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Structure and properties of hydrogels prepared

from cellulose in NaOH/urea aqueous solutions

ARTICLE in CARBOHYDRATE POLYMERS · AUGUST 2010

Impact Factor: 4.07 · DOI: 10.1016/j.carbpol.2010.04.033

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Carbohydrate Polymers 82 (2010) 122–127

Contents lists available at ScienceDirect

Carbohydrate Polymers
journal homepage: www.elsevier.com/locate/carbpol

Structure and properties of hydrogels prepared from cellulose in NaOH/urea

aqueous solutions
Chunyu Chang a , Lingzhi Zhang a , Jinping Zhou a,∗ , Lina Zhang a , John F. Kennedy b
a
Department of Chemistry, Wuhan University, Wuhan, Hubei 430072, China
b
Chembiotech Laboratories, Advanced Science and Technology Institute, 5, The Croft, Buntsford Drive, Stoke Heath, Bromsgrove, Worcestershire, B60 4JE, UK

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

Article history: Hydrogels have been successfully prepared from cellulose in NaOH/urea aqueous solution by using
Received 31 October 2008 epichlorohydrin (ECH) as a cross-linker, and via heating and freezing methods. Structure and properties
Received in revised form 29 March 2010 of the hydrogels were measured with UV–vis spectroscopy, SEM, XRD, solid-state 13 C NMR, rheome-
Accepted 14 April 2010
try and water absorption testing. The results indicated that hydrogels prepared by heating displayed
Available online 21 April 2010
macroporous inner structure, while fiber-like structure could be observed in the hydrogels prepared by
freezing. The light transparency and equilibrium swelling ratio of the hydrogels decreased, while the
Keywords:
reswelling water uptake and the storage modulus increased, with an increase of the cellulose content.
Cellulose
Hydrogel
Compared with the hydrogels post-treated by freezing, the hydrogels prepared by heating displayed bet-
Cross-linking ter light transmittance, higher equilibrium swelling ratios and reswelling water uptakes, and relatively
Transparency weaker mechanical strength. Therefore, the structure and properties of the hydrogels could be adjusted
Swelling by changing the cellulose content and the post-treatment methods.
© 2010 Elsevier Ltd. All rights reserved.

1. Introduction Cellulose is the most abundant polysaccharide available

worldwide, and is considered an almost inexhaustible source
Hydrogels are defined as three-dimensional network of of raw material for the increasing demand for environmentally
hydrophilic polymers, which can absorb and retain a significant friendly and biocompatible products (Klemm, Heublein, Fink,
amount of water. To obtain the network, chemical cross-linking & Bohn, 2005). Cellulose-based hydrogels can be obtained by
(Denizli, Can, Rzaev, & Guner, 2004; Kiritoshi & Ishihara, 2004; chemical cross-linking of water-soluble cellulose derivatives using
Molina, Gomez-Anton, & Pierola, 2007; Zhao, Liao, Gao, & Liu, 2006), small difunctional molecules as cross-linker (Rodríguez, Alvarez-
physical entanglement (Saito, Sakurai, Sakakibara, & Saga, 2003), Lorenzo, & Concheiro, 2003; Sannino et al., 2004; Yan, Qian, & Zhu,
ionic bonds (de la Torre, Torrado, & Torrado, 2003; Kang, Park, Lee, 2001). The synthesis of cellulose-based hydrogels by radiation is
& Son, 2007; Masci, Husu, Murtas, Piozzi, & Crescenzi, 2003; Wong, also a convenient method (Chauhan, Lal, & Mahajan, 2004; Ibrahim,
Díez-Pascual, & Richtering, 2009) and hydrogen bonds (Jin, Liu, El Salmawi, & Zahran, 2007; Liu, Zhai, & Ha, 1999; Soderqvist
Zhang, Chen, & Niu, 2006) are used in the preparation of hydrogels. Lindblad, Albertsson, Ranucci, Laus, & Giani, 2005). A new
Polymer hydrogels have been widely utilized as drug delivery, food, method for preparing cellulose-based hydrogels had been tried
cosmetics, high water-absorbing resin, contact lenses, corneal, by Marsano, Bianchi, and Viscardi (2004). N-isopropylacrylamide
implant, substitutes for skin, tendons, ligaments, cartilage, and (NIPA) monomer solution was absorbed into a dried porous
bone, because of their excellent hydrophilicity, permeability, com- hydropropyl cellulose (HPC) network and cross-linked inside the
patibility and low coefficient of friction (Calvert, 2009; Chang, Duan, network by N,N -methylenebisacrylamide at 25 ◦ C. Moreover,
Cai, & Zhang 2010; Chan, Whitney, & Neufeld, 2009; Liu & Fan, 2005; Xie and Hsieh provided a two-step initiation and polymerization
Yamamoto, Takahashi, & Tabata, 2003). The hydrogels from natural process for the preparation of PNIPAAm hydrogel-cellulose com-
polymers, especially polysaccharides, are promising for application posites. All the cellulose-supported hydrogels exhibited a lower
in the biomaterial field, because of their unique advantages, such extent of phase temperature over a wider temperature range
as abundance, non-toxicity, biocompatibility, biodegradability, and than the free PINPAAm hydrogels (Xie & Hsieh, 2003). Yoshimura,
biological functions (Cavalieri et al., 2006; Prabaharan & Mano, Matsuo, and Fujioka (2006) prepared novel biodegradable super-
2006; Yu, Lu, & Xiao, 2007; Zhai, Yoshii, Kume, & Hashim, 2002). absorbent hydrogels from cotton cellulose and succinic anhydride
in the presence of 4-dimethylaminopyridine as an esterification
catalyst. Liu et al. (2004) reported a rapid temperature-responsive
∗ Corresponding author. Tel.: +86 27 87219274; fax: +86 27 68754067. sol–gel reversible poly(N-isopropylacrylamide)-g-methylcellulose
E-mail address: [email protected] (J. Zhou). (PNIPAAm-g-MC) copolymer hydrogel. However, hydrogels pre-

0144-8617/$ – see front matter © 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbpol.2010.04.033
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C. Chang et al. / Carbohydrate Polymers 82 (2010) 122–127 123

pared from unsubstituted cellulose have been scarcely reported, of 200–800 nm by using an ultraviolet–visible spectrophotometer
because of the insolubility of cellulose in aqueous solutions and in (Shimadzu UV-160A). Scanning electron micrographs (SEM) were
most organic solvents. taken with a Hitachi S-570 microscope. The hydrogels swollen to
Previously, we reported that novel cellulose hydrogels were equilibrium in distilled water at 30 ◦ C were frozen in liquid nitro-
synthesized through a “one-step” method from unsubstituted gen and snapped immediately, and then freeze-dried. The fracture
cellulose, which was dissolved directly in NaOH/urea aqueous solu- surface of the hydrogel was sputtered with gold, and was observed
tion, by using epichlorohydrin (ECH) as cross-linker (Zhou, Chang, and photographed.
Zhang, & Zhang, 2007). Furthermore, the unique gelation behavior Hydrogels were freeze-dried and were cut into particle-like
of cellulose in NaOH/urea aqueous solution has been studied, and size, and vacuum-dried for 24 h at 50 ◦ C before measurements of
either heating or cooling treatment could result in the gel forma- XRD and NMR. XRD measurement was carried out on an X-ray
tion (Cai & Zhang, 2006). As an extension of our previous work, we diffractometer (D/MAX-1200, Rigaku Denki, Japan). An XRD pat-
attempt to prepare hydrogels from cellulose in NaOH/urea aque- tern with Cu K␣ radiation (1.5406 × 10−10 m) at 40 kV and 30 mA
ous solution by different post-treatments, i.e., heating and freezing was recorded in the range 2 = 6–40◦ at a scanning speed of 2◦ /min.
methods. Structure and properties of the two series of hydrogels 13 C cross-polarization magnetic angle spinning (CP/MAS) solid-

were investigated and compared. state NMR spectra were recorded on an Infinity Plus spectrometer
(13 C frequency = 100 MHz) with a CP/MAS unit at ambient temper-
2. Experimental ature. The spinning rate and the contact time were 5.0 kHz and
5.0 ms, respectively. Pulse width was 2.10 ␮s, spectra width was
2.1. Materials 50,000 kHz, acquisition time was 20.48 ms, and the spectrum was
accumulated 2000 times.
Whatman CF-11 fibrous cellulose powder (Catalogue No.
4021050) was used as the starting cellulose; the weight average 2.4. Swelling and reswelling measurements
molecular weight (Mw ) was determined to be 3.46 × 104 by static
laser light scattering. Epichlorohydrin (ECH) was analytical-grade, The hydrogels were incubated in distilled water for at least 24 h
and was used without further purification. at 25 ◦ C. The swelling ratios (SR) of the hydrogels were measured
gravimetrically after the sample surfaces had been wiped with
2.2. Preparation of hydrogels moistened filter paper to remove water, and defined as
Ws − Wd
An aqueous solution of 6 wt% NaOH/4 wt% urea consisted of 60 g SR(%) = × 100 (1)
Wd
of NaOH, 40 g of urea and 900 mL of dilute water, and the resulting
solution was filtered with a G2 sand filter to be used as solvent of where Wd and Ws are the weights of dried and swollen hydrogels,
cellulose. A cellulose solution was prepared according to our previ- respectively.
ous work (Zhang & Zhou, 2003), that is, a certain amount of CF-11 The vacuum-dried hydrogels were immersed in distilled water
was dispersed into 100 g of solvent with stirring for 5 min and then to rehydrate at 25 ◦ C. The reswelling kinetics of the hydrogels was
was stored in a refrigerator (−5 to −10 ◦ C) for 12 h. The frozen solid measured gravimetrically. The samples were removed from water
was thawed and stirred extensively at room temperature to obtain at regular time intervals. After the sample surfaces had been wiped
a colorless and transparent cellulose solution. with moistened filter paper to remove water, the weights of the
In a typical synthesis procedure, a certain amount of ECH gels were recorded. Water uptake (WU) was defined as
was added dropwise to the 100 g cellulose solution mentioned Wt
previously, and the mixture was stirred at 25 ◦ C for 1 h. Two post- WU(%) = × 100 (2)
Wd
treatment methods, heating the mixture to 50 ◦ C for 20 h (Gel-H
series) or freezing the mixture to −20 ◦ C for 20 h (Gel-F series), were where Wt is the weight of the swollen hydrogel at a designated time
carried out for gelation of the mixtures. Hydrogels as-obtained were (t) during swelling.
washed with a large amount of distilled water to remove NaOH and
urea completely, and then vacuum-dried or freeze-dried by using 2.5. Rheological measurement
a lyophilizer (CHRIST Alpha 1-2, Germany). According to Table 1,
by changing the content of cellulose from 2 wt% to 4 wt%, and the Viscoelastic measurements were performed on an ARES-RFS III
amount of ECH from 9 mL to 5 mL, six colorless and transparent rheometer (TA Instruments, U.S.A.). Hydrogels were prepared in
cellulose hydrogels were prepared, and coded as Gel-H2, Gel-H3, the form of disks with a diameter of 30 mm and thickness of 2 mm.
Gel-H4, Gel-F2, Gel-F3 and Gel-F4, respectively. Samples were tested using parallel plate geometry with a diameter
of 50 mm. Samples were first subjected to a strain sweep test in
which they were deformed at different shear strains, and the mod-
2.3. Characterization
ulus G was independent of the applied strain. A deformation of 10%
was chosen in the subsequent tests to ensure that each measure-
Cellulose hydrogels were cut into thickness of l cm and the trans-
ment was made in linear viscoelastic region. A frequency sweep
mittance of hydrogels was measured over the wavelength range
test was conducted on each sample from 0.1 to 100 Hz at 25 ◦ C.

Table 1
3. Results and discussion
Chemical composition and reactive conditions of the cellulose hydrogels.

Code Vcellulose (mL) ccellulose (wt%) VECH (mL) Methods Time (h) 3.1. Morphology and structure
Gel-H2 100 2 9 Heating 20
Gel-H3 100 3 7.4 Heating 20 Table 1 displays the reaction conditions of the cellulose hydro-
Gel-H4 100 4 5 Heating 20
gels by heating and freezing methods. With increasing of cellulose
Gel-F2 100 2 9 Freezing 20 content from 2 wt% to 4 wt%, the amount of ECH added into the
Gel-F3 100 3 7.4 Freezing 20 solution decreased from 9 mL to 5 mL due to the physical cross-
Gel-F4 100 4 5 Freezing 20
linking and chain entanglement of cellulose molecules. Based on
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124 C. Chang et al. / Carbohydrate Polymers 82 (2010) 122–127

Fig. 1. Photographs of the cellulose hydrogels: (a) Gel-H2 and (b) Gel-F2.

the Williamson etherification and the alkali-catalyzed oxalkyla-

tion, cellulose dissolved in NaOH/urea aqueous solution could be
chemically cross-linked by ECH to form hydrogels, and without
addition of an extra base because of the basicity of the solvent sys-
tem. On the other hand, physically cross-linked gels could form in
the cellulose—NaOH/urea aqueous solution at either higher tem-
perature (above 30 ◦ C), or lower temperature (below −3 ◦ C), or
for longer gelation time (Cai & Zhang, 2006). Therefore, hydrogels
treated by heating and freezing methods are thought to be both
chemically and physically cross-linked. In a heating process, physi-
cal cross-linking of the hydrogels is mainly attributed to the random
chain entanglement for the desolvation of cellulose molecules,
forming an amorphous structure. While in a freezing process, phys-
ical cross-linking is mainly attributed to a slower and stronger
self-association of the chains as a result of the strong hydrogen
bonding among cellulose chains and molecules of solvent, resulting
in a denser cross-linked structure. It is well known that poly(vinyl
alcohol) (PVA) aqueous solution will form a gel if the cryogenic Fig. 2. The transparency of cellulose hydrogels prepared by heating and freezing
treatment is applied (Hassan & Peppas, 2000; Hassan, Ward, & methods.
Peppas, 2000; Stauffer & Peppast, 1992). These phenomena result
from the formation of inter-molecular hydrogen bonds when the Fig. 4 shows the SEM images of the cellulose hydrogels prepared
PVA chains come together. by heating and freezing methods with different cellulose content.
Fig. 1 shows the photographs of the cellulose hydrogels (diame- Gel-H series (post-treated by heating method) display macrop-
ter × height, 7 cm × 4 cm) treated by heating (Gel-H2) and freezing orous inner structure, and the pore size decreases with an increase
(Gel-F2) methods. Clearly, the transparency of Gel-H2 is better than of the cellulose concentration. Interestingly, fiber-like structure
that of Gel-F2, but Gel-F2 displays a relative higher mechanical could be observed in the fracture surfaces of the Gel-F series (post-
strength. The transmittances of ultraviolet and visible light for the
cellulose hydrogel samples are shown in Fig. 2. In the wavelength
range between 400 and 800 nm, all samples presented a relatively
high transparency. It can be seen that the transparency of the cel-
lulose hydrogels cross-linked with ECH decreased with increasing
cellulose content. Along with the chemical composition of cellu-
lose hydrogels, the transparency for hydrogels are basically in the
order of Gel-H2 > Gel-H3 > Gel-H4 and Gel-F2 > Gel-F3 > Gel-F4. This
maybe due to greater aggregation of cellulose chains when the
hydrogels are prepared from relative higher concentration. How-
ever, transparency of the hydrogels from the freezing method was
lower than that from heating. The freezing method may lead to the
increase of crystalline regions within the three-dimensional net-
work structure, which resulted in the loss of light transparency.
The results could be confirmed by the XRD patterns of the hydro-
gels of Gel-H2 and Gel-F2 as shown in Fig. 3. Gel-H2 and Gel-F2
display similar diffraction peaks at 2 = 20◦ and 22◦ , which cor-
respond to the (1 1 0) and (2 0 0) planes of cellulose II crystalline
form. Apparently, the crystallinity of Gel-F2 is higher than that of
Gel-H2. Fig. 3. XRD patterns of the cellulose hydrogels of Gel-H2 and Gel-F2.
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C. Chang et al. / Carbohydrate Polymers 82 (2010) 122–127 125

Fig. 4. SEM images of the cellulose hydrogels prepared by heating (top) and freezing (bottom) methods: (a) Gel-H2, (b) Gel-H3, (c) Gel-H4, (d) Gel-F2, (e) Gel-F3 and (f)
Gel-F4.

13
Fig. 5. C CP/MAS solid-state NMR of the cellulose hydrogels prepared by heating method (left) and by freezing method (right).
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126 C. Chang et al. / Carbohydrate Polymers 82 (2010) 122–127

Fig. 6. Equilibrium swelling ratio of the hydrogels in distilled water as a function of Fig. 7. Reswelling kinetics of the cellulose hydrogels in distilled water at 25 ◦ C.
the cellulose concentration at 25 ◦ C.

The vacuum-dried hydrogel samples were allowed to hydrate

treated by freezing method), which were rather different than those
in distilled water at 25 ◦ C, and the time kinetic curves are illus-
of Gel-H series. The fiber-like structure is probably due to a slow
trated in Fig. 7. It can be clearly seen the swelling capabilities of
and strong self-association of the cellulose chains at the lower tem-
all cellulose hydrogels were increased by time, but after a certain
perature, which become more obvious and orderly with increasing
period time they showed a constant swelling behavior and the pro-
gelation concentration.
cess was transformed to an equilibrium swelling state. Compared to
Solid-state NMR methods have been widely applied in high-
Gel-F series, the hydrogels Gel-H series need a longer time to reach
resolution NMR studies of materials, which allow the identification,
swelling equilibrium. As shown in Fig. 7, the reswelling capabilities
analysis and characterization of different kinds of solids and also
of the Gel-H series approached 100% after a long period. However,
give various information on their molecular mobility (Capitani, Del
the hydrogels Gel-F series could not swell as much as 50% due to
Nobile, Mensitieri, Sannino, & Segre, 2000; Delval, Crini, Bertini,
a dense structure formed via freezing. Moreover, the desiccation
Filiatre, & Torri, 2005). Fig. 5 shows the solid-state CP/MAS 13 C
stage promoted a reduction in the average distance among cross-
NMR spectra of the cellulose hydrogels. For all of the hydrogels,
linking sites, which caused a substantial increment in the actual
a broadening of peaks in the range 55–90 ppm could be observed.
cross-linking density, and in turn, an important reduction in water
Comparing with the 13 C NMR spectrum of the regenerated cellulose
uptake.
(Zhou et al., 2007), the C4 and C6 signals of the hydrogels showed
The dynamic mechanical characterization was useful for under-
a large loss of resolution and became shoulder peaks of the broad-
standing the structure of hydrogels and consequently their possible
ening region with the increase of cross-linking agent. This could be
applications. Fig. 8 shows the linear viscoelastic frequency sweep
explained by the lower mobility of carbons of anhydrous d-glucose
response of the cellulose hydrogels. All of them exhibited weak fre-
units induced by the chemical cross-linking of cellulose with ECH.
quency dependence from 0.1 to 100 rad/s with the dynamic storage
Moreover, the extent of chemical cross-linking of the hydrogels are
modulus (G ), suggesting that the hydrogels were highly elastic. The
in the order of Gel-H2 > Gel-H3 > Gel-H4 and Gel-F2 > Gel-F3 > Gel-
storage modulus of the hydrogels increased with the increasing of
F4, which agreed well with the addition amount of ECH and the
the cellulose concentration. This suggested that cellulose molecu-
molar ratio of ECH to cellulose.
lar chains play an important role on the improving of mechanical
strength of the hydrogels. Comparing with Gel-H series, the hydro-
3.2. Properties of the hydrogels
gels prepared by freezing at the same polymer content exhibited

The influences of the cellulose contents and post-treatment

methods on swelling ratios of the hydrogels in distilled water
are found in Fig. 6. With the increase of cellulose concentration,
swelling ratios of the hydrogels decreased. It is well known that the
cross-linking degree is one of the important factors for determining
the water absorbency of hydrogels. Except for the chemical cross-
linking of cellulose by ECH, physical cross-linking of the polymer
chains plays an important role in the swelling ratio of the hydrogels.
With increasing cellulose concentration, physical cross-linking of
the hydrogels is strengthened by more and more inter-molecular
hydrogen bonds and chain entanglements, resulting in the decrease
of swelling ratios. Moreover, at the same cellulose concentration,
hydrogels Gel-H series displayed relatively higher swelling ratios
than those of the Gel-F series. It indicated that more rigid and stable
hydrogen bonding could be established by molecular rearrange-
ment in cellulose during the freezing process. Strong interactions
and partial crystallinity existed in the hydrogels obtained by freez-
ing, which hinders the penetration of water molecules, resulting in
that the swelling degree of hydrogels by freezing being lower than Fig. 8. Frequency dependence of the dynamic storage modulus (G ) of the hydrogels
that of by heating. at a strain of 10% and at 25 ◦ C.
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C. Chang et al. / Carbohydrate Polymers 82 (2010) 122–127 127

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