Synthesis and characterization of glutaraldehyde‐crosslinked calcium alginate for fluoride removal from aqueous solutions

A novel biosorbent was developed by the crosslinking of an anionic biopolymer, calcium alginate, with glutaraldehyde. The glutaraldehyde‐crosslinked calcium alginate (GCA) was characterized by Fourier transform infrared spectroscopy and porosity and surface area analysis. The batch equilibrium and column flow adsorption characteristics of fluoride onto the biosorbent were studied. The effects of the pH, agitation time, concentration of adsorbate, and amount of adsorbent on the extent of adsorption were investigated. The experimental data were fitted to the Langmuir and Freundlich adsorption isotherms. The data were analyzed on the basis of the Lagergren pseudo‐first‐order, pseudo‐second‐order, and Weber–Morris intraparticle diffusion models. The maximum monolayer adsorption capacity of the GCA sorbent as obtained from the Langmuir adsorption isotherm was found to be 73.5 mg/g for fluoride. The χ² and sum of squares of the error analysis were used to correlate the equilibrium isotherm models and kinetics. In addition, breakthrough curves were obtained from column flow experiments. The experimental results demonstrate that the GCA beads could be used for the defluoridation of drinking water through adsorption. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Characterization of semi‐interpenetrating polymer network polystyrene cation‐exchange membranes

Polystyrene cation exchange membranes were prepared by a PVC‐based semi‐interpenetrating polymer network (IPN) method. The reaction behaviors during polymerization and sulfonation in the preparation method were investigated. The prepared membranes were characterized in terms of the physical and electrochemical properties. The membranes exhibited reasonable mechanical properties (tensile strength, 13 MPa, and elongation at break, 52%) for an ion‐exchange membrane with the ratio of polystyrene–divinylbenzene (DVB)/poly(vinyl chloride) (PVC) (R_St‐DVB/PVC) of below 0.9. Fourier transform infrared/attenuated total reflectance, differential scanning calorimetry, and scanning electron microscopy studies revealed the formation of a homogeneous membrane. The resulting membrane showed membrane electrical resistance of 2.0 Ω cm² and ion‐exchange capacity of 3.0 meq/g dry membrane. The current–voltage (I–V) curves of the membrane show that the semi‐IPN polystyrene membranes can be properly used at a high current density, and that the distribution of cation‐exchange sites in the membrane was more homogenous than that in commercial membranes. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1488–1496, 2003     

Synthesis and characterization of Na‐alginate/acrylamide hydrogel and its application in dye removal

Sodium‐alginate/acrylamide (Na‐alginate/AAm) cross‐linked hydrogel was prepared by using gamma irradiation. The gel content and the water absorbency behavior of the obtained hydrogel were investigated. The thermal and morphological properties of the prepared hydrogel were studied using thermogravimetric analysis and scanning electron microscopy. The thermal stability of Na‐alginate significantly changed when mixed with AAm. The adsorption of basic violet 7 dye on the prepared hydrogel was studied under different experimental conditions. The adsorption process for the basic dye was proven pH dependent. The maximum amount adsorbed (mg/g) of the Na‐alginate/AAm for the dye was found to be 78.1.0 mg/g at pH 9.0. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and characterization of a semi‐interpenetrating network gel polymer electrolyte

Poly(PEG200 maleate) was synthesized as a new type crosslinkable prepolymer and the semi‐interpenetrating polymer network (semi‐IPN) gel electrolytes were prepared by means of thermal polymerization. Their intrinsic properties were characterized by FTIR spectroscopy, differential scanning calorimetry (DSC), X‐ray diffractions (XRD), scanning electron microscopy, alternating current impedance (AC impedance), and linear sweep voltammetry. The prepared polymer hosts are transparent and have good mechanical properties. The results of DSC and XRD confirm that the prepared hosts are in amorphous state and they can hold enough liquid electrolytes, which is favorable for Li⁺ ions to transport via both the absorbed liquid electrolyte and the gel of the entire systems. The semi‐IPN gel electrolytes exhibit high ionic conductivity on the order of 10^?3 S cm^?1. Their electrochemical stability up to +4.6 V against Li⁺/Li also makes them potential candidates for application as polymer electrolytes in devices. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Swelling characterizations of chitosan and polyacrylonitrile semi‐interpenetrating polymer network hydrogels

Temperature‐ and pH‐responsive semi‐interpenetrating polymer network (semi‐IPN) hydrogels constructed with chitosan and polyacrylonitrile (PAN) were studied. The characterizations of semi‐IPN hydrogels were investigated using Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC). IPN hydrogels exhibited a relatively high swelling ratio, 23.31%–145.20% at room temperature. The swelling ratio of hydrogels depends on pH and temperature. DSC was used to determine the amount of free water in IPN hydrogels. The amount of free water increased with increasing chitosan content in the semi‐IPN hydrogels. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2011–2015, 2003     

Towards improving wet‐adhesion in a metal oxide‐polymer coating system

An investigation using a variable radius roll adhesion test (VaRRAT) revealed an irreversible increase in the wet‐adhesion in a metal–oxide–polymer system, under specific experimental conditions. This observation is further confirmed by the T_g measurements and the ATR‐FTIR studies. The increase in wet‐adhesion is attributed to late H₂O‐catalyzed curing of the previously partially cured polymers (epoxy ring opening), as well as the formation of nanocomposite layer within the epoxy primer matrix, because of precipitation of the nanocrystals including zinc ammine complexes formed as a result of dissolution of the zinc/aluminum alloy as well as the metal oxide pigments by the amine crosslinker. High activation energy of ～100 kJ mol^?1 indicated a chemical process to be responsible for the adhesion gain. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3318–3327, 2006     

Semi‐interpenetrating networks based on poly(N‐isopropyl acrylamide) and poly(N‐vinylpyrrolidone)

Three series of novel semi‐interpenetrating polymer networks, based on crosslinked poly(N‐isopropylacrylamide), PNIPA, and different amounts of the linear poly(N‐vinylpyrrolidone), PVP, were synthesized to improve the mechanical properties and thermal response of PNIPA gels. The effect of the incorporation of the linear PVP into the temperature responsive networks on the temperature‐induced transition, swelling/deswelling behavior, and mechanical properties was studied. Polymer networks with four different crosslinking densities were prepared with varying molar ratios (25/1 to 100/1) of the monomer (N‐isopropylacrylamide) to the crosslinker (N,N′‐methylenebisacrylamide). The hydrogels were characterized by determination of the equilibrium degree of swelling, the dynamic shear modulus and the effective crosslinking density, as well as tensile strength and elongation at break. Furthermore, the deswelling kinetics of the hydrogels was studied by measuring their water retention capacity. The inclusion of the linear hydrophilic PVP in the PNIPA networks increased the equilibrium degree of swelling. The tensile strength of the semi‐interpenetrating networks (SIPNs) reinforced with linear PVP was higher than that of the PNIPA networks. The elongation at break of these SIPNs varied between 22% and 55%, which are 22 – 41% larger than those for pure PNIPA networks. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and properties of carboxymethyl cellulose‐graft‐poly(acrylic acid‐co‐acrylamide) as a novel cellulose‐based superabsorbent

A new cellulose‐based superabsorbent polymer, carboxymethyl cellulose‐graft‐poly(acrylic acid‐co‐acrylamide), was prepared by the free‐radical grafting solution polymerization of acrylic acid (AA) and acrylamide (AM) monomers onto carboxymethyl cellulose (CMC) in the presence of N,N′‐methylenebisacrylamide as a crosslinker with a redox couple of potassium persulfate and sodium metabisulfite as an initiator. The influences of reaction variables such as the initiator content, crosslinker content, bath temperature, molar ratio of AA to AM, and weight ratio of the monomers to CMC on the water absorbency of the carboxymethylcellulose‐graft‐poly(acrylic acid‐co‐acrylamide) copolymer were investigated. The copolymer's structures were characterized with Fourier transform infrared spectroscopy. The optimum reaction conditions were obtained as follows: the bath temperature was 50°C; the molar ratio of AA to AM was 3 : 1; the mass ratio of the monomers to CMC was 4 : 1; and the weight percentages of the crosslinker and initiator with respect to the monomers were 0.75 and 1%, respectively. The maximum water absorbency of the optimized product was 920 g/g for distilled water and 85 g/g for a 0.9 wt % aqueous NaCl solution. In addition, the superabsorbent possessed good water retention and salt resistance. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1382–1388, 2007     

Thermal characterizations of semi‐interpenetrating polymer networks composed of poly(ethylene oxide) and poly(N‐isopropylacrylamide)

Poly(N‐isopropylacrylamide) (PNIPAAm)/poly(ethylene oxide) (PEO) semi‐interpenetrating polymer networks (semi‐IPNs) synthesized by radical polymerization of N‐isopropylacrylamide (NIPAAm) in the presence of PEO. The thermal characterizations of the semi‐IPNs were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and dielectric analysis (DEA). The melting temperature (T_m) of semi‐IPNs appeared at around 60°C using DSC. DEA was employed to ascertain the glass transition temperature (T_g) and determine the activation energy (E_a) of semi‐IPNs. From the results of DEA, semi‐IPNs exhibited one T_g indicating the presence of phase separation in the semi‐IPN, and T_gs of semi‐IPNs were observed with increasing PNIPAAm content. The thermal decomposition of semi‐IPNa was investigated using TGA and appeared at around 370°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3922–3927, 2003     

A novel pH‐sensitive gelatin–DNA semi‐interpenetrating polymer network hydrogel

Gelatin and DNA were mixed together in various ratios followed by the addition of glutaraldehyde as a cross‐linker. FT‐IR spectroscopy confirmed the formation of a semi‐interpenetrating polymer network (semi‐IPN) between the gelatin and DNA. The gelatin–DNA semi‐IPN hydrogel underwent, reversibly, remarkable changes in swelling degree in response to the variation of pH. In the low‐pH range, the hydrogel showed a lower swelling degree; with an increment in pH, the hydrogel was highly swollen, which is considered to originate from the complexation and de‐complexation between gelatin and DNA, as was verified by turbidity measurements. Higher contents of DNA result in an increase in the swelling degree, which is presumably due to the easy outward expansion of free DNA moieties. The permeability coefficient, P, for a model molecule, cimetidine, through the semi‐IPN hydrogel membranes was determined in pH 1.0 and pH 12.0 buffer solutions. The results show that the permeation of cimetidine is responsive to pH change, and an evident variation in the P values occurs in response to the pH of the media. Copyright © 2004 Society of Chemical Industry     

Fourier transform infrared and wide‐angle X‐ray diffraction studies of the thermal cyclization reactions of high‐molar‐mass poly(acrylonitrile‐co‐itaconic acid)

The stabilization reactions of a high‐molar‐mass poly(acrylonitrile‐co‐itaconic acid) precursor in air at 200, 220, and 240°C were studied with Fourier transform infrared. Principally, the cyclization of nitrile groups leading to the ladder structures of tetrahydropyridine occurred. Evidence for oxidative reactions causing the conversion of the C? C structure to C?C and generating groups such as ? OH and C?O was also obtained. As the temperature of stabilization was increased, the rate of the reaction increased without causing great changes in the Fourier transform infrared spectral patterns. The maximum nitrile conversion achievable was limited by the temperature of stabilization. Although the reaction stagnated at 40 and 80% at 200 and 220°C, it was practically complete in about an hour at 240°C. Higher temperatures also favored the formation of extended conjugated structures. Wide‐angle X‐ray diffraction studies of the polymer stabilized at 300 and 400°C in argon confirmed that the aromatization index value and the crystallinity of the polymer increased proportionally to the temperature of pyrolysis. An analysis of the wide‐angle X‐ray diffraction pattern and the elemental composition of the stabilized polymer implied the formation of the tetrahydropyridine structure at 400°C. The higher pyrolysis temperature favored the formation of the lattice constituted by this group. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3055–3062, 2006     

Preparation and characteristic of a sodium alginate/carboxymethylated bacterial cellulose composite with a crosslinking semi‐interpenetrating network

A novel ionic crosslinking sodium alginate (SA)/carboxymethylated bacterial cellulose (CM‐BC) composite with a semi‐interpenetrating polymer network (semi‐IPN) structure was developed in this study. The composite was prepared through the blending of an SA gel with CM‐BC then crosslinking by Ca²⁺ followed by a freeze‐drying process. Scanning electron microscopy showed the composite matrix organized in a three‐dimensional network of CM‐BC interpenetrated against SA molecular chains with a quantity of calcium alginate microspheres upon the surface. The swelling ratios of the composite were enhanced by 183, 198, and 212% with the supplementation of CM‐BC weight fractions of 25, 50, and 75%, respectively; the swelling ratios changed with changing pH. The tensile modulus, tensile strength, and elongation at break of SA were enhanced by 165, 152, and 188%, respectively, with the addition of 50 wt % CM‐BC. This study demonstrated that the semi‐IPN structure dramatically changed the swelling and mechanical properties of the composite, and the semi‐IPN will be a promising candidate for biomedical applications such as wound dressings and skin tissue engineering. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39848.     

Molecular interactions in poly(methacrylic acid)/poly(N‐isopropyl acrylamide) interpenetrating polymer networks

The molecular interactions between the component networks in poly(methacrylic acid)/poly(N‐isopropyl acrylamide) (PMAA/PNIPAAm) interpenetrating polymer networks (IPNs) were investigated using attenuated total reflectance (ATR)‐Fourier transform IR (FTIR) spectroscopy. Hydrogen‐bond formation was noted between the carboxyl groups of PMAA and the amide groups of PNIPAAm. The ATR‐FTIR results showed shifts in the carboxylic and amide groups, indicating the existence of hydrogen bonding between these two individual networks within the IPNs. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1077–1082, 2001     

Preparation and characterization of pH‐ and temperature‐responsive semi–interpenetrating polymer network hydrogels based on linear sodium alginate and crosslinked poly(N‐isopropylacrylamide)

In this study, pH‐ and temperature‐responsive hydrogels based on linear sodium alginate (SA) and crosslinked poly(N‐isopropylacrylamide) (PNIPAAm) were prepared by semi‐interpenetrating network (semi‐IPN) technique. The dually responsive hydrogels were characterized by FTIR, DSC, and SEM, and their temperature‐ and pH‐responsive behaviors were investigated by measuring equilibrium swelling ratios and pulsatile swelling experiments. The results showed that these hydrogels underwent volume phase transition at around 33°C irrespective of the pH value of the medium, but their pH sensitivity was evident only below their volume phase transition temperature. Under basic conditions, the swelling ratios of SA/PNIPAAm semi‐IPN hydrogels were greater than that of pure PNIPAAm hydrogel and increased with increasing SA content incorporated into the hydrogels, but the case was inverse under acidic conditions. The pulsatile swelling experiments indicated that the higher the SA content in SA/PNIPAAm semi‐IPN hydrogels, the faster the response rate to both pH and temperature change. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1931–1940, 2005     

The influence of lixiviates on the thermal degradation of diglycidyl ether of bisphenol A n=0/1,2‐diaminecyclohexane studied by dynamic mechanical analysis and thermogravimetry‐fourier transform infrared spectroscopy

The influence of the lixiviates originated in a municipal landfill on the thermal degradation of a polymeric system composed of a diglycidyl ether of bisphenol A (n = 0) and 1,2‐diaminecyclohexane was studied by dynamic mechanical analysis. Storage modulus (E′), loss modulus (E″), and glass transition temperature were measured to make a comparative study between the samples before and after being exposed to the chemical compounds in the lixiviate agents. The different data obtained were analyzed to check the resistance of these materials to chemical attack and the possibility of their use as coating materials in plants where those reagents were present. Thermal stability of the system diglycidyl ether of bisphenol A/1,2‐diaminecyclohexane exposed to the attack of lixiviates has also been studied by thermogravimetric analysis. A quantitative study of the gases originated during thermal degradation of the epoxy/diamine system made by infrared spectroscopy. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 443–453, 1999     

Sorption of textile dye from aqueous solution by macroporous amino‐functionalized copolymer

Macroporous poly(glycidyl methacrylate‐co‐ethylene glycol dimethacrylate) (PGME) was synthesized by suspension copolymerization and functionalized with diethylene triamine (PGME‐deta). The effect of pH, contact time, and sorbent mass on sorption efficiency of initial and functionalized copolymer sample for removal of Acid Orange 10 dye from aqueous solutions was studied. No dye was sorbed by nonfunctionalized copolymer, indicating that sorption of Acid Orange 10 by PGME‐deta is specific, through amino groups. The isotherm data are best fitted by Langmuir model, indicating homogeneous distribution of active sites in PGME‐deta as well as monolayer sorption. Sorption kinetics study showed that the sorption of Acid Orange 10 by PGME‐deta obeys the pseudo‐second‐order kinetic model. It was shown that PGME‐deta selectively sorbs Acid Orange 10 from binary solution with Bezaktiv Rot reactive dye. The comparison of sorption characteristics of PGME‐deta with activated carbon showed that this functionalized copolymer might be used as an alternative sorbent for textile dyes. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of modified bismaleimide/polysulfone semi‐interpenetrating polymer networks

The present work reports a new method of preparing semi‐interpenetrating polymer network (semi‐IPN) membranes through in situ polymerization of bismaleimide (BMI) within polysulfone (PSF). It was found that BMI could be polymerized at ambient conditions in the presence of a proton donor and PSF without the use of an initiator or a catalyst. Chemical structure characterization of these semi‐IPNs by Fourier transform infrared attenuated total reflection (FTIR‐ATR) revealed the possibility of imide cleavage and formation of amic acid when BMI polymerization was continued for a longer time while X‐ray photoelectron spectroscopy (XPS) revealed the protonation of imide nitrogen at shorter polymerization time. It was also found that size of thermoset BMI phase within the PSF thermoplastic has a significant impact on glass‐transition temperature of resulting semi‐IPN. By controlling the thermoset/thermoplastic phase separation of semi‐IPNs through dope composition and formation techniques, gas separation membranes with comparable selectivity and permeance that were up to 12 times higher than corresponding PSF membranes were formed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 369–379, 2006     

Insolubilization of sodium chondroitin sulfate by forming a semi‐interpenetrating polymer network with acrylic acid: A potential carrier for colon‐specific drug delivery

To reduce the highly hydrophilic property of chondroitin sulfate (ChS), a semi‐interpenetrating polymer network (semi‐IPN) of chondroitin sulfate/polyacrylic acid (PAA) was prepared as a drug carrier by crosslinking acrylic acid with diethyleneglycol diacrylate. The swelling properties of the semi‐IPNs with different concentrations of crosslinking agent were correlated. The moisture sorption profiles were evaluated using differential thermal analysis. Ketoprofen was used as a drug probe to evaluate the performance of the drug released from the semi‐IPN matrices. The prepared semi‐IPNs demonstrated significant swelling reduction properties with both gastric and intestinal fluids compared with those of both the pure ChS and the ChSAA blend without the crosslinking agent. The amount of accumulated drug released from the semi‐IPNs was less than 30 wt % at pH 1.2 and up to 80 wt % at pH 7.4. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 114–122, 2002