Extension birefringence

Figure 4. Entanglement network cross-linked in a state of simple extension. Birefringence-strain curves calculated for cross-link network, trapped entanglement network, and their sum also expermentally measured (0, exp , calc.), for Polymer B at 20.0°C. v = 0.97x10 ", v., = 1.85x10 " mol...

Equation (32a) has been very successful in modelling the development of birefringence with extension ratio (or equivalently draw ratio) in a rubber, and this is of a different shape from the predictions of the pseudo-affine deformation scheme (Eq. (30a)). There are also very significant differences between the predictions of the two schemes for P400- In particular, the development of P400 with extension ratio is much slower for the network model than for the pseudo-affine scheme. 

The photoelastic measurements were carried out in simple extension using strip specimens. In addition to the force/ also the optical retardation S (hence also the birefringence An <5) could be determined and the modulus G, the deformational-optical function A and the stress-optical coefficient C = A/G were calculated using the equations [31]... 

A final piece of evidence against both finite extensibility and internal viscosity is provided by flow birefringence studies. One would expect each to produce variations in the stress optical coefficient with shear rate, beginning near the onset of shear rate dependence in the viscosity (307). Experimentally, the stress-optical coefficient remains constant well beyond the onset of shear rate dependence in r for all ranges of polymer concentration (18,340). 

As has been pointed out (63), this is a rather artificial model and, moreover, its application is quite unnecessary. In fact, (a> can be calculated from the refractive index increment (dnjdc), as has extensively been done in the field of light scattering. This procedure is applicable also to the form birefringence effect of coil molecules, as the mean excess polarizability of a coil molecule as a whole is not influenced by the form effect. It is still built up additively of the mean excess polarizabilities of the random links. This reasoning is justified by the low density of links within a coil. In fact, if the coil is replaced by an equivalent ellipsoid consisting of an isotropic material of a refractive index not very much different from that of the solvent, its mean excess polarizability is equal to that of a sphere of equal volume [cf. also Bullough (145)]. 

Scattering or form birefringence contributions will cause a deviation in the stress optical rule. As seen in equation (7.36), these effects do not depend on the second-moment tensor, but increase linearly with chain extension. 

Extensive work investigating the stress-optical rule has also been performed on polymer solutions [101]. Here the rule can be successfully applied if the solvent contributions to the birefringence are properly subtracted. Care must be taken, however, to avoid form birefringence effects if there is a large refractive index contrast between the polymer and the solvent. 

The flow-strength criteria stated in equation (10.2) has been examined experimentally by Fuller and Leal [72] and Dunlap and Leal [149] using four- and two-roll mills, respectively. These devices allow one to systematically vary the flow type (the relative amount of pure extension to pure rotation). The birefringence was measured for dilute and semidilute polymer solutions as a function of both the magnitude and type of the flow. Simple molecular models of flexible polymer chains suggest that such data, when plotted as a... 

J. A. van Aken and H. Janeschitz-Kriegl, Rheol. Acta, Simultaneous measurement of transient stress and flow birefringence in one sided compression (biaxial extension) of a polymer melt, Rheol. Acta, 20,419 (1981). 

This electro-optical effect, commonly observed as transient changes in optical birefringence of a solution following application, removal, or reversal of a biasing electric field E(t), has been used extensively as a probe of dynamics of blopolymer solutions, notably by O Konski, and is a valuable tool because it gives information different in form, but related to, results from conventional dielectric relaxation measurements. The state of the subject to 1975 has been comprehensively presented in two review volumes edited by O Konski (25). The discussion here is confined to an outline of a response theory treatment, to be published in more detail elsewhere, of the quadratic effect. The results are more general than earlier ones obtained from rotational diffusion models and should be a useful basis for further theoretical and experimental developments. 

Figure 9A. After layering the composition at point P, Fig. 8 on water a birefringent layer was formed in the aqueous part after 20 days, disappearing in 8 days point P. It was replaced by a fairly extensive isotropic liquid middle phase, which was gradually reduced to zero in 52 days. The aqueous phase was slowly depleted lasting more than 150 days.

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