Glass transition temperatures polymeric systems

A novel concept has been found that allows radiation curable coating systems to develop excellent adhesion to metal surfaces. This concept utilizes certain specially designed high Tg (glass transition temperature) polymeric... 

Elastomeric Modified Adhesives. The major characteristic of the resins discussed above is that after cure, or after polymerization, they are extremely brittie. Thus, the utility of unmodified common resins as stmctural adhesives would be very limited. Eor highly cross-linked resin systems to be usehil stmctural adhesives, they have to be modified to ensure fracture resistance. Modification can be effected by the addition of an elastomer which is soluble within the cross-linked resin. Modification of a cross-linked resin in this fashion generally decreases the glass-transition temperature but increases the resin dexibiUty, and thus increases the fracture resistance of the cured adhesive. Recendy, stmctural adhesives have been modified by elastomers which are soluble within the uncured stmctural adhesive, but then phase separate during the cure to form a two-phase system. The matrix properties are mosdy retained the glass-transition temperature is only moderately affected by the presence of the elastomer, yet the fracture resistance is substantially improved. 

With continuous development of systems for controlled drug release, new materials are being used whose influence on peptide stability must be carefully examined. Thus, the model hexapeptide Val-Tyr-Pro-Asn-Gly-Ala (Fig. 6.30) embedded in poly (vinyl alcohol) and poly(vinyl pyrrolidone) matrices had rates of deamidation that increased with increasing water content or water activity, and, hence, with decreasing glass transition temperature (Tg). However, the degradation behavior in the two polymers differed so that chemical reactivity could not be predicted from water content, water activity, or T% alone. Furthermore, the hexapeptide was less stable in such hydrated polymeric matrices than in aqueous buffer or lyophilized polymer-free powders [132],... 

The mobility of the ions in polymer electrolytes is linked to the local segmental mobility of the polymer chains. Significant ionic conductivity in these systems will occur only above the glass transition temperature of the amorphous phase, Tg. Therefore, one of the reqnirements for the polymeric solvent is a low glass-transition temperature for example, Tg = —67°C for PEO. 

Glass Transition Temperature. If the glass transition temperatures of the polymeric components are known and the glass transition temperature of the polyblend is determined, one of two things can happen. If the polyblend shows two distinct transitions corresponding to the parent polymers, it is incompatible. If the polyblend shows one transition only, the system is compatible. Since the glass transition temperature is a measure of the segmental mobility of a polymer, it must be sensitive... 

The thermal stability of poly(vinyl chloride) is improved greatly by the in situ polymerization of butadiene or by reaction with preformed cis-1,4-polybutadiene using a diethyl-aluminum chloride-cobalt compound catalyst system. The improved thermal stability at 3-10% add-on is manifested by greatly reduced discoloration when the modified poly-(vinyl chloride) is compression molded at 200°C in air in the absence of a stabilizer, hydrogen chloride evolution at 180°C is retarded, and the temperature for the onset of HCl evolution and the peak decomposition temperature (DTA) increase, i.e. 260°-280°C and 290°-325° C, respectively, compared with 240°-260°C and 260°-280°C for the unmodified homopolymer, in the absence of stabilizer. The grafting reaction may be carried out on suspension, emulsion, or bulk polymerized poly(vinyl chloride) with little or no change in the glass transition temperature. 

Summary In this chapter, a discussion of the viscoelastic properties of selected polymeric materials is performed. The basic concepts of viscoelasticity, dealing with the fact that polymers above glass-transition temperature exhibit high entropic elasticity, are described at beginner level. The analysis of stress-strain for some polymeric materials is shortly described. Dielectric and dynamic mechanical behavior of aliphatic, cyclic saturated and aromatic substituted poly(methacrylate)s is well explained. An interesting approach of the relaxational processes is presented under the experience of the authors in these polymeric systems. The viscoelastic behavior of poly(itaconate)s with mono- and disubstitutions and the effect of the substituents and the functional groups is extensively discussed. The behavior of viscoelastic behavior of different poly(thiocarbonate)s is also analyzed. 

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