Semicrystalline polymers transitions

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)... 

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. 

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. 

A novel approach is used to compatibilise a blend without addition of premade copolymers or functionalisation of polymers lacking functional groups. Solid-state shear pulverisation (S3P) processes polymers at temperatures below the melt transition (for semicrystalline polymers) or the glass transition (for amorphous polymers). The polymer, introduced as pellets or flakes into the pulveriser. 

Fig. 2.18. Schematic DSC thermogram of a semicrystalline polymer = glass transition temperature = crystallization temperature = melting temperature = decomposition temperature...

Composite-based PTC thermistors are potentially more economical. These devices are based on a combination of a conductor in a semicrystalline polymer—for example, carbon black in polyethylene. Other fillers include copper, iron, and silver. Important filler parameters in addition to conductivity include particle size, distribution, morphology, surface energy, oxidation state, and thermal expansion coefficient. Important polymer matrix characteristics in addition to conductivity include the glass transition temperature, Tg, and thermal expansion coefficient. Interfacial effects are extremely important in these materials and can influence the ultimate electrical properties of the composite. 

A polymer may be amorphous, crystalline, or a combination of both. Many polymers actually have both crystalline and amorphous regions, i.e., a semicrystalline polymer. The Tg is a transition related to the motion in the amorphous regions of the polymer [3,8,9], Below the Tg, an amorphous polymer can be said... 

Fig. 23.4 Typical transition behavior in mechanical storage modulus for a semicrystalline polymer. The subscripts a and c refer to the amorphous and crystalline phases, of the polymer, with aa as the main 7g process.

We note that semicrystalline polymers, where the break points are indicative of Tm, require more energy because they must undergo the phase transition of fusion. For example, about 700kJ/kg are needed to heat HDPE to 200°C, while for the same processing temperature PS requires about 350 kJ/kg, that is, half the energy. 

Above Tm, the viscosity of the melt has Arrhenius-type dependence, decreasing (exponentially) with increasing temperature. Therefore a sharp transition is observed in both mechanical and viscous properties of semicrystalline polymers at Tm, resulting in a physical situation that is closer to the classic melting interface of monomeric crystals where, on one side, there is a viscous liquid, and on the other side, an elastic solid. 

AH/R = 8.525 K 1 for PB H-300, is known. Finally, we note that the nonisothermal temperature profiles here exist only in the absence of a phase transition, which occurs in the gas-assisted injection-molding process, at least with semicrystalline polymers. 

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