Glass transition influencing factors

The size of the group attached to the main chain carbon atom can influence the glass transition point. For example, in polytetrafluoroethylene, which differs from polyethylene in having fluorine instead of hydrogen atoms attached to the backbone, the size of the fluorine atoms requires the molecule to take up a twisted zigzag configuration with the fluorine atoms packed tightly around the chain. In this case steric factors affect the inherent flexibility of the chain. 

These three factors influence the ability of the polymer to crystallise, the melting point of any resulting crystalline regions, and also the glass transition temperature. It is the last of these features of polymeric materials which we will concentrate on for the rest of this chapter. 

A third factor influencing the value of Tg is backbone symmetry, which affects the shape of the potential wells for bond rotations. This effect is illustrated by the pairs of polymers polypropylene (Tg=10 C) and polyisobutylene (Tg = -70 C), and poly(vinyi chloride) (Tg=87 C) and poly(vinylidene chloride) (Tg =- 19°C). The symmetrical polymers have lower glass transition temperatures than the unsymmetrical polymers despite the extra side group, although polystyrene (100 C) and poly(a-meth-ylstyrene) are illustrative exceptions. However, tacticity plays a very important role (54) in unsymmetrical polymers. Thus syndiotactic and isoitactic poly( methyl methacrylate) have Tg values of 115 and 45 C respectively. 

Lett., 71, 262 (2005). The Decisive Influence of Local Chain Dynamics on the Overall Dynamic Structure Factor Close to the Glass Transition. 

Several factors can be identified as being crucial for the foaming of immiscible polymer blends the blend morphology, the phase size of the blend constituents, the interfacial properties between the blend partners, and, last but not least, the properties of the respective blend phases such as the melt-rheological behavior, the glass transition temperature, the gas solubility, as well as the gas diffusion coefficient. Most of these factors also individually influence the melt-rheological behavior of two-phase blends. 

In order to select materials that will maintain acceptable mechanical characteristics and dimensional stability one must be aware of both the normal and extreme thermal operating environments to which a product will be subjected. TS plastics have specific thermal conditions when compared to TPs that have various factors to consider which influence the product s performance and processing capabilities. TPs properties and processes are influenced by their thermal characteristics such as melt temperature (Tm), glass-transition temperature (Tg), dimensional stability, thermal conductivity, specific heat, thermal diffusivity, heat capacity, coefficient of thermal expansion, and decomposition (Td) Table 1.2 also provides some of these data on different plastics. There is a maximum temperature or, to be more precise, a maximum time-to-temperature relationship for all materials preceding loss of performance or decomposition. Data presented for different plastics in Figure 1.5 show 50% retention of mechanical and physical properties obtainable at room temperature, with plastics exposure and testing at elevated temperatures. 

The influence of factors such as chemical structure, molecular weight, cross-linking and plasticizers in the glass transition of polymers can be related to the changes that they provoke on the free volume fraction, which, as we already know, reaches a critical value at the glass transition temperature. The factors affecting the glass transition can be classified into two types (1) molecular factors, i.e., those related to the chemical structure of the polymer chain, and (2) external or controllable factors. 

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