Crystalline Zones

The conformation adopted by a molecule in the crystalline structure will also affect the density. Whereas polyethylene adopts a planar zigzag conformation, because of steric factors a polypropylene molecule adopts a helical conformation in the crystalline zone. This requires somewhat more space and isotactic polypropylene has a lower density than polyethylene. 

Chlorination may be carried out with both high-density and low-density polyethylene. When carried out in solution the chlorination is random but when carried out with the polymer in the form of a slurry the chlorination is uneven and due to residual crystalline zones of unchlorinated polyethylene the material remains a thermoplastic. 

The commercial poly-(4-methypent-1-ene) (P4MP1) is an essentially isotactic material which shows 65% crystallinity when annealed but under more normal conditions about 40%. For reasons given later the material is believed to be a copolymer. In the crystalline state P4MP1 molecules take up a helical disposition and in order to accommodate the side chains require seven monomer units per two turns of the helix (c.f. three monomers per turn with polypropylene and polybut-I-ene). Because of the space required for this arrangement the density of the crystalline zone is slightly less than that of the amorphous zone at room temperature. 

Perhaps the most astounding property of this material is the high degree of transparency. This arises first because both molecules and crystals show little optical anisotropy and secondly because crystalline and amorphous zones have similar densities. They also have similar refractive indices and there is little scatter of light at the interfaces between amorphous and crystalline zones. 

X-ray studies indicate that the vinyl chloride polymer as normally prepared in commercial processes is substantially amorphous although some small amount of crystallinity (about 5% as measured by X-ray diffraction methods) is present. It has been reported by Fuller d in 1940 and Natta and Carradini in 1956 that examination of the crystalline zones indicates a repeat distance of 5.1 A which is consistent with a syndiotactic (i.e. alternating) structure. Later studies using NMR techniques indicate that conventional PVC is about 55% syndiotactic and the rest largely atactic in structure. 

Figure 20.6 shows the disposition of the molecules in the elementary cell as detennined by Prietschk. It will be seen that in the crystalline zone the molecules pack in such a way that the methyl groups attached to the pivotal carbon atom extend toward the back of the carbonate group of the neighbouring chain. 

In most cases crystal densities differ from the densities of amorphous polymers. This leads to differences in refractive index, which in turn cause scatter of light at boundaries between amorphous and crystalline zones. Such materials are opaque except in certain instances where the crystal structure can be carefully oriented to prevent such scatter of light. 

Another model assumes that gel zones are formed by hydrated lead dioxide (PbO(OH)2) and act as bridging elements between the crystallite particles. Electrons can move along the polymer chains of this gel and so cause electronic conductivity between the crystalline zones 137],... 

In the case of crystaUizable polychloroprene, the cross-link density has been found to be lower in the crystalline region as compared to the amorphous portion of the mbber due to the lower radical mobility in the former. The cross-links are found to be intramolecular in the crystalline zone [387]. 

Samples of the poly(dialkylphosphazenes) 1 and 2 displayed X-ray powder diffraction patterns characteristic of crystalline regions in the materials. The peaks in the diffraction pattern of 1 were of lower amplitude and greater angular breadth than those of 2. These data indicate that poly(diethylphosphazene) (2) is highly crystalline while poly(dimethyl-phosphazene) (1) is more amorphous with smaller crystalline zones. This high degree of crystallinity is probably responsible for the insolubility of 2 as noted above. All of the phenyl substituted polymers 3-6 were found to be quite amorphous in the X-ray diffraction studies, a result that is further evidence for an atactic structure of the poly(alkylphenylphosphazenes) 3 and 4 and for a random substitution pattern in the copolymers 5 and 6. 

However Iring et al. [47] found that the induction period for oxidation of solid isotactic PP is longer than that for atactic polymer. Their result is in accordance with the high crystallinity of isotactic PP and with the resistance of its crystalline zones to oxidation. 

During the delamination of the cell wall which takes place during refining (Figure 5.9), there is an increase in the water accommodated within non-crystalline zones, and the cell wall water content typically rises from around 1 to 3 g per g of dry fibre (Figure 5.10). 

Adsorption of water is accompanied with swelling of wood. Since cellulose constitutes almost 50% of the wood substance, its fractional contribution to sorption is the highest. Swelling of wood is thus manifested by the adsorption of water by hydroxyl groups located on surface of micells and amorphous regions of cellulose, crystalline zones being impenetrable. Reduction in... 

The viscoelastic properties of the crystalline zones are significantly different from those of the amorphous phase, and consequently semicrystalline polymers may be considered to be made up of two phases each with its own viscoelastic properties. The best known model to study the viscoelastic behavior of polymers was developed for copolymers as ABS (acrylonitrile-butadiene-styrene triblock copolymer). In this system, spheres of rubber are immersed in a glassy matrix. Two cases can be considered. If the stress is uniform in a polyphase, the contribution of the phases to the complex tensile compliance should be additive. However, if the strain is uniform, then the contribution of the polyphases to the complex modulus is additive. The... 

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