Composites Communications 22 (2020) 100480

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Composites Communications
journal homepage: www.elsevier.com/locate/coco

Enhanced cryogenic mechanical properties of carbon fiber reinforced epoxy

composites by introducing graphene oxide
Cheng-Bing Qu a, b, Yong Huang a, Fei Li a, Hong-Mei Xiao a, Yu Liu a, Qing-Ping Feng a,
Gui-Wen Huang a, Na Li a, Shao-Yun Fu c, d, *
a
Key Laboratory of Technology on Space Energy Conversion, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing, 100190, PR China
b
University of Chinese Academy of Sciences, Beijing, 100190, PR China
c
College of Aerospace Engineering, Chongqing University, Chongqing, 400044, PR China
d
State Key Laboratory of Power Transmission Equipment and System Security and New Technology, Chongqing University, Chongqing, 400044, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: In this work, graphene oxide (GO) with a content in a range of 0.0–0.5 wt% was introduced to modify epoxy
GO-Modified epoxy resin resin. The room temperature (RT) and cryogenic temperature (77 K) mechanical properties were systematically
Continuous carbon fiber-reinforced composite studied for the carbon fiber/GO-modified epoxy composites prepared by hot-press molding process. The results
Cryogenic mechanical properties
show that a good dispersion of GO in epoxy resin leads to an enhanced carbon fiber-epoxy matrix interfacial
Hot-press molding
adhesion. It is observed that the cryogenic mechanical properties of the CF/epoxy composites are obviously
enhanced by introducing GO. The optimal GO content is found to be 0.2 wt% for effectively improving the
cryogenic flexural and interlaminar shear strength of carbon fiber reinforced epoxy composites. In addition, it is
exhibited that the mechanical properties at 77 K of CFRP composites are higher than those at RT. Consequently,
the modification of epoxy resin by introducing GO is a promising means for achieving high cryogenic mechanical
performance CFRP composites.

1. Introduction strength etc. of epoxy composites would depend on matrix mechanical

In order to significantly reduce the weight of launch vehicles and
increase their load-carrying capabilities, carbon fiber reinforced poly­
mer (CFRP) composites are the most possible potential candidate ma­
terials to replace traditional metallic materials to fabricate cryogenic
fuel tanks etc. for next generation reusable launch vehicles due to their
high stiffness-to-weight ratio and high strength-to-weight ratio [1–3]. In
the future, the predictable CFRP cryogenic fuel tanks are not only as fuel
containers at ultra-low temperatures but also as load-carrying structures
during launch and flight operations [4–6]. Therefore, the cryogenic
mechanical properties of CFRP composites are of great importance for
their successful applications in cryogenic environments.
It is well known that the mechanical properties of CFRP composites
are governed by the properties of carbon fibers (CFs), the mechanical
behavior of matrix (e.g. epoxy resin) and the interfacial adhesion be­
tween CFs and epoxy matrix at environmental temperatures [7–9]. For a
given CF/epoxy system with fixed CF volume fractions, the resulting
mechanical properties such as flexural strength and interlaminar shear
properties and fiber-matrix interfacial adhesion. There are two major
effective strategies to improve the interfacial interaction between fibers
and polymeric matrices. One is the surface treatment of fibers (CFs or
glass fibers) by various methods including electrochemical, electro­
phoretic deposition process, grafting, coating and discharge plasma
treatments, etc [8,10–15]. The surface treatment methods have been
reported with improved mechanical and tribological properties at high
complexity and cost. The other is to disperse nanoparticles in epoxy
resins to modify epoxy matrices. This approach has been proven effec­
tive in suppressing crack propagation in epoxy matrices, and thus
resulting in the improvement of strength and toughness etc. of polymer
composites [16–20].
Blending a secondary component to modify epoxy matrix is a rela­
tively convenient and cost-effective approach without compromising
much processing ease and meanwhile modifying epoxy mechanical
properties [16,21–23] and even improving carbon fiber-epoxy interfa­
cial adhesion [17,24]. He et al. [23] reported that the epoxy composites
based on modified epoxy matrix by blending functionalized and ordered

* Corresponding author. College of Aerospace Engineering, Chongqing University, Chongqing, 400044, PR China.
E-mail address: syfu@cqu.edu.cn (S.-Y. Fu).

https://doi.org/10.1016/j.coco.2020.100480
Received 12 July 2020; Received in revised form 2 September 2020; Accepted 2 September 2020
Available online 8 September 2020
2452-2139/© 2020 Elsevier Ltd. All rights reserved.
C.-B. Qu et al.
Fe3O4/CNTs with a weight loading of 0.5 wt% led to the increased
tensile strength and modulus of epoxy composites by 14.6% and 20.0%
at 77 K respectively compared to the neat epoxy case. Meanwhile, there
have been reports about dispersing GO in epoxy resin for improving the
mechanical properties of carbon fiber/epoxy composites [18,19,25,26].
This approach has been proven quite effective in suppressing crack
propagation in epoxy matrix and resulting in improved strength and
toughness of epoxy composites [18,19]. Pathak et al. [18] studied the
effect of GO content in a range from 0.0 to 0.6 wt% on the flexural
properties and interlaminar shear strength (ILSS) at room temperature
(RT) of T-300 carbon fiber reinforced epoxy composites. It was found
that the increase in the mechanical properties of CFRP composites is
attributed to the improvement in the mechanical properties of epoxy
matrix and interfacial interaction by hydrogen bonding and mechanical
interlocking of GO between reinforcement and matrix. Hung et al. [19]
dispersed GO in epoxy matrix to improve the mechanical properties at
RT and 77 K of carbon fiber reinforced epoxy composites. It was found
that GO could effectively improve the mechanical properties of CF/e­
poxy composites at both temperature conditions as compared to pristine
composites. Jenkins et al. [26] investigated the effectiveness of gra­
phene oxide as nanofiller in enhancing epoxy/carbon fiber-reinforced
composite in a narrow temperature range (-10-40 ◦ C). GO was
dispersed in epoxy matrix system through the combination of mechan­
ical and sonication methods. The CF/GO-modified epoxy composite
samples were then tested to determine their shear and flexural proper­
ties. It was found that the composites’ flexural strength and flexural
modulus were obviously increased by introducing GO.
As mentioned above, the cryogenic mechanical properties are of
significance for the successful applications of carbon fiber reinforced
epoxy composites. Though the RT mechanical properties of carbon fiber
reinforced composites based on GO-modified epoxy have been investi­
gated but the knowledge about the RT mechanical behaviors cannot be
directly transferred to the cryogenic temperature case for polymer
composites. For example, it was reported that the cryogenic mechanical
properties of CF/epoxy composites were higher than those at RT
[27–29]. It was regarded that CFs and epoxy resins had higher me­
chanical properties and their interfacial adhesion was stronger at cryo­
genic temperatures than at RT, leading to the higher cryogenic
mechanical properties. On the other hand, the cryogenic mechanical
properties of CF/epoxy composites were lower than those at RT [5,19,
29]. It was hypothesized that the initial exposure to cryogenic envi­
ronment would have an adverse effect on the mechanical properties of
CF/epoxy composites. Namely, the matrix tended to deform after
cryogenic conditioning, but was resisted by the stiff fibers causing re­
sidual stresses at the fiber/matrix interface and resulting in transverse
cracks and interfacial debonding. It seems that the cryogenic mechanical
properties would depend on epoxy mechanical properties and CF-epoxy
interfacial adhesion at cryogenic temperatures. Therefore, no inference
can be made before a systematic investigation is conducted on the effect
of introducing GO into epoxy resin on the cryogenic mechanical prop­
erties of CF/epoxy composites and a systematic study on the cryogenic
mechanical properties of carbon fiber reinforced composites based on
modified epoxy resin by GO should be of great necessity.
In the present work, as a blending secondary component of GO with
different contents in epoxy matrix was used to fabricate unidirectional
CFRP composites by hot-press process. The effects of GO content on the
cryogenic flexural properties and interlaminar shear strength (ILSS) at
77 K of CFRP composites were systematically investigated and
compared with those at RT. It was observed that the cryogenic flexural
and interlaminar shear properties of CF reinforced epoxy composites
were greatly enhanced by the introduction of GO at proper contents in
epoxy resin. Consequently, dispersing GO at proper contents in epoxy
resin is a promising means to significantly improve the cryogenic me­
chanical properties of CF/epoxy composites.
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Composites Communications 22 (2020) 100480
2. Experimental section
2.1. Materials
Epoxy resin DGEBA (WSR615) was obtained from BLUESTAR Nan­
tong Star Synthetic Materials Co., Ltd. Nantong, China. The curing agent
(DETDA) was purchased from Albemarle Corporation Charlotte, USA.
Graphite powders were provided from Qingdao AoKe ShiMo Co. Ltd,
China. Unidirectional carbon fiber fabrics (CF) (T700SC, 12 K, and
diameter about 7 μm) were purchased from Toray Industries, Japan.
Acetone, hydrochloric acid, potassium permanganate and concentrated
sulfuric acid, were provided by Beijing Chemical Works and used as
received. Sodium nitrate was obtained from Tianjin JinKe Fine Chemical
Industry Research Institute, China. All components were commercial
products, and they were used as received without further purification.
2.2. Preparation of GO
Graphene oxide (GO) was produced through the acid oxidation of
graphite powders in a way similar to the Hummers’ method [30]. The
obtained graphite oxide was subsequently dispersed in deionized water
to form a suspension. The resulting suspension was then treated by
sonication for 3 h to exfoliate the graphite oxide to layer GO [31]. Af­
terwards, the product was dried in a vacuum oven at 80 ◦ C for 24 h to
obtain GO. After that, the prepared GO was dispersed in acetone under
stirring to form a suspension of 2 mg/ml, and the suspension was then
treated by sonication for 2 h to form homogeneous GO acetone solution.
2.3. Preparation of GO-modified epoxy matrix
The homogeneous GO acetone solution was mixed with epoxy pre­
cursor DGEBA under stirring for 6 h at 80 ◦ C to evaporate excess
acetone. Then, the curing agent DETDA was added to the mixture under
stirring for another 6 h at 50 ◦ C to obtain a homogenous GO-modified
epoxy mixture. Finally, the GO-modified epoxy mixture was degassed
by a vacuum rotary pump at 50 ◦ C for 1 h to remove the air bubbles
dissolved in mixture and residual acetone. Meanwhile, the pure epoxy
matrix was also prepared under the same condition. The epoxy matrix
was modified by incorporating GO of different wt% contents from 0.0 to
0.5% and the formulations of GO-modified epoxy resin are listed in
Table S1 (Supporting Information).
2.4. Preparation of CF/GO-modified epoxy composites
The CFs were refluxed in acetone at 80 ◦ C for 72 h, then the CFs were
treated in deionized water by sonication for 1 h, after that washed with
deionized water repeatedly, and dried under vacuum at 90 ◦ C for 5 h to
remove sizing agent.
The preparation of CF/GO-modified epoxy composites was similar to
our previous work and the details could be found therein [32]. A brief
description is presented in Fig. S1 (Supporting Information) for the
preparation process of CF/GO-modified epoxy composites. The
GO-modified epoxy matrix was impregnated into the CFs by hand paste
process, and eight impregnated CF layers in a [0◦ ] configuration were
stacked in a mold. Firstly, it was cured at 80 ◦ C for 1.5 h, then contin­
ually cured at 140 ◦ C for another 1.5 h. After that, it was cured under a
pressure of 5 MPa kept at 140 ◦ C for 1.5 h. Finally, the composites were
post cured at 130 ◦ C for 10 h, to ensure a complete chemical reaction
between epoxy and curing agent to form full cross-linking in matrix. The
different GO contents (0.0, 0.05, 0.1, 0.2, 0.35 and 0.5 wt%) in the epoxy
matrix of CF/epoxy composites were named respectively as CF/EP,
CF/0.05 GO-modified EP, CF/0.1 GO-modified EP, CF/0.2 GO-modified
EP, CF/0.35 GO-modified EP and CF/0.5 GO-modified EP. The speci­
mens for the three-point bending mechanical tests were cut from the
composite plates into approximately 80 mm (length) × 12.5 mm
(width) × 2 mm (thickness) according to ASTM D 7264. And the
C.-B. Qu et al.
specimens for the short beam shear test were approximately 20 mm
(length) × 10 mm (width) × 2 mm (thickness) according to ASTM D
2344.
2.5. Characterizations
Scanning electron microscope (SEM) images for the flexural testing
failure surfaces of CF/EP and CF/GO-modified EP composites at RT and
77 K were obtained with a Hitachi S-4800 Microscope (Japan). The
samples for the SEM observation were prepared by directly spraying a
thin gold layer on the sample surfaces. The surface morphology of GO
was investigated using a Nanoscope IIIa Atomic Force Microscopy
(AFM). The samples for AFM imaging were prepared by depositing
colloidal suspensions of GO on freshly cleaved mica surfaces.
The phase purity of the graphite and GO was characterized by X-ray
diffraction (XRD) on an X-ray diffractometer with Cu Κα radiation (λ =
1.5418 Å). Raman spectroscopy is an essential non-destructive tech­
nique for structure interpretation of carbon based materials. The Raman
spectra of graphite and GO were carried out on a Renishaw invia-Reflex
(England) with a 532 nm Ar laser. Fourier transform infrared (FTIR)
spectra for graphite and GO were recorded using an Excalibur 3100 FTIR
(Varian, USA) between 500 and 4000 cm− 1. Dried graphite and GO were
mixed with KBr powders and pressed into tablets for this characteriza­
tion, respectively.
The volume fractions of CFs in CF/EP and CF/GO-modified EP
composites were measured using solid-liquid densimeter ET-320D
(Etnaln, China) and calculated according to the Archimedes principle.
The volume of CFs was calculated in terms of equation (1):
Vf =
Dc − Dm
(1)
Df − Dm
where Vf is the volume of CFs in CFRP composites, Dc, Dm and Df rep­
resents the density of CFRP composites, epoxy matrix and CFs, respec­
tively. In this work, the volume fraction of CFs in all CFRP composites
was roughly in the range between 56% and 57%.
The three-point bending test and short beam shear test were con­
ducted by an INSTRON 5882 Universal testing machine under a 100 kN
load cell with a crosshead speed of 1 mm/min according to ASTM D
7264 and D 2344, respectively. At least five specimens from each
composite have been tested at each temperature (RT and 77 K). The 77 K
temperature condition was achieved by dipping the samples fixed on the
clamps in a liquid nitrogen filled cryostat designed in our laboratory
[33]. And the schematic diagrams of RT and cryogenic testing system for
three-point bending tests are given in Fig. S2 (Supporting Information).
The whole specimen was dipped in the liquid nitrogen environment for
over 15 min to reach the thermal equilibrium condition before the
cryogenic mechanical testing. Afterwards, the specimen was tested in
the nitrogen environment. A constant span to thickness ratio of
three-point bending test was 16:1 and deflections was larger than 10% of
the support span, the flexural stress and flexural modulus were calcu­
lated respectively by equations (2) and (3):
3PL
σf = (2)
2bh2
ΔP⋅L3
Ef = (3)
4b⋅h3 ⋅Δf
where σ f is the flexural strength of the composites (MPa), P is the
maximum load (N), L, b and h represents the span length (mm), width
(mm) and thickness (mm) of the specimen, respectively. Ef is the flexural
modulus of the composites (GPa), △P is the load deviation from a
reference load (N) and △f is the deflection form a reference deflections
(mm).
The ILSS of the samples is estimated according to the following
equation (4):
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Composites Communications 22 (2020) 100480
3F
τM = (4)
4bh
where τM is the ILSS (MPa), F is the maximum load (N), b and h repre­
sents the width (mm) and thickness (mm), respectively.
3. Results and discussion
3.1. Characterization of GO and carbon fibers
The AFM image of GO is shown in Fig. 1a. Analysis of the AFM image
reveals that the thickness of the GO nanosheet is around 0.5–1 nm,
indicating that the GO sheet has been indeed achieved after oxidation
and exfoliation. It is well known that a pristine graphene sheet is flat
with a thickness of 0.34 nm, however the GO sheet in the AFM image is a
little “bumpy” than expected due to the presence of covalently bound
oxygen and the displacement of the sp3-hybridized carbon atoms slightly
above and below the original graphene plane [34].
The X-ray diffraction (XRD) patterns of graphite powders and GO are
displayed in Fig. 1b. A sharp peak at 2θ = 26.54◦ for graphite corre­
sponds to the diffraction of the (002) graphite plane composed of well-
ordered graphenes with an interlayer spacing of 0.335 nm [35]. For GO,
the sharp peak of the diffraction of (002) plane disappears and is
replaced by a broad peak appearing at around 2θ = 11.78◦ due to a large
number of different oxygenic functional groups and defects are intro­
duced. The observed peak indicates that the graphene layers have been
sufficiently disordered. It means that the graphite oxide has been suc­
cessfully exfoliated to form layered GO nanosheets after oxidation and
exfoliation. The interlayer spacing of GO can be calculated according to
the Bragg’s law (5):
nλ = 2d sin θ (5)
where n is the diffraction series, λ is the X-ray wavelength, and d is the
interlayer spacing of GO. The calculated value of d is 0.74 nm. That is,
the interlayer spacing has been increasd form 0.335 nm for the graphite
to 0.74 nm for the exfoliated GO by oxygenic functional groups.
Raman spectroscopy is another useful and non-destructive technique
used to reveal the structural information of carbon-based materials such
as graphite and GO. Fig. 1c shows the typical Raman spectra of graphite
and GO, which includes two predominant D and G bands. The D band
reveals lattice distortion and defects, and the G band is attributed to the
first order scattering of E2g mode of hexagonal carbon lattice. For
graphite, the weak 1342 cm− 1 (D band) and narrow 1567 cm− 1 (G band)
indicate its dominant sp2 carbon while the intensity-enhanced D band at
1347 cm− 1 and the broadening G band at 1604 cm− 1 imply the
appearance of sp3 carbon in GO after oxidation [36,37].
Functional groups on the surfaces of GO and graphite were evaluated
by FTIR and the results are shown in Fig. 1d. It exhibits that graphite
does not contain while GO contains oxygen-based functional groups.
The broad and intense peak of GO at 3406 cm− 1 is attributed to O–H
stretching of carboxyl groups. The peak at 1724 cm− 1 assigned to C– –O
stretching vibrations of carbonyl groups. The peaks at 1616 cm− 1 and
1361 cm− 1 are attributed to the skeletal vibration of aromatic C– – C and
the stretching vibration of alkoxyl C–OH, respectively. 1225 cm− 1 and
1045 cm− 1 peaks indicate the symmetric and asymmetric stretching
vibrations of C–O–C (epoxy ring) [38,39]. At the same time, the pres­
ence of various oxygen-containing functional groups could enable GO to
disperse well in acetone and epoxy matrix [18].
The FTIR spectrum of CF is shown in Fig. 1e. It can be seen that the
predominant characteristic absorption signals include a peak at 3742
cm− 1 attributed to O–H stretching of carboxyl groups, while the peaks at
2926 cm− 1, 1710 cm− 1 and 1261 cm− 1 are attributed to the symmetric
stretching C–H, C– – O and C–O bonds, respectively. It is well known that
reactive groups (namely epoxy carbon) can react with hydroxyl to form
ether bond, implying that GO tends to react with CFs and form strong
C.-B. Qu et al.
Fig. 1. Characterization of GO and CF. (a) AFM image and line profile of GO, (b) XRD patterns of graphite and GO, (c) Raman spectra of graphite and GO, (d) FTIR
spectra of graphite and GO, (e) FTIR spectra of de-sized carbon fiber.
bonding [10,19].
3.2. Mechanical properties of CFRP composites
Fig. 2a and b shows the representative load-displacement curves of
the unidirectional CFRP composites with the various contents of GO in
epoxy matrix under flexural tests at RT and 77 K, respectively. As shown
in Fig. 2a and b, the load-displacement curves of all the specimens
exhibit a linearly elastic behavior until the maximum load is reached.
Then, the load drops off with a jagged-shape failure at RT as shown in
Fig. 2a. It is obviously observed that the fracture pattern has been
changed with the addition of GO, and the mode of failure would help to
provide more energy dissipation compared to the case of GO-free CFRP
composites [19].
In contrast, at 77 K (Fig. 2b), the load drops off sharply followed by
catastrophic failure. The main reason of the different failure modes
between RT and 77 K could be attributed to the transition of failure
modes at cryogenic environment [7,40]. It is seen that both maximum
flexural load and flexural displacement at break at 77 K are significantly
higher than those at RT. For instance, the maximum load and
displacement of CF/0.2 GO-modified EP at cryogenic temperature is
twice of that at RT. In addition, it should be noted that both the slope of
load-displacement curves and the maximum applied load increase when
the ambient temperature is lowered down from RT to 77 K. The
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Composites Communications 22 (2020) 100480
maximum load and load-displacement slope, and thus flexural strength
and flexural modulus, can be obtained from Fig. 2a and b as a function of
the GO percentage from zero to 0.5 wt%.
Fig. S3 displays the macroscopic morphologies of the CFRP com­
posites after three-point bending tests at RT and 77 K. As shown in
Fig. S3a, for the CF/EP composite, compressive fracture and delamina­
tion mainly occur in the top layers. By contrast, with the addition of GO,
compressive fracture, slight delamination and fiber breakage simulta­
neously happen at the top half region. It can be seen that the GO
modified epoxy matrix has a significant effect on the fracture modes of
the CFRP composites. At 77 K (Fig. S3b), for all composites, both
compressive (the top layer) and tensile (the bottom layer) fractures
simultaneously occur, accompanied by obvious delamination and fiber
breakage at those regions. By contrast, for the CF/0.2 GO-modified EP,
lighter delamination and severer fiber breakage are observed in the
tensile fracture region. This phenomenon means that the introduced GO
effectively reduces the debonding between CFs and epoxy matrix.
The flexural properties of CF/EP and CF/GO-modified EP at RT and
77 K are depicted in Fig. 2c–f as a function of the weight percentage of
the GO from zero to 0.5 wt%. The standard deviation is represented by
error bars. As shown in Fig. 2c–f, it is obvious that the flexural properties
at both RT and 77 K are sensitive to the GO concentration. Furthermore,
the flexural strength and flexural modulus increase with increasing the
content of GO, and reach the maximum values at the 0.2 wt% content of
C.-B. Qu et al.
Fig. 2. Typical three-point bending load-displacement curves of the CF/GO-modified EP composites at (a) 300 K and (b) 77 K with different mass fractions of GO in
epoxy matrix, effect of the GO content on the flexural strength and the modulus of the CF/GO-modified EP composites, (c) and (e) at 300 K, (d) and (f) at 77 K.
GO at both RT and 77 K. Although the flexural properties of CF/GO-
modified EP composites are declined when the GO content was 0.5 wt
% at both RT and 77 K, but the flexural strength and modulus of CF/GO-
modified EP composites are still higher than those of CF/EP composites.
The results clearly show the fact that the mechanical properties of CFRP
composites can be enhanced effectively by dispersing GO in epoxy ma­
trix at both RT and 77 K. And the observations in Fig. 2c–f will be
explained afterwards.
The enhancement (6.4% at RT and 4.9% 77 K shown in Fig. 2c and
d at 0.2 wt% GO) in the flexural strength of CF/GO-modified EP com­
posites after introducing GO content in epoxy resin is mainly attributed
to two aspects. The one is that epoxy matrix is strengthened by the
introduction of GO [16], and the other is that a strong interfacial
bonding is formed between CFs and epoxy matrix via GO [8,19]. The
reinforced epoxy matrix and the good interfacial adhesion ensure good
load transfer from epoxy matrix to the CFs, allowing the CFRP to bear a
high applied load.
The detailed explanations of the two aspects are as follows, respec­
tively. First, the GO has much greater mechanical properties than epoxy
matrix, the addition of GO will partially contribute to the enhancement
in the mechanical properties of the epoxy matrix, and then improve the
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Composites Communications 22 (2020) 100480
flexural properties of the CFRP composites. It has been reported in our
previous work [16] that the strength of epoxy composite can be highly
enhanced by the addition of graphene nanosheets since the reinforcing
effect can be realized by the graphene nanosheets with a good dispersion
at low contents. Second, the interfacial adhesion between epoxy matrix
and CFs is greatly enhanced by the addition of GO, which has been
shown to be a prospective sizing material to enhance the interfacial
strength between epoxy matrix and CFs [10,33]. As shown in Fig. 1d, GO
contains various oxygen-containing functional groups such as epoxide,
hydroxyl and carbonyl groups. Simultaneously, it can be seen from
Fig. 1e that the FTIR result of CFs confirms the presence of oxygenous
functional groups such as hydroxyl, carbonyl and carboxylic on the
surface of CFs. More GO nanosheets will be located at the interfaces
between epoxy matrix and CFs with increasing the GO content, then the
interlocking and bridging effect between epoxy matrix and CFs via GO
will be gradually built [8,18,19].
Fig. S4 a shows the fracture surface of the epoxy matrix without GO.
Roughly, Fig. S4 exhibits the dispersion of GO in the epoxy matrix.
Compared to the pristine epoxy, when the GO content is 0.1 wt% and
0.2 wt% respectively, agglomeration is rarely seen in the epoxy matrix
as shown in Figs. S4b and c. However, the aggregation of GO would take
C.-B. Qu et al.
place as shown in Fig. S4d as the GO content is increased over 0.2 wt%.
At present, in order to better explain the enhancement effect of GO
on the mechanical properties of CFRP composites, Fig. S5 (Supporting
Information) shows the schematic diagram to simulate the dispersion of
GO in epoxy matrix. It can be seen form Fig. S5a that the GO shows an
almost perfect dispersion in the epoxy matrix for the very low GO con­
tent case such as 0.05 wt%. Nonetheless, the enhancement of GO to
epoxy matrix is limited due to the very low content of GO. As shown in
Fig. S5b, as the GO content increases, there would be very small GO
aggregates, the dispersion of GO with 0.1 wt% in epoxy matrix is still
excellent. As the GO content increases further and reaches 0.2 wt%
(Fig. S5c), there would be a few small GO aggregates but the introduc­
tion of GO achieves the best degree in the enhancing efficiency due to its
relatively high GO content. However, at the 0.5 wt% GO content
(Fig. S5d), different sizes of GO aggregates would appear in the epoxy
matrix [16], the effect of GO aggregation would exert a deteriorated
effect on the mechanical properties of CF/epoxy composites. The
micro-sized cracks might easily initiate at the GO aggregate sites and
propagated throughout the epoxy matrix. Consequently, the flexural
strength of CFRP composite would be lowered by the addition of GO at
the high GO concentrations. Therefore, only a small amount of 0.2 wt%
of GO is needed to optimize the flexural properties of CF/GO-modified
EP composites.
Also, Fig. 2e and f exhibit that the flexural modulus of CF/GO-
modified EP composites with various GO contents is higher (9.6% at
RT and 7.1% at 77 K at 0.2 wt% GO) than that of CF/EP composites
without GO both at RT and 77 K, which may be attributed to the
improvement of epoxy matrix modulus after adding GO. It has been
widely reported that the Young’s modulus of epoxy composites increases
with the increase of GO content in the composites because GO has a
much higher Young’s modulus than the epoxy matrix [10,16]. As the GO
content increases over 0.2 wt%, the viscosity of GO/epoxy blending
would be dramatically increased and GO aggregates would appear in the
epoxy matrix. As a result, CFs might not be fully impregnated by the
GO/epoxy blend. This would bring about the reduction of the modulus
of CF/GO-modified EP composite when the GO content is over 0.2 wt%
and such as reaches 0.5 wt%. The above results are in agreement with
the previous studies conducted at RT [10,19]. Yet, the flexural proper­
ties of CF/GO-modified EP composites at 77 K are greater than those of
CF/GO-modified EP composites at RT. The mechanisms of the
enhancement phenomenon will be explained later.
Furthermore, Fig. 2c–f reveals that the flexural strength and modulus
at 77 K are consistently greater than those at RT for the samples with the
same compositions. These are several reasons for the observation. First,
the mechanical strength and modulus of the unmodified or modified
epoxy matrix will be increased as the temperature decreases from RT to
77 K [16]. It is due to the fact that the molecules of epoxy will shrink to
get shorter and accumulate more tightly, and then the binding forces
between molecules become larger at 77 K [16]. Moreover, the thermal
shrinkage of the epoxy matrix will increase the clamping stress of matrix
to GO because of the different thermal expansion directions of epoxy
matrix and GO as the temperature decreases from RT to 77 K. Therefore,
a bigger load will be needed to break the epoxy matrix at 77 K compared
to at RT. Consequently, the strength of epoxy matrix will be higher at
cryogenic temperature than at RT, and epoxy matrix would bring about
a higher contribution to the mechanical properties of CFRP composites.
Secondly, the modulus of epoxy matrix modified with GO would be
greater at 77 K than at RT [16]. Lastly, as the temperature decreases
from RT to 77 K, the thermal shrinkage of epoxy matrix would grip the
CFs and GO tightly. Moreover, the relatively strong interfacial bonding
at cryogenic temperature leads to a great stress transfer from epoxy
matrix to GO and CFs, and the interlocking and bridging effect provided
by GO between matrix and CFs become more effective due to the
additional interfacial bonding from the thermal effect [18]. Thus, the
flexural properties CFRP composites would bear a large load before
break failure at 77 K than at RT. Consequently, the CFRP composite
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Composites Communications 22 (2020) 100480
flexural properties at 77 K would be higher than those at RT [33].
Interlaminar shear strength (ILSS), which depends on the interfacial
interaction of epoxy matrix and CFs, is one of the most important me­
chanical parameters for CFRP composites. In order to further confirm
the enhancing effect of GO on the interfacial performance, we investi­
gated the ILSS of CFRP composites at both RT and 77 K. As shown in
Fig. 3, it is clearly verified that the ILSS of CFPR composites initially
increases with the GO content and reaches the maximum at the 0.2 wt%
GO content at both RT and 77 K, corresponding to an increase of
~17.6% and 8.7% respectively. The above results imply that the addi­
tion of GO to the epoxy matrix makes the interface stronger and results
in a better load transfer from the matrix to the CFs due to the hydrogen
bonds that are formed between GO, epoxy matrix and CFs [33].
Afterwards, the ILSS of CF/GO-modified EP decreases when the GO
content exceeds 0.2 wt%. The decrease of the composite ILSS should be
attributed to two aspects. On the one hand, as shown in Fig. S5, the
excessive GO would aggregate in the epoxy matrix to form stress con­
centration sites reducing the mechanical properties of epoxy matrix. On
the other hand, a significant amount of GO would react with the hard­
ener resulting in weakness in bonding between epoxy and DETDA
molecules. Cross-linking extent between epoxy matrix and hardener
would then weaken the interfacial interaction between epoxy, GO and
CF [19]. However, the ILSS of CFRP composites at 77 K is higher than
that at RT due to the formation of enhanced interface bonding between
matrix and CFs as the temperature drops from RT to 77 K.
It is well known that GO has the opposite coefficient of expansion as
epoxy matrix at 77 K, and the interfacial bonding between epoxy matrix
and CFs is enhanced at cryogenic temperature because a larger clamping
force from the shrinkage of matrix to CFs via expanded GO. Then the
enhanced interfacial adhesion improves the efficiency of stress transfer
from epoxy matrix to CFs, allowing the CF/GO-modified EP composites
to bear a higher applied load, and thereby increases the ILSS of CFRP
composites. It is worth noting that the change trend of flexural proper­
ties of CF/GO-modified EP composites is basically the same as that of
ILSS with the various GO contents at both RT and 77 K.
3.3. Micrographs of fracture surfaces
In order to further understand the role of GO dispersed in epoxy
matrix in enhancing the mechanical properties at cryogenic temperature
of CFRP composites, the three-point bending fracture surfaces of the
composites at 77 K are investigated using SEM and compared with those
at RT as shown in Fig. 4. It can be seen from Fig. 4a that the broken CFs
has smooth and clean surface and debonding failures obviously occur at
the interface between CF and epoxy matrix, indicating that the interfa­
cial adhesion is relatively weak for the CF/EP composites without the
additional of GO at RT [20]. Fig. 4b–e shows the fracture surfaces of
CF/GO-modified EP composites with various contents of GO at RT. For
those composites, the failure surface of CF becomes much rougher with
the increase GO content and even a big amount of epoxy matrix adheres
on the surface of broken CF compares with that of CF/EP composites.
This is possibly attributed to mechanical interlock and the chemical
bond between GO, CFs and epoxy matrix.
Actually, the surface roughness of CFs is playing important role in
improvement of mechanical properties of CFRP composites. Then the
above phenomenon implies that the interfacial adhesion is relatively
strong for the presence of GO and the efficiency of stress transfer form
matrix to CF is enhanced. Especially, for the CF/0.2 GO-modified EP
composites, more epoxy matrix attached to the surface of broken CF as
shown in Fig. 4d. Finally there will be a better load transfer form epoxy
matrix to CFs, leading to a transition in failure mode from interface
debonding to interface debonding and matrix failure simultaneously as
indicated by their load-displacement curves at RT (see Fig. 2a). How­
ever, at the 0.5 wt% GO content, the surfaces of the broken CFs with
both smooth and epoxy matrix-attached are observed in Fig. 4e, and it
becomes relatively smoother compared with that of the CF/0.2 GO-
C.-B. Qu et al. Composites Communications 22 (2020) 100480

Fig. 3. Effect of the GO content on the ILSS of the CF/GO-modified EP composites: (a) 300 K, (b) 77 K.

Fig. 4. SEM images of three-point bending failure surfaces of (a) CF/EP composite at RT, (b) CF/0.05 GO-modified EP composite at RT, (c) CF/0.1 GO-modified EP
composite at RT, (d) CF/0.2 GO-modified EP composite at RT, (e) CF/0.5 GO-modified EP composite at RT, (f) CF/EP composite at 77 K, (g) CF/0.2 GO-modified EP
composite at 77 K, (h) CF/0.5 GO-modified EP composite at 77 K.

7
C.-B. Qu et al.
modified EP composites. This shows that the CF/epoxy interfacial
adhesion is the optimal for the 0.2 wt% GO added to epoxy matrix while
a further increase in the GO content to 0.5 wt% will lead to a reduce
interfacial adhesion strength but it is still greater than CF/EP compos­
ites. The reasons are the excess GO agglomeration occurring in epoxy
matrix and the surface of CFs meanwhile the possible reaction between
GO and hardener reduces the cross-linking density in matrix at the 0.5
wt% content, leading to a reduced interfacial adhesion [10,18,19].
These observations in the three-point bending fracture surfaces of CFRP
composites with different GO contents are consistent with the result for
the CFRP flexural properties and ILSS at RT.
To better understand the role of GO modification epoxy matrix at 77
K in enhancing the mechanical properties of the CFRP composites, the
flexural testing fracture surfaces of the composites are investigated by
SEM as shown in Fig. 5. It can be seen from Fig. 5a that the surface of CFs
is relatively clean and little epoxy matrix is attached on CFs, indicating
that the interfacial adhesion between CFs and matrix is considerably
weak, and then the debonding would occur easily at the interface.
Fig. 5b–f shows the delaminating surfaces of CF/GO-modified EP com­
posites with different GO contents. It is obviously observed that the
fracture surfaces of epoxy matrix become much rougher and much more
epoxy matrix is adhered on the surfaces of CFs in CF/GO-modified EP
composites after the addition of GO, indicating that the interface
interaction between epoxy matrix and CFs becomes stronger via GO.
This phenomenon implies the failure modes of CF/GO-modified EP
composites transfer from interface debonding to epoxy matrix failure
especially at 77 K.
At 77 K, the contracted epoxy matrix will increase the clamping force
to GO and CFs as the temperature decreases from RT to 77 K, leading to a
stronger interface adhesion between GO, CFs and epoxy matrix. As a
result, the enhanced interfacial region held epoxy matrix and CFs
Fig. 5. SEM images of three-point bending delaminating area of (a) CF/EP composite, (b) CF/0.05 GO-modified EP composite, (c) CF/0.1 GO-modified EP composite,
(d) CF/0.2 GO-modified EP composite, (e) CF/0.35 GO-modified EP composite, (f) CF/0.5 GO-modified EP composite at 77 K.
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Composites Communications 22 (2020) 100480
together, which is responsible for the transition in failure mode from
interfacial debonding to epoxy matrix failure [41]. At the 0.5 wt% GO
content, the micrograph of Fig. 5f shows that although a big amount of
epoxy matrix is adhered on the surfaces of CFs, there are many matrix
clusters on the fracture surface due to the aggregation of excessive GO in
the epoxy matrix. The agglomeration of redundant GO may lead to stress
concentration that initiates more micro-cracks, thus resulting in the
decrease of stress transfer efficiency from epoxy matrix to CFs [42].
So as to give an explanation for the differences of the mechanical
properties at RT and 77 K with the addition GO for the CFRP composites,
the fracture surfaces of CF/EP composites, CF/0.2 GO-modified EP
composites and CF/0.5 GO-modified EP composites at 77 K are given in
Fig. 4f –h, respectively. It can be seen from the high magnification SEM
micrographs for the fracture surfaces of CF/GO-modified EP composites
at 77 K that the surface roughness of broken CFs also changes with the
increase of GO content and is the roughest when GO is 0.2 wt%. In
addition, it is clearly observed that the fracture surfaces of CF/GO-
modified EP composites at 77 K become relatively rougher compared
to the RT case. This is due to the fact that the thermal shrinkage of the
epoxy matrix will increase the clamping force of the matrix to GO and
CFs as the temperature decreases from RT to 77 K, leading to a relatively
strong interfacial adhesion of GO, epoxy matrix and CFs. Thus, the
greater interfacial bonding at 77 K leads to a better stress transfer from
matrix to CFs and GO.
As a result, the mechanical properties of CF/GO-modified EP com­
posites at 77 K are consistently higher than those at RT. On the other
hand, the epoxy matrix will shrink and the binding force will increase as
the temperature decreases from RT to 77 K. The above changes would
bring about a higher strength of the matrix at 77 K than RT, making a
higher contribution to the CFRP composite strength. Better load transfer
efficiency from epoxy matrix to CFs and higher strength of matrix,
C.-B. Qu et al.
leading to a transition in failure mode from the interface of CF/epoxy
destroyed to matrix failure at 77 K. Consequently, due to the enhance­
ment of interface and matrix strength, more fibers would appear to
fracture simultaneously at 77 K, improving the mechanical properties of
CF/GO-modified EP composites.
4. Conclusions
In summary, the unidirectional CF/EP and CF/GO-modified EP
composites have been prepared and their RT and cryogenic mechanical
properties have been studied. The results show that the introduction of
0.2 wt% GO content led to the highest flexural strength, flexural
modulus and ILSS at RT with an enhancement of 6.4%, 9.6% and 17.6%,
and at 77 K with an enhancement of 4.9%, 7.1% and 8.7% compared to
the neat epoxy matrix case, respectively. Micrographic examinations
showed that the introduction of GO resulted in the clearly enhanced
carbon fiber/epoxy interfacial adhesion. Moreover, the CF/epoxy
interface adhesion at 77 K is obviously stronger than that at RT.
Consequently, the introduction of GO into epoxy matrix could greatly
enhance the cryogenic flexural and interlaminar shear properties of
CFRP composites at 77 K, which is beneficial for the successful appli­
cations of CFRP composites in cryogenic environments.
Credit author statement
Cheng-Bing Qu: Investigation, Methodology, Conceptualization,
Writing-original draft. Yong Huang: Supervision. Fei Li: Methodology,
Funding acquisition. Hong-Mei Xiao: Methodology. Yu Liu: Formal
analysis. Qing-Ping Feng: Resources. Gui-Wen Huang: Investigation. Na
Li: Resources. Shao-Yun Fu：Conceptualization, Supervision, Writing-
review & editing.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
This work is financially supported by National Natural Science
Foundation of China (Nos. U1837204 and 11802307). Authors are
highly grateful to Mr. Fan-Ming Zhao for Mechanical Testing.
Appendix A. Supplementary data
Supplementary data related to this article can be found at https://do
i.org/10.1016/j.coco.2020.100480.
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