Semicrystalline polymers properties

As was mentioned in the paragraph titled Semicrystalline Polymer Properties in the section titled Practical Importance and Common Methods for Measurement, it is possible to vary the heat distortion temperatures of some semicrystalline polymers appreciably by annealing at a temperature between Tg and Tm to enhance the crystallinity. 

Because of the capacity to tailor select polymer properties by varying the ratio of two or more components, copolymers have found significant commercial appHcation in several product areas. In fiber-spinning, ie, with copolymers such as nylon-6 in nylon-6,6 or the reverse, where the second component is present in low (<10%) concentration, as well as in other comonomers with nylon-6,6 or nylon-6, the copolymers are often used to control the effect of sphemUtes by decreasing their number and probably their size and the rate of crystallization (190). At higher ratios, the semicrystalline polyamides become optically clear, amorphous polymers which find appHcations in packaging and barrier resins markets (191). 

Poly(phenylene sulfide) (PPS) is another semicrystalline polymer used in the composites industry. PPS-based composites are generally processed at 330°C and subsequently cooled rapidly in order to avoid excessive crystallisation and reduced toughness. The superior fire-retardant characteristics of PPS-based composites result in appHcations where fire resistance is an important design consideration. Laminated composites based on this material have shown poor resistance to transverse impact as a result of the poor adhesion of the fibers to the semicrystalline matrix. A PPS material more recently developed by Phillips Petroleum, AVTEL, has improved fiber—matrix interfacial properties, and promises, therefore, an enhanced resistance to transverse impact (see PoLYAffiRS containing sulfur). 

In a semicrystalline polymer, the crystals are embedded in a matrix of amorphous polymer whose properties depend on the ambient temperature relative to its glass transition temperature. Thus, the overall elastic properties of the semicrystalline polymer can be predicted by treating the polymer as a composite material... 

These differences on the stress-strain behavior of P7MB and PDTMB show the marked influence of the mesomorphic state on the mechanical properties of a polymer. When increasing the drawing temperatures and simultaneously decreasing the strain rate, PDTMB exhibits a behavior nearly elastomeric with relatively low modulus and high draw ratios. On the contrary, P7MB displays the mechanical behavior typical of a semicrystalline polymer. 

Aliphatic polyesters are low-melting (40-80°C) semicrystalline polymers or viscous fluids and present inferior mechanical properties. Notable exceptions are poly (a-hydroxy acid)s and poly (ft -hydroxy acid)s. 

Wholly aromatic polyesters, in which both R1 and R2 are aromatic, are either high-7 amorphous polymers or veiy high melting semicrystalline polymers that often exhibit liquid crystalline properties. 

Regiodefects are less readily incorporated into crystallites than defect-free chain sequences. In semicrystalline polymers, increasing levels of misinsertion result in reduced crystallinity. This can affect numerous physical properties, resulting in reduced modulus, lower heat distortion temperature, and decreased tensile strength. 

The properties of a semicrystalline polymer are controlled by its degree of crystallinity, the alignment of crystallites relative to one another, the number and type of links between the crystallites and amorphous regions, and the overall orientation of molecules within the material. 

Nylons are semicrystalline polymers whose properties are controlled primarily by their amide concentration, molecular orientation, crystallization conditions, and the level of absorbed water. As discussed earlier, the level of crystallinity and hence product stiffness, is maximized by high concentrations of amide groups, high orientation, slow cooling, and the absence of absorbed water. 

Processes such as film extrusion, fiber spinning, injection molding, and drawing tend to impart orientation to products made from semicrystalline polymers. Mechanical, dielectric, and optical properties, to mention only three, are often strongly influenced by orientation. X-ray diffraction offers a direct approach to studying crystallite orientation because the Intensity that is diffracted into a detector placed at an appropriate position is directly proportional to the number of crystal lattice planes that are in the correct orientation for diffraction. The principles of such measurements are well described in textbooks 0,2). 

In contrast to the mature instrumental techniques discussed above, a hitherto nonexistent class of techniques will require substantial development effort. The new instruments will be capable of measuring the thermal (e.g., glass transition temperatures for amorphous or semicrystalline polymers and melting temperatures for materials in the crystalline phase), chemical, and mechanical (e.g., viscoelastic) properties of nanoscale films in confined geometries, and their creation will require rethinking of conventional methods that are used for bulk measurements. 

They produced high performance electrets from thin polymer films metallized so as to yield high capacitance. Both electrical and mechanical properties of these transducers have been remarkable examples of how applications of science of solids, including knowledge of electron traps, conduction processes in insulators and the viscoelastic phenomena of semicrystalline polymers, can be combined.(6) Incidentally, similar ideas have been applied to optimization of the properties of particle microphones, through assemblies of perfectly microspherical polymer carbon systems. These have shown what limits of performance... 

It is of course important to note that the overall rate of crystallization is not only determined by the growth rate of the spherulites, but also by the amount of nuclei being present in the system. This possibility is used as an effective method to influence the total crystallization rate of commercial polymeric materials in a controlled manner and to influence the size of spherulites and thus the physical properties of finished articles made from semicrystalline polymers. 

Poly(ether ether ketone) (PEEK) is an aromatic, high performance, semicrystalline polymer with extremely good thermal stability, chemical resistance, and electrical and mechanical properties. This polymer shows little solubility in organic solvents due to the crystallinity. One of the first ways to characterize PEEK was by sulfonating the polymer. By adding sulfonic acid groups to the backbone, the crystallinity decreased and solubility increased.Commercially available Victrex appears to be one of the more interesting poly(arylene ether) s used for postmodification. 

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