ABSTRACT:Relaxation behavior in polytrifluoroethylene (PTrFE) with varied crystallinity and swollen with benzene was investigated by mechanical and dielectric measurements. PTrFE showed the ct, /3, and /3' relaxation in decreasing order of temperature. The f3 relaxation observed around -20°C at I 00 Hz was considered to consist of two components assigned to the amorphous and crystalline regions. The /3' relaxation found in a lower temperature region below -50°C was related to molecular motions around the defects of anomalous linkages such as head-to-head and tail-to-tail. In swollen PTrFE, the ct relaxation due to the micro-Brownian motions of main chains shifted from 50°C to -l0-0°C in mechanical measurements. The f3 relaxation for swollen samples decreased in intensity or vanished. This was interpreted by considering that the component assigned to the amorphous regions did not occur or was concealed by the ct relaxation shifted to lower temperature. Relaxation behavior of the component assigned to the crystalline regions was revealed in swollen samples and related to reorientation of chains adjacent to the row vacancy defects at chain end.KEY WORDS Polytrifluoroethylene / Swelling / Dielectric Relaxation / Overlapped Relaxation / Component / Defects / Chain End / Anormalous Linkage / In polytrifluoroethylene (PTrFE) two relaxations, designated as a and /3 in decreasing order of temperature, were found by some authors. 1 -4 The a relaxation was attributed to the micro-Brownian motions of the main chains. The f3 relaxation shifted to low temperature and increased in magnitude with increasing crystallinity. 1 • 2 • 4 The similar shift to the f3 relaxation was observed for the y relaxation of polychlorotrifluoroethylene (PCTFE) and ascribed to overlapping of two components, Ya and Ye, in the amorphous and crystalline regions, respectively. 5 Thus the /3 relaxation of PTrFE was considered to consist of two components in the amorphous and crystalline regions. 1 • 2 It was inferred that the crystalline relaxation was likely related to row vacancy defects at the chain end in crystals as considered in the Ye relaxation of PCTFE. Yagi observed the same behavior of the f3 relaxation in mechanical measurements and ascribed the f3 relaxation partly to local molecular motions around defects of anomalous linkages of headto-head and tail-to-tail. 4 Furukawa et a/. 6 studied the dielectric properties of PTrFE and vinylidene fluoride-trifluoroethylene (VDFTrFE) copolymer with entire range of comonomer content. They ascribed the relaxation found at -20°c and l kHz in the copolymers to the rotational molecular motions of the all trans segments to gauche in the amorphous regions similar to those of the ferroelectric relaxation in crystalline regions. In contrast to this assignment, it was considered in the mechanical study 1 that the relaxation for copc,.>lymers with 48 to 71 mol% TrFE was related to the micro-Brownian motions of VDF rich sequences and that the 251