The dielectric relaxation behavior of a series of amorphous poly(3-hydroxybutyrate-co-3-hydroxyvalerate) P(3-HB-co-3-HV) having the hydroxyvalerate content: 0, 7, 14, 20 and 24 mol%, was investigated at the temperature and frequency ranges of 08–1008C and 10 3 –10 5 Hz, respectively. The dielectric spectra showed that the crystallization process starts during the temperature scan measurements at t 308C regardless of the 3-HV-content. All samples of P(3-HB-co-3-HV) exhibited very similar relaxation spectra indicating the preservation of the main features of P(3-HB). However, some differences were observed in the relaxation spectra including the peak height, the onset crystallization temperature and the activation behavior. It is suggested that these differences observed in the various samples of the copolyester containing different 3-HV content are mainly controlled by: (1) the rate of crystallization, (2) the ultimate percentage of crystallinity, and; (3) the heating rate of measurements. Comparison of the onset crystallization temperature, Tonset, of different samples showed that the higher the 3-HV contents, the higher is onset temperature. However, measurements of Tonest, at different heating rates showed the lower the rate, the weaker is the composition dependence of the onset temperature, so that the zero-rate onset temperature could be considered to be independent of the 3-HV content and equals that of pure P(3-HB). In addition, the study of the kinetics of cold crystallization showed that while the onset crystallization time is shortened from 14 to 4 min. by increasing the 3-HV-content from 0 to 24% HV, the offset crystallisation time is extended from 65 to 150 min. Moreover, by fitting the experimental results using Avrami equation to calculate the mechanistic exponent “n” the results showed surprisingly that “n” changes from 3.8 to t 2, t 2 and t 1 for samples containing 0, 7, 14, 20 and 24% HV, respectively. This change indicated the existence of mechanistic changes in the cold crystallization process. The results obtained are discussed and correlated to the literature data.
Посилання на статтю:
II. Dielectric investigation of cold crystallization of poly(3hydroxybutyrate) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) / Ashraf A. Mansour, Gamal R. Saad, Amany H. Hamed // Polymer. – 1999. – N 40. – P. 5377–5391.