Equilibrium elasticity measurements

A new stress-relaxation two-network method is used for a more direct measurement of the equilibrium elastic contribution of chain entangling in highly cross-linked 1,2-polybutadiene. The new method shows clearly, without the need of any theory, that the equilibrium contribution is equal to the non-equilibrium stress-relaxation modulus of the uncross-linked polymer immediately prior to cross-linking. The new method also directly confirms six of the eight assumptions required for the original two-network method. 

There exist a number of experimental methods for determination of structure sensitive parameters of a system undergoing branching and crosslinking. However, evaluation of some of the results requires application of a theoretical approach to the phenomenon the measurement is concerned with. Then, we may be testing two theories at once. The equilibrium elasticity is one example, since there exist alternative rubber elasticity theories. However, certain conclusions can always be made. 

Cross-link densities were characterized above T by equilibrium modulus measurements employing rubber elasticity theory. The results indicate that this method yields surprisingly reasonable values. 

Previous studies on PDB networks, which were reputed to be well-characterized, are therefore vitiated by the non-quantitative chemistry of the networks, the effect of strain-induced crystallization, and the question of equilibrium attainment during elastic measurements. Departures from theory can not be attributed to the highly speculative contributions from interchain entanglements. PBD of high cis-1,4... 

Using the equilibrium equations of the elasticity theory enables one to determine the stress tensor component (Tjj normal to the plane of translumination. The other stress components can be determined using additional measurements or additional information. We assume that there exists a temperature field T, the so-called fictitious temperature, which causes a stress field, equal to the residual stress pattern. In this paper we formulate the boundary-value problem for determining all components of the residual stresses from the results of the translumination of the specimen in a system of parallel planes. Theory of the fictitious temperature has been successfully used in the case of plane strain [2]. The aim of this paper is to show how this method can be applied in the general case. 

A solid, by definition, is a portion of matter that is rigid and resists stress. Although the surface of a solid must, in principle, be characterized by surface free energy, it is evident that the usual methods of capillarity are not very useful since they depend on measurements of equilibrium surface properties given by Laplace s equation (Eq. II-7). Since a solid deforms in an elastic manner, its shape will be determined more by its past history than by surface tension forces. 

Radiation probes such as neutrons, x-rays and visible light are used to see the structure of physical systems tlirough elastic scattering experunents. Inelastic scattering experiments measure both the structural and dynamical correlations that exist in a physical system. For a system which is in thennodynamic equilibrium, the molecular dynamics create spatio-temporal correlations which are the manifestation of themial fluctuations around the equilibrium state. For a condensed phase system, dynamical correlations are intimately linked to its structure. For systems in equilibrium, linear response tiieory is an appropriate framework to use to inquire on the spatio-temporal correlations resulting from thennodynamic fluctuations. Appropriate response and correlation functions emerge naturally in this framework, and the role of theory is to understand these correlation fiinctions from first principles. This is the subject of section A3.3.2. 

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