Semicrystalline polymers crystallization

According to the WAXS studies, after extrusion, the bristles are distinguished by a rather isotropic structure. Figure 11.3(a) is typical for a semicrystalline polymer crystallized in a completely isotropic state. As a matter of fact, this WAXS pattern is talcen from the extruded sample after the melt blending. It must be noted that the same conclusion was drawn from the SEM observation of the same sample (Figure 11.2(a)). It is important to note that although the extrudate has the shape of a bristle (the same as that after drawing), any preferred orientation is absent. This means that the shape of... 

Lamellar morphology variables in semicrystalline polymers can be estimated from the correlation and interface distribution fiinctions using a two-phase model. The analysis of a correlation function by the two-phase model has been demonstrated in detail before [30,11] The thicknesses of the two constituent phases (crystal and amorphous) can be extracted by several approaches described by Strobl and Schneider [32]. For example, one approach is based on the following relationship ... 

A crystalline or semicrystalline state in polymers can be induced by thermal changes from a melt or from a glass, by strain, by organic vapors, or by Hquid solvents (40). Polymer crystallization can also be induced by compressed (or supercritical) gases, such as CO2 (41). The plasticization of a polymer by CO2 can increase the polymer segmental motions so that crystallization is kinetically possible. Because the amount of gas (or fluid) sorbed into the polymer is a dkect function of the pressure, the rate and extent of crystallization may be controUed by controlling the supercritical fluid pressure. As a result of this abiHty to induce crystallization, a history effect may be introduced into polymers. This can be an important consideration for polymer processing and gas permeation membranes. 

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... 

Crystalline polyimide powders, 304 Crystalline transition temperature. See Melting temperature (Tm) Crystallization rate, for processing semicrystalline polymers, 44 CTE. See Coefficient of thermal expansion (CTE)... 

Ivanov, D.A. and Magonov, S.N., Atomic Force Microscopy Studies of Semicrystalline Polymers at Variable Temperature, in Polymer Crystallization Observations, Concepts and Interpretations, Sommer, J.-U. and Reiter, G., Eds., Springer, Heidelberg, Germany, 2003, chap. 7. 

Why would a manufacturer of polymeric items be interested in the rate of crystallization within a semicrystalline polymer ... 

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. 

We have adapted a commercially available x-ray diffractometer normally used for structure determinations on single crystals to operate as a very flexible device for performing x-ray pole figure determinations and related studies on polymeric materials. Descriptions of crystallite orientations, as provided by pole figures, are useful in studying many aspects of the behavior of products made from semicrystalline polymers. This paper describes the software that we have written for our pole figure facility. Except for some vendor-provided routines to drive the hardware Interface all of our software is written in FORTRAN. Menu driven operation is provided to maximize user convenience. 

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). 

The crystallization process of flexible long-chain molecules is rarely if ever complete. The transition from the entangled liquid-like state where individual chains adopt the random coil conformation, to the crystalline or ordered state, is mainly driven by kinetic rather than thermodynamic factors. During the course of this transition the molecules are unable to fully disentangle, and in the final state liquid-like regions coexist with well-ordered crystalline ones. The fact that solid- (crystalline) and liquid-like (amorphous) regions coexist at temperatures below equilibrium is a violation of Gibb s phase rule. Consequently, a metastable polycrystalline, partially ordered system is the one that actually develops. Semicrystalline polymers are crystalline systems well removed from equilibrium. 

D.A. Ivanov and S. Magonov, Atomic force microscopy studies of semicrystalline polymers at variable temperature. In G. Reiter, J.-V. Sommer (Eds.), Polymer Crystallization, Springer, Berlin, 2003, p. 98. 

Anantawaraskul, S., Soares,. B. P. and Wood-Adams, P. M. Fractionation of Semicrystalline Polymers by Crystallization Analysis Fractionation and Temperature Rising Elution Fractionation. Vol. 182, pp. 1-54. 

The volume inside the semicrystalline polymers can be divided between the crystallized and amorphous parts of the polymer. The crystalline part usually forms a complicated network in the matrix of the amorphous polymer. A visualization of a single-polymer crystallite done [111] by the Atomic Force Microscopy (AFM) is shown in Fig. 9. The most common morphology observable in the semicrystalline polymer is that of a spherulitic microstructure [112], where the crystalline lamellae grows more or less radially from the central nucleus in all directions. The different crystal lamellae can nucleate separately... 

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. 

Many semicrystalline polymers are polymorphic and exist in different crystal forms. When PBT fiber is uniaxially stretched [75], the contracted gauche-trans-gauche a-crystal chain is extended to a fully trans conformation of a y-crystal. Above 20% strain, the crystal form is 100% y-crystal with a longer c-axis triclinic cell dimension. Thus, it is reasonable to ask whether the... 

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