Glassy polymers expansion

The properties of glassy polymers such as density, thermal expansion, and small-strain deformation are mainly determined by the van der Waals interaction of adjacent molecular segments. On the other hand, crack growth depends on the length of the molecular strands in the network as is deduced from the fracture experiments. 

Au is the difference between the liquid and glassy volumetric expansion coefficients and the temperatures are in kelvin. "The WLF equation holds between I], or / f 10 K and abftut 100 K above 7A,. Above this temperature, for thermally stable polymers, Berry and Fox (28) have shown that a useful extension of the WLF equation is the addition of an Arrhenius term with a low activation energy. 

Creep rates of three glassy polymers are much greater during electron irradiation than before or after. Radiation heating is eliminated as a possible cause. Essentially the same concentration of unpaired electrons and ratio of cross-linking to scission were found in polystyrene samples in the presence or absence of stress. The effects of radiation intensity, stress, and temperature on creep during irradiation are examined. The accelerated creep under stress is directly related to a radiation-induced expansion in the absence of stress. This radiation expansion is decreased by increase in temperature or plasticizer content and decrease in sample thickness. It is concluded that gas accumulation within the sample during irradiation causes both the expansion under no stress and the acceleration of creep under stress. 

The results of the delayed stress on radiation studies presented above (Figure 7) are also consistent with the mechanism of gas buildup within the polymer specimens as the cause of the accelerated creep. An additional interesting conclusion is that applied stress should increase the rate at which gases diffuse out of a polymer specimen. This is not unreasonable in view of the fact that this conclusion is reached for stress application during irradiation, when expansion of the polymer matrix by the internally generated gas would be expected to facilitate gas diffusion. (Actually, one would expect increased gas diffusion in stressed glassy polymers, even in the absence of radiation, owing to the low Poisson ratio in such materials.)... 

Of the thermodynamic quantities just mentioned, only the determination of the expansion coefficient or other quantities reflecting its change have assumed practical importance for the identification of secondary transitions in glassy polymers. The most efficient methods for the investigation of the dynamics and intensity of molecular motions have so far been those based on the interference between molecular motion and the oscillating magnetic, electric or mechanical force field. In recent years, methods which employ various probes or labels in the study of molecular mobility have increasingly been used. 

The swelling mechanism is well established in rubbers (Flory, 1943). The expansion force generated by the solvent penetration is equilibrated by the entropic force linked to chain stretching. Little is known, in contrast, for the case of glassy polymers where plasticization effects are not sufficient to induce a devitrification. Swelling can be defined by... 

Polymers above their Tg are in a state of equilibrium much like simple liquids. However, upon cooling below Tg, polymers are not able to achieve an equilibrium state since the polymer chain segments lack sufficient mobility to reach this state in realizable time scales. Thus, glassy polymers exist in a nonequilibrium state that is a function of the prior history of the sample. It is useful to think of simple volumetric thermal expansion where at equilibrium the specific volume at a given temperature and pressure is Veq(T,p) the specific volume of a rubbery polymer is given by Veq. The... 

The coefficient of volumetric thermal expansion of a "glassy" polymer (T[Pg.33]

Table 3.1. Coefficients of thermal expansion, in units of 1(KVK, for glassy polymers (ag) and for rabbery polymers (ocr) [11] and glass transition temperatures (Tg), in degrees Kelvin. 

The stress-strain behavior of thermosets (glassy polymers crosslinked beyond the gel point) is not as well-understood as that of elastomers. Much data were analyzed, in preparing the previous edition of this book, for properties such as the density, coefficient of thermal expansion, and elastic moduli of thermosets [20,21,153-162]. However, most trends which may exist in these data were obscured by the manner in which the effects of crosslinking and of compositional variation were superimposed during network formation in different studies, by... 

For more soluble gases like methane and carbon dioxide, the solubility, in glassy polymers with a large difference between the volume expansion coefficients of the liquid and glassy states, is non-linear. The values of for PET, PC and PMMA are 8.0, 4.3 and 1.3 x lO C, respectively, and only the first two polymers show this anomalous effect. Some gas is physically adsorbed on the surface of sub-microscopic holes in the polymer. Figure 11.1 shows how the concentration of CO2 increases with pressure p in PET, a polymer used in carbonated drinks containers. The solubility is described by... 

An overview of the physics of glassy polymers and the relationships between molecular mechanisms and macroscopic physical, mechanical and transport properties of polymer glasses is presented. The importance of local translational and/or rotational motions of molecular segments in the glass is discussed in terms of the implications for thermodynamic descriptions of the glass (configurational states and energy surfaces) as well as history dependent properties such as expansivity, refractive index, gas permeability, and viscoelastic mechanical behaviour. 

The microhardness of glassy polymers decreases with increasing temperature because of thermal expansion (9). At the glass-transition temperature Tg, the onset of liquid-like motions takes place. The motions of long segments above Tg require more free volume and lead to a fast decrease of microhardness with temperature. The microhardness of several glassy polymers, measured at room temperature, has been shown to be directly proportional to its glass-transition temperature (10). 

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