Polyimide-SiO2-TiO2 nanocomposite structural study probing free volume, physical properties, and gas transport

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Abstract

Polyimide-SiO2-TiO2 nanocomposite membrane permeability, diffusivity, and selectivity were evaluated using polyimide block copolymers designed from 6F and [6F-DABA], and [SiO2-TiO2] using He, H2, CO2, O2, N2, and CH4. Nanocomposite membranes were synthesized using an in-situ sol-gel method to improve the integration of inorganic and organic phases. Metal alkoxide type and polymer functional groups were key factors affecting physical properties and gas transport. [6F-DABA]-[SiO2-TiO2] nanocomposite fractional free volume (FFV) increased 29% as compared to the unmodified [6F-DABA] polyimide. Dynamic Mechanical Thermal Analysis revealed that [SiO2-TiO2] and [TiO2] within functionalized multi-block reduced chain mobility. This led to a Tg increase from 334 °C to 359 °C, and tanδ to decrease from 1.9 to 0.35. In general, inorganic concentration and composition retarded polymer segmental motions, inhibited polymer chain packing, and increase predicted FFV. [6F-DABA-50]-[SiO2-TiO2] membrane's exhibited a simultaneous gas selectivity and permeability improvement. He permeability improved from 58 (unmodified polyimide) to 83 Barrers, and He/CH4 gas selectivity increased from 221 (unmodified) to 334. Membrane gas separation performance of several organic-inorganic materials exceeded Robeson's “upper bound.”

Original languageEnglish (US)
Pages (from-to)110-122
Number of pages13
JournalJournal of Membrane Science
Volume542
DOIs
StatePublished - Jan 1 2017

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Nanocomposites
gas transport
Free volume
polyimides
Polyimides
nanocomposites
Physical properties
physical properties
Gases
membranes
Membranes
permeability
selectivity
Permeability
Polymers
polymers
gases
inorganic materials
alkoxides
block copolymers

Keywords

  • 6FDA (6F) and 6FDA-DABA (6F-DABA) Polyimide
  • Gas transport
  • Organic-Inorganic nanocomposite
  • Physical properties
  • SiO and TiO Sol-gel Chemistry

ASJC Scopus subject areas

  • Biochemistry
  • Materials Science(all)
  • Physical and Theoretical Chemistry
  • Filtration and Separation

Cite this

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title = "Polyimide-SiO2-TiO2 nanocomposite structural study probing free volume, physical properties, and gas transport",
abstract = "Polyimide-SiO2-TiO2 nanocomposite membrane permeability, diffusivity, and selectivity were evaluated using polyimide block copolymers designed from 6F and [6F-DABA], and [SiO2-TiO2] using He, H2, CO2, O2, N2, and CH4. Nanocomposite membranes were synthesized using an in-situ sol-gel method to improve the integration of inorganic and organic phases. Metal alkoxide type and polymer functional groups were key factors affecting physical properties and gas transport. [6F-DABA]-[SiO2-TiO2] nanocomposite fractional free volume (FFV) increased 29{\%} as compared to the unmodified [6F-DABA] polyimide. Dynamic Mechanical Thermal Analysis revealed that [SiO2-TiO2] and [TiO2] within functionalized multi-block reduced chain mobility. This led to a Tg increase from 334 °C to 359 °C, and tanδ to decrease from 1.9 to 0.35. In general, inorganic concentration and composition retarded polymer segmental motions, inhibited polymer chain packing, and increase predicted FFV. [6F-DABA-50]-[SiO2-TiO2] membrane's exhibited a simultaneous gas selectivity and permeability improvement. He permeability improved from 58 (unmodified polyimide) to 83 Barrers, and He/CH4 gas selectivity increased from 221 (unmodified) to 334. Membrane gas separation performance of several organic-inorganic materials exceeded Robeson's “upper bound.”",
keywords = "6FDA (6F) and 6FDA-DABA (6F-DABA) Polyimide, Gas transport, Organic-Inorganic nanocomposite, Physical properties, SiO and TiO Sol-gel Chemistry",
author = "Fei Huang and Cornelius, {Christopher J}",
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doi = "10.1016/j.memsci.2017.08.003",
language = "English (US)",
volume = "542",
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T1 - Polyimide-SiO2-TiO2 nanocomposite structural study probing free volume, physical properties, and gas transport

AU - Huang, Fei

AU - Cornelius, Christopher J

PY - 2017/1/1

Y1 - 2017/1/1

N2 - Polyimide-SiO2-TiO2 nanocomposite membrane permeability, diffusivity, and selectivity were evaluated using polyimide block copolymers designed from 6F and [6F-DABA], and [SiO2-TiO2] using He, H2, CO2, O2, N2, and CH4. Nanocomposite membranes were synthesized using an in-situ sol-gel method to improve the integration of inorganic and organic phases. Metal alkoxide type and polymer functional groups were key factors affecting physical properties and gas transport. [6F-DABA]-[SiO2-TiO2] nanocomposite fractional free volume (FFV) increased 29% as compared to the unmodified [6F-DABA] polyimide. Dynamic Mechanical Thermal Analysis revealed that [SiO2-TiO2] and [TiO2] within functionalized multi-block reduced chain mobility. This led to a Tg increase from 334 °C to 359 °C, and tanδ to decrease from 1.9 to 0.35. In general, inorganic concentration and composition retarded polymer segmental motions, inhibited polymer chain packing, and increase predicted FFV. [6F-DABA-50]-[SiO2-TiO2] membrane's exhibited a simultaneous gas selectivity and permeability improvement. He permeability improved from 58 (unmodified polyimide) to 83 Barrers, and He/CH4 gas selectivity increased from 221 (unmodified) to 334. Membrane gas separation performance of several organic-inorganic materials exceeded Robeson's “upper bound.”

AB - Polyimide-SiO2-TiO2 nanocomposite membrane permeability, diffusivity, and selectivity were evaluated using polyimide block copolymers designed from 6F and [6F-DABA], and [SiO2-TiO2] using He, H2, CO2, O2, N2, and CH4. Nanocomposite membranes were synthesized using an in-situ sol-gel method to improve the integration of inorganic and organic phases. Metal alkoxide type and polymer functional groups were key factors affecting physical properties and gas transport. [6F-DABA]-[SiO2-TiO2] nanocomposite fractional free volume (FFV) increased 29% as compared to the unmodified [6F-DABA] polyimide. Dynamic Mechanical Thermal Analysis revealed that [SiO2-TiO2] and [TiO2] within functionalized multi-block reduced chain mobility. This led to a Tg increase from 334 °C to 359 °C, and tanδ to decrease from 1.9 to 0.35. In general, inorganic concentration and composition retarded polymer segmental motions, inhibited polymer chain packing, and increase predicted FFV. [6F-DABA-50]-[SiO2-TiO2] membrane's exhibited a simultaneous gas selectivity and permeability improvement. He permeability improved from 58 (unmodified polyimide) to 83 Barrers, and He/CH4 gas selectivity increased from 221 (unmodified) to 334. Membrane gas separation performance of several organic-inorganic materials exceeded Robeson's “upper bound.”

KW - 6FDA (6F) and 6FDA-DABA (6F-DABA) Polyimide

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