کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
5186573 | 1381107 | 2006 | 12 صفحه PDF | دانلود رایگان |
Free volume data from positron annihilation lifetime spectroscopy (PALS) experiments are combined with a Simha-Somcynsky (S-S) equation of state analysis of pressure-volume-temperature (PVT) data to model free volume contributions to structural mobility in a series of poly(n-alkyl methacrylate)s. From the PALS data the glass transition temperature, Tg, decreases (from 382 to 224 ± 5 K) and a given mean free volume is observed at lower temperatures as the side-chain length increases (going from methyl- to hexyl-). This is evidence of an internal plasticization whereby the side-chains reduce effective packing of molecules. By comparing PALS and PVT data, the hole number per mass unit, Nhâ², is calculated using different methods; this varies between 0.54 and 0.86 Ã 1021 gâ1. It is found that the extrapolated free volume becomes zero at a temperature T0â² that is smaller than the Vogel temperature T0 of the α-relaxation. The α-relaxation frequencies can be fitted by the free volume theory of Cohen and Turnbull, but only when the free volume Vf is replaced by (Vf â ÎV) where ÎV( = Ef(T0 â T0â²), Ef is the thermal expansivity of Vf) varies between 0.060 and 0.027 ± 0.003 cm3/g, decreasing with side-chain length, apart from poly(n-hexyl methacrylate) where ÎV increases to 0.043 ± 0.003 cm3/g. One possible interpretation of this is that the α-relaxation only occurs when, due to statistical reasons, a group of m or more unoccupied S-S cells are located adjacent to one another. m is found to vary between 8 and 2 for poly(methyl methacrylate) and poly(n-butyl methacrylate), respectively. We found that no specific feature in the free volume expansion was consistently in coincidence with the dynamic crossover.
Journal: Polymer - Volume 47, Issue 22, 18 October 2006, Pages 7774-7785