Transport properties of crosslinked acrylonitrile butadiene rubber/poly(ethylene‐co‐vinyl acetate) blends

The diffusion and transport of organic solvents through crosslinked nitrile rubber/poly(ethylene‐co‐vinyl acetate) (NBR/EVA) blends have been studied. The diffusion of cyclohexanone through these blends was studied with special reference to blend composition, crosslinking systems, fillers, filler loading, and temperature. At room temperature the mechanism of diffusion was found to be Fickian for cyclohexanone–NBR/EVA blend systems. However, a deviation from the Fickian mode of diffusion is observed at higher temperature. The transport coefficients, namely, intrinsic diffusion coefficient (D*), sorption coefficient (S), and permeation coefficient (P) increase with the increase in NBR content. The sorption data have been used to estimate the activation energies for permeation and diffusion. The van't Hoff relationship was used to determine the thermodynamic parameters. The affine and phantom models for chemical crosslinks were used to predict the nature of crosslinks. The experimental results were compared with the theoretical predictions. The influence of penetrants transport was studied using dichloromethane, chloroform, and carbon tetrachloride. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1815–1831, 1999     

Solubility and diffusivity of methylmethacrylate and butylacrylate monomers in a MMA–BA copolymer

Mutual diffusion coefficients and sorption isotherms of methyl methacrylate (MMA) and butyl acrylate (BA) monomers in methyl methacrylate‐butyl acrylate copolymer (MMA‐BA) have been measured by gravimetric sorption. MMA is found to have higher solubility and diffusion rates in the copolymer than BA. Sorption data for MMA were interpreted using classical Flory‐Huggins thermodynamic theory with a constant interaction parameter (χ). A modified version of this theory has been applied to correlate the sorption data of BA, which exhibit a temperature and concentration‐dependent χ parameter. For MMA, the isotherm data reveal enhanced polymer‐solvent interactions with increasing temperature, while for BA the data indicate a drive toward phase separation with increasing temperature. Despite the difference in thermodynamic behavior, both monomers are found to exhibit Fickian diffusion and the diffusivity data are correlated reasonably well with the Vrentas‐Duda free volume theory. Some deviation between the free‐volume correlation and the experimental data is observed at the lowest temperature and BA concentration examined. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1996–2006, 2007     

Cure temperature influence on natural rubber—A small angle X‐ray scattering study

To analyze the natural rubber behavior during vulcanization under different cure treatments, an experimental investigation using small angle X‐ray scattering was performed. To achieve this, a set of samples were prepared using sulfur and N‐t‐butyl‐2‐benzothiazole sulfenamide as accelerator and then cured at temperatures between 403 and 463 K reaching their optimum mechanical properties considering rheometer tests. The crosslink density of the samples was evaluated by means of the swelling technique in solvent. In the usual Lorentz corrected representation of the X‐ray scattered intensity, a maximum was observed in the plots corresponding to the cured samples, revealing a highly correlated structure. This maximum shifted toward higher values of the scattering vector when the cure temperature of the samples increased. This behavior is discussed in terms of the crosslinks type present in the vulcanized rubber network at different cure temperatures. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2966–2971, 2007     

Molecular transport of aromatic hydrocarbons through nylon‐6/ethylene propylene rubber blends: Relationship between phase morphology and transport characteristics

Molecular transport of aromatic hydrocarbons through nylon/ethylene propylene rubber (EPR) blend has been investigated in the temperature range of 25 to 65 °C. The effect of blend ratio on the transport behavior was studied in detail. Nylon/EPR‐50/50 blend shows the lowest uptake among all the systems studied. This behavior is related to blend morphology, density, and crystallinity of the blend composition. The transport property was correlated with the extent of interfacial adhesion in the blends. The effects of temperature and penetrant size on the sorption behavior were examined. Thermodynamic and Arrhenius parameters were evaluated from the diffusion data. Theoretical and experimental diffusion results were compared. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2136–2153, 2000     

Transport and mechanical properties of blends of poly(ϵ‐caprolactone) and a modified montmorillonite‐ poly(ϵ‐caprolactone) nanocomposite

The structural characterization and transport properties of blends of a commercial high molecular weight poly(?‐caprolactone) with different amounts of a montmorillonite‐poly(?‐caprolactone) nanocomposite containing 30 wt % clay were studied. Two different vapors were used for the sorption and diffusion analysis—water as a hydrophilic permeant and dichloromethane as anorganic permeant—in the range of vapor activity between 0.2 and 0.8. The blends showed improved mechanical properties in terms of flexibility and drawability as compared with the starting nanocomposites. The permeability (P), calculated as the product of the sorption (S) and the zero‐concentration diffusion coefficient (D₀), showed a strong dependence on the clay content in the blends. It greatly decreased on increasing the montmorillonite content for both vapors. This behavior was largely dominated by the diffusion parameters. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1118–1124, 2002     

Sorption and pervaporation properties of sulfonyl‐containing polyimide membrane to aromatic/non‐aromatic hydrocarbon mixtures

Sorption of single‐component vapors of benzene (Bz), n‐hexane (Hx), and cyclohexane (Cx), and of binary liquid mixtures of Bz/Hx and Bz/Cx in a polyimide from 3,3′,4,4′‐diphenylsulfone‐tetracarboxylic dianhydride (DSDA) and 2,8(6)‐dimethyl‐3,7‐diaminobenzothiophene‐5,5‐dioxide (DDBT) were investigated in detail at 333 K. Sorption and desorption of vapors followed the non‐Fickian kinetics and the sorption isotherms were concave to the vapor activity. For the binary liquids, the sorption isotherms of the Bz component were concave to the Bz composition in feed, whereas those of Hx and Cx were convex because of competitive sorption. As a result, the solubility selectivity was much larger than the sorption ratio of pure liquids. The concentration‐averaged diffusion coefficients of Bz (D̄_Bz) and Hx (D̄_Hx) were evaluated using the sorption and pervaporation data of the polyimide membrane toward the binary mixtures. A kind of coupling effect of the coexisting component on D̄ was observed. That is, D̄ of penetrant with smaller molecular size (Hx and Bz for Bz/Hx and Bz/Cx systems, respectively) was reduced by the presence of penetrant with larger molecular size (Bz and Cx, respectively) and vice versa. D̄_Bz was similar to D̄_Hx, but much larger than D̄_Cx. The difference in PV behavior between Bz/Hx and Bz/Cx systems for glassy polymer membranes was understood based on the aforementioned features of sorption and diffusion. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2954–2964, 2000     

Transport of benzene and methyl‐substituted benzenes through carbon black‐filled epoxidized natural rubber

Sorption and diffusion of benzene and methyl‐substituted benzenes were investigated through epoxidized natural rubber (ENR) reinforced with four types of carbon black: superabrasion furnace (SAF), intermediate superabrasion furnace (ISAF), high‐abrasion furnace (HAF), and semireinforcing furnace (SRF). Kraus equation has been used to investigate the extent of reinforcement for the different types of carbon black used in the experiments. Effect of the type and concentration of the carbon black on solvent uptake and mechanism of diffusion were studied in detail. The rate constant for diffusion of the solvents in epoxidized natural rubber vulcanizate based on different carbon black type, and loading was investigated. Diffusion constant was found to decrease with increase in the degree of reinforcement. The interaction constant values were experimentally determined. The sorption data were used to determine the activation energy for the diffusion process and the enthalpy and entropy of the sorption process. The experimental results were compared with theoretical predictions. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 415–427, 1999     

Assessing the transport properties of organic penetrants in low‐density polyethylene using free volume models

Three models, two of them relying on free volume—the Cohen–Turnbull–Fujita (CTF) model and the Vrentas–Duda (VD) model, and the third being empirical using an exponential concentration dependence of the diffusivity, were applied to desorption data for a series of alkane penetrants (2,2‐dimethylbutane, cyclohexane, n‐hexane, n‐decane, and n‐tetradecane) in low‐density polyethylene. The CTF model described the desorption data very well and better than the exponential diffusion law. The VD model with the attractive feature of being based on independently determined parameters was unsuccessful in describing the desorption data. Diffusivity data indicated that the three components outside the crystal core were less accessible to n‐tetradecane than to the other penetrants. This indication was further substantiated by solubility data. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 723–734, 2007     

Effect of substituent polarity,bulk, and substitution site toward enhancing gas permeation in dibromohexafluorobisphenol‐a based polyarylates

The gas permeation properties of polyarylates were tuned by varying nature and site of substituents present on both of its monomers, viz., bisphenol and dicarboxylic acid. The phenyl rings of hexafluorobisphenol‐A were substituted in asymmetric manner by polar bromine to obtain dibromohexafluorobisphenol‐A. This bisphenol was polymerized with equimolar mixture of iso‐ and terephthalic acid (base case), bromo‐ and nitroterephthalic acid (polar group substituted acids), 4,4′‐hexafluoroisopropylidene bis(benzoic acid), and t‐butyl isophthalic acid (bulky group containing acids). Physical properties and gas permeation properties of these polyarylates were investigated to assess combined effects of asymmetric nature of bisphenol substitution, polar nature of substituent bromine, hexafluoroisopropylidene group present at the bridge position of bisphenol, and substituent present on the acid moiety. The combination of these substituent types led these polyarylates to lie near Robeson upper bound. The gas sorption analysis and estimation of diffusivity in these polyarylates shed a light on observed variations in gas permeation properties by attempted structural variations. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3156–3168, 2007     

First solvent‐free synthesis of poly(N‐methylolacrylamide) via frontal free‐radical polymerization

We report the first synthesis of poly (N‐methylolacrylamide) (PNMA) via free‐radical frontal polymerization (FP) with solid monomers at ambient pressure. The appropriate amounts of reactants (N‐methylolacrylamide) (NMA) and initiator (ammonium persulfate) were mixed together at ambient temperature without solvent. FP was initiated by heating the wall of the tube with a soldering iron, and the resultant hot fronts were allowed to self‐propagate throughout the reaction vessel. Once initiated, no further energy was required for polymerization to occur. To suppress the fingers of molten monomer, a small amount of nanosilica was added. We also produced PNMA with dimethyl sulfoxide (DMSO) or N‐methyl‐2‐pyrrolidone, as solvent by FP, to study the macrokinetics in FP of PNMA without fillers. The front velocity and front temperature dependence on the ammonium persulfate and N‐methyl‐2‐pyrrolidone concentration were investigated. The polymer was analyzed by thermogravimetric analysis. Results show that without postpolymerization solvent removal, waste production can be reduced. Solvent‐free FP could be exploited as a means for preparation of PNMA with the potential advantage of higher throughput than solvent‐based methods. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4322–4330, 2007     

2,6‐Diaminopyridine and Acrylamide‐Based Copolymers with Upper Critical Solution Temperature‐type Behavior in Aqueous Solution

A novel copolymer based on supramolecular motif 2,6‐diaminopyridine and water‐soluble acrylamide, poly[N‐(6‐acetamidopyridin‐2‐yl) acrylamide‐co‐acrylamide], was synthesized via reversible addition–fragmentation chain transfer (RAFT) polymerization with various monomer compositions. The thermoresponsive behavior of the copolymers was studied by turbidimetry and dynamic light scattering (DLS). The obtained copolymers showed an upper critical solution temperature (UCST)‐type phase transition behavior in water and electrolyte solution. The phase transition temperature was found to increase with decreasing amount of acrylamide in the copolymer and increasing concentration of the solution. Furthermore, the phase transition temperature varied in aqueous solutions of electrolytes according to the nature and concentration of the electrolyte in accordance with the Hoffmeister series. A dramatic solvent isotope effect on the transition temperature was observed in this study, as the transition temperature was almost 10–12 °C higher in D₂O than in H₂O at the same concentration and acrylamide composition. The size of the aggregates below the transition temperature was larger in D₂O compared to that in H₂O that can be explained by deuterium isotope effect. The thermoresponsive behavior of the copolymers was also investigated in different cell medium and found to be exhibited UCST‐type phase transition behavior in different cell medium. Such behavior of the copolymers can be useful in many applications including biomedical, microfluidics, optical materials, and in drug delivery. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2064–2073     

Sorption,diffusion, and permeation of ethylbenzene in poly(1‐trimethylsilyl‐1‐propyne)

The solubility, diffusivity, and permeability of ethylbenzene in poly(1‐trimethylsilyl‐1‐propyne) (PTMSP) at 35, 45 and 55 °C were determined using kinetic gravimetric sorption and pure gas permeation methods. Ethylbenzene solubility in PTMSP was well described by the generalized dual‐mode model with χ = 0.39 ± 0.02, b = 15 ± 1, and C^′_H = 45 ± 4 cm³ (STP)/cm³ PTMSP at 35 °C. Ethylbenzene solubility increased with decreasing temperature; the enthalpy of sorption at infinite dilution was −40 ± 7 kJ/mol and was essentially equal to the enthalpy change upon condensation of pure ethylbenzene. The diffusion coefficient of ethylbenzene in PTMSP decreased with increasing concentration and decreasing temperature. Activation energies of diffusion were very low at infinite dilution and increased with increasing concentration to a maximum value of 50 ± 10 kJ/mol at the highest concentration explored. PTMSP permeability to ethylbenzene decreased with increasing concentration. The permeability estimated from solubility and diffusivity data obtained by kinetic gravimetric sorption was in good agreement with permeability determined from direct permeation experiments. Permeability after exposure to a high ethylbenzene partial pressure was significantly higher than that observed before the sample was exposed to a higher partial pressure of ethylbenzene. Nitrogen permeability coefficients were also determined from pure gas experiments. Nitrogen and ethylbenzene permeability coefficients increased with decreasing temperature, and infinite dilution activation energies of permeation for N₂ and ethylbenzene were −5.5 ± 0.5 kJ/mol and −74 ± 11 kJ/mol, respectively. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1078–1089, 2000     

Sorption and diffusion of methanol and water in PVDF‐g‐PSSA and Nafion® 117 polymer electrolyte membranes

Sorption and diffusion properties of poly(vinylidene fluoride)‐graft‐poly(styrene sulfonic acid) (PVDF‐g‐PSSA) and Nafion® 117 polymer electrolyte membranes were studied in water/methanol mixtures. The two types of membranes were found to have different sorption properties. The Nafion 117 membrane was found to have a maximum in‐solvent uptake around 0.4 to 0.6 mole fraction of methanol, while the PVDF‐g‐PSSA membranes took up less solvent with increasing methanol concentration. The proton NMR spectra were recorded for membranes immersed in deuterated water/methanol mixtures. The spectra showed that the hydroxyl protons inside the membrane exhibit resonance lines different from the resonance lines of hydroxyl protons in the external solvent. The spectral features of the lines of these internal hydroxyl groups in the membranes were different in the Nafion membrane compared with the PVDF‐g‐PSSA membranes. Diffusion measurements with the pulsed field gradient NMR (PFG‐NMR) method showed that the diffusion coefficient of the internal hydroxyl groups in the solvent immersed Nafion membrane mirrors the changes in the diffusion coefficients of hydroxyl and methyl protons in the external solvent. For the PVDF‐g‐PSSA membranes, a decrease in the diffusion coefficient of the internal hydroxyl protons was seen with increasing methanol concentration. These results indicate that the morphology and chemical structure of the membranes have an effect on their solvent sorption and diffusion characteristics. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 3277–3284, 2000     

Solvent‐induced crystallization in poly(ethylene terephthalate) during mass transport

Solvent transport in poly(ethylene terephthalate) (PET) and related phase transformation were investigated. The data of mass sorption were analyzed according to Harmon's model for Case I (Fickian), Case II (swelling), and anomalous transport. This transport process in PET is accompanied by the induced crystallization of the original amorphous state. The transformation was examined by wide‐angle X‐ray scattering, small‐angle X‐ray scattering, differential scanning calorimetry, and Fourier transform infrared spectroscopy. During this process, the matrix is under a strain state that causes different kinetic paths of crystallization as compared with that by thermal annealing. This state of strain assists the development of the solvent‐induced crystallization. The model regarding crystallization was proposed in terms of the study of long period L, the crystal thickness l_c, and the thickness of amorphous layer l_a obtained from the one‐dimensional correlation function and interface distribution function. Different kinetic paths were discovered for different crystallization processes. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1444–1453, 2002     

Pressure and temperature dependence of the gas‐transport properties of dense poly[2,6‐toluene‐2,2‐bis(3,4‐dicarboxylphenyl)hexafluoropropane diimide] membranes

The gas‐transport properties of poly[2,6‐toluene‐2,2‐bis(3,4‐dicarboxylphenyl)hexafluoropropane diimide] (6FDA‐2,6‐DAT) have been investigated. The sorption behavior of dense 6FDA‐2,6‐DAT membranes is well described by the dual‐mode sorption model and has certain relationships with the critical temperatures of the penetrants. The solubility coefficient decreases with an increase in either the pressure or temperature. The temperature dependence of the diffusivity coefficient increases with an increase in the penetrant size, as the order of the activation energy for the diffusion jump is CH₄ > N₂ > O₂ > CO₂. Also, the average diffusion coefficient increases with increasing pressure for all the gases tested. As a combined contribution from sorption and diffusion, permeability decreases with increases in the pressure and the kinetic diameter of the penetrant molecules. Even up to 32.7 atm, no plasticization phenomenon can be observed on flat dense 6FDA‐2,6‐DAT membranes from their permeability–pressure curves. However, just as for other gases, the absolute value of the heat of sorption of CO₂ decreases with increasing pressure at a low‐pressure range, but the trend changes when the feed pressure is greater than 10 atm. This implies that CO₂‐induced plasticization may occur and reduce the positive enthalpy required to create a site into which a penetrant can be sorbed. Therefore, a better diagnosis of the inherent threshold pressure for the plasticization of a glassy polymer membrane may involve examining the absolute value of the heat of sorption as a function of pressure and identifying the turning point at which the gradient of the absolute value of the heat of sorption against pressure turns from a negative value to a positive one. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 354–364, 2004     

Influence of different alkyl‐methylimidazolium tetrafluoroborate ionic liquids on the structure of pebax® films. Consequences on thermal,mechanical, and water sorption and diffusion properties

In this work, three ionic liquids (ILs) differing by the length of the alkyl chain linked to their cation were incorporated in a Pebax^® copolymer matrix through a solvent cast process for composition from 0 to 70 wt % IL. The copolymer/IL miscibility was investigated via IR Spectroscopy, Differential Scanning Calorimetry and Scanning Electron Microscopy. The three ILs dissolved in the copolymer soft phase for ILs content below 30 wt % whereas they formed segregated dispersed domains at higher loadings. The plasticizing effect of the ILs was examined through DSC and thermomechanical analyses. In the range of IL amount from 0 to 30 wt %, no significant differences were observed in the thermomechanical properties as a function of the IL structure. At higher IL content, the films based on 1‐ethyl‐methylimidazolium tetrafluoroborate sustained better properties. All films exhibited a good thermal stability up to 300 °C. The water sorption isotherms were modeled with GAB equation and both the kinetic and thermodynamic parameters of the sorption mechanism were investigated. A non‐monotonic evolution of the GAB parameters and diffusion coefficient as a function of the IL content was evidenced. Moreover, different behaviors were observed as a function of the IL nature and structuration within the copolymer matrix. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 811–824     

Experimental and theoretical investigation of anomalous sorption kinetics in the methanol vapor–poly(methyl methacrylate) system at 35 °C

Non‐Fickian sorption kinetics of methanol vapor in a poly(methyl methacrylate) film of 8 μm, at 35 °C, are presented. The behavior of the system was studied in series of interval absorption runs. The relevant diffusion and viscous relaxation processes were studied by kinetic analysis of the sorption kinetic curves, using the relaxation‐dependent solubility model. The sorption isotherm concaves upward at high activities, typical to Florry–Huggins behavior, while it exhibits a convex‐upward curvature at low methanol vapor activities, indicating sorption in the excess free volume of the polymer matrix. Thermodynamic diffusivity presents a complex functional dependence on the concentration, while relaxation rate is found to be a function of concentration as well as of concentration interval. Relaxation rate becomes increasingly concentration‐dependent as the effective glass transition of the system is approached. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3173–3184, 2006     

Self‐assembly of star‐shaped polystyrene‐block‐polypeptide copolymers synthesized by the combination of atom transfer radical polymerization and ring‐opening living polymerization of α‐amino acid‐N‐carboxyanhydrides

The self‐assembling nature and phase‐transition behavior of a novel class of triarm, star‐shaped polymer–peptide block copolymers synthesized by the combination of atom transfer radical polymerization and living ring‐opening polymerization of α‐amino acid‐N‐carboxyanhydride are demonstrated. The two‐step synthesis strategy adopted here allows incorporating polypeptides into the usual synthetic polymers via an amido–amidate nickelacycle intermediate, which is used as the macroinitiator for the growth of poly(γ‐benzyl‐L ‐glutamate). The characterization data are reported from analyses using gel permeation chromatography and infrared, ¹H NMR, and ¹³C NMR spectroscopy. This synthetic scheme grants a facile way to prepare a wide range of polymer–peptide architectures with perfect microstructure control, preventing the formation of homopolypeptide contaminants. Studies regarding the supramolecular organization and phase‐transition behavior of this class of polymer‐block‐polypeptide copolymers have been accomplished with X‐ray diffraction, infrared spectroscopy, and thermal analyses. The conformational change of the peptide segment in the block copolymer has been investigated with variable‐temperature infrared spectroscopy. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2774–2783, 2006     

Effect of precursor chain‐length on the formation and stability of poly(ethylene glycol)‐based supramolecular star polymers

A homologous series of guanosine end‐functionalized poly(ethylene glycol)s have been prepared, and their assembly–disassembly behavior in the presence of potassium cations has been systematically examined upon changing the concentration, temperature, nature of solvent, amount of cation, and type of anion using ¹H‐NMR, UV/Vis, and circular dichroism spectroscopy. The results revealed a strong dependence of the assembly formation, and the stability of the formed supramolecular ensemble on the chain‐length of the assembly precursor. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Phase behavior study of poly(N‐tertbutylacrylamide‐co‐acrylamide) in the mixture of water–methanol: The role of polymer–nonsolvent second‐order interactions

The phase behavior of poly(N‐tertbutylacrylamide‐co‐acrylamide) (PNTBAM) in pure water and mixture of water–methanol is studied at different temperatures. The different compositions of PNTBAM are prepared by free‐radical polymerization technique and their phase behavior is studied by turbidimetry. The effects of copolymer and solvent composition on the phase behavior of the copolymers are discussed. It has been suggested that the inhomogenities in polymer chains are responsible for lowering the rate of phase transition by increasing the N‐tertbutylacrylamide (NTBAM) and methanol contents in copolymer and mixture, respectively. For the first time we have revealed that there are second‐order binary interactions in the water–methanol which are dominant in the special range of copolymer composition. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 455–462, 2009