Conformational elasticity

The transition of the polymer from the rubbery to the glassy state principally changes the deformation behaviour and mechanical response of the material. The dominant role of intermolecular forces in the glassy state of polymer fully suppresses the effect of the conformational elasticity of network chains, at least at low strains. 

In an un-cross-linked amorphous polymer, above its glass temperature, the molecular chains are continuously wriggling from one conformation to another. If a mechanical stress is imposed on such a system of wriggling chains, it can respond in three distinct ways instantaneous elastic response retarded (conformational) elastic response or viscous flow. Actually, in order to fit experimental data adequately, the retarded elastic element must be expanded into a whole series of such elements, some with shorter and some with longer response times. The local "kinkiness" of the chains can be straightened out (by stress) more rapidly than the... 

The time-temperature equivalence principle makes it possible to predict the viscoelastic properties of an amorphous polymer at one temperature from measurements made at other temperatures. The major effect of a temperature increase is to increase the rates of the various modes of retarded conformational elastic response, that is, to reduce the retarding viscosity values in the spring-dashpot model. This appears as a shift of the creep function along the log t scale to shorter times. A secondary effect of increasing temperature is to increase the elastic moduli slightly because an equilibrium conformational modulus tends to be proportional to the absolute temperature (13). 

The first theories that implemented a proper balance of intramolecular interactions and conformational elasticity of the branches were developed by Daoud and Cotton [21] and by Zhulina and Birshtein [22-24]. These theories use scaling concepts (the blob model), originally developed by de Gennes and Alexander to describe the structure of semidilute polymer solutions [64] and planar polymer brushes [65, 66]. Here, the monomer-monomer interactions were incorporated on the level of binary or ternary contacts (corresponding to good and theta-solvent conditions, respectively), and both dilute and semidilute solutions of star polymers were considered. Depending on the solvent quality and the intrinsic stiffness of the arms, the branches of a star could be locally swollen, or exhibit Gaussian statistics [22-24]. 

Figure 32.5 Chain conformational elasticity is a vector force tending to cause the chain ends (labeled N and 1) to be near each other, on average.

Another simplified model is the freely jointed or random flight chain model. It assumes all bond and conformation angles can have any value with no energy penalty, and gives a simplified statistical description of elasticity and average end-to-end distance. 

The expansion of the coil domain produces an elastic restoring force which opposes the expansion by tending to restore the molecule to its most probable conformation. 

The critical property for conformal coatings is resistance to chemicals, moisture, and abrasion. Other properties, such as the coefficient of thermal expansion, thermal conductivity, flexibiHty, and modulus of elasticity, are significant only in particular appHcations. The dielectric constant and loss tangent of the conformal coating are important for high speed appHcations. 

To understand the global mechanical and statistical properties of polymeric systems as well as studying the conformational relaxation of melts and amorphous systems, it is important to go beyond the atomistic level. One of the central questions of the physics of polymer melts and networks throughout the last 20 years or so dealt with the role of chain topology for melt dynamics and the elastic modulus of polymer networks. The fact that the different polymer strands cannot cut through each other in the... 

The physical processes that occur during indentation are schematically illustrated in Fig. 31. As the indenter is driven into the material, both elastic and plastic deformation occurs, which results in the formation of a hardness impression conforming to the shape of the indenter to some contact depth, h. During indenter withdrawal, only the elastic portion of the displacement is recovered, which facilitates the use of elastic solutions in modeling the contact process. 

This coacervation process forms the basis for the self-assembly, which takes place prior to the crosslinking. The assembly of tropoelastin is based on an ordering process, in which the polypeptides are converted from a state with little order to a more structured conformation [8]. The insoluble elastic fiber is formed via the enzymatic crosslinking of tropoelastin (described in Sect. 2.1). Various models have been proposed to explain the mechanism of elasticity of the elastin fibers. 

Macromolecules differ from small molecules in a number of critical properties. First, the linear chain structure confers elasticity, toughness, and strength on the solid state system. This is a consequence of the reorientational freedom of the skeletal bonds and of their ability to absorb impact or undergo elastic deformation by means of conformational changes rather than bond cleavage. 

---