Sorption,diffusion, and swelling characteristics of sodium alginate and its blend membranes with poly(vinyl alcohol) in water–acetic acid mixtures

Sorption, diffusion, and swelling characteristics of sodium alginate and its blend membranes with poly(vinyl alcohol) were investigated for water–acetic acid mixtures by using a gravimetric method at 30, 40, and 50°C. The membranes were characterized by X‐ray diffraction and Fourier transform infrared techniques. Concentration‐independent diffusion coefficients were obtained by applying Fick's relationship before completion of equilibrium sorption. Permeation coefficients were calculated from sorption and diffusion coefficients. Concentration profiles of liquids were computed considering the sheet geometry for the membrane by solving Fick's equation under suitable boundary conditions. Arrhenius activation parameters were computed for the transport processes. Experimental results and calculated quantities were discussed to understand membrane–solvent interactions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1139–1150, 2004     

Synthesis and characterization of modified chitosan microspheres: Effect of the grafting ratio on the controlled release of nifedipine through microspheres

The grafting of acrylamide onto a chitosan backbone was carried out at three acrylamide concentrations (polymer/monomer ratio = 1:1, 1:2, and 1:3). The synthesis of the grafted polymer was achieved by K₂S₂O₈‐induced free‐radical polymerization. Microspheres of polyacrylamide‐g‐chitosan crosslinked with glutaraldehyde were prepared to encapsulate nifedipine (NFD), a calcium channel blocker and an antihypertensive drug. The microspheres of polyacrylamide‐g‐chitosan were produced by a water‐in‐oil emulsion technique with three different concentrations of glutaraldehyde as the crosslinking agent. Fourier transform infrared (FTIR) spectroscopy and differential scanning calorimetry (DSC) were used to characterize the grafted copolymers, and the microspheres were prepared from them. FTIR and DSC were also used to analyze the extent of crosslinking. The microspheres were characterized by the particle size; the water transport into these microspheres, as well as the equilibrium water uptake, were studied. Scanning electron microscopy confirmed the spherical nature of the particles, which had a mean particle size of 450 μm. Individual particle dynamic swelling experiments suggested that with an increase in crosslinking, the transport became case II. The release of NFD depended on the crosslinking of the network and on the amount of drug loading. Calculating the drug diffusion coefficients with the initial time and later time approximation method further supported this. The drug release in all 27 formulations followed case II transport, and this suggested that the time dependence of the NFD release followed zero‐order kinetics. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2940–2949, 2003     

Sodium alginate–poly(hydroxyethylmethacrylate) interpenetrating polymeric network membranes for the pervaporation dehydration of ethanol and tetrahydrofuran

Interpenetrating polymeric network (IPN) membranes of sodium alginate (NaAlg) and various amounts of poly(hydroxyethylmethacrylate) (PHEMA) have been prepared and tested for the pervaporation dehydration of ethanol and tetrahydrofuran (THF). The presence of hydrophilic PHEMA in the IPN matrix was found to be responsible for increase in membrane selectivity to water. NaAlg–PHEMA IPN membrane containing 20 wt % of PHEMA exhibited a selectivity of 571 to water for the water–ethanol mixture and 857 for water–THF mixture. These data are much better than those observed for the pristine NaAlg membrane. However, flux of the IPN membranes was smaller than that of pristine NaAlg membrane. Comparatively higher flux values were observed for water–THF mixture than for water–ethanol mixture. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3324–3329, 2006     

Sorption/diffusion of aqueous mixtures of 1,4‐dioxane/tetrahydrofuran through blend membranes of poly(vinyl alcohol) and sodium alginate: Their compatibility and pervaporation separation studies

Blend membranes of poly(vinyl alcohol) (PVA) and sodium alginate (NaAlg) were prepared by solution casting and crosslinked with glutaraldehyde (GA). Polymer blend compatibility was studied in water by measuring solution viscosity at 30°C. From the viscosity data, interaction parameters were determined to find the blend compatibility. Thickness of the membranes ranged between 35 and 40 μm. Circular disc‐shaped samples were cut from the thin membranes to perform gravimetric sorption experiments in water + 1,4‐dioxane and water + tetrahydrofuran mixtures at 30°C. Diffusion coefficients were calculated using Fick's equation. Concentration profiles of liquids were computed by solving Fick's equation under suitable boundary conditions. Diffusion coefficients show a dependence on the composition of the blends as well as composition of binary mixtures. A correlation was attempted between concentration profiles and diffusion coefficients of the transporting liquids. Degree of swelling and sorption coefficients were calculated from the gravimetric sorption data. Sorption kinetics was studied using an empirical equation to understand the nature of sorption–diffusion anomalies. Membrane selectivity for water + 1,4‐dioxane and water + tetrahydrofuran mixtures were calculated from the pervaporation experiments. A correlation between sorption and membrane selectivity was attempted. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 178–188, 2005     

Preparation and characterization of novel semi‐interpenetrating 2‐hydroxyethyl methacrylate‐g‐chitosan copolymeric microspheres for sustained release of indomethacin

A novel semi‐interpenetrating (semi‐IPN) graft copolymer of 2‐hydroxyethyl methacrylate (HEMA) with chitosan (CS) has been prepared in the form of microspheres, using water‐in‐oil (W/O) emulsion technique. Microspheres were characterized by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and X‐ray diffractometry (X‐RD) to confirm the crosslinking and polymorphism of indomethacin (IDM). The X‐RD and DSC techniques indicated a molecular‐level dispersion of IDM in the IPN matrix. Scanning electron micrographs (SEM) taken at the cross section of the microspheres have shown rough surfaces around the microspheres. The sustained release characteristics of the matrices for IDM, an anti‐inflammatory drug, were investigated in pH 7.4 media. Particle size and size distribution of the microspheres were studied by laser light diffraction particle size analyzer. The drug was released in a sustained manner for up to 12 h. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Blend membranes of chitosan and poly(vinyl alcohol) in pervaporation dehydration of isopropanol and tetrahydrofuran

Blend membranes of a natural polymer, chitosan, with a synthetic polymer, poly(vinyl alcohol) (PVA), were prepared by solution casting and crosslinked with a urea formaldehyde/sulfuric acid (UFS) mixture. Chitosan was used as the base component in the blend system, whereas PVA concentration was varied from 20 to 60 wt %. Blend compatibility was studied by differential scanning calorimetry, and Fourier transform infrared spectroscopy was used to study membrane crosslinking. Membranes were tested for pervaporation dehydration of isopropanol and tetrahydrofuran (THF) at 30°C in close proximity to their azeotropic compositions. Membrane performance was assessed by calculating flux and selectivity. Swelling experiments performed in water + organic mixtures at 30°C were used to explain the pervaporation results. The blend membrane containing 20 wt % PVA when tested for 5 and 10 wt % water–containing THF and isopropanol feeds exhibited selectivity of 4203 and 17,991, respectively. Flux increased with increasing concentration of water in the feed. Selectivity was highest for the 20 wt % PVA‐containing blend membrane. The results of this study are unique in the sense that the crosslinking agent used—the UFS mixture—was novel. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1918–1926, 2007     

Polymeric sodium alginate interpenetrating network beads for the controlled release of chlorpyrifos

Novel polymeric sodium alginate (Na‐Alg) interpenetrating network (IPN) beads have been prepared by crosslinking Na‐Alg blend with gelatin (GE) or egg albumin (EA) using glutaraldehyde (GA) as the crosslinking agent. These beads were used for the controlled release of chlorpyrifos. The swelling experiments were performed in water at different temperatures, and these data were used to calculate the molecular mass (M_C) between crosslinks as well as diffusion coefficients. Diffusion coefficients calculated from desorption data were lower by about two orders of magnitude than those calculated from sorption results. Higher values of M_C were obtained for the gelatin‐based IPNs than the neat Na‐Alg and egg albumin‐based matrices. Size of the beads did not vary significantly either by the network or by increasing the exposure time to the crosslinking agent. The scanning electron microscopy (SEM) was used to understand the surface characteristics of the beads. Differential scanning calorimetry (DSC) indicated a molecular level dispersion of chlorpyrifos in the polymer matrix. The percentage entrapment efficiency showed a dependence on the type of network polymer as well as time of exposure to the crosslinking agent. The encapsulation efficiency decreased with an increase in time of exposure to the crosslinking agent. In vitro release experiments have been performed to follow the release kinetics of chlorpyrifos from the matrices. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 911–918, 2002     

Preparation and characterization of novel polyurethanes containing 4,4′‐{oxy‐1,4‐diphenyl bis(nitromethylidine)}diphenol schiff base diol

Four novel segmented polyurethanes (PUs) based on4,4′‐{oxy‐1,4‐diphenyl bis(nitromethylidine)}diphenol (ODBNMD) diol with different diisocyanates such as 4,4′‐diphenylmethane diisocyanate, toluene 2,4‐diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate have been prepared by solution method. The structures of ODBNMD and PUs have been confirmed by Fourier transform infrared (FTIR), nuclear magnetic resonance (¹H‐NMR and ¹³C‐NMR), UV‐visible, and fluorescence spectroscopies. The segmented PUs were further characterized by thermogravimetry (TGA), differential scanning calorimetry (DSC), and wide‐angle X‐ray diffraction. FTIR confirmed hydrogen bonding interactions, whereas TGA and DSC suggested that introduction of aromatic/phenyl ring in the main chain considerably increased the thermal stability. POLYM. ENG. SCI., 54:24–32, 2014. © 2013 Society of Plastics Engineers     

Synthesis and characterization of moisture‐cured polyurethane membranes and their applications in pervaporation separation of ethyl acetate/water azeotrope at 30°C

NCO‐terminated polyurethane membranes were prepared using diisocyanate, diol, and trimethylolpropane (TMP) using an NCO/OH ratio of 1.6 : 1. Prepolymer was chain‐extended using cellulose acetate butyrate (CAB) in the ratios of 2 : 1, 4 : 1, and 3 : 1 of NCO/OH. Polyurethane (PU) membranes were characterized by differential scanning calorimeter (DSC) and thermogravimetry (TGA) to investigate their thermal properties. Equilibrium sorption studies were carried out at 30°C in water and ethyl acetate media as well as in their binary mixtures. The influence of CAB on pervaporation (PV) separation of an ethyl acetate/water (92/8, w/w, i.e., azeotropic composition) mixture was investigated. Membranes in this study showed a selectivity of 42.42 with a flux value of 0.187 kg/m/h for 3 : 1% NCO/OH containing PU membrane. In order to gain a more detailed picture of the molecular transport phenomenon, we performed the sorption gravimetric experiments at 30°, 35°, 40°, and 50°C to compute diffusion, swelling, sorption, and permeability coefficients of PU membranes in the azeotropic mixture of ethyl acetate and water. Activation parameters for diffusion and permeation were computed from the Arrhenius equation to understand the polymer/solvent interactions. Sorption trends and diffusion anomalies were established through an empirical equation after estimating the diffusion parameters. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3405–3414, 2007     

Encapsulation efficiency and release kinetics of solid and liquid pesticides through urea formaldehyde crosslinked starch,guar gum,and starch + guar gum matrices

This article presents our preliminary experimental data on the release kinetics and encapsulation efficiency of urea formaldehyde (UF) crosslinked matrices of starch (St), guar gum (GG), and starch + guar gum (St + GG) for the controlled release of solid (chlorpyrifos) and liquid (neem seed oil) pesticides. The data reveal variable release rates in relation to the polymer type and especially the pesticide type. It is possible to slow the release rates of pesticides using cheaply available materials such as starch and guar gum. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2863–2866, 2001