Glass transition temperature importance

Polymer systems have been classified according to glass-transition temperature (T), melting poiat (T ), and polymer molecular weight (12) as elastomers, plastics, and fibers. Fillers play an important role as reinforcement for elastomers. They are used extensively ia all subclasses of plastics, ie, geaeral-purpose, specialty, and engineering plastics (qv). Fillets are not, however, a significant factor ia fibers (qv). 

The melt temperature of a polyurethane is important for processibiUty. Melting should occur well below the decomposition temperature. Below the glass-transition temperature the molecular motion is frozen, and the material is only able to undergo small-scale elastic deformations. For amorphous polyurethane elastomers, the T of the soft segment is ca —50 to —60 " C, whereas for the amorphous hard segment, T is in the 20—100°C range. The T and T of the mote common macrodiols used in the manufacture of TPU are Hsted in Table 2. 

Thermal Properties. Thermal properties include heat-deflection temperature (HDT), specific heat, continuous use temperature, thermal conductivity, coefficient of thermal expansion, and flammability ratings. Heat-deflection temperature is a measure of the minimum temperature that results in a specified deformation of a plastic beam under loads of 1.82 or 0.46 N/mm (264 or 67 psi, respectively). Eor an unreinforced plastic, this is typically ca 20°C below the glass-transition temperature, T, at which the molecular mobility is altered. Sometimes confused with HDT is the UL Thermal Index, which Underwriters Laboratories estabflshed as a safe continuous operation temperature for apparatus made of plastics (37). Typically, UL temperature indexes are significantly lower than HDTs. Specific heat and thermal conductivity relate to insulating properties. The coefficient of thermal expansion is an important component of mold shrinkage and must be considered when designing composite stmctures. 

The glass transition temperature of a random copolymer usually falls between those of the corresponding homopolymers since the copolymers will tend to have intermediate chain stiffness and interchain attraction. Where these are the only important factors to be considered a linear relationship between Tg and copolymer composition is both reasonable to postulate and experimentally verifiable. One form of this relationship is given by the equation... 

In the case of a crystalline polymer the maximum service temperature will be largely dependent on the crystalline melting point. When the polymer possesses a low degree of crystallinity the glass transition temperature will remain of paramount importance. This is the case with unplasticised PVC and the polycarbonate of bis-phenol A. 

A report130 of DSC measurements on polybenzimidazole fibers describes important differences for the glass transition temperature depending on die mechanical treatment of the fiber. An as-spun fiber exhibits a Tg at 387°C instead of 401°C for a drawn fiber free to shrink or 435°C for a drawn fiber widi fixed length. 

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