Amorphous crystal-like region

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. 

Finally, in a semi-crystalline polymer there are amorphous partitions between regions of crystalline phase (Figure 4.1 c). For many materials these partitions are not completely in the glassy state at room temperature. So what we really have is a mixture of solid crystal islets separated by a kind of grout made from a rubber-like polymer. Clearly, such material should be less fragile, with lower values of Young s modulus, than a polymeric glass. 

According to Hosemann-Bonart s model8), an oriented polymeric material consists of plate-like more or less curved folded lamellae extended mostly in the direction normal to that of the sample orientation so that the chain orientation in these crystalline formations coincides with the stretching direction. These lamellae are connected with each other by some amount of tie chains, but most chains emerge from the crystal bend and return to the same crystal-forming folds. If this model adequately describes the structure of oriented systems, the mechanical properties in the longitudinal direction are expected to be mainly determined by the number and properties of tie chains in the amorphous regions that are the weak spots of the oriented system (as compared to the crystallite)9). 

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