Aging of polymers of intrinsic microporosity studied by sorption and permeation
September 11-16, 2016
Polymers of intrinsic microporosity (PIMs)1 seem to be effective materials for gas and vapor separations.2 However, gas separation efficiency of PIMs can be strongly influenced by the material aging process connected with the changes of PIMs inner structure.3 With respect to potential industrial applications, the investigation of such changes and their effect on gas and vapor transport is necessary. In this work, we present a detailed study of i) CO2 sorption in PIM-1 via momentary measurements during four years and ii) methanol permeation in PIM-11 and EA-TB-PIM2 via continuous and momentary experiments. Sorption experiments were performed gravimetrically using a self-developed apparatus equipped with McBain’s spiral balances. In this case, PIM-1 membranes were pre-treated (soaking in ethanol with consequent drying at different temperatures) in order to study the influence of temperature on PIM-1 aging. Methanol permeation experiments were performed using a differential flow permeameter with H2 and He as carrier gases. Permeation experiment were performed with PIM-1 and PIM-EA-TB methanol treated membranes. CO2 sorption measurements revealed that, assuming the validity of the solution-diffusion model, the decrease of permeability during aging can be attributed directly to the decrease of diffusivity, whereas solubility is time independent in the studied period of four years. Although higher preparation temperature led to the initial drop of diffusivity, this process stabilized separation performance of PIMs over time (Figure 1). MeOH permeation experiments confirmed previous findings from CO2 tests, that the permeability decrease during the aging is a diffusivity controlled process. Moreover, it was found that the momentary permeation data can be mathematically transferred to continuous data, which are more relevant for applications but more difficult to measure. The nature of aging process was studied by infrared spectroscopy. We have found that aging of PIMs does not influence their chemical structure and; therefore, they undergo only the so called physical-aging.
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Marek Lanč, Kryštof Pilnáček, Ondřej Vopička, Johannes C. Jansen, Peter M. Budd, Neil B. McKeown, and Karel Friess, "Aging of polymers of intrinsic microporosity studied by sorption and permeation" in "Advanced Membrane Technology VII", Isabel C. Escobar, Professor, University of Kentucky, USA Jamie Hestekin, Associate Professor, University of Arkansas, USA Eds, ECI Symposium Series, (2016). http://dc.engconfintl.org/membrane_technology_vii/75