Physical Constants of Poly(vinyl chloride)

Collins, E. A.; Daniels, Charles A.; Witenhafer, D. E.

doi:10.1002/0471532053.bra028

Cited by 3 publications

(5 citation statements)

References 95 publications

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“…The more excess free volume a polymer has, the more sorption sites are available that can accommodate penetrant molecules without requiring the creation of gaps in the polymer. TFE/BDD87 has a high excess free volume fraction (0.21 based on volume dilatometry estimates), while the excess free volume fraction of PVC is only 0.03 based on carbon dioxide sorption data . For penetrant molecules that partition into the densified matrix, the energy required to mix penetrant and polymer is proportional to the mismatch in their solubility parameters .…”

Section: Resultsmentioning

confidence: 99%

“…TFE/BDD87 has a high excess free volume fraction (0.21 based on volume dilatometry estimates), 7 while the excess free volume fraction of PVC is only 0.03 based on carbon dioxide sorption data. 29 For penetrant molecules that partition into the densified matrix, the energy required to mix penetrant and polymer is proportional to the mismatch in their solubility parameters. 17 All of the penetrants examined in this study have solubility parameters lower than that of TFE/BDD87 (δ ) 8.2 (cal/cm 3 ) 1/2 ), 30 while the solubility parameter of PVC is 9.4 (cal/cm 3 ) 1/2 .…”

Section: Solubilitymentioning

confidence: 99%

See 1 more Smart Citation

Gas Sorption, Diffusion, and Permeation in Poly(2,2-bis(trifluoromethyl)-4,5-difluoro-1,3-dioxole-co-tetrafluoroethylene)

et al. 1999

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The solubility and permeability of H2, O2, N2, CO2, CH4, C2H6, C3H8, CF4, C2F6, and C3F8 in TFE/BDD87, a random copolymer prepared from 87 mol % 2,2-bis(trifluoromethyl)-4,5-difluoro-1,3-dioxole [BDD] and 13 mol % tetrafluoroethylene [TFE], are reported as a function of temperature and pressure. Sorption isotherms of all penetrants except hydrogen are concave to the pressure axis and are well-described by the dual-mode model. Hydrogen exhibits linear sorption isotherms. In contrast to previous results in hydrocarbon-rich polymers, the solubility of perfluorocarbon penetrants is higher in TFE/BDD87 than that of their hydrocarbon analogues. The solubility of all penetrants in TFE/BDD87 decreases with increasing temperature. Enthalpies of sorption become more negative as penetrant size increases. Fluorocarbon enthalpies of sorption at infinite dilution are significantly more exothermic than those of their hydrocarbon analogues, suggesting more favorable interactions between fluorocarbon penetrants and perfluorinated TFE/BDD87 than between hydrocarbon penetrants and this polymer. Perfluorocarbon permeability coefficients are nearly an order of magnitude lower than those of their hydrocarbon analogues due to the larger size of the fluorocarbons and their subsequently lower diffusivities. The permeability of TFE/BDD87 increases with increasing temperature, indicating that activation energies of permeation (E p) are positive. E p values in TFE/BDD87 are smaller than those of conventional glassy polymers. Diffusion coefficients of the lower sorbing gases (O2, N2, CO2, CH4, CF4) exhibit a concentration dependence that is consistent with dual-mode transport in unplasticized glassy polymers. For more strongly sorbing C2H6, C3H8, C2F6, and C3F8, diffusion coefficients increase exponentially with increasing penetrant concentration, suggesting plasticization. Activation energies of diffusion in TFE/BDD87 are positive and increase linearly with penetrant diameter squared. Relative to conventional glassy polymers, E D values in TFE/BDD87 are low. However, |E D| is larger than |ΔH S|. TFE/BDD87 is easily plasticized by the larger, more soluble penetrants and is susceptible to penetrant-induced conditioning. The level of conditioning is highest for the largest, most soluble penetrant examined (C3F8), and the conditioned state gradually relaxes toward that of the as-cast state.

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Section: Resultsmentioning

confidence: 99%

Section: Solubilitymentioning

confidence: 99%

Gas Sorption, Diffusion, and Permeation in Poly(2,2-bis(trifluoromethyl)-4,5-difluoro-1,3-dioxole-co-tetrafluoroethylene)

et al. 1999

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“…The diffusion coefficient of phenobarbital in 33% PVC/DOS membranes is in the order of 10 -8 cm 2 /s . Diffusion coefficients for small, aromatic, organic molecules such as benzene in pure PVC are ∼10 -13 cm 2 /s . Therefore, it is reasonable to think that the higher the polymer content, the slower the diffusional kinetics will be.…”

Section: Resultsmentioning

confidence: 99%

“…In calculating δ H 2 of a plasticized PVC membrane, we have used the volume-weighted average δ H 2 of the components as shown in eq 1, where Φ p and Φ d are volume fractions of PVC and DOS in the membrane phase, respectively. δ Hp 2 and δ Hd 2 are cohesive energy densities of PVC and DOS …”

Section: Methodsmentioning

confidence: 99%

Effect of Polymer Concentration on Partitioning and Molecular Recognition in Plasticized Poly(vinyl chloride)

Zhao

Chen

et al. 2003

Anal. Chem.

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Mixtures of poly(vinyl chloride) (PVC) with plasticizers have been used in ion-selective electrodes for many years. The same material has proven useful in solid-phase microextraction (SPME), both with and without artificial receptors. We hypothesized that by changing the polymer concentration in plasticized PVC membranes containing artificial receptor from the standard 33 wt %, the selectivity of the extraction of barbiturates over similar molecules could be improved. Partition coefficients and receptor-substrate formation constants of a target species, phenobarbital, in membranes with various polymer concentrations were determined. Diffusion coefficients of the solute phenobarbital in receptor-free membranes were also determined. Kamlet-Taft solvatochromic properties beta and pi* were measured for the PVC/dioctyl sebacate materials. Cohesive energy densities were calculated for the same materials. Partition coefficients for phenobarbital (from aqueous solution to membrane) decrease as [PVC] increases, while the formation constants for the complex of the solute with its receptor increase. Diffusion coefficients decrease as the polymer concentration increases as well. The increase in polymer concentration brings about a decrease in hydrogen-bonding basicity and an increase in dipolarity and cohesive energy density. The values of the solvatochromic parameters determined at various compositions are highly correlated; thus, it is impossible to calculate how much each factor contributes to the changes associated with partition and complex formation. The solvatochromic "polarizability correction factor" has been determined to be 0 for PVC. In SPME experiments at 30%, 40%, and 50% (w/w) PVC, as polymer concentration increases, selectivity for barbiturate extraction over other cyclic imides becomes better in the presence of barbiturate receptor and worse without receptor.

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“… λ (nm) n 589 T (°C) Ref. Remark 486.1 1.54806 [3] 589.3 1.54151 [3] 656.3 1.53843 [3] 589.3 1.54–1.55 [4] 589.3 1.52–1.57 [5] 589 1.4831 20 [5] 589 1.5381 20 [5] 589 1.5066 20 [5] PVC molding compound—rigid 589 1.541 25 [5] 589 1.484 25 [5] rigid 589 1.52–1.55 [5] rigid 589 1.539 [6] 589 1.539 [7] – 1.548 27 [8] Method: grain immersion method 589 1.55 [9] 589 1.57 [10] Method: Benford refractometer 589 1.544 [7] …”

Section: Datamentioning

confidence: 99%

Scattering-angle-dependent Christiansen color spectra data of poly(vinyl chloride) (PVC) suspended in styrene liquid and a comprehensive data list of wavelength-dependent refractive indices of PVC

2018

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This paper reports transmission and scattering spectra of poly(vinyl chloride) (PVC) in styrene liquid, which is derived from Christiansen effect. The spectra were measured by varying scattering angles. Further discussion on Christiansen color was provided in the paper entitled "Transmitting and scattering colors of porous particles of poly(vinyl chloride) based on Christiansen effect" (Samitsu et al., 2018) [1]. The paper additionally provides refractive indices of PVC reported in literatures because Christiansen effect has close relationship with wavelength-dependent refractive index, i.e. optical dispersion. The values have considerable range probably depending on samples and determination methods for refractive index. The comprehensive data list is therefore potentially useful for studying refractive index of polymers.

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Physical Constants of Poly(vinyl chloride)

Cited by 3 publications

References 95 publications

Gas Sorption, Diffusion, and Permeation in Poly(2,2-bis(trifluoromethyl)-4,5-difluoro-1,3-dioxole-co-tetrafluoroethylene)

Gas Sorption, Diffusion, and Permeation in Poly(2,2-bis(trifluoromethyl)-4,5-difluoro-1,3-dioxole-co-tetrafluoroethylene)

Effect of Polymer Concentration on Partitioning and Molecular Recognition in Plasticized Poly(vinyl chloride)

Scattering-angle-dependent Christiansen color spectra data of poly(vinyl chloride) (PVC) suspended in styrene liquid and a comprehensive data list of wavelength-dependent refractive indices of PVC

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