Research Article

Cite This: ACS Sustainable Chem. Eng. 2019, 7, 8215−8225 pubs.acs.org/journal/ascecg

Fabrication of Bacterial Cellulose/Polyaniline Nanocomposite Paper

with Excellent Conductivity, Strength, and Flexibility
Guiqiang Fei,† Yu Wang,† Haihua Wang,*,† Yongning Ma,† Qian Guo,† Wenhuan Huang,† Dong Yang,†
Yanming Shao,† and Yonghao Ni‡
†
Shaanxi Key Laboratory of Chemical Additives for Industry, Shaanxi University of Science and Technology, 7# Xuefu Road,
Weiyang district, Xi’an 710021, Shaanxi province, China
‡
Limerick Pulp and Paper Center, University of New Brunswick, 3 Bailey Drive, Fredericton, New Brunswick E3B 5A3, Canada
*
S Supporting Information
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ABSTRACT: Bacterial cellulose/polyaniline (BC/PANI)

nanocomposites display many potential applications in various
fields. However, the conductivity and mechanical properties
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remain a challenge. Here, we developed a novel method to

prepare BC/PANI nanocomposites via the chemical grafting
of PANI onto epoxy modified BC (EBC), followed by the
grafting of polyacrylamide (PAM). For comparison, an in situ
BC/PANI sample was also prepared. The grafting reaction
between PANI and EBC and the retention of PANI on EBC
were confirmed by FTIR, X-ray photoelectron spectroscopy,
and elemental analysis. The cross-section morphology of BC
transformed into a three-dimensional and continuous network
structure with the incorporation of PANI. The effects of epoxy
and PAM contents on the morphology, conductivity, and
mechanical properties of PANI-g-EBC and PANI-g-EBC3/PAM nanocomposites were investigated. Compared with those of
the in situ BC/PANI sample, the conductivity of PANI-g-EBC increased from 0.12 to 1.08 S/cm, while the stress increased
from 8.18 to 18.47 MPa. With the addition of PAM, the conductivity of PANI-g-EBC/PAM nanocomposite paper further
increased to 1.43 S/cm, and the stress increased to 47.94 MPa. The conductivity of PANI-g-EBC3/PAM nanocomposites only
decreased from 1.43 to 1.36 S/cm after refolding 160 times. PANI-g-EBC and PANI-g-EBC3/PAM nanofibers could be
blended with conventional plant cellulose fiber to prepare flexible and high strength conductive composite paper.
KEYWORDS: Conductive nanocomposites, Epoxy chloropropane, Modified BC, Polyaniline, Polyacrylamide

■ INTRODUCTION
High-strength, flexible, and conductive cellulose nanocompo-
sites have received growing interest.1,2 As an important potential
application in flexible electronic devices,3−5 the development of
conductive paper has become an active research field. Polyani-
line (PANI) is considered as one of the most promising
conducting polymer materials due to its facile synthesis, good
environmental stability, and controllable electrical conductivity
via simple doping/dedoping chemistry.6,7 PANI has also been
used as a conductive polymer to improve the performance of
flexible electronic devices.8,9 However, its conjugated structure
imparts PANI with poor processability. Therefore, fabricating
PANI composites becomes a continuing trend to extend the
PANI application.10
Cellulose is a considerably attractive material due to its
abundance in nature, renewability, biodegradability, biocompat-
ibility, and good mechanical properties.11,12 Among them,
bacterial cellulose (BC) has received more and more attention
since BC is pure and does not contain hemicelluloses, lignin,
pectin, or wax.13 BC is produced from bacteria cultivations via
biosynthesis, bacteria may include gluoconacetobacter xyliums
and acetobacter xylinus.14,15 BC possesses unique characteristics
including high crystallinity, specific surface area, low thermal
expansion, three-dimensional porous structure, and anisotropic
thermal conductivity in addition to good mechanical properties
and biocompatibility.13,16 Therefore, combining BC and PANI
to make flexible and conductive BC/PANI nanocomposite
membranes is an interesting concept.
The in situ polymerization of aniline onto a BC membrane
leads to the formation of BC/PANI nanocomposites.17−19 Hu et
al. synthesized BC/PANI nanocomposites via in situ oxidative
polymerization of aniline in the presence of BC membranes.19
The highest conductivity was 0.05 S/cm, and its stress decreased
by almost 4 times as a result of the PANI incorporation into BC
membranes. Lin et al. developed a new route of limited
interfacial polymerization by which aniline monomer was
Received: December 2, 2018
Revised: April 4, 2019
Published: April 9, 2019

© 2019 American Chemical Society 8215 DOI: 10.1021/acssuschemeng.8b06306

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ACS Sustainable Chemistry & Engineering
polymerized on the surface of BC membranes.20 The surface
resistivity decreased to 40.1 Ω.cm, and the stress decreased by
three times with the incorporation of PANI. The conductivity of
BC/PANI nanocomposites made by this approach was very low.
Recently some methods were put forward to improve the
conductivity. For instance, protic ionic liquid based on N-
butylguanidinium tetrafluoroborate (BG-BF4) was introduced
to BC/PANI nanocomposites. The conductivity increased from
10−4 to 10−2 S/cm; however, significant decrease of the stress of
such membranes to 5−6 MPa was observed.21 Wan et al.
increased the conductivity of BC/PANI from 0.82 to 1.7 S/cm
with the addition of graphene.22
In situ polymerization of aniline onto BC nanofibers is
another approach to synthesize BC/PANI nanocomposites and
subsequently flexible composite paper is obtained using the
vacuum filtration technique.11,12 Wang et al. obtained BC/PANI
nanocomposites by in situ polymerization of aniline on wet BC
nanofibers in DMF/H2O medium, and the conductivity reached
5.1 S/cm when the aniline content was 200% based on the
weight of BC nanofibers.11 The crystalline structure of BC was
fully hindered by amorphous PANI coating, which may affect
the mechanical properties of BC/PANI nanocomposites.
Gopakumar et al. also obtained nanocomposites for sustainable
microwave absorbers through the in situ polymerization of
aniline on cellulose nanofibers, the conductivity is 0.314 S/cm.12
Relative high mechanical properties can be achieved for the BC/
PANI nanocomposites prepared using the first approach, since
BC membranes of high modulus and stress were used as raw
material. But the conductivity was very low, and stress also
decreased significantly with the incorporation of PANI.
Additionally, this approach is difficult to scale since the product
yield is limited. The second approach is able to produce a large
amount of BC/PANI nanocomposites, but the conductivity
improves by compromising the mechanical properties. Having
satisfactory results between conductivity and mechanical
properties for BC/PANI nanocomposites remains a big
challenge.
Herein, a novel approach was proposed to prepare BC/PANI
nanocomposites with high conductivity and mechanical proper-
ties. First, epoxy groups were incorporated into the BC structure
by chemical grafting of epoxy chloropropane (ECP) onto BC.
Then PANI was chemically grafted onto epoxy modified BC
(PANI-g-EBC) to improve the interaction and compatibility
between PANI and BC, as well as to promote the formation of
more uniform and continuous conductive paths. Afterward, a
moderate amount of polyacrylamide (PAM) was introduced
into PANI-g-EBC3 nanofibers to further improve the con-
ductivity and mechanical properties via enhancing the
interactions between fibers and PANI while maintaining the
crystal characteristic of BC. The structure, morphology, and
properties of PANI-g-EBC and PANI-g-EBC3/PAM nano-
composites were systematically investigated. PANI-g-EBC and
PANI-g-EBC3/PAM nanofibers can also be blended with plant
cellulose fiber to make flexible and conductive paper, and the
related properties were also studied.
■
EXPERIMENTAL SECTION
Materials. Aniline was supplied by Tianjin Chemical Reagent
Factory and distilled under reduced pressure before utilization.
Bacterial cellulose (BC) was obtained from Guilin Qi Hong
Technology Co., Ltd. Epoxy chloropropane (ECP) was supplied by
Tianjin Tianli Chemical Reagent Co., Ltd. Hydrochloric acid (HCl)
was provided by Tianjin Institute of Chemical Reagents. Ammonium
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persulfate (APS) was bought from Hedong District of Tianjin Hongyan
reagent Factory. NaOH was obtained from Tianjin Tianli Chemical
Reagent Co, Ltd. Polyacrylamide (PAM) was purchased from Tianjin
Hongyan Reagent Factory.
Preparation of Epoxy Modified BC (EBC). A 0.2 wt % BC
solution was prepared by diluting BC in distilled water under vigorous
stirring for 20 min. The solution was heated up to 80 °C, then ECP of
different content was added. The pH value was adjusted to 11 with 1
mol/L NaOH. Epoxy modified BC (EBC) solution was thereby
obtained after 5 h reaction. The as-prepared samples were named
EBC1, EBC2, EBC3, EBC4, and EBC5, in which the 1−5 represent the
mass fraction of ECP as 1.1, 2.2, 3.3, 4.4, and 5.5 g/L, respectively.
Preparation of PANI-g-EBC, in situ BC/PANI, and PANI-g-
EBC3/PAM Nanocomposite Paper. A 98.05 μL portion of aniline
was added into the above EBC solution, and the reaction was kept at 80
°C for 2 h. Then the reaction system was placed in an ice−water bath
and the solution was cooled down to 5 °C. Afterward, 0.455 g
ammonium persulfate (APS) was dropped into the reaction solution,
after which 1 mol/L HCl was utilized to adjust the pH value to 1−2.
After 24 h, polyaniline grafted EBC (PANI-g-EBC) suspensions were
obtained, and the samples were named as PANI-g-EBC1, PANI-g-
EBC2, PANI-g-EBC3, PANI-g-EBC4, and PANI-g-EBC5 based on the
ECP content. In situ BC/PANI was prepared according to the same
procedure as above-mentioned except that the EBC was replaced by
BC.
PAM of different concentrations was added into 100 g PANI-g-
EBC3 suspensions, the temperature was heated up to 60 °C, and the
reaction was kept for 2 h to prepare PANI-g-EBC3/PAM suspensions.
The samples were designated as PANI-g-EBC3/PAM1, PANI-g-
EBC3/PAM2, PANI-g-EBC3/PAM3, PANI-g-EBC3/PAM4, and
PANI-g-EBC3/PAM5 when the PAM concentration was 0.4, 0.6, 0.8,
1.0, and 1.2 g/L, respectively.
Vacuum filtration technique was adopted to fabricate nano-
composite paper. After filtration, the nanocomposite paper was washed
several times with distilled water and freeze-dried in a LGJ-12 freeze-
dryer for 24 h. The PANI-g-EBC, in situ BC/PANI, and PANI-g-
EBC3/PAM nanocomposite paper was obtained after being peeled off
the filter paper.
Preparation of Conventional Plant Cellulose Fiber/Nano-
fiber Nanocomposite Paper. The PANI-g-EBC3 suspension or
PANI-g-EBC3/PAM suspension was mixed with plant cellulose fiber at
different ratios in a blender with a stirring speed of 3000 rpm. Then, the
obtained suspension was formed into paper with a handsheet machine
and the as-prepared paper was pressed and dried at 105 °C (0.5 MPa)
for 5 min, followed by drying at room temperature for 12 h. As a result,
the conductive nanocomposite papers were fabricated, in which the
mass fractions of PANI-g-EBC3 and PANI-g-EBC3/PAM2 are 5%,
10%, 15%, 20%, 25%, 30%, respectively. Nanocomposite (60 g/m2)
paper sheets were prepared according to TAPPI methods (T205 SP-
95).
Characterizations. The structure of prepared nanocomposites was
characterized by Fourier transformed infrared (FTIR, VECTOR-22,
Germany) and X-ray photoelectron spectroscopy (XPS, AXIS SUPRA,
UK). The surface and cross-section morphology were observed by
scanning electron microscopy (SEM, S-4800, Hitachi, Japan) and
transmission electron microscopy (TEM, S-570, US). The elemental
composition was analyzed by organic elemental analysis (Vario EL III,
Germany). The conductivity was measured by four-point probe
technique (BD-86A, China). The mechanical properties were
measured using a universal testing machine (GT-U55, China). The
thermal stability of samples was performed by thermogravimetric
analyses (TGA, TGA Q500, US). The crystalline phases were
characterized by X-ray diffraction instrument (XRD, R-600, Japan).
The tearing index, folding endurance, and tensile index test were
measured according to a paper bursting tester (DCP-MIT13, China),
paper folding tester (DCP-MIT135A, China), and stress tester (062/
969921, China)
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Figure 1. Synthesis mechanism of EBC (A) and PANI-g-EBC nanocomposites (B); schematic model of PANI-g-EBC nanocomposites (C); and TEM
images of PANI, BC, EBC, and PANI-g-EBC nanocomposites (D).
Figure 2. SEM images of PANI-g-EBC nanocomposites formed with the reaction time of 0 min, 20 min, 40 min, 3 h, 6 h, 10 h, 16 h, and 24 h.
■ RESULTS AND DISCUSSION
Structure, Morphology, and Conductivity Analysis of
EBC and PANI-g-EBC Nanocomposite. The synthesis
mechanisms of EBC and PANI-g-EBC were exhibited in Figure
1A and B. ECP was incorporated into nanosized bacterial
cellulose (BC) via the condensation reaction between epoxy
groups in ECP and −OH groups in BC. PANI was subsequently
chemically grafted into BC through the reaction between epoxy
groups and amine groups; the schematic model is shown in
Figure 1C. The corresponding TEM morphology is shown in
Figure 1D. Pure PANI displayed spherical morphology with
particle sizes in the range of 20−90 nm, and BC presented 3D
network fabric structure. The incorporation of ECP into BC did
not significantly alter the network structure of BC. The PANI-g-
EBC sample displayed a 3D network structure constituted by
PANI modified BC nanofibers. Some spherical PANI particles
were also evident in the TEM image of PANI-g-EBC
nanocomposite. In our previous study, when conductive
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polymer/cellulose fibers were prepared through in situ oxidation
polymerization, conductive polymers not only deposited on the
fiber surface but also distributed inside the cellulose fiber wall to
form 3D conductive networks.23 Correspondingly, PANI can
also form 3D conductive networks on the surface and inside of
the EBC nanofiber, the spherical particles only represent a
fraction of PANI, and partial PANI form uniform and
continuous conductive film. The SEM morphology of PANI-
g-EBC nanocomposites formed with different reaction times was
also provided, as shown in Figure 2. As the reaction proceeded,
more and more PANI particles formed on the EBC nanofibers,
favorably forming a continuous conductive network.
The XPS N 1s spectra of aniline-g-EBC and PANI-g-EBC
nanocomposites were shown in Figure 3A and 3B, respectively.
Two distinct peaks corresponding to −NH2 and −NH species
were found at 399.4 and 398.4 eV (Figure 3A), which can be
ascribed to free aniline monomers and −NH groups formed by
the reaction of amine groups in PANI with epoxy groups in
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Figure 3. High resolution XPS N 1s spectra of aniline-g-EBC (A) and PANI-g-EBC nanocomposite (B); FTIR spectra of BC, EBC, PANI, PANI-g-
EBC nanocomposites (C); SEM images of EBC (D); SEM surface (E) and cross-sectional (F) images of BC; SEM surface (G) and cross-sectional
images (H) of PANI-g-EBC3 nanocomposites.
EBC.24,25 It also indicates the presence of aniline in the reaction
system as free monomers. Three peaks at 399.1, 398.4, and 397.6
eV corresponding to positively charged nitrogen (−NH3+),
benzenoid amine (−NH−), and quinoid amine (−N) were
identified for the PANI-g-EBC nanocomposite (Figure 3B),
demonstrating the oxidation polymerization of aniline mono-
mers with the addition of initiator APS.25 The related peak area
ratio was shown in Table 1, and the presence of the −NH3+ peak
confirmed the doped PANI.
Table 1. Peak Ratio Calculated Based on XPS Spectra
peak area ratio (%)
−NH2 −NH3+ −NH− -N
samples (399.4 eV) (399.1 eV) (398.4 eV) (397.6 eV)
aniline-g- 21.49 78.51
EBC
PANI-g- 12.22 39.69 48.09
EBC
FTIR spectra of BC and EBC were shown in Figure 3C. In the
FTIR spectra of BC, those at 3340, 2800−3000, and 1055 cm−1
were ascribed to the −OH, C−H stretching modes, and
absorption peaks of C−O−C, respectively.20 The characteristic
absorption peaks of BC were also observed in the FTIR spectra
of EBC, indicative of the intact BC structure. However, a new
peak at 910 cm−1 was detected in the FTIR spectra of EBC,
which can be assigned to the epoxy group, demonstrating the
successful incorporation of ECP into BC.26 In Figure 3C, the
characteristic peaks of PANI at 1467 and 1564 cm−1 were found
in the spectra of PANI-g-EBC nanocomposites, and the
characteristic absorption peak of epoxy group at 910 cm−1
disappeared, supporting the successful grafting of PANI into
EBC.27 SEM surface images of EBC, BC, PANI-g-EBC3 and
cross-sectional images of BC and PANI-g-EBC3 nanocompo-
sites were also shown in Figure 3D, E, G, F, and H, respectively.
The surface morphology of BC, EBC, and PANI-g-EBC3
nanocomposites displayed 3D network structures; furthermore,
the 3D network structure of PANI-g-EBC3 became more
compact compared with BC. Additionally, a layered structure
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was evident for the cross section of BC (Figure 3F), while dense
3D network structure was found for the PANI-g-EBC3
nanocomposites (Figure 3H).
Effects of Epoxy Content on Structure and Properties
of PANI-g-EBC. The epoxy content of PANI-g-EBC nano-
composites was determined through a hydrochloric acid−
acetone method, as shown in the Supporting Information (eq
S1),28 and it increased from 0.026 to 0.151 mol/100 g when the
ECP concentration was increased from 1.1 to 3.3 g/L and, then,
increased to 0.168 mol/100 g when the ECP concentration was
further increased to 5.5 g/L (Table S1). The retention of ECP
on BC increased from 44.1% to 85.3% by increasing the ECP
concentration from 1.1 to 3.3 g/L, then decreased to 56.9% by
further increasing the ECP concentration to 5.5 g/L. The
decrease of retention could be due to the self-polymerization of
ECP at a higher ECP concentration, the self-polymerization
mechanism of ECP is shown in Figure S1.29 As the epoxy
content increased, the retention of PANI increased from 47.7%
to 99.8% (Table S2). It is also worthy to note that the PANI
retention in BC/PANI was 41.1%, which is much lower than
that of PANI-g-EBC. The results indicate that the incorporation
of epoxy groups into BC is beneficial for the graft and retention
of PANI on BC.
The SEM and TEM morphology of PANI-g-EBC nano-
composites was shown in Figure 4. Significant PANI aggregation
was observed for the PANI-g-EBC1 sample due to the limited
amount of epoxy groups on BC, which was also supported by the
TEM analysis. By increasing the ECP concentration, the large
PANI aggregations disappeared, demonstrating the uniform
distribution of PANI in BC. Partial PANI was also evident inside
BC, indicating that aniline monomers penetrate into porous BC,
leading to the oxidative polymerization inside BC, as
demonstrated by TEM morphology. Our previous study showed
that the oxidative polymerization did occur on the fiber surface
and inside the porous fiber wall,23 which is beneficial to increase
the connected conductive paths, thereby increasing the
conductivity. By further increasing the ECP concentration,
fibers became aggregated, as a result of excessive interactions
among fibers. The representative models for PANI-g-EBC1,
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Figure 4. SEM (A), TEM (B), and representative models (C) for PANI-g-EBC1, PANI-g-EBC3, and PANI-g-EBC5 nanocomposites.

Figure 5. Electrical conductivity of PANI-g-EBC1, PANI-g-EBC2, PANI-g-EBC3, PANI-g-EBC4, and PANI-g-EBC5 composites (A); stress−strain
curves of PANI-g-EBC1, PANI-g-EBC2, PANI-g-EBC3, PANI-g-EBC4, and PANI-g-EBC5 composites (B); TGA decomposition curves of PANI-g-
EBC1, PANI-g-EBC3, and PANI-g-EBC5 (C); DTG curves of PANI-g-EBC1, PANI-g-EBC3, and PANI-g-EBC5 composites (D).

PANI-g-EBC3, and PANI-g-EBC5 are also given in Figure 4C,
which shows that the PANI-g-EBC samples form uniform and
connected conductive paths.
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The conductivity reached the max of 1.08 S/cm for the PANI-
g-EBC3 sample, which can be attributed to the formation of
more uniform and conductive paths (Figure 5A). In contrast, the
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Figure 6. XRD pattern (A), stress−strain curves (B), TGA decomposition curves (C), and DTG curves (D) of BC/PANI and PANI-g-EBC
nanocomposites.

Figure 7. TEM morphology (A, G), SEM surface morphology (B, H), SEM cross-section morphology (C, I), high magnification SEM images (D, J),
EDS mapping (E, K), and schematic model (F, L) of BC/PANI nanocomposites and PANI-g-EBC nanocomposites

decreased conductivity for samples PANI-g-EBC4 and PANI-g-
EBC5 can be ascribed to the inhomogeneous distribution of
PANI in these samples. In addition, excessive aniline monomers
react directly with epoxy groups, resulting in decreased
conductivity. The stress of PANI-g-EBC nanocomposites is
also investigated, as shown in Figure 5B. By increasing the ECP
concentration from 1.1 to 3.3 g/L, the stress increased from
12.41 to 18.47 MPa, the elongation at break also increased from
2.49% to 3.46%. At a low ECP concentration, the formation of
large PANI aggregations led to decreased interactions among
fibers, thereby decreasing the mechanical properties. By
increasing the ECP concentration, the stress increased due to
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the enhanced interactions among fibers. TGA and DTG curves
of PANI-g-EBC nanocomposites were also provided (Figure 5C
and D). The decomposition temperature at weight loss of 10%
for PANI-g-EBC3 nanocomposites increased to 342 °C, which
was compared to that of PANI-g-EBC1 (297 °C) and that of
PANI-g-EBC5 nanocomposite (320 °C). The DTG results also
indicated that the temperature at the maximum decomposition
rate increased from 274 to 352 °C for the PANI-g-EBC sample,
which can also be attributed to the increased interactions.
Comparison Study between in situ BC/PANI and PANI-
g-EBC Nanocomposites. Figure 6A shows XRD patterns of
BC/PANI and PANI-g-EBC nanocomposites, those at 14.7°,
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Figure 8. Schematic of reaction between PANI-g-EBC3 fiber and PAM and representative model of PANI-g-EBC3/PAM nanocomposites.
Figure 9. FTIR spectra of PANI-g-EBC3/PAM nanocomposites with different PAM content (A); XRD patterns of PANI-g-EBC3/PAM
nanocomposites (B); and UV spectra of PANI-g-EBC3/PAM nanocomposites (C).
18.2°, and 22.7° were typical for BC.18 The peak intensity
increased for the PANI-g-EBC sample, indicative of increased
crystallinity degrees. Compared with BC/PANI blend, the stress
of PANI-g-EBC also increased from 8.18 to 18.47 MPa, and the
elongation at break increased from 2.12% to 2.93% (Figure 6B).
The improved mechanical properties can be ascribed to the
increased 3D network structure and crystallinity, as discussed in
the previous section. TGA results (Figure 6C) revealed that the
decomposition temperature of PANI-g-EBC nanocomposites
was enhanced to 342 °C compared with BC/PANI nano-
composites (267 °C) when the weight loss was 10%. DTG
results also showed that the temperature at the maximum
decomposition for PANI-g-EBC increased from 315 to 352 °C,
indicative of the enhanced thermal stability (Figure 6D).
The TEM morphology of BC/PANI nanocomposites showed
that BC/PANI nanocomposites were composed of free PANI
particles and fiber networks with distinct PANI agglomerations
on fibers (Figure 7A). SEM surface (Figure 7B), cross-sectional
(Figure 7C) morphology, and high magnification SEM images
(Figure 7D) also indicated the presence of PANI aggregation on
the fiber surface. In contrast, few free PANI particles appeared in
the TEM morphology of PANI-g-EBC, only some PANI
particles were evident on the fiber surface (Figure 7G).
Compared with the cross-sectional morphology of BC/PANI,
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the PANI-g-EBC showed more compact structure, with finer
fibrils (Figure 7I), which is responsible for the fact that the
PANI-g-EBC sample exhibited higher conductivity and
mechanical properties. The electrical conductivity of PANI-g-
EBC3 was 1.08 S/cm, which was almost one order higher than
that of BC/PANI blend, supporting the conclusion that the
chemical graft method was much more efficient for improving
the uniform distribution of PANI in nanocomposites, thereby
improving conductive networks, thus the conductivity. EDS
mapping images of N element on nanofibers show that N
elements uniformly distribute on the surface of nanofibers,
forming the interconnected conductive network (Figure 7E and
K).
Improvement of Conductivity and Mechanical Prop-
erties with PAM Addition. To further improve the
conductivity and mechanical properties of composite paper,
polyamide (PAM) was added to the PANI-g-EBC3 system.
PAM is able to impart more hydrogen bonding between PANI
and PANI-g-EBC3 fibers, thereby forming interpenetrating
networks with PANI-g-EBC3 fiber and increasing the
mechanical properties; the reaction schematic and model of
PANI-g-EBC3/PAM are shown in Figure 8.
FTIR spectra of PANI-g-EBC3/PAM nanocomposites are
shown in Figure 9A. For the PANI-g-EBC3/PAM sample, the
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peak at 1668 cm−1 was ascribed to the CO stretching modes, However, some PAM desorbed from nanofibers by further
indicative of PAM.30 The characteristic absorption peaks of increasing the PAM concentration, which is responsible for the
PANI at 1480 and 1560 cm−1 also appeared in the FTIR spectra decreased N content (Table 2).
of PANI-g-EBC3/PAM.27 Figure 9B showed XRD patterns of By increasing the PAM concentration from 0.4 to 1.2 g/L, the
PAM, BC, and PANI-g-EBC3/PAM nanocomposites. The XRD fiber network becomes denser and denser, and small spherical
patterns BC showed typical peaks at 14.4°, 16.6°, and 22.7°18,31 PANI particles are also formed on the surface of fibers (Figure
all of which appeared in the PANI-g-EBC3/PAM sample, 10A). At a high PAM concentration (e.g., 1.2 g/L), PAM might
demonstrating that the crystalline structures of BC are intact in form polymer films on the fiber surface. In comparison with
the presence of PAM. By increasing the PAM content, these PANI-g-EBC3, the stress of PANI-g-EBC3/PAM increased
peaks became weaker and weaker. The UV absorption spectrum from 18.97 to 47.94 MPa, the elongation at break increased from
of PANI-g-EBC3/PAM (Figure 9C) showed a shoulder-like 2.93% to 4.58% (Figure 10B), which can be ascribed to the
absorption at 220−350 nm, corresponding to π−π* benzenoid enhanced interaction between fibers as a result of PAM addition.
rings and a strong absorption of polaron band at 740−800 Moreover, the decomposition temperature at the weight loss of
nm.32,33 Additionally, those at 220−350 nm of the PANI-g- 10% for PANI-g-EBC3/PAM1, PANI-g-EBC3/PAM3, and
EBC3/PAM2 nanocomposites red-shifted and became stronger PANI-g-EBC3/PAM5 is 207, 236, and 252 °C, respectively,
compared to those of the PANI-g-EBC3/PAM5, indicative of indicative of increased thermal stability due to the enhanced
conductive conjugated double bonds. As the PAM concen- interactions (Figure 10C).
tration increased from 0.0 to 0.6 g/L, the N content increased The conductivity of PANI-g-EBC3/PAM nanocomposites
from 2.496% to 4.072% and then decreased to 2.555% by increased from 1.24 to 1.43 S/cm when the PAM concentration
increasing the PAM concentration further to 1.2 g/L (Table 2). was increased from 0.4 to 0.6 g/L and then decreased to 1.02 S/
cm when the PAM concentration increased to 1.2 g/L (Figure
Table 2. Elemental Content of PANI-g-EBC3 and PANI-g- 10D). The main reason for the decreased conductivity at a very
EBC3/PAM Nanocomposites high PAM concentration is that PAM is nonconductive, and
excessive amounts on the fiber surface destroyed the conductive
samples N (%) C (%) O (%) H (%)
paths. The conductivity of PANI-g-EBC3/PAM (1.43 S/cm)
PANI-g-EBC3 2.496 46.950 44.383 6.171 was also higher than that of PANI-g-EBC3 (1.08 S/cm, Table 3).
PANI-g-EBC3/PAM1 2.348 46.43 45.084 6.138
PANI-g-EBC3/PAM2 4.072 48.90 40.967 6.061 Table 3. Electrical Conductivity of PANI-g-EBC3, PANI-g-
PANI-g-EBC3/PAM3 3.993 48.91 41.024 6.073 EBC3/PAM, and BC/PANI/PAM Nanocomposites
PANI-g-EBC3/PAM4 3.736 48.73 41.460 6.074
PANI-g-EBC3/PAM5 2.555 46.72 44.579 6.146 samples electrical conductivity (S/cm)
PANI-g-EBC3 1.08
PANI-g-EBC3/PAM 1.43
By increasing the PAM concentration, more and more PAM was BC/PANI/PAM 0.97
adsorbed on PANI-g-EBC3 nanofiber via hydrogen bonding.

Figure 10. SEM surface morphology of PANI-g-EBC3/PAM1, PANI-g-EBC3/PAM3, PANI-g-EBC3/PAM5 nanocomposites (A); mechanical
properties (B) and TG thermograms (C) of PANI-g-EBC3/PAM nanocomposites; and electrical conductivity of PANI-g-EBC3/PAM
nanocomposites (D).

8222 DOI: 10.1021/acssuschemeng.8b06306

ACS Sustainable Chem. Eng. 2019, 7, 8215−8225
ACS Sustainable Chemistry & Engineering Research Article

Figure 11. Electrical conductivity of PANI-g-EBC (A) and PANI-g-EBC3/PAM2 (B) nanocomposites under different bending conditions.

Figure 12. Volume resistivity (A), tear index (B), folding endurance (C), and tensile index (D) of composite paper with different contents of PANI-g-
EBC3 conductive fibers; surface resistivity (E), tearing index (F), folding endurance (G), and tensile index (H) of conductive nanocomposite paper
with different contents of PANI-g-EBC3/PAM conductive fibers; strengthening mechanism of nanosized conductive fiber on composite paper (I); and
bending, rolling, and folding photograph of nanocomposite paper (J).

The conductivity of BC/PANI/PAM (0.97 S/cm, Table 3) was
also higher than that of BC/PANI (0.12 S/cm). These results
support the notion that moderate amounts of PAM can improve
the nanocomposite conductivity via enhancing the interactions
among fibers and PANI (Table 3). The conductivity of PANI-g-
8223
EBC and PANI-g-EBC3/PAM2 nanocomposites under differ-
ent bending conditions was also measured (Figure 11). The
conductivity of PANI-g-EBC3 nanocomposites was 10.18%
lower after folding 50 times. In contrast, the conductivity of
PANI-g-EBC3/PAM nanocomposite was only 4.89% lower after
DOI: 10.1021/acssuschemeng.8b06306
ACS Sustainable Chem. Eng. 2019, 7, 8215−8225
ACS Sustainable Chemistry & Engineering
folding 160 times. The conductivity of PANI-g-EBC3/PAM
under bending conditions improved with the PAM addition.
Preparation of Flexible Conductive Nanocomposite
Paper. PANI-g-EBC3 and PANI-g-EBC3/PAM2 conductive
fibers were blended with original cellulose fibers to make flexible
conductive nanocomposite paper; the resistivity, tearing index,
folding endurance, and tensile index of the nanocomposite paper
are shown in Figure 12. By increasing the PANI-g-EBC3 content
from 5% to 30%, the resistivity decreased from 9.92 to 3.21 kΩ/
cm, the tearing index increased from 6.15 to 9.02 mN·m2/g, the
folding endurance increased from 13 to 50 times, and the stress
increased from 13 to 30.11 N·m/g, followed by a slight decrease
when the PANI-g-EBC3 addition was higher than 20%. The
tearing index, folding endurance, and tensile index for the
original paper made of the original cellulose fibers were 5.49
mN·m2/g, 9 times, and 8.89 N·m/g, respectively. The results
suggest that the incorporation of nanosized PANI-g-EBC3
conductive fibers into conventional cellulose fibers can enhance
the interactions among cellulose fibers, thereby significantly
increasing the paper strength.
Compared with PANI-g-EBC3/plant fiber nanocomposite
paper, the resistivity of PANI-g-EBC3/PAM2/cellulose fiber
nanocomposite paper decreased from 3.13 to 1.56 kΩ/cm with
the addition of only 10% PANI-g-EBC3/PAM2 nanofibers. The
tearing index, folding endurance, and tensile index reached
17.92 mN·m2/g, 171 times, and 43.67 N·m/g when the PANI-g-
EBC3/PAM2 content was 25%, which was much higher than
those of the PANI-g-EBC3 nanocomposite paper (9.02 mN·m2/
g, 50 times, and 30.11 N·m/g). The as-prepared nanocomposite
paper was foldable, rollable, and bendable (Figure 12J). It can be
concluded that the incorporation of PANI-g-EBC3/PAM2
nanofibers is able to generate strong conductive networks for
cellulose fibers, leading to comprehensive improvement of
conductivity and mechanical properties.
The strengthening mechanism of adding nanosized con-
ductive fibers is summarized in Figure 12I. Generally, paper
strength depends mainly on the hydrogen bonds between fibers.
The incorporation of nanofibers is able to increase the number
of hydrogen bonds between fibers, and functions as “bridges” to
connect the plant cellulose fibers; furthermore, the increased
interactions between fibers also leads to denser and stronger 3D
networks, as demonstrated by the SEM results (Figure 12Ib). By
increasing the amount of nanofibers, more and more nanofibers
are inserted into cellulose fibers, there are more interactions
between nanofibers and original fibers. Nanofibers simulta-
neously functionalize as nanofillers and bridges for original
fibers, thereby improving the interaction between fibers to
improve the mechanical properties of composite paper, the
bridging-filling function mechanism is shown in Figure 12Ic.
However, when the cellulose fibers are totally filled with PANI-
g-EBC3 fibers, the original hydrogen bonds between fibers are
almost totally destroyed and replaced by the interactions
between conductive nanofibers. The interactions between
conductive nanofibers are weakened since the surface of
nanofibers was covered by conductive PANI, resulting in
decreased mechanical properties (Figure 12Id).
■ CONCLUSION
The conductivity and mechanical properties of bacterial
cellulose/polyaniline (PANI) nanocomposites were signifi-
cantly improved by chemical grafting of PANI onto epoxy
modified BC (EBC), and a higher graft efficiency of PANI on
EBC was achieved by increasing the epoxy content. PANI
8224
Research Article
aggregations on fiber surfaces occurred at a low epoxy range, and
fiber aggregation was observed at a high epoxy range. In contrast,
more uniform and connected networks were formed when the
epoxy content was 0.151 mol/100 g, resulting in the improved
conductivity and mechanical properties. PANI-g-EBC nano-
composite paper also displayed higher conductivity and
mechanical properties than that of the in situ BC/PANI sample.
By adding moderate amounts of PAM into PANI-g-EBC, the
conductivity and mechanical properties of PANI-g-EBC3/PAM
nanocomposite paper were further improved, which is due to the
enhanced interactions between fibers and the PAM-aided denser
fiber networks. A slight decrease in the conductivity of PANI-g-
EBC3/PAM nanocomposite was observed after 160 folds. Based
on bridging-filling function mechanisms, the as-prepared PANI-
g-EBC and PANI-g-EBC3/PAM nanofibers can also blend with
conventional cellulose fibers to make flexible and conductive
composite paper of high strength. These novel nanocomposites
may have prosperous applications in various fields such as
flexible electronic devices and antistatic and electromagnetic
materials.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acssusche-
meng.8b06306.
Data and discussion on the determination of the epoxy
value (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*Tel.: +86-18681808820. E-mail address: whh@sust.edu.cn.
ORCID
Yonghao Ni: 0000-0001-6107-6672
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
The authors express sincere thanks to the Key Research and
Development Program of Shaanxi Province−International
Cooperation Project (No. 2018KW-007), Key Research and
Development Program of Shaanxi Province (No. 2017GY154),
Innovation Supporting Plan of Shaanxi Province−Innovation
Research Team (No. 2018TD-015), National Natural Science
Foundation of China (No. 21505089), Scientific Research
Foundation (SRF) for Returned Overseas Chinese scholars
(ROCS), and State Education Ministry (SEM) (No. [2012]
1707).
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