can have beneficial effects on their mechanical properties
[6,17]. We have recently shown that the exfoliation of GNPs down to
the few layer (< 10 layer) range, can significantly improve the tribo-
logical properties of Si3N4 composites [8]. The friction coefficient of
Si3N4/FL-GNP samples has been reduced to its half while the wear re-
sistance was increased almost twenty times. Here we proposed to in-
vestigate the effect of thin unoxidized few-layer GNPs prepared by a
simple melamine assisted ball milling process [8,18,19] on the fracture
toughness of Si3N4 composites. Our aim was to substantially improve
the toughness of Si3N4 composites without oxidizing the structure of
graphene platelets.
2. Experimental
For sample preparation, 90 wt% Si3N4 (Ube, SN-ESP) powder has
been used, together with 6 wt% Al2O3 (Alcoa, A16) and 4 wt% Y2O3
(H.C. Starck, grade C) powders as sintering aids. The powder mixture
was milled in ethanol using an attritor mill (Union Process, type 01-HD/
HDDM) at 4000 rpm for 5 h. As filler phase we used commercially
available graphene nanoplatelets (ACS Material) with a nominal
thickness of 6–8 nm and average lateral dimensions of about 25 µm. To
obtain even thinner few-layer nanoplatelets (FL-GNPs), 30 mg of GNP
powder has been processes in a planetary mill (225 RPM, 30 min) with
the addition of 90 mg of melamine. The resulting solid mixtures were
dispersed in 20 ml water and sonicated for 30 min. A washing process in
water ensures the removal of the melamine from the FL-GNP powder
after the exfoliation. The melamine addition to the ball milling process
results in a more efficient exfoliation and thinner FL-GNPs, as demon-
strated in a previous paper based upon Raman and Transmission
Electron Microscopy investigations [8]. 3 and 5 wt% of GNP or FL-GNP
powder has been added to the ceramic powder mixtures, and homo-
genized by mechanical milling at 600 RPM for 30 min. The as-prepared
powder mixtures have been subjected to spark plasma sintering (SPS,
HD P5, FCT - SYSTEME GMBH, GERMANY). The powders were sintered
into discs of 2 cm diameter and 5 mm thickness, at 1700 °C in vacuum,
with 10 min holding time. A 100 °C min −1 heating rate was used for all
samples using on/off current pulses of 12/2, 5500 A and 7.2 V. A uni-
axial compression of 50 MPa and chamber pressure of 1 mbar has been
maintained during sintering.
The structure and morphology of GNPs have been investigated by a
Philips CM-20 transmission electron microscope (TEM) at 200 keV. The
microstructural characterization of the sintered samples has been car-
ried out by a LEO (ZEISS) 1540 XB field emission scanning electron
microscope, a Zeiss Axio imager optical microscope, and a Bruker AXS
D8 X-ray diffractometer. The Vickers hardness and fracture toughness
values have been obtained from micro-indentation experiments on a
hardness tester (KS Prüftechnik) applying a load of 10 Kp for 10 s. The
micro-indentation measurements have been performed on the sample
surfaces parallel to the uniaxial pressure direction applied during the
sintering. The fracture toughness values of composites have been cal-
culated with the Anstis formula [20], using a Young's modulus value of
E = 250 GPa.
3. Results and discussion
The morphology of the GNPs prepared both with and without
melamine addition has been investigated by transmission electron mi-
croscopy. TEM measurements revealed that the lateral sizes of the GNPs
prepared both with and without melamine are of several microns, while
the GNPs prepared with melamine addition are thinner (see Fig. 1), in
agreement with our previous findings [8]. The microstructure of the
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Ceramics International 45 (2019) 6858–6862
sintered composites has been investigated by Scanning Electron Mi-
croscopy (SEM) and XRD measurements. We have acquired SEM images
of fracture surfaces of all Si3N4 composite samples (see Fig. 2). From
these SEM images it is also apparent that FL-GNPs prepared by mela-
mine assisted exfoliation form much thinner inclusions in the ceramic
matrix than the conventional GNPs. We note that thinner graphene
platelets are harder to identify in the SEM images due to the limited
resolution and contrast. This can give the impression that the graphene
content is actually lower in FL-GNP composites, which is clearly not the
case.
Upon careful inspection, SEM images reveal the presence of a large
amount of thin few-layer graphene flakes (e.g., as can be seen by
zooming into Fig. 2d).
XRD measurements have been employed to reveal the phase com-
position of the composites (Fig. 3).
XRD data clearly indicates the presence of both alpha and beta Si3N4
phase, even though the starting powder comprised only the alpha
phase. This is due to the high temperatures (1700 °C) employed during
the sintering process. The presence of ZrO2 in a few percent con-
centration in all samples is due to the ZrO2 balls used for the milling.
The fracture toughness and Vickers hardness values obtained from
micro-indentation measurements are shown in Fig. 4. The micro-in-
dentation tests have been performed on polished sample surfaces par-
allel with the uniaxial pressing direction applied during the sintering.
The fracture toughness of the reference monolithic Si3N4 sample was
5.1 ± 0.3 MPa m1/2. For composites reinforced with conventional
GNPs, the fracture toughness increased by about 30% and 50% for 3
and 5 wt% filler content, respectively. These trends are in good agree-
ment with the literature for unoxidized GNP additions [4,13,14].
The best results have been obtained for 3 wt% of FL-GNPs, where
the fracture toughness increased by more than 100% to
10.5 ± 0.2 MPa m1/2 as compared to the monolithic reference sample.
This value equals the highest toughness value previously reported for
Si3N4 composites [4]. However, previously such large improvements of
the toughness could only be obtained by employing graphene oxide
[15], while here we used unoxidizied FL-GNPs. The full benefits of
using unoxidized graphene platelets can be harnessed in tribological
applications, as we have shown previously [6,8]. By contrast, graphene
oxide reinforced composites are characterized by a limited improve-
ment of the tribological properties [15,16]. We attribute the substantial
toughness improvement of our sample, matching those of graphene
oxide, to the ability to prepare thin graphene flakes even without oxi-
dizing their structure [8]. Thinner flakes provide much larger contact
areas (per constant GNP content), and a more homogeneous distribu-
tion within the matrix. Larger contact areas improve the stress transfer
between the ceramic matrix and the flakes, while a more homogeneous
distribution ensures that during their propagation cracks encounter
more often GNPs. Besides providing thin flakes, graphene oxide also has
the advantage that its surface is chemically functionalized [21] that can
enhance the chemical adhesion to the ceramic matrix. Our FL-GNPs
lack the surface chemical moieties characteristic to graphene oxide, in
turn their intrinsic mechanical properties are expected to be better
compared to oxidized graphene flakes [22,23]. Better intrinsic me-
chanical properties also enable us to preserve better the lateral size of
the flakes during processing (e.g. milling). Our optical microscopy and
SEM investigations reveal that graphene flakes with larger lateral size
can fully stop the propagation of cracks, while shorter GNPs only de-
flect the crack propagation (Fig. 5).
When increasing the FL-GNP content to 5 wt% we found that the
toughness of the composites decreases to values similar to that obtained
with conventional GNPs. We also note that a pronounced anisotropy in
the orientation of the graphene flakes can be clearly observed (see
Fig. 2), as also reported previously [24]. The graphene sheets tend to
align perpendicular to the direction of the uniaxial pressure applied
during the sintering. This results in a twofold anisotropy in the
toughness (crack propagation lengths). On one hand, there is a
O. Tapasztó et al. Ceramics International 45 (2019) 6858–6862

Fig. 1. Transmission electron microscopy images of: a) FL-GNPs prepared by melamine addition and b) GNPs prepared without melamine addition.

Fig. 2. Scanning electron microscopy images of fracture surfaces of Si3N4 composites with: a) 3 wt% GNPs; b) 3 wt% FL-GNPs; c) 5 wt% GNPs and d) 5 wt% FL-GNPs.

difference between the toughness values measured on sample surfaces
(planes) parallel and perpendicular to the pressing direction applied
during sintering. As we specified above for 3 wt% FL-GNP samples the
toughness value measured in the parallel plane was KIC║
= 10.5 ± 0.2 MPa m1/2. In the perpendicular plane we measured a
lower toughness value of KIC ⊥ = 7.8 ± 0.2 MPa m1/2. Moreover, an
in-plane anisotropy in the crack propagation length within the sample
surface parallel to pressure direction can also be observed. Cracks
propagating perpendicular to the aligned GNP sheets have a much
higher chance to encounter graphene flakes than cracks propagating in
the direction parallel to the sheets. This implies that such composites
are particularly efficient in suppressing crack propagation in the di-
rection of the uniaxial pressure applied during sintering.
As concerning the hardness values, we found that by increasing the
graphene content the hardness of the composites decreases. The main
reason for this is that the graphitic fillers provide softer spots as com-
pared to the Si3N4 matrix, and they can also promote pore formation,
further softening the composites [25]. However, while this decrease
becomes more pronounced with increasing filler content, samples re-
inforced with 5 wt% FL-GNPs display 30% higher hardness values than
the 5 wt% GNP samples. A possible explanation for this is that the pore
formation near FL-GNP additions is reduced as compared to thicker

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Fig. 3. Characteristic X-ray diffractograms of the composites.

Fig. 4. Fracture toughness (a) and hardness (b) values of Si3N4 composites prepared with different type and concentration of graphene nanoplatelet additions.

Fig. 5. a) Optical microscopy image of an indentation mark and the resulting cracks evidencing the stopping of crack propagation by FL-GNPs of large lateral size. b)
SEM micrograph showing a crack deflection by a shorter GNP.

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Table 1
The apparent density, fracture toughness and hardness of the investigated composites.
Material GNP content (wt%) Apparent density (g/cm3) Fracture toughness (MPa m1/2) Hardness HV1 (GPa)

Si3N4 0 3.31 5.1 ± 0.3 17.5 ± 0.4

Si3N4/GNP 3 3.27 6.6 ± 0.4 13.9 ± 0.9
Si3N4/FL-GNP 3 3.29 10.5 ± 0.2 13.7 ± 0.5
Si3N4/GNP 5 3.21 7.5 ± 0.4 12.8 ± 0.4
Si3N4/FL-GNP 5 3.29 7.6 ± 0.5 9.8 ± 0.4

GNPs, as also indicated by the measured density values (Table 1). In
contrast to the toughness values, we did not observe a significant ani-
sotropy of the hardness.
4. Conclusions
We have investigated how decreasing the thickness of graphene
nanoplatelets affects the fracture toughness and hardness of the Si3N4/
GNP composites. We found that the improvement in fracture toughness
depends both on the filler content and the GNP thickness. The best
results have been obtained with the addition of 3 wt% of few-layer
graphene nanoplatelets, which increased the fracture toughness of
Si3N4 composites by more than 100% up to 10.5 ± 0.2 MPa m1/2. This
increase is much higher than previously achieved with unoxidized
GNPs, and is comparable to the highest fracture toughness values ob-
tained with graphene oxide filler. The reasons for the outstanding
toughening efficiency of FL-GNPs are their more homogeneous disper-
sion in the matrix and large lateral size (aspect ratio). The hardness of
the composites has been reduced by increasing the graphene content;
however, at 5 wt% filler content the hardness is 30% higher for com-
posites prepared by FL-GNPs, as compared to conventional GNPs.
Acknowledgements
The work has been supported by NKFIH - OTKA grant PD 121368.
L.T. acknowledges support from the ERC Starting Grant NanoFab2D
project.
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