Pure and mixed fluid sorption and transport in Celazole® polybenzimidazole: Effect of plasticization

Bye, Kelly P.; Loianno, Valerio; Pham, Tram Ngoc; Liu, Ran; Riffle, Judy S.; Galizia, Michele

doi:10.1016/j.memsci.2019.03.031

Cited by 36 publications

(30 citation statements)

References 62 publications

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“…The trend of the Fickian diffusivity at 25 C as a function of concentration (cf. Figure 5e) is consistent with the results of barometric sorption experiments [15] . However, diffusion coefficients retrieved via FTIR experiments are about one order of magnitude lower compared to those obtained during barometric sorption experiments (cf.…”

Section: Sorption Equilibrium and Kinetics Obtained Via Ftir Spectrsupporting

confidence: 90%

“…Figure 5E and Ref. [15]). The latter, indeed, would cause a marked decrease of diffusion coefficient with concentration.…”

Section: Absorbance Spectramentioning

confidence: 81%

“…where M ∞ is the mass of penetrant sorbed at equilibrium, α is the fraction of penetrant sorbed during the relaxation stage, τ is the relaxation time, L is the film thickness, and D is the concentration-averaged diffusion coefficient evaluated over the concentration jump during the sorption experiment [15] :…”

Section: Small Molecule Diffusion and Transport In Polymersmentioning

confidence: 99%

“…They were prepared using the same protocol as for FTIR measurements. LiCl was completely removed from the PBI samples by soaking them in deionized water for 48 hr [6,15,23] . In both the laboratories, water (99.99% grade) and methanol (99.8% grade) were purchased from Sigma-Aldrich.…”

Section: Membrane Fabricationmentioning

confidence: 99%

“…Such information is crucial to develop robust membrane materials for organic solvent nanofiltration (OSN). Recently, Bye et al [ 15 ] reported that PBI undergoes plasticization upon exposure to liquid methanol, which is one of the most used organic solvents in the chemical industry. To explain the molecular origin of PBI plasticization, the competitive hydrogen bonding mechanism was hypothesized.…”

Section: Introductionmentioning

confidence: 99%

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Plasticization mechanism in polybenzimidazole membranes for organic solvent nanofiltration: Molecular insights from in situ FTIR spectroscopy

Loianno

Bye

Galizia

et al. 2020

Journal of Polymer Science

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Despite substantial research efforts being devoted to design polymer membranes for organic solvent nanofiltration (OSN) exhibiting enhanced plasticization resistance, detailed studies of membrane structural stability in chemically challenging environments are rare. This study sets forth a multiscale method, which combines in situ FTIR measurements in the transmission mode with sorption and transport measurements, to investigate the molecular mechanism of polymer plasticization upon exposure to organic species. We recently reported that polybenzimidazole (PBI), a polymer that has been considered for OSN application, experiences severe plasticization upon exposure to methanol. FTIR measurements suggest that the mechanism of PBI plasticization relies on competitive hydrogen bonding. According to this mechanism, methanol molecules disrupt the hydrogen bonded network characteristic of dry PBI, by forming mutual polymer/penetrant hydrogen bonds, which enhances polymer chain mobility and favors polymer plasticization. The analysis of the isosteric heat of sorption supports the picture sketched above. The method developed in this study can be readily extended to many other systems of practical interest in membrane science, to shed fundamental light on the phenomenon of plasticization, whose molecular aspects are still largely unknown. Equally important, this study provides some useful guidelines to design OSN membrane materials.

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Section: Sorption Equilibrium and Kinetics Obtained Via Ftir Spectrsupporting

confidence: 90%

“…Figure 5E and Ref. [15]). The latter, indeed, would cause a marked decrease of diffusion coefficient with concentration.…”

Section: Absorbance Spectramentioning

confidence: 81%

Section: Small Molecule Diffusion and Transport In Polymersmentioning

confidence: 99%

Section: Membrane Fabricationmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Plasticization mechanism in polybenzimidazole membranes for organic solvent nanofiltration: Molecular insights from in situ FTIR spectroscopy

Loianno

Bye

Galizia

et al. 2020

Journal of Polymer Science

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Regulating Molecular Interactions in Polybenzimidazole Membrane for Efficient Vanadium Redox Flow Battery

Su,

Liu,

Zhu

et al. 2024

ChemSusChem

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The tightly bonded structure of polybenzimidazole (PBI) membrane is the origin of its poor proton conductivity, which severely hinders achieving a cost‐effective membrane for vanadium redox flow battery (VRFB). It desires a strategy to relax the membrane structure to significantly improve the proton conductivity and maintain its structure stability. Therefore, this work proposes a novel strategy through regulating molecular interactions within PBI membrane to loosen up the structure of PBI membrane and dramatically enhance the proton conductivity. The interactions in PBI membrane are switched by DMSO/water and acid through sequentially treating membrane with these solutions. The efficient PBI membrane prepared using this strategy demonstrates an outstanding performance for VRFB, with the proton conductivity enhanced by 3850% (from 1.9 to 76.3 mS cm−1), and VRFB achieves a high energy efficiency of 80.5% under 200 mA cm−2. More importantly, this work shed lights on the structure‐property relationship of PBI membrane, and the mechanism in enhancing proton conductivity is unraveled, which is of great significance for the development of VRFB membranes.

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Characterization of swelling behavior and elastomer properties of acrylate polymers containing 2-ethylhexyl and isobornyl esters

et al. 2022

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In this work, a comparative study of the swelling behavior of poly (1, 7, 7-trimethyl-2-bicyclo [2.2.1] heptanyl) prop-2-enoate) (poly (IBOA)) and its copolymer (poly (IBOA)-co-2-EHA)), prepared by radical polymerization with the addition of a low concentration of crosslinking agent and photoinitiator, was performed. The obtained networks were characterized by FTIR to show the conversion of acrylic band before and after polymerization and by differential scanning calorimetry (DSC).The copolymer network has a single glass transition temperature (Tg) that decreases relative to the poly (IBOA). The swelling study of (poly (IBOAco-2-EHA) was carried out by gravimetric method, in a series of polar (methanol, ethanol, propan-1-ol, butan-1-ol, pentan-1-ol, hexan-1-ol and heptan-1-ol) and non-polar (toluene) isotropic solvents. Solubility, interaction and diffusion parameters that influence the swelling of copolymer in the solvents were calculated. The wellestablished order of swelling (toluene > heptan-1-ol > hexan-1-ol > pentan-1-ol > butan-1-ol > propan-1-ol > ethanol > methanol) in the copolymer was clearly observed and moreover the degree of swelling increased with the presence of EHA in the copolymer. A simple diffusion model was applied (Fick's model) to interpret the swelling data. It was found that the nature of solvent shifts the mechanism from diffusion-controlled in the case of alcohols to non Fickian one for toluene. For a long period, the experimental results were well correlated with the second order diffusion kinetics of Schott.

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Pure and mixed fluid sorption and transport in Celazole® polybenzimidazole: Effect of plasticization

Cited by 36 publications

References 62 publications

Plasticization mechanism in polybenzimidazole membranes for organic solvent nanofiltration: Molecular insights from in situ FTIR spectroscopy

Plasticization mechanism in polybenzimidazole membranes for organic solvent nanofiltration: Molecular insights from in situ FTIR spectroscopy

Regulating Molecular Interactions in Polybenzimidazole Membrane for Efficient Vanadium Redox Flow Battery

Characterization of swelling behavior and elastomer properties of acrylate polymers containing 2-ethylhexyl and isobornyl esters

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