Yield behavior molecular theories

This paper rerports an investigation of the yield behavior of several amine and anhydride cured DGEBA resin systems. The Argon theory is used to assess the controlling molecular parameters from the experimental results. Such parameters are then compared with the known chemical structures of the resins. The mechanisms of plastic flow in thermoset polymers such as epoxies is demonstrated. 

The Argon theory, therefore, consistently interprets the yield behavior of both thermosets and thermoplastics. This indicates that crosslinks in thermosets do not introduce appreciable deviation to the kink formation process described. This point is also supported by Ygmani and Young s finding of the molecular parameters, z and a, being insensitive to crosslinking density for DGEBA cured with different amount of TETA. 

The fundamental assumption of the classical rheological theories is that the liquid stmcture is either stable (Newtonian behavior) or its changes are well dehned (non-Newtonian behavior). This is rarely the case for flow of multiphase systems. For example, orientation of sheared layers may be responsible for either dilatant or pseudoplastic behavior, while strong interparticle interactions may lead to yield stress or transient behaviors. Liquids with yield stress show a plug flow. As a result, these liquids have drastically reduced extrudate swell, B = d/d (d is diameter of the extrudate, d that of the die) [Utracki et al, 1984]. Since there is no deformation within the plug volume, the molecular theories of elasticity and the relations they provide to correlate, for example either the entrance pressure drop or the extmdate swell, are not applicable. 

Kinetic energy is energy of motion. The kinetic energy of an object with mass m and velocity u is K.E. = mu. The kinetic-molecular theory of gases is a model for describing gas behavior. It is based on a set of assumptions and yields equations from which various properties of gases can be deduced. 

Decreasing the degree of crosslinking will increase the water uptake for a mass of dry gel, though compromises in the efficiency will result. The effect of crosslinks on the separation of vitamin B-12, a nonionic solute of molecular weight 1355, is shown in Fig. 4 [16]. As the crosslink density decreases, the polymer chain length between crosslinks increases, yielding a looser structure which vitamin B-12 can more easily penetrate. The behavior fits well with the prediction from Flory excluded volume theory [16] ... 

Above about 45°C, however, considerable yielding can be observed. Note that the transition between brittle and ductile behavior occurs at a temperature that is significantly below the T. Various theories have been advanced to explain yielding phenomena in polymers, some involving free volume arguments while others involve various types of molecular motion. As far as we can make out, none of these are entirely satisfactory and we won t discuss them here. Instead, we will finish off our discussion of stress/strain behavior by considering rubber elasticity. 

A scientific theory, like a mathematical system, never yields more than is built into it in the way of assumptions or postulates. The phenomenological approach presented in the preceding chapters could no more than characterize the kinetic behavior of systems in terms of the macroscopic variables used to describe them. We have obtained from this approach the kinetic quantities and rate constants or, in terms of the Arrhenius formulation, the frequency factors and the energies of activation. These quantities constitute our phenomenological category of kinetic language. If we are to relate them to the molecular properties of the reacting species, we must construct a new theory and a new nomenclature which starts with the molecule as the unit under consideration. 

The validity of the viscoelastic model (5.32) has been tested against experimental and molecular dynamics simulation results [26, 27, 28]. The detailed comparison has established that the viscoelastic model works remarkably well for wavenumbers k km, where km denotes the first peak position of the static structure factor S k). However, it has also been found that the situation is not so satisfactory for smaller wavenumbers, where the viscoelastic model is shown in some circumstances to yield even qualitatively incorrect results. This failure was attributed to the fact that the single relaxation time model (5.31) cannot describe both the short-time behavior of the memory function, dominated by the so-called binary collisions, and in particular the intermediate and long-time behavior where in the liquid range additional slow processes play an important role (see the next subsection). It is obvious that these conclusions demand a more rigorous consideration of the memory function, which lead to the development of the modern version of the kinetic theory. Nevertheless, the viscoelastic model provides a rather satisfactory account of the main features of microscopic collective density fluctuations in simple liquids at relatively large wavenumbers, and its value should not be undervalued. 

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