Preparation and Properties of Bacterial Cellulose/Alginate

Blend Bio-Fibers
Shuai Zhang, Jin Luo

Dnghua University, College of Textiles, Songjiang, Shanghai CHINA

Correspondence to:
Shuai Zhang email: [email protected]
ABSTRACT
LiOH/urea/thiourea aqueous systems have been form, sodium alginate, through the incorporation of
successfully applied to the dissolution of bacterial sodium salt. However, because of its highly
cellulose (BC) and alginate (AL) to prepare blend hydrophilic character due to both of its carboxyl and
fibers. Morphology, compatibility and mechanical hydroxyl groups, the mechanical strength of the AL
properties of the blend fibers were investigated by materials in the wet state is very weak to limit its
scanning electron microscopy (SEM), Fourier application.
transform infrared spectroscopy (FTIR) and tensile
tests. The analyses indicated a good miscibility In our laboratory, solubility of cellulose in
between alginate and bacterial cellulose, because of LiOH/urea/thiourea aqueous solution has been
the strong interaction from the intermolecular studied, and regenerated cellulose fibers were
hydrogen bonds. The mechanical properties of prepared successfully from cotton linters. 5 In this
BC/AL blend fibers were significantly improved by study, we attempted to prepare blend fibers from
introducing bacterial cellulose. bacterial cellulose and alginate using the aqueous
LiOH/urea/thiourea as co-solvent. To the best of our
INTRODUCTION knowledge, this type of blend fiber was first prepared
Biopolymers have been considered as alternatives for in this work.
non-biodegradable petroleum-based polymers
because of their abundance, renewability, low cost, EXPERIMENTAL
and good biodegradability. Cellulose is the most Materials
abundant natural biopolymer on the earth, The bacterial cellulose used in our experiments was
synthesized by plants, algae and also some species of purchased from Hainan YIDA Food Industry Co.
bacteria. Unlike cellulose from plants, bacterial (China). Sodium alginate was purchased from the
cellulose (BC) is chemically pure and free of lignin Branched Factory of Shanghai Chemical Reagent Co.
and hemi-cellulose. BC has high crystallinity and a (China).
high degree of polymerization. Plant-derived
cellulose and BC have the same chemical Preparation Of Blend Solution
composition but different structures and physical BC was cut into small pieces (0.2X0.2 cm2),
properties. The BC network structure comprises dispersed in the aqueous solvent (LiOH: urea:
cellulose nanofibrils 3-8 nm in diameter, and the thiourea: H2O=4.6:10:4.5:80.1, ratio by weight), and
crystalline regions are normal cellulose I. The stirred for 5 min at room temperature to obtain a BC
specific properties such as the nanometric structure, slurry. The slurry was then cooled to -20 in a
unique physical and mechanical properties together freezer and held at -20 until it became a solid
with its higher purity have lead to a great number of frozen mass for 12 h. The frozen solid was then
commercial products. 1-3 allowed to thaw and was stirred extensively at room
temperature to obtain clear BC solution (I). Certain
Alginate (AL) is a binary linear hetero amounts of sodium alginate were dissolved in
polysaccharide containing one, four-linked LiOH/thiourea/urea aqueous solution at room
α-L-guluronic acid and β-D-mannuronic acid, and temperature to obtain alginate solution (II). The total
has been widely used in the field of controlled release, concentration of solid biopolymers in the solution
ion exchange, and in the vapor-permeation was controlled to be 6 wt%. A mixture of I and II
membrane-separation technique. 4 Alginate can be with weight ratio 80:20 was stirred at room
transformed into the most widely used water-soluble temperature for 10 min and then filtered and
Journal of Engineered Fibers and Fabrics 69 http://www.jeffjournal.org
Volume 6, Issue 3 - 2011
degassed at 10℃ by centrifuging. The final of 10 kV and 15 mm working distance. The
composition of the fibers in relative weight stress-strain experiments were made using a universal
components of alginate and BC was 20:80. tensile tester (XQ-1, Donghua University, China).
According to ASTM D2256-80, the fibers samples
Preparation Of Novel Blend Fibers were conditioned for 24 h in standard atmosphere
A laboratory scale wet-spinning apparatus was used before testing of the dry mechanical properties of the
to prepare the blend fibers, as schematically shown in fibers. However, the wet mechanical properties of the
Figure 1. The spinning dope I, II and blend solution fibers were tested after the fibers were immersed in
were introduced into the cylinder at room the distilled water at 20℃ for 3 minutes. The gauge
temperature, respectively. A pressure of 0.1 MPa was length was 20 mm and the tensile speed was 5
applied to the spinning dope to extrude it into mm/menthe pre-tensile forces of dry fibers and wet
coagulation bath using a spinneret of 12 orifices, the fibers were determined to be 0.08cN/dtex and
orifice diameter (d) was 0.1 mm. The 10 wt % H2SO4 0.04cN/dtex according to their linear densities,
aqueous solution was selected as the coagulation bath. respectively. The tester gave tress, strain, tensile
The temperature of the coagulation bath was preset curve and their averages from the sixty observations
for 20℃. The apparent jet stretch ratio (the ratio of automatically. All the experiments were made at an
the take-up velocity to the dope extrusion velocity) atmospheric condition of 20℃ and relative humidity
was 90 %, the fibers were subsequently washed in 60 %.
water at boil and further drawn up, while the
post-drawing ratio was adjusted as 120 %. After RESULTS AND DISCUSSION
spinning and washing thoroughly, the regenerated Infrared (IR) spectroscopy is useful for studying
bacterial cellulose fibers (RBC), regenerated alginate hydrogen bonding and miscibility because the
fibers (RAL), blend fibers(BC/AL) were gradually strength of the hydrogen bond and the fraction of
dried by a heating roller (surface temperature hydrogen-bonded groups can be directly investigated
65-80℃) and wound on a spool. from the spectra. The IR spectra of the blend fibers
and are shown in Figure 2.

FIGURE 1. Sketch of multifilament spinning machine:1-A

pressure extruder with a stainless cylinder having cooling jacket;
2-gauging device; 3-coagulation bath(10 wt% H2SO4 aqueous
solution, 20℃); 4-Nelson-type roller; 5-water spray device;
6-washing bath(hot water, 50℃); 7-post drawing roller; 8-post
treatment device (finishing oil bath); 9-heating roller;10-take-up FIGURE 2. The FTIR spectra of regenerated bacterial cellulose
device. (RBC), alginate (AL) and BC/AL blend fibers.

Characterization The stretching vibration of hydroxyl groups in the

The FTIR spectrums (4000-400 cm-1) of blend fibers RBC, BC/AL, and AL appears at 3000–3600 cm-1.
were recorded using a Nicolet 410 spectrometer with The -OH stretching-vibration bands of the blend
a resolution of 4 cm-1 and 128 scans per sample. The fibers were broadened and shifted to a lower wave
fiber was frozen in liquid nitrogen, snapped number compared to RC and AL, indicating that a
immediately, and vacuum-dried. SEM stronger hydrogen bond occurred between RC and
characterization was performed by using a JEOL AL. The strong band of AL at 1622 cm−1 was
JSM-5600LV microscope, at an acceleration voltage

Journal of Engineered Fibers and Fabrics 70 http://www.jeffjournal.org

Volume 6, Issue 3 - 2011
assigned to the carboxyl group, while the carboxyl extremely important for the tailoring of the final
group bands for BC/AL shifted from 1622 to product properties. The SEM micrographs of blend
1608cm−1, indicating the specified intermolecular fibers are shown in Figure 3. The BC/AL blend
hydrogen bonds between -OH of BC and C=O of AL bio-fibers showed a circular shape with fairly regular
forms. The band at 1735 cm-1 for AL belongs to C=O size along the fiber axis. However, the micro void can
in AL, but disappeared in the blend fibers. This be seen in the cross-section of the blend fibers, which
difference would also be derived from specified can be considered as the evidences of partly phase
interaction between the hydroxyl group of cellulose separation. Here, we proposed that, in the blend
and carboxyl group of AL. Similar observations were solution, alginate partly destroyed the interaction
previously discussed in the preparation of cotton between solvent and BC chains by a much stronger
cellulose/AL blend membranes. 6 interaction between carboxyl groups of AL and then
the exposed hydroxyl groups of BC prompted the
It is well known that the mechanical properties of formation of a new physical crosslinking network
fibers, especially the blend fibers are strongly with a bigger pore size than that of pure regenerated
dependent on their morphologies and, therefore, the cellulose itself (Figure 3-c).
control of the morphology of polymer blend is

a b c

FIGURE 3. SEM images of (a) the surface, (b) cross-section of the BC/AL blend fibers and (c) cross-section of the RBC fibers.

The presence of alginate in the cellulose-alginate TABLE I. Mechanical properties of bacterial BC/AL blend fibers
composite could enhance the molecular motion of and pure RBC fibers.
cellulose in the blend and perturbed the strong
hydrogen bond of pure cellulose resulting in the
reduction in mechanical strengths. It can be found
from Table I that the BC/AL blend fibers were a little
weaker than regenerated cellulose fibers under either
dry or wet state. As we know that alginate materials
was mechanically weak and much weaker under wet
state, the mechanical properties of the blend fibers of
alginate with bacterial cellulose were obviously
stronger than alginate materials, which is another
indicator for the strong intermolecular hydrogen
bonding between two polymers in the blends. The CONCLUSION
effect of alginate content on the mechanical Novel blend bio-fibers of bacterial cellulose/alginate
properties of the BC/AL blend fibers was similar to were prepared in LiOH/urea/thiourea aqueous solvent
those previously observed in the blend membranes of by coagulating with 10 wt % H2SO4 aqueous solution
BC and alginate blend in NaOH/urea,7 cellulose for the first time. The blend fibers of 20 wt % AL and
cuoxam with alginate,8 and cotton cellulose and 80 wt % BC demonstrated a homogeneous structure
alginate blend in NaOH/urea aqueous solution. 9 with a certain level of miscibility of the blend. The
FTIR spectra displayed the specified interaction
between the hydroxyl group of BC and the carboxyl
group of AL. The values of tensile strength and

Journal of Engineered Fibers and Fabrics 71 http://www.jeffjournal.org

Volume 6, Issue 3 - 2011
elongation at break for the blend bio-fibers reached [9] Zhou, J.; Zhang, L.; structure and properties of
1.57 cN/dtex and 10.8%, respectively. The blend membranes prepared from cellulose
mechanical properties of the blend fibers were and alginate in NaOH/urea aqueous solution;
slightly improved compared to those of the pure AL Journal of Polymer Science: Part B: Polymer
materials. To this end, BC/AL blend fibers have great Physics 2001, 39, 451-458.
potential as new regenerated biodegradable fibers
with structural and physic-mechanical properties AUTHORS’ ADDRESSES
comparable to those of pure regenerated cellulose Shuai Zhang
fibers. Its biomedical application can be expected, Jin Luo
especially for the tissue engineering scaffold. Dnghua University
College of Textiles
REFERENCES 2999 North Renmin Road
[1] Klemm, D.; Schumann, D.; Udhardt, U.; Songjiang, Shanghai 201620
Marsch, S.; Bacterial synthesized cellulose - CHINA
Artificial blood vessels for microsurgery;
Progress in Polymer Science 2001, 26,
1561-1603.
[2] Klemm, D.; Heublein, B.; Fink, H. P.; Bohn,
A.; Cellulose: Fascinating biopolymer and
sustainable raw material; Angewandte
Chemie - International Edition 2005, 44 ,
3358-3393.
[3] Czaja, W.; Krystynowicz, A.; Bielecki, S.;
Brown, R. M.; Microbial cellulose-The
natural power to heal wounds; Biomaterials
2006, 27, 145-151.
[4] Kalyani, S.; Smitha, B.; Sridhat, S.; Krishnaiah,
A.; Pervaporation separation of
ethanol–water mixtures through sodium
alginate membranes, Desalination 2008, 229,
68-81.
[5] Zhang, S.; Li, F. X.; Yu, J. Y.; Dissolution of
cellulose in LiOH complex aqueous solution
and preparation of regenerated cellulose
fiber; Chemical Fibers International 2009,
59, 169-171.
[6] Yang, G.; Zhang, L.; Peng, T.; Zhong, W.;
Effects of Ca2+ bridge cross-linking on
structure and pervaporation of
cellulose/alginate blend membranes; Journal
of Member Science 2000, 175, 53-60.
[7] Phisalaphong, M.; Suwanmajo, T.; Tammarate,
P.; Synthesis and Characterization of
Bacterial Cellulose/Alginate Blend
Membranes; Journal of Applied Polymer
Science 2008, 107, 3419-3424.
[8] Zhang. L. N.; Zhou, D.; Wang, H.; Cheng, S.;
Ion exchange membranes blended by
cellulose cuoxam with alginate; Journal of
Membrane Science 1997, 124, 195-201.

Journal of Engineered Fibers and Fabrics 72 http://www.jeffjournal.org

Volume 6, Issue 3 - 2011