Forces also interchain

The properties of elastomeric materials are also greatly iafluenced by the presence of strong interchain, ie, iatermolecular, forces which can result ia the formation of crystalline domains. Thus the elastomeric properties are those of an amorphous material having weak interchain iateractions and hence no crystallisation. At the other extreme of polymer properties are fiber-forming polymers, such as nylon, which when properly oriented lead to the formation of permanent, crystalline fibers. In between these two extremes is a whole range of polymers, from purely amorphous elastomers to partially crystalline plastics, such as polyethylene, polypropylene, polycarbonates, etc. 

There are two principal forces that govern the abdity of a polymer to crystallise the interchain attractive forces, which are a function of the chain stmcture, and the countervailing kinetic energy of the chain segments, which is a function of the temperature. The fact that polymers consist of long-chain molecules also iatroduces a third parameter, ie, the imposition of a mechanical force, eg, stretching, which can also enhance interchain orientation and favor crystallisation. 

It must be pointed out that deviations from such a simple relationship do occur. For example, since random copolymerisation tends to promote disorder, reduce molecular packing and also reduce the interchain forces of attraction, the Tg of copolymers is often lower than would be predicted by the linear relationship. Examples are also known where the Tg of the copolymer is higher than predicted. This could occur where hydrogen bonding or dipole attraction is possible between dissimilar comonomer residues in the chain but not between similar residues, i.e. special interchain forces exist with the copolymers. 

In addition to homopolymers of varying molecular and particle structure, copolymers are also available commercially in which vinyl chloride is the principal monomer. Comonomers used eommercially include vinyl acetate, vinylidene chloride, propylene, acrylonitrile, vinyl isobutyl ether, and maleic, fumaric and acrylic esters. Of these the first three only are of importance to the plastics industry. The main function of introducing comonomer is to reduce the regularity of the polymer structure and thus lower the interchain forces. The polymers may therefore be proeessed at much lower temperatures and are useful in the manufacture of gramophone records and flooring compositions. 

The solvation by plasticiser also gives celluloid thermoplastic properties owing to the reduction in interchain forces. On the other hand since the cellulose molecule is somewhat rigid the product itself is stiff and does not show rubbery properties at room temperature, cf. plasticised PVC. 

Table 8 presents a survey of the basic elastic constants of a series of polymer fibres and the relation with the various kinds of interchain bonds. As shown by this table, the interchain forces not only determine the elastic shear modulus gy but also the creep rate of the fibre. 

Even within the limitations of fixed conformation, early force fields were deficient. The predicted unit cell dimensions were too small by more than 20 percent This situation was remedied by adjusting nonbonded potentials describing the fluorine-fluorine and carbon-fluorine interactions until predicted unit cell dimensions adequately reproduced experimentally measured values. This fitting was actually carried out using structural information from several polymers and was not an ad hoc parameterization for PTFE. It should also be pointed out that reproducing PTFE cell dimensions was a process of achieving an approximately correct interchain spacing for an approximate helix since the actual crystalline structure was not known at that time. Subsequently, it has become... 

Hooke s law relates stress (or strain) at a point to strain (or stress) at the same point and the structure of classical elasticity (see e.g. Love, Sokolnikoff) is built upon this linear relation. There are other relationships possible. One, as outlined above (see e.g. Green and Adkins) involves the large strain tensor Cjj which does not bear a simple relationship to the stress tensor, another involves the newer concepts of micropolar and micromorphic elasticity in which not only the stress but also the couple at a point must be related to the local variations of displacement and rotation. A third, which may prove to be very relevant to polymers, derives from non-local field theories in which not only the strain (or displacement) at a point but also that in the neighbourhood of the point needs to be taken into account. In polymers, where the chain is so much stiffer along its axis than any interchain stiffness (consequent upon the vastly different forces along and between chains) the displacement at any point is quite likely to be influenced by forces on chains some distance away. 

A variety of polymeric subunits is used to make polyurethanes. These include polyesters and polyethers. The major interchain linkages are molecular forces such as hydrogen bonding and the London force. Depending on the type of chain extender and processing temperature, there also may be biuret or allophanate cross-links. 

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