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The document provides a table listing the glass transition temperatures and melting temperatures for various common polymeric materials. It then discusses several factors that influence melting and glass transition temperatures, including chain stiffness, size and type of side groups, molecular weight, and degree of branching. Chain stiffness, bulky side groups, polar side groups, and higher molecular weight tend to increase the melting temperature, while branching decreases melting temperature.
The document provides a table listing the glass transition temperatures and melting temperatures for various common polymeric materials. It then discusses several factors that influence melting and glass transition temperatures, including chain stiffness, size and type of side groups, molecular weight, and degree of branching. Chain stiffness, bulky side groups, polar side groups, and higher molecular weight tend to increase the melting temperature, while branching decreases melting temperature.
The document provides a table listing the glass transition temperatures and melting temperatures for various common polymeric materials. It then discusses several factors that influence melting and glass transition temperatures, including chain stiffness, size and type of side groups, molecular weight, and degree of branching. Chain stiffness, bulky side groups, polar side groups, and higher molecular weight tend to increase the melting temperature, while branching decreases melting temperature.
5 Crystallization, Melting, and Glass Transition Phenomena ● 485
Table 16.2 Melting and Glass Transition Temperatures for
Some of the More Common Polymeric Materials Glass Transition Melting Temperature Temperature Material [ ⴗC ( ⴗF )] [ ⴗC ( ⴗF )] Polyethylene (low density) ⫺110 (⫺165) 115 (240) Polytetrafluoroethylene ⫺97 (⫺140) 327 (620) Polyethylene (high density) ⫺90 (⫺130) 137 (279) Polypropylene ⫺18 (0) 175 (347) Nylon 6,6 57 (135) 265 (510) Polyester (PET) 69 (155) 265 (510) Polyvinyl chloride 87 (190) 212 (415) Polystyrene 100 (212) 240 (465) Polycarbonate 150 (300) 265 (510)
melting and glass transition temperatures of a number of polymers are contained
in Table 16.2 and Appendix E.
FACTORS THAT INFLUENCE MELTING AND GLASS
TRANSITION TEMPERATURES Melting Temperature During melting of a polymer there will necessarily occur a rearrangement of the molecules in the transformation from ordered to disordered molecular states. Molec- ular chemistry and structure will influence the ability of the polymer chain molecules to make these rearrangements, and, therefore, will also affect the melting temper- ature. Chain stiffness, which is controlled by the ease of rotation about the chemical bonds along the chain, has a pronounced effect. The presence of double-chain bonds and aromatic groups lowers chain flexibility and causes an increase in Tm . Furthermore, the size and type of side groups influence chain rotational freedom and flexibility; bulky or large side groups tend to restrict molecular rotation and raise Tm . For example, polypropylene has a higher melting temperature than poly- ethylene (175⬚C versus 115⬚C, Table 16.2); the CH3 methyl side group for polypro- pylene is larger than the H atom found on polyethylene. The presence of polar side groups (viz. Cl, OH, and CN), even though not excessively large, leads to significant intermolecular bonding forces and relatively high Tms. This may be verified by comparing the melting temperatures of polypropylene (175⬚C) and polyvinyl chloride (212⬚C). For a specific polymer, melting temperature will also depend on molecular weight. At relatively low molecular weights, increasing M (or chain length) raises Tm (Figure 16.9). Furthermore, the melting of a polymer takes place over a range of temperatures, and, thus, there will exist a range of Tms, rather than a single melting temperature. This is because, every polymer will be composed of molecules having a variety of molecular weights (Section 15.5), and because Tm depends on molecular weight. For most polymers, this melting temperature range will normally be on the order of several degrees Celsius. Those melting temperatures cited in Table 16.2 and Appendix E are near the high ends of these ranges. Degree of branching will also affect the melting temperature of a polymer. The introduction of side branches introduces defects into the crystalline material and
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