TY - JOUR
T1 - Relaxation in liquids, polymers and plastic crystals - strong/fragile patterns and problems
AU - Angell, Charles
N1 - Funding Information:
The author is grateful for the support of his research in this area by the NSF under Solid State Chemistry Grant No. DMR8805597.
PY - 1991/6/11
Y1 - 1991/6/11
N2 - An overview of relaxational phenomenology is given in a manner intended to highlight a number of the important problems which, notwithstanding much recent sophisticated investigation, continue to confront the field. The rapidly lengthening timescale for diffusional and/or reorientational motion, which provokes the glass transition, is examined within the framework of the 'strong' and 'fragile' classification of both liquids and plastic crystals. The behavior patterns observed are related to the topological features of the potential energy hypersurfaces which may characterize each extreme. In view of the implication that the observed glass transition is the kinetically obscured reflection of an underlying higher order thermodynamic transition which could be associated with a diverging length scale (at least for fragile systems), the problem of the basic diffusional length scale at the glass transition, using a probe molecule approach, is considered. Then, details of the kinetics of relaxation under isothermal conditions are reviewed to decide on the range of deviations from Debye behavior which may be encountered. A correlation with fragility is strongly indicated. The phenomena of serial decoupling of relaxational modes from the main structural relaxation as Tg is approached is outlined and, finally, the additional phenomena that may be encountered in experiments that explore the state-dependence (or non-linearity) of relaxation are briefly examined.
AB - An overview of relaxational phenomenology is given in a manner intended to highlight a number of the important problems which, notwithstanding much recent sophisticated investigation, continue to confront the field. The rapidly lengthening timescale for diffusional and/or reorientational motion, which provokes the glass transition, is examined within the framework of the 'strong' and 'fragile' classification of both liquids and plastic crystals. The behavior patterns observed are related to the topological features of the potential energy hypersurfaces which may characterize each extreme. In view of the implication that the observed glass transition is the kinetically obscured reflection of an underlying higher order thermodynamic transition which could be associated with a diverging length scale (at least for fragile systems), the problem of the basic diffusional length scale at the glass transition, using a probe molecule approach, is considered. Then, details of the kinetics of relaxation under isothermal conditions are reviewed to decide on the range of deviations from Debye behavior which may be encountered. A correlation with fragility is strongly indicated. The phenomena of serial decoupling of relaxational modes from the main structural relaxation as Tg is approached is outlined and, finally, the additional phenomena that may be encountered in experiments that explore the state-dependence (or non-linearity) of relaxation are briefly examined.
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U2 - 10.1016/0022-3093(91)90266-9
DO - 10.1016/0022-3093(91)90266-9
M3 - Article
AN - SCOPUS:0026413564
SN - 0022-3093
VL - 131-133
SP - 13
EP - 31
JO - Journal of Non-Crystalline Solids
JF - Journal of Non-Crystalline Solids
IS - PART 1
ER -