Anomalous thermochromic transition of poly(di‐n‐octylsilane)

Abstract

AbstractThe thermochromic behavior of poly(di‐n‐octylsilane) {[Si(C8H17)2]n; PDOS} was studied by ultraviolet (UV) absorption, differential scanning calorimetry, and X‐ray diffraction measurements. The structure of PDOS in the low‐temperature phase strongly depended on not only the temperature but also the rate of cooling, that is, the thermal history. Temperature‐dependent UV absorption spectra were highly dependent on thermal hysteresis. Cooled rapidly (10 K/min), PDOS showed two absorption peaks at 3.32 and 3.51 eV in low‐temperature‐ordered phases, whereas a single absorption peak at 3.32 eV became predominant with slow cooling (0.3 K/min). The appearance of the two peaks at low temperatures suggested that a mixture of different conformations was introduced by rapid cooling. A fiber diffraction pattern measured at 240 K after rapid cooling also showed evidence of the existence of novel conformation. A temperature‐dependent powder X‐ray diffraction pattern changed significantly between 270 and 280 K. Rapid cooling reduced the intensity of the X‐ray diffraction peak in this temperature region. This intensity change was explained by the conformational mixture in the polymer. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 1085–1092, 2001