Showing papers on "Permeation published in 2001"

Zeolite NaA Membrane: Preparation, Single-Gas Permeation, and Pervaporation and Vapor Permeation of Water/Organic Liquid Mixtures

Abstract: Zeolite NaA membranes were prepared reproducibly by a one-time-only hydrothermal synthesis with a short reaction time of 3 h at 373 K using a gel with the composition Al2O3:SiO2:Na2O:H2O = 1:2:2:120 (in moles) and porous α-alumina support tubes seeded with zeolite NaA crystals. A dense intergrown zeolite crystal layer of about 30 μm in thickness was formed on the outer surface. The zeolite NaA membranes were highly permeable to water vapor but impermeable to every gas unless dried completely. The completely dried membranes displayed gas permeation behavior attributed to Knudsen diffusion, indicating the presence of interstitial spaces between the zeolite crystal particles, or nonzeolitic pores. The membranes displayed excellent water-permselective performance in pervaporation (PV) and vapor permeation (VP) toward water/organic liquid mixtures. With an increase in temperature, both the permeation flux Q and the separation factor α increased, and the membrane performance was much better for VP than for PV. ...

Evaluation of a Sol-Gel Derived Nafion/Silica Hybrid Membrane for Polymer Electrolyte Membrane Fuel Cell Applications: II. Methanol Uptake and Methanol Permeability

Abstract: Sol-gel derived Nafion/silica hybrid membranes were investigated as a potential polymer electrolyte for direct methanol fuel cell applications. Methanol uptake and methanol permeability were measured in liquid and vapor phase as a function of temperature, methanol vapor activity, and silica content. Decreased methanol uptake from liquid methanol was observed in the hybrid membranes with silica contents of 10 and 21 wt %. The hybrid membrane with silica content of ≈20 wt % showed a significant lower methanol permeation rate when immersed in a liquid methanol-water mixture at 25 and 80°C. Methanol uptake from the vapor phase by the hybrid membranes appears similar to that of unmodified Nafion. Methanol diffusion coefficients, as determined from sorption experiments, were slightly lower in the hybrid membranes than in unmodified Nafion. However, in direct permeation experiments, significantly lower methanol vapor permeability was seen only in the hybrid membrane with silica content of ≈20 wt %. Based on these results, Nafion/silica hybrid membranes with high silica content have potential as electrolytes for direct methanol fuel cells operating either on liquid or vapor-feed fuels. © 2001 The Electrochemical Society. All rights reserved.

Structure-motion-performance relationship of flux-enhanced reverse osmosis (RO) membranes composed of aromatic polyamide thin films.

Abstract: The present paper explores the role of dimethyl sulfoxide (DMSO) used as an additive to modify the morphological as well as the molecular nature of aromatic polyamide during the formation of thin-film-composite (TFC) membranes. In addition, it elucidates the mechanism of enhancing the reverse osmosis (RO) permeation of the resulting membranes in proportion to the addition of DMSO. Morphological studies by atomic force microscopy (AFM) observed that as the concentration of DMSO increased, the surface roughness and the surface area of the aromatic polyamide TFC membranes became higher and larger, compared to FT-30 membrane for which DMSO was not added during interfacial reaction. Such morphological changes were brought about from fluctuating interface through reducing the immiscibility between aqueous/organic phases by DMSO and provided more opportunities to have contact with water molecules on the surface, participating in the enhancement of the water permeability. Chemical composition studies by X-ray photoelectron spectroscopy (XPS) revealed that there was a considerable increase of the cross-linked amide linkages relative to the linear pendant carboxylic acid groups in the TFC membranes of more DMSO addition. The increase of such amide linkages as hydrogen bonding sites facilitated the diffusion of water molecules through the thin films and played a favorable role in elevating water flux without considerable loss of salt rejection. Relaxation and motion analyses by 1H solid-state nuclear magnetic resonance (NMR) spectroscopy also confirmed the XPS revelation on the basis of measurements of the spin-lattice relaxation time in the rotating frame, T1rho, and determination of the correlation time, tau(c), for the aromatic polyamides forming thin films. The trend of longer tau(c)'s with the increase of DMSO concentration reflected the thin-film aromatic polyamides of less locally mobile chains, accompanied by the higher degree of cross-linking and, hence, the greater number of amide groups. The combined results of AFM, XPS, and solid-state NMR provided a robust explanation for the mechanism of flux enhancement of the aromatic polyamide TFC membranes with the addition of DMSO, which would contribute to not only a fundamental understanding of the process but also an advanced designing of the so-called "tailor-fit" TFC membranes.

High Throughput Prediction of Oral Absorption: Improvement of the Composition of the Lipid Solution Used in Parallel Artificial Membrane Permeation Assay

Abstract: The purpose of the present study was to improve the composition of the lipid solution used in parallel artificial membrane permeation assay for the precise prediction of oral absorption. We modified the composition of lipid solution, which was used to make a lipid membrane on the filter support. First, we changed the chain length of organic solvent (PC/alkyldienes [C7-C10]). A negative charge was then added to the membrane to mimic the intestinal membrane (PC/stearic acid/1,7-octadiene and PC/PE/PS/PI/cholesterol/1,7-octadiene). Finally, we examined the predictability of the PC/PE/PS/PI/CHO/1,7-octadiene membrane using structurally diverse compounds. Permeability coefficients of tested compounds were increased as the chain length of alkyldiene became shorter. The addition of a negative charge to the membrane increased the permeability of the basic compounds. However, the negatively charged membrane with stearic acid showed different permeability profiles from PC/PE/PSIPI/CHO. The predictability of the PC/...

Polarity and permeation profiles in lipid membranes

Abstract: The isotropic 14N-hyperfine coupling constant, a, of nitroxide spin labels is dependent on the local environmental polarity. The dependence of a in fluid phospholipid bilayer membranes on the C-atom position, n, of the nitroxide in the sn-2 chain of a spin-labeled diacyl glycerophospholipid therefore determines the transmembrane polarity profile. The polarity variation in phospholipid membranes, with and without equimolar cholesterol, is characterized by a sigmoidal, trough-like profile of the form {1 + exp [(n − no)/λ]}−1, where n = no is the point of maximum gradient, or polarity midpoint, beyond which the free energy of permeation decreases linearly with n, on a characteristic length-scale, λ. Integration over this profile yields a corresponding expression for the permeability barrier to polar solutes. For fluid membranes without cholesterol, no ≈ 8 and λ ≈ 0.5–1 CH2 units, and the permeability barrier introduces an additional diffusive resistance that is equivalent to increasing the effective membrane thickness by 35–80%, depending on the lipid. For membranes containing equimolar cholesterol, no ≈ 9–10, and the total change in polarity is greater than for membranes without cholesterol, increasing the permeability barrier by a factor of 2, whereas the decay length remains similar. The permeation of oxygen into fluid lipid membranes (determined by spin-label relaxation enhancements) displays a profile similar to that of the transmembrane polarity but of opposite sense. For fluid membranes without cholesterol no ≈ 8 and λ ≈ 1 CH2 units, also for oxygen. The permeation profile for polar paramagnetic ion complexes is closer to a single exponential decay, i.e., no lies outside the acyl-chain region of the membrane. These results are relevant not only to the permeation of water and polar solutes into membranes and their permeabilities, but also to depth determinations of site-specifically spin-labeled protein residues by using paramagnetic relaxation agents.

Permeability, Diffusion and Solubility of Gases in Polyethylene, Polyamide 11 and Poly (Vinylidene Fluoride)

Abstract: The gases transport coefficients, permeability, diffusion and solubility, are determined by the time lag method on a specific permeation cell. Three semicrystalline polymers, polyethylene (PE), polyamide 11 (PA11) and poly(vinylidene fluoride) (PVF2), are studied in the presence of helium (He), argon (Ar), nitrogen (N2), methane (CH4) and carbon dioxide (CO2) for temperatures ranging from 40 to 80°C in the case of PE, and from 70 to 130°C for both other materials. The applied pressures are, in the majority of tests, of 10 MPa for He, Ar, N2 and CH4, and of 4 MPa for CO2, except in some particular cases where the influence of pressure was studied. In the case of PE, the influence of the volume fraction of the amorphous phase, ranging from 0. 21 to 0. 70, the influence of temperature and the influence of the nature of the gas on the transport processes are investigated. Also, the independence of these phenomena related to pressure and sample thickness, between 0. 5 and 6 mm, is shown. For PA11, after determining the influence of temperature and of the nature of the gas used, the effect of the plasticizer incorporation in this polymer was studied. Regarding PVF2, apart the classic parameters that are temperature and the kind of gas used, we compare the coefficients of transport of CH4 and CO2 in PVF2 made up by extrusion or by compression moulding. For each polymer, it is shown that permeability, diffusion and solubility depend on temperature following Arrhenius' laws. It also seems that diffusion is directly related to the gases molecule size and that the solubility coefficient can be linked to the epsilon/K gases parameter. The comparison of the results obtained with the available data in the literature seems satisfactory.

Water sorption and permeation in chitosan films: Relation between gas permeability and relative humidity

Abstract: The water sorption of chitosan has been studied at 20 °C. Water transport is governed by a Fickian process for relative humidities lower than 0.4, and in that range of partial pressures, the diffusion coefficient is concentration-dependent. At a higher activity, anomalous diffusion is observed. The sorption isotherm is well described by the Guggenheim-Anderson-de Boer (GAB) model, and the clustering phenomenon observed at high relative pressures can be studied with the parameters of this model. The water permeability coefficient greatly increases with the relative pressure, and the water plasticization effect leads to a loss of the gas barrier properties under wet conditions. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 3114–3127, 2001

Study of Self-Diffusion of Monovalent and Divalent Cations in Nafion-117 Ion-Exchange Membrane

Abstract: The self-diffusion coefficients of monovalent (Na+, K+, Cs+, and Ag+) and divalent (Ca2+, Sr2+, Ba2+, and Zn2+ ) cations in Nafion-117 have been measured using the “nonstationary radiotracer diffusion method” for the first time. This method is based on the analysis of absorption/desorption of radiotracer ions in the membrane sample as a function of time using an analytical solution of Fick's second law. It has been found to be simple and faster than that of the commonly used “radiotracer permeation method”. An attempt has been made to interpret the self-diffusion data based on the free-volume theory. The self-diffusion coefficients for monovalent and divalent ions, normalized with respect to their aqueous diffusion coefficients, correlate well with the polymer volume fractions. However, separate trends are observed for monovalent and divalent ions. The factors that lead to higher self-diffusion coefficients of the counterions in the membrane appear to lower their selectivity coefficients.

Experimental studies of gas permeation through microporous silica membranes

Abstract: Permeation mechanism of inorganic gases was studied experimentally and theoretically through microporous silica membranes prepared by the sol-gel method. Inorganic gas permeation was measured using the membranes with subnano pores in diameter. The permeance of He increased with increasing temperature for various cases, while that of CO 2 , O 2 and N 2 decreased. In particular, the observed temperature dependency of CO 2 was greater than those of other gases. In such small pores, the interaction energy between a permeant molecule and the pore wall can affect gas-permeation properties. A simple gas-permeation model is used considering the effect of the attractive or repulsive pore-wall potential field, which deviates from the ambient gas phase of the gas molecule concentration (pressure) in a pore. The model can explain the experimental gas-permeation properties successfully. Potential curves of CO 2 and N 2 in a silica pore were also calculated to predict the permeation ratio of CO 2 /N 2 . This model can help understand further the gas-permeation mechanism in micropores.

Aromatic Permeation through Crystalline Molecular Sieve Membranes

Abstract: The fluxes of aromatic molecules (p-xylene, o-xylene, and benzene) were measured as a function of temperature and feed partial pressure through several molecular sieve membranes (SAPO-5, SAPO-11, and mordenite) and three types of MFI membranes (silicalite-1, ZSM-5, and boron-substituted ZSM-5). Single-file diffusion appeared to control transport through the SAPO and mordenite membranes. Hence, those membranes showed ideal selectivities greater than 1 for benzene over the xylene isomers but no separation selectivities for the mixtures. Surface diffusion and activated gaseous transport were the controlling mechanisms for the MFI membranes. The highest p-xylene/o-xylene selectivities were obtained for a boron-substituted ZSM-5 membrane. At feed partial pressures of 2.1 kPa and at a temperature of 425 K, the best selectivities were 130 (ideal) and 60 (separation). Zeolite pores preferentially permeated p-xylene and took as long as 8 h to reach steady state. Nonzeolite pores preferentially permeated o-xylene a...