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solution (Sec. 9-3a). The biosynthesis of cotton proceeds with an enzymatic ordering of the polymer chains in spite of the rigid polymer chains. Excess chain rigidity in polymers due to extensive crosslinking, as in phenol formaldehyde and urea formaldehyde polymers, completely prevents crystallization. Chain exibility also effects the ability of a polymer to crystallize. Excessive exibility in a polymer chain as in polysiloxanes and natural rubber leads to an inability of the chains to pack. The chain conformations required for packing cannot be maintained because of the high exibility of the chains. The exibility in the cases of the polysiloxanes and natural rubber is due to the bulky Si O and cis-ole n groups, respectively. Such polymers remain as almost completely amorphous materials, which, however, show the important property of elastic behavior. 1-5c Thermal Transitions
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Polymeric materials are characterized by two major types of transition temperatures the crystalline melting temperature Tm and the glass transition temperature Tg . The crystalline melting temperature is the melting temperature of the crystalline domains of a polymer sample. The glass transition temperature is the temperature at which the amorphous domains of a polymer take on the characteristic properties of the glassy state brittleness, stiffness, and rigidity. The difference between the two thermal transitions can be understood more clearly by considering the changes that occur in a liquid polymer as it is cooled. The translational, rotational, and vibrational energies of the polymer molecules decrease on cooling. When the total energies of the molecules have fallen to the point where the translational and rotational energies are essentially zero, crystallization is possible. If certain symmetry requirements are met, the molecules are able to pack into an ordered, lattice arrangement and crystallization occurs. The temperature at which this occurs in Tm . However, not all polymers meet the necessary symmetry requirements for crystallization. If the symmetry requirements are not met, crystallization does not take place, but the energies of the molecules continue to decrease as the temperature decreases. A temperature is nally reached the Tg at which long-range motions of the polymer chains stop. Long-range motion, also referred to as segmental motion, refers to the motion of a segment of a polymer chain by the concerted rotation of bonds at the ends of the segment. [Bond rotations about side chains, e.g., the C 3 and C CH COOCH3 bonds in poly(methyl methacrylate), do not cease at Tg .] Whether a polymer sample exhibits both thermal transitions or only one depends on its morphology. Completely amorphous polymers show only a Tg . A completely crystalline polymer shows only a Tm . Semicrystalline polymers exhibit both the crystalline melting and glass transition temperatures. Changes in properties such as speci c volume and heat capacity occur as a polymer undergoes each of the thermal transitions. Figure 1-9 shows the changes in speci c volume with temperature for completely amorphous and completely crystalline polymers (the solid lined plots). Tm is a rst-order transition with a discontinuous change in the speci c volume at the transition temperature. Tg is a second-order transition involving only a change in the temperature coef cient of the speci c volume. (A plot of the temperature coef cient of the speci c volume versus temperature shows a discontinuity.) The corresponding plot for a semicrystalline polymer consists of the plot for the crystalline polymer plus the dotted portion corresponding to the glass transition. A variety of methods have been used to determine Tg and Tm , including dilatometry (speci c volume), thermal analysis, dynamic mechanical behavior, dielectric loss, and broad-line NMR. The most commonly used method is differential scanning calorimetry (DSC). DSC re ects the change in heat capacity of a sample as a function of temperature by measuring the heat ow required to
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