By H. F. Mark (auth.), H. Henning Kausch, John A. Hassell, Robert I. Jaffee (eds.)
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In the direction of orientation it has a high tensile strength and ductile extensibility; it is resistant to environmental stress-crazing and stress-cracking. 4 MECHANICAL BEHAVIOR 19 Molecular orientation occurs inevitably in most mechanical fabrication operations, the pattern of orientation in the part being governed by the process kinematics - the pattern of flow and deformation followed by the polymer during fabrication. The effects of orientation can be either favorable or unfavorable, depending on the directions of orientation relative to the stresses encountered in service.
Thus they play an important role in time-dependent mechanical deformations, whether small or large, and in processes of rupture. Measurements of linear viscoelasticity provide information about rates of molecular motion through the identification of spectra of relaxation times which can, to some degree, be related to characteristic motional modes. We first review here, briefly, the current state of knowledge for dilute polymer solutions, which are instructive because molecular theory is comparatively well developed, although the results are not directly applicable to most practical situations.
2 DILUTE POLYMER SOLUTIONS In describing the viscoelastic properties of very dilute polymer solutions, the bead-spring molecular model has been quite successful. The molecule is represented as arbitrarily divided into submolecules; the fric- DEFORMATIONS AND MOLECULAR MOTIONS 29 tional resistance to translational motion is concentrated at the junctions between them (beads); the submolecules are long enough to have a Gaussian distribution of configurations, and distortion of this distribution increases the free energy (entropy springs).