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Mechanical reinforcement fibers produced by
gel-spinning of poly-acrylic acid (PAA) and
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Cite this: DOI: 10.1039/c3nr00288h
graphene oxide (GO) composites†
Received 16th January 2013
Zaixing Jiang,ab Qiang Li,b Menglin Chen,b Jingbo Li,a Jun Li,a Yudong Huang,*a
Accepted 28th April 2013
Flemming Besenbacherb and Mingdong Dong*b
DOI: 10.1039/c3nr00288h
www.rsc.org/nanoscale
Graphene oxide (GO) with extraordinary chemical, thermal and
mechanical properties offers possibilities in a variety of applications.
Many materials have been fabricated through physical blending of
GO with other materials, while, the chemical functionalization of GO
has generally been considered challenging. Here, we report the
preparation of a novel GO-functionalized fibrous material in which
individual compliant GO sheets are cross-linked by PAA chains in a
near-vertical fashion. This new fibrous material outperforms many
other common fibers in stiffness and strength. Combined with
straightforward manufacturing methods, the fibers should find
applications in a wide range of areas.
The possibility of making bers from viscous substances (glue
or resins) was predicted as early as the 17th century, but it was
not until 1853 that the Englishman Audemars rst proposed the
formation of threads from a solution of a mixture of ethanol
and ether.1,2 Due to their high tensile strength, high ultimate
elongation, good shape retention, and stability under exposure
to light, bacteria, moisture, chemical agents and heat, chemical
bers have wide applications not only in civilian areas but also
in military elds.3 The physicomechanical and physicochemical
properties of chemically modied bers can be delicately tuned
during the fabrication process by modication of the raw
material, as well as through post modication of the bers.4,5
Recently, using the latest nanomaterials to fabricate bers has
become a hot topic for researchers. Graphene is a two-dimen-
sional single atomic planar sheet of sp2 hybridized carbon
atoms, whose research history can be traced back to 1859. The
term graphene was coined as a combination of graphite and the
suffix -ene by Hanns-Peter Boehm, who described single-layer
a
Department of Polymer Science and Technology, School of Chemical Engineering and
Technology, Harbin Institute of Technology, Harbin 150001, People's Republic of
China. E-mail: huangyd@hit.edu.cn
b
Interdisciplinary Nanoscience Center (iNANO), Aarhus University, DK-8000, Aarhus C,
Denmark. E-mail: dong@inano.au.dk
† Electronic supplementary information (ESI) available. See DOI:
10.1039/c3nr00288h
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carbon foils in 1962.6–8 Interest in graphenes increased
dramatically aer Novoselov and Geim et al. reported on the
unusual electronic properties of single layers of the graphite
lattice.9–11 The world physicists rejoice for the discovery of this
exciting material, because of its amazing physical perfor-
mances, such as extremely high charge mobility (>200 000 cm2
V 1 s 1 for suspended graphene), zero effective mass, ballistic
transport even at room temperature and so on.12–16 Meanwhile,
a huge polyaromatic hydrocarbon sheet is indeed the dream
material to which world chemists aspire.17–19 The successful
preparation of graphene oxide (GO) meets the needs of world
chemists. The preparation of GO is based on the chemical
exfoliation of graphite, which enables GO preparation on a large
scale.20–23 This material not only has a lamellar structure, but
also has a large amount of functional groups on its surface,
such as hydroxyl, epoxide, carbonyl and carboxylic groups.24–26
The high density of oxygen functionalities on the GO sheet
surface makes them highly hydrophilic, so a very stable aqueous
dispersion can be yielded.27,28 But the disadvantage is that many
reactions for hydroxyl and carboxyl groups, such as dehydration
reactions, are limited in the aqueous dispersions.29,30 Thus, it is
a challenge to maintain the homogenous dispersion of GO
sheets and meanwhile to promote the reaction of the functional
groups on the GO surface. Therefore, more and more materials
based on GO have been fabricated, while most of them are
prepared by physical mixing.29,31 Synthesis of the GO polymer
through a chemical reaction has so far been elusive, not to
mention the preparation of GO polymer bers.
Here, we successfully prepare a novel chemical ber material
based on GO sheets with PAA using the esterication reaction.
The method, used for GO based polymer synthesis, is called the
gel-desiccation approach. The acrylic acid (AA) was chosen
because it can not only be polymerized in aqueous solution but
also be used for crosslinking GO by a chemical reaction. In this
approach, the AA and initiator were rst homogenously dis-
solved in GO aqueous solution with the aid of ultrasound. Then
upon polymerization of AA at 60  C, the homogenous GO/
polyacrylic acid (PAA) gel was yielded (Fig. S1†). Lastly, during
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the heat aided spinning process, the bers formed with in situ
cross-linking of GO with PAA by the esterication reaction
between hydroxyl groups of GO and carboxyl groups of PAA. The
schematic diagram of the GO ber crosslinked by PAA (named
as PGO ber) preparation is illustrated in Scheme 1.
The synthesis of the GO based polymer is meaningful not
only for the foundation of graphene oxide chemistry, but also
for the development of graphene chemistry. Furthermore, the
PGO ber yielded also shows excellent mechanical perfor-
mance, which has broad applications in industrial elds, such
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as preparation of special clothing, reinforcement of rubber and
plastic, reinforcement of cement, etc. The yielded PGO bers
were characterized by SEM, XRD, FTIR and XPS. Fig. 1a and b
show the SEM images of the PGO ber (the cross-section of the
ber in Fig. 1b is obtained from brittle failure in nitrogen
liquid). As is seen, the ber appears heart-shaped and the
diameter is about 8 mm. The heart-shape of the ber may relate
to the spinning process and the contraction aer the esteri-
cation reaction. The XRD spectrum of a typical PGO ber
sample demonstrated a peak at 12.4 degree (marked with a ve-
pointed star) which is related to the orientation of graphene
oxide, resulting from drawing of the bers during the spinning
process.32,33 The large-scale of PAA chains leads to the existence
of the amorphous phase in the PGO ber (Fig. 1c). In addition,
the esterication reaction between GO and PAA is conrmed by
the FT-IR spectrum (Fig. 1d). The bands at 3628.3 cm 1 and
1021.2 cm 1 can be assigned to the O–H stretching vibration
and C–O stretching vibration of the hydroxyl group, respec-
tively. The bands at 1632.5 cm 1 and 1136.5 cm 1 are assigned
to the C]O stretching vibration and the C–O–O stretching
vibration of the carboxylate group respectively. The weaker
bands at 1823.1 cm 1 and 1770.6 cm 1 are presumably due to
the C]O stretching vibration of anhydride groups. The weak
bands at 1530.8 cm 1 and 1454.1 cm 1 may be attributed to the
C]C stretching vibration of benzene. So lots of groups, such as
Scheme 1 Schematic diagram for PGO fiber preparation. (a) Preparation of GO sheets. (b) Preparation of the GO/PAA gel. (c) PGO fiber spinning. These mainly consist
of two preparation steps: (I) preparation of GO/PAA gels. In this case, the AA is polymerized in GO aqueous solution. (II) Spinning of PGO fibers. In the spinning process,
there are three critical parameters: the length of the heating tube, the temperature of the heating tube and the rotation speed of the spinning roller.
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the hydroxyl group, carboxyl group, ester group, anhydride
group, are detected in the PGO ber. It is noteworthy that the
existence of ester groups reveals the occurrence of a cross-
linking reaction between GO and PAA. On the other hand, the
existence of the hydroxyl group and carboxyl group indicates an
incomplete esterication reaction, which is also conrmed by
XPS analysis. XPS survey spectra of the PGO ber, shown in
Fig. 1e, demonstrated the elemental composition of 72.37% of
C and 27.63% of O. The deconvolution of the C 1s core level
spectrum gave three Gaussian components: the peak at a
binding energy of 284.3 eV arises from C–C; the peak at a higher
binding energy, 286.5 eV, arises from C–O groups; the peak at
289 eV corresponds to O]C–O. Another piece of direct evidence
for cross-linked PGO is the swelling experiment (Fig. S2†). As
seen in a typical picture for the swelling experiment (Fig. 1f), the
crosslinked PGO ber is insoluble in water, while the uncros-
slinked PGO bers are readily soluble in water (Fig. S3†).
The effect of GO contents on the mechanical performances
of PGO bers is also studied (see Fig. S4†). It is found that the
mechanical performances of the PGO bers are improved with
the GO content increase. In a typical stress–strain curve three
regimes of deformation can be observed for mechanical tests of
the PGO ber: (I) straightening, (II) almost linear (‘elastic’), and
(III) plastic (Fig. 2a). The yield parts I and II may stem from the
tension of the PGO chain. Part III is considered from further
orientation of GO sheets in the tensile test. In the nal stage of
the ber tensile test, the GO sheets are further orientated by the
straightened PAA chain, which is also proved by the XRD
spectrum (Fig. 2b). As seen in Fig. 2b, the peak at 12.4 degree
has been further enhanced compared with that in Fig. 1c.
Further GO sheet orientation can be obviously seen in the cross-
section images of the PGO ber by SEM (Fig. 2c). Fig. 2c shows
well-packed layers through almost the entire cross-section of
the ber samples, clearly visible from the high-resolution
images (the inset images in Fig. 2c). In addition, the rupture of
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Fig. 1 (a and b) SEM images of the PGO fiber. (a) Cross-section images of the PGO fiber. (b) Side-view of the PGO fiber. (c) XRD patterns of PGO fibers. (d) FT-IR spectra
of the PGO fiber. (e) Typical XPS survey spectra of the PGO fiber. The inset picture shows the wide-survey XPS. (f) Swelling experiment for the PGO fiber (more
information can be obtained from Fig. S2 and S3†). (I) PGO fiber before the swelling experiment. (II) PGO fiber after swelling in water.

PGO samples is not accompanied by any slippage of its
lamellae, and produces almost straight and at fracture
surfaces. This suggests good material homogeneity and strong
interlayer binding. More importantly, the yielded PGO bers
reveal very high tensile modulus and fracture strength (Fig. 2d).
The average modulus of PGO bers is determined to be
59.2 GPa (average from 50 tested samples) with the highest
being 71.5 GPa. Due to the ultra-high modulus of the GO sheet,
PGO bers have the superb high modulus which is much higher
than those reported for common bers and natural bers. The
average tensile strength of the PGO ber is determined to be
764.5 MPa (average from 50 tested samples) with the highest
being 1154.5 MPa. Although the tensile strength of PGO bers is
not as high as their modulus, it is also higher than those
reported for common bers and only a little lower than that of
spider ber (one of the bers with the highest strength in
nature) (see Fig. 2d). The stable covalent bond between the PAA
chain and GO and further orientation of the GO sheet in the
drawing process for the ber may be attributed to the high
tensile strength of the PGO ber. Due to the excellent
mechanical performances of the PGO ber, it has wide appli-
cations in industrial elds including preparation of special
clothing, reinforcement of rubber and plastic, reinforcement of
cement, etc.
In summary, a novel ber, based on chemical polymerization
of GO sheets, is yielded through a new gel-desiccation
approach. The novel PGO ber shows excellent mechanical
performance, particularly its ultra-high modulus. The excellent
mechanical property of GO endows this material with remark-
able strength when compared with traditional bers. The
straightforward synthesis process using inexpensive starting
materials such as GO and AA should further facilitate the large-
scale fabrication of PGO bers, which opens the door for their
widespread applications in fabrics and reinforcement of

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Fig. 2 (a) Stress–strain curve for a PGO fiber. The deformation can be divided into three regimes: (I) straightening, (II) ‘elastic’ and (III) plastic (more information can be
obtained from Fig. S4†). (b) XRD spectrum of the PGO fiber after tensile testing. (c) Middle- and high-resolution SEM side-view images of the PGO fiber after tensile
testing. The scaly structure of the PGO fiber fracture surface can be seen more clearly in their SEM images. (d) Comparison of PGO tensile strength and modulus with a
set of common chemical fibers and natural fibers (spider fiber (SS)).34–36

composites. Furthermore, the PGO ber has great potential for
use as a precursor for carbon ber preparation. Based on the
excellent mechanical performance and special structure of PGO
bers, a novel carbon ber, whose performance is close to the
theoretical strength, can be fabricated through the elimination
of skin-core structure and the improvement of crystal structure.
The work is currently under investigation in our group.
Acknowledgements
The authors acknowledge nancial support from iNANO
through the Danish National Research Foundation and the
National Natural Science Foundation of China to the Sino-
Danish Center of excellence on “The Self-assembly and Func-
tion of Molecular Nanostructures on Surfaces”, the Carlsberg
Foundation, and the Villum Foundation. The authors would
like to thank the National Natural Science Foundation of China
(no. 51003021), China Postdoctoral Science Special Foundation
(no. 201003420, no. 20090460067).
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