高分子物理解析.ppt

Introduction to Polymer Physics Prof. Dr. Yiwang Chen School of Materials Science and Engineering, Nanchang University, Nanchang 330047 Chapter 2 Solid-state properties 2.1 Interaction of Molecules in Polymer van der Waals forces and Hydrogen bonding Static force is the force between polar molecules All polar molecules have permanent dipolar moment. The strength of static force between permanent dipoles depends on strength of dipolar moment and orientation degree. The interactional potential between two polar molecules with dipolar moment ?1 and ?2, and R of distance is: k is the Boltzman constant and T is temperature Static force usually ranges from 13 to 21 kJ/mol Induced force is the interactional force between the permanent dipole of polar molecule and induced dipolar moment of another molecule induced by polar molecule. For two molecules with dipolar moment ?1 and ?2, and polarizability of ?1 和 ?2, their interactional potential is: Induced force usually ranges from 6 to13 kJ/mole Chromoscatter force is the interaction of instant dipolar moments of molecules. It depends on ionization energy I, polarizability ?, and inter-distance R: It usually ranges from 0.8 to 8 kJ/mole 以上三种力统称范德华力，永久存在于一切分子之间的一种吸引力。这种吸引力没有方向性和饱和性。作用范围小于1纳米，作用能约比化学键小1－2个数量级。 氢键是极性很强的X－H键上的氢原子，与另一个键上电负性很大的原子Y上的孤对电子相互吸引而形成的一种键（X－H---Y）。 氢键有饱和性和方向性，氢键与化学键相似，键能比化学键小得多，不超过40千焦/摩尔。 Cohesive Energy Density 在高聚物中，由于分子量很大，分子链很长，分子间的作用力很大，高分子的聚集态只有固态（晶态和非晶态）和液态，没有气态。 高聚物分子间作用力的大小通常采用内聚能或内聚能密度来表示。内聚能定义为克服分子间的作用力，把一摩尔液体或固体分子移到其分子间的引力范围之处所需要的能量： ?E是内聚能，?Hv是摩尔蒸发热（或摩尔升华热?Hs），RT是转化为气体时所做的膨胀功。 内聚能密度（Cohesive Energy Density）是单位体积的内聚能： 为摩尔体积 对于低分子化合物，其内聚能近似等于恒容蒸发热或升华热，可直接由热力学数据估计其内聚能密度，而高聚物不能气化，不能直接测定它的内聚能，只能用低分子溶剂相比较的办法进行估计。 2.2 The Amorphous state Completely amorphous polymers like atactic polystyrene exist as long, randomly coiled, interpenetrating chains that are capable of forming stable, flow-restricting entanglements at sufficiently high-molecular-weight. In the melt, thermal energy is suff