Plastics amorphous polymer

Fig. 11-11. Modulus versus leiiiperatuie for a plasticized amorphous polymer.

The mode of action of plasticizers can be explained using the Gel theory [35 ]. According to this theory, the deformation resistance of amorphous polymers can be ascribed to the cross-links between active centres which are continuously formed and destroyed. The cross-links are constituted by micro-aggregates or crystallites of small size. When a plasticizer is added, its molecules also participate in the breaking down and re-forming of these cross-links. As a consequence, a proportion of the active centres of the polymer are solvated and do not become available for polymer-to-polymer links, the polymer structure being correspondingly loosened. 

Styrene co-butadiene is a rubbery amorphous polymer with a glass transition temperature well below room temperature. Polystyrene co-butadiene is an important component of several commercial families of plastic that contain polystyrene blocks. 

At the high polymer concentration used in plasticized systems the viscosity of amorphous polymer is given by the modified Rouse theory at low molecular weight, M - 2Mr [from equation (47)] and by the modified Doi-Edwards equation at high molecular weight. In the first case... 

The flexibility of amorphous polymers is reduced drastically when they are cooled below a characteristic transition temperature called the glass transition temperature (Tg). At temperatures below Tg there is no ready segmental motion and any dimensional changes in the polymer chain are the result of temporary distortions of the primary covalent bonds. Amorphous plastics perform best below Tg but elastomers must be used above the brittle point, or they will act as a glass and be brittle and break when bent. 

The value of TMWV is dependent on the cohesive energy density (CED) of amorphous polymers, the extent of crystallinity in crystalline polymers, and the effect of reinforcements in polymeric composites. Thus, while a low molecular weight amorphous polymer may be satisfactory for use as a coating or adhesive, a chain length generally above 100 is often required if the polymer is to be used as an elastomer or plastic. 

In terms of the mechanical behavior that has already been described in Sections 5.1 and Section 5.2, stress-strain diagrams for polymers can exhibit many of the same characteristics as brittle materials (Figure 5.58, curve A) and ductile materials (Figure 5.58, curve B). In general, highly crystalline polymers (curve A) behave in a brittle manner, whereas amorphous polymers can exhibit plastic deformation, as in... 

Finally, the use of low-molecular-weight species to improve flow properties called plasticizers normally reduces stiffness, hardness, and brittleness. Plasticization is usually restricted to amorphous polymers or polymers with a low degree of crystallinity because of the limited compatibility of plasticizers with highly crystalline polymers. Other additives, such as antioxidants, do not affect the mechanical properties significantly by themselves, but can substantially improve property retention over long periods of time, particularly where the polymer is subject to environmental degradation. 

A distinction should be made between solvent plasticizers and nonsolvent plasticizers. With an amorphous polymer, any plasticizer is a solvent plasticizer— i.e., under suitable conditions the polymer would eventually dissolve in the plasticizer. With a crystalline or semicrystalline polymer, there are some compounds which enter both the crystalline (ordered) and the amorphous (disordered) regions. These are true plasticizers-sometimes they are called primary plasticizers. If, on the other hand, only the amorphous regions are penetrated, the compound may be considered as a nonsolvent plasticizer, also known as a secondary plasticizer, or softener. Such softeners are used sometimes as diluents for the primary plasticizer. 

In conclusion, we may state that viscoelastic data presented in this paper further reaffirm the contention that polyvinyl chloride has a network structure with microcrystallites acting as cross-links. Incorporation of plasticizer affected PVC in a way similar to amorphous polymers mainly by lowering Tg of the amo-rophous regions. Microcrystallites appear to be stable even in the presence of... 

In the early literature it is suggested that polycarbonates can be easily plasticized with common plasticizers. Plasticization of polycarbonate has been investigated by Kozlov et al. (12). These authors described the influence of plasticization on softening points and mechanical properties of bisphenol A polycarbonates. They conclude that the behavior of plasticized polycarbonate is similar to that encountered for most amorphous polymers. The influence of crystallization effects promoted by the plasticizer was not taken into account. 

The purpose of this paper is to investigate the mechanical properties (plastic deformation, micromechanisms of deformation, fracture) of several amorphous polymers considered in [1], i.e. poly(methyl methacrylate) and its maleimide and glutarimide copolymers, bisphenol A polycarbonate, aryl-aliphatic copolyamides. Then to analyse, in each polymer series, the effect of chemical structure on mechanical properties and, finally, to relate the latter to the motions involved in the secondary transitions identified in [ 1] (in most cases, the p transition). 

Before analysing the mechanical behaviour of amorphous polymers, it is useful to briefly give information on their molecular characteristics, the main descriptors used for plastic deformation and fracture, the micromechanisms of deformation, and some of the experimental procedures. 

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