Studies on syntheses and permeabilities of special polymer membranes.: 15. Permeation characteristics of nylon-12 cellulose acetate blends

The permeation characteristics of nylon-12-cellulose acetate polymer blend membranes in the separation of polymers, poly(vinyl alcohols), from their aqueous solutions were investigated under various conditions. The permeation characteristics were influenced markedly by the ratio of nylon-12-cellulose acetate, the feed concentration, the operating pressure and temperature. It was found that the changes of polymer ratio and the concentration of blended polymer were related to the change of microporous structure of the resulting membranes. When the cellulose acetate content was higher a significant compaction of the membrane occurred under pressure. It was found that there was a concentration polarization of poly(vinyl alcohol) molecules on the membrane surface, whose thickness increased with increase in molecular weight of poly(vinyl alcohol) and in feed concentration. The bursting strength of the polymer blend membranes swollen with water increased considerably as the cellulose acetate content in the blended polymer increased.     

Studies on syntheses and permeabilities of special polymer membranes. X. Effects of conditions of membrane preparation on permeation characteristics of cellulose acetate membranes in separation of aqueous polymer solutions

The effects of casting solvents, dissolution temperature of casting solution, and pH and temperature of gelation solution, etc. on the permeation characteristics of cellulose acetate membranes in the separation of polymers from their aqueous solutions were investigated, using aqueous solutions of poly(ethylene glycol) and poly(vinyl alcohol) as feed. The permeation characteristics were influenced significantly by the conditions of membrane preparation and of the permeation. It was found that a concentration polarization at the membrane surface occurred with poly(vinyl alcohol) molecules, but it was very small with poly(ethylene glycol). The above results were discussed in detail from points of view of structure of the resulting membranes and the interactions between the solvent, the solute in the feed and the cellulose acetate molecules.     

Studies on syntheses and permeabilities of special polymer membranes. V. Effect of casting solution composition on permeation characteristics of cellulose acetate membranes in separation of aqueous polymer solutions

The permeation characteristics of cellulose acetate membranes in separation of polymers from their aqueous solutions were investigated by changing the preparation conditions of the membranes, that are the solvent evaporation period and the casting solution composition consisting of a mixture of cellulose acetate (CA), acetone (A), and formamide (FA). The rates of pure water permeability were influenced remarkably by the solvent evaporation period and the casting solution composition. When the solvent evaporation period was short, the rates of pure water permeability increased with a decrease in A/CA, increase in FA/A, and increase in FA/CA in the casting solution. From the experimental results using poly(vinyl alcohol) as poly(ethylene glycol) as feed solute, it was seen that the changes of solvent evaporation period and casting solution composition related to the change of microporous structure of the resulting membranes. The effect of feed concentration and operating pressure on the permeation characteristics were also studied. There was found a concentration polarization of poly(vinyl alcohol) molecules on the surface of the membrane, and a compaction of the membrane occurred under pressure.     

Studies on syntheses and permeabilities of special polymer membranes: 24. Permeation characteristics of poly(vinylidene fluoride) membranes

The permeation characteristics of poly(vinylidene fluoride) membranes were investigated by changing the preparation conditions of the membranes, the composition of the casting solution, membrane thickness, time of heat treatment and temperature, etc.; and by changing the permeation conditions, operating temperature, the feed concentration, and the feed solute, etc. Aqueous solutions of poly(vinyl alcohol) and poly(ethylene glycol) were used as feed. The permeation characteristics were influenced significantly by the change of the above conditions and were dependent on the structure of resulting membrane, the viscosity of feed, the form of polymer molecules in aqueous solution, and the concentration polarization of polymer solute molecules onto the membrane surface. The permeation through very swollen membranes (ca. 85% in water content) followed the viscous flow.     

Studies on syntheses and permeabilities of special polymer membranes. 27. Concentration of poly(styrene sulphonic acid) in various aqueous solutions using poly(vinylidene fluoride) membranes

The permeation characteristics of poly(vinylidene fluoride) membranes in the separation and concentration of poly(styrene sulphonic acid), from various aqueous solutions were investigated under various conditions. The rejection of the polymer from its aqueous solution was high, because electrostatic repulsions between the charges along polymer chains cause chain extension. When a salt, such as sodium chloride, and sulphuric acid were added to the aqueous solution and the pH was changed, the configuration of the poly(styrene sulphonic acid) molecules changed significantly with the added amounts of salt. The permeation characteristics were influenced markedly by the conformational changes of polymer molecules and the viscosities of permeating liquids. The rejections were dependent on the conformational changes: the permeation rates were mainly governed by the viscosities. Poly(vinylidene fluoride) membranes had much superior resistance to acid, i.e. even when immersed in concentrated sulphuric acid for 7 days, the permeation characteristics did not change at all. The membranes were also effective for the concentration of poly(styrene sulphonic acid) and the removal of sulphuric acid from aqueous mixtures since the concentration of these solutes were optimum.     

Studies on syntheses and permeabilities of special polymer membranes. VI. Permeation characteristics of cellulose nitrate membranes and cellulose membranes

The permeation characteristics of cellulose nitrate membranes and cellulose membranes were investigated using aqueous solutions of poly(ethylene glycol) as feed. To gain cellulose membranes the nitro groups in cellulose nitrate were converted to hydroxyl groups. It was found that cellulose nitrate membranes separate poly(ethylene glycol) 6000 but not any cellulose membrane did separate poly(ethylene glycol) 20 000.     

Studies on syntheses and permeabilities of special polymer membranes: 38. Formation mechanism of finger-like cavities in membranes from cellulose nitrate and single solvent

The relationship between the permeation characteristics of an aqueous polymer solution and the asymmetric structure of cellulose nitrate membranes was investigated under various conditions. The conditions and mechanism of the formation of finger-like cavities in cellulose nitrate membranes are discussed in some detail.     

Studies on syntheses and permeabilities of special polymer membranes

Summary The permeabilities of various cellulose ester membranes and cellulose membranes were investigated using pure water and aqueous solution of glycerol as feed. In all membranes, the permeation rate for aqueous solution of glycerol was greater than for pure water. The permeation rates of cellulose ester membranes increased with an increase in number of carbon atoms of the substituent group in cellulose ester.     

Studies on syntheses and permeabilities of special polymer membranes. 40. Formation conditions of finger-like cavities of cellulose nitrate membranes

The permeation characteristics for polymer aqueous solution and asymmetric structure of cellulose nitrate membranes, in particular the finger-like cavity in the back sponge layer of these membranes, were investigated by changing the preparation conditions of the membranes— the casting solvent, evaporation period, and gelation medium. The formation of the finger-like cavity was dependent on absorption of a water molecule into the casting mixture from the atmosphere during the solvent evaporation process and the exchange velocity between the casting solvent and the gelation medium. The mechanism and conditions for the formation of a finger-like cavity in cellulose nitrate membranes were discussed.     

Studies on syntheses and permeabilities of special polymer membranes: 33. Permeation behaviour of aqueous alcohol solution through cellulose membranes

The permeabilities of various aqueous alcohol solutions through cellulose membranes were investigated by changing the preparation conditions of membranes, the feed concentration, and the feed solute, etc. The permeation rates for aqueous solutions of alcohols, glycols, glycerol, trihydroxyl benzene were greater than for pure water. This permeation phenomenon could be explained by some permeation models considering water cluster, activation of water molecules (second bound water-like) attached weakly to the bound water in cellulose membrane, and the surface of cellulose membrane, and plasticization of cellulose molecules.     

Characteristics of permeation and separation of aqueous alcoholic solutions with chitosan derivative membranes

Permeation and separation characteristics for the feed vapours from aqueous alcoholic solutions through chitosan derivative membranes such as chitosan acetate (GA-ChitoA), chitosan (GA-Chito), and carboxymethyl chitosan acetate (GA-CM-ChitoA) membrane crosslinked with glutaraldehyde were investigated by evapomeation. The GA-Chito and GA-CM-ChitoA membranes prepared from casting solutions containing an optimum amount of glutaraldehyde showed a high permeation rate and high water permselectivity for an azeotropic composition in an aqueous ethanol solution. The permselectivity for water through the GA-CM-ChitoA membrane in evapomeation was in the order of aqueous solutions of methanol < ethanol < 1-propanol. The effect of the chemical and physical structure of these hydrophilic membranes on the permeation and separation characteristics is discussed.     

Separation of aqueous organic liquid solutions through polymer membranes

Characteristics of permeation and separation for aqueous dimethyl sulfoxide, acetic acid and ethanol solutions through some polymer membranes such as chitosan, poly(vinyl chloride) and poly(dimethyl siloxane) membrane were studied by evapomeation. In temperature difference controlling evapomeation (TDEV), when the temperature of the feed solution was kept constant and the temperature of the membrane surroundings was changed, permselectivity for water increased in the chitosan and poly(vinyl chloride) membranes; in the poly(dimethyl siloxane) membrane the perm-selectivity for ethanol increased while decreasing the temperature of the membrane surroundings. Permeation and separation mechanisms for aqueous organic liquid solutions through the above polymer membranes by the TDEV method are discussed.     

Studies on syntheses and permeabilities of special polymer membranes. XIV. Permeation characteristics of modified nylon 12 membranes

The permeation characteristics and the burst strength of nylon 12 membranes treated with heat in various solutions such as aqueous solutions of formic acid, formic acid/formalin, and sodium hydroxide/ formalin were investigated under various conditions. They were significantly influenced by the treatment solution, temperature and time, and the concentration of acid and alkali in the treatment solution. In particular, nylon 12 membranes treated with formic acid/formalin remarkably improved the permeation characteristics and the burst strength. These phenomena were discussed from the standpoint of the effective pore size and pore number in the membrane, and the form and aggregation of polymer molecules forming the membrane.     

Studies on synthesis and permeability of special polymer membranes

Summary The permeation characteristics of polymer blend membranes from poly(vinylidene fluoride) and poly-(ethylene glycol) to aqueous polymer solution were investigated under carefully controlled conditions. The permeation characteristics were influenced significantly by the blend ratio, the temperature and time of heat treatment, which changed the structure of the resulting membranes.     

Studies on syntheses and permeabilities of special polymer membranes. IV. Permeation characteristics of improved cellulose nitrate membranes

For the purpose of the application of cellulose nitrate membranes for artificial kidneys, the permeation characteristics and the bursting strength of three types of membranes, which were prepared from a system of cellulose nitrate/methyl alcohol/1,4-dioxane/barium perchlorate (CN-1), from a system of cellulose nitrate/methyl alcohol/formamide (CN-2), and a poly(ethylene terephthalate) cloth coated with the casting solution of CN-2 (CN-3), were investigated under various conditions. It was found that permeabilities of these membranes were influenced significantly by the preparation methods of the membranes and the permeation conditions, and they depended upon the structure of the resulting membranes and the interaction between the polymer in the membrane and the feed. In blood filtrations, the permeation rates of our three types of membranes had about four-fold values than a cuprophane membrane, and moreover no protein was found in the blood filtrate. The bursting strength of the membranes swollen with water was in the order CN-3 > cuprophane > CN-2 > CN-1, and this ratio was calculated to be about 5.9:1.0:0.5:0.3     

Studies on syntheses and permeabilities of special polymer membranes. 37. Permeabilities of poly(γ-methyl L-glutamate) membranes

The permeation characteristics of poly(γ-methyl L-glutamate) (PMLG) membranes in the separation of polymers, poly(ethylene glycol) and poly(vinyl alcohol), from their aqueous solutions were influenced by the compaction of membrane swollen with water under pressure. The rate of pure water permeability up to an operating temperature of 70°C was governed by a change in the secondary-structure of PMLG. In addition, the permeabilities of alcohols through PMLG membrane were discussed.     

Studies on syntheses and permeabilities of special polymer membranes. III. Permeation of aqueous alcohol solutions and binary organic liquid mixtures through alkali bridged poly(vinyl alcohol) membranes

The preparation conditions of water insoluble poly(vinyl alcohol) membranes were investigated using three kinds of monovalent alkali metal compounds, namely, lithium hydroxide, sodium hydroxide, and potassium hydroxide. The mechanism for the formation of water insoluble membranes is discussed. The permeabilities of pure alcohols were improved by adding ethylene glycol to the casting solutions and they depended upon the radii of alkali metal ions and the density of locations bridged with these ions. The permeation and separation characteristics of three different alcohol/water systems and three different alcohol/benzene systems through alkali bridged poly(vinyl alcohol) membranes were studied by changing the feed composition of the binary mixtures. In alcohol/water solutions, the depression of permeation depended upon the compaction of membrane under pressure. The permeation rate of water/lower alcohol solution was faster than that of water/higher alcohol solution in all feed compositions. Separation of water/alcohol at given water contents increased with an increase in the molecular length of the alcohols. In the three different alcohol/benzene systems, the permeation rates increased with an increase in the alcohol fraction in feed, and the permeation rate of benzene/lower alcohol mixture was faster than that of benzene/higher alcohol mixture in all feed compositions. Separation of benzene/alcohol mixtures at given benzene contents decreased with an increase in the molecular length of alcohols. These phenomena are discussed from the standpoint of the molecular size, the molecular shape, and the physicochemical natures of the permeating species and the polymer membrane.     

Investigations on nylon 4 membranes: Synthesis and transport properties. II. Transport properties of nylon 4 polymer membranes

The reverse osmosis, ultrafiltration, and dialysis properties of nylon 4 membranes to separations of sodium chloride, urea, a series of ethylene glycols and other compounds in the aqueous phase were investigated. The nylon 4 membranes were prepared from a formic acid solution with and without organic or inorganic additives. The effects of polymer concentration, amount of additives, casting time, and temperature on the membrane performance in terms of salt separation and product rate were investigated. The tensile properties of the nylon 4 membranes in both the dry and wet states were determined. It was found that the highest salt separation of a 0.1% sodium chloride solution did not exceed 53.3%. However, these membranes showed some intersting dialysis properties which were comparable to those of commercial cellophane and cellulose acetate membranes.     

Separation of liquid mixtures by using polymer membranes. III. Water–alcohol separation by pervaporation through modified PAN membrane

The modification of polyacrylonitrile membrane with ethanolamine was carried out, and the permeation characteristics in pervaporation were examined using the aqueous alcohol solutions. In pervaporation of a water/alcohol solution, preferential permeation of water was observed for all these membranes because of the hydrogen-bonding interaction. The selectivity of the modified polyacrylonitrile (PAN) membrane depended on operating temperature, but was independent on the thickness of the membrane. Furthermore, it was found that the membrane with more ethanolamine content had a higher affinity to water. The effect of feed concentration and the molecular size of the permeating species on the separation factor and permeation flux was also investigated.     

Permeability through cellulose membranes grafted with vinyl monomers in a homogeneous system. VIII. N-vinylpyrrolidone-grafted cellulose membranes

The homogeneous grafting of N-vinylpyrrolidone (NVP) onto cellulose was carried out in a dimethyl sulfoxide/paraformaldehyde (DMSO/PF) solvent system. The diffusive permeabilities of solutes through the NVP-grafted cellulose membranes, apparent activation energy for solute permeation through them, states of water in them, and their microphaseseparated structures were investigated. The solute permeability through the grafted membranes was superior to that through the cellulose membrane cast from the DMSO/PF solution of cellulose. The total water and nonfreezing water contents of the grafted membranes were larger than those of the cellulose membrane. The difference in permeability through the membranes was not correlated quantitatively with the amount of each state of water in them. Activation energies for permeation of solutes through the grafted membranes were similar to those through the cellulose membrane. © 1994 John Wiley & Sons, Inc.