In this work thermal relaxations of chitosan are reported by using a novel methodology that includes subtraction of the dc conductivity contribution, the exclusion of contact and interfacial polarization effects, and obtaining a condition of minimum moisture content. When all these aspects are taken into account, two relaxations are clearly revealed in the low frequency side of the impedance data. We focus on the molecular motions in neutralized and non‐neutralized chitosan analyzed by dielectric spectroscopy in the temperature range from 25 to 250 °C. Low and high frequency relaxations were fitted with the Havriliak and Negami model in the 10−1 to 108 Hz frequency range. For the first time, the low frequency α‐relaxation associated with the glass‐rubber transition has been detected by this technique in both chitosan forms for moisture contents in the range 0.05 to 3 wt % (ca. 18–62 °C). A strong plasticizing effect of water on this primary α‐relaxation is observed by dielectric spectroscopy and is supported by dynamic mechanical analysis measurements. In the absence of water (<0.05 wt %) the α‐relaxation is obscured in the 20–70 °C temperature range by a superposition of two low frequency relaxation processes. The activation energy for the σ‐relaxation is about 80.0–89.0 kJ/mol and for β‐relaxation is about 46.0–48.5 kJ/mol and those values are in agreement with that previously reported by other authors. The non‐neutralized chitosan possess higher ion mobility than the neutralized one as determined by the frequency location of the σ‐relaxation. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2259–2271, 2009

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The modification of achira starch a thermoplastic biopolymer is shown. Glycerol and sorbitol, common plasticizers, were used in the molten state with organic acids such as oleic acid and lactic acid obtaining thermodynamically more stable products. The proportion of starch:plasticizer was 70:30, and the acid agent was added in portions from 3%, 6%, and 9% by weight. These mixtures were obtained in a torque rheometer for 10 min at 130 °C. The lactic acid managed to efficiently promote the gelatinization process by increasing the available polar sites towards the surface of the material; as a result, there were lower values in the contact angle, these results were corroborated with the analysis performed by differential scanning calorimetry and X-ray diffraction. The results derived from oscillatory rheological analysis had a viscous behavior in the thermoplastic starch samples and with the presence of acids; this behavior favors the transitions from viscous to elastic. The mixture of sorbitol or glycerol with lactic acid promoted lower values of the loss module, the storage module, and the complex viscosity, which means lower residual energy in the transition of the viscous state to the elastic state; this allows the compounds to be scaled to conventional polymer transformation processes.

Starch is a biopolymer with enormous potential for generating new biodegradable packages due to its easy availability and low cost. However, due to its weak functional properties, limitation of its interaction with some hydroxyl groups and evaluation of blends with other polymers are necessary in order to improve its performance. Glycerol-plasticized acetylated corn starch films were developed using the casting method, and the impact of incorporating chitosan (TPS:CH) in various proportions (75:25, 50:50, and 25:75 v/v) was studied in the present research. The effect of chitosan ratios on the physical, mechanical, water-vapor barrier, and thermal properties of the film was studied. Chitosan-protonated amino groups promoted the formation of intermolecular bonds, improving tensile strength, thermal stability, hydrophobicity, water adsorption capacity, and the gas barrier of starch films. The results show that the film composed of TPS25-CH75 proved to be the best barrier to water vapor; thus, these composite films are excellent choices for developing biodegradable packaging for the food industry.