Cross-linking deformed states

In the lightly cross-linked polymers (e.g. the vulcanised rubbers) the main purpose of cross-linking is to prevent the material deforming indefinitely under load. The chains can no longer slide past each other, and flow, in the usual sense of the word, is not possible without rupture of covalent bonds. Between the crosslinks, however, the molecular segments remain flexible. Thus under appropriate conditions of temperature the polymer mass may be rubbery or it may be rigid. It may also be capable of ciystallisation in both the unstressed and the stressed state. 

The first five of these techniques involve deformation and this has to be followed by some setting operation which stabilises the new shape. In the case of polymer melt deformation this can be affected by cooling of thermoplastics and cross-linking of thermosetting plastics and similtir comments can apply to deformation in the rubbery state. Solution-cast film and fibre requires solvent evaporation (with also perhaps some chemical coagulation process). Latex suspensions can simply be dried as with emulsion paints or subjected to some... 

Such considerations appear to be very relevant to the deformation of polymethylmethacrylate (PMMA) in the glassy state. At first sight, the development of P200 with draw ratio appears to follow the pseudo-affine deformation scheme rather than the rubber network model. It is, however, not possible to reconcile this conclusion with the temperature dependence of the behaviour where the development of orientation reduces in absolute magnitude with increasing temperature of deformation. It was proposed by Raha and Bowden 25) that an alternative deformation scheme, which fits the data well, is to assume that the deformation is akin to a rubber network, where the number of cross-links systematically reduces as the draw ratio is increased. It is assumed that the reduction in the number of cross-links per unit volume N i.e. molecular entanglements is proportional to the degree of deformation. 

These experimental results show conclusively that the deformation factor occurring in the theoretical equation of state offers only a crude approximation to the form of the actual equilibrium stress-strain curve. The reasons behind the observed deviation are not known. It does appear, however, from observations on other rubberlike systems that the type of deviation observed is general. Similar deviations are indicated in TutyP rubber (essentially a cross-linked polyisobutylene) and even in polyamides having network structures and exhibiting rubberlike behavior at high temperatures (see Sec. 4b). 

The reversible recovery of a deformed elastomer to its original (undeformed) state is due to an entropic driving force. The entropy of polymer chains is minimum in the extended conformation and maximum in the random coil conformation. Cross-linking of an elastomer to form a network structure (IX) is... 

Early descriptions of the changes in cytoplasmic structure that occurred during pseudopodia formation referred to a soluble (Sol) and a gelled or semisolid (Gel) state. Thus, it was assumed that the cytoplasm in the organelle-free peripheral cytoplasm was in the Sol state, whilst in pseudopodia (which resist deformation by mechanical forces) it is in the Gel state. Thus, the control of neutrophil functions via changes in cytoplasmic structure may be explained by understanding this so-called Sol —> Gel transition. It is perhaps more convenient to think of this transition as the processes that elongate and cross-link actin filaments. 

Gross mobility of entire chains must be low. The cohesive energy forces between chains of elastomers permit rapid, easy expansion. In its extended state, an elastomeric chain exhibits a high tensile strength, whereas at a low extension it has a low modulus. Polymers with low cross-link density usually meet the desired property requirements. The material after deformation returns to its original shape because of the cross-linking. This property is often referred to as elastic memory. 

---