Semicrystalline polymers conditions

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. 

According to the principles of polycondensation, all of the above reactions will also take place during SSP. The conditions for the latter, however, are different as this process is carried out at lower temperatures in a non-homogeneous environment. In order to examine the kinetics of SSP, some assumptions have to be made to simplify the analysis. These are based on the idea that the reactive end groups and the catalyst are located in the amorphous regions. Polycondensations in the solid state are equilibrium reactions but are complicated by the two-phase character of the semicrystalline polymer. 

Semicrystalline polymer A material consisting of a combination of crystalline and amorphous regions. Essentially, all common plastics and elastomers with the tendency to crystallize are semicrystalline. The degree of crystallization depends on the structure of the polymer and the conditions of fabrication. 

A distinction should be made between solvent plasticizers and nonsolvent plasticizers. With an amorphous polymer, any plasticizer is a solvent plasticizer— i.e., under suitable conditions the polymer would eventually dissolve in the plasticizer. With a crystalline or semicrystalline polymer, there are some compounds which enter both the crystalline (ordered) and the amorphous (disordered) regions. These are true plasticizers-sometimes they are called primary plasticizers. If, on the other hand, only the amorphous regions are penetrated, the compound may be considered as a nonsolvent plasticizer, also known as a secondary plasticizer, or softener. Such softeners are used sometimes as diluents for the primary plasticizer. 

Under isothermal conditions, the fracture mode of amorphous polymers, or of the amorphous component in semicrystalline polymers, depends on the relationship between (Affa — wo-) and (l/0 — yo-). Combination of Equations 3 and 4 leads to the following relationships. If... 

The membrane must not be attacked by the solvent and must permit the solvent to permeate fast enough to achieve osmotic equilibrium in a reasonable time. If the membrane is too permeable, however, large leakage errors will result. Cellulose and cellulose acetate membranes are (he most widely used types with synthetic polymer solutions. Measurements at the relatively elevated temperatures needed to dissolve semicrystalline polymers are hampered by a general lack of membranes that are durable under these conditions. 

Crystalline lamellae are the basic units in the microstructures of solid semicrystalline polymers. The lamellae are observed to be organized into two types of larger structural features depending on the conditions of the bulk solidification process. 

The major feature of polymers that have been bulk crystallized under quiescent conditions are polycrystalline structures called sphemlites. These are roughly spherical supercrystalline structures which exhibit Maltese cross-extinction patterns when examined under polarized light in an optical microscope. Spheruliies are characteristic of semicrystalline polymers and are also observed in low-molecular-weight materials that have been crystallized from viscous media. Sphemlites are aggregates of lamellar crystallites. They are not single crystals and include some... 

The fatigue lifetime data for prenotched (knit-line) samples of poly butylene terephthalate (PBT), a semicrystalline polymer, were unrevealing in that no fatigue crack growth could be induced under any of the conditions teted (Fig. 34). At higher... 

During polymer processing non-isothermal crystallization conditions, mechanical deformation, and shear forces may alter the morphology and orientation of polymers both at the surface and in the bulk. In addition, orientation effects of semicrystalline polymers that crystallize in contact with solids are considered. 

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