Studies on molecular transport of n‐alkanes through poly(tetrafluoroethylene‐co‐propylene) elastomeric membrane

Molecular transport of a series of n‐alkanes through commercial TFE elastomer (FA 150L) has been studied in the temperature range 30–50 °C using sorption‐gravimetric method. The Fickian diffusion equation was used to calculate the diffusion coefficients, which were dependent on the size of the alkanes and temperature. The diffusion coefficients at 30°C varied from 4.53 × 10^?8 cm²/s (n‐heptane) to 0.18 × 10^?8 cm²/s (n‐hexadecane). The liquid concentration profiles have also been computed using analytical solution of Fick's equation with the appropriate initial and boundary conditions and these were presented as a function of penetration depth of molecular migration and time of immersion. These results have been discussed in terms of molecular size of alkanes as well as temperature. In all the liquid penetrants, the transport phenomenon was found to follow the anomalous behavior. From the temperature dependence of diffusion and permeation coefficients, the Arrhenius activation parameters have been estimated. These parameters do not exhibit any systematic variation with the size of the penetrants. The resulting low diffusion coefficients, contribute to the superior barrier performance of the membrane, is due, in part, to the high glass transition temperature of Aflas? TFE elastomer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2228–2235, 2006     

Swelling kinetics of linseed oil‐based polymers

Kinetics of swelling and sorption behavior of copolymers (based on linseed oil, styrene, divinylbenzene, and acrylic acid via cationic and thermal polymerization) is studied in tetrahydrofuran (THF) at different temperatures. The values of n in the transport equation are found to be below 0.4, showing non‐Fickian or pseudo‐Fickian transport in the polymers. The dependence of diffusion coefficient on the composition and temperature has also been studied for the linseed oil‐based polymers. The diffusion coefficient in cationic samples decreases with an increase in the oil contents in the samples. In case of thermal samples, the diffusion coefficient first increases up to 30% oil contents and then decreases. The diffusion coefficient decreases with an increase in temperature for all of the linseed oil polymer samples. The sorption coefficient increases with an increase in the oil contents for all samples. The crosslink density (calculated from the THF swelling) ranges from 20.16 to 92.34 × 10⁶ mol/cm³ for cationic samples and 20.62 to 86.01 × 10⁶ mol/cm³ for thermal samples. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Molecular transport characteristics of a chlorosulfonated polyethylene geomembrane in the presence of aromatic esters

Results of a study on sorption and diffusion of chlorosulfonated polyethylene geomembrane with methyl benzoate, ethyl benzoate, methyl salicylate, iso-butyl salicylate, phenyl acetate, and diethyl phthalate in the temperature range 25–60°C are presented. A gravimetric sorption method is used to calculate the diffusion and permeation coefficients from the Fickian relationship. The diffusion results are dependent on penetrant–membrane interactions, temperature, and on penetrant concentration. The values of diffusion coefficients range from 0·02 × 10^?7 cm² s^?1 for diethyl phthalate at 25°C to 1·81 × 10^?7 cm² s^?1 for ethyl benzoate at 60°C. The activation energies for diffusion range from 21 to 50 kJ mol^?1. The values of heat of sorption ranged between 2·2 and 6·4 kJ mol^?1. Sorption results are also analyzed using a first-order sorption kinetic equation. Experimental results and calculated parameters are used to discuss the transport behavior. None of the esters used have shown any chemical attack toward the geomembrane.     

Sorption studies of propylene in polypropylene. Diffusivity in polymer particles formed by different polymerization processes

Propylene was polymerized in gas phase and liquid phase by using a novel nonporous Ziegler–Natta‐catalyst system. The polymer particles formed at different polymerization times were used for sorption measurements. In both cases it was found that the effective diffusion coefficient is increasing with increasing size of polymer particles and the effective diffusion coefficients of polymer particles formed by liquid‐phase polymerization are larger than those of polymer particles produced by gas‐phase polymerization. The effective diffusion coefficients of polymer particles are in the range of 2 × 10^?11 to 1.6 × 10^?10 m²/s with activation energies from 34 to 22 kJ/mol. The analyzed polymer particles have average diameters between 250 and 875 μm. The solubility of propylene in polypropylene particles can be described by the law of Henry at conditions studied. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2642–2648, 2006     

Swelling behavior of polyelectrolyte complex hydrogels composed of chitosan and hyaluronic acid

Polyelectrolyte complex (PEC) hydrogels composed of various weight ratios of chitosan and hyaluronic acid were prepared. The PEC hydrogels were formed by the reaction of the oppositely charged chitosan polymers. The PEC films swelled in water rapidly, reaching equilibrium within 30 min, and exhibited relatively high swelling ratios, 243–322%, at 25°C. The swelling ratio increased with increasing temperature. The transport phenomena of all PEC samples were non‐Fickian and diffusion and relaxation controlled. The diffusion coefficients of the PEC films ranged from 2.22 × 10^?6 to 10.05 × 10^?6 cm²/s. The activation energy of the polyelectrolyte complexes ranged from 37.14 to 54.58 kJ/mol and proved to be hydrophilic. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1097–1101, 2004     

Study on Convective Drying Characteristics of Dredged Sludge from Dian Lake

In this work, the thin layer drying behavior of dredged sludge from Dian Lake by convective drying methods was investigated. The results showed that the Modified Page-I model was more suitable for thin-layer drying of dredged sludge. The values of the diffusion coefficients at each temperature were obtained using Fick’s second law of diffusion, and it was varied from 6.472×10^?9 to 1.143×10^?8 m²/s when the temperature was changed from 100 to 160°C for the dredged sludge of 10 mm. When the thickness was changed from 5 to 20 mm, the diffusion coefficients were varied from 4.036×10^?9 to 2.648×10^?8 m²/s at 140°C. The activation energy of moisture diffusion was 13.1 kJ/mol.     

Experimental study of diffusivity of hexane in bitumen-saturated porous media under high temperature/pressure conditions

Solvent mass transfer plays a key role in a thermal gravity drainage process involving solvent. The diffusion coefficients of solvent in such a process are not well studied. This article presents the effective diffusion coefficients of solvent in bitumen-saturated sands under high temperature/pressure conditions measured using a CT scanning technique. Experimental results show that the effective diffusion coefficient of n-hexane in bitumen-saturated sands varied with the solvent concentration or with the viscosity of solvent–bitumen mixture (i.e., D_e ∝ c^0.4 or D_e ∝ μ_m^−0.46). The solvent concentration weighted diffusion coefficient of n-hexane in the bitumen under the condition 160–170°C/1,900 kPa had an order of magnitude of about 10⁻⁵ cm²/s for solvent volume concentration less than 0.2. The penetration distance of n-hexane in bitumen-saturated sands depended on the nonlinearity of diffusion and had a value of −2 cm after 1-day diffusion. The stronger the nonlinearity of diffusion, the shorter the penetration distance.     

Adsorption of phenazine dyes using poly(hydroxamic acid) hydrogels from aqueous solutions

Swelling and adsorption properties of poly(hydroxamic acid), (PHA) hydrogels in aqueous solutions of some phenazine dyes such as Neutral Red, Safranin T, and Janus Green have been investigated. PHA hydrogels containing N,N′ methylenebisacrylamide or ethyleneglycoldimethacrylate were used in experiments on swelling, diffusion and adsorption of the dyes. The equilibrium swelling (S_eq) values of PHA hydrogels in aqueous solutions of the phenazine dyes were calculated as 2.16–33.25 g g^?1. Swelling kinetic parameters such as initial swelling rate, swelling rate constant, and maximum swelling were found. Dye diffusion into hydrogels was found to be non‐Fickian in character. Diffusion coefficients are ranged 1.32 × 10^?6 cm² s^?1 ? 44.70 × 10^?6 cm² s^?1. Adsorption of the phenazine dyes onto PHA hydrogels was studied by batch technique. PHA hydrogels in the phenazine dye solutions showed the dark coloration. The data was found that Freundlich isotherm model fits. According the Freundlich constants, the adsorption isotherms are of S‐type in Giles classification. All swelling and binding parameters for PHA‐EGDMA were found to be higher than those for PHA‐NNMBA. The type of crosslinker influenced the swelling, binding, and sorption more than the type of dye. Finally, it can be said that PHA hydrogels may be used a sorbent for removal of dyes. POLYM. ENG. SCI., 58:310–318, 2018. © 2017 Society of Plastics Engineers     

Effect of polymer–clay interaction on solvent transport behavior of fluoroelastomer–clay nanocomposites and prediction of aspect ratio of nanoclay

Diffusion and sorption of methyl ethyl ketone and tetrahydrofuran through fluoroelastomer‐clay nanocomposites were investigated in the temperature range of 30–60°C by swelling experiments. Slightly non‐Fickian transport behavior was found for these nanocomposites, having variation of type of nanoclay and loading. Different transport parameters depend on the size and shape of the penetrant molecules. The results were used to study the effect of nanoclay on the solvent transport‐properties of nanocomposites and their interactions with solvents. The diffusion coefficient of methyl ethyl ketone at 30°C for neat rubber was 1.43 × 10^?8 cm² s^?1, while those of the unmodified and the modified clay filled samples at 4 phr loading were 0.24 × 10^?8 and 0.50 × 10^?8 cm² s^?1, respectively. At 8 and 16 phr loading of the unmodified clay, it was found to be 0.44 × 10^?8 and 0.64 × 10^?8 cm² s^?1, respectively. The samples were also reswelled after deswelling. Surprisingly, transport behavior became Fickian on reswelling. Interestingly, ratio of diffusion coefficients of the filled system to the neat system was found to be almost same for the first time swelling and reswelling experiments. The results showed that better polymer‐clay interaction in the case of the unmodified‐clay filled nanocomposites is responsible for enhanced solvent‐resistance property. From the permeation data, for the first time, aspect ratio of nanoclays in different composites was calculated and found to have good correlation with the morphology data obtained from transmission electron microscopy. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Bending-beam measurement of solvent diffusions in polyimides: Theoretical and experimental

A general formula correlating the bending curvature variation ratio of a layered structure caused by solvent-induced swelling in its polymer overcoat with diffusion time under case II diffusion has been presented. In the event of case II diffusion, the diffusion front velocity, v, can be calculated by using this formula and measured by a bending-beam apparatus. At room temperature, the diffusion of n-methyl-pyrrolidone (NMP) solvent in the film of pyromellitic phenylene diamine (PMDA-PDA) is case II. While in PMDA-B (-benzidine) and benzophenone tetracarboxylic dianhydride (BPDA-PDA), no diffusion progress can be observed. But, the diffusion in 6F-dianhydride- (6FDA-PDA) is case I with D = 0.85 × 10^?9 cm²/s. It becomes anomalous when mixing with 25% PMDA-B, but becomes case II diffusion with more PMDA-B. The preabsorbed moisture in the films does not affect the v value. In PMDA-PDA, v = 7.3 × 10^?8 cm/s. In the 25/75 and 50/50 6FDA-PDA/PMDA-B blends, v = 6.3 and 11.3 × 10^?8 cm/s.     

Swelling kinetics of linseed oil‐based nanocomposites

The solvent‐resistance properties of the montmorillonite‐filled conjugated linseed oil‐based nanocomposites are studied in tetrahydrofuran through equilibrium swelling method at different temperatures. The values of “n” in solvent transport equation are found to be below “0.5,” showing the non‐Fickian diffusion in the polymer. The dependence of the diffusion coefficient on the composition, percentage of clay, and temperature has been studied for nanocomposite samples. The diffusion coefficient increases with an increase in the clay contents and temperature. The crosslink density of the nanocomposites ranges from 101.07 to 237.46 × 10⁶ mol/cm³. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Dynamic adsorption behaviors between Cu2+ ion and water‐insoluble amphoteric starch in aqueous solutions

Dynamic adsorption behavior between Cu²⁺ ion and water‐insoluble amphoteric starch was investigated. The sorption process occurs in two stages: external mass transport occurs in the early stage and intraparticle diffusion occurs in the long‐term stage. The diffusion rate of Cu²⁺ ion in both stages is concentration dependent. In the external mass‐transport process, the diffusion coefficient (D₁) increases with increasing initial concentration in the low‐ (1 × 10^?3‐4 × 10^?3M) and high‐concentration regions (6 × 10^?3‐10 × 10^?3M). The values of adsorption activation energy (k_d1) in the low‐ and high‐concentration regions are 15.46–24.67 and ?1.80 to ?11.57 kJ/mol, respectively. In the intraparticle diffusion process, the diffusion coefficient (D₂) increases with increasing initial concentration in the low‐concentration region (1 × 10^?3‐2 × 10^?3M) and decreases with increasing initial concentration in the high‐concentration region (4 × 10^?3‐10 × 10^?3M). The k_d2 values in the low‐ and high‐concentration regions are 9.96–15.30 and ?15.53 to ?10.71 kJ/mol, respectively. These results indicate that the diffusion process is endothermic in the low‐concentration region and is exothermic in the high‐concentration region for both stages. The external mass‐transport process is more concentration dependent than the intraparticle diffusion process in the high‐concentration region, and the dependence of concentration for both processes is about equal in the low‐concentration region. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2849–2855, 2001     

Removal of phosphate anions from aqueous solutions using polypyrrole‐coated sawdust as a novel sorbent

This work was focused on the removal of phosphate ions using polypyrrole‐coated sawdust as a novel cost‐effective sorbent. The phosphate uptake followed the Langmuir sorption isotherm, and the sorption capacity at 20, 35, and 50°C was found to be 17.33, 23.41, and 30.39 mg/g, respectively; this indicated favorable sorption at higher temperatures. The kinetic uptake data were modeled with the Lagergren equation, first‐order and second‐order kinetic models, and the simple Elovich model. The results indicated that the Lagergren model best described the uptake data. The intraparticle diffusion coefficient, as determined for 250–211‐ and 630–600‐μm sorbent particles at 20°C, was found to be 287.3 × 10^?2 and 228.3 × 10^?2 mg g^?1 min^?1, respectively. The intraparticle diffusion was also confirmed with the Bangham equation. The sorption mean free energy, calculated with the Dubinin–Radushkevich equation, was found to be 10.98 kJ/mol, thus confirming an ion‐exchange regulated sorption process. The positive value of the enthalpy change (i.e., 4.23 kJ/mol) confirmed the endothermic nature of the sorption process. The negative values of the change in the standard free energy were indicative of the spontaneous nature of the sorption process. Finally, the activation energy of the sorption process for 250–212‐μm particles, determined with the Arrhenius equation, was found to be 41.68 J/mol. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Kinetics and diffusion processes in colour removal from effluent using wood as an adsorbent

The rates of adsorption of a basic dye, Astrazone Blue, and an acidic dye, Telon Blue, on wood have been studied. The rate controlling step is mainly intraparticle diffusion, although a small resistance due to a boundary layer is experienced. The activation energies for the adsorption of Astrazone Blue and Telon Blue on wood are 16.8 kJ mol^?1 and 9.6 kJ mol^?1, respectively. The diffusion coefficients vary from 6×10^?13 cm² s^?1 to 18×10^?13 cm² s^?1 for Astrazone Blue at 18°C and from 3 × 10^?13 cm² s^?1 to 8 × 10^?13 cm² s^?1 for Telon Blue at 18°C. The variation in diffusivities is attributed to boundary layer effects.     

In vitro dynamic swelling behaviors of polyhydroxamic acid hydrogels in the simulated physiological body fluids

Summary Influence of some simulated physiological body fluids on the dynamic swelling behaviour of polyelectrolytic hydroxamic acid hydrogels (PHA) was investigated at 37 °C in vitro. The simulated physiological body fluids are distilled water, human sera, physiological saline (0.89 % NaCl), isoosmotic phosphate buffer at pH 7.4, gastric fluid at pH 1. 1, (gylicine-HCl buffer), urea (0.3 mol L⁻¹), and the aquatic solutions of K₂HPO₄ and KNO₃ (the sources of K+). The values of equilibrium swelling of PHA hydrogels varied in the range of 130–4625%, while the values of equilibrium fluid content of the hydrogels varied in the range of 57–97%. The initial rate of swelling, diffusional exponent, and, diffusion coefficient were calculated using swelling kinetics data. Diffusion of the fluids into the hydrogel was found to be non-Fickian character. The diffusion coefficients of the hydrogel varied between 0.6×10⁻⁶– 8.1×10⁻⁶ cm² s⁻¹. Received: 15 March 2000/Accepted: 18 December 2000     

Diffusion of methyl esters of higher fatty acid in polypropylene

Diffusion coefficients of several methyl esters of linear higher fatty acid (C₁₀?C₁₈) into polypropylene (PP) were determined, over the temperature range of 50 to 110°C, using a mass uptake technique. The relations between an amount of mass uptake and t^1/2 were linear within 10 min, indicating Fickian diffusion. The diffusion coefficients were in the range of 4.6×10^?8 to 6.2×10^?12 cm² sec^?1, increased with temperature, and decreased with increasing n-alkyl chain length of fatty acid. The plots of In D vs. the molecular weight of methyl esters were approximately linear. The temperature dependence of diffusion followed an Arrhenius relationship, and the activation energies were in the range of 133 ? 147 KJ mol^?1 and increased with an increase in n-alkyl chain length of corresponding fatty acid. The diffusion coefficients were discussed with the interaction between methyl esters of higher fatty acid and PP. The diffusion coefficients of methyl esters, at the simultaneous diffusion process, were always higher than that derived from the single diffusion process, except for methyl decanoate with lower molecular weight. The difference in diffusion coefficients in single and simultaneous diffusion was discussed thermodynamically. © 1994 John Wiley & Sons, Inc.     

Synthesis and properties of radiation‐induced acrylamide–acrylic acid hydrogels

Acrylamide (AAm)/acrylic acid (AAc) hydrogels in the cylindirical form were prepared by γ‐irradiating binary systems of AAm/AAc with 2.6–20.0 kGy γ‐rays. The effect of the dose and relative amounts of AAc and pH on the swelling properties, diffusion behavior of water, diffusion coefficients, and network properties of hydrogel systems was investigated. The swelling capacities of AAm/AAc hydrogels were in the range of 1000–3000%, while poly(acrylamide) (PAAm) hydrogels swelled in the range of 450–700%. Water diffusion into hydrogels was found to be non‐Fickian‐type diffusion. Diffusion coefficients of AAm/AAc hydrogels were found between 0.79 × 10^?5 and 2.78 × 10^?5 cm² min^?1. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3570–3580, 2002     

Pervaporation separation of water–acetic acid mixtures through NaY zeolite‐incorporated sodium alginate membranes

The pervaporation (PV) separation and swelling behavior of water–acetic acid mixtures were investigated at 30, 40, and 50°C using pure sodium alginate and its zeolite‐incorporated membranes. The effects of zeolite loading and feed composition on the pervaporation performance of the membranes were analyzed. Both the permeation flux and selectivity increased simultaneously with increasing zeolite content in the polymer matrix. This was discussed on the basis of a significant enhancement of hydrophilicity, selective adsorption, and molecular sieving action, including a reduction of pore size of the membrane matrix. The membrane containing 30 mass % of zeolite showed the highest separation selectivity of 42.29 with a flux of 3.80 × 10^?2 kg m^?2 h^?1 at 30°C for 5 mass % of water in the feed. From the temperature dependency of diffusion and permeation data, the Arrhenius activation parameters were estimated. The E_p and E_D values ranged between 72.28 and 78.16, and 70.95 and 77.38 kJ/mol, respectively. The almost equal magnitude obtained in E_p and E_D values signified that both permeation and diffusion contribute equally to the PV process. All the membranes exhibited positive ΔH_s values, suggesting that the heat of sorption is dominated by Henry's mode of sorption. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2101–2109, 2004     

Immobilization influence on the water sorption and diffusion in poly(3-hydroxybutyrate)

The temperature dependency of water vapor sorption and diffusion in poly(3-hydroxybutyrate) (PHB) was studied for the first time. Equilibrium sorption and diffusion kinetics were determined by a quartz McBain's vacuum microbalance technique in the temperature range of 303–333 K. A probability of water molecule interaction with the polymer matrix was analyzed for wet PHB films by FTIR spectroscopy technique. Sorption isotherms are interpreted as the solution of free water molecules estimated by the Flory–Huggins equation and the sorption of water molecules immobilized on the carbonyl groups of PHB. The immobilization effect was described by a Langmuir-type equation. The dependency of diffusivity on water concentration was described in the frames of Fujita's immobilization model in which the growing function D_w versus C_w characterized the filling degree of carbonyl groups as sites of immobilization in the polymer. Enthalpy of free water sorption (12 kJ/mol) and water immobilization (42 kJ/mol), as well as the activation energy of water diffusion coefficients (71 kJ/mol), in noncrystalline areas of PHB were determined. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 981–985, 1999     

Permeability of polyglutamic acid ester membranes to benzene vapor

Permeability of poly(γ-methyl L -glutamate) (PMLG), poly(γ-hexahydrobenzyl L -glutamate)-(PHBLG), and poly(γ-n-amyl L -glutamate) (PALG) membrane to benzene vapor was studied. Permeability coefficients of all the membranes were large, of the order of 10^?9–10^?6 cm³(STP) cm/cm² sec cm Hg, and increased markedly with increasing relative vapor pressure and temperature. The large permeability was due to the large diffusion coefficient. The sorption behavior of the PALG–benzene system was interpreted in terms of the theory of the mixing of solvent with side chains. The Arrhenius plots of diffusion coefficients for PMLG and PHBLG showed a break at about 29 and 40°C, respectively, where the volume-expansion curves of each polymer also showed a break, which is thought to be related to the side-chain motion. The diffusivity data for PALG were examined in terms of Fujita's free-volume theory, and it was found that the value of the average free-volume fraction in the pure polymer for PALG was much larger than that for vinyl polymers. This means that the side-chain motion of PALG is easy and is the reason that the diffusion coefficients for PALG are large. These results indicate that the diffusion of benzene in these polypeptides takes place in the side-chain regions between helices.