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Machiel van Essen
Membrane Materials and Processes, Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, P.O. Box 513, 5600, MB Eindhoven, the Netherlands

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Journal article
Published: 12 June 2021 in Journal of Membrane Science
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In this work, the effectiveness of metal-organic frameworks (MOFs) with sheet-like morphologies was assessed as function of the MOF microporosity and MOF-matrix compatibility. Zeolitic imidazolate frameworks (ZIFs, a MOF subclass) with sheet-like/platelet morphologies were incorporated in Matrimid/PBI matrices resulting in mixed matrix membranes (MMMs). The ZIFs were either permeable (ZIF-301) or impermeable (ZIF-95X) for gases with a kinetic diameter bigger than or equal to the kinetic diameter of CO2. Additionally, MMMs containing impermeable graphene nanosheets were fabricated as reference to confirm the ZIF-95X impermeability. The MMMs containing the ZIF-301 nanoplatelets showed enhanced CO2 permeabilities. Analysis of the N2 and CO2 solubility and diffusivity showed that this permeable additive enhances the solubility of both gases, but only increases the N2 diffusivity through the ZIF-301 MMM. This signified that for MMMs with sheet-like MOFs the MOF micropore volume should only be accessible for one gas such that the sheet-like morphology effectively increases the tortuosity for the other species. Contrarily, the MMMs containing impermeable ZIF-95X and graphene showed declined MMM separation performances. Analysis of the N2 and CO2 diffusivities showed the presence of defective interfaces in these MMMs and proved that an increased tortuosity is only effective if the additive-matrix interface is defect free.

ACS Style

Machiel van Essen; Raymond Thür; Menno Houben; Ivo F.J. Vankelecom; Zandrie Borneman; Kitty Nijmeijer. Tortuous mixed matrix membranes: A subtle balance between microporosity and compatibility. Journal of Membrane Science 2021, 635, 119517 .

AMA Style

Machiel van Essen, Raymond Thür, Menno Houben, Ivo F.J. Vankelecom, Zandrie Borneman, Kitty Nijmeijer. Tortuous mixed matrix membranes: A subtle balance between microporosity and compatibility. Journal of Membrane Science. 2021; 635 ():119517.

Chicago/Turabian Style

Machiel van Essen; Raymond Thür; Menno Houben; Ivo F.J. Vankelecom; Zandrie Borneman; Kitty Nijmeijer. 2021. "Tortuous mixed matrix membranes: A subtle balance between microporosity and compatibility." Journal of Membrane Science 635, no. : 119517.

Journal article
Published: 10 June 2021 in Journal of Membrane Science
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The time-dependent CO2-induced plasticization behavior of glassy Matrimid® 5218 polymer membranes at supercritical conditions up to 120 bar was investigated. Glassy polyimide membranes were conditioned with both gaseous CO2 and liquid-like sc-CO2. The plasticization behavior during permeation and sorption was correlated with the intrinsic membrane properties and the CO2 fluid properties. In the gaseous region the CO2 concentration increased slightly over time, while in the liquid-like sc-CO2 region the CO2 concentration remained constant over time and showed no hysteresis, indicating an induced glass transition. Contrary to the CO2 sorption the CO2 permeability showed more pronounced time-dependent behavior which increases with feed pressure because of polymer membrane plasticization. Despite the strong time-dependency, the CO2 permeability was independent of the feed pressure in the liquid-like sc-CO2 region. This difference in time-dependent behavior between sorption and permeation is due to the presence of a concentration gradient during permeation experiments. In addition, the permeability showed significant hysteresis. Exposure to liquid-like sc-CO2 resulted in a highly plasticized membrane and changed the permeation behavior at all subsequent feed pressures, due to slow polymer chain relaxation rates. Clearly, these relationships proof that the permeation history is a critical aspect for time-dependent plasticization phenomena at high CO2 pressures.

ACS Style

Menno Houben; Machiel van Essen; Kitty Nijmeijer; Zandrie Borneman. Time-dependent plasticization behavior of polyimide membranes at supercritical conditions. Journal of Membrane Science 2021, 635, 119512 .

AMA Style

Menno Houben, Machiel van Essen, Kitty Nijmeijer, Zandrie Borneman. Time-dependent plasticization behavior of polyimide membranes at supercritical conditions. Journal of Membrane Science. 2021; 635 ():119512.

Chicago/Turabian Style

Menno Houben; Machiel van Essen; Kitty Nijmeijer; Zandrie Borneman. 2021. "Time-dependent plasticization behavior of polyimide membranes at supercritical conditions." Journal of Membrane Science 635, no. : 119512.

Full paper
Published: 23 December 2020 in Advanced Materials Interfaces
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In this work, the influence of the zeolitic imidazolate framework 78 (ZIF‑78) morphology, with 1D pores, on the mixed matrix membrane (MMM) CO2/N2 mixed gas separation performance is investigated as well as the influence of the feed composition and pressure. Low aspect ratio and a high aspect ratio ZIF‑78 particles are synthesized and incorporated in Matrimid with 10 and 20 wt% additive content. High pressure CO2 and N2 sorption measurements show that both the low and high aspect ratio ZIF‑78 metal–organic frameworks (MOFs) exhibit similar sorption behavior. The incorporation of ZIF‑78 into Matrimid results in improved CO2 permeabilities up to 39%, without compromising the selectivity, relative to native Matrimid membranes. Both at low and high CO2 partial pressures, the MMMs containing the different ZIF‑78 morphologies show equal CO2 permeabilities, indicating that the ZIF‑78 morphology and consequently the aspect ratio are insignificant for these particular MMMs, contradicting previous observations in literature. Thus, depending on the MOF/polymer system, the MOF morphology and aspect ratio can be considered as a design aspect. Finally, a clear influence of feed composition and pressure on the MMM solubility coefficient and diffusivity is observed, emphasizing the importance of the mixed gas composition and measurement conditions.

ACS Style

Machiel van Essen; Luuk Van Den Akker; Raymond Thür; Menno Houben; Ivo F. J. Vankelecom; Zandrie Borneman; Kitty Nijmeijer. Investigation of ZIF‐78 Morphology and Feed Composition on the Mixed Gas CO 2 /N 2 Separation Performance in Mixed Matrix Membranes. Advanced Materials Interfaces 2020, 8, 1 .

AMA Style

Machiel van Essen, Luuk Van Den Akker, Raymond Thür, Menno Houben, Ivo F. J. Vankelecom, Zandrie Borneman, Kitty Nijmeijer. Investigation of ZIF‐78 Morphology and Feed Composition on the Mixed Gas CO 2 /N 2 Separation Performance in Mixed Matrix Membranes. Advanced Materials Interfaces. 2020; 8 (5):1.

Chicago/Turabian Style

Machiel van Essen; Luuk Van Den Akker; Raymond Thür; Menno Houben; Ivo F. J. Vankelecom; Zandrie Borneman; Kitty Nijmeijer. 2020. "Investigation of ZIF‐78 Morphology and Feed Composition on the Mixed Gas CO 2 /N 2 Separation Performance in Mixed Matrix Membranes." Advanced Materials Interfaces 8, no. 5: 1.

Journal article
Published: 23 November 2020 in Journal of Membrane Science
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The high-pressure permeation and sorption behavior of supercritical carbon dioxide (sc-CO2) in glassy Matrimid® 5218 polymer membranes were extensively investigated. The effect of pressure (0–120 bar) and temperature (25–55 °C) was examined. The observations were related to the intrinsic membrane properties, plasticization phenomena and the CO2 fluid properties. The phase transition from gaseous (-like sc) CO2 to liquid (-like sc) CO2 has the largest influence on the CO2 fluid properties and therefore was found to have the most influence on the CO2 sorption and CO2 permeability. The CO2 sorption was directly dependent on the CO2 density in the liquid (-like sc) regime. The CO2 permeability of Matrimid® 5218 showed typical CO2-induced plasticization behavior in the gaseous (-like sc) CO2 regime. When entering the liquid (-like sc) CO2 regime, the extent of plasticization was found to be independent of the applied feed pressure in this regime. The membranes showed strong hysteresis with pressure. The permeation history of the membrane thus has a large influence on the time-dependent permeability behavior. Clearly, the CO2 permeability behavior at these high pressures in glassy Matrimid® 5218 is determined by a combination of the CO2 fluid density and plasticization phenomena.

ACS Style

Menno Houben; Romy van Geijn; Machiel van Essen; Zandrie Borneman; Kitty Nijmeijer. Supercritical CO2 permeation in glassy polyimide membranes. Journal of Membrane Science 2020, 620, 118922 .

AMA Style

Menno Houben, Romy van Geijn, Machiel van Essen, Zandrie Borneman, Kitty Nijmeijer. Supercritical CO2 permeation in glassy polyimide membranes. Journal of Membrane Science. 2020; 620 ():118922.

Chicago/Turabian Style

Menno Houben; Romy van Geijn; Machiel van Essen; Zandrie Borneman; Kitty Nijmeijer. 2020. "Supercritical CO2 permeation in glassy polyimide membranes." Journal of Membrane Science 620, no. : 118922.

Journal article
Published: 17 July 2020 in Membranes
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Metal-organic frameworks (MOFs) as additives in mixed matrix membranes (MMMs) for gas separation have gained significant attention over the past decades. Many design parameters have been investigated for MOF based MMMs, but the spatial distribution of the MOF throughout MMMs lacks investigation. Therefore, magnetically aligned and enriched pathways of zeolitic imidazolate framework 8 (ZIF−8) in Matrimid MMMs were synthesized and investigated by means of their N2 and CO2 permeability. Magnetic ZIF−8 (m–ZIF−8) was synthesized by incorporating Fe3O4 in the ZIF−8 structure. The presence of Fe3O4 in m–ZIF−8 showed a decrease in surface area and N2 and CO2 uptake, with respect to pure ZIF−8. Alignment of m–ZIF−8 in Matrimid showed the presence of enriched pathways of m–ZIF−8 through the MMMs. At 10 wt.% m–ZIF−8 incorporation, no effect of alignment was observed for the N2 and CO2 permeability, which was ascribed anon-ideal tortuous alignment. However, alignment of 20 wt.% m–ZIF−8 in Matrimid showed to increase the CO2 diffusivity and permeability (19%) at 7 bar, while no loss in ideal selectivity was observed, with respect to homogeneously dispersed m–ZIF−8 membranes. Thus, the alignment of MOF particles throughout the matrix was shown to enhance the CO2 permeability at a certain weight content of MOF.

ACS Style

Machiel Van Essen; Esther Montrée; Menno Houben; Zandrie Borneman; Kitty Nijmeijer. Magnetically Aligned and Enriched Pathways of Zeolitic Imidazolate Framework 8 in Matrimid Mixed Matrix Membranes for Enhanced CO2 Permeability. Membranes 2020, 10, 155 .

AMA Style

Machiel Van Essen, Esther Montrée, Menno Houben, Zandrie Borneman, Kitty Nijmeijer. Magnetically Aligned and Enriched Pathways of Zeolitic Imidazolate Framework 8 in Matrimid Mixed Matrix Membranes for Enhanced CO2 Permeability. Membranes. 2020; 10 (7):155.

Chicago/Turabian Style

Machiel Van Essen; Esther Montrée; Menno Houben; Zandrie Borneman; Kitty Nijmeijer. 2020. "Magnetically Aligned and Enriched Pathways of Zeolitic Imidazolate Framework 8 in Matrimid Mixed Matrix Membranes for Enhanced CO2 Permeability." Membranes 10, no. 7: 155.