Glasses coexistence with crystals

The situation in polymers is completely different. In most polymer systems, the degree of molecular order is somewhere iu betweeu the firll positional order of a single crystal and the complete positional disorder of a liquid or a glass. In polymers, ciystalline domains coexist with amorphous regions. Therefore, a semi-ciystalline polymer is in a non-equilibrium situation. 

The temperature dependence of the FE and glassy volume fractions was determined for the four different compositions mentioned above (Fig. 10). Whereas D-RADP-0.20 exhibits a quasi-continuous sequence of local PE-FE phase transitions with a coexistence range of about 20 K and a pure FE phase state throughout the whole crystal below 135 K [17], in D-RADP-0.25 part of the crystal remains in the PE or glass state, respectively, down to very low temperatures. This is also observed in D-RADP-0.30, while in D-RADP-0.35 (not shown) no FE polarization could be observed at all. 

Fig. 4 Schematic phase diagrams of a polymer solution showing LL phase separation with UCST behavior. Curve s is the spinodal, curve b is the binodal, and curve g is the glass transition temperature as a function of polymer concentration. BP indicates the Berghmans point, (a) LL phase separation is the only thermodynamic transformation of the system [17,25, 36]. (b) Curve c shows the crystallization temperature of a polymer fully miscible in a solvent as a function of concentration in the solution [17, 25], The LL phase coexistence curve (combined with vitrification) is a (classical) metastable process that lies beneath the crystallization curve c. In route 1, a polymer solution is supercooled at ALj, and the only active process is polymer crystallization. In route 2, the initially homogeneous solution is supercooled to a larger undercooling than namely AL2. Crystallization may compete either with LL phase separation when reaching point C, or LL phase separation coupled with vitrification when reaching point D. At C, crystallization may take place in the polymer-rich phase. At D, both LL phase separation and crystallization may become arrested by vitrification...

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