Synthesis and characterization of super‐absorbent hydrogels based on hemicellulose

A kind of novel hemicellulose‐based hydrogel with excellent water absorbency was synthesized by the graft copolymerization of acrylic acid (AA), acrylic amide (AM) with hemicellulose. The various factors that influenced the water absorbency of the modified hemicellulose were studied, including AA content, hemicellulose content, neutralization degree of AA, and weight ratio (to monomer) of cross‐linker and initiator. The optimal conditions were found as follows: m(AA) : m(AM) : m(hemicellulose) = 15 : 3.5 : 1, the neutralization degree of AA was 75%, and weight ratio (to monomers) of the cross‐linker and the initiator was 0.03% and 1.0%, respectively. The maximum absorbencies toward distilled water and 0.9 wt % NaCl solution were 1128 g/g and 132 g/g, respectively. The characteristics of the hydrogels were also investigated by Fourier Transform InfraRed (FT‐IR), scanning electron microscope (SEM), and atomic force microscope (AFM). The results indicated that the undulant surface and broad network structure offer the hydrogels excellent water absorbency. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42441.     

Preparation of antibacterial temperature‐sensitive silver‐nanocomposite hydrogels from N‐isopropylacrylamide with green tea

This article reports the temperature‐sensitive, green tea (GT)‐based silver‐nanocomposite hydrogels for bacterial growth inactivation. The temperature‐sensitive hydrogels were prepared via free‐radical polymerization using temperature‐sensitive N‐isopropylacrylamide (NIPAM) monomer with GT as the hydrogel matrix. The nanocomposite hydrogels were encapsulated with silver ions via swelling method, which was later reduced to silver nanoparticles using Azadirachta indica leaf extract. The temperature‐sensitive silver nanocomposite hydrogels were analyzed by using Fourier transforms infrared, UV–visible spectroscopy, differential scanning calorimetry–thermogravimetric analysis, X‐ray diffraction, scanning electron microscopy, and transmission electron microscopy. The prepared hydrogels exhibited higher phase volume transition temperature than the NIPAM. The inhibition zone study of the inactivation of bacteria on the developed hydrogels was carried out against Gram negative (Escherichia coli) and Gram positive (Staphylococcus aureus), which revealed that the prepared hydrogels are helpful for the inactivation of these bacteria due to the high stabilization of antibacterial properties of the silver nanoparticles. The developed hydrogels are promising for biomedical applications. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45739.     

Control of swelling properties of polyvinyl alcohol/hyaluronic acid hydrogels for the encapsulation of chondrocyte cells

Hydrogel scaffolds for tissue engineering are important biomaterials. The target in this study was to prepare polyvinyl alcohol/hyaluronic acid hydrogels for the encapsulation of chondrocyte cells by a simple cross‐linking reaction. Control of the swelling properties and morphology of the hydrogels for cultivation of chondrocytes was studied. The hydrogels were prepared from polyvinyl alcohol and hyaluronic acid derivatives bearing primary amine and aldehyde functionalities, respectively. The formation of the hydrogel upon mixing the aqueous solutions of the polymer derivatives took place at room temperature in a few seconds. The swelling properties of the hydrogels were found to depend on the polymer concentration and degree of substitution of the modified polymers. Scanning electron microscopy studies showed that the hydrogels had a suitable porous morphology for cell encapsulation. Furthermore, in vitro cell viability tests with the hydrogels showed no cytotoxicity for chondrocytes and that the cells grew well in the hydrogel scaffolds. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42272.     

Preparation of high-performance deproteinized natural rubber/chitosan composite films via a green and sulfur-free method

To solve the environment and health issues arose from the sulfur vulcanization, a facile and completely eco-friendly method of latex-assembly and in situ cross-linking is developed to prepare fully bio-based and high-performance rubber films. The films are featured by a “reinforced concrete” structure composed of dynamically cross-linked chitosan framework and unvulcanized deproteinized natural rubber (DPNR) matrix. The self-assembly of DPNR latex particles and chitosan, as well as the in situ cross-linking of chitosan in the film forming process are confirmed by transmission electron microscope and dynamic light scattering. As green rubbers without vulcanization, the as-designed composite films possess excellent mechanic properties comparable to those of the sulfur vulcanized DPNR film, whose tensile strength and toughness reach 15.2 MPa and 77.6 MJ m⁻³ respectively. Moreover, the films exhibited appropriate permeability to moisture and achievable reprocessing, which have potential applications in wearable devices.     

Phenol removal from wastewater using eco-friendly hybrid hydrogels

The intent of this study was to evaluate the ability of low-cost polyacrylamide/starch hybrid hydrogels in removing organic pollutants from wastewater, using phenol as a model compound, besides of investigating the adsorption/desorption behavior as a function of hydrogels composition. The results indicated that the hydrogel with the lowest amount of starch and crosslinking agent exhibited the maximum phenol adsorption capacity, 21 mg g⁻¹. The adsorption isotherm data were described by Langmuir and Freundlich adsorption isotherm models. According to linear regression analysis, the Freundlich isotherm model was the best fit among the isotherm models for the adsorption process. Furthermore, desorption study revealed a minimum of about 60% of phenol release, indicating reusability to wastewater treatment.     

Preparation and evaluation of composite microspheres of polyacrylamide‐grafted polysaccharides

The poor mechanical strength and instability of polysaccharide's gel takes away opportunities for versatile application. The grafting of polyacrylamide (PAM) onto polysaccharide was found to be an efficient tool for transforming its properties and obtaining stable and robust composite microspheres (CMs). In this study, free‐radical polymerization reaction was used for the grafting of PAM onto the polysaccharide backbone, and their hydrogel CMs were obtained through an ionotropic gelation method. Porous and buoyant CMs were obtained through the incorporation of sodium bicarbonate into the reaction mixture. Characterizations were done through Fourier transform infrared spectroscopy, thermal and scanning electron microscopy analysis. The mechanical strength and squeezing capacity were evaluated extensively through a modified syringe method developed in‐house. The squeezing capacity of grafted CMs diminished with the formation of a complex interpenetrating network. The Young's modulus, swelling kinetics, mechanical strength, and squeezing capacity of the grafted microspheres were compared extensively. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2912–2922, 2013     

Thermoresponsive hydrogels based on renewable resources

This work aims to synthesize novel thermoresponsive hydrogels from renewable resources, bacterial cellulose (BC), and castor oil (CO), and to investigate the effect of CO on physical and thermal behaviors of BC/Poly(N-isopropylacrylamide) (PNIPAM) hydrogels. The structural properties of the hydrogels are analyzed by Fourier-transform infrared (FTIR) spectroscopy. Differential scanning calorimeter (DSC) technique and thermogravimetric analysis (TGA) are also performed to examine the thermal properties of the hydrogels. The morphological differences of the hydrogels are analyzed by scanning electron microscope (SEM). The thermoresponsive performances of the hydrogels are examined by swelling and deswelling behaviors. The hydrogel with CO is found to be more sensitive to temperature changes than the one without CO. Deswelling study demonstrates 91 and 25% of water loss for hydrogels with and without CO, respectively. The present study shows a novel approach to synthesize thermoresponsive hydrogels with renewable resources for biomedical applications. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48861.     

Preparation and characterization of starch‐based composite films reinforced by corn and wheat hulls

Biodegradable films, with starch as a matrix, were developed and reinforced with wheat and corn hulls. The effect of the particle size of the filler on the microstructure and mechanical and barrier properties of starch‐based films was investigated. We observed that the addition of hulls enhanced the modulus, tensile strength, and impact strength of the starch matrix at the expense of its elongation. The water‐vapor transmission rate results show that corn starch was more efficient in reducing the water‐vapor permeability than wheat hulls. Scanning electron microscopy observations indicated that the compatibility of both fillers with the matrix was quite good; this was expected because all of the components used in this study were hydrophilic and exhibited polar behavior. Optical microscopy and X‐ray diffraction observations indicated that the processing conditions did not affect the crystalline and geometric structures of the hulls. Because all of the components used in this study were from food resources, the films could also be used for edible packaging. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45159.     

Development of biodegradable natural rubber latex composites by employing corn derivative bio-fillers

This study aims to investigate the viability of employing corn-based fillers (powdered corn grain [CG], corn flour [CF] and cornstarch [CS]) to improve the biodegradability of natural rubber latex (NRL) composites by varying filler loading from 0 to 50 phr. Notable variation in both physical and mechanical properties were observed for the different filler types, with CG-filled NRL demonstrating the better adhesion with NRL. Thus, CG-filled composites were selected for investigation of biodegradability. Increased CG loading in NRL compounds enhanced biodegradation; with over 70% degradation observed for 50 phr CG loading upon 15 weeks of soil burial. However, the trade-off between mechanical properties and biodegradability limits the CG loading in the NRL matrix to 20 phr for manufacturing NRL-based products. It was observed that NRL with CG filler loading of 20 phr conforms to the ASTM D3578 standard for manufacturing rubber gloves; with 50% biodegradation upon 15 weeks of soil burial.     

Preparation of aqueous soluble polyamides from renewable succinic acid and citric acid as a new approach to design bio‐inspired polymers

A novel type of aqueous soluble polyamides were prepared as renewable substitutes for ecologically benign poly(aspartic acid) by polymerization of succinic acid ester and hexamethylene diamine in the presence of citric acid ester. The copolymerization resulted in the formation of poly(amide imide) intermediates, which were hydrolyzed to aqueous solutions of polyamides. The hydrolyzed products were confirmed to be copolymers of succinamide and citramide with COOH side chains, similar to poly(aspartic acid). The polyamides showed strong chelating abilities to Ca²⁺ and Pb²⁺ metals, comparable to poly(aspartic acid). Interestingly, they also demonstrated antifreeze activities in water by reducing the ice fractions. The polyamides represent a new class of metal chelators and antifreeze protein mimics derived from succinamide and citramide. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39807.     

Preparation of aerochitin‐TiO2 composite for efficient photocatalytic degradation of methylene blue

An aerochitin–titania (TiO₂) composite was successfully synthesized and characterized by Fourier transform infrared spectroscopy, X‐ray diffraction, thermogravimetric analysis, field emission scanning electron microscopy, and N₂ adsorption isotherms. The photocatalytic activity of the composite was investigated on the degradation of the model organic pollutant, methylene blue (MB) dye, under UV irradiation. The aerochitin–TiO₂ composite showed excellent adsorptive and photocatalytic activity with a degradation degree of 98% for MB. The first‐order rate constants for the photodegradation MB by TiO₂ nanoparticles and aerochitin–TiO₂ composite were found to be (3.49 ± 0.04) × 10^?3 and (1.82 ± 0.02) × 10^?2 min^?1. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45908.     

Development and characterization of composite chitosan/active carbon hydrogels for a medical application

Composite chitosan/active carbon (AC) hydrogels were elaborated by a novel route, consisting in exposing the chitosan solution to ammonia vapors. This vapor‐induced gelation method was compared with the conventional elaboration process, a direct immersion of the chitosan solution in liquid ammonia. The hydrogels were characterized to evaluate their potential application as wound‐dressings, mostly regarding their morphology, mechanical properties, swelling behavior, and sorption capacities for malodorous compounds emitted from wounds as diethylamine (DEA). The influence of elaboration route, chitosan concentration, and AC incorporation was studied. The results show that freeze‐dried hydrogels have a porous asymmetric structure dependent on the chitosan concentration and which promotes exudates drainage. The nanostructure of the parent hydrogel is semi‐crystalline and slightly dependent on the gelation conditions. It confers on hydrogel an acceptable mechanical behavior (compressive modulus up to 1.08·10⁵ Pa). Hydrogels including AC display enhanced sorption kinetics for DEA, with sorption capacities up to 49 mg g^?1. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Comparative study on the properties of cross-linked cellulose nanocrystals/chitosan film composites with conventional heating and microwave curing

Cross-linking of chitosan film composites was carried out by using conventional heating and microwave curing methods in this study. Non-cross-linked and glutaraldehyde (GA) cross-linked neat chitosan and cellulose nanocrystals (CNC)/chitosan film composites were cured by either conventional oven heating or microwave irradiation. Tensile strength and Young's modulus of chitosan composites were enhanced significantly by the addition of CNC and GA especially for the microwave-cured samples. The changes in chemical interaction of the chitosan film composites was determined by Fourier transform infrared (FTIR) spectroscopy. The microwave-cured GA-cross-linked chitosan film composites were more thermally stable than non-cross-linked and conventionally heated GA-cross-linked chitosan film composites due to the formation of a more stable structure between GA and chitosan. Nevertheless, the reduced antimicrobial efficacy of film composites against Escherichia coli, Bacillus subtilis, and Saccharomyces cerevisiae was observed in cross-linked film composites compared with non-cross-linked composites.     

Laccase‐catalyzed polymerization drying of Chinese lacquer sap with TiO2 nanoparticles

Nano‐TiO₂/lacquer hybrid coatings are prepared by the blend of nano‐TiO₂ and lacquer sap. Nano‐TiO₂ particles are involved in the laccase‐catalyzed polymerization process of urushiol, which improves the properties of lacquer film. With increasing nano‐TiO₂ from 0 to 5 wt %, the drying time of lacquer film to reach hardened dryness decreases from >12 h to 8 h 30 min under 30 °C and 80% relative humidity. Gel permeation chromatography analysis shows that the addition of nano‐TiO₂ accelerates the polymerization of urushiol. It is also related to the formation of Ti? O? C bonds due to the reaction between nano‐TiO₂ and the radicals produced by laccase‐catalyzed oxidation. The pencil hardness, flexibility, and adhesion of hybrid lacquer film can be improved and reach 4H, 1 mm, and grade 2, respectively. Its inhibition rate against Escherichia coli and Staphylococcus aureus increases from 22.6% and ?21.4% to 49.2% and 67.8%, respectively. Furthermore, nano‐TiO₂ hybrid lacquer films also possess higher thermo‐stability than the raw lacquer film. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45865.     

Biodegradable poly(lactic acid)/cellulose-based superabsorbent hydrogel composite material as water and fertilizer reservoir in agricultural applications

The work presents a fully degradable superabsorbent composite material to be used in agricultural and horticultural applications. It is designed to retain and release fertilizer solutions to the soil in a controlled manner, permitting resource optimization. Because of its ability to absorb and release large amounts of saline water, a natural superabsorbent hydrogel derived from cellulose was chosen. Potassium nitrate was chosen to model the fertilizer. Poly(lactic acid) was added to the final composition in order to delay solution release. The composite material was obtained using easily available and low-cost starting materials and using a simple manufacturing process, using a standard mixer. After being analyzed for morphological (scanning electron microscopy), physical (X-ray diffraction), chemical (energy-dispersive X-ray spectroscopy), and thermal properties (thermogravimetric analysis and differential scanning calorimetry), the material was tested using two different Mediterranean cultivations (Pomodoro di Morciano di Leuca and Cicoria Otrantina) and two different kinds of soil (red and white soils). The analysis revealed different water release characteristics for different soils. These findings have been confirmed by measuring plant growth for both species, as well as fruit yield of the tomatoes. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47546.     

Preparation of pectin‐inorganic composite material as accumulative material of metal ions

Pectin is one of the biopolymers in the cell walls of all plant tissues, but the pectin‐containing materials have been discarded as industrial waste in food‐processing factories. We prepared a water‐insoluble pectin‐inorganic composite material by mixing pectin and a silane coupling reagent, bis(3‐trimethoxysilylpropyl)amine. The mechanical strength of the pectin‐inorganic composite material was higher than that of the pectin material without the addition of an inorganic component. In addition, the thermal stability of the composite material increased with the addition of the inorganic component. Furthermore, when the pectin‐inorganic composite materials were incubated in an aqueous solution of Cu(II), Zn(II), or In(III), these composite materials effectively accumulated not only the heavy metal ions, but also rare‐earth metal ions. Additionally, based on the infrared (IR) measurements, the metal ion accumulative mechanism into the composite material is described. As a result, the IR spectra suggested an electrostatic interaction between the metal ion and carboxy group in the pectin. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42056.     

Damage modeling of degradable polymers under bulk erosion

Unit micro‐cell models with different architectures were designed to simulate the degradation process and chemical damage behavior of degradable polymers under bulk erosion. The pores in the micro‐cell models were introduced to mimic the state of rapid water diffusion into the polymers under bulk erosion, while three different arrangements of pores were considered to investigate their effects on the degradation rate of different polymers with the same molecular weight. Different porosity levels were also used to study the degradation responses of the polymers having different molecular weights. A heat and mass transfer analogy was adopted to enable the analysis to be run on a general purpose finite element (FE) code. In the present work, a finite element software package ABAQUS incorporated with a user‐defined material subroutine was used to perform the analysis, in which a heat transfer function was utilized to simulate Fickian mass diffusion for the polymers through analogy. With the proposed method, the effects of chemical damage on the mechanical properties of the degradable polymers under bulk erosion could be predicted and the predicted trend of the mass loss of the polymers followed experimental results obtained from the open literature. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Tung oil‐based thermosetting polymers for self‐healing applications

Several bio‐renewable thermosetting polymers were successfully prepared from tung oil through cationic polymerization for the use as the healing agent in self‐healing microencapsulated applications. The tung oil triglyceride was blended with its methyl ester, which was produced by saponification followed by esterification. The changes in storage modulus, loss modulus, and glass transition temperature as functions of the methyl ester content were measured using dynamic mechanical analysis. In addition, the fraction of cross‐linked material in the polymer was calculated by Soxhlet extraction, while proton nuclear magnetic resonance, Fourier transform infrared spectroscopy and TEM were used to investigate the structure of the copolymer networks. The thermal stability of the thermosets as a function of their methyl ester blend contents was determined by thermogravimetric analysis. Finally, the adhesive properties of the thermosets were studied using compressive lap shear and the fracture surfaces were analyzed using SEM. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40406.     

Hydrogels from dextran and soybean oil by UV photo‐polymerization

In this work, hydrogels were synthesized by UV photo‐polymerization of hydrophilic dextran functionalized with acrylate groups (Dex‐A) and hydrophobic acrylate epoxidized soybean oil (AESO). The acrylation of dextran was accomplished by reacting dextran (M_w 70,000 g mol^?1) with acryloyl chloride and pyridine. The Dex‐A was characterized by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR). Five rigid hydrogels were prepared using the weight ratios of Dex‐A and AESO as 10/90, 20/80, 30/70, 40/60, and 50/50. The hydrogels were characterized by FTIR, thermal gravimetric analyses (TGA) and scanning electronic microscopy (SEM). The experimental results demonstrated that the swelling and release profiles of the Dex‐A/AESO hydrogels can be tailored by varying the ratio of Dex‐A and AESO thus varying the balance of hydrophilicity and hydrophobicity of the network structures and the crosslinking density. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41446.     

Hydrogels of starch/carboxymethyl cellulose crosslinked with sodium trimetaphosphate via reactive extrusion

Hydrogels are materials with advantages in specific applications, such as, retention of food active compounds. This work aims to develop starch (S)/carboxymethyl cellulose (CMC) hydrogels with porous structure, using reactive extrusion to promote crosslinking with sodium trimetaphosphate (STMP). The expansion, porosity, degree of substitution, gel fraction, swelling properties, and FTIR are studied, comparing S, S/CMC, S/STMP, and S/CMC/STMP formulations. Samples containing STMP present the same degree of substitution (0.050 ± 0.001). Higher porosity and percentage of open pores are observed in the mixed hydrogel (S/CMC/STMP). Crosslinking increase the swelling capacity at pH 7, and this property, just like the gel fraction, are sensitive to pH variations. The hydrogel S/CMC present the highest swelling rate compared with the other samples, suggesting strong interaction between components. The reactive extrusion process is efficient to produce starch and starch/CMC hydrogels crosslinked with STMP and the overall results demonstrate the advantages of the mixed hydrogel.