Crystalline Elasticity

Sample (vol%) Degree of crystallinity (%) Elastic modulus, E (GPa) (% increase) Lower and upper bounds for E (GPa) Tensile strength, rru (MPa) (% increase)... 

We now understand why rubber-like materials must heat on stretching and cool on relaxing, in complete analogy to the behavior of ideal gases and in contrast to normal crystalline elasticity. 

The bulk properties of a polymeric material—for example, viscosity, crystallinity, elasticity, and the glass/melting point—are determined by the conformation of the polymer chains. For a conjugated polymer, the conjugation length, the electronic structure, and the electrical/optical properties of this polymer are strongly related to the conformational structure of the polymer chain. 

The thermoplastic elastomer polyurethanes, TPU, may be of two general types partly crystalline elastic fibers (see preceding paragraph) or softer elastomers, depending on the relative length of the soft segment. Those polyurethanes based on polyester soft segments tend to be more resistant to hydrocarbons, while the polyether types are more resistant to hydrolysis but tend to swell more in aqueous environments (144). The block copolymer characteristics of polyurethanes are discussed further in Chapter 13. 

First, temperature can determine the polymer state, that is, whether it is predominantly glassy, crystalline, elastic, or fluid. The specific temperatures for each state depend on composition and molecular weight. The softening of a polymer system, on raising the temperature, results in a lower stress and lower rate of energy input at a given shear rate. In consequence, there is a reduction in rupture and an increase in Thus, results at different temperatures are more similar and better compared at the same shear stress or rate of energy application. In many experiments, however, it has been easier to make the comparison at constant shear rate because of the mode of instrument operation. 

Polyolefins. In these thermoplastic elastomers the hard component is a crystalline polyolefin, such as polyethylene or polypropylene, and the soft portion is composed of ethylene-propylene rubber. Attractive forces between the rubber and resin phases serve as labile cross-links. Some contain a chemically cross-linked rubber phase that imparts a higher degree of elasticity. 

In the last three chapters we have examined the mechanical properties of bulk polymers. Although the structure of individual molecules has not been our primary concern, we have sought to understand the influence of molecular properties on the mechanical behavior of polymeric materials. We have seen, for example, how the viscosity of a liquid polymer depends on the substituents along the chain backbone, how the elasticity depends on crosslinking, and how the crystallinity depends on the stereoregularity of the polymer. In the preceding chapters we took the existence of these polymers for granted and focused attention on their bulk behavior. In the next three chapters these priorities are reversed Our main concern is some of the reactions which produce polymers and the structures of the products formed. 

Polyacetaldehyde, a mbbery polymer with an acetal stmcture, was first discovered in 1936 (49,50). More recentiy, it has been shown that a white, nontacky, and highly elastic polymer can be formed by cationic polymerization using BF in Hquid ethylene (51). At temperatures below —75° C using anionic initiators, such as metal alkyls in a hydrocarbon solvent, a crystalline, isotactic polymer is obtained (52). This polymer also has an acetal [poly(oxymethylene)] stmcture. Molecular weights in the range of 800,000—3,000,000 have been reported. Polyacetaldehyde is unstable and depolymerizes in a few days to acetaldehyde. The methods used for stabilizing polyformaldehyde have not been successful with poly acetaldehyde and the polymer has no practical significance (see Acetalresins). 

A good compilation of the functions of fats in various food products is available (26). Some functions are quite subtle, eg, fats lend sheen, color, color development, and crystallinity. One of the principal roles is that of texture modification which includes viscosity, tenderness (shortening), control of ice crystals, elasticity, and flakiness, as in puff pastry. Fats also contribute to moisture retention, flavor in cultured dairy products, and heat transfer in deep fried foods. For the new technology of microwave cooking, fats assist in the distribution of the heating patterns of microwave cooking. 

Content of Ot-Olefin. An increase in the a-olefin content of a copolymer results in a decrease of both crystallinity and density, accompanied by a significant reduction of the polymer mechanical modulus (stiffness). Eor example, the modulus values of ethylene—1-butene copolymers with a nonuniform compositional distribution decrease as shown in Table 2 (6). A similar dependence exists for ethylene—1-octene copolymers with uniform branching distribution (7), even though all such materials are, in general, much more elastic (see Table 2). An increase in the a-olefin content in the copolymers also results in a decrease of their tensile strength but a small increase in the elongation at break (8). These two dependencies, however, are not as pronounced as that for the resin modulus. 

Typical stress—strain curves are shown in Figure 3 (181). The stress— strain curve has three regions. At low strains, below about 10%, these materials are considered to be essentially elastic. At strains up to 300%, orientation occurs which degrades the crystalline regions causing substantial permanent set. 

The pseudocross-links, generated by the hard-segment interactions, are reversed by heating or dissolution. Without the domain crystallinity, thermoplastic polyurethanes would lack elastic character and be more gum-like in nature. In view of the outlined morphology, it is not surprising that many products develop their ultimate properties only on curing at elevated temperature, which allows the soft- and hard-phase segments to separate. 

Creep of polymers is a major design problem. The glass temperature Tq, for a polymer, is a criterion of creep-resistance, in much the way that is for a metal or a ceramic. For most polymers, is close to room temperature. Well below Tq, the polymer is a glass (often containing crystalline regions - Chapter 5) and is a brittle, elastic solid -rubber, cooled in liquid nitrogen, is an example. Above Tq the Van der Waals bonds within the polymer melt, and it becomes a rubber (if the polymer chains are cross-linked) or a viscous liquid (if they are not). Thermoplastics, which can be moulded when hot, are a simple example well below Tq they are elastic well above, they are viscous liquids, and flow like treacle. 

Whilst the crystalline fibres and their thermoplastic counterparts are no longer of importance, elastic polyurethane fibres, commonly known as spandex fibres, are of significance. These will be considered further in Section 27.4.1. 

Typically, a semicrystalline polymer has an amorphous component which is in the elastomeric (rubbery) temperature range - see Section 8.5.1 - and thus behaves elastically, and a crystalline component which deforms plastically when stressed. Typically, again, the crystalline component strain-hardens intensely this is how some polymer fibres (Section 8.4.5) acquire their extreme strength on drawing. 

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