TY - JOUR
T1 - Hybrid organic-inorganic 6FDA-6pFDA and multi-block 6FDA-DABA polyimide SiO2–TiO2 nanocomposites
T2 - Synthesis, FFV, FTIR, swelling, stability, and X-ray scattering
AU - Huang, F.
AU - Tahmasbi Rad, A.
AU - Zheng, W.
AU - Nieh, M. P.
AU - Cornelius, C. J.
N1 - Publisher Copyright:
© 2016 Elsevier Ltd
PY - 2017/1/13
Y1 - 2017/1/13
N2 - A series of hybrid polyimide-SiO2–TiO2 nanocomposites were fabricated from functionalized multi-block polyimides, tetraethyl orthosilicate (TEOS), and titanium isopropoxide (TIP). Polyimides were solution imidized utilizing 4,4'-hexafluoroisopropylidene diphthalic anhydride (6FDA), and stoichiometric amounts of 4,4'-hexafluoroisopropylidene diamine (6FpDA) and 3,5-diaminobenzoic acid (DABA). Organic and inorganic phase compatibility and interfacial interactions were dependent upon metal alkoxide type and polyimide carboxylic acid functional group concentration (COOH). The glass transition temperature (Tg) of [6F-DABA-25] composites increased 25 °C from 334 °C to 359 °C as measured with dynamic mechanical analysis (DMA). Polyimide swelling experiments using THF demonstrated that TiO2 created interpenetrating networks within the hybrid nanocomposite preventing dissolution, but pure SiO2 systems readily dissolved in the solvent. The mean TiO2 domain size within these composites was 102 nm, which was 10 times smaller than SiO2 (1194 nm). WAXS revealed a significant increase in hybrid composite domain spacing from 9.63 Å to 26.5 Å. This led to a reduction in the polyimde's effective density within the composites from 1.45 g/cm3 to 1.35 g/cm3, which was attributed to increasing interchain distance and decreasing chain packing density. These results are attributed to enhanced interactions between functionalized polymer chains and inorganic domains containing TiO2 and SiO2–TiO2 versus SiO2.
AB - A series of hybrid polyimide-SiO2–TiO2 nanocomposites were fabricated from functionalized multi-block polyimides, tetraethyl orthosilicate (TEOS), and titanium isopropoxide (TIP). Polyimides were solution imidized utilizing 4,4'-hexafluoroisopropylidene diphthalic anhydride (6FDA), and stoichiometric amounts of 4,4'-hexafluoroisopropylidene diamine (6FpDA) and 3,5-diaminobenzoic acid (DABA). Organic and inorganic phase compatibility and interfacial interactions were dependent upon metal alkoxide type and polyimide carboxylic acid functional group concentration (COOH). The glass transition temperature (Tg) of [6F-DABA-25] composites increased 25 °C from 334 °C to 359 °C as measured with dynamic mechanical analysis (DMA). Polyimide swelling experiments using THF demonstrated that TiO2 created interpenetrating networks within the hybrid nanocomposite preventing dissolution, but pure SiO2 systems readily dissolved in the solvent. The mean TiO2 domain size within these composites was 102 nm, which was 10 times smaller than SiO2 (1194 nm). WAXS revealed a significant increase in hybrid composite domain spacing from 9.63 Å to 26.5 Å. This led to a reduction in the polyimde's effective density within the composites from 1.45 g/cm3 to 1.35 g/cm3, which was attributed to increasing interchain distance and decreasing chain packing density. These results are attributed to enhanced interactions between functionalized polymer chains and inorganic domains containing TiO2 and SiO2–TiO2 versus SiO2.
KW - 6FDA-6FPDA and multi-block 6FDA-DABA polyimides
KW - SiO–TiO hybrid organic-inorganic nanocomposites
KW - Sol-gel chemistry
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U2 - 10.1016/j.polymer.2016.11.046
DO - 10.1016/j.polymer.2016.11.046
M3 - Article
AN - SCOPUS:84999017231
SN - 0032-3861
VL - 108
SP - 105
EP - 120
JO - Polymer
JF - Polymer
ER -