Crystalline structure, addition polymers

Polypropylene is not one or even 100 products. Rather it is a multidimensional range of products with properties and characteristics interdependent on the type of polymer (homopolymers, random, or block copolymer), molecular weight and molecular weight distribution, morphology and crystalline structure, additives, fillers and reinforcing fillers, and fabrication techniques. 

Polymer compounds vary considerably in the amount of heat required to bring them up to processing temperatures. These differences arise not so much as a result of differing processing temperatures but because of different specific heats. Crystalline polymers additionally have a latent heat of fusion of the crystalline structure which has to be taken into account. 

We find an additional crystalline structure in rapidly quenched isotactic polypropylene products. In these materials, the polymer chains do not have the necessary time to orient,... 

The properties of the polycarbonate of bisphenol A are directly related to the structure of the polymer. The molecular stiffness associated with this polycarbonate arises from the presence of the rigid phenyl groups on the molecular chain or backbone of the polymer and the additional presence of two methyl side groups. The transparency of the material arises from the amorphous (noncrystalline) nature of the polymer. A significant crystalline structure is not observed in the polycarbonate of bisphenol A because intermolecular attractions between phenyl groups of neighboring polymer chains in the melt lead to a lack of flexibility of the chains that deters the development of a crystalline structure. 

Throughout the text we will relate polymer structure to the properties of the polymer. Polymer properties are related not only to the chemical nature of the polymer, but also to such factors as extent and distribution of crystallinity, distribution of polymer chain lengths, and nature and amount of additives, such as fillers, reinforcing agents, and plasticizers, to mention a few. These factors influence essentially all the polymeric properties to some extent including hardness, flammability, weatherability, chemical stability, biological response, comfort, flex life, moisture retention, appearance, dyeability, softening point, and electrical properties. 

Crystalline regions of polymers can be represented as combinations of folded chains forming lamellar structures. Amorphous regions are less ordered than crystalline regions. Additional orientation of polymer chains occurs. This results in increased strength in the order of the orientation. 

This approach can offer several advantages. First, polymers can be formed from monomers that do not give polymer under more typical reaction conditions. Second, under some cases, the crystalline structure acts as a template giving the order that might otherwise be difficult to achieve. Third, removal and interference by solvent or additives is eliminated as they are not present. Fourth, the polymers produced by this technique are often different from those from the same monomer except that produced using typical reaction techniques. 

Optical properties are related to both the degree of crystallinity and the actual polymer structure. Most polymers do not possess color site units, so are colorless and transparent. But, some phenolic resins and polyacetylenes are colored, translucent, or opaque. Polymers that are transparent to visible light may be colored by the addition of colorants, and some become opaque as a result of the presence of additives such as fillers, stabilizers, moisture, and gases. 

As seen, diffusion in nonporous gel membranes differs from that in macro-porous or microporous membranes. Various theories based on solute diffusion through the macromolecula r free volume in the membrane have been proposed. It is clear from these theories that structural parameters of the polymer network such as degree of swelling, molecular weight between crosslinks, and crystallinity in addition to factors such as solute size and solvent free volume play important roles in this type of transport. 

Polymers don t behave like the atoms or compounds that have been described in the previous sections. We saw in Chapter 1 that their crystalline structure is different from that of metals and ceramics, and we know that they can, in many cases, form amorphous structures just as easily as they crystallize. In addition, unlike metals and ceramics, whose thermodynamics can be adequately described in most cases with theories of mixing and compound formation, the thermodynamics of polymers involves solution thermodynamics—that is, the behavior of the polymer molecules in a liquid solvent. These factors contribute to a thermodynamic approach to describing polymer systems that is necessarily different from that for simple mixtures of metals and compounds. Rest assured that free energy will play an important role in these discussions, just as it has in previous sections, but we are now dealing with highly inhomogeneous systems that will require some new parameters. 

In addition to the opportunities for new materials synthesis and characterization along these lines, transport properties, rheology, and processing techniques for liquid crystal polymers are essentially unexplored. Experiences with synthesis of polymer structure based on these liquid crystal templates may open up other creative avenues for template synthesis, for example, inside other crystalline structures, chlathrates, or zeolites, or on surfaces [4], Composites, alloys, or mixtures of liquid crystalline and flexible polymers may produce new materials. 

Biodegradability, or the rate of biodegradation, depends on many factors such as the structure of polymers, biodegradation conditions, the hydrophobicity of polymers, filler type and content, the presence of additives and substituents, crystallinity, and the stereoconfiguration of polymers (93,94). Therefore, appropriate measures need to be taken before designing a composite. 

The chemical structure of a polymer determines whether it will be crystalline or amorphous in the solid state. Both tacticity (i.e., syndio-tactic or isotactic) and geometric isomerism (i.e., trans configuration) favor crystallinity. In general, tactic polymers with their more stereoregular chain structure are more likely to be crystalline than their atactic counterparts. For example, isotactic polypropylene is crystalline, whereas commercial-grade atactic polypropylene is amorphous. Also, cis-pol3nsoprene is amorphous, whereas the more easily packed rans-poly-isoprene is crystalline. In addition to symmetrical chain structures that allow close packing of polymer molecules into crystalline lamellae, specific interactions between chains that favor molecular orientation, favor crystallinity. For example, crystallinity in nylon is enhanced because of... 

Indeed, as obvious from both exemples given in Fig. 2, the transition could thus be determined accurately within 0.1-0.2 decades of test speeds with few samples in a relative short time frame. Moreover, as the apparent values (Kimax) are always lower than the effective parameters (Keff), none of the material descriptor would be overestimated. In addition, since Kjmax-values have been shown to provide a semi-quantitative evaluation (in terms of test speed or temperature) of fracture resistance parameters, a coherent material comparison would be possible over the whole investigated range. This remark remains true as long as the grades have similar rp. For iPP grades, it should be checked (and considered with more caution) when materials exhibit different particle and matrix melt flow rates, or different crystalline structures. It should also be investigated in detail when different polymer families (ABS versus HIPS or rubber modified iPP) are compared. 

Differential scanning calorimetry (DSC), X-ray diffraction (XRD), and infrared spectroscopy are the common techniques used in the characterization of the structure of the congealed solid. Thermal analytic methods, such as DSC and differential microcalorimetric analysis (DMA), are routinely used to determine the effect of solutes, solvents, and other additives on the thermomechanical properties of polymers such as glass transition temperature (Tg) and melting point. The X-ray diffraction method is used to detect the crystalline structure of solids. The infrared technique is powerful in detecting interactions, such as complexation, reaction, and hydrogen bonding, in both the solid and solution states. 

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