Orientation in linear amorphous polymers

Anisotropic behaviour is also exhibited in optical properties and orientation effects can be observed and to some extent measured by birefringence methods. In such oriented materials the molecules are in effect frozen in an unstable state and they will normally endeavour to take up a more coiled conformation due to rotation about the single bonds. If an oriented sample is heated up the molecules will start to coil as soon as they possess sufficient energy and the mass will often distort. Because of this oriented materials usually have a lower heat distortion temperature than non-oriented polymers. 

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Orientation in linear amorphous polymers Crystalline Polymers... 

In fluorescence spectroscopy, the orientation distribution of the guest probe is not necessarily identical to the actual orientation of the polymer chains, even if it is added at very small concentrations (i.e., a probe with high fluorescence efficiency). As a matter of fact, it is generally assumed that long linear probes are parallel to the polymer main chain, but this is not necessarily the case. Nevertheless, if the relation between the distribution of the probe axes and those of the polymer axes is known, the ODF of the structural units can be calculated from that of the probe thanks to the Legendre s addition theorem. Finally, the added probe seems to be mainly located in the amorphous domains of the polymer [69] so that fluorescence spectroscopy provides information relative to the noncrystalline regions of the polymeric samples. 

The template-assisted synthetic strategies outlined above produce micro- or mesoporous stmetures in which amorphous or crystalline polymers can form around the organic template ligands (174). Another approach is the use of restricted spaces (eg, pores of membranes, cavities in zeolites, etc.) which direct the formation of functional nanomaterials within thek cavities, resulting in the production of ultrasmaU particles (or dots) and one-dimensional stmetures (or wkes) (178). For example, in the case of polypyrrole and poly(3-methylthiophene), a solution of monomer is separated from a ferric salt polymerization agent by a Nucleopore membrane (linear cylindrical pores with diameter as small as 30 nm) (179—181). Nascent polymer chains adsorb on the pore walls, yielding a thin polymer film which thickens with time to eventually yield a completely filled pore. De-encapsulation by dissolving the membrane in yields wkes wherein the polymer chains in the narrowest fibrils are preferentially oriented parallel to the cjlinder axes of the fibrils. 

Linear viscoelasticity is valid only imder conditions where structural changes in the material do not induce strain-dependent modulus. This condition is fulfilled by amorphous polymers. On the other hand, the structural changes associated with the orientation of crystalline polymers and elastomers produce anisotropic mechanical properties. Such polymers, therefore, exhibit nonlinear viscoelastic behavior. 

ANISOTROPY OF THERMAL CONDUCTIVITY IN ORIENTED LINEAR AMORPHOUS HIGH POLYMERS. PH.D. THESIS. 

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