Chinese Journal of Polymer Science Vol. 27, No.

5, (2009), 739−746 Chinese Journal of

Polymer Science
©2009 World Scientific

PREPARATION AND PROPERTIES OF CHITOSAN/LIGNIN COMPOSITE FILMS*

Long Chen, Chang-yu Tang, Nan-ying Ning, Chao-yu Wang, Qiang Fu** and Qin Zhang**
College of Polymer Science and Engineering, State Key Laboratory of Polymer Materials Engineering,
Sichuan University, Chengdu 610065, China

Abstract Biodegradable composite films based on chitosan and lignin with various composition were prepared via the
solution-casting technique. FT-IR results indicate the existence of hydrogen bonding between chitosan and lignin, and SEM
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images show that lignin could be well dispersed in chitosan when the content of lignin is below 20 wt% due to the strong
interfacial interaction. As a result of strong interaction and good dispersion, the tensile strength, storage modulus, thermal
degradation temperature and glass transition temperature of chitosan have been largely improved by adding lignin. Our work
provides a simple and cheap way to prepare fully biodegradable chitosan/lignin composites, which could be used as
packaging films or wound dressings.

Keywords: Chitosan; Lignin; Biodegradable composites.

INTRODUCTION
Chitosan is a nontoxic, biodegradable and biocompatible cationic polysaccharide, produced by the partial
deacetylation of chitin, isolated from naturally occurring crustacean shells. It mainly consists of beta (1-4)-2
amino-2-deoxy-D-glucose units. The chemical structure of chitosan is shown in Fig. 1(a). Chitosan has been
widely studied for biosensors, tissue engineering, separation film, water treatment and so on, due to its good
biocompatibility, biodegradability and multiple functional groups[1]. However, the high price as well as the
relative poor mechanical properties and thermal stability of chitosan restrict its wide application.

Fig. 1 (a) Chemical structure of chitosan; (b) Chemical structures of the three principal phenolic molecules of lignin

*
This work was financially supported by the National Natural Science Foundation of China (No. 50533050).
**
Corresponding authors: Qiang Fu ( 傅强 ), E-mail: qiangfu@scu.edu.cn
Qin Zhang ( 张琴 ), E-mail: Zhangqin511@163.com
Received October 20, 2008; Revised November 24, 2008; Accepted December 2, 2008
 740 L. Chen et al.

Blending with other polymers is a promising way to modify chitosan and extend its application. The blends
of chitosan with petroleum polymers are only partially degradable[2, 3]; while those with biodegradable materials,
such as starch[4], collagen[5] and soy protein[6] have good degradability and good mechanical properties as well as
thermal stability.
Lignin is an abundant non-toxic amorphous natural polymer and an inexpensive by-product of paper
industry. Today’s annual global production of lignin amounts to some 50 million tons. At present most of lignin
is discarded as waste from the pulp and paper making industry, and is mainly used as fuel. Its macromolecule
structure is chemically complex, and the main monomer units constituting lignin molecules are 2-methoxy-4-
propylphenol (guaiacol) in soft wood and a mixture of guaiacol and 1,5-dimethoxy-4-propylphenol (syringol) in
hardwood. The chemical structures of the three principal phenolic molecules of lignin are shown in Fig. 1(b).
As a cheap phenolic biopolymer, lignin offers attractive potential as a filler and additive, especially with
respect to the modification of biodegradable polymers. Many work of lignin-filled thermoplastics including
polypropylene[7], soy protein[8], poly(L-lactic acid)[9], polycaprolactone (PCL)[10] and other biodegradable
polymers have been reported. Usually the addition of lignin deteriorates the mechanical properties of plastics due
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to the poor miscibility. However, an increase of tensile strength and glass transition temperature of soy protein
has been observed by adding nanoscale lignin at a load of 6 wt%[8].
Developing fully biodegradable polymer composites composed of biodegradable matrix and filler has
attracted more attentions. In this work, a series of biodegradable composites was prepared from chitosan and
lignin. The structure and properties of the composites were characterized by Fourier transform infrared
spectroscopy (FTIR), mechanical thermal analysis (DMA), scanning electron microscopy (SEM),
thermogravimetric analysis (TGA), swelling experiment and tensile tests. The main purpose of this work is to
prepare chitosan based biodegradable composites with improved mechanical properties by adding cheap lignin.
We expect a significant impact on the application of chitosan where both mechanical and biodegradable
properties are required, such as packaging films or wound dressings.

EXPERIMENTAL
Materials
Chitosan powder, with a deacetylation degree of 90%, was purchased from Zhejiang Golden-Shell Biochemical
Co. Ltd. (Yuhuan, China), the viscosity-average molecular ( M η ) weight of chitosan was determined to be
ca. 344080, based on viscosity measurements at 30°C in 0.1 mol/L aqueous acetic acid-0.2 mol/L aqueous
sodium chloride solution following the Mark-Houwink equation[11]:

[η ] = 6.589 ×10−3 M η 0.88

The lignin was an industrial product and obtained as a purified commercial polymer from Shandong
Xuemei Paper Industry Co. Ltd (Yiyuan China). Prior to its utilization, lignin was dissolved in 80% aqueous
acetic acid, insoluble fractions was removed by filter through a filter paper, and the soluble fraction in about
76 wt% of the total amount was dried at 60°C for use. Lignin exhibits spherulite morphology (Fig. 2).

Fig. 2 SEM images of lignin

 Preparation and Properties of Chitosan/Lignin Composite Films 741

Preparation of Blend Films

The chitosan/lignin blend films were fabricated by means of a casting/solvent evaporation method. The chitosan
solution was prepared by dissolving chitosan in a 2% (V/V ) aqueous acetic acid solution with a 20 g/L chitosan
concentration, while lignin of different content was dissolved in a 80% (V/V ) aqueous acetic acid solution with a
lignin concentration ranged from 2.6 g/L to 27 g/L, then the solution of lignin was slowly added to that of
chitosan under vigorous stirring for 4 h at room temperature, then cast the mixture of the solutions on a glass
dish. The cast films were degassed and dried at 50°C in an oven to remove the solvents. The thicknesses of the
films were about 0.09 mm. One set of samples was prepared, the content of lignin in chitosan matrix ranged
from 5 wt% to 35 wt%. It should be noted that for all the solutions including the pure chitosan the residual acetic
acid could not be removed by using NaOH solution after film casting, because lignin will be dissolved in NaOH
solution, which will cause a change of the composition. Though acetic acid remained in the films could affect the
mechanical properties to certain extent, a relative comparison of the properties among the samples should be all
right.
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Characterization and Measurements

Fourier transmission infrared spectra (FTIR)
Fourier transmission infrared spectra (FTIR) were obtained by using a Nicolet 560 MAGNA IR spectrometer.
Scanning electron microscope (SEM)
The dispersion of lignin in chitosan matrix was measured by a JEOL JSM-5900LV SEM instrument. The
specimens were first fractured in liquid nitrogen, and then the fractured surface was gold coated and observed
under an acceleration voltage of 20 kV.
Mechanical properties
The tensile strength and elongation of the samples were measured on an Instron universal testing machine at
room temperature with a tensile rate of 5 mm/min according to ISO527-3: 1995(E). At least five samples were
measured, and the average values were reported.
Dynamic mechanical analysis (DMA)
The dynamic mechanical analysis (DMA) was carried out using a TA Instruments Q800 DMA. All the samples
were measured in a dual cantilever mode over the temperature range of 35°C to 200°C at a heating rate of
3 K/min and at a frequency of 20 Hz. Specimen dimensions were 40 mm × 6 mm × 0.1 mm.
Thermogravimetric analysis (TG)
TGA was performed on a WRT-2P TGA instrument under flowing nitrogen (20 mL/min) atmosphere at
10 K/min.
Water vapor permeability
The water vapor permeability (WVP) of the films was determined gravimetrically according to ASTM E-96-97
method (ASTM, 1980). The films were fixed on to the circular opening of permeation cell-containing anhydrous
calcium chloride (15.5 g, 0% RH) using melted paraffin. The cups were then weighed and kept at 80% relative
humidity and 24°C in a humidity chamber. The cups were weighed at 1 h intervals until the change in weight
became constant. The water vapor transferred through the films at different time intervals was determined from
the weight gain of the cups. Changes in the weight of the permeation cell were recorded and plotted as a function
of time. The slope of each line (dm/dt) was calculated by linear regression (r2 > 0.996). The WVP was calculated
from the equation:
WVP = L ( A∆P ) dm dt

Where, dm/dt is the slope of the cup weight versus time curve, L is the film thickness, A is the film-exposed area
and ∆P is the water vapor pressure across the film. By assuming that the water vapor pressure inside the cup is
 742 L. Chen et al.

equal to zero, due to the presence of anhydrous calcium chloride, ∆P becomes equal to the vapor pressure at the
film outer surface in the system.
Swelling experiment
Films were immersed in distilled water at 32°C. After an immersion period of 24 and 48 h, they were removed
from the water, dried with a filter paper, and weighed. The water uptake was calculated according to equation:
mw − md
Water uptake (%) = × 100
md

Where, mw and md were the film wet and dry weights, respectively.

RESULTS AND DISCUSSION

FTIR Spectroscopy
FT-IR was employed to investigate the interaction between chitosan and lignin. Figure 3 shows the FT-IR
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spectra of lignin, chitosan and chitosan/lignin (20%) blends. It is apparent from Fig. 3 that the characteristic
bands of lignin at 1605, 1513, 1460 and 1425 cm−1 correspond to aromatic ring vibration of the phenylpropane
―
skeleton. A wide adsorption band located at 3420 cm−1 is assigned to aromatic and aliphatic O H groups while
＝ ――
the band at 1718 cm−1 is related to C O stretching. The band at 1217 cm−1 corresponds to C O C stretching
― ―
of aryl ether and 1117 cm−1 corresponds to C O C stretching of ether. It can be observed that several
noticeable changes occur in the spectrum of chitosan/lignin (20%) in comparison with the spectrum of pure
chitosan. The band of chitosan at 3440 cm−1 for hydroxyl groups is shifted to 3420 cm−1, and the intensity is
―
weakened; 1653 cm−1 for amide I is shifted to 1647 cm−1; 1090 cm−1 for C O stretching is shifted to 1082 cm−1.
All the clearly measurable changes in wave number indicate obvious interactions among the hydroxyl, carbonyl
and ether groups of the two components. It can be attributed to the hydrogen bonding possibly formed between
hydroxyl, carbonyl groups in chitosan and carbonyl, hydroxyl, ether groups in lignin. However, not much change
―
of N H stretching can be observed, which is located at 3366 cm−1 for both the blend and pure chitosan. The
same situation can be seen for the bands of amide II. This result suggests that the hydrogen bonding is mainly
formed between the hydroxyl and carbonyl groups in chitosan with lignin, as is shown in Fig. 4. One could not
easily find the characteristic band of lignin in the blend, probably due to the overlap with that of chitosan.
However, by careful examination, still one can see weak bands of lignin at 1511 and 1455 cm−1 in the spectrum
of chitosan/lignin (20%) in an enlarged scale (see the right part of Fig. 3).

Fig. 3 FT-IR spectra of (a) lignin, (b) chitosan/lignin (20%) and (c) chitosan
 Preparation and Properties of Chitosan/Lignin Composite Films 743

Fig. 4 Formation of hydrogen bond formed between chitosan and lignin molecule
SEM
Figure 5 presents the SEM micrographs illustrating the morphology of chitosan and chitosan/lignin blend films.
The SEM micrograph of pure chitosan (Fig. 5a) shows a smooth surface. For blends containing 10 wt% (Fig. 5b)
and 20 wt% (Fig. 5c) of lignin, one observes evenly dispersed lignin particles in chitosan matrix. Especially in
the SEM of chitosan/lignin (20%) (Fig. 5c), the surface is very rough. A very good interfacial adhesion is
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evidenced between lignin and chitosan. However, obvious cavity and agglomerates are observed as the content
of lignin is increased to 30 wt%, as shown in Fig. 5(d).

Fig. 5 SEM images of chitosan/lignin blend films

a) Chitosan; b) Chitosan/lignin (10%); c) Chitosan/lignin (20%); d) Chitosan/lignin (30%)

Tensile Properties
The tensile strength (TS) and elongation at break (E) values of chitosan/lignin composite films are shown in
Fig. 6. One can see that the tensile strength of chitosan is greatly increased with the content of lignin increasing,
and the maximum enhancement is observed when the content of lignin reaches to 20 wt%. The tensile strength
increases by about 55% from 43.3 MPa for pure chitosan to 68 MPa for the chitosan/lignin (20%) composites.
However, a further increase of lignin content results in a sharp decrease of tensile strength. The elongation at
break shows a slight decrease as the content of lignin increasing. A significant reduction can be observed when
the content of lignin is over 20 wt%. The increase of tensile strength and decrease of elongation at break when
the content of lignin reaches 20 wt% could be attributed to the presence of hydrogen-bond between lignin and
chitosan molecules as indicated in FT-IR spectra and good dispersion of lignin in chitosan matrix as suggested
by SEM images. The sharp decreases of tensile strength and elongation at break of the composites when the
content of lignin exceeds 20 wt% may be due to the agglomeration of lignin.
 744 L. Chen et al.
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Fig. 6 Effects of content of lignin on the tensile strength and elongation at break of the blend films

Kharade et al.[7] reported that the tensile strength of polypropylene decreased from 33.7 MPa to 23.3 MPa
with the addition of 20 wt% lignin. Chen et al.[8] reported the tensile strength of soy protein increased from
14.5 MPa to 23.1 MPa with the addition of 6 wt% lignin, but a further increase of lignin content resulted in a
tensile strength decease of soy protein. In our work, the tensile strength of chitosan is improved by about 55% at
a high load of lignin (20 wt%). It provides a new way for the application of lignin as filler for plastics.
DMA
Dynamic mechanical analysis is a sensitive technique to investigate the property enhancement and relaxation
processes in relation to the molecular motions associated with the internal changes that occur in polymer
composites. Figure 7(a) displays the storage modulus (E′) as a function of temperature for chitosan and
chitosan/lignin composite films. Their corresponding thermograms for damping tangent (tanδ) are presented in
Fig. 7(b). Storage modulus is a measure of the stiffness of the material. All the chitosan/lignin composites show
much higher storage modulus than that of pure chitosan over the temperature region studied. That is: the stiffness
of the composite films is largely enhanced by the addition of lignin. Again this enhancement can be ascribed to
strong interaction between chitosan and lignin, and also to the higher stiffness of lignin molecules. At this
moment we failed to measure the storage modulus value of the used lignin because it could be easily dissolved
before melting (the melting temperature is higher than the degradation temperature). Thus a comparison between
the storage modulus of blends and that of pure lignin is not possible. Also one observes not much change of the

Fig. 7 (a) Temprature dependence of storage modulus (E′) of chitosan/lignin blend films;
(b) tanδ curves of chitosan/lignin blend films
 Preparation and Properties of Chitosan/Lignin Composite Films 745

storage modulus among the blend films with different contents of lignin, and this needs to be understood in our
future work.
Two obvious transitions are recorded in each plot of storage modulus, corresponding to the peaks registered
in the tanδ curves, around 100°C and 150°C, respectively. Sakurai et al.[12] reported the glass transition
temperature (Tg) of chitosan, determined by DSC and dynamic mechanical analysis (DMA) measurements, was
203°C. Recently, Dong et al.[13] studied the Tg of chitosan using four different techniques, and found the Tg of
chitosan was around 140−150°C. Cervera et al.[14] found the Tg of chitosan to be 130−139°C by using DSC. In
our work, it’s reasonable to assign the peaks around 140−150°C to Tg, and the peaks around 100°C to β
relaxation. From Fig. 7(a), one can see a large decrease of storage modulus at 100°C but a slight decrease of
storage modulus at 140°C for pure chitosan. However, one can see a large decrease of storage modulus at 150°C
but a slight decrease of storage modulus at 100°C for the composites. This may be due to the breakage of the
hydrogen bond between the chitosan and lignin as the temperature is above the glass transition temperature.
Figure 7(b) shows a great increase of Tg of composite films compared with that of pure chitosan (140°C). Tg is
shifted to 155°C, 160°C and 157°C for composites containing 10 wt%, 20 wt% and 30 wt% of lignin,
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respectively.
It is known that interactions between polymer chains, such as ionic interaction, hydrogen bonding and
cross-linking, can contribute to the shift of Tg of a polymer. The enhancement of storage modulus and the shift of
Tg to a higher temperature by the addition of lignin suggest that there exist remarkable interactions between
chitosan and lignin, and this is basically in agreement with FTIR analysis.
TGA
Figure 8 exhibits TG and DTG curves of chitosan, lignin and chitosan/lignin (20%). All data of the samples,
regarding their Td (defined as a temperature corresponding to a weight loss of 20%), Tmax (temperature at
maximum degradation rate, determined by DTG curves), and WLwater (weight loss of water), are summarized in
Table 1.

Fig. 8 (A) TG thermograms of chitosan, lignin and chitosan/lignin (20%);

(B) DTG thermograms of chitosan, lignin and chitosan/lignin (20%)

The initial weight loss around 100°C is due to the evaporation of water. The WLwater of composite films
decreases with increasing the content of lignin. For chitosan, Td is 203°C; for lignin, Td is 331°C; for the
composite, it exhibits degradation behavior intermediate to those of the pure components. The Td of the
composites is shifted to a higher temperature with the incorporation of lignin, indicating that lignin has a
stabilizing effect on the degradation of chitosan.
 746 L. Chen et al.

Table 1. Data collected from TG and DTG thermograms, water vapor permeability and water adsorption
after 24 h and 48 h of chitosan and chitosan/lignin composites films
Water adsorption
Sample Td (°C) Tmax (°C) WLwater (%) WVP × 106 (gm−1kPa−1h−1)
24 h 48 h
Chitosan 203 302 19 5.43 117 120
Chitosan/lignin (10%) 233 311 12 5.86 124 129
Chitosan/lignin (20%) 243 305 16 6.34 127 131
Chitosan/lignin (30%) 267 291 5 5.26 135 132
Lignin 331 396 3 − − −

Water Vapor Permeability and Swelling Property

The calculated average values of WVP and water uptake percentage are presented in Table1. As shown in the
table, the WVP of chitosan/lignin (10%) and chitosan/lignin (20%) is a little higher than that of pure chitosan,
but WVP of chitosan/lignin (30%) is lower than that of pure chitosan. Water adsorption is increased with the
increasing of lignin content. There are two factors which could affect the WVP and water adsorption. The strong
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intermolecular interaction between chitosan and lignin molecules would lead to a good compatibility of the two
components, and thus a decrease of WVP and water adsorption. The OH and OCH3 on the backbone of lignin
could cause an additional increase of water adsorption. Hence one observes not very much improved WVP and
water adsorption, compared with those of pure chitosan film.

CONCLUSIONS
Biodegradable blend films composed of chitosan and lignin with various compositions have been successfully
prepared via the solution-casting technique. The IR absorption peaks corresponding to the chitosan hydroxyl,
carbonyl and ether groups have a tendency to shift to lower wave number, indicating the existence of a
hydrogen-bonding interaction between chitosan and lignin. SEM suggests a good dispersion as the content of
lignin is below 20 wt%. The tensile strength, storage modulus, glass transition temperature and degradation
temperature of the blend films have been largely increased, companied with only a slight decrease of elongation,
compared with those of pure chitosan.

ACKNOWLEDGEMENT We are grateful for Ms. Xinyan Zhang in the Center of Analysis and Test of Sichuan University.

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