First Clear-Cut Experimental Evidence of a Glass Transition in a Polymer with Intrinsic Microporosity: PIM-1

Yin, Huajie; Chua, Yeong Zen; Yang, Bin; Schick, Christoph; Harrison, Wayne; Budd, Peter M.; Böhning, Martin; Schönhals, Andreas

doi:10.1021/acs.jpclett.8b00422

Cited by 79 publications

(93 citation statements)

References 40 publications

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“…61 The architectural attributes for AquaPIMs 1-3 take form as a microporous polymer membrane for aqueous electrochemical devices by solvent casting since the T g for PIMs is higher than their temperature of decomposition (i.e., PIMs are not thermally processable). 62 We prepared both freestanding and supported membranes using solvent-casting techniques from inks formulated in N-methyl-2-pyrrolidone (100-300 mg mL À1 ). Of the three polymers, membranes cast from AquaPIM 1 were the most robust to handle a wide range of electrolyte formulations and membrane thicknesses, on or off a support such as Celgard 3501.…”

Section: Resultsmentioning

confidence: 99%

Design Rules for Membranes from Polymers of Intrinsic Microporosity for Crossover-free Aqueous Electrochemical Devices

Baran

Braten

Sahu

et al. 2019

Joule

102

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Placement of amidoxime functionalities within the pores of microporous polymer membranes yields a new family of selective membranes for aqueous electrochemical cells-which we call AquaPIMs. At high pH, where amidoximes are ionized, AquaPIM membranes feature concomitantly high conductivity and transport selectivity when compared to other membranes, including Nafion. Design rules are laid out, tying membrane architecture and pore chemistry to membrane stability, conductivity, and transport selectivity in aqueous electrolytes over a broad range of pH. These attributes dictate whether it is possible to operate aqueous electrochemical cells without the influence of active-material crossover.

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Section: Resultsmentioning

confidence: 99%

Design Rules for Membranes from Polymers of Intrinsic Microporosity for Crossover-free Aqueous Electrochemical Devices

Baran

Braten

Sahu

et al. 2019

Joule

102

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“…All reported measurements were conducted in air atmosphere, because no differences were found between measurements carried out in air and under protective argon atmosphere. Results for PIM-1 have been reported earlier 26 and are included here for comparison with PIM-EA-TB and DMDPH-TB. The Tg of PIM-EA-TB was first roughly located between 600 K and 800 K by analyzing images of the sample after each heating run carried out by increasing the upper temperature limit stepwise.…”

mentioning

confidence: 99%

“…Consistent with the ladder-like rigid structure of PIM-EA-TB this value is high and, as expected, also higher than the Tg of PIM-1 (644 K) at the same heating rate (see below). 26 Pictures of the PIM-EA-TB film on the sensor surface were taken under a microscope after subsequent heating runs at 10 4 K s -1 ( Figure S1 in the Supporting Information). Figures 2C and 2D display the effect when the glass transition region is crossed.…”

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confidence: 99%

Effect of Backbone Rigidity on the Glass Transition of Polymers of Intrinsic Microporosity Probed by Fast Scanning Calorimetry

et al. 2019

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Polymers of Intrinsic Microporosity (PIMs) of high performance have developed as materials with a wide application range in gas separation and other energy-related fields. Further optimization and long-term behavior of devices with PIMs require an understanding of the structure-property relationships including physical aging. In this context the glass transition plays a central role, but with conventional thermal analysis a glass transition is usually not detectable for PIMs before their thermal decomposition. Fast scanning calorimetry provides evidence of the glass transition for a series of PIMs, as the time scales responsible for thermal degradation and for the glass transition are decoupled by employing ultrafast heating rates of tens of thousands K s-1. The investigated PIMs were chosen considering the chain rigidity. The estimated glass transition temperatures follow the order of the rigidity of the backbone of the PIMs.

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“…After curing, this peak should reduce or disappear. PIM polymers are thermally stable that no T g can be observed before the polymer degradation . As‐electrospun and thermally treated HPIM NFM shows no difference in DSC, they both give two endothermic peaks at 158 and 218 °C.…”

Section: Resultsmentioning

confidence: 98%

Fabrication of Thermally Crosslinked Hydrolyzed Polymers of Intrinsic Microporosity (HPIM)/Polybenzoxazine Electrospun Nanofibrous Membranes

Satilmiş

Uyar

2018

Macro Chemistry & Physics

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In this study, thermally crosslinked hydrolyzed polymers of intrinsic microporosity (HPIM)/polybenzoxazine electrospun nanofibrous membranes (NFMs) are successfully produced. The nanofibers having 800 ± 260 to 670 ± 150 nm average fiber diameters from HPIM and blends of HPIM/ benzoxazine (BA‐a) ranging from HPIM:(BA‐a) weight ratio of 9:1 to 2:1 w/w are produced by electrospinning. Self‐standing HPIM/(BA‐a) NFMs are thermally step‐wise cured resulting in crosslinked HPIM/Poly(BA‐a) NFMs. Structural characterization of as‐electrospun HPIM/(BA‐a) and crosslinked HPIM/Poly(BA‐a) NFM is conducted by FT‐IR spectroscopy to trace the ring opening and crosslinking reactions. Elemental analysis and XPS studies show an increase in carbon content and reduction in nitrogen content due to the crosslinking reaction. Decomposition temperature (T d) of HPIM NFM increases from 218 to 270 °C with the crosslinking based on the DSC. DMA analysis shows that the mechanical strength of the NFMs has increased significantly with crosslinking. Young's moduli of HPIM NFM is increased from 16 ± 7 to 67 ± 1 MPa for crosslinked HPIM/Poly(BA‐a)%33 NFM. Similarly, higher storage modulus is observed for HPIM/Poly(BA‐a) NFMs compared to HPIM NFM. The crosslinked HPIM/Poly(BA‐a) NFMs keep their fibrous morphology after solvent treatment in dimethylformamide revealing their structural stability compared to pristine HPIM NFM.

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First Clear-Cut Experimental Evidence of a Glass Transition in a Polymer with Intrinsic Microporosity: PIM-1

Cited by 79 publications

References 40 publications

Design Rules for Membranes from Polymers of Intrinsic Microporosity for Crossover-free Aqueous Electrochemical Devices

Design Rules for Membranes from Polymers of Intrinsic Microporosity for Crossover-free Aqueous Electrochemical Devices

Effect of Backbone Rigidity on the Glass Transition of Polymers of Intrinsic Microporosity Probed by Fast Scanning Calorimetry

Fabrication of Thermally Crosslinked Hydrolyzed Polymers of Intrinsic Microporosity (HPIM)/Polybenzoxazine Electrospun Nanofibrous Membranes

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