Glassy polymers plasticization

Hachisuka, H., T. Sato, T. Imai, Y. Tsujita, A. Takizawa and T. Kinoshita, Glass transition temperature of glassy polymers plasticized by CO2 gas. Polymer Journal, 1990, (22-1), 77-79... 

Atomistically detailed models account for all atoms. The force field contains additive contributions specified in tenns of bond lengtlis, bond angles, torsional angles and possible crosstenns. It also includes non-bonded contributions as tire sum of van der Waals interactions, often described by Lennard-Jones potentials, and Coulomb interactions. Atomistic simulations are successfully used to predict tire transport properties of small molecules in glassy polymers, to calculate elastic moduli and to study plastic defonnation and local motion in quasi-static simulations [fy7, ( ]. The atomistic models are also useful to interiDret scattering data [fyl] and NMR measurements [70] in tenns of local order. 

It must be above its glass transition temperature, which means that the polymer chains have sufficient thermal energy to move freely. Many rubbery materials have glass transition temperatures around 200 K, below which they are glassy, like plastics. 

Apparently local motions indicating differences in packing are closely related to the mechanical properties of glassy polymers. One of the puzzling features of the P-relaxation in PC as in other glassy polymers 3 6 76 77) is that it often is suppressed if the glass transition temperature is lowered by adding a plasticizer. The material then becomes brittle, which severely limits the applications of such polymers. Such low... 

Water molecules combine the tendency to cluster, craze and plasticize the epoxy matrices with the characteristic of easily diffusion in the polymer1 10). The morphology of the thermoset may be adversaly influenced by the presence of the sorbed moisture. The diffusion of the water in glassy polymers able to link the penetrant molecules is, therefore, characterized by various mechanisms of sorption which may be isolated giving useful information on the polymer fine structure. 

Attempts have been made in the past to explain the plasticity of glassy polymers based on different theories (a review of which can be found in (1)). Most of the earlier approaches are based on models non-specific about the molecular deformation process. The theory by Argon... 

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. 

Since glassy polymers tend to become plasticized by C02, it is important to determine the magnitude to which CO2 effects plasticization. This is achieved in monitoring nonlinear effects of gas permeability of mixtures containing CO2. CO2 shows a higher sorption than expected. This is attributed to the presence of acrylonitrile moieties in the ABS copolymer. 

The area below the absorption curve is proportional to the number of protons in the sample which permits the decrease of free plasticizer to be calculated from the change of this area upon cooling. For each sample the area below the curve is constant, regardless of whether the absorption is narrow or broad. Below the glass temperature the narrow component of the absorption curve can be attributed to the plasticizer, whereas the broad component represents the glassy polymer and that part of the plasticizer which is already immobilized. 

We shall conclude with some remarks on the structure of glassy polymers. If one frequently speaks of glass structures, this does not mean that there exists one definite glass structure similar to a crystal. In a macromolecular solid-e.g., the polystyrene-plasticizer system, entirely different glasses are obtainable, the macroscopic composition of which is always the same (8). In Figure 10 the full... 

Carbon-13 rotating-frame relaxation rate measurements are used to elucidate the mechanism of gas transport in glassy polymers. The nmr relaxation measurements show that antiplasticization-plasticization of a glassy polymer by a low molecular weight additive effects the cooperative main-chain motions of the polymer. The correlation of the diffusion coefficients of gases with the main-chain motions in the polymer-additive blends shows that the diffusion of gases in polymers is controlled by the cooperative motions, thus providing experimental verification of the molecular theory of diffusion. Carbon-13 nmr relaxation... 

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... 

Sanders, E.S. (1988) Penetrant-induced plasticization and gas permeation in glassy polymers. Journal of Membrane Science,... 

---