Solute diffusion in swollen membranes. IX. Scaling laws for solute diffusion in gels

A scaling law was developed for the diffusion coefficient of spheroidal and ellipsoidal solutes in nonporous, equilibrium-swollen hydrogels. The law relates the solute diffusion coefficient to the solute size, the gel mesh size, and the gel equilibrium volume degree of swelling. The law was verified by appropriate data of low and high molecular weight solute diffusion through hydrogels such as swollen networks of poly(vinyl alcohol), poly(2-hydroxyethyl methacrylate), cellulose, and others. An additional scaling law was developed which relates the rate of release of a small or large molecule from an equilibrium swollen hydrogel with time and with morphological characteristics of the polymeric network.     

聚醚共聚酰胺(PEBA)膜的溶胀和渗透汽化行为研究

用涂布法制备出PEBA均质膜,分别测试了膜在纯醋酸正丁酯、水以及醋酸正丁酯稀水溶液中的溶胀率,并考察了浸泡时间、温度和溶液浓度对溶胀率的影响;结果表明:PEBA膜在水中溶胀很小,对醋酸正丁酯具有优先吸附能力;溶胀率随浸泡时间的延长、浸泡液浓度和温度的升高而逐渐上升。渗透汽化实验表明膜对醋酸正丁酯的良好选择性,膜的渗透通量和分离因子随着浓度的增加而增加,渗透通量随着温度的升高而增加,但分离因子随温度的升高而减小;当原料液浓度为0.6%(wt)时,醋酸正丁酯的渗透通量为143.9g·m-2·h-1,分离因子达到236.9。     

Diffusion in aqueous polymer solutions

The diffusion of Direct Blue 76 dye in aqueous dilute polymer solutions was studied using the capillary method. The polymer systems studied included dilute solution of carboxymethyl cellulose, poly(ethylene oxide), and polyacrylamide. It was found that the diffusion coefficient of Direct Blue 76 in carboxymethyl cellulose is higher than that in pure water, while in polyacrylamide and poly(ethylene oxide) solutions the value is lower than that in pure water. The diffusion coefficient of Direct Blue was found to decrease with increasing polymer concentration in case of poly(ethylene oxide) and polyacrylamide, while in case of carboxymethyl cellulose the diffusion coefficient increases with polymer concentration. The effect of temperature on the diffusion coefficient of Direct Blue 76 in the three polymers was found to obey the Arrhenius equation. The activation energy for diffusion of Direct Blue 76 in water, poly(ethylene oxide), polyacrylamide, and carboxymethyl cellulose was found to be 4.38, 7.7, 5.44, and 5 kcal, respectively, for polymer concentration of 0.25 g/l.     

交联直写海藻酸盐水凝胶中空纤维的凝胶率与溶胀度

以海藻酸钠为原料、氯化钙为交联剂,反应直写制备海藻酸钙水凝胶中空纤维及组织工程支架.纤维的凝胶率和溶胀度直接影响支架的成形质量与所装载细胞的存活率.浸取分离所直写中空纤维的未交联部分,分析材料浓度对凝胶率的影响;以滴注凝固浴制备的海藻酸钙微球为对照组,分析直写工艺的溶胀度表现.结果表明,以4%海藻酸钠与3%氯化钙材料交联直写的中空纤维凝胶率和纤维形貌较好地满足了直写工艺的要求;随着海藻酸钠浓度的增加,中空纤维的溶胀度先减小后小幅升高并趋于稳定;随着氯化钙浓度的增加,凝胶纤维的溶胀度逐渐减小;反应直写工艺由于较小的两相接触表面,其溶胀度比凝固浴制备凝胶微球高2～5倍,更高的含水率有利于保障所装载细胞的活性和传质.     

Swelling–deswelling behavior of poly(acrylamide‐co‐maleic acid) hydrogels

In this study the poly(acrylamide‐co‐maleic acid) hydrogels containing small amounts of maleic acid have been synthesized, and the effect of pH, ionic strength, and nature of counterions on the equilibrium water uptake has been investigated. The incorporation of small amount of maleic acid results in the transition of swelling mechanism from Fickian to non‐Fickian. The equilibrium mass swelling has been found to increase with pH of the swelling medium while increase in ionic strength causes a decrease in the swelling. The amount of maleic acid present in the hydrogel affects the swelling behavior in rather an unusual way. With lower acid contents, the equilibrium mass swelling increases while higher concentrations of maleic acid cause a decrease in the degree of swelling. The hydrogels have been found to undergo a number of swelling–deswelling cycles when pH of the swelling medium changes from 8.0 to 2.0. Hydrogels require more time to deswell compared to the time required for swelling, which has been explained on the basis of the fact that gels follow different mechanisms for the two processes. Various swelling parameters such as equilibrium mass swelling, diffusion coefficient, intrinsic diffusion coefficient, swelling exponent, etc., have been evaluated. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2782–2789, 2001     

Thermoreversible hydrogels. IV. Effect of some factors on the swelling behavior of N-tetrahydrofurfurylacrylamide

A thermoreversible hydrogel, poly(N-tetrahydrofurfurylacrylamide) [poly-(NTHFAAm) gel], was prepared from N-tetrahydrofurfurylacrylamide, which was synthesized from N-tetrahydrofurfurylamine and acryloyl chloride (through acylation), with N,N′-methylenebisacrylamide, a crosslinker, in various aqueous solutions. The influences of temperature, gel thickness, and polymerization media on the swelling behaviors in water were investigated. The effect of the gel thickness on the swelling ratio for NTHFAAm gel indicated that the equilibrium swelling time and diffusion coefficient for the thinner gel were faster than those for the thicker gels. The effects of different polymerization media on the gel swelling ratio showed that the larger the solvent molecular size and the poorer the miscibility of the monomer and solvent, the higher the swelling ratio and diffusion coefficient. The drug release profiles in the various gels were also investigated. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1597–1603, 1998     

Radiation synthesis and characterization of 2‐hydroxyethyl‐methacrylate‐based hydrogels containing di‐ and tri‐protic acid and its application on wastewater treatment

Radiation‐crosslinked 2‐hydroxyethylmethacrylate/citric acid (HEMA/CAc), 2‐hydroxyethylmethacrylate/tartaric acid (HEMA/TA), and 2‐hydroxyethylmethacrylate/succinic acid (HEMA/Sc) copolymers were prepared by using ⁶⁰Co γ‐rays. The gel fraction yield and the swelling behavior of the prepared hydrogels were studied. It was shown that increasing irradiation doses was accompanied by an increase in yield of gel fraction and a decrease in swelling degree. The parameters of equilibrium swelling, maximum swelling, initial swelling rate, swelling exponent, and diffusion coefficient of the hydrogels were determined by studying the swelling behavior of the hydrogels prepared. It was seen that the equilibrium swelling degree increases as the content of acid increases, as a result of introducing more hydrophilic groups. When the hydrophilic polymer (acids) varies in the content range of 40–80 mg, swelling exponents (n) decreases, thereby indicating a shift in the water‐transport mechanism from the anomalous (non‐Fickian)‐type to the Fickian‐type. Characterization and some selected properties of the prepared hydrogels were studied, and accordingly the possibility of its practical use in the treatment of industrial wastes such as dyes and heavy metals (Fe, Ni, Co, and Cu) were also studied. The effect of treatment time, pH of feed solution, initial feed concentration, and temperature on the dye and heavy metals uptake was determined. The uptake order for a given metal was HEMA/TA hydrogel > HEMA/CAc > HEMA/Sc hydrogel. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

SWELLING PROPERTIES OF POLY(N-VINYLIMIDAZOLE) HYDROGELS

The swelling capacity of poly(N-vinylimidazole) hydrogels in aqueous solutions and organic solvents was measured as a function of polymer network structure. In pure water, the swelling capacity decreases monotonously upon increasing the crosslinker ratio and the total comonomers concentration in the polymerization feed mixture. In methanol a similar behaviour was observed while in ethanol, the swelling capacity shows an abrupt change from large values to 0.01 grams of water per gram of dry gel, that is to say, PVI experience swollen-collapsed transitions with small changes of the gel crosslinking degree. Molecular weight of chains between crosslinks, determined from swelling measurements in methanol, scales with the product of the crosslinker and total comonomers concentrations in the feed mixture to m1.14-0.05. The dependence of the polymer solvent interaction parameter on the polymer concentration inside the swollen gel was also determined for water and ethanol.     

Preparation of poly(acrylic acid‐co‐acrylamide)/kaolin and release kinetics of urea from it

A series of poly(acrylic acid‐co‐acrylamide)/kaolin [poly(AA‐co‐Am)/kaolin] composites were prepared by aqueous solution copolymerization of partially neutralized acrylic acid and acrylamide in the presence of kaolin nanopowder, which was synthesized to act as a release carrier of urea fertilizer. The superabsorbent composite was swollen in aqueous solution of urea to load urea, and the effect of urea concentration on the swelling was investigated. Furthermore, the effects of the contents of crosslinker, kaolin, and acrylamide, the neutralization degree of acrylic acid, and temperature, pH, and ionic strength of release medium on water absorbency and diffusion coefficient of urea release from poly(AA‐co‐Am)/kaolin were studied systematically. It was found that urea loading percentage could be adjusted by urea concentration of swelling medium, and urea diffusion coefficient could be regulated through the contents of crosslinker, kaolin, and acrylamide, and the neutralization degree of acrylic acid. Additionally, temperature and ionic strength of release medium may also affect the urea release process. The conclusions obtained could provide theoretical basis for urea diffusion behavior in superabsorbent used in agriculture. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Release of vitamin B12 from poly(N‐vinyl‐2‐pyrrolidone)‐crosslinked polyacrylamide hydrogels: A kinetic study

Hydrogels, composed of poly(N‐vinyl‐2‐pyrrolidone) and crosslinked polyacrylamide, were synthesized and the release of vitamin B₁₂ from these hydrogels was studied as a function of the degree of crosslinking and pH of the external swelling media. The three drug‐loaded hydrogel samples synthesized with different crosslinking ratios of 0.3, 0.7, and 1.2 (in mol %) follow different drug‐release mechanisms, that is, chain relaxation with zero‐order, non‐Fickian and Fickian, or diffusion‐controlled mechanisms. To establish a correlation between their swelling behavior and drug‐release mechanism, the former was studied by the weight‐gain method and, at the same time, the concentration of the drug released was studied colorimetrically. Various swelling parameters such as the swelling exponent n, gel‐characteristic constant k, penetration velocity v, and diffusion coefficient D were evaluated to reflect the quantitative aspect of the swelling behavior of these hydrogels. Finally, the drug‐release behavior of the hydrogels was explained by proposing the swelling‐dependent mechanism. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1706–1714, 2000     

Thermoreversible hydrogels. VIII. Effect of a zwitterionic monomer on swelling behaviors of thermosensitive hydrogels copolymerized by N‐isopropylacrylamide with N,N′‐dimethyl (acrylamidopropyl) ammonium propane sulfonate

A series of thermosensitive hydrogels were prepared from the various molar ratios of N‐isopropylacrylamide, zwitterionic monomer, N,N′‐dimethyl (acrylamidopropyl) ammonium propane sulfonate (DMAAPS), and N,N′‐methylene‐bis‐acrylamide. The influence of the amount of DMAAPS in the copolymeric gels on the swelling behaviors in water, various saline solutions, and various temperatures was investigated. Results indicated that the higher the DMAAPS content in the hydrogel system, the higher the swelling ratio and the gel transition temperature. In the saline solution results showed that, when the salt concentration was greater than the minimum salt concentration (MSC) of poly(DMAAPS), the deswelling behavior of the N‐isopropylacrylamide gel was suppressed more effectively when more DMAAPS was added into the copolymeric gels; but the swelling ratios of the present copolymeric gels did not significantly change while the salt concentration was lower than the MSC of poly(DMAAPS). In addition, only the sample containing 12 mol % DMAAPS (D4) exhibited an antipolyelectrolyte's swelling behavior when the salt concentration was greater than the MSC of poly(DMAAPS). In other words, only when the amount of DMAAPS added into the gel is over some proportion, can the hydrogel show an antipolyelectrolyte's swelling behavior in concentrated salt solution. In saline solutions, the anion effects were greater than the cation effects in the presence of common anion (Cl⁻) with different cations and common cation (K⁺) with different cations for these gels. Finally, the more DMAAPS content in the hydrogel, the higher the diffusion coefficient in dynamic swelling. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2170–2180, 1999     

Effect of porosigen on the swelling behavior and drug release of porous N‐isopropylacrylamide/poly(ethylene glycol) monomethylether acrylate copolymeric hydrogels

A series of porous thermoreversible hydrogels were prepared from N‐isopropylacrylamide (90 mol %) and poly(ethylene glycol) methylether acrylate (10 mol %), which was derived from poly(ethylene glycol) monomethylether, N,N′‐methylenebisacrylamide, and porosigen, or poly (ethylene glycol) (PEG) with different molecular weights (MWs). The influence of pore volume in the gel on the physical properties, swelling kinetics, and solute permeation from these porous gels was investigated. The results show that the surface areas, pore volumes, and equilibrium swelling ratios for the porous gels increased with increasing MW of PEG, but the shear moduli and effective crosslinking densities decreased with increasing MW of PEG. The results from the dynamic swelling kinetics show that the transport mechanism was non‐Fickian. The diffusion coefficients of water penetrating into the gels increased with increasing pore volume of the gels. In addition, we also studied solute permeation through the porous gel controlled by temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5490–5499, 2006     

Development and evaluation of pH-dependent interpenetrating network of acrylic acid/polyvinyl alcohol

The objective of the present work was to synthesize interpenetrating networks (IPNs) of acrylic acid/polyvinyl alcohol (AA/PVA) by free radical polymerization using N,N-methylenebisacrylamide (MBAAm) and glutaraldehyde as cross-linkers. The IPNs were evaluated for swelling, diffusion coefficient and network parameters by using Flory–Huggins theory, i.e., the average molecular weight between cross-links (M _c), polymer volume fraction in swollen state (V _2,s), number of repeating units between cross-links (M _r) and cross-linking density (N). It was found that the degree of swelling of AA/PVA interpenetrating network increases greatly within the pH range 5–7 depending on composition. The gel fraction and porosity increased by increasing the concentration of AA or PVA, while by increasing the degree of cross-linking, porosity decreased and gel fraction increased. Selected samples were loaded with chlorpheniramine maleate as a model drug. Drug release was studied in USP, hydrochloric acid buffer solution of pH 1.2 and phosphate buffer solutions of pH 5.5 and 7.5. Drug release data were fitted into various kinetics models, e.g., zero-order, first-order, Higuchi and Peppas models. The results of the kinetics investigation showed that the drug release from IPNs followed non-Fickian diffusion. Fourier transform infrared spectra confirmed the formation of cross-linked IPNs as there was a shifting to lower frequency of 1,713–1,718 cm^?1 with reduced intensity, while scanning electron microscopy revealed uniform distribution of drug in IPNs.     

Thermoreversible hydrogels. IX. Swelling behaviors of thermosensitive hydrogels copolymerized by N‐isopropylacrylamide with 1‐vinyl‐3‐(3‐sulfopropyl) imidazolium betaine

A series of thermosensitive hydrogels were prepared from the various molar ratios of N‐isopropylacrylamide, 1‐vinyl‐3‐(3‐sulfopropyl) imidazolium betaine (VSIB), and N,N′‐methylene‐bis‐acrylamide. The influence of the amount of VSIB in the copolymeric gels on the swelling behaviors in water, in various saline solutions, and at various temperatures was investigated. The results indicated that the higher the VSIB content in the hydrogel system, the higher the swelling ratio and the gel transition temperature. In the saline solution the results showed that when the concentration of salt is higher than the minimum salt concentration (MSC) of poly(VSIB), the deswelling behavior of the copolymeric gel was more effectively suppressed as more VSIB was added to the copolymeric gels. In addition, only the sample containing 12 mol % VSIB (V4) exhibited an antipolyelectrolyte's swelling behavior when the concentration of salt was higher than the MSC of poly(VSIB). This means that the swelling ratio of the hydrogel can be improved with a higher concentration salt solution. In addition, the anion effects were larger than the cation effects in the presence of a common anion (Cl⁻) with different cations and a common cation (K⁺) with different anions for the hydrogel. Finally, the more VSIB in the hydrogel, the higher the diffusion coefficient in dynamic swelling. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 14–23, 2000     

Synthesis of copolymeric hydrogels using gamma radiation and their utilization in the removal of some dyes in wastwater

Copolymer hydrogels were prepared by γ‐radiation copolymerization of maleic acid (MA) and 2‐hydroxyethylacrylate (HEA) or acrylamide (AAm). The effect of AAm/MA and HEA/MA composition and irradiation dose on the gel fraction yield in the prepared hydrogels was determined. It was found that as the content of MA increased, the gel fraction yield decreased. The increase of irradiation dose resulted in increasing the crosslinked network structure and consequently the gel percent. The parameters of equilibrium swelling, maximum swelling, initial swelling rate, diffusion exponent, and diffusion coefficient of the hydrogels were calculated and evaluated, and it was found that water diffusion to the hydrogels generally was a non‐Fickian diffusion type. Characterization of the prepared hydrogels was studied and accordingly the possibility of its practical use in the treatment of waste dyes from aqueous solution was studied. The effect of treatment time, the pH of the feed solution, initial feed concentration, and temperature on the dye uptake was also investigated. The maximum uptake of the investigated dyes was higher for HEA/MA hydrogel than that for AAm/MA hydrogel. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:3720–3731, 2006     

Swelling-induced surface instability of a hydrogen-bonded LBL film and its self-healing

Thin hydrogel films attached to a rigid substrate can only swell along the direction perpendicular to the substrate, which generates compressive stress within the gel. When the stress is sufficiently large, the free surface of the gel will locally buckle and fold against itself to form various wrinkling patterns. Here we show that hydrogen-bonded layer-by-layer (LBL) films of poly(vinyl pyrrolidone) (PVPON) and poly(acrylic acid) (PAA) also swell in ethanol/water mixtures. Like ordinary hydrogel films attached to a substrate, the LBL films also undergo mechanical instability when their swelling degree is large enough. By adjusting the composition and pH of the ethanol/water mixture, the swelling degree of the film can be adjusted, which further decides whether the mechanical instability occurs or not. Like ordinary hydrogel films, the surface wrinkling of the PVPON/PAA films occurs via a nucleation-growth process. Unlike ordinary hydrogels, the critical swelling degree for the onset of wrinkling for PVPON/PAA films increases with increasing film thickness. More importantly, the wrinkling patterns can be healed automatically, because the transient network of PVPON/PAA films allows for the relief of compressive stress via its rearrangement. The phenomenon observed here may provide a possible way to erase the undesired wrinkling patterns on constrained hydrogel films.     

Radiation-induced grafting of acrylamide and methacrylic acid individually onto carboxymethyl cellulose for removal of hazardous water pollutants

Carboxymethyl cellulose hydrogels were synthesized by grafting of acrylamide (AAm) and methacrylic acid (MAAc) individually with different concentrations onto carboxymethyl cellulose (CMC) using direct radiation grafting technique. It was found that for both Poly(CMC/AAm) and Poly(CMC/MAAc), the grafting yield and grafting ratio increase with the increasing monomer concentration. Also, it is noted that both grafting ratio and grafting yield of Poly(CMC/AAm) are higher than that of Poly(CMC/MAAc). The effect of different monomer concentrations on gel (%) and swelling behavior was studied. It is found that the increasing monomer concentration increases gel (%). For Poly(CMC/AAm) hydrogels, the swelling behavior decreases with increasing AAm concentration due to high crosslinking hydrogel formation, while as MAAc content increases, swelling behavior increases up to Poly(CMC/MAAc) 1:25 wt%. Swelling kinetics and diffusion mechanism indicate that the water penetration obeys non-Fickian transport mechanism. The structures and properties of the original CMC and the prepared Poly(CMC/MAAc) and Poly(CMC/AAm) were characterized using different analytical tools such as Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), and scanning electron microscope (SEM). This study provides a solution to the discharge of different pollutants from wastewater. The adsorption capacity of Poly(CMC/MAAc) and Poly(CMC/AAm) hydrogels toward heavy metals, Cu⁺² and Co⁺², dyes such as acid blue dye and methyl green, and organic contaminants such as 4-chlorophenol and 2,4-Dichlorophenoxy acetic acid has been investigated.     

魔芋葡甘聚糖复合凝胶的制备及其溶胀性能研究

通过在水中复配魔芋葡甘聚糖(KGM)、黄原胶(XG)和β-环糊精(β-CD),制备了KGM/XG/β-CD复合水凝胶。探讨了β-CD含量对凝胶平衡溶胀度的影响,并探讨了介质pH和温度对凝胶溶胀度的影响。结果表明,当m(KGM):m(XG):m(β-CD)=1:1:1时,复合凝胶的平衡溶胀度最大;复合凝胶的溶胀度在溶胀初期增加很快,随着溶胀时间的延长,溶胀度增加变慢,约7 h内基本达到平衡;随着介质pH的增大或体系温度从25℃增加至37℃,KGM/XG/β-CD复合凝胶的溶胀度随之增大。     

Preparation and properties of modified PHEMA hydrogel with sulfonated PEG graft

A novel poly(ethylene glycol) (PEG) macromer with a methacryloyl and sulfonic acid group at each end of the chain was prepared. Modified hydroxyethyl methacrylate (HEMA) based hydrogels were synthesized by crosslinking polymerization of HEMA in the presence of the above‐mentioned PEG macromer. The effect of the sulfonated PEG graft was examined by comparing the swelling properties with those of a pure poly(hydroxyethyl methacrylate) (PHEMA) hydrogel. The modified PHEMA hydrogel exhibited increasing water absorbency with increasing sulfonated PEG content up to 15 wt %. These hydrogels with the sulfonated PEG graft exhibited a more hydrophilic character than the pure PHEMA gel. Also the swelling degree varied slightly with pH, showing increased swelling at higher pH probably due to the presence of the anionic sulfonate group on the PEG end chain. In addition, the protein adsorption test showed a lower level of fibrinogen adsorption from the sulfonated poly(ethylene glycol) (SPEG) modified gel than on the homo PHEMA hydrogel. Interestingly, scanning electron microscopy showed that the porous and rather uniform morphology of the gels changed with increasing sulfonated PEG content in PHEMA. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2484–2489, 2007     

Microstructure dependent diffusion of water-ethanol in swollen poly(vinyl alcohol): A molecular dynamics simulation study

Molecular dynamics (MD) simulation was used to study the swelling properties of poly(vinyl alcohol) (PVA) in ethanol solutions containing 15, 30 and 45 wt% water. The characteristics of the swollen PVA, intrinsic relation between the microstructure of the swollen PVA and the diffusion of water and ethanol in the PVA matrix were analyzed. It was found that the free volume of the swollen PVA reduced with reductions in the degree of crystallinity was accompanied by an increase in the mobility of PVA chains. Water located mostly in the hydrophilic region of the hydroxyl groups of PVA chains; and hydrogen bonding formed between water and PVA. It was also noted water clusters form in the swollen PVA, whose size increased with increasing degree of swelling, whereas ethanol molecules disperse almost individually in the PVA matrix. The diffusion coefficients of water and ethanol in the swollen PVA are predicted to increase linearly with increasing swelling.