高分子物理Chapter 6 Molecular Motion of Polymer.pptVIP

Chapter 6 Molecular Motion of Polymer 6.1 Thermal Motion of Polymer 一 、The Major Characteristic of Polymer Molecular Motion 1. Multiplicity of motion units（运动单元的多重性 ) 整链运动 (Whole chain) 链段运动 (Chain segment) 链节运动 (Chain node) 侧基运动 (Side chain) One view is that the glass transition marks an isoviscous state. This means that, as a polymer is cooled from its melt state, viscosity increases rapidly to a common (maximum) value, ca. 1012 Pa-s (1013 poise) at Tg, for all glassy materials-both low-molecular-weight and polymeric. A second view is that the glass transition represents a state of isofree volume. Free volume, Vf, may be defined as the difference between an actual volume (or specific volume), V, of the polymer at given temperature and its equilibrium volume at absolute zero, V0, The volume at absolute zero can be approximated by the sum of the van der Waals volumes of each chain segment, which can be easily obtained by group-contribution methods. The concept of free volume has significant importance for a number of other related subjects in polymer science, including time-temperature superposition of viscoelastic properties, melt viscosity, and permeability. The glass-transition temperature of amorphous polymers can vary widely with the chemical structure of the polymer chain. In general, polymers with flexible backbones and small substituent groups have low Tg, while those with rigid backbones, such as polymers containing main-chain aromatic groups, have high Tg. 2. Thermodynamical theory The glass transition approximates an Ehrenfest second-order transition. This means that a discontinuity should be observed in the second derivatives of the Gibbs free energy. Three possible second derivatives can be used to provide a basis for the experimental measurement of Tg. From the first law of thermodynamics, dH=TdS+VdP, a relation between Cp and entropy can be obtained as Substitution of above equation into eq.(1) indicates that a second-order transition should occur