NEW CARBON MATERIALS

Volume 34, Issue 5, Oct 2019

Online English edition of the Chinese language journal

Cite this article as: New Carbon Materials, 2019, 34(5): 489-498 RESEARCH PAPER

Effects of the oxygen content of reduced graphene oxide

on the mechanical and electromagnetic interference
shielding properties of carbon fiber/reduced graphene
oxide-epoxy composites
Ye Li, Shi-tai Liu, Jian-ming Sun, Shuang Li, Jun-lin Chen, Yan Zhao*
School of Materials Science and Engineering, Beihang University, Beijing 100191, China
Abstract: Unidirectional carbon fiber/reduced graphene oxide nanosheet-epoxy laminate composites (CF/RGONs-epoxy) were produced by
impregnating the CFs with epoxy acetone solutions containing RGONs, followed by solvent evaporation and curing at 180 °C under 0.6 MPa. The
RGONs were prepared by the Hummers method and reduced to different oxygen contents using hydrazine monohydrate by adjusting the
reduction temperature. The effect of the content of RGONs on the mechanical properties and electromagnetic interference (EMI) shielding
effectiveness of the composites was investigated. Results indicate that in contrast to the detrimental effect of GO on the flexural and thermal
properties, the addition of RGONs improves the mechanical property and EMI shielding effectiveness of the composites without sacrificing their
thermal properties. RGONs with a relatively lower oxygen content show more apparent mechanical reinforcement while RGONs with a relatively
higher oxygen content show a more obvious improvement on EMI shielding effectiveness. The improved interfacial properties are mainly
ascribed to the toughening effects of the RGONs.
Key Words: Reduced graphene oxide; Carbon fiber reinforced composites; Single fiber fragmentation test; Interfacial property;
Electromagnetic interference

1 Introduction

In recent years, hierarchical strategies to improve their
multifunctional performance of composites have attracted
much attention, in which a nanoscale reinforcement is utilized
alongside traditional microscale reinforcing fibers [1]. A
variety of carbon nanotubes (CNTs) and functionalized CNTs
are always used as the nanoscale reinforcements that are
introduced into conventional fiber-reinforced polymers [2-6].
However, the impurities from the catalysts, the intrinsic
bundling of carbon nanotubes and high costs are main
obstacles that hamper their applications. The graphene
nanosheets (RGONs) are used as alternative nanoscale
reinforcements to solve these problems [7-9]. It can be
anticipated that the light weight and high strength of graphene
are effective to improve mechanical properties of the
composites reinforced by carbon fibers. Its excellent electrical
property may also provide good electromagnetic interference
(EMI) shielding performance in the meantime [10]. However,
due to the intrinsic structure of graphene and absence of
chemical functional groups on the surface, graphene tends to
agglomerates through van der Waals interactions, leading to
poor dispersion in polymer matrix.
To overcome this limitation, graphene oxide (GO) is
always used as a reinforcement in the polymer matrix
composite. Polymer nanocomposites modified with GO
normally show a significant enhancement on properties even
at low loadings [11, 12]. Disappointedly, it has been reported that
GO has a detrimental effect on thermal property of composites
[13-15]
. Besides, oxidation in GO preparation from graphite will
destroy integrity of aromatic network in graphene sheets,
which is expected to decrease the enhancement effect on EMI
shielding effectiveness. A slight reduction of oxygen content
on GO can partially restore the electrical property and thermal
property and afford the nanomaterials with a good
dispersibility in composites as well. Chemical reduction of
GO sheets has been performed with several reducing agents
and among them hydrazine monohydrate was found to be
highly effective and most widely used [16,17]. Here we report a
synthesis method to prepare reduced GO (RGO) nanosheets in
different reduction degrees by adjusting various reaction
temperature, which enabled a gradual reduction of the
oxygen-containing functional groups. As it is known, the
oxygen content of graphene nanosheets (RGONs) is of vital
importance for the composite performance, but how the
oxygen-containing functional group content of RGONs
influences the mechanical and EMI shielding properties of
composites has been rarely reported.
Concerning hierarchical structure of the composites,
there are two main fabrication approaches, dispersion of

Received date: 2 Jul 2019; Revised date: 2 Sep 2019

*Corresponding author. E-mail: jennyzhaoyan@buaa.edu.cn
Copyright©2019, Institute of Coal Chemistry, Chinese Academy of Sciences. Published by Elsevier Limited. All rights reserved.
DOI: 10.1016/S1872-5805(19)60026-0
 Ye Li et al. / New Carbon Materials, 2019, 34(5): 489-492

nanoscale reinforcements into the polymer matrix, followed its reinforcing mechanism, which suggests a toughening effect
by an infusion of resin into fibers, [18, 19] and direct attachment that is dominant. Furthermore, mechanical properties of the
of nanoscale reinforcements onto the fiber surface by different composites fabricated by this method are as good as the
ways such as growth on fibers of fabrics by CVD [20, 21] and traditional polymer-based structural composites, making it
spraying on fabrics [22, 23]. It can be found that fabric was possible to scale up from laboratory research to industrial
always used as a reinforcement in these ways from the applications.
published papers because of its convenience to design and
fabricate. Multiscale reinforcement can enhance the 2 Experimental
performance of fiber-reinforced composites dominated by the
fiber-matrix interphase such as interlaminar shear strength 2.1 Preparation of RGONs with different oxygen contents
(ILSS) significantly [2, 3]. For example, Elena Bekyarova [15]
Graphite oxide was prepared through the Modified Hummers’
reported that the ILSS of CF/epoxy composites increased from
method, in which natural graphite powder was oxidized by
nearly 45 to 65 MPa by infusing resin with 0.5% single-walled
potassium nitrate and potassium permanganate in a sulfuric
CNTs (SWCNTs) into a carbon fabric. Sang-Bok Lee [23]
acid solution [26]. The previous work in our group proved that
realized a 13% improvement of ILSS up to 73MPa by using
by slightly raising reaction temperature and extending reaction
electrophoretic deposition (EPD) technique to deposit
time under a controllable condition, a complete oxidation can
multi-walled CNTs (MWCNTs) on a carbon fabric. Although
be gained [27]. GO was achieved through exfoliating the gained
there is a great improvement on interfacial properties, the
graphite oxide via sonication in water.
absolute values of ILSS are not encouraging, which are not as
RGO was prepared by reducing as-prepared GO via
high as that of unidirectional high-performance composites
hydrazine monohydrate in a aqueous solution after the pH
widely used in aerospace industry, [24,25] due to low fiber
value of the solution was adjusted by NaOH to 9—10 [28]. To
volume fractions and low collimation degrees of composites
prevent GO nanosheets from heavy agglomeration, a few
reinforced by a fabric.
drops of NaOH solution was added to increase the zeta
In this study, CF-reinforced polymer (CFRP) composites
potential of the sheets by a charge repulsion effect. A
modified with RGO nanosheets in a controlled reduction
thorough RGO reduction was achieved at 80 °C [16]. Here,
degree has been prepared through a wet process, which shows
reaction temperatures were adjusted to 40 °C and 60 °C to
both improvement in mechanical property and EMI shielding
achieve a RGO reduction to different degrees, namely RGO1
effectiveness without sacrificing thermal property.
and RGO2, respectively. After the reduction process, the final
Unexpectedly, a composite with RGO at a higher reduction
product was immediately washed with deionized water,
degree shows a more obvious enhancement in mechanical
acetone and ethanol for several times, then dried in a vacuum
properties, while a composite with RGO at a lower reduction
oven under 70°C. The schematic diagram of synthesis process
degree shows a more significant EMI shielding effectiveness.
is shown in Fig. 1.
The single fiber fragmentation test was designed to understand

Fig. 1 A schematic illustration of the synthesis procedure of graphene nanosheets with different oxygen contents.
 Ye Li et al. / New Carbon Materials, 2019, 34(5): 489-492
2.2 Characterization of RGONs
The chemical characteristics of RGONs with different
oxygen contents was conducted by a ThermoVG
ESCALAB250 X-ray photoelectron spectrometer (XPS). The
spectra were performed with an Mg Ka X-ray source (1 253.6
eV) at a power of 300 W. The XPS data were fitted according
to the Gaussian — Lorentzian function. Atomic force
microscope (AFM) images of RGO were observed on a Veeco
NanoScope IV. The RGO was dispersed in tetrahydrofuran
and dip-coated onto mica plate surfaces before testing.
2.3 Fabrication of CF/RGONs-epoxy composites
The procedure for preparing the unidirectional
CF/RGONs-Epoxy composites is the same as the one that
reported in our previous work [15], which is presented in
Scheme 1. Here, we introduce it briefly. Different loading
amounts of RGONs were sonicated and dispersed in
tetrahydrofuran for 2 h, followed by adding epoxy resin, and a
mixture of diglycidyl of bisphenol-A (E54) and diamino
diphenyl methane (Ag80). The resulting suspension (1 mg/mL)
was sonicated for another 1 h, followed by rotary-evaporation
in order to remove tetrahydrofuran. A curing agent, diamino
diphenyl sulfone (DDS), was dispersed in acetone and mixed
with the epoxy containing RGONs to make a solution with a
density of 0.93 g/mL. CFs (CCF300) were impregnated by the
resulting epoxy solution for manufacturing prepregs, which
were dried at 50 °C for 24 h to remove solvent completely.
Then the prepregs were laid up unidirectionally and cured at
150 °C for 1 h and 180 °C for 2 h with a pressure of 0.6 MPa.
The final fiber volume fractions of the fabricated composite
laminates were in the range of 63% to 65%.
Fig. 2 A schematic illustration of the preparation
process of unidirectional CF/RGONs/epoxy composites.
2.4 Characterization
The flexural strength and stiffness were measured under
a three-point bend configuration according to the GB/T
3356-1999 using a minimum of five specimens. The ILSS was
tested on an Instron 5967 testing machine according to the
short beam shear test standard (JC/T 773-2010) on a minimum
of five specimens. The scanning electron microscopy (SEM)
images of the composites were obtained on a Carl Zeiss
SUPRA 55VP field emission scanning electronic microscope.
The samples were coated with Au by sputtering before
observation.
2.5 Single fiber fragmentation test (SFFT)
Single fiber fragmentation test (SFFT) is used to reveal
the reinforcing mechanism of RGO on the interfacial property.
RGO1 was coated on fibers by 2 different methods and IFSS
was tested to evaluate their effect on the interfacial properties
of the resulting composites. In the method A, RGO was
dispersed in tetrahydrofuran by ultrasonication for 2 h to
obtain a stable suspension with a concentration of 1 wt. %. In
the method B, epoxy resin was added into aforementioned
RGO/tetrahydrofuran solution followed by further sonication
for 1 h. RGO content is 0.1 wt.% of the epoxy resin.
Reference samples were also prepared using CFs with pure
THF or epoxy/ tetrahydrofuran solution without addition of
RGO. Then, the CFs were pulled through suspension and
dried subsequently at 120 °C and 70 °C for 12 h. To achieve a
good impregnation of the fibers and to avoid excess resin
being attached on the fibers, the pulling speed was maintained
at a low level.
Single carbon fiber was carefully separated from the
deposited-RGO fibers and imbedded in the center of a mold.
Then the resin was cast into the mold carefully to avoid
damaging the single fiber. The specimen with a dog-bone
shape was loaded within a polarized light microscope and
monitored after curing. As specimen is loaded in tension, the
fiber will break into two parts at the fracture strain. Then the
load will be transferred through interfacial shear stress,
leading to the repetition of fiber fracture. The region around
the broken fiber ends exhibit a colored pattern between
crossed polarizers because of matrix plasticization, which is
called birefringence. [29-31]. Hence, the fracture process of the
fiber and the lengths between each two break points can be
observed and measured with the help of a light microscope.
When the remaining fiber fragments are so short that the shear
stress becomes insufficient to cause any further break, it is
called break saturation [32]9. The fragment length at break
saturation point was measured and IFSS was calculated
according to the Kelly-Tyson equation [33] by assuming a
constant IFSS:
d f f
 (1)
2lc
Where τ is the interface shear stress, df is the fiber
diameter, σf is the fiber strength and lc is the critical fragment
length.
4
lc  l
3 (2)
 Ye Li et al. / New Carbon Materials, 2019, 34(5): 489-492

(3)
where Pt and P0 refer to the power of transmitted and
incident electromagnetic, respectively, SER, SEA, SEM refer to
the shielding effectiveness caused by reflection, absorption
and multiple reflection, respectively. When SE is larger than
10 dB, SEM can be neglected [10]. SER and SEA can be
Fig. 3 A schematic illustration of the sample preparation process
calculated based on the complex permittivity and permeability
of the single fiber fragmentation test (SFFT): (a) refers to A method,
as the following equation [35-37]；
RGO being deposited on carbon fiber directly, (b) refers to B method,
RGO being dispersed in a diluted epoxy solution and deposited on (4)
carbon fibers indirectly. (c) A picture of the dog-bone shaped SFFT
sample.

Where l is the average fragment length at break
saturation. As the fragment lengths of fiber satisfies the
3-parameters Weibull distribution, l is the Weibull
expectation of fragment lengths [34].
2.6 EMI shielding effectiveness
The EMI shielding effectiveness (SE) can be calculated
as the following equation:
褰 െ ͳ Ͳ ‫כ‬ 褰 褰
ͳ
Where d is the thickness of the tested material, δ is the
skin depth, is the magnetic permeability, ω is the angular
frequency, is the frequency dependent conductivity
which is equal to ωε0ε ″ , ε ″ is the imaginary part of
permittivity and ε0 is the permittivity of the free space. In
order to achieve the complex permittivity and permeability,
dielectric measurements were carried out on a 8722ES vector
network analyzer in the frequency range of 8.2-12.4 GHz
(X-band). Composite samples were cut into a rectangular
shape (22.86×10.16×2 mm3) and inserted in a copper sample
褰 holder, which was connected between the waveguide flanges
of the network analyzer.

Fig. 4 Curve-fitting of C1s XPS spectra of GO and RGO (a: GO; b: RGO1; c: RGO2).

Table 1 XPS surface compositions of GO and RGO.

C/O ratios 284.5 sp2C 285.6 sp3C 286.7-C-O- 287.8-C=O 288.8-COO-
GO 2.34 28.17% 24.13% 21.11% 18.28% 8.32%
RGO1 3.42 49.87% 25.65% 9.57% 6.85% 8.06%
RGO2 5.10 61.05% 22.82% 5.21% 4.81% 6.11%
 Ye Li et al. / New Carbon Materials, 2019, 34(5): 489-492
3 Results and discussion
The XPS was employed to evaluate the precise oxygen
contents of GO and RGO. By analyzing C1s to O1s peak in
the XPS spectra of GO and RGO, the atomic ratios of C/O
was obtained. The gradual increase of the atomic C/O ratios of
GO (2.34), RGO1 (3.42) and RGO2 (5.10) with increasing the
reaction temperature indicates that GO was reduced RGO to
different C/O levels. In another word, RGO was successfully
prepared with a controlled reduction degree by changing
reaction temperature. With increasing the reaction temperature,
the oxygen content declines gradually, revealing that a higher
reaction temperature leads to a higher reduction degree. The
percentages of functional groups on GO, RGO1, and RGO2
were estimated from fitting C1s curves in Fig. 4 and are listed
in Table 3. Compared with the XPS results of GO, it is found
that the percentages of sp2C on RGO1 increase and the
percentage of the oxygen-containing functional groups
decreases significantly after reduction . Due to a higher
Fig. 5 AFM images of (a) RGO1 and (b) RGO2 dispersed in tetrahydrofuran.
Plots of the storage modulus versus temperature are
represented in Fig. 6 and summarized in Table 1. It can be
observed that the addition of RGO1 and RGO2 has no effects
on Tg, which is consistent with that of blank sample within the
measurement uncertainties. In contrast, GO decreases Tg by
~4°C due to the decreased cross-linking density caused by the
reaction between matrix and chemical groups on the graphene
surface [13-15]. The recovery of Tg after reduction of
oxygen-containing functional groups shows that a decline of
oxygen-containing functional groups successfully suppressed
the detrimental effect of oxygen-containing functional groups
on the thermal property of the resulting composite.
Flexural strength and stiffness were tested under the
reaction temperature, a relatively small decline of the oxygen
functional group percentage is found accompanied by a
further increase of sp2C content on RGO2.
Atomic force microscopy is a reliable technique to
characterize the dispersibility of nanomaterials in a solution.
Dispersibility is a key factor to influence mechanical
properties of a composite reinforced by nanomaterials.
Tetrahydrofuran was used as solvent to disperse nanofillers,
hence study on dispersion quality of RGONs in
tetrahydrofuran is necessary. As seen in Fig. 5a, RGO1 was
well dispersed in tetrahydrofuran as multi-layered sheets
without serious graphitic layer restacking. After being reduced
at a higher reduction temperature for RGO2，the aggregations
of graphene layers is more common to be observed due to a
higher content of sp2C. Besides, the RGO2 nanosheets have
been torn into fragments in irregular shape with more defects,
which is demonstrated by the small size of RGO2 in Fig. 5b.
three-point-loading conditions. The results, illustrated in Fig.
7, show that an incorporation of GO at a loading of 0.1wt.%
has detrimental effect on flexural properties of the resulting
composite. However ， an introduction of RGO into the
composite leads to an increase of flexural strength by ~4%。
Flexural property is closely associated with the cross-linking
density of a composite [38]. Hence, the decline of flexural
strength may be attributed to the same reason as the decrease
of Tg. To understand the reinforcing effect of RGO on flexural
property, bending fracture morphology is observed under
SEM, which is shown in Fig. 8. Crack propagation along the
interface is clear in the CF/Epoxy composite, as shown in Fig.
8a, while it’s hard to be observed in the CF/RGONs-Epoxy
 Ye Li et al. / New Carbon Materials, 2019, 34(5): 489-492

Fig. 7 Flexural properties of CF/RGONs-epoxy composites.

Fig. 6 Storage modulus curves and tan curves obtained by DMTA
analysis.

Table 2 Tg of CF/RGONs-epoxy composites obtained by DMTA analysis.

Blank GO RGO1 RGO2
Tg（ C）
o
193.89 189.39 193.10 193.59

Fig. 8 SEM images of bending fractured surfaces of (a) the CF/epoxy composite, (b) CF/RGONs-epoxy composite with 0.1 wt% RGO1 and
(c) CF/RGONs-epoxy composite with 0.1 wt% RGO2.

The ILSS values of CFs-reinforced polymer composites

Fig. 9 ILSS of CF/RGONs-epoxy composites, dash line
representing ILSS of blank sample.
composites. For the samples with RGO, the surface of the
fibers is covered and connected by the modified resin. The
phenomenon accounts for the increase in interfacial property
of the samples, which may also contribute to the flexural
property [38]. Short beam shear test is an indispensable method
to evaluate interfacial property of a composite. In order to
verify our inference, the short beam shear test was conducted.
modified with RGO at different loads (0.05 wt%, 0.1 wt%,
0.2 wt%, 0.4 wt%) are demonstrated in Fig. 9. With the
addition of RGO at a relatively low loading, the multiscale
hybrid composites show a higher ILSS than the ones using
pure epoxy as matrix. The introduction of RGO1 and RGO2
both lead to the high enhancement of ILSS by increase of
5.7% and 7.7% respectively at a 0.1 wt% loading, indicating
the optimized reinforcing effect and dispersion effect at that
point. As RGO1 has more oxygen-containing functional
groups, it’s expected to have a better reinforcing effect.
Surprisingly, the reinforcing effect of RGO2 on ILSS exceeds
that for RGO1 at a loading of 0.1 wt%. The unexpected
phenomenon suggests that chemical bonding between
nanomaterials and bulk material is not the main reinforcing
mechanism for RGO. With a higher loading, the dispersion
quality of RGO2 decreases more quickly, resulting in the
more significant detrimental effect of RGO2 on ILSS.
Although the reinforcing effect of RGO2 is not as good as that
of GO [15], the overall enhancement of mechanical property
makes it more feasible for practical applications.
 Ye Li et al. / New Carbon Materials, 2019, 34(5): 489-492
In order to illustrate the reinforcing effect of RGO on the
interfacial property in depth, the single fiber fragmentation
test was designed and performed. As illustrated in the
experimental section, two different methods are used to
prepare RGO-modified carbon fibers. Method A is to deposit
RGO on carbon fibers directly and Method B is to coat the
carbon fibers with a diluted epoxy solution containing RGO.
As dispersion of RGO1 in tetrahydrofuran is better than that
for RGO2，we used RGO1 here to reduce scattering of micro
test results. In order to avoid damage or reinforcing effect
introduced during treatment process, reference samples which
went through the same treatment process except that RGO was
not added were also prepared. By comparing the interfacial
shear strength (IFSS) of the modified carbon fibers with its
respective blank sample, the effect of RGO on interfacial
property of the composites can be evaluated. The
birefringence images at break saturation are shown in Fig. 10.
After the treatment by the method A, the birefringence
patterns become thinner and flatter, which is an indication of
interfacial debonding, being associated with weak fiber-matrix
interface. For the method B treatment, X shaped break points
become sharper with increasing loading amounts. This
birefringence behavior is caused by the plastic deformation of
surrounding matrix which is a consequence of strong interface.
As the birefringence patterns can be indicative of interfacial
performance, we can conclude that the RGO that was
deposited directly decreases the interfacial property, while the
RGO that was coated with epoxy has a positive effect on
improving IFSS. IFSS was calculated according to the
Kelly-Tyson equation, which is shown in Fig. 11. The two
different treatments show opposite effect on IFSS, which is
consistent with our indication from birefringence patterns.
IFSS decreases by 26.3% with the RGO deposited directly,
while it increases by 21.1% with the RGO coated containing
epoxy. It’s worthy to mention that samples coated by pure
THF or the diluted epoxy solution without RGO were also
tested as reference samples, which shows that the treatment
method has little effect on IFSS. In another words, it is the
RGO deposition that makes the difference on IFSS.
Fig. 10 The birefringence images of the carbon fiber at break
saturation in SFFT： (b) refers to samples treated by the method A
(direct deposition), showing weak interface, (d) refers to samples
treated by the method B (indirect deposition), showing strong
interface, (a) and (c) are reference samples for (b) and (d),
respectively.
Fig. 11 IFSS of the CF/ RGONs-epoxy composites tested by
SFFT, showing (a) a decline of IFSS by 26.3% after direct deposition
of RGO and (b) an enhancement of IFSS by 21.1% after indirect
deposition of RGO.
In order to investigate the effect of the addition of RGO
by the direct deposition method on fiber surface morphology,
SEM observation was taken（Fig.12）. From the SEM images,
it can be found that after the addition, RGO nanosheets prefer
to fill the longitudinal grooves due to π െ π stacking between
carbon fibers and graphene sheets. As a result, the RGO
reduces the surface area of carbon fibers and prevents the
interphase from being impregnated, leading to a decline of
IFSS. In contrast to the direct deposition method, the RGO
added by coating epoxy-containing RGO improves the
roughness of carbon fibers. After sizing treatment, the RGO
nanosheets coated with epoxy can be observed to become
bulged on the surface of carbon fibers. The attached graphene
nanosheets take part in the crack deflection process, by which
an initial crack tilts and twists when it encounters a rigid
inclusion [10]. Its effect on the composite is like inorganic
nanoparticles, such as CaCO3, SiO2, which improve interfacial
property through dissipating energy. The small pieces and a
slight aggregation of RGO2 may provide superior crack
deflection effect and energy dissipation capability to RGO1,
resulting in a more effective enhancement on the interfacial
properties of the composites than RGO1.
Fig. 13 shows the shielding effectiveness for the
composites with and without addition of RGO. The reflection
effect (SER) can be found to play a crucial role in the shielding
effectiveness, which is larger than that of the composites
reinforced solely by nanomaterials such as graphene [10],
nanotube [35] and barium ferrite [36]. High SER in our study is
mainly contributed from a high volume fraction of carbon
fibers in the composites. The addition of RGO mainly
contributes to the enhancement of shielding effectiveness from
reflection. AFM observation proves that RGO1 is dispersed
more homogeneously than RGO2, leading to the formation of
more interfaces and an increased heterogeneity, which is
beneficial to the improvement of SER. Furthermore, the
introduced interfaces between RGO, epoxy and carbon fibers
also contributes to the increase of space charge polarization
and orientation polarization, leading to the improvement in
 Ye Li et al. / New Carbon Materials, 2019, 34(5): 489-492
Fig. 12 SEM topographical images of carbon fibers (a) blank sample, (b) after the method A treatment, RGO wraps and fills the longitudinal
grooves and (c) after the method B treatment, bulge is observed on the surface of carbon fibers.
Fig. 13 Shielding effectiveness (SER and SEA) as a function of
frequency, showing the effectiveness of RGO on the SE of the
composites.
SEA. Although RGO2 has more advantages in electron
polarization ， the interface polarization and functional group
polarization make RGO1 as effective as RGO2 in improving
shielding effectiveness from absorption, especially in the high
frequency region [39].
4 Conclusions
Two approches to prepare unidirectional CF/epoxy
composites with matrix modified by RGONs of different
oxygen contents were investigated. RGONs with different
oxygen contents were successfully prepared by adjusting
reaction temperature. In contrast to the detrimental effect of
GO on flexural property and thermal property of composite,
the addition of RGONs is able to improve mechanical
property and EMI shielding effectiveness of the composites
without sacrificing their thermal property. By comparing the
reinforcing effect of RGONs with different oxygen contents,
it’s unexpectedly found that RGONs with a relatively lower
oxygen content show more reinforcing effect on mechanical
property of the resulting composite, while RGONs with a
relatively higher oxygen content show a more enhancement
effect on EMI shielding effectiveness of the resulting
composite. The improved interfacial property is mainly
ascribed to toughening effects of RGONs. The presented
approach shows a great application potential in advanced
industry area where high-performance composite with
improved overall mechanical property is strongly needed.
References
[1] Qian H, Greenhalgh E S, Shaffer M S P et al. Carbon
nanotube-based hierarchical composites: A review[J]. J Mater
Chem, 2010, 20(23):4751-4752.
[2] Chou T W, Gao L, Thostenson E T, et al. An assessment of the
science and technology of carbon nanotube-based fibers and
composites[J]. Compos Sci Technol, 2010, 70(1):1-9.
[3] Bekyarova E, Thostenson E T, Yu A, et al. Multiscale carbon
nanotube-carbon fiber reinforcement for advanced epoxy
composites[J]. Langmuir, 2007, 23(7):3970-3974.
[4] Davis D C, Wilkerson J W, Zhu J, et al. Improvements in
mechanical properties of a carbon fiber epoxy composite using
nanotube science and technology[J]. Compos Struct, 2010,
92(11):265-2.
[5] Yavari F, Rafiee MA, Rafiee J, et al. Dramatic increase in fatigue
life in hierarchical graphene composites[J]. ACS Applied
Materials & Interfaces, 2010, 2(10):2738-2743.
[6] Day R J, Rodrigez J V. Investigation of the micromechanics of the
microbond test[J]. Composites Science and Technology, 1998,
58(6): 907-914.
[7] Zhang X, Fan X, Yan C, et al. Interfacial microstructure and
properties of carbon fiber composites modified with graphene
oxide[J]. Acs Applied Materials & Interfaces, 2012, 4(3):1543.
[8] Chen L, Jin H, Xu Z, et al. A design of gradient interphase
reinforced by silanized graphene oxide and its effect on carbon
fiber/epoxy interface[J]. Materials Chemistry & Physics, 2014,
145(1-2):186-196.
[9] Hadden C M, Klimek-Mcdonald D R, Pineda E J, et al.
Mechanical properties of graphene nanoplatelet/carbon
fiber/epoxy hybrid composites: Multiscale Modeling and
Experiments[J]. Carbon, 2015, 95:100-112.
 Ye Li et al. / New Carbon Materials, 2019, 34(5): 489-492
[10] Liang J, Wang Y, Huang Y, et al. Electromagnetic interference
shielding of graphene/epoxy composites[J]. Carbon, 2009, 7(3),
922-925.
[11] Rafiee M A, Rafiee J, Wang Z, et al. Enhanced mechanical
properties of nanocomposites at low graphene content[J]. ACS
Nano 2009, 3(12):3884-3890.
[12] Liu M, Duan Y, Wang Y, et al. Diazonium functionalization of
graphene nanosheets and impact response of aniline modified
graphene/bismaleimide nanocomposites[J]. Materials & Design
2014, 53:466-474.
[13] Liu Q, Zhou X, Fan X, et al. Mechanical and thermal properties
of epoxy resin nanocomposites reinforced with graphene
oxide[J]. Polymer-Plastics Technology and Engineering, 2012,
51(3), 251-256.
[14] Wang S, Tambraparni M, Qiu J, et al. Thermal expansion of
graphene composites[J]. Macromolecules, 2009, 42(14),
5251-5255.
[15] Li Y, Zhao Y, Sun J, et al. Mechanical and electromagnetic
interference shielding properties of carbon fiber/graphene
nanosheets/epoxy composite[J]. Polymer Composites, 2016,
37(8), 2494-2502
[16] Park S, An J, Potts J R, et al. Hydrazine-reduction of
graphite-and graphene oxide[J]. Carbon, 2011, 49(9),
3019-3023.
[17] Stankovich S, Dikin D A, Piner R D, et al. Synthesis of
graphene-based nanosheets via chemical reduction of exfoliated
graphite oxide[J]. Carbon, 2007, 45(7), 1558-1565.
[18] Bekyarova E, Thostenson E T, Yu A, et al. Functionalized
single-walled carbon nanotubes for carbon fiber-epoxy
composites[J]. J Phys Chem C, 2007,111(48):17865-17871.
[19] Yan Z, Yuexin D, Lu Y, et al. The dispersion of SWCNTs treated
by dispersing agents in glass fiber reinforced polymer
composites[J]. Compos Sci Technol, 2009,69(13):2115-2118.
[20] Garcia EJ, Wardle BL, John Hart A. Joining prepreg composite
interfaces with aligned carbon nanotubes[J]. Compos Part
A-Appl S 2008,39(6):1065-1070.
[21] Qian H, Bismarck A, Greenhalgh ES, et al. Hierarchical
composites reinforced with carbon nanotube grafted fibers: The
potential assessed at the single fiber level[J]. Chem
Mater.2008,20(5):1862-1869.
[22] An Q, Rider A N, Thostenson E T. Hierarchical composite
structures prepared by electrophoretic deposition of carbon
nanotubes onto glass fibers[J]. ACS Appl Mat Interfaces, 2013,
5(6):2022-2032.
[23] Lee S B, Choi O, Lee W, et al. Processing and characterization of
multi-scale hybrid composites reinforced with nanoscale carbon
reinforcements and carbon fibers[J]. Compos Part A-Appl S
2011, 42(4):337-344.
[24] Luo Y F, Zhao Y, Duan YX. Surface and wettability property
analysis of CCF300 carbon fiber with different sizing or without
sizing[J]. Mater Design 2011, 32 (2):941-946.
[25] Sun P, Zhao Y, Luo YF, et al. Effect of temperature and cyclic
hygrothermal aging on the interlaminar shear strength of carbon
fiber/bismaleimide (BMI) composite[J]. Mater Design 2011,
32(8):4341-4347.
[26] Hummers Jr, Offeman RE Preparation of graphitic oxide[J]. J.
Am. Chem. Soc, 1958, 80(6), 1339-1339.
[27] Wang Y, Zhao Y, Bao TJ et al. Preparation of Ni-reduced
graphene oxide nanocomposites by Pd-activated electroless
deposition and their magnetic properties[J]. Appl Surf Sci, 2012,
258(22), 8603-8608.
[28] Park S, An J, Piner RD, et al. Aqueous suspension and
characterization of chemically modified graphene
sheets[J]. Chem Mater, 2008, 20(21), 6592.
[29] Greve L, Pickett A K, Payen F. Experimental testing and
phenomenological modeling of the fragmentation process of
braided carbon/epoxy composite tubes under axial and oblique
impact[J]. Compos Part B-Eng, 2008, 39(7-8):1221-1232.
[30] Netravali A N, Henstenburg R B, Phoenix S L. Interfacial shear
strength studies usingthe single-filament-composite test I:
Experiments on graphite fibers in Epoxy[M]. POLYM
COMPOSITE, 1989,10(4):226-241
[31] Kislev T. Marom G. Berglund L. et al. On the nature of the
opaque cylindrical regions formed at fiber break sites in a
fragmentation test[J]. Adv Compos Mater, 2002, 11(1):7-13
[32] Botelho E C, Pardini L C, Rezende M C. Hygrothermal effects
on the shear properties of carbon fiber/epoxy composites[J]. J
Adv Mater, 2006, 41(21):7111–7118.
[33] Kelly A, Tyson W R. Tensile properties of fiber-reinforced
metals: Copper/tungsten and copper/molybdenum[J]. J Mech
Phys Solids, 1965, 13 (6): 329-350.
[34] Khalili A, Kromp K. Statistical properties of Weibull
estimators[J]. J Mater Sci 1991, 26:6741-6752
[35] Singh A P, Gupta B K, Mishra M, et al. Multiwalled carbon
nanotube/cement composites with exceptional electromagnetic
interference shielding properties[J]. Carbon, 2013, 56, 86-96.
[36] Ohlan A, Singh K, Chandra A, et al. Microwave absorption
behavior of core−shell structured poly (3, 4-ethylenedioxy
thiophene)− barium ferrite nanocomposites[J]. ACS applied
materials & interfaces, 2010, 2(3), 927-933.
[37] Singh A P, Garg P, Alam F, et al. Phenolic resin-based composite
sheets filled with mixtures of reduced graphene oxide, γ-Fe2O3
and carbon fibers for excellent electromagnetic interference
shielding in the X-band[J]. Carbon, 2012, 50(10), 3868-3875.
[38] Zhamu A, Hou Y, Zhong W H, et al. Properties of a
reactive-graphitic-carbon-nanofibers-reinforced epoxy[J]. Polym
Composite, 2007, 28(5), 605-611.
[39] Wen B, Wang X X, Cao W Q, et al. Reduced graphene oxides:the
thinnest and most lightweight materials with highly efficient
microwave attenuation performances of the carbon world[J].
Nanoscale,2014, 6(11):5754-5761.