Materials Letters 81 (2012) 131–134

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Porous bacterial cellulose prepared by a facile surfactant-assisted foaming method in

azodicarbonamide-NaOH aqueous solution
Na Yin, Shiyan Chen ⁎, Zhe Li, Yang Ouyang, Weili Hu, Lian Tang, Wen Zhang, Bihui Zhou, Jingxuan Yang,
Qiushu Xu, Huaping Wang ⁎⁎
State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai, 201620, PR China

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

Article history: Bacterial cellulose (BC) with a porous structure was prepared via a facile surfactant-assisted foaming method
Received 7 November 2011 in azodicarbonamide (AC)-NaOH aqueous solution under mild condition. The time-saving and flexible
Accepted 26 April 2012 procedure comprises immersing and foaming of BC membranes in AC solution, washing and subsequent
Available online 5 May 2012
freeze drying. The results showed that BC with the surfactant Tween 80 assisted foaming treatment had
the homogeneous and interconnected spherical macroporous structure with the pore size up to 20 μm.
Keywords:
Porous materials
Compared to native BC, its mesoporous surface area was increased from 56.87 m 2/g to 169.86 m2/g, the
Microstructure porosity was increased from 28.3% to 90.8% and the maximum water adsorption was increased from 997%
Bacterial cellulose to 7611%.
Foaming Crown Copyright © 2012 Published by Elsevier B.V. All rights reserved.
Azodicarbonamide
Surfactant

1. Introduction Azodicarbonamide (AC) is one of the most favored nontoxic

Porous carbon materials with shaped and interconnected porous
structures are of particular interest because of their distinct
adsorption capability and facilitated mass transport [1,2]. As the
most abundant and renewable polymer, cellulose has been used to
construct porous materials for adsorption, separation, gas storage
and other applications [3–8]. In the earlier studies, bacterial cellulose
(BC) has attracted considerable attention due to its remarkable
properties including high tensile strength, good water holding
capacity, high crystallinity and excellent biocompatibility [9].
Moreover, the presence of an ultrafine network architecture with
distinct tunnel and a large number of nanopores makes BC a potential
scaffold for mass production of porous cellulose materials [10].
Development of an environmentally friendly technique for
fabrication of porous BC is important. The key factor is the regulation
and control of porous structures. Several research groups have
attempted to obtain the structure in BC by drying with supercritical
carbon dioxide (scCO2) [11,12]. However, it is difficult to achieve
the shaped and homogeneous porous structure. The special scCO2
equipment and strict experimental conditions limit its large-scale
preparation and wide range of application. Therefore, it is a great
challenge to find an effective method to fabricate this promising BC
structure.
⁎ Corresponding author. Tel.: + 86 21 67792950; fax: + 86 21 67792726.
⁎⁎ Corresponding author. Tel.: + 86 21 67792951; fax: + 86 21 67792726.
E-mail addresses: chensy@dhu.edu.cn (S. Chen), wanghp@dhu.edu.cn (H. Wang).
chemical foaming agents. Therefore, AC has been widely used for
producing porous materials [13]. Up to now, preparation of porous
BC via AC foaming has not been reported. Generally, in order to obtain
a homogenous and shaped macroporous structure, BC should be
dissolved in suitable solvents to generate a cellulose gel solution
prior to foaming so that the AC particles can be evenly dispersed.
Even if BC was dissolved, it would be transformed for the regenerated
cellulose with the loss of BC characteristics [10]. In addition, fast gas
release rate during AC decomposition will lead to difficulties in
forming the structure due to the strong hydrogen bonds between
BC nanofibers [14]. Herein, we exploit a new approach to fabricate
porous BC using AC-NaOH aqueous solution. Moreover, the new
technique offered an opportunity to produce the porous BC in large
scale and at a low cost.
2. Experimental
2.1. Preparation of porous BC
Briefly, AC solution was prepared by adding 3 g AC and 4 g NaOH
into 200 ml of ultrapure water. Then water-wet BC pellicles
(40 mm × 60 mm × 3 mm) with 200 mg of dry cellulose were
immersed in a breaker containing a mixture of AC solution and
0.5 ml surfactant. After that the stabilizer 3 w/v % polyvinyl acetate
(PVA) aqueous solution which can provide extra adequate steric
stabilization to prevent the formed foams from aggregating was
added into the breaker. Subsequently the mixture was heated at

0167-577X/$ – see front matter. Crown Copyright © 2012 Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2012.04.133
132 N. Yin et al. / Materials Letters 81 (2012) 131–134

Fig. 1. Schematic for the preparation of porous BC.

60 °C for 30 min. Finally, BC membranes were washed. The sample
treated by AC solution, AC solution added Tween 80 and AC solution
added Span 80 was labeled as BC-1, BC-2 and BC-3 respectively.
Thereafter, the control sample BC was identified as native BC. The
resultant samples were freeze-dried at −52 °C for 24 h before further
characterization.
2.2. Characterization
The morphologies of the samples were visualized by using Hitachi
S-4800 FE-SEM. The Brunauer–Emmett–Teller (BET) surface area of
the samples with pore size in the range from 0.1 to 100 nm was
investigated by nitrogen sorption with Micromeritics ASAP 2020.
Freeze-dried BC was immersed in ultrapure water for 48 h until it
gets fully saturated and the porosity (P) of the sample was
determined using the following equation: P = (W2 − W1) / (ρ × V1),
where W1 and W2 represent the weight of the samples before and
after immersing. V1 is the volume of the sample before immersing
and ρ is a constant of the density of water [15].
Freeze-dried BC was immersed in ultrapure water to study its
water absorption performance. Water absorption (Wb) at time t was
calculated using the following equation: Wb = [(Wt − W0) /W0] × 100%,
where W0 is the specimen's initial weight and Wt is the weight after
immersion time t [10].
3. Results and discussion
Fig. 1 gives a schematic diagram of the fabrication mechanism of
the porous BC. The ultrafine network architecture of BC gives a good
channel for AC in NaOH aqueous solution penetration through the
inner network of BC [16]. A number of the hydroxyl groups of BC
could interact with the amine groups of AC to form the hydrogen
bonds which ensure the uniform distribution of AC on the surface of
the BC nanofibers. After being heated to 60 °C and AC being

Fig. 2. FE-SEM images of the internal surfaces of (a) BC, (b) BC-1, (c) BC-2 and (d) BC-3, and the cross section of BC-2: (e) and (f).
 N. Yin et al. / Materials Letters 81 (2012) 131–134 133

Table 1
BET surface area and mesoporosity of the BC samples.

Sample Treatment Porosity BET surface Pore volume Pore diameter

(%) area (m2/g) (cm3/g) (nm)

BC – 28.3% 56.87 0.263 19.52

BC-1 AC solution 81.2% 143.22 0.381 25.47
BC-2 AC solution + 90.8% 169.86 0.439 28.83
Tween 80
BC-3 AC solution + 87.1% 152.65 0.412 26.70
Span 80

decomposed, gas comprising ammonia, carbon dioxide and nitrogen

was released, which formed bubbles to expand the tangle network
structure in BC [12].
Nevertheless, the strong hydrogen bond and rapid yield of gas
limited the regular and massive macropore formation in the wet BC
membrane. It has been proven that the addition of surfactants into
the polymer gel solution resulted in a spherical and homogeneous
porous structure during foaming [17]. In this study, Tween 80 and
Span 80 were selected to be added into the AC solution due to their
excellent foaming stability, and were expected to disperse along the
network of BC for forming stable bubbles. They tended to absorb
onto gas–liquid interfaces with a hydrophobic part and a hydrophilic
part for stabilizing the bubbles to interrupt the hydrogen bonds [18].
The FE-SEM image of the native BC shows an ultrafine 3D
nanoporous network structure with random fiber orientation in
Fig. 2a. From Fig. 2b, a small percentage of macropores (2–8 μm)
with an irregular shape were formed, which was similar to the
structure of the BC aerogels by scCO2 drying [11]. However, Fig. 2c
exhibits an orderly open-porous cellulose network, which consists
of a well uniform and spherical macropore system with a diameter
of up to 20 μm and a mesoporous structure. Fig. 2e, f confirmed the
presence of uniformly interconnected macropores formed by the
clew-type agglomeration of cellulose ribbons. Whereas, the 3D
network structure of BC-3 exhibited a few disordered macropores
(2–12 μm) without interconnection despite the presence of Span 80.
It is explained that Tween 80 has a better performance for controlling
pore bubble formation than Span 80 due to producing higher surface Fig. 3. (a) Water absorption curves of the BC samples and (b) the maximum water
elasticity of the interface between gas and liquid [19]. absorption curves with different pore volumes and thicknesses.
The results of the BET surface area and mesoporosity of the samples
are listed in Table 1. The pore diameters of BC, BC-1, BC-2, and BC-3 are water storage area. Moreover, interconnected and open macropores
19.52 nm, 25.47 nm, 28.83 nm and 26.70 nm, respectively, which have shown to make solution flow more quickly. As a result, BC-2
indicates that the BC nanofibrous network has been enlarged during showed the largest water adsorption rate. The structure had an
foaming. Besides, the thickness of BC, BC-1, BC-2 and BC-3 was outstanding water absorption ability, which endowed BC more
measured to be 0.11 mm, 3.18 mm, 3.96 mm and 3.53 mm, respectively promising applications.
by using a vernier caliper. As is known to all, the volumetric swell of the
BC membranes causes the increase of the thickness. BC-2 has the 4. Conclusions
highest porosity, pore volume and thickness in this study. The highest
pore volume and the largest BET surface area of BC-2 might be ascribed The porous BC has been prepared by a simple and effective Tween
to the presence of Tween 80, which promoted the enlargement of the 80 assisted AC foaming approach. Compared to other methods,
original nanopore network. foaming technique could generate 3D macropores in BC wet state
The high porosity and large surface area of BC allow rapid without shrinkage even after freeze drying. BC with homogenous
adsorption of aqueous liquids [7,20]. Fig. 3 displays the water and interconnected spherical macropores (10–20 μm) with tertiary
adsorption process for native BC and porous BC. After a fast water mesoporous network was formed. In addition, the water adsorption
adsorption during the first stage, the water sorption slowed down, increased up to 7611% with the increased mesoporosity and the
and gradually got to a plateau after 10 min, which is in accordance spherical macropore formation of BC.
with the BC water sorption pattern [21]. BC shows water adsorption
of about 992% after 20 min due to its dense mesh network, the large
Acknowledgments
water adsorption results from the macropore formation and enlarged
ultrafine fibril network. Hence, BC-1, BC-2 and BC-3 absorbed much
This work was financially supported by the Program of
more water reaching the water adsorption levels of 6590%, 7611%
Introducing Talents of Discipline to Universities (B07024).
and 6771%, respectively. In addition, Fig. 3 shows the maximum
water adsorption increases with the increasing of pore volume of
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