Natural polymers glass transition temperature

It was noted that, above the glass-transition temperature, the polymer is able to have considerable conformational freedom involving concerted motion over 50 atoms, which results in a decrease in modulus by a factor of about 10". The polymer is still far from the melt and the chain entanglements result in a material with viscoelastic properties. The rubbery nature may be seen from the tendency of the polymer to recover when a stress is applied. This recovery is a consequence of the higher order conferred on the chains when they are distorted so that when the stress is released there will be an entropic drive to return to the coiled state (Queslel and Mark, 1989). It is this entropic recovery that results in the shrinking of a loaded crosslinked elastomer (shown schematically in Figure 1.14) when it is heated. 

The thermal resistance of latex-modifled mortar and concrete is governed by the nature, especially glass transition temperature of polymers used, polymer-cement ratio, and heating conditions, and ultimately by the thermal degradation of the polymers. Figure 4.59f l indicates the thermal resistance of SBR-, PAE-, and EVA-modified mortars at 100 to 200°C. The flexural strength of most latex-modified mortars at 100°C tends to initially... 

DSC is often used in conjunction with TA to determine if a reaction is endothermic, such as melting, vaporization and sublimation, or exothermic, such as oxidative degradation. It is also used to determine the glass transition temperature of polymers. Liquids and solids can be analyzed by both methods of thermal analysis. The sample size is usually limited to 10-20 mg. Thermal analysis can be used to characterize the physical and chemical properties of a system under conditions that simulate real world applications. It is not simply a sample composition technique. Much of the data interpretation is empirical in nature and more than one thermal method may be required to fully understand the chemical and physical reactions occurring in a sample. Condensation of volatile reaction products on the sample support system of a TA can give rise to anomalous weight changes. 

The glass-transition temperature, T, of dry polyester is approximately 70°C and is slightly reduced ia water. The glass-transitioa temperatures of copolyesters are affected by both the amouat and chemical nature of the comonomer (32,47). Other thermal properties, including heat capacity and thermal conductivity, depend on the state of the polymer and are summarized ia Table 2. 

In methacrylic ester polymers, the glass-transition temperature, is influenced primarily by the nature of the alcohol group as can be seen in Table 1. Below the the polymers are hard, brittle, and glass-like above the they are relatively soft, flexible, and mbbery. At even higher temperatures, depending on molecular weight, they flow and are tacky. Table 1 also contains typical values for the density, solubiHty parameter, and refractive index for various methacrylic homopolymers. 

This combination of monomers is unique in that the two are very different chemically, and in thek character in a polymer. Polybutadiene homopolymer has a low glass-transition temperature, remaining mbbery as low as —85° C, and is a very nonpolar substance with Htde resistance to hydrocarbon fluids such as oil or gasoline. Polyacrylonitrile, on the other hand, has a glass temperature of about 110°C, and is very polar and resistant to hydrocarbon fluids (see Acrylonitrile polymers). As a result, copolymerization of the two monomers at different ratios provides a wide choice of combinations of properties. In addition to providing the mbbery nature to the copolymer, butadiene also provides residual unsaturation, both in the main chain in the case of 1,4, or in a side chain in the case of 1,2 polymerization. This residual unsaturation is useful as a cure site for vulcanization by sulfur or by peroxides, but is also a weak point for chemical attack, such as oxidation, especially at elevated temperatures. As a result, all commercial NBR products contain small amounts ( 0.5-2.5%) of antioxidant to protect the polymer during its manufacture, storage, and use. 

As the temperature is decreased, free-volume is lost. If the molecular shape or cross-linking prevent crystallisation, then the liquid structure is retained, and free-volume is not all lost immediately (Fig. 22.8c). As with the melt, flow can still occur, though naturally it is more difficult, so the viscosity increases. As the polymer is cooled further, more free volume is lost. There comes a point at which the volume, though sufficient to contain the molecules, is too small to allow them to move and rearrange. All the free volume is gone, and the curve of specific volume flattens out (Fig. 22.8c). This is the glass transition temperature, T . Below this temperature the polymer is a glass. 

Poly(vinyl acetate) is too soft and shows excessive cold flow for use in moulded plastics. This is no doubt associated with the fact that the glass transition temperature of 28°C is little above the usual ambient temperatures and in fact in many places at various times the glass temperature may be the lower. It has a density of 1.19 g/cm and a refractive index of 1.47. Commercial polymers are atactic and, since they do not crystallise, transparent (if free from emulsifier). They are successfully used in emulsion paints, as adhesives for textiles, paper and wood, as a sizing material and as a permanent starch . A number of grades are supplied by manufacturers which differ in molecular weight and in the nature of comonomers (e.g. vinyl maleate) which are commonly used (see Section 14.4.4)... 

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