Sorption and dilation properties of poly(<i>p</i>‐phenylene sulfide) under high‐pressure carbon dioxide

Bourbon, Dominique; Kamiya, Yuichi; Mizoguchi, Keishin

doi:10.1002/polb.1990.090281112

Cited by 12 publications

(6 citation statements)

References 24 publications

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“…Partial molar volumes of carbon dioxide in 13 different rubbery polymers as a function of temperature: polybutadiene (PB), poly(ethylene- co -vinyl acetate) (PE- co -VA), poly(vinylidene fluoride) (PVDF), , low-density polyethylene (PE), poly(ethyl methacrylate) (PEMA), poly(dimethyl siloxane) (PDMS), ,,,, poly(tetrafluoroethylene- co -perfluoromethylvinylether) (PTFE- co -MVE), poly(tetrafluoroethylene) (PTFE), poly( p -phenylene sulfide) (PPS), poly(ethylene terephthalate) (PET), poly(benzyl methacrylate) (PBMA), poly(methyl methacrylate) (PMMA), and cross-linked poly(ethylene oxide) (XLPEO, this work). The line corresponds to the prediction of eq 15.…”

Section: Resultsmentioning

confidence: 99%

“…where V j CO2 is given in cm 3 /mol and T in K. Following this standard data treatment procedure, we compare our PMVs for CO 2 in XLPEO with available literature data for 12 rubbery polymers [51][52][53][54][55]57,[62][63][64][65][66][67][68][69][70] in Figure 9. The prediction of eq 15 is also included in the referred figure as a continuous line.…”

Section: Partial Molar Volumesmentioning

confidence: 99%

“…The explanation is given in terms of the internal pressure of the liquid solvent, π, which is directly linked to the solubility parameter (π ≈ δ 2 ). The solute is thought to behave like a gas being compressed to its liquid-like volume by the internal pressure 52 poly(ethylene-co-vinyl acetate) (PE-co-VA), 54 poly(vinylidene fluoride) (PVDF), 68,70 low-density polyethylene (PE), 51 poly(ethyl methacrylate) 53 (PEMA), poly(dimethyl siloxane) (PDMS), 57,62,66,67,69 poly-(tetrafluoroethylene-co-perfluoromethylvinylether) (PTFE-co-MVE), 70 poly(tetrafluoroethylene) (PTFE), 70 poly(p-phenylene sulfide) (PPS), 65 poly(ethylene terephthalate) (PET), 64 poly(benzyl methacrylate) (PB-MA), 55 poly(methyl methacrylate) (PMMA), 63 and cross-linked poly-(ethylene oxide) (XLPEO, this work). The line corresponds to the prediction of eq 15.…”

Section: Partial Molar Volumesmentioning

confidence: 99%

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Sorption, Dilation, and Partial Molar Volumes of Carbon Dioxide and Ethane in Cross-Linked Poly(ethylene oxide)

Ribeiro

Freeman

2008

Macromolecules

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Experimental gas solubility and sorptive dilation data are reported for carbon dioxide and ethane in a cross-linked poly(ethylene oxide) rubber prepared by photopolymerization of poly(ethlyene glycol)diacrylate. Five different operating temperatures (253 e T (K) e 308) were considered, with a maximum gas pressure of 2.16 MPa (21.3 atm). The importance of taking sorptive dilation into account in the determination of gas solubility in polymers by the pressure-decay method was demonstrated. Sorption isotherms in terms of gas fugacity were described by the Flory-Huggins model. In the case of ethane, the Flory-Huggins interaction parameter was a decreasing function of temperature. In contrast, for carbon dioxide, a single parameter represented all isotherms. Dilation and sorption data were combined to calculate the partial molar volume (PMV) of the gases in the polymer, which was an increasing function of temperature. The PMV data were compared to the available literature data for other rubbery polymers and liquids. The chemical structure of the polymer influenced the PMV of the sorbed gas, and a correlation between matrix (i.e., solvent or polymer) solubility parameter and PMV was found.

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Section: Resultsmentioning

confidence: 99%

Section: Partial Molar Volumesmentioning

confidence: 99%

Section: Partial Molar Volumesmentioning

confidence: 99%

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Sorption, Dilation, and Partial Molar Volumes of Carbon Dioxide and Ethane in Cross-Linked Poly(ethylene oxide)

Ribeiro

Freeman

2008

Macromolecules

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“…In both cases, sorption is “irreversible” (i.e., the microscopic pathways for uptake and release are different). The pore deformation mechanism has precedence in the sorption of gases to glassy synthetic polymers (Kamiya et al, 1989; Bourbon et al, 1990; Stamatialis et al, 1997; Kamiya et al, 1998). In brief, the unrelaxed free volume of the sorbent is postulated to increase during the sorption step as a result of pore (“hole”) creation and dilation of existing holes.…”

Section: Hysteresis Indices (Hi) In the Literaturementioning

confidence: 99%

A Thermodynamically Based Method to Quantify True Sorption Hysteresis

2005

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Sorption of organic chemicals to soils and sediments often shows true hysteresis (i.e., nonsingularity of the sorption-desorption isotherm not attributable to known experimental artifacts). Since true sorption hysteresis is fundamentally important to contaminant fate, a way to quantify it is desirable. Previously proposed indices of hysteresis are empirical and usually depend on the isotherm model. True sorption hysteresis to synthetic and natural organic solids has been attributed to irreversible alteration of the solid during the sorption-desorption cycle. Given this mechanism, we propose the Thermodynamic Index of Irreversibility (TII) for quantifying hysteresis in soils where natural organic matter dominates the sorption process. The TII is based on the difference in free energy between the real desorption state and the hypothetical fully reversible state. The index is 0 for completely reversible systems and approaches 1 as the process tends toward complete irreversibility. It does not require any assumptions about the physical properties or molecular composition of the solid, and it does not depend on a specific equilibrium model. A sensitivity analysis of measurement errors provides general recommendations for the setup of sorption-desorption experiments. The TII was applied to sorption of 1,4-dichlorobenzene (DCB) to two high-organic soils, Pahokee peat (PP) and Amherst soil (AS), and a low-rank coal reference material, Beulah-Zap lignite (BZL). Common artificial causes of hysteresis were eliminated. Hysteresis was significant in the peat and the coal. The TII was clearly concentration dependent for both solids; it decreased with concentration for the peat, but increased with concentration for the coal. The TII allows quantification of hysteresis as a function of sorbate-sorbent combination, concentration, time, and other variables.

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“…Metal ion adsorption on inorganic surfaces may involve metastable complexes with the surface that evolve into more stable complexes or precipitates over time ( , ). Sorption hysteresis of gases, vapors, and solutes in glassy organic polymers is due to metastability in the sorbent itself ( − ). This mechanism is commonly referred to as “low-pressure” () or “pore-deformation” hysteresis.…”

Section: Introductionmentioning

confidence: 99%

An Isotope Exchange Technique to Assess Mechanisms of Sorption Hysteresis Applied to Naphthalene in Kerogenous Organic Matter

Sander

Pignatello

2005

Environ. Sci. Technol.

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The sorption of organic compounds to natural sorbents is often found to show hysteresis. The objective of this study was to develop an experimental technique based on the use of 14C isotopes to distinguish hysteresis due to experimental artifacts from true hysteresis due to thermodynamically irreversible processes. The study was also designed to investigate causation of true hysteresis (irreversible sorption). The technique determines the rates and the degree of isotope exchange (IE) on equilibrated sorption and desorption points at different constant bulk chemical concentrations. The technique was applied to the sorption of naphthalene (NAPH) on Beulah-Zap lignite, a low rank reference coal composed mainly of kerogen. Sorption of bulk was found to be reversible below 10(-5) g L(-1), but irreversible above 10(-4) g L(-1). Complete isotope exchange on sorption and desorption points that defined an irreversible cycle demonstrated that hysteresis was true. A comparison of normalized uptake and release kinetics of labeled and bulk NAPH at different concentrations revealed slow structural deformation processes of the sorbent during bulk sorption and desorption. This is taken as corroborating evidence for the pore deformation hypothesis of hysteresis in which incoming sorbate molecules induce quasi-reversible changes in the organic matter that lead to different pathways for sorption and desorption. Although unable to rule it out completely, the data demonstrate that physical entrapment of sorbate molecules plays a minor, if any, role to the observed hysteresis in this system.

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Sorption and dilation properties of poly(p‐phenylene sulfide) under high‐pressure carbon dioxide

Cited by 12 publications

References 24 publications

Sorption, Dilation, and Partial Molar Volumes of Carbon Dioxide and Ethane in Cross-Linked Poly(ethylene oxide)

Sorption, Dilation, and Partial Molar Volumes of Carbon Dioxide and Ethane in Cross-Linked Poly(ethylene oxide)

A Thermodynamically Based Method to Quantify True Sorption Hysteresis

An Isotope Exchange Technique to Assess Mechanisms of Sorption Hysteresis Applied to Naphthalene in Kerogenous Organic Matter

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