Composites: Part A 87 (2016) 19

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Composites: Part A
journal homepage: www.elsevier.com/locate/compositesa

Multiscale graphene oxidecarbon fiber reinforcements for advanced

polyurethane composites
Shuai Jiang a,b, Qifeng Li a,, Junwei Wang a, Zhenglong He a, Yuhua Zhao a, Maoqing Kang a
a
Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
b
University of Chinese Academy of Sciences, Beijing 100049, China

a r t i c l e i n f o a b s t r a c t

Article history: Multiscale graphene oxide/carbon fiber (GO/CF) reinforcements were developed for polyurethane (PU)
Received 19 February 2016 elastomer composites. GO was first coated on CF surface by electrophoretic deposition (EPD), aiming
Received in revised form 5 April 2016 to improve the CF/PU interfacial adhesion. The EPD process improved the mechanical anchoring and
Accepted 6 April 2016
chemical interaction between CFs and PU through increased surface roughness and oxygen content of
Available online 8 April 2016
CFs, thereby improved the CF/PU interfacial shear strength. The fibers were then mechanically mixed
with GO to achieve a multiscale reinforcement. The strengthening of the matrix, especially the local stiff-
Keywords:
ening of fiber/matrix interphase, is beneficial for the interfacial mechanical anchoring. The multiscale
A. Carbon fibers
A. Graphene
reinforcement resulted in an improvement of 46.4% in the tensile strength of PU elastomer. Compared
A. Polymer-matrix composites (PMCs) with untreated-CF/PU, individual process of EPD treatment and mechanical mixing of GO resulted in
B. Mechanical properties an improvement of 16.9% and 13.9% of the strength, respectively. The enhanced reinforcing performance
of GO-deposited CFs was attributed to the improved fibermatrix interfacial adhesion.
2016 Elsevier Ltd. All rights reserved.

1. Introduction functional composites based on a polymer matrix, mechanical

Carbon fiber reinforced polymer (CFRP) composites attracted
both academic and industrial interest due to their unique
attributes: light-weight and high-strength. CFRP materials are
displacing traditional metallic materials in a wide range of
high-performance structural applications, such as aerospace and
automotive industries [1,2]. CF/epoxy resin as a common CFRP
composite system appeared in most studies [3]. Rare attention
was paid to polyurethane (PU), which represents one of the most
rapidly developing branches in polymer industry [4]. PU elas-
tomers, with distinguished elasticity, toughness and wear resis-
tance, play an increasingly important role in the fields of
structure and wear-resistant materials [4,5]. However, pure PU
elastomers possess a low stiffness and poor heat-resistance, which
severely limit their advanced applications [6]. CFs were proved to
be effective fillers for improving the thermal and mechanical prop-
erties of PU materials [57].
It is generally accepted that mechanical properties of CFRP com-
posites depend directly on the properties of their individual con-
stituents as well as the interaction degree between the
reinforcements and polymer matrix [8,9]. In structural or
Corresponding author.
E-mail address: liqf@sxicc.ac.cn (Q. Li).
damage in the polymer matrix or debonding at the matrix-filler
interface is usually responsible for the decrease in intended prop-
erties [10]. A good fibermatrix interface offers effective load
transfer from the polymer to the reinforcement, which is essential
to reduce the stress concentrations and improve the bulk mechan-
ical performance [2]. However, the poor interfacial adhesion
between CFs and PU, caused intrinsically by the chemically inert
surface of CFs, limits the mechanical and thermal performance of
PU composites.
Therefore, we present here the design of multiscale reinforce-
ments for PU composites, which aims to improve simultaneously
(i) the mechanical strength of PU matrix by dispersing nanofillers
throughout the matrix and (ii) the fibermatrix interfacial adhe-
sion by modifying nanofillers onto primary reinforcing fibers.
Graphene oxide (GO) was selected as the nanofiller here due to
its unique properties. Graphene, one-atom-thick two-dimensional
planar sheet of sp2 bonded carbon atoms that are densely packed
in a honeycomb crystal lattice, is regarded as the thinnest mate-
rial in the universe and predicted to have a variety of unique prop-
erties, such as high thermal conductivity, extraordinary electronic
transport property and superior mechanical properties [11,12].
These intrinsic properties make graphene promising for a wide
range of frontier applications including thermally and electrically
conducting nanocomposites, electronic circuits, sensors as well as

http://dx.doi.org/10.1016/j.compositesa.2016.04.004
1359-835X/ 2016 Elsevier Ltd. All rights reserved.
2 S. Jiang et al. / Composites: Part A 87 (2016) 19
transparent and flexible electrodes for displays and solar cells
[1215]. However, pristine graphene is usually incompatible with
polymer matrix due to its chemical inertness. GO sheets are heav-
ily oxygenated graphene which bears hydroxyl, epoxide, diols,
ketones and carboxyl groups, thereby exhibiting better compatibil-
ity with polymer matrix [12]. Incorporation of nanofillers that are
compatible with the polymer matrix could effectively improve the
mechanical properties of CFRP composites [1618].
Chemical grafting [19], electrophoretic deposition (EPD)
[2022] and nanocomposite sizing [23] have been reported to be
effective techniques for attaching GO sheets onto CFs to obtain a
hierarchical fibrous reinforcement. EPD represents an effective
and versatile approach for the deposition of nanomaterials on CF
surface. Moreover, online EPD process allows a continuous deposi-
tion which is compatible with CF production process. A subsequent
thermal annealing process could afford a stable binding of GO on
CF surface [20]. Recently, Huang et al. reported the deposition of
GO thin film on CF surface by ultrasonically assisted EPD process.
Such GO-deposited CFs exhibited a significant increase in surface
roughness in comparison with the bare CFs, which leads to an
improvement in the interfacial shear strength (IFSS) between CFs
and resin matrix through enhanced mechanical interlocking [20].
Similarly, grafting CNTs onto fiber surface was also found to
enhance the interfacial strength via increased chemical bonding,
mechanical interlocking and/or local stiffening of the polymer
chains at the fiber/matrix interface, all of which are beneficial to
improve the stress transfer efficiency [24].
In this study, multiscale GO/CF reinforcements were developed
for a simultaneous strengthening of the PU matrix as well as the
CF/PU interface. GO sheets were first modified on CF surface by
EPD. The fibers were then mixed with GO sheets in PU matrix. In
the designed system, CFs serve as a structure reinforcement and
GO sheets distribute uniformly to reinforce the PU matrix, thereby
achieving a multiscale reinforcement. The effect of EPD treatment
on the surface morphology and chemical composition of CFs, as
well as the CF/PU interfacial shear strength were investigated.
The performance of GO/CF multiscale reinforcements on the
mechanical properties of PU elastomer was studied. To further
investigate the respective contribution of EPD and mechanical
mixing of GO to the final reinforcing performance of multiscale
reinforcements, composites adopting individual EPD or mechanical
mixing were prepared and their mechanical properties were
compared. The reinforcing mechanism was explored based on the
surface morphology, roughness, and chemical composition of CFs,
the CF/PU interfacial shear strength, the mechanical properties of
CF/PU composites, and the surface morphology of the fractured
CF/PU specimens for mechanical test.
2. Experimental section
2.1. Materials
CFs used in this study were PAN-based epoxy resin-sized T300
(3000 single filaments per tow, nominal diameter is 7 lm, tensile
strength is 3.53 GPa) supplied by Toray Industries, Inc. 3 mm short
CFs were obtained by cutting continuous T300 CFs technically sup-
ported by Zhonglibangye Co. Ltd. China. Graphene oxide, prepared
according to Ref. [25], was kindly supplied by Chengmeng Chens
group, Institute of Coal Chemistry, Chinese Academy of Sciences,
Taiyuan, China. 4,40 -diphenylmethane diisocyanate (WANNATE -
MDI-100, purity P 99.6%, chromaticity (PtCo) 6 30, hydrolyzed
chlorine percent (%) 6 0.005, cyclohexane insoluble (%) 6 0.3)
was supplied by Wanhua Chemical Group Co. Ltd. China. Polyethy-
lene propylene glycol adipate (ODX-218, Mw = 2000, hydroxyl
value: 53.5058.50, acid value 6 0.5, melting point: 3545 C,
moisture (%) < 0.03, chromatic number 6 50) was supplied by
Huada Chemical Group Co. Ltd. China. 1, 4-Butylene glycol (BDO,
P99.9%) was purchased from BASF Co. Germany. All the other
chemicals (analytical grade) were purchased from Tianli Chemical
Reagent Co. Ltd. China and used as received.
2.2. Desizing of CFs
As-received epoxy resin-sized T300 CFs were desized by ace-
tone in a Soxhlet extractor at 75 C for 24 h, followed by vacuum
drying at 60 C for 8 h, obtaining desized CFs. All the CFs used after-
wards in this study are desized CFs if not specified.
2.3. Electrophoretic deposition of GO on the surface of CFs
An online EPD setup was established based on a CF bundle as
the positive electrode, a graphite cathode plate as well as a pH
10.0 aqueous solution as the media prepared by adding 0.1 M
sodium hydroxide solution to pH 7.0 phosphate buffer solution.
Typical concentration of GO aqueous dispersion was 0.25 g/L. The
voltage used here was 0 V (control sample) and 3 V. The resulting
samples of GO-deposited CFs were then denoted as CFGO-0 and
CFGO-3, respectively. During the EPD process, bubbling was
observed at both the working and counter electrodes due to the
electrolysis of water. Therefore sonication was used to immedi-
ately remove the newly-formed bubbles in order to avoid the
trapped gas pockets that may impede the deposition [20].
Afterwards, GO-deposited CFs were annealed at 150 C for 1 h to
improve the weak interaction between GO and CFs [20]. The online
EPD and annealing system is inspired by Ref. [16] and schemati-
cally illustrated in Fig. 1.
2.4. Preparation of CF/PU composites
In this study, CF/PU composites were prepared through a pre-
polymerization method. MDI and ODX-218 were used as hard seg-
ments and soft segments, respectively. First, 160.0 g of ODX-218
was vacuum dehydrated at 120 C for 3 h to remove the traces of
moisture. Then, calculated amount of carbonaceous fillers (1 wt%
CFs and/or 0.1, 0.2 or 0.3 wt% GO) were added to ODX-218 with
stirring in a three-neck round-bottom flask. In the case of mechan-
ical mixing GO and CFs in PU matrix, GO sheets were first added
into ODX-218 under stirring at 500 rpm to achieve a uniform dis-
tribution followed by adding chopped CFs. Afterwards, excessive
MDI (76.3 g) was added in GO/ODX-218 dispersion and the content
of free NCO groups after pre-polymerization was set at 8%.
Reaction was maintained at 80 C for 120 min. Afterwards, air bub-
bles were removed from pre-polymers with a vacuum pump for
30 min. The chain extension reaction was carried out by fast stir-
ring for 2 min after adding 19.2 g of chain extender BDO into
pre-polymers. Then, 100.0 g of chain-extended pre-polymer was
press vulcanized in a steel picture-frame mold at 120 C for 1 h
at a pressure of 10 MPa, followed by oven curing at 120 C for
24 h and further curing at room temperature for 24 h. The dimen-
sion of the resulting CF/PU composites is 18 cm 18 cm 2 mm.
The schematic illustration of the distribution of carbonaceous
fillers in PU composites was shown in Fig. 2.
2.5. Analysis and characterization techniques
X-ray photoelectron spectroscopy analysis (XPS, AXIS ULTRA
DLD, Japan) was used to characterize the chemical composition
and elemental distribution of CF surface. A monochromatic Al Ka
X-ray source which provides photons with energy of 1486.6 eV
was used. Scanning electron microscopy (SEM, JSM-7001F) was
used to characterize the morphology of CFs and GO sheets. For
 S. Jiang et al. / Composites: Part A 87 (2016) 19
Fig. 1. Online electrophoretic deposition and annealing system for the coating of GO on the surface of CFs. (For interpretation of the references to colour in this figure legend,
the reader is referred to the web version of this article.)
Fig. 2. Schematic illustration of the construction of multiscale GO/CF reinforce-
ments for advanced PU composites. (For interpretation of the references to colour in
this figure legend, the reader is referred to the web version of this article.)
the characterization of the fracture surface of tensile test speci-
mens of PU composites, scanning electron microscopy (2800B,
KYKY) was used. Test samples were first coated with gold layer
by spraying before measurement to improve the resolution for
SEM observation. The microstructure of GO sheets was character-
ized by using transmission electron microscope (TEM, JEM-2010).
Interfacial shear strength (IFSS) between CFs and PU matrix was
examined by single fiber micro-debond test (Tohei Sayon Corpora-
tion, Japan), which was performed by pulling a fiber out from the
cured PU resin droplets with a loading rate of 0.5 lm/s. The values
of IFSS were calculated according to Eq. (1),
F max
IFSS
p  df  le
where Fmax is the maximum load recorded, df is CF diameter, and le
is the embedded length [26]. Mechanical properties of CF/PU com-
posite materials, e.g. tensile strength, Youngs modulus and tear
strength, were tested at ambient temperature by using an Electron
3
Omnipotence Experiment Machine (SANS-CMT6503, Shenzhen Sans
Testing Machine Co., China) at a crosshead speed of 250 mm/min.
Tensile strength and Youngs modulus of PU composites were tested
by using dumbbell specimens according to standard GB/T528-1998.
Tear strength (Ts) was tested by using Die C specimens according to
standard GB/T529-1999 and calculated according to Eq. (2),
F max
Ts 2
d
where Fmax is the maximum load recorded and d is the thickness of
CF/PU specimens. The detailed shape and size of the specimens for
above mechanical tests are given in Fig. S1. Average results of three
measurements were reported here. To determine the content of free
NCO in the pre-polymers, a method of back titration was used.
Firstly, 20 mL toluene was added in an Erlenmeyer flask which con-
tained 3 g of pre-polymers. After the pre-polymer dissolved, 10 mL
of di-n-butylamine/toluene solution with known concentration was
added and stirred for 20 min. Then 50 mL of isopropanol was added
in the solution followed by adding 35 droplets of 1 wt% bromophe-
nol blue solution. A calibrated HCl solution with concentration
around 0.5 mol L1 was used to titrate the excessive di-n-
butylamine until the color of solution changed from blue to yellow.
Then the -NCO content was defined as follows:
V o  V s  C HCl  4:2
NCO% 3
mprepolymer
where the Vs is the volume of HCl solution used for titration and V0
is a blank volume that was used for titrating the di-n-butylamine
without adding pre-polymers. CHCl and mprepolymer represent the
concentration of HCl solution and the weight of pre-polymer,
respectively.
3. Results and discussion
3.1. Surface chemical elemental composition of GO and CFs
XPS was used to characterize the elemental compositions of GO
1
and CF surface. The wide-scan XPS spectra of GO, CFs, CFGO-0 and
CFGO-3 are given in Fig. 3. The peaks at around 284.6, 532.2 and
399.5 eV are attributed to C1s, O1s and N1s, respectively. The cor-
responding element contents are listed in Table 1. The surfaces of
GO and CFs are mainly composed of carbon and oxygen, only a
small amount of nitrogen exists on CF surface. To further
4 S. Jiang et al. / Composites: Part A 87 (2016) 19
Fig. 3. XPS overall spectra of GO sheets and the surface of CFs before and after electrophoretic deposition of GO sheets. (For interpretation of the references to colour in this
figure legend, the reader is referred to the web version of this article.)
Table 1
Summary of element composition of GO and CF surface.
Samples Surface elements abundance (%)
C O N and 103.18%, respectively. An increase of oxygen content on CF
GO 63.71 36.29
CFs 90.50 6.80 2.70
CFGO-0 84.08 13.81 2.11
CFGO-3 72.33 25.96 1.71
investigate the distribution of functional groups on GO and CF sur-
face, the XPS C1s spectra was fitted into six peak components with
binding energies at around 284.6, 285.0, 286.1, 288.2, 289.4 and
290.6 eV (see Fig. 4), which are attributed to Cg sp2, Cd sp3,
CAO, C@O, C(O)O and pp, respectively [27]. In the case of CFs,
another component of CAOAC@O at 286.6 eV was fitted to inves-
tigate the desizing efficiency of Soxhlet extraction.
In the case of GO, a high content of oxygen (36.29 wt%) was
detected on GO sheets. Oxygen-containing species were
introduced onto GO surface during its preparation process [28].
Graphite oxide was synthesized from natural graphite powders
by a modified Hummers method [29], during which oxygen-
containing functional groups formed on the edge and defects of
GO sheets (see Fig. 4A). The CAO components mainly originate
from epoxy and hydroxyl groups in the basal plane of GO sheets.
The C@O bonds are mainly from the single ketones which decorate
on the edges of GO sheets [30]. C@O bonds may also be bound to
the basal plane as carbonyl groups [31,32]. The C(O)O [31,33,34]
and the quinone species [35] are present primarily at the edges
of GO sheets.
In the case of desized-CFs, a content of 6.80 wt% oxygen was
detected on CF surface. The percentage of epoxy group (CAOAC@O,
286.6 eV, see Fig. 4B) is 2.62%, indicating that epoxy sizing [36] of
CFs was effectively removed by acetone extraction in comparison
with that of 21.82% before desizing as we have reported before
[5]. Meanwhile, the components at 286.1 eV (CAO), 288.2 eV
(C@O) and 289.4 eV (C(O)O) revealed the existence of oxygen-
containing functional groups on CF surface. These polar groups
originated from the electrochemical oxidation treatment during
the fabrication of CFs.
After EPD of GO sheets, oxygen content of CF surface was dra-
matically increased from 6.80% of CFs to 25.96% of CFGO-3. The
increase of oxygen content was due to the deposition of highly
oxygenated GO sheets. Correspondingly, the content of CAO,
O/C C@O and C(O)O components got an increase of 73.84%, 23.63%
surface without applying voltage was also observed. The increased
0.5696
0.0751
oxygen content on CFGO-0 was due to the adsorption of dispersed
0.1643 GO sheets. A co-proof was provided by SEM and AFM characteriza-
0.3589 tion, in which a small amount of GO was found depositing on CF
surface (see Fig. 5b1-3).
3.2. Surface morphology and roughness of carbon fibers
SEM and AFM were used to study the surface morphology and
quantified surface roughness of CFs before and after EPD treat-
ment. Desized CF surface is relatively neat with a few narrow
grooves parallel to the longitudinal direction of CFs (see Fig. 5a1).
These grooves, originating from the producing process of T300
CFs, resulted in an average roughness of 14.6 nm on CF surface
(see Fig. 5a2). The high roughness provides extra contact points
for the mechanical interlocking and chemical interaction between
CFs and PU matrix. The grooves on the surface of T300 were also
reported to be beneficial for catching the nanotubes [36].
For the fibers CFGO-0, the roughness of CF surface was
increased to 21.4 nm due to the adsorption of GO sheets (see
Fig. 5b2). The SEM and TEM micrographs of GO sheets are shown
in Fig. S2. In the case of CFGO-3, negatively charged GO sheets
migrated toward the positive CF electrode and subsequently
deposited on the fiber surface from an aqueous GO dispersion
(see Fig. 1). Most of deposited GO sheets were found uniformly
coated on CF surface which can be identified by the AFM images
(see Fig. 5c2). The deposition of GO sheets resulted in an increase
of the surface roughness to 30.3 nm. A small fraction of thick GO
sheets with multiple layers deposited loosely on CF surface due
to their high rigidity (see Fig. 5c1). Through a subsequent anneal-
ing process, a covalent binding between the deposited GO layers
as well as between GO sheets and CFs can be achieved [20]. The
deposition of GO is beneficial to repair graphite sheet defects on
CFs and locally stiffen the polymer chains at fiber/matrix interface
thereby enhancing the mechanical interlocking and improving the
stress transfer [36]. A content of 0.9 wt% GO was found depositing
on CF surface by comparing the weights of desized-CFs and CFGO-3
with the length of 2 m.
 S. Jiang et al. / Composites: Part A 87 (2016) 19 5

Fig. 4. C1s XPS fine scan spectra of (A) GO, (B) CFs, (C) CFGO-0 and (D) CFGO-3. (For interpretation of the references to colour in this figure legend, the reader is referred to the
web version of this article.)

Fig. 5. Surface morphology and roughness of (a) CF, (b) CFGO-0 and (c) CFGO-3; (a1c1): SEM; (a2c2): AFM. (For interpretation of the references to colour in this figure
legend, the reader is referred to the web version of this article.)
6 S. Jiang et al. / Composites: Part A 87 (2016) 19

and the covalent bonding between the GO-deposited CFs and PU

matrix are responsible for the improvement of IFSS. The IFSS result
achieved in this study is comparable with previous reports for the
modification of CF surface with carbon nanomaterials. For exam-
ple, Zhang et al. [23] reported that the IFSS of the CF/epoxy com-
posites was increased by 36.3% through grafting GO on CF
surface. Huang et al. [20] adopted a EPD and thermal annealing
process to coat GO sheets on CFs. The EPD treatment increased
the IFSS between CFs and epoxy by 70%. Guo et al. [37] reported
a ultrasonically assisted EPD for the deposition of CNTs on CF sur-
face. The deposition of CNTs improved the CF/epoxy IFSS by 68.8%.

3.4. Mechanical properties and fracture surface morphology of GO/PU

composites

Fig. 6. Interfacial shear strength between CFs and PU matrix before and after the
electrophoretic deposition of GO on CFs. (For interpretation of the references to
colour in this figure legend, the reader is referred to the web version of this article.)
3.3. Interfacial shear strength (IFSS) between CFs and PU matrix
Single fiber micro-debond test was performed to evaluate the
interfacial shear strength between CFs and PU matrix. Compared
with the desized-CFs, the IFSS of CFGO-0 got an improvement of
14.9% to 22.10 MPa (see Fig. 6). The increase of IFSS was mainly
due to the adsorption of GO sheets on CF surface. In the case of
CFGO-3, the EPD of GO on CF surface improved the IFSS to
33.54 MPa with an improvement of 74.4%. Both the enhanced
mechanical interlocking due to the increased surface roughness
In the first step, the reinforcing effect of GO sheets on the
mechanical properties of PU elastomer was studied. Pure PU elas-
tomer exhibited a tensile strength of 42.37 MPa. The strength was
improved to 49.31 MPa by introducing 0.1 wt% GO sheets into the
material, with an improvement of 16.4%. The polar oxygen-
containing groups on the highly oxygenated GO sheets are benefi-
cial to improve the interfacial adhesion between GO and PU,
thereby promote load transfer from matrix to the reinforcement.
When 0.2 wt% of GO was incorporated, the tensile strength of PU
composites was improved from 49.31 to 51.07 MPa with another
improvement of 4.2%. However, the tensile strength of PU compos-
ites dropped to 40.74 MPa when the GO content was increased to
0.3 wt%. One possible reason for this decline of mechanical
strength can be the insufficient wetting of high content of GO by
PU matrix. Defects could form between these GO sheets and hence

Fig. 7. (a) Tensile strength (b) Youngs modulus and (c) tear strength of PU composites with different contents of GO; (d1g1) SEM micrographs of the fractured surface
morphology of GO/PU specimens for tensile test; (d2g2) high resolution micrographs of (d1g1), defects are pointed out by red arrows in g2. (For interpretation of the
references to colour in this figure legend, the reader is referred to the web version of this article.)
 S. Jiang et al. / Composites: Part A 87 (2016) 19 7

decrease the mechanical properties of the resulting composites.
The Youngs modulus, which defines the relationship between
stress and strain of GO/PU composites, exhibited a similar trend
as the tensile strength with the highest value at the loading
amount of 0.2 wt% GO (see Fig. 7b). Tear strength, also called tear
resistance, reflects the ability of a material can withstand the
effects of tearing. Tear strength of GO/PU was slightly improved
when 0.1 wt% GO was incorporated due to the reinforcing effect
of uniformly distributed GO sheets on the resin matrix. The surface
morphology of fractured specimens for mechanical test was char-
acterized by SEM. As shown in Fig. 7dg, the lamellar morphology
of fracture surface became clearer as the GO content increased.
3.5. Mechanical properties and fracture surface morphology of CF/PU
composites loaded with GO by mechanical mixing
In a second step, the reinforcing effect of GO sheets on the
mechanical properties of CF/PU composites was investigated by
mechanical mixing GO sheets with CFs in PU matrix (see Fig. 8).
Compared with pure PU, composite loaded with 1 wt% CFs exhib-
ited a tensile strength of 50.59 MPa, with an improvement of
19.4%. Through mechanically mixing 0.1 wt% GO in the CF/PU com-
posite, tensile strength of the material got a 16.6% improvement to
57.62 MPa. In this case, a multiscale reinforcement was con-
structed by CFs and GO sheets in the composites, in which CFs
served as the structure reinforcement and GO sheets distributed
uniformly to reinforce the PU matrix. The tensile strength of the
materials started to decrease when the loading amount of GO
was increased to 0.2 wt%. In fact, sufficient wetting of the fillers
are essential for the mechanical properties of the composites. In
the case of mechanical mixing of GO and CFs, there is a competition
between the dispersed CFs and GO sheets upon the wetting by PU
matrix. Insufficient wetting of GO may result in defects, which
deteriorate the resulting composites. Also, the existence of high
content of GO sheets makes it difficult for the uniform distribution
of short CFs. Therefore the decline of mechanical properties started
at a lower loading content of GO when CFs coexist. Similarly,
another decline in tensile strength was observed when 0.3 wt%
GO was loaded.
Youngs modulus of the GO/CF/PU composites was improved as
the content of GO increased from 0 to 0.3 wt%. This increase in the
elastic modulus can be attributed to the increased stiffness of the
materials due to the incorporation of GO sheets. Tear strength of
CF/PU was improved by incorporating GO sheets and the highest
value occurred at 0.2 wt% GO content. When the GO content was
further increased, tear strength of the material started to decrease
possibly due to the insufficient wetting of GO by PU matrix.
3.6. Mechanical properties and fracture surface morphology of PU
composites reinforced with CFs treated by EPD of GO on CF surface
In this part, the effect of EPD of GO on CF surface on the
mechanical properties of CF/PU composites was investigated. For
the desized-CF/PU, de-bonding at fibermatrix interface and holes
at the fractured surface were observed when the fibers were
pulled out from PU matrix during the mechanical tests (see
Fig. 9d). Almost no resin fragments remain on the pulled-out CF
surface, indicative of the poor fibermatrix interfacial adhesion.
Deposition of GO could improve the mechanical properties of PU
composites through enhanced chemical interaction and

Fig. 8. (a) Tensile strength (b) Youngs modulus and (c) tear strength of PU composites mechanically mixed with 1 wt% CFs and different contents of GO; (d1g1) SEM
micrographs of the fractured surface morphology of mechanically mixed GO/CF/PU composites; (d2g2) high resolution micrographs of (d1g1), defects are pointed out by
red arrows in g1. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
8 S. Jiang et al. / Composites: Part A 87 (2016) 19

Fig. 9. (a) Tensile strength (b) Youngs modulus and (c) tear strength of PU composites reinforced by nothing (control), desized-CFs, CFGO-0, CFGO-3 and GO&CFGO-3; (d1
g1) SEM micrographs of the fractured surface morphology of PU composites reinforced by desized-CFs, CFGO-0, CFGO-3 and GO&CFGO-3; (d2g2) high resolution
micrographs of (d1g1). (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

mechanical interlocking at CF/PU interface. CFGO-0, as a control
sample, represents fibers which were immersed in EPD solution
but no voltage applied. GO sheets deposited on the surface of
CFGO-0 by gravity or adsorption (see Fig. 5b2). Compared with
desized-CF composites, tensile strength and tear strength of
CFGO-0/PU composite exhibited an improvement of 6.66% and
11.47%, respectively. CFGO-3 represents the fibers modified with
GO sheets by EPD with 3 V voltage applied. EPD treatment
improved the mechanical properties of the resulting composites,
with an improvement of 16.9% in the tensile strength, 28.1% in
the Youngs modulus, and 23.1% in the tear strength. The improve-
ment of mechanical properties can be attributed to the enhanced
interfacial adhesion of CF/PU composites (Fig. 6) through mechan-
ical anchoring and chemical interaction provided by the increased
surface roughness (Fig. 5 c2) and abundant functional groups from
the deposited GO sheets (Fig. 4D).
In comparison with CF/PU composites, fewer holes were formed
by pulling CFGO-3 out of PU matrix during the mechanical test (see
Fig. 9f). A closer examination of the pulled-out CFGO-3 reveals a
thick layer of matrix resin attached on CF surface, indicating high
degree of interfacial adhesion between the CFGO-3 and PU matrix
(see Fig. 9f2). This observation is consistent with the IFSS results.
The deposition of GO sheets improved the CF/PU interfacial
adhesion due to the increased surface roughness and the increased
content of oxygen-containing groups.
In the final step, the multiscale reinforcement was constructed
by mechanically mixing 0.1 wt% GO sheets with 1 wt% CFGO-3 in
PU matrix thereby achieving a combined enhancement of both
the interfacial adhesion and polymer matrix. Tensile strength
of PU elastomer was effectively improved by the multiscale
reinforcement, with an improvement of 46.4%. Compared with
untreated-CF/PU composites, individual process of EPD or mechan-
ical mixing of GO resulted in an improvement of 16.9% or 13.9% in
the tensile strength of the composites, respectively, indicative of
their respective contribution to the final reinforcing performance
of the multiscale reinforcements. Compared with CF/PU, the
improvement in the tensile strength of GO/CFGO-3/PU is 22.6%,
which is actually less than the sum of the improvements resulted
from both single strategies (30.8%). One possible reason is that
the 3 mm CFs and GO sheets dispersed independently in PU matrix
and resist locally the applied strain. Therefore the mechanical
properties of the composites depend largely on the properties of
PU matrix.
4. Conclusions
In this study, a multiscale reinforcement was constructed for
improving the mechanical properties of PU elastomer. GO sheets
were first modified on CF surface by online EPD to improve the
fibermatrix interfacial interaction. The fibers were then blended
in PU matrix with GO sheets. Therefore, a multiscale reinforcement
was achieved in which CFs served as structure reinforcements and
GO distributed uniformly to reinforce the PU matrix. The multi-
scale reinforcement improved the tensile strength of PU elastomer
by 46.4%. In addition, individual EPD and mechanical mixing of GO
resulted in an improvement of 16.9% and 13.9% of the strength
compared with the CF/PU composites, indicating their respective
contribution to the final reinforcing effect. The presented reinforc-
ing methodology promises to be a practical method to improve
simultaneously the interfacial adhesion and the polymer matrix,
 S. Jiang et al. / Composites: Part A 87 (2016) 19
thereby provide a multiscale reinforcement for the CFRP
composites.
Acknowledgements
The authors gratefully acknowledge financial support from the
Major Science and Technology Project in Shanxi Province (No.
20111101058) and the Joint Foundation of National Natural
Science Foundation of China & China National Petroleum
Corporation (No. U1362107).
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.compositesa.
2016.04.004.
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