本研究對poly(ethylene oxide)與一系列聚酯類高分子進行作用力參數與球晶成長速率相關性之探討，其中聚酯類高分子分別由poly(ethylene adipate)到poly(hexamethylene sebacate)，CH2/COO比則是由3到7。由於本研究中各系統的玻璃轉移溫度(Tg)皆在-60oC左右，因此以動力學的角度藉由觀察球晶成長速率，對相容性作進一步的探討；克服熔點接近的問題後，再以熱力學觀點延伸對PEO與聚酯類高分子的相容性，其中與PEO相容的聚酯類有poly(ethylene adipate)、poly(propylene adipate)、poly(butylene adipate)和poly(ethylene azelate)，CH2/COO比則是3.0~4.5，得到的作用力參數皆呈負值，隨著聚酯類高分子結構上的差異作用力參數的值亦有所不同，可在PEO/poly(propylene adipate)系統中(CH2/COO=3.5)，得到一個最低的作用力參數。接著進一步藉由球晶成長速率，對聚酯類高分子結構作相關性的探討，亦可得到與作用力參數相同的趨勢。另一方面此研究亦討論LiClO4與PEO混摻後對結晶動力的影響，球晶成長速率會明顯地抑制，並呈現級數量的下降，而球晶型態則有類似羽毛狀的結構，這說明LiClO4與PEO間確實存有強作用力。而當LiClO4摻入PEO/PVPh，抑制球晶成長更是明顯，並在長時間觀察球晶型態後發現不定型區明顯增多，而為改質PEO電解質提供一個有效的方法。

Crystalline/crystalline polymer blend systems of poly(ethylene oxide) (PEO) and a homologous series of polyesters, from poly(ethylene adipate) to poly(hexamethylene sebacate), of different CH2/COO ratios (from 3.0 to 7.0) were examined. Correlation between interactions, miscibility, and spherulite growth rate was discussed. Owing to proximity of blend constituents’ Tg’s, the miscibility in the crystalline/crystalline blends was mainly justified by thermodynamic and kinetic evidence extracted from characterization on the PEO crystals grown from mixtures of PEO and polyesters at melt state. By overcoming experimental difficulty in assessing the phase behavior of two crystalline polymers with closely-spaced Tg’s, this work has further extended the range of polyesters that can be miscible with PEO. The interaction parameters (12) for miscible blends of PEO with polyesters [poly(ethylene adipate), poly(propylene adipate), poly(butylene adipate), and poly(ethylene azelate) with CH2/COO=3.0~4.5] are all negative but the values vary with the polyester structures, with a maximum for the blend of PEO/poly(propylene adipate) (CH2/COO=3.5). Furthermore, the values of interactions are apparently dependent on the structures of the polyester constituent in the blends; and miscibility and interaction strength for the miscible PEO/polyester systems correlate in the same trend with the PEO crystal growth rates in the blends. However, the doping distinctly influenced the crystalline domains of LiClO4-doped PEO or LiClO4-doped PEO/PVPh blend system. LiClO4 doping in PEO exerted significant retardation on PEO crystal growth. The growth rates for LiClO4-doped PEO were order-of-magnitude slower than those for the salt-free neat PEO. Dramatic changes in spherulitic patterns were also seen in that feather-like dendritic spherulites are resulted, indicating strong interactions. Introduction of both miscible amorphous PVPh polymer and LiClO4 salt in PEO even more significantly suppressed the crystallizing tendency of PEO, which can potentially be a useful new approach of PEO electrolyte modification.

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