Study on superabsorbent composite—VII. Effects of organification of attapulgite on swelling behaviors of poly(acrylic acid‐co‐acrylamide)/sodium humate/organo‐attapulgite composite

A novel multifunctional superabsorbent composite from acrylic acid (AA), acrylamide (AM), sodium humate (SH) and organo‐attapulgite (organo‐APT), PAA‐AM/SH/organo‐APT, was synthesized by aqueous solution polymerization, using N,N′‐methylenebisacrylamide (MBA) as a crosslinker and ammonium persulfate (APS) as an initiator. The organification of APT with hexadecyltrimethyl ammonium bromide (HDTMABr) was proved by FT‐IR. The effects of organo‐APT (HDTMA‐APT) content in the superabsorbent composite and organification degree of it on water absorbency of the superabsorbent composite were studied. The effects of incorporated HDTMA‐APT on swelling rate, water absorbency in various saline solutions and reswelling capability of the superabsorbent composite were also investigated. The results indicate that organification of APT had a remarkable influence on swelling behaviors of the superabsorbent composites. Comparing with the composite doped with APT, water absorbency for the composite incorporated with 10 wt% HDTMA‐APT was enhanced from 996 to 1282 g g^?1 in distilled water and from 63 to 68 g g^?1 in 0.9 wt% NaCl solution, respectively. The superabsorbent composite acquired its highest water absorbency when the organification degree of APT was 8.02 wt%. Water absorbency of the composites in various saline solutions decreased with the increasing concentration, especially for the multivalent cations. In addition, swelling rate and reswelling capability of the superabsorbent composite were also improved by introducing HDTMA‐APT into the composite compared with that of incorporating APT. Copyright © 2006 John Wiley & Sons, Ltd.     

Preparation of poly(vinylalcohol)/poly(acrylamide‐co‐vinyl imidazole)/γ‐Fe2O3 semi‐IPN nanocomposite and their application for removal of heavy metal ions from water

A series of magnetic semi‐interpenetrating polymer network (semi‐IPN) hydrogels was prepared in one‐stage strategy composed of linear poly(vinyl alcohol) (PVA) chains and magnetic γ‐Fe₂O₃ nanoparticles entrapped within the cross‐linked poly(acrylamide‐co‐vinylimidazole) (poly(AAm‐co‐VI)) network. The influence of PVA, weight ratio of AAm:VI, γ‐Fe₂O₃, and MBA on the swelling properties of the obtained nanocomposite hydrogels was evaluated. The prepared magnetic semi‐IPN hydrogels were fully characterized and used as absorbent for removal of Pb(II) and Cd(II) from water. Factors that influence the metal ion adsorption such as solution pH, contact time, initial metal ion concentration, and temperature were studied in details. The experimental results were reliably described by Langmuir adsorption isotherms. The adsorption capacity of semi‐IPN nanocomposite for Pb(II) and Cd(II) were175.80 and 149.76 mg g^?1, respectively. The kinetic experimental data indicated that the chemical sorption is the rate‐determining step. According to thermodynamic studies, Pb(II) and Cd(II) adsorption on the hydrogels was endothermic and also chemical in nature. The prepared magnetic PVA/poly(AAm‐co‐VI) semi‐IPN hydrogels could be employed as efficient and low‐cost adsorbents of heavy metal ions from water. Copyright © 2016 John Wiley & Sons, Ltd.     

Preparation and properties of superabsorbent containing starch and sodium humate

Starch and sodium humate were utilized as raw material for synthesizing starch‐g‐poly(acrylic acid)/sodium humate (St‐g‐PAA/SH) superabsorbent by graft copolymerization reaction of starch (St) and acrylic acid (AA) in the presence of sodium humate (SH) in aqueous solution. The effect of weight ratio of AA to St, initial monomer concentration, neutralization degree of AA, amount of crosslinker, initiator and SH on water absorbency of the superabsorbent were studied. The swelling rate and swelling behavior in NaCl solution as well as reswelling ability of the superabsorbent were systematically investigated. The results showed that the superabsorbent synthesized under optimal conditions with SH content of 7.7 wt% and St content of 11.5 wt% exhibits water absorbency of 1100 g/g in distilled water and 86 g/g in 0.9 wt% NaCl solution, respectively. Introducing SH into the St‐g‐PAA polymeric network can improved the swelling rate and reswelling capability of the superabsorbent. Copyright © 2008 John Wiley & Sons, Ltd.     

Synthesis and properties of poly(acrylamide‐co‐acrylic acid)/polyacrylamide superporous IPN hydrogels

Poly(acrylamide‐co‐acrylic acid)/polyacrylamide [P(AM‐co‐AA)/PAM] hydrogel with superporous and interpenetrating network (IPN) structure was prepared by a prepolymerization reaction and a synchronous polymerization reaction and frothing process. Scanning electron microscope (SEM) images show that the resultant hydrogel possesses abundant interconnected pores. DSC indicates that the porous structure enhances the swelling ratio and reduces the interaction between water and the hydrogel. In contrast, the IPN by PAM decreases water absorbency and enhances water retentivity. It is found that a superporous stucture in the hydrogel increases the equilibrium swelling ratio and decreases the compressive strength of the hydrogel. On the other hand, the increase in AM oligomer (oligo‐AM) amount decreases the equilibrium swelling ratio and improves the compressive strength of the hydrogel. Therefore, the two‐steps synthesis method can be used to construct a hydrogel with superporous and IPN structure. The swelling and mechanical properties of the hydrogel can be improved effectively. Copyright © 2008 John Wiley & Sons, Ltd.     

Study on superabsorbent of maleic anhydride/acrylamide semi‐interpenetrated with poly(vinyl alcohol)

A series of superabsorbents of maleic anhydride (MAH)/acrylamide (AM) interpenetrated with poly(vinyl alcohol) (PVA) were prepared by aqueous polymerization, using N,N‐methylenebiacrylamide (NNMBA) as a crosslinker and ammonium persulfate (APS) as an initiator. The samples were characterized by Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), and scanning electron microscope (SEM). The effects of reaction variables on the water absorbency of the superabsorbents in distilled water and in 0.9 wt% NaCl solution were investigated. In addition, the effect of the PVA content on the swelling rate and sensitivity to saline of the superabsorbents were also investigated. The results showed that the absorbency, both in 0.9 wt% NaCl solution and in distilled water, first decreased and then increased with increasing PVA content. Moreover, the resultant superabsorbent had a higher absorption rate and it became less sensitive to saline by incorporating certain amount of PVA into the network of the hydrogel. Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis and characterization of κ‐carrageenan/poly(N,N‐diethylacrylamide) semi‐interpenetrating polymer network hydrogels with rapid response to temperature

In this study, a novel classical thermo‐ and salt‐sensitive semi‐interpenetrating polymer network (semi‐IPN) hydrogel composed of poly(N,N‐diethylacrylamide) (PDEAm) and κ‐carrageenan (KC) was synthesized by free radical polymerization. The structure of the hydrogels was studied by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). FTIR and SEM revealed that the semi‐IPN hydrogels possessed the structure of H‐bonds and larger number of pores in the network. Compared to the PDEAm hydrogel, the prepared semi‐IPN hydrogels exhibited a much faster response rate to temperature changes and had larger equilibrium swelling ratios at temperatures below the lower critical solution temperature (LCST). The salt‐sensitive behavior of the semi‐IPN hydrogels was dependent on the content of KC. In addition, during the reswelling process, semi‐IPN hydrogels showed a non‐sigmoidal swelling pattern. Copyright © 2008 John Wiley & Sons, Ltd.     

The controlled release behavior and pH‐ and thermo‐sensitivity of alginate/poly(vinyl alcohol) blended hydrogels

Poly(vinyl alcohol) (PVA) was blended with sodium alginate (Alg) in various ratios and crosslinked with calcium chloride and made into hydrogel membranes. The dependence of the swelling behavior of these Alg‐Ca/PVA hydrogels on pH was investigated. The temperature‐dependent swelling behavior of the semi‐interpenetrating network (semi‐IPN) hydrogels was examined at temperatures from 2 to 45°C and the enthalpy of mixing (ΔH_mix) was determined at various temperatures. The molecular structure of the hydrogels was studied by infrared spectroscopy and their water structure in the semi‐IPN hydrogels was measured by differential scanning calorimetry (DSC). The influence of Ca²⁺ content on the network structure of Alg‐Ca/PVA hydrogels was investigated in terms of the compressive elastic modulus, effective crosslinking density, and the polymer–solvent interaction parameter based on the Flory theory. The loading of alizarin red S (ARS) followed the Langmuir isotherm mechanism and the release kinetics of ARS from the Alg‐Ca/PVA hydrogels followed the Fickian diffusion mechanism. Copyright © 2008 John Wiley & Sons, Ltd.     

Antimicrobial loading into and release from poly(ethylene glycol)/poly(acrylic acid) semi‐interpenetrating hydrogels

Electrostatic interactions within a semi‐interpenetrating network (semi‐IPN) gel can control the postsynthesis loading, long‐term retention, and subsequent release of small‐molecule cationic antibiotics. Here, electrostatic charge is introduced into an otherwise neutral gel [poly(ethylene glycol) (PEG)] by physically entrapping high‐molecular‐weight poly(acrylic acid) (PAA). The network structure is characterized by small‐angle neutron scattering. PEG/PAA semi‐IPN gels absorb over 40 times more antibiotic than PAA‐free PEG gels. Subsequent soaking in physiological buffer (pH 7.4; 0.15 M NaCl) releases the loaded antibiotics for periods as long as 30 days. The loaded gels elute antibiotics with diffusivities of 4.46 × 10^?8 cm²/s (amikacin) and 2.08 × 10^?8 cm²/s (colistin), which are two orders of magnitude less than those in pure PEG gels where diffusion is controlled purely by gel tortuosity. The release and hindered diffusion can be understood based on the partial shielding of the charged groups within the loaded gel, and they have a significant effect on the antimicrobial properties of these gels. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 64–72     

Syntheses and properties of superabsorbent composites based on natural guar gum and attapulgite

Utilization of raw materials available in nature and their application to derive other useful products without any adverse impact on the environment has long been a desired goal. In this work, guar gum (GG) and attapulgite (APT) clay were used as raw materials for preparing guar gum‐g‐poly(acrylic acid)/attapulgite (GG‐g‐PAA/APT) superabsorbent composites through the graft copolymerization of GG, partially neutralized acrylic acid (AA) and APT in aqueous solution. The effects of reaction conditions such as concentrations of the initiator and crosslinker, APT content, etc. on water absorbency were investigated. The composite prepared under optimal conditions gave the best absorption of 529 g/g sample in distilled water and 61 g/g sample in 0.9 wt% NaCl solution. Swelling behaviors revealed that the superabsorbent composites retained a high water absorbency over a wide pH range of 4–11, and the developed composites also exhibited improved reswelling and water‐retention capabilities. The superabsorbent composites can be utilized as eco‐friendly water‐manageable materials for agricultural and horticultural applications. Copyright © 2008 John Wiley & Sons, Ltd.     

Preparation and properties of poly(N‐isopropylacrylamide)/poly(N‐isopropylacrylamide) interpenetrating polymer networks for drug delivery

A novel poly(N‐isopropylacrylamide) (PNIPA)/PNIPA interpenetrating polymer network (IPN) was synthesized and characterized. In comparison with conventional PNIPA hydrogels, the shrinking rate of the IPN hydrogel increased when gels, swollen at 20 °C, were immersed in 50 °C water. The phase‐transition temperature of the IPN gel remained unchangeable because of the same chemical constituent in the PNIPA gel. The reswelling kinetics were slower than those of the PNIPA hydrogel because of the higher crosslinking density of the IPN hydrogel. The IPN hydrogel had better mechanical strength because of its higher crosslinking density and polymer volume fraction. The release behavior of 5‐fluorouracil (5‐Fu) from the IPN hydrogel showed that, at a lower temperature, the release of 5‐Fu was controlled by the diffusion of water molecules in the gel network. At a higher temperature, 5‐Fu inside the gel could not diffuse into the medium after a burst release caused by the release of the drug on the surface of the gel. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1249–1254, 2004     

Preparation and characterization of poly(acrylic acid)‐iron rich smectite superabsorbent composites

A novel poly(acrylic acid)‐iron rich smectite (IRS) superabsorbent composite was synthesized by graft copolymerization reaction of acrylic acid (AA) in the presence of N,N‐methylenebisacrylamide (MBA) as a crosslinker. IRS was used to strengthen the hydrogel products in the polymerization process. Water absorbencies for these superabsorbent composites in water and saline solutions were investigated. IRS caused a reduced equilibrium swelling as low as 8–26%. However, grafted IRS particles resulted in improved gel strength as high as 66% compared to the IRS‐free sample. IRS modified superabsorbent hydrogel composites exhibited higher thermal stability compared to the IRS‐free sample. The pH dependent reversible swelling behavior of hydrogels was also investigated. It is found that the swelling process is pH dependent and reversible for synthesized superabsorbent. Superabsorbent hydrogel composites were characterized by thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). FTIR spectroscopy was confirmed grafting of acrylic chains onto the surface of IRS particles. From the standpoint of these results, these strengthened and thermostabilized hydrogels may be considered as good candidates for a controlled release study and agricultural applications. Copyright © 2007 John Wiley & Sons, Ltd.     

Alcohol elastomer based on superabsorbents

A microporous superabsorbent of poly(acrylic acid‐g‐cetyltrimethylammonium bromide) (PAA‐g‐CTAB) is synthesized by aqueous polymerization method. With the use of the superabsorbent as a host backbone, a large amount of alcohol is absorbed inside the micropores of PAA‐g‐CTAB to form an alcohol elastomer with an alcohol absorbency of 32 g/g. As a new kind of quasi‐solid‐state fuel, the alcohol elastomer is safe, low cost, and easy to use. The alcohol absorbency of the superabsorbent and the combustion properties of the alcohol elastomer can be adjusted by tuning the polymerization reaction conditions. The flame reactions in the alcohol elastomer arouse more interest for the alcohol elastomer. Copyright © 2011 John Wiley & Sons, Ltd.     

Investigation of swelling,drug release and diffusion behaviors of poly(N‐isopropylacrylamide)/poly (N‐vinylpyrrolidone) full‐IPN hydrogels

The synthesis of sequential full interpenetrating polymer networks (IPNs) based on poly (N‐isopropylacrylamide) (PNIPAAm) and negatively charged poly(N‐vinyl‐2‐pyrrolidone) (PNVP) was described and their swelling, drug release, and diffusion studies were investigated. PNIPAAm was used as a host network. According to swelling experiments, IPNs gave relatively lower swelling ratios compared to PNIPAAm hydrogel due to the higher cross‐linking density. Lidocaine (LD) was used as a model drug for the investigation of drug release behavior of IPNs. LD uptake of the IPNs were found to increase from 24 to 166 (mg LD / g dry gel) with increasing amount of PNIPAAm and AMPS contents in the IPN structure. It was observed that the specific interaction between drug and AMPS co‐monomer influenced the drug release profile. In the diffusion transport mechanism study in water, the results indicated that the swelling exponents n for all IPNs are in the range from 0.50 to 0.72. This implies that the swelling transport mechanism was transferred from Fickian to non‐Fickian transport, with increasing AMPS content and NIPAAm character in the IPN structure. In addition, diffusion of LD within the IPNs showed similar trend. The incorporation of AMPS leads to an increase in electrostatic interaction between charge sites on carboxylate ions and cationic LD molecules. Therefore, the highest diffusion coefficient (D) of drug was found for IPN2 sample. Copyright © 2007 John Wiley & Sons, Ltd.     

Synthesis of versatile poly(PMMA‐b‐VI) macromonomer‐based hydrogels via infrared laser ignited frontal polymerization

In this work, poly((PMMA‐b‐VI)‐co‐AA) (MMA = methyl methacrylate; VI = 1‐vinylimidazole; AA = acrylic acid) hydrogels and poly((PMMA‐b‐VI)‐co‐AA)/TPU (TPU = thermoplastic polyurethane) IPN (interpenetrating polymer networks) hydrogels have been fabricated via versatile infrared laser ignited frontal polymerization by using poly(PMMA‐b‐VI) macromonomer as the mononer. The frontal velocity and T_max (the highest temperature that the laser beam detected at a fixed point) can be adjusted by varying monomer weight ratios, the concentration of BPO (BPO = benzoyl peroxide) and the amount of TPU. Moreover, the addition of TPU enhances the reactant viscosity to suppress the “fingering” of frontal polymerization (FP) and decrease T_max of the reaction, providing a new inert carrier (TPU) to assist FP. Through the characterization of Fourier transform‐infrared spectroscopy (FT‐IR), scanning electron microscope (SEM), and differential scanning calorimetry (DSC), the desired structure can be proved to exist in the IPN hydrogels. Furthermore, poly((PMMA‐b‐VI)‐co‐AA)/TPU IPN hydrogels possesses more excellent mechanical behaviors than hydrogels without IPN structure. Besides, the poly((PMMA‐b‐VI)‐co‐AA) hydrogels present splendid sensitive properties toward substances of different flavor including sourness (CA, citric acid or GA, gluconic acid), umami (SG, sodium glutamate), saltiness (SC, sodium chloride), sweetness (GLU, glucose), enabling their potential as artificial tongue‐like sensing materials. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1210–1221     

Synthesis and optical properties of organic–inorganic hybrid semi‐interpenetrating polymer network gels containing polyfluorenes

Organic–inorganic hybrid semi‐interpenetrating polymer network (semi‐IPN) gels containing polyfluorenes (PFs) are synthesized by hydrosilylation reaction of joint and rod molecules in toluene, where PFs are poly(9,9‐dihexylfluorene‐2,7‐diyl) (PF6) or, poly(9,9‐dioctylfluorene‐2,7‐diyl) (PF8), joint molecules are 1,3,5,7‐tetramethylcyclotetrasiloxane (TMCTS), or 1,3,5,7,9,11,13,15‐octakis(dimethylsilyloxy)pentacyclo‐[9,5,1,1,1,1]octasilsesquioxane (POSS), and rod molecules are 1,5‐hexadiene (HD) or 1,9‐decadiene (DD). The semi‐IPN gels containing low molecular weight PF6 show higher photoluminescence efficiency (?_g) than the toluene solution of PF6L (?_s). The semi‐IPN gels composed of long rod molecule of DD and cubic joint molecule of POSS show the most effective increase in the emission intensity. The emission intensity of PF6L increases as formation of the network in the POSS‐DD semi‐IPN gel. The POSS‐DD semi‐IPN gels containing high molecular weight PF6 and PF8 also show the increase of emission intensity than those of the toluene solutions. The semi‐IPN synthesized in cyclohexane show syneresis and phase separation between network structure and PF chains. The semi‐IPN gels containing PF8 show emission peaks at 450 and 470 nm derived from β‐sheet structure of PF8. A systematic study clears correlation between emission property and network structure and/or composition of semi‐IPN gels. The semi‐IPN gels provide emissive self‐standing soft materials with high efficiency and in a narrow wavelength range emission. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 973–984     

Swelling kinetics of poly(aspartic acid)/poly(acrylic acid) semi‐interpenetrating polymer network hydrogels in urea solutions

Semi‐interpenetrating network (semi‐IPN) hydrogels, composed of poly(aspartic acid) (PAsp) and poly(acrylic acid) (PAAc) with various ratios of PAsp to AAc, were prepared. In this work, swelling kinetics was investigated through calculating some parameters. The swelling ratios were measured at room temperature, using urea solutions as liquids to be absorbed. Compared to in deionized water, the hydrogels showed larger swelling ratios in urea solutions, which might be attributed to the chemical composition of urea. The equilibrium swelling ratio could achieve 600 g/g, and the equilibrium urea/water contents were more than 0.99. The diffusion exponents were between 0.5 and 0.7, suggesting that the solvent transport into the hydrogel was dominated by both diffusion and relaxation controlled systems. Therefore, the PAsp/PAAc semi‐IPN hydrogels were appropriate to carry substances in a urea/water environment for pharmaceutical, agricultural, environmental, and biomedical applications. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 666–671, 2010     

Heterogeneity of glass transition dynamics in polyurethane‐poly(2‐hydroxyethyl methacrylate) semi‐interpenetrating polymer networks

The peculiarities of segmental dynamics over the temperature range of ?140 to 180 °C were studied in polyurethane‐poly(2‐hydroxyethyl methacrylate) semi‐interpenetrating polymer networks (PU‐PHEMA semi‐IPNs) with two‐phase, nanoheterogeneous structure. The networks were synthesized by the sequential method when the PU network was obtained from poly(oxypropylene glycol) (PPG) and adduct of trimethylolpropane (TMP) and toluylene diisocyanate (TDI), and then swollen with 2‐hydroxyethyl methacrylate monomer with its subsequent photopolymerization. PHEMA content in the semi‐IPNs varied from 10 to 57 wt %. Laser‐interferometric creep rate spectroscopy (CRS), supplemented with differential scanning calorimetry (DSC), was used for discrete dynamic analysis of these IPNs. The effects of anomalous, large broadening of the PHEMA glass transition to higher temperatures in comparison with that of neat PHEMA, despite much lower T_g of the PU constituent, and the pronounced heterogeneity of glass transition dynamics were found in these networks. Up to 3 or 4 overlapping creep rate peaks, characterizing different segmental dynamics modes, have been registered within both PU and PHEMA glass transitions in these semi‐IPNs. On the whole, the united semi‐IPN glass transition ranged virtually from ?60 to 160 °C. As proved by IR spectra, some hybridization of the semi‐IPN constituents took place, and therefore the effects observed could be properly interpreted in the framework of the notion of “constrained dynamics.” The peculiar segmental dynamics in the semi‐IPNs studied may help in developing advanced biomedical, damping, and membrane materials based thereon. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 963–975, 2007     

Hydrophilic nanocomposites based on polyurethane/poly(2‐hydroxyethyl methacrylate) semi‐IPNs and modified/unmodified nanosilica for biomedical applications

Nanocomposites based on sequential semi‐interpenetrating polymer network (semi‐IPN) of cross‐linked polyurethane and linear poly(2‐hydroxyethyl methacrylate) with 0.25 and 3 wt % of nanosilica filler were prepared and investigated. The unmodified silica, carboxyl‐modified, and amino‐modified silica were used in an attempt to control the microphase separation of the polymer matrix by polymer–filler interactions. A variety of experimental techniques were used to study morphology, thermal transitions, mechanical properties, and polymer dynamics of the nanocomposites. Special attention was paid to the investigation of the hydration properties of the nanocomposites in the perspective of biomedical applications. The results show that the good hydration properties of the semi‐IPN matrix are preserved in the nanocomposites. Effects of water on polymer dynamics were found to be particularly pronounced for the secondary β_sw,_PHEMA and the β_PU relaxations, in agreement with interpretations in terms of hydrogen bonding interactions with specific groups in the structure of the two polymers. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 397–408     

Synthesis,characterization and evaluation of semi‐IPN hydrogels consisted of poly(methacrylic acid) and guar gum for colon‐specific drug delivery

The semi‐IPN hydrogels consisting of poly(methacrylic acid) and guar gum (GG) are prepared at room temperature using water as solvent. 5‐aminosalicylic acid (5‐ASA) is entrapped in the hydrogel in the synthesis of hydrogel and all entrapment efficiencies are found above 85%. The hydrogel shows excellent pH‐sensitivity. It exhibited minimum swelling in an acidic pH medium through the formation of a complex hydrogen‐bonded structure and maximal swelling due to the electrostatic repulsion due to the ionization of the carboxylic groups in pH 7.4 medium. The degradation in vitro shows that the degree of degradation (R%) depended on the concentration of cross‐linking agent and content of GG. The hydrogel shows a minimum release of 5‐ASA due to the complex hydrogen bonded structure of the hydrogels in the medium of pH 2.2. The enzymatic degradation of hydrogels by cecal bacteria can accelerate the release of 5‐ASA entrapped in the hydrogel in pH 7.4 medium. Copyright © 2007 John Wiley & Sons, Ltd.     

Fabrication and characterization of poly(vinyl alcohol)/chitosan hydrogel thin films via UV irradiation

A series of poly(vinyl alcohol)/chitosan (PVA/CTS) hydrogel thin films were prepared via ultraviolet (UV) irradiation, with acrylic acid (AA) monomer added as a crosslinker without the addition of any other photo-initiator. The swelling behaviors, intermolecular chemical bonds, molecular structures, thermal behaviors, degrees of crystallinity, morphologies of the surfaces and internal structure, and their relationship to the AA content were characterized using Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). Poly(acrylic acid) (PAA) and its chemical crosslinks formed in hydrogel films via free-radical reactions were confirmed using FTIR and DSC analyses. The XRD patterns indicated that the degree of crystallinity of the hydrogel films decreased as the PAA content was increased. SEM micrographs showed that a uniform interconnected pore structure was formed through the entire hydrogel structure, and a gradient in the crosslinking density through the film thickness was observed to result from extended irradiation times. The swelling behaviors revealed that the formation of PAA and its crosslinking in the hydrogel thin films improved the pH stability and controlled the degree of swelling while retaining a high swelling rate. The successful formation of chemical crosslinking without any specific photo-initiator improves the natural characteristics of CTS and PVA and imparts the resulting PVA/CTS hydrogel thin films with properties that make them very promising in biomedical applications.