Industrial Crops and Products 85 (2016) 198–203

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Industrial Crops and Products

journal homepage: www.elsevier.com/locate/indcrop

Large scale preparation of graphene oxide/cellulose paper with

improved mechanical performance and gas barrier properties by
conventional papermaking method
Quanbo Huang a , Manman Xu a , Runcang Sun a,b , Xiaohui Wang a,∗
a
State Key Laboratory of Pulp and Paper Engineering, South China University of Technology, Guangzhou 510640, China
b
Institute of Biomass Chemistry and Technology, Beijing Forestry University, Beijing 100083, China

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

Article history: Graphene oxide (GO)/cellulose paper was prepared by adding aqueous dispersion of GO into cellulose
Received 12 November 2015 fiber pulp in a traditional papermaking procedure. Cationic polyacrylamide (CPAM) was added as a mor-
Received in revised form 28 January 2016 dant to induce the self-assembly of GO layers on the fiber surfaces. The surface morphology, mechanical
Accepted 2 March 2016
properties and gas permeability of GO/cellulose paper with varying GO contents were investigated by
Available online 17 March 2016
scanning electron microscopy (SEM), tensile test, burst test, tear test and densometer. It was found that
CPAM could prevent the self-aggregation of GO in fiber matrix and increase the loading efficiency of GO
Keywords:
to up to 16 wt% without sacrificing the mechanical performances of the paper. This finding permitted the
Paper
Graphene oxide large scale preparation of GO/cellulose paper with high doping amount of GO, which exhibited dense and
Cellulose compact geometry and low gas permeability ideal for potential packaging applications.
Gas permeability © 2016 Elsevier B.V. All rights reserved.
Mechanical strength

1. Introduction To overcome these issues, adding filler in pulp during paper-

Cellulosic paper has widely and traditionally been used in
packaging for a long time. It is suitable to pack the food, glass,
precious products and electronic devices and so on for its non-
toxic, light, inexpensive and cushioning properties. Compared with
plastic materials, cellulosic paper is sustainable, biodegradable and
eco-friendly, but its low mechanical and gas barrier properties
cannot meet the requirement of some perishable foods, prescrip-
tion medicines or precise instruments (Hernandez et al., 2000;
Lange and Wyser, 2003). Although the regenerated cellulose films
prepared from some cellulose solvent systems such as ionic liq-
uids (Wang et al., 2012), N-methylmorpholine-N-oxide hydrate
(NMMO) monohydrate solvent (Kim et al., 2011), and aqueous
NaOH/urea solutions (Han et al., 2011) have decreased the poros-
ity of pristine cellulosic papers and thus enhanced the mechanical
performance and barrier property. Nevertheless, the fabrications of
regenerated cellulose films are complex, costly and not competitive
for large-scale and continuous production.
∗ Corresponding author at: State Key Laboratory of Pulp and Paper Engineering,
South China University of Technology, China.
E-mail addresses: fewangxh@scut.edu.cn, alicewang1225@163.com (X. Wang).
making is a facile and common method. Impermeable layered and
plate-like organic nanoclays, such as montmorillonite and rectorite,
have been used to increase the barrier property of many polymeric
films, including polyethylene (Durmus et al., 2007), poly(vinyl alco-
hol) (Strawhecker and Manias, 2000), and regenerated cellulose
films (Farmahini-Farahani et al., 2015; Ho et al., 2012; Yang et al.,
2014). However, when using conventional processing techniques,
it is also a challenge to obtain completely exfoliated nanoclays
(Huang et al., 2014).
Meanwhile, graphene oxide (GO), that can be obtained by oxi-
dizing graphite using strong acids, has a similar layered structure to
graphite and nanoclays, but the plane of carbon atoms in graphene
oxide is heavily decorated by oxygen-containing groups, which not
only expand the interlayer distance but also make the atomic-thick
layers hydrophilic (Cai et al., 2008; Lerf et al., 1998). As a result, GO
has not only excellent mechanical properties, but also excellent
dispersibility in aqueous solution (Paredes et al., 2008; Zhang et al.,
2010), which is appropriate as a nanofiller in papermaking.
Recent studies indicate that the composite of cellulose and GO
exhibits excellent performance, especially improved mechanical
property and low gas permeability. For instance, Han et al., 2011
prepared blended films of cellulose and GO using alkali aqueous
solution as solvent, resulting in a 98% increase in tensile strength
and a 60% enhancement in Young’s modulus by addition of only

http://dx.doi.org/10.1016/j.indcrop.2016.03.006
0926-6690/© 2016 Elsevier B.V. All rights reserved.
 Q. Huang et al. / Industrial Crops and Products 85 (2016) 198–203
Scheme 1. Schematic illustration of the fabrication process of GO/cellulose paper with different content of GO.
7.5 wt.% GO. Huang et al., 2014 used a simple and environmentally
friendly method to fabricate GO/regenerated cellulose films that
the permeability coefficient of O2 (Po2 ) was reduced by over three
orders of magnitude at a low GO loading of 1.64 vol%. However, the
self-aggregation of GO sheets usually appears when the GO content
was high, probably due to the van der Waals interactions between
the layers of GO nanosheets. As a result, the mechanical properties
would be reduced and the homogeneity of films/papers would be
disrupted (Wang et al., 2012). As we know, cellulose pulp (Rojas and
Neuman, 1999) and GO nanosheets (Li et al., 2008) are both negative
charged in aqueous suspensions, which prevents the adsorption
of GO nanosheets on cellulose fibers. Therefore, there is a strong
need to find an effective way to prevent the self-aggregation of GO
nanosheets in the composites, and also improve the adsorption of
GO onto the cellulose fibers to form stable composites.
Cationic polyacrylamide (CPAM), a water-soluble cationic poly-
mer decorated with carbamoyl group, is a commonly used retention
and drainage agent in papermaking industry (Asselman and
Garnier, 2000; Raj et al., 2015). So, CPAM is very suitable to use
in the fabrication of graphene oxide/cellulose paper. Herein, we
used a simple, efficient, low cost and large-scale method to fab-
ricate a novel GO/cellulose paper through modern papermaking
machine. The as-prepared paper has potential of reaching high
loading ratio and uniform distribution of GO nanosheets in cellulose
fiber matrix and thus obtain improved mechanical performance
and low gas permeability. The current study provides an easy, ver-
satile and applicable way to produce functional inorganic paper in
large scale for potential applications in value-added fields, such as
active packaging, energy, etc.
2. Material and methods
2.1. Materials
Cellulose fibers were obtained by defibering the dissolved wood
pulp (Pinus radiata, ␣-cellulose content: 93.2%), which was pro-
vided by Shan Dong Sun Paper Industry Joint Stock Co., Ltd. The
graphite flakes (particle size < 45 ␮m) used in experiments were
purchased from Nanjing XF NANO Materials Tech Co., Ltd. Cationic
polyacrylamide (CPAM), KMnO4 , concentrated H2 SO4 , concen-
trated HCl, and H2 O2 aqueous solutions were all of analytical
reagent grade and used directly without further purification.
199
2.2. Preparation of graphene oxide dispersion
The GO was prepared from natural graphite by a modified Hum-
mers method (Marcano et al., 2010). In brief, 1.0 g of the graphite
flakes were added to cold concentrated H2 SO4 (46 ml). Then 3.0 g
of KMnO4 was added slowly with an ice bath under stirring to keep
the reaction temperature. After even agitation, the ice-bath was
removed and the mixture was heated at 35 ◦ C for 1.5 h, and then
46 ml water was added slowly and continuously. Next, the reaction
temperature was maintained at 98 ◦ C for 30 min before 140 ml cool
water was added to stop the reaction. 10 ml 30 wt% H2 O2 solution,
1000 ml HCl solution (1:10) and deionized water was used succes-
sively to reduce the residual KMnO4 and MnO2 to colorless MnSO4
salts, remove the sulfate ion and control the pH of the washed
solution to around 6.0, respectively. Finally, brown powder was
obtained after freeze-dried the suspension. As-prepared powder
was dispersed in water and the aqueous dispersion (5 mg/ml) of
GO was obtained by an ultrasonic treatment of dispersion for 1 h to
yield a stable brown solution.
2.3. Fabrication of GO/cellulose paper
GO/cellulose paper with different content of GO ranging from
1 wt% to 16 wt% was prepared using a handsheet former in lab-
oratory. Same procedure can be performed on fourdrinier paper
machine in paper mill as well. The basis weight of the GO/cellulose
paper was around 120 g/m2 . The ratio of CPAM and GO was kept
0.04:1 in weight. Before being used, CPAM was processed as poly-
mer solution (0.001 g/ml) with stirring velocity below 100 rpm. As
illustrated in Scheme 1: first, the pulp board was dispersed in water
(2.0% wt/vol) with vigorous stirring in hydrapulper. And then in
the mixing tank I, CPAM was coated on the cellulose fiber through
electrostatic interaction to form the CPAM-coated cellulose slurry
with stirring velocity around 150 rpm in one minute. Next in the
mixing tank II, GO was absorbed onto the CPAM through elec-
trostatic interaction with stirring velocity around 300 rpm in two
minute. Consequently, CPAM acts as an intermediate that induces
the self-assembly of cellulose fibers and GO nanosheets. In addition,
CPAM enhances the retention of GO during the filtration process
in the following step. Finally, the slurry (0.5% wt/vol) was send to
the headbox and GO/cellulose paper was obtained through three
sections of the papermaking machine.
200 Q. Huang et al. / Industrial Crops and Products 85 (2016) 198–203
Fig. 1. (a) UV–vis spectrum of GO dispersed in water. (b) FTIR spectra of GO powder. (c) XRD pattern of GO and graphite powders. (d) AFM image of GO exfoliated in water.
2.4. Characterization
UV–vis spectra were obtained by TU-1810 (Beijing, China) with a
scan range of 200–800 nm. Fourier transform infrared spectroscopy
(FT-IR) was conducted on a Bruker spectrometer (TENSOR27,
Switzerland) at wavelengths in the range of 500–4000 cm−1 . The
zeta potential of intrinsic fiber, GO, and CPAM aqueous solution
were investigated by dynamic light scattering(DLS) on a Zeta sizer
3000HS instrument (England) at 90◦ scattering angle at 25 ◦ C.
Atomic Force Microscopy (AFM) Nanoscope III (Veeco Co., Ltd., USA)
was employed to observe GO. X-ray diffraction (XRD) of the paper
was determined by a D/max-IIIA X-ray diffractometer, in which
the high-intensity monochromatic nickel-filtered Cu K radiation
(␭= 0.15418 nm) was generated at 40 kV and 40 mA. Samples were
scanned at a speed of 1◦ /min, range from 2␪ = 10–40◦ with step
size of 0.02◦ at room temperature. The surface morphologies of
the papers were investigated by field emission scanning electron
microscopy (Hitachi, S-3700N, Japan). The tensile test was carried
out using a micro tensile tester (INSTRON, 5565, USA) with a 50 mm
gauge length (dimensions 15 cm × 100 cm) at a tensile velocity of
2 mm/min. The burst strength was determined by TAPPI method T
403 om-02 (2002) on burst tester (L&W, CE180, Sweden). The tear
strength was measured according to TAPPI method T 414 om-04
(2004) using a tear tester (L&W, 009, Sweden) and the air perme-
ability tests were conducted on a permeability tester (L&W, 116,
Sweden) by TAPPI method T 547 om-02 (2004). To ensure data
accuracy and repeatability of mechanical property measurements,
at least four tests were carried out for each paper.
3. Results and discussion
3.1. Characterization of GO
Fig. 1a shows the UV–vis spectroscopy of GO. It yields a maxi-
mum absorbance at 230 nm, corresponding to ␲ → ␲* transitions
of aromatic C C bonds, and a shoulder peak at around 300 nm,
assigned to n → ␲* transitions of C O bonds (Paredes et al., 2008).
The FTIR spectrum of GO (Fig. 1b) suggests the abundant functional
groups on GO. The broad and intense absorption band at 3421 cm−1
is from the O H stretching vibration. The band at 1710 cm−1 is
related to the C O stretching vibration of carboxyl groups (Marcano
et al., 2010) at the edges of the GO sheets. The peak at 1627 cm−1
is attributed to aromatic C C stretching. In addition, the peaks at
1398, 1253 and 1072 cm−1 correspond to the O H stretching vibra-
tions of C OH (Pham et al., 2010), C O of epoxy (Luong et al., 2011)
and C O of alkoxy groups (Bagri et al., 2010), respectively. We fur-
ther characterized the crystalline structure of GO by XRD. Fig. 1c
shows the XRD pattern of the pristine graphite and GO powders.
Compared with the pristine graphite, the characteristic diffraction
peak of exfoliated GO appears at 10.43◦ . The inter-layer space (d-
spacing) was determined to be 0.76 nm, which is consistent with
the values that reported previously (Dubin et al., 2010; Liao et al.,
2011; Park et al., 2009). This value is larger than the d-spacing
(0.34 nm) of pristine graphite (2␪ = 26.54◦ ) because of the intro-
duction of oxygenated functional groups on carbon sheets. AFM
characterization is the most direct method to quantify the degree
of exfoliation to single GO sheet. Fig. 1d shows the AFM image of
GO dispersion in water after deposited on a cleaved mica surface
through a drop-casting method. The thickness of as-prepared GO
measured from the vertical distance of the AFM image was about
0.96 nm, corresponding to the thickness of individual, single-layer
nanosheets. The step height of the GO sheet has been measured
to be in the range of 0.8–1.0 nm, owing to the oxygen-containing
groups on its surface (Marcano et al., 2010).
3.2. Morphological analysis of GO/cellulose paper
Fig. 2 demonstrates the obvious changes in the surface mor-
phology of the paper with different GO content. With increasing
content of GO, the spacing between the cellulose fibers became
 Q. Huang et al. / Industrial Crops and Products 85 (2016) 198–203
Fig. 2. SEM images of the GO/cellulose paper with different content of GO: (a) 0 wt%, (b) 5 wt%, (c) 10 wt%, (d) 15 wt%.
Table. 1
Zeta potential of intrinsic fiber, GO, and CPAM aqueous solution.
Sample Cellulose fiber GO
Zeta potential (mV) −11.8 −25.2
closer, and the paper became smoother and denser. As we can
see in Table 1, the zeta potential of intrinsic fiber and GO aqueous
dispersion is −11.8 mV and −25.2 mV, respectively. Therefore, the
positively charged CPAM with zeta potential of +24.7 mV acted as an
adhesive coated on the negatively charged surface of cellulose fiber
through electrostatic interaction in the Mixing Tank I. As a result,
the negatively charged GO nanosheets would be more inclined to
be trapped on the CPAM-coated fiber in the Mixing Tank II. Dur-
ing the papermaking process, the pressure from the papermaking
machine would decrease the moisture content of the GO/cellulose
paper and draw the fibers closer, which facilitated the formation
of hydrogen bonds between the GO sheets and cellulose fibers.
The stronger interaction between GO and cellulose fibers would
enhance the mechanical properties of paper effectively.
Moreover, as a two-dimensional material with a high specific
surface area, GO can self-assemble into a free-standing hydrogel via
hydrothermal reduction (Xu et al., 2010). So, similar to the gelation
of RGO hydrogel, the GO nanosheets coated on the cellulose fiber
could help densify the GO/cellulose paper in the drying process
with the increasing temperature. As Fig. 2d shows, with the high
GO content (15 wt%), the paper becomes compact and dense, favor-
ing high mechanical behavior and low gas permeability. According
to Fig. S3, the existence of GO could help to promote dewatering,
and thus reduce the energy consumption of papermaking in some
degree.
3.3. Mechanical properties of GO/cellulose paper
The typical stress-strain curves for the papers are presented in
Fig. 3a. With the increase of GO content, the maximum tensile stress
and tensile strain at the breaking point gradually increased. Simi-
lar trends were found with the changes of tensile strength (Fig. 3b)
and elongation at break (Fig. 3d). The Young’s modulus of the paper
201
calculated from the slop of the curve is showed in Fig. 3c. Improved
Young’s modulus was obtained with increasing GO content. The
CPAM enhancement could be due to the strong interfacial adhesion and
24.7 interaction between GO and the cellulose fibers driven by the van
der Waals interactions and hydrogen bonding. (Xu et al., 2015) The
mechanical locking between the cellulose fibers coated with GO
nanosheets preventing the inter-fibers sliding might also be a rea-
son. (Kang et al., 2012) The reinforcement effect of GO in the paper
also presented in the burst strength (Fig. 3e) and tearing strength
(Fig. 3f). Compared with the pure cellulose fiber paper, the burst
strength of the paper increased by 81.4% at 4 wt% of GO, which
indicates its potential as packaging material. Experimental results
in Figs. S1 and S2 show that whether CPAM was added to the fiber
slurry before or after the addition of GO, the GO/cellulose paper
exhibit almost the same mechanical property, suggesting the addi-
tion sequence of CPAM doesn’t affect the function of GO. It was
also noteworthy that increasing mechanical factors were observed
even with quite high content of GO (16 wt%). This result is differ-
ent from the previous reports (Rahatekar et al., 2009; Wang et al.,
2012; Zhang et al., 2007), in which obvious decrease in mechani-
cal factors were found with high GO contents. This was probably
owing to a more stable and stronger GO/fiber complex with higher
loading capacity was achieved in this system based on the CPAM
induced self-assembly.
3.4. Structural properties of GO/cellulose paper
The gas barrier property of the GO/cellulose paper was stud-
ied by a determination of air permeability as shown in Fig. 4.
Initially, the air permeability decreases sharply with the increase
of GO content, and then the curve became flatter after the
GO content was higher than 4 wt% while the decreasing trend
was kept till the GO content reached 16 wt%. The smallest
gas permeability 0.094 ␮m/Pa s was obtained with 16 wt% GO
contents, which decreased by 99.85% compare with pure cellu-
losic paper (64.3 ␮m/Pa · s). and this number is lower than the
paper (0.29 ␮m/Pa s) surface-sized with 12.58 g/m2 alkyl ketene
dimer/nanocrystalline cellulose emulsion (Yang et al., 2016).
The obviously reduced air permeability was probably due to
202 Q. Huang et al. / Industrial Crops and Products 85 (2016) 198–203

Fig. 3. Stress-strain curves (a) of the paper with different content of GO (0 wt%–16 wt%). Different properties related to strength: (b) Tensile strength, (c) Young’s modulus,
(d) Elongation at break, (e) Tearing strength, (f) Bust strength of the papers with different content of GO (0 wt%–16 wt%).

the enhanced interaction between the cellulose fibers and GO
nanosheets. GO nanosheets with abundant oxygen groups are
inclined to show uniform dispersion and ordered alignment in poly-
mer matrices by van der Waals interactions and hydrogen bonds
between GO nanosheets and polymer chains (Huang et al., 2014;
Pan et al., 2011; Xu et al., 2009; Yang et al., 2010), which would
endow the composite film/fiber low gas permeability. Moreover,
the finished paper would become smoother and denser (Fig. 2d)
with increased GO content, which is also in favor of obtaining
decreased gas permeability. This could be proved by the reduced
paper thickness with higher GO content. As shown in Fig. 4, when
the GO content increases, the thickness of the GO/cellulose paper
shows a similar decreasing trend with the gas permeability, sug-
gesting the paper became more dense and compact.
functional groups was successfully prepared and added to the cel-
lulose pulp as a nanoscale filler, and CPAM was applied to induce the
layer-by-layer self-assembly of GO on cellulose fibers. Compared to
pure cellulose paper, the mechanical performances of GO/cellulose
papers improved continuously with the increase of GO contents,
and no deterioration appeared even with 16 wt% GO content. The
paper also presented excellent gas barrier property by the addition
of only 4 wt% GO, which decreased by 71.6% compare with pure
cellulosic paper. The high mechanical performances and low gas
permeability of the GO/cellulose paper make its promising candi-
date as packaging materials.
Acknowledgements

This work was financially supported by the Independent Study

4. Conclusions
In summary, the GO/cellulose paper with high mechanical per-
formances and low gas permeability was obtained by a simple,
efficient, low cost and large-scalable method. GO with abundant
Projects of the State Key Laboratory of Pulp and Paper Engineer-
ing (2015C08, 2015ZD03), the Science and Technology Program
of Guangzhou, China (2014J4100039), the New Century Excellent
Talents in University (NCET-13-0215), the Fundamental Research
Funds for the Central Universities, SCUT (201522036) and the
 Q. Huang et al. / Industrial Crops and Products 85 (2016) 198–203 203

70 Kang, Y.R., Li, Y.L., Hou, F., Wen, Y.Y., Su, D., 2012. Fabrication of electric papers of
0.26 graphene nanosheet shelled cellulose fibres by dispersion and infiltration as
flexible electrodes for energy storage. Nanoscale 4, 3248–3253.
60 a Kim, C.-J., Khan, W., Kim, D.-H., Cho, K.-S., Park, S.-Y., 2011. Graphene
0.25
b oxide/cellulose composite using NMMO monohydrate. Carbohydr. Polym. 86,
50
Air permeability(μm/Pa·s)

903–909.

Thickness of paper(mm)
·
0.24
40
0.23
30
0.22
20
0.21
10
0.20
0 with high electrical and mechanical performances. J. Mater. Chem. 21, 13991.
0.19
0 3 6 9 12 15 18
GO content(wt%)
Fig. 4. Air permeability (a) and thickness (b) of papers with the increase of GO.
Opening Project of the Key Laboratory of Polymer Processing Engi-
neering, Ministry of Education, China (KFKT-201401).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.indcrop.2016.03.
006.
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