Journal of the Chilean Chemical Society - <B>FTIR AND TGA STUDIES OF CHITOSAN COMPOSITE FILMS</B>

Journal of the Chilean Chemical Society

ISSN 0717-9707 versin on-line

J. Chil. Chem. Soc. v.49 n.4 Concepcin dic. 2004

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J. Chil. Chem. Soc., 49, N 4 (2004): pgs: 291-295

FTIR AND TGA STUDIES OF CHITOSAN COMPOSITE FILMS

GALO CARDENAS*1 AND S. PATRICIA MIRANDA1

1Lab.

Quitina/Quitosano, Departamento de Polmeros, Facultad de Ciencias Qumicas,

Edmundo Larenas 129, Universidad de Concepcin, Concepcin, CHILE, e-mail :
gcardena@udec.cl
2Lab. Biotecnologa Facultad de Estudios Superiores, Cuautitln, Avda 1 de Mayo s/n,
Cuautitln Izcalli, Estado de Mxico, MXICO

ABSTRACT
The synthesis of chitosan and resulting chitosan composite films was carried out using
glycerol, tween, and beeswax as additives to prepare the composites films, after which a
complete study by FTIR was carried out for all the chitosan composite films. Several
differences in the absorption bands were seen for each composite, confirming the presence
of the material incorporated therein. Thermal stability was studied by thermogravimetric
analysis, which further verified the differences between pure chitosan films and the series
of composite films. The composite films are good alternatives to existing food storage
materials due to important similarities with commercial polypropylenes, not to mention
their environmental advantages as regards improved degradability.

INTRODUCTION
Crustacean skeletons (prawn, shrimps, krill and crabs) are the raw materials used to obtain
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Journal of the Chilean Chemical Society - <B>FTIR AND TGA STUDIES OF CHITOSAN COMPOSITE FILMS</B>

chitin, which is generally obtained from fisheries, often at environmental risk. In general,
chitin can display a variety of chemical characteristics, such as varying molecular weight
and acetylation degree, depending on its source of origin and the method used for its
1

separation. The most important derivative of chitin is the biopolymer chitosan, which is
found in nature as a component of the cell walls of fungi and can be obtained via the
23

deacetylation of chitin with concentrated alkali. , Usually, this deacetylation is not

complete, and several treatments are required which can alter the molecular weight of the
resulting product. Generally, chitosan is formed by a mixture of -(1,4)-D-Nacetylglucosamine and -(1,4)-D-glucosamine. The relation between these units along the
polymeric chain depends on the conditions used in the deacetylation process. In fact, the
term chitosan is not used only to refer to a chemical structure. In practical terms, chitosan
is a polymer with a sufficient degree of deacetylation to be soluble in weak acids, otherwise
4

the presence of chitin can be detected .

There is considerable research on the synthesis of films and membranes using synthetic
polymers to improve their biocompatibility and expanded use as biomaterials. For example,
Kim and coworkers prepared some similar membranes using 76% deacetylated chitosan.
They showed that the crosslinking of this blend strongly correlates with the increase in the
strength the membrane and the thermal stability of the blend. These membranes show
characteristic swelling depending on pH, and they were used as materials for the slow
56
release of riboflavine and insulin , .

Some authors have studied membranes prepared from blends of chitosan and polyvinyl
alcohol (PVA). Several initial studies have shown that chitosan forms a clear and
homogeneous blend with PVA whose resistance is greater than that of the pure
78
components. ,

Moreover, transport of halogenated ions and diffusion of cattle serum albumin in

9

membranes prepared from these cross-linked blends have been observed .

Nakatsuka studied the permeability and diffusion of vitamin B12 in chitosan membranes and
in cross-linked chitosan/PVA blends. While the cross-linked chitosan/PVA decreases the
swelling equilibrium of the hydrogel in the blend composition increases in proportion to the
PVA content of the sample. In both membranes the diffusion coefficient of vitamin B-12 was
1
affected because it depends only on the degree of hydration. 0

Hasegawa and coworkers prepared some films from a chitosan-cellulose blend in

trifluoroacetic acid (TFA) as solvent and using the casting technique. After the films had
dried, they were treated with sodium hydroxide. The films were transparent, quite strong
and flexible without the addition of tensioactive products; moreover, when polymer blends
were prepared in a composition range of 0 to 100% of each polymer, an increase in the
11

tension force of the film with 30% chitosan was observed. Based on these analyses, it is
postulated that the increase in plasticity is probably due to the presence of intermolecular
interactions between both polysacharides and water molecules. Subsequent thermal
treatment of the films suggests a destruction of those interactions in the interphase region,
leading to a decrease in mechanical force and in Young's modulus.

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Journal of the Chilean Chemical Society - <B>FTIR AND TGA STUDIES OF CHITOSAN COMPOSITE FILMS</B>

By investigating the thermal behavior of polymers as a function of weight loss with heat, it
is possible to obtain information about their stability. Thermogravimetric analysis (TGA) has
been widely used to study the thermal stability and characteristics of the thermal
decomposition of polymers. TGA and DSC studies of other chitosan-based polymers (Mv
=100,000 g/mol) have reported a decomposition temperature of 310 C.

12

These results are

13

similar to values reported previously by our group. In this work we report the
characterization by FTIR and TGA of a series of chitosan composite films.

EXPERIMENTAL
Synthesis of chitosan
The chitin was obtained by treatment with HCl 1N and NaOH 2% at 100 C for 2 h. The
chitin was placed in a 10 L glass reactor with mechanical stirrer. The solid/liquid was added
in a 1:15 ratio. The mixture was stirred at 500 rpm and heated at 90 C. A 10% (w/v)
solution of NaBH4 was added to avoid oxidation and depolymerization. Reaction time was
90 min. The final product was washed with hot water to eliminate sodium hydroxide. The
product was dried at room temperature.
Chitosan molecular weight
The molecular weight is a critical component and is highly dependent on the polymerization
14

method used. In our case, the method reported by Rinaudo and coworkers was used. For
chitosan the K and a values are strongly dependent on the degree of deacetylation.
To obtain the highest. Mv, the viscosity molecular weight was calculated by the MarkHouwink equation, [] = KMa, where K = 0.076 and a= 0.76. The curve was adjusted and
the intercept afforded the reduced viscosity. Two different chitosans were used: one of Mv
= 263,600 g/mol and degree of deacetylation of 92%, and another of Mv = 134,300 g/mol
and deacetylation degree of 86%.
Chitosan composite films.
From a solution of 2 % chitosan in 2 % acetic acid using magnetic stirring, chitosan
composite films were obtained after casting. The films were produced by adding a platicizer
such as glycerol, an emulsifier such as Tween, and beeswax in several ratios to obtain a
homogeneous mixture. The films were cast at room temperature in Petri dishes previously
washed with ethanol.
Infrared spectroscopy
Infrared spectra were measured using an FT-IR Nicolet Magna 5PC spectrophotometer
coupled to a PC with OMNIC analysis software. The films were placed in the holder directly
in the IR laser beam. Spectra were recorded at a resolution of 4 cm-1 and 64 scans were
accumulated.
Thermogravimetric analysis
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Journal of the Chilean Chemical Society - <B>FTIR AND TGA STUDIES OF CHITOSAN COMPOSITE FILMS</B>

A Perkin-Elmer Model TGA-7 thermogravimetric system with a microprocessor driven

temperature control unit and a TA data station, was used. The mass of the samples was
generally in the range of 2-3 mg. The sample pan was placed in the balance system
equipment and the temperature was raised from 25 to 550 C at a heating rate of 10 C
per minute. The mass of the sample pan was continuously recorded as a function of
temperature.

RESULTS AND DISCUSSION

Polysacharides usually have a strong affinity for water, and in the solid state these
macromolecules may have disordered structures which can be easily hydrated. The
hydration properties of these polysacharides depend on primary and supra macromolecular
15

structure. The chitosan composite films that were prepared showed a macro morphology
similar to cellophane and commercial polypropylenes. Since the stability of the films is
critical for a variety of applications, a comprehensive study of the chitosan and chitosan
composite films was carried out by TGA. Their thermal stability and thermal behavior was
obtained. The composition of the chitosan composite films was obtained by IR studies.
Table 1 summarizes the TGA and FTIR data of the low molecular weight chitosan films (Mv
= 134,300 g/mol). In the series of films the decomposition temperature (TD) is similar to
that of chitosan (TD = 313 C) (Fig. 1). The Q-8 composite chitosan film was shown to be
the most stable (TD =317 C) (Fig. 2). In this film (Q-8) the TD = 460 C can be attributed to
the presence of the emulsifier, while the (Q-11) film shows a TD = 165 C due to the
plasticizer and a TD = 457 C from the emulsifier. The Q-9 and Q-10 films had a similar
weight loss of around 28% with lower thermal stability than chitosan.

Table 1. TGA and FTIR of Chitosan Composite Films of low molecular weight

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Journal of the Chilean Chemical Society - <B>FTIR AND TGA STUDIES OF CHITOSAN COMPOSITE FILMS</B>

Fig. 1.- Thermogram of chitosan (Q-6).

Fig. 2.- Thermogram of chitosan-tween (Q-8).

It is interesting to note that with regard to the Q-11 composite films, the films containing
Tween plus a plasticizer and beeswax have the lowest weight loss (22%), which means that
the higher stability films were produced at 36% weight loss at 550 C. Similar behavior was
observed for commercial polypropylenes (Fig. 3). This stability is probably due to the
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Journal of the Chilean Chemical Society - <B>FTIR AND TGA STUDIES OF CHITOSAN COMPOSITE FILMS</B>

increased hydrogen bonding interaction between glycerol and chitosan and between
sorbitan oleic esters from Tween16 and the esters and fatty acids from beeswax and
glycerol with chitosan. This good thermal behavior has potential for a variety of industrial
applications.

Fig. 3.- Thermogram of polypropylene film (PP-2).

From these data, chitosan with similar degree of deacetylation exhibit a decomposition
12

temperature of TD = 313 C, the same as the 313 C reported by Kittur , who concludes
that decomposition temperatures decrease with decreasing acetyl units. This reasoning was
shown using chitosan with the same number of acetyl groups but different molecular
weight. It is generally agreed that a decrease in the degree of polymerization results in a
17

reduction in thermal stability. In chitosan, the decomposition process of the N-acetylated

compound is overlapped by the N-deacetylated unit, thereby increasing the widening
process seen at temperatures up to 400 C. In our case, even though the molecular weight
and degree of deacetylation were different, both chitosans had almost the same TD and
percentage weight loss at 550 C.
Table 1 evaluates low molecular weight chitosan composite films (Mv = 134,300 g/mol).
18

These films show the typical bands already reported for solids prepared in KBr pellets
(see Fig. 4). The Q-7 film neutralized via casting shows a very small difference with the Q-6
film, where the nNH appears at 1583 cm-1, most probably due to the unprotonated amino
group. The Q-8 film shows a band at 1570 cm-1 corresponding to nCOO- from the esters of
the Tween emulsifier (See Fig. 5) which was not seen in the film without neutralization. The
Q-9 film showed a chitosan band corresponding to nNH from amide II and nNH, in addition
to the OH band at 3363 cm-1 from glycerol and the different nC-O at 1062 cm-1.

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Journal of the Chilean Chemical Society - <B>FTIR AND TGA STUDIES OF CHITOSAN COMPOSITE FILMS</B>

Fig. 4.- FT-IR of chitosan (Q-1).

Fig. 5.- FT-IR of chitosan-tween film (Q-8).

The Q-10 film with chitosan and beeswax is a complex mixtures of saturated long chain
aliphatic compounds (acid, alcohols, esters and hydrocarbons). The band at 1637 cm-1 is a
19,20
.

mixture of amide II from chitosan and nC=C from fatty acids.

The nCH2 corresponding

to the acids at 1420 cm-1 is different from that of chitosan at 1407 cm-1. The propylene
spectrum shows the typical bands of nC-H at 2886 cm-1 and nCH2 at 1429 cm-1. The OH
band is due to humidity in the film (See Fig. 6).
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Journal of the Chilean Chemical Society - <B>FTIR AND TGA STUDIES OF CHITOSAN COMPOSITE FILMS</B>

Fig. 6.- FT-IR of polyproylene film (PP-2).

Table 2 summarizes data pertinent to films prepared with high molecular weight chitosan
(Mv = 263.000 g/mol). The TGA of these chitosan films shows a TD = 313.5 C, similar to
that of the lower Mv, but also higher than the composite chitosan films, which had values
around 295 C. The total weight loss at 550 C is almost identical to the 36% displayed by
the low Mv composites. Due to the small amount of emulsifier and of beeswax in some
cases, it was not possible to observe the decomposition temperature assigned either to the
emulsifier or the beeswax. For the P-3 films, however, we can attribute the TD of 450 C to
the emulsifier (polyoxyethylene sorbitan monooleate), while in the P-5 film the TD = 475 C
corresponds to the beeswax .

Table 2. TGA and FTIR of Chitosan Composite Films of high molecular weight.

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Journal of the Chilean Chemical Society - <B>FTIR AND TGA STUDIES OF CHITOSAN COMPOSITE FILMS</B>

The main difference in the low and high molecular weights is that the low molecular weight
films possessed a degree of acetylation of about 86 % with a higher chitin percentage
remaining. This results in greater thermal stability. Conversely, the higher Mv films with
92% deacetylation shwed lower thermal stability. In the Q-10 and P-5 composite films with
fatty acid the thermal peak shown is most probably due to the presence of the acid. In the
Q-11 and P-6 composite films, the observed thermal behavior was similar, but in the P-6
the plastifier peak is absent, probably due to the small amount of acid used.
FTIR analysis shows that the P-2 films exhibited resolved NH and OH bands when the films
are neutralized. The chitosan film with emulsifier shows three bands: nNH and nOH from
chitosan, and nOH from the fatty acid in the beeswax. This also can be attributed to the
band at 1659 cm-1 (Esto no calza con lo anterior) (P-3 film). The bands at 1029 and 1149
cm-1 are probably due to the nC-O signal from the glycerol (P-4 film). In the P-5 film the
absence of a nC-O band was seen, only the bands from chitosan similar to P-1 film at 1155
and 1090 cm-1 appear. The P-6 film showed nNH, nOH and nNH bands corresponding to the
presence of the plastifier and emulsifier in the films. It is interesting to see that the film
containing the three additives is quite similar to pure QS. Only the NH and OH bands

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Journal of the Chilean Chemical Society - <B>FTIR AND TGA STUDIES OF CHITOSAN COMPOSITE FILMS</B>

appear separately. This is a consequence of the small amount of components.

It should be noted that the chitosan showed good antifungal activity21 when applied directly
22 23

to microorganisms, indicating its potential as a natural fungicide. , Thus, chitosan films

have significant potential as food storage materials, particularly when synthesized with
selected additives to improve their mechanical properties

24

CONCLUSIONS
1. 00Only a slight difference in the composition of the low and high molecular weight
chitosan composite films was observed via IR studies due to the minimal amount of
incorporated chitin.
2. 00TGA results suggest that the films with low MW are more stable due to the lower
deacetylation degree and higher chitin content.
3. 00The amounts of incorporated emulsifier and lipid acid are as low as 1 % and thus their
concentration in the resulting composite films were too low to be detected by FTIR.
4. 00Thermal stability measurements indicate that the Q-11 composite films are quite
similar to existing commercial available polypropylene films used for wrapping fruits and
vegetables. Given our results, the chitosan composite materials have the potential to
replace current polypropylene films, especially when taking into account their advantageous
fungicide and bactericide properties.

ACKNOWLEDGEMENTS
The authors would like to thanks the financial support of Ctedras (S. P .Miranda) and
Innova Bo Bo 03-BI-212-L1 (G. Crdenas). We also thank the Laboratories of the
Facultad de Ciencias Qumicas, Universidad de Concepcin .

REFERENCES
1.- Muzzarelli R. A.A., Chitin, Oxford, 1977.
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Grottammare, Italy, 1977, 71.
5.- J.H. Kim, J.Y. Kim, Lee Y.M. and. Kim K.Y, J. Appl. Polymer Sci., 1992, 44, 1823.
6.- Kim, J.Y. Kim, Lee Y.M and Kim K.Y, J. Appl. Polymer Sci., 1992, 45, 1711.
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Journal of the Chilean Chemical Society - <B>FTIR AND TGA STUDIES OF CHITOSAN COMPOSITE FILMS</B>

7.- Miya M, Yoshikawa S, Iwamoto R and Miya S. , Kobunshu, J. Appl. Polymer Sci., 1983,
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12.- Kittur, F.S, Harish Prashanth, K.V, Udaya Sankar, K, Tharanathan, R.N, Carbohydrate
Polymers, 2002, 49, 185.
13.- ( i) Crdenas, G,.Bernal L, Tagle L.H., Thermochim. Acta 1992, 195, 33; (ii) Crdenas,
G., Retamal J, Tagle L. H, Intern. J. Poly- meric Mater. 1993, 21, 137.
14.- Rinaudo, M, Milas, M, Ledung, P, Int. J. Biol. Macromol. 1993, 15, 282.
15.- Ratner, B.D, Hofman, A.S In: Andrady editor ACS Symposium Series, Washington DC,
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16.- Atlas Surfactants, Atlas Powder Company Chemical Division, Wilmington 99, Delaware
pg 4.
17.- Taboada, E, Ph.D. Thesis, Universidad de Concepcin, January 2003.
18.- (i) Crdenas, G, Parra, O, Taboada, E, Int. J. Biol. Macromol. 2001, 28, 167; (ii)
Miranda, S.P., Garmica, O., Lara-Saohom, V., Crdenas, G, J. Chil. Chem. Soc. 2004, 2, 49.
19.- Vandenabeele, P, Moens, L, Edwards, H, Analytica Chimica Acta 2000, 407, 261.
20.- Schmdit, J.O (Misrahi, A., Lensky, Y. eds) "Bee Products: Chemi cal Composition and
Application", Plenum Press, N.Y. 1996, 15-26.
21.- Hadwiger, A.L and Beckman J.M, Plant Physiol. 1980, 66, 205.
22.- Hadwiger, A.L and Loschke D.C., Phytopathology 1981, 71, 756.
23.- Young, H.D. and Kauss H, Plant Physiol 1982, 70, 1449.
24.- Miranda, S. P. and Crdenas, G, Proceeding of Iberoamerican Symposium of Polymers,
Acapulco, Mxico, 2002, 606, 673.

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(Received: June 30, 2004 - Accepted: August 31, 2004)

2008 Sociedad Chilena de Qumica

Paicav 170, Depto. 19
P.O. Box 2613, Concepcin, Chile
Phone 41-2227815, Fax 41-2235819

schqjournal@entelchile.net

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