Novel gigahertz frequency dielectric relaxations in chitosan films

• Published in: Soft matter Vol. 1; no. 43; pp. 8673 - 8684
• Main Authors: Kumar-Krishnan, Siva, Prokhorov, Evgen, Ramírez, Marius, Hernandez-Landaverde, Martín A, Zarate-Triviño, Diana G, Kovalenko, Yu, Sanchez, Isaac C, Méndez-Nonell, Juan, Luna-Bárcenas, Gabriel
• Format: Journal Article
• Language: English
• Published: England 21.11.2014
• Subjects: Activation energy; Chitosan; Chitosan - chemistry; Cooling; Dielectric relaxation; Dielectric Spectroscopy; Heating; Hydrogen bonding; Membranes, Artificial; Microwaves; Vibration; Water loss
• ISSN: 1744-683X; 1744-6848
• DOI: 10.1039/c4sm01804d

Molecular relaxations of chitosan films have been investigated in the wide frequency range of 0.1 to 3 × 10 9 Hz from −10 °C to 110 °C using dielectric spectroscopy. For the first time, two high-frequency relaxation processes (in the range 10 8 to 3 × 10 9 Hz) are reported in addition to the low frequency relaxations α and β. These two relaxation processes are related to the vibrations of OH and NH 2 /NH 3 + , respectively. The high-frequency relaxations exhibit Arrhenius-type dependencies in the temperature range 10 °C to 54 °C with negative activation energy; this observation is traceable to hydrogen bonding reorientation. At temperatures above the glass transition temperature (54 °C), the activation energy changes from negative to positive values due to breaking of hydrogen bonding and water loss. Upon cooling in a sealed environment, the activation energies of two relaxation processes are nearly zero. FTIR and XRD analyses reveal associated structural changes upon heating and cooling. These two new high-frequency relaxation processes can be attributed to the interaction of bound water with OH and NH 2 /NH 3 + , respectively. A plausible scenario for these high-frequency relaxations is discussed in light of impedance spectroscopy, TGA, FTIR and XRD measurements. Temperature-dependence relaxation time of OH side groups versus 1/ T for chitosan films in the heating and cooling process. The solid lines represent Arrhenius-type dependence fitting. Schematic of proposed molecular interactions.