Amorphous polymers orientation

Semiciystalline Polymers There are two cases to be considered in the stress-strain relationships of semicrystalline plastics. If the amorphous portion is rubbery, then the plastic will tend to have a lower modulus, and the extension to break will be very large see polyethylene. Table 11.1. If the amorphous portion is glassy, however, then the effect will be much more like that of the glassy amorphous polymers. Orientation of semicrystalline polymers is also much more important than for the amorphous polymers. A special case involves fibers, where tensile strength is a direct function of the orientation of the chains in the fiber direction. 

Orientation in linear amorphous polymers Crystalline Polymers... 

Miscibility or compatibility provided by the compatibilizer or TLCP itself can affect the dimensional stability of in situ composites. The feature of ultra-high modulus and low viscosity melt of a nematic liquid crystalline polymer is suitable to induce greater dimensional stability in the composites. For drawn amorphous polymers, if the formed articles are exposed to sufficiently high temperatures, the extended chains are retracted by the entropic driving force of the stretched backbone, similar to the contraction of the stretched rubber network [61,62]. The presence of filler in the extruded articles significantly reduces the total extent of recoil. This can be attributed to the orientation of the fibers in the direction of drawing, which may act as a constraint for a certain amount of polymeric material surrounding them. 

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. 

The strengths of polymers in the glassy state exceed those of amorphous polymers at temperatures above Tg, but they are generally much inferior to the strengths attainable in oriented crystalline polymeric substances. 

Anisotropic materials have different properties in different directions (1-7). 1-Aamples include fibers, wood, oriented amorphous polymers, injection-molded specimens, fiber-filled composites, single crystals, and crystalline polymers in which the crystalline phase is not randomly oriented. Thus anisotropic materials are really much more common than isotropic ones. But if the anisotropy is small, it is often neglected with possible serious consequences. Anisoiropic materials have far more than two independent clastic moduli— generally, a minimum of five or six. The exact number of independent moduli depends on the symmetry in the system (1-7). Anisotropic materials will also have different contractions in different directions and hence a set of Poisson s ratios rather than one. 

An amorphous polymer in a state of molecular alignment is not a stable structure - it is metastable. It can uansition either to a more perfectly ordered, crystalline structure, or to a more disordered, nonoriented structure In either case, the free energy of the system is reduced. Given enough time and/or thermal energy, an oriented amorphous polymer will transition in either or both of these directions. 

Cast film extrusion of polyolefins has been developed to obtain flexible films with a high level of transparency by freezing the amorphous polymer structure of the melt on a chill roll. Cast films are mono-oriented in extrusion direction. 

With the exception of PC, amorphous, non-oriented polymers did not produce measurable amounts of broken segments when subjected to tension. As has been shown in previous paragraphs, large axial stresses capable of chain scission in amorphous polymers can only be transmitted into the chain by friction of slipping chains requiring strong intermolecular interactions. In addition, macroscopic fracture occurs before a widespread chain overloading and scission occurs, which is opposite to the behavior of semicrystalline polymers. 

A good applications-oriented measure of the use temperature for a ma-teral is the heat distortion or heat deflection test (HDT). The HDT is described by ASTM-D648 as the temperature at which a sample of defined dimensions (5 X Vi X Vs (or Va) in.) deflects under a flexural load of 66 or 264 psi placed at its center. In case of a largely amorphous polymer, the HDT temperature is typically slightly (10 to 20 °C) lower than the Tg as determined by DSC or DTA, whereas with more-crystalline polymers, it more closely correlates with the Tm. The HDT temperature is a useful indicator of the temperature limits for structural (load-supporting) applications. A loaded cantilever beam is used in another heat deflection test called the Martens method. 

Atactic PMMA is a brittle amorphous polymer with low elongation at break. Without molecular orientation, PVDF has also a low elongation under tensile stress as shown in Figine 7.9. However, the elongation of PVDF/PMMA blends... 

On the other hand, WAXS measurements of PE melt clearly indicate a range of intermolecular distance correlations of about 25 A [3]. Together with the relatively high density of polymer melts, the fact that the first interchain halo in WAXS patterns of oriented amorphous polymers tends to lie in the equatorial direction and the relatively high WAXS intensity of the interchain halo support the idea of parallel chain segments on the short range scale. 

A general concept for describing all kinds of order in chain molecules, ranging from crystalline order to liquid crystalline order and then to order in oriented and isotropic amorphous polymers, is introduced in the third article written by Pieper and Kilian. After the presentation of the basic concept, experimental results obtained on different polymers including phases with rotatory segmental motion are discussed. 

The use of femtosecond pulses in nonlinear optics has one obvious advantage high peak power, necessary to observe the nonlinear effect, can be obtained from low total power in the pulse. This made samples with a low damage threshold amenable for HRS measurements. One example of such sample is amorphous polymer films. These films do not have the optical quality of single crystals. They are more susceptible to optical damage. With the femtosecond pulses, we have been able to perform HRS measurements on solid thin films, to study the orientational correlation between nonlinear optical chromophores in the film.10 13... 

Biaxially oriented films such as PET and PEN are birefringent. For LC displays which depend on light of known polarization this means that birefringent films, which would change the polarization state, are unlikely to be used as substrates. Films based on amorphous polymer are not birefringent and are more suitable for LC displays. Birefringence is not an issue with OLED, electrophoretic displays, or, indeed, some LC displays. 

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