Proton conductivity and structural properties of precursors mixed PVA/PWA-based hybrid composite membranes

A new class of hybrid nanocomposite membranes containing poly(vinyl alcohol) (PVA), phosphotungstic acid (PWA), 3-glycidyloxypropyltrimethoxysilane (GPTMS), 3-mercaptopropyltrimethoxysilane (MPTMS) and glutaraldehyde (GA) were prepared by a sol–gel method. The aim of this research study was to investigate these novel and highly proton-conducting membranes including their properties, and performances for proton exchange membrane fuel cells (PEMFCs) operating at low temperature. 'Swelling' was observed at room temperature for all the composites. The manner in which the conductivity depended on temperature and humidity was determined and a maximum conductivity value of 2.5?×?10^?2 S cm^?1 was found at a 140°C and 30 % relative humidity (RH) for the PVA/PWA/GPTMS/MPTMS/P₂O₅/GA (50/5/15/10/10/10 wt.%) hybrid composite membrane. It was suggested that the conductivity depended strongly on the nature of the organic/inorganic components as well as on the acid concentration. X-ray diffraction (XRD) results demonstrated that this membrane had an amorphous phase, and Fourier transform infrared spectroscopy (FTIR) results confirmed the composite formation. Finally, membrane-electrode assemblies with a loading of 0.1 mg cm^?2 of Pt/C on a prepared electrode gave rise to a current density of 309 mA cm^?2 at 0.5 V.     

Antimicrobial nanocomposite films made of poly(lactic acid)–cellulose nanocrystals (PLA–CNC) in food applications—part B: effect of oregano essential oil release on the inactivation of Listeria monocytogenes in mixed vegetables

Antimicrobial nanocomposite films containing oregano essential oil (EO) were prepared by solvent casting. Film matrix was composed of supramolecular poly(lactic acid)–cellulose nanocrystals (PLA–CNC) nanocomposite. Bioactive PLA–CNC–oregano films were prepared by incorporating oregano EO as an antimicrobial agent. Resulting films were then converted into packaging applied on mixed vegetables as a food model and stored for 14 days at 4 °C to determine their antimicrobial capacity against Listeria monocytogenes, their physico-chemical/structural properties and their total phenols (TP) release during storage, in order to evaluate the effect of oregano EO. It was observed the addition of oregano EO did not affect the water vapor permeability (WVP) of films, but increased their elongation at break (Eb) and reduced their tensile strength (TS) and tensile modulus (TM) at day 0. However, TS, TM, Eb and WVP values of control and bioactive films were increased slightly after 14 days of storage. FTIR analysis allowed characterizing the molecular interactions of oregano EO with PLA–CNC matrix via the identification and interpretation of their respective vibration bands. Microbiological analysis of mixed vegetables inoculated with L. monocytogenes (3 log CFU g^?1) indicated that PLA–CNC–oregano films induced a quasi-total inhibition of bacteria in vegetables at day 14 and therefore demonstrated a strong antimicrobial capacity in situ. The percentage of TP release from bioactive films was determined by Folin–Ciocalteu’s method and results showed that TP release increased continuously from day 0 to day 14, up to 16.6 % at day 14. These results allowed demonstrating the strong antimicrobial capacity of PLA–CNC–oregano films for food packaging applications in vegetable produce.     

Self-assembled films based on polypyrrole and carbon nanotubes composites for the determination of Diuron pesticide

In this work, polypyrrole (PPy) and its respective composite with functionalized multi-walled carbon nanotubes (MWCNT) were obtained by chemical polymerization of the monomer pyrrole in aqueous solution. The obtained PPy as well as its composite (PPy-MWCNT) were characterized by Fourier transform infrared spectroscopy (FTIR) and were used to produce nanostructured self-assembled (SA) films deposited onto glass substrates covered with indium tin oxide (ITO). The SA films were produced with alternated layers of polystyrene sulphonated (PSS) and were characterized by UV-visible, cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and scanning electron microscopy (SEM) analyses. The applicability of the SA films was evaluated by square wave voltammetry (SWV) with standard additions of aliquots of Diuron pesticide in Britton-Robinson buffer solutions (pH = 2.0). The results showed an oxidation peak at 0.23 V which increases in function of the Diuron concentration for both the SA films. It was also observed that the SA film based on the composite (PPy-MWCNT/PSS) showed a peak current intensity about ten times higher in comparison with its unmodified counterpart (PPy/PSS) for a Diuron concentration of 4.29 × 10^?5 mol L^?1, indicating a synergic effect between PPy and MWCNT in the composite. The limits of quantification (LOQ) and limits of detection (LOD) were respectively 8.6 × 10^?7 mol L^?1 and 2.6 × 10^?7 mol L^?1.     

Controlled Production of Exopolysaccharides from Enterobacter A47 as a Function of Carbon Source with Demonstration of Their Film and Emulsifying Abilities

The bacterium Enterobacter A47 has demonstrated the ability to synthesise distinct exopolysaccharides (EPS) as a function of the substrate used. The culture's performance was evaluated in experiments using either glucose or xylose, as single carbon sources, and compared with the substrate (glycerol) used in previous studies. The highest EPS production (13.23 g L^?1) was obtained in the glucose fed assay, with a volumetric productivity of 3.38 g L^?1 day^?1. The use of xylose resulted in lower productivity (1.39 g L^?1 day^?1). The synthesised polymers have the same main sugar monomers (fucose, glucose, galactose and glucuronic acid), but their relative proportion varied with the substrate used. The acyl groups' content and composition were also affected by the substrate used. The polymers produced from glycerol (EPS-s) and glucose (EPS-g) had identical shear-thinning behaviour and good emulsion-stabilising capacity and their films had similar mechanical and water vapour properties. However, the emulsions stabilised with EPS-g were less stable and destabilised within short periods of time or when subjected to heat and freezing/thawing procedures. On the other hand, the polymer produced from xylose had little emulsion-stabilising capacity and lower apparent viscosity than EPS-s and EPS-g, but its films were considerably more elastic.     

Casting of poly (vinyl alcohol)/glycidyl methacrylate reinforced with titanium dioxide nanoparticles for proton exchange fuel cells

Gamma irradiation was used for cross-linking poly (vinyl alcohol) (PVA) and glycidyl methacrylate (GMA) mixtures of different compositions. Specifically, 0.5 wt% titanium dioxide (TiO₂) nanoparticles were added and blended well with the casting mixture prior to exposure to the irradiation dose. Next, 10 kGy was found to be the optimum dose for achieving the desired physical and chemical properties of the membrane. Characterizations of the cast membranes were carried out by Fourier transformer infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and positron annihilation lifetime spectroscopy (PALS). The properties of the membrane were also characterized by ion exchange capacity (IEC), water uptake, and tensile strength and were assessed in relation to application in proton exchange membrane fuel cells (PEMFCs). A maximum proton conductivity of 7.3 × 10^?2 S cm^?1 was obtained for the membrane having 20 % GMA, 80 % PVA, and 0.5 % TiO₂, and its activity and durability in a membrane electrode assembly (MEA) were compared to those of a commercial Nafion® 1350.     

Electrochemical determination of bisphenol A based on PHD/MWCNTs modified glassy carbon electrode

A novel electrochemical sensor for the determination of bisphenol A (BPA) was fabricated by block polyelectrolyte composite films, which composed of diblock polyelectrolyte poly (2-hydroxyethyl methacrylate)-b-poly (2-(dimethylamino) ethyl methacrylate) (PHEMA-b-PDMAEMA, noted as PHD in the later content) and multi-walled carbon nanotubes (MWCNTs). The tertiary amino groups of PDMAEMA can be protonated at physiological pH. The protonated PDMAEMA can thus interact with the negatively charged BPA through electrostatic attraction to increase the BPA sorption capacity and enhance the ability for highly sensitive detection of BPA. The PHD/MWCNTs composite films combine the electrocatalytic property of MWCNTs and the electrostatic attraction of protonated PHD. Because of the above-mentioned excellent property of the composite films, the PHD/MWCNTs/glassy carbon electrode exhibited good electrocatalytic activity to electrooxidation of BPA. The wide linear response range of the BPA sensor was from 4.56 × 10^?5 g L^?1 to 2.28 × 10^?2 g L^?1 with a lower detection limit of 2.28 × 10^?6 g L^?1 (S/N = 3) and high sensitivity 2442.86 μA L g^?1 cm^?2. The current reached the steady-state current with a shorter response time less than 4 s. The proposed method was successfully applied to determine BPA in real samples (PVC food package, milk, tap water and pond water) and satisfactory results were obtained. These results indicated that the block polyelectrolyte composite have potential applicability of the BPA sensor.     

Physical-Mechanical Behavior and Water-Barrier Properties of Biopolymers-Clay Nanocomposites

The preparation and characterization of biodegradable films based on starch-PVA-nanoclay by solvent casting are reported in this study. The films were prepared with a relation of 3:2 of starch:PVA and nanoclay (0.5, 1.0, and 1.5% w/v), and glycerol as plasticizer. The nanoclays before being incorporated in the filmogenic solution of starch-PVA were dispersed in two ways: by magnetic stirring and by sonication. The SEM results suggest that the sonication of nanoclay is necessary to reach a good dispersion along the polymeric matrix. FTIR results of films with 1.0 and 1.5% w/v of sonicated nanoclay suggest a strong interaction of hydrogen bond with the polymeric matrix of starch-PVA. However, the properties of WVP, tensile strength, percentage of elongation at break, and Young’s modulus improved to the film with sonicated nanoclay at 0.5% w/v, while in films with 1.0 and 1.5% w/w these properties were even worse than in film without nanoclay. Nanoclay concentrations higher than 1.0 w/v saturate the polymer matrix, affecting the physicochemical properties. Accordingly, the successful incorporation of nanoclays at 0.5% w/v into the matrix starch-PVA suggests that this film is a good candidate for use as biodegradable packaging.     

Influence of some lime-containing additives on the thermal behavior of urea

Urea is one of the main nitrogen fertilizers used in agriculture. But being well soluble in water, hardly 50% of its nitrogen is assimilated by plants. One possibility to eliminate this disadvantage is to use coating agents for modification of urea to obtain a controlled-realized fertilizer. The aim of this research was to study the influence of different lime-containing additives on the thermal behavior and decomposition kinetics of urea in oxidizing atmosphere. Commercial fertilizer-grade urea (46.4% N) and analytical-grade CaO, MgO, CaCO₃, MgCO₃ were used in the experiments. In addition, one Estonian limestone and one dolomite sample were used as additive or coating material. The experiments with a Setaram Setsys 1750 thermoanalyzer coupled to a Nicolet 380 FTIR Spectrometer by a heated transfer line were carried out under non-isothermal conditions up to 900 °C at the heating rate of 5 °C min^?1 and to calculate kinetic parameters, additionally, at 1, 2, and 10 °C min^?1 in the atmosphere containing 80% of Ar and 20% of O₂. The differential isoconversional method of Friedman was used to calculate the kinetic parameters. The results obtained indicate that thermooxidative decomposition of urea as well as the blends of urea with lime-containing materials and urea prills coated with limestone or dolomite powder follows a complex reaction mechanism.     

Microbial Fed-batch Production of 1,3-Propanediol Using Raw Glycerol with Suspended and Immobilized Klebsiella pneumoniae

The production of 1,3-propanediol (1,3-PD) was investigated with Klebsiella pneumoniae DSM 4799 using raw glycerol without purification obtained from a biodiesel production process. Fed-batch cultures with suspended cells revealed that 1,3-PD production was more effective when utilizing raw glycerol than pure glycerol (productivity after 47 h of fermentation, 0.84 g?L^?1?h^?1 versus 1.51 g?L^?1?h^?1 with pure and raw glycerol, respectively). In addition, more than 80 g/L of 1,3-PD was produced using raw glycerol; this is the highest 1,3-PD concentration reported thus far for K. pneumoniae using raw glycerol. Repeated fed-batch fermentation with cell immobilization in a fixed-bed reactor was performed to enhance 1,3-PD production. Production of 1,3-PD increased with the cycle number (1.06 g?L^?1?h^?1 versus 1.61 g?L^?1?h^?1 at the first and fourth cycle, respectively) due to successful cell immobilization. During 46 cycles of fed-batch fermentation taking place over 1,460 h, a stable and reproducible 1,3-PD production performance was observed with both pure and raw glycerol. Based on our results, repeated fed batch with immobilized cells is an efficient fermentor configuration, and raw glycerol can be utilized to produce 1,3-PD without inhibitory effects caused by accumulated impurities.     

Influence of the Addition of Lauric Acid to Films Made from Gelatin,Triacetin and a Blend of Stearic and Palmitic Acids

Summary: The objective of this research was to verify the influence of adding increasing amounts of lauric acid on the functional properties of homogenized films made from gelatin, triacetin and a blend of palmitic and stearic acids. The films were characterised with respect to their visual aspect, water vapour permeability (WVP), water solubility, mechanical properties (tensile strength and percent elongation), oxygen permeability (O₂P), opacity (OP) and melting and glass transitions temperatures. The films produced were malleable and macroscopically homogeneous. The addition of 1% of lauric acid to the film of gelatin, triacetin and blend of palmitic and stearic acids (5.84 ± 0.31 gmm · m⁻² dkPa) caused a slight decrease in WVP. The additions of 2.5% (5.70 ± 0.76 gmm · m⁻² dkPa), 5% (5.38 ± 0.64 gmm · m⁻² dkPa) and 10% (4.50 ± 0.55 gmm · m⁻² dkPa) of lauric acid were sufficient to make a significant difference in the WVP at the higher levels used. As compared to the gelatin and triacetin film, the addition of lauric acid at all the concentrations studied resulted in a slight increase in the film solubility. The addition of hydrophobic substances to gelatin/triacetin films (15.26 ± 0.28 cm³ · µm · m⁻² dkPa) favoured an increase in O₂P permeability, this effect being greater in the films made from gelatin, triacetin, blend of palmitic and stearic acids and 10% lauric acid (24.48 ± 0.07 cm³ · µm · m⁻² dkPa). The increasing addition of lauric acid significantly reduced the tensile strength and increased elongation of the films composed of gelatin, triacetin and blend that being more evident at the concentrations of 5% (67.58 ± 1.23 MPa and 11.45 ± 0.57%) and 10% (63.50 ± 1.56 MPa and 12.90 ± 0.57%). The addition of 1% (OP, 27%) and 10% (OP, 28%) of lauric acid induced no visible effect on the opacity of the films. The thermogrammes showed three transitions for the gelatin/triacetin/stearic-palmitic blend/1% lauric acid films (−57.42 °C, 23.74 °C and 44.11 °C) and two for the gelatin/triacetin/stearic-palmitic acids blend/10% lauric acid films (−56.22 °C and 17.35 °C). As observed by DSC, the addition of fatty acids resulted in the appearance of more than one melting peak for all films in relation to the gelatin and triacetin film.     

The conducting polymer electrolyte based on polypyrrole-polyvinyl alcohol and its application in low-cost quasi-solid-state dye-sensitized solar cells

The effect of polypyrrole (PPy) on the polyvinyl alcohol (PVA)-potassium iodide (KI)-iodine (I₂) polymer electrolytes has been investigated and optimized to use in a dye-sensitized solar cell (DSSC). The different weight ratios of PVA: PPy (93: 2, 91: 4, 89: 6, 87: 8, and 85: 10 wt%) polymer electrolytes (PE) were prepared by solution casting. Structural, complex formation and surface roughness of the prepared electrolytes was confirmed by X-ray diffraction, FTIR, and atomic force microscopy (AFM) respectively. Conductivity plots of all polymer films showed increasing trend with temperature and concentration of PPy. The activation energy of the optimized system found to be 0.871 kJ mol^?1. UV-visible spectrum was adopted to characterize the absorption spectra of the material revealed that increase in the absorbance with increasing PPy content and shifting the absorbance maximum towards lower energy. The indirect band gap decreased from 3.78 to 2.14 eV and direct band gap decreased from 3.88 to 2.71 eV. The EIS analyses revealed the lower charge transfer resistance of 3.029 Ω cm² at the interface between CE and PE. The excellent performance was observed in the fabricated DSSCs using PVA (85%)/PPy (10%)/KI (5%)/I₂ polymer electrolyte with a short-circuit current density of 11.071 mA cm^?2, open-circuit voltage of 0.644 V, fill factor of 0.575, and photovoltaic conversion efficiency of 4.09% under the light intensity of 100 mW cm^?2. Hence, the PPy content in polymer electrolyte influences the remarkable performance of low-cost DSSC.     

Gene Cloning, Expression, and Characterization of a Thermostable Xylanase from Nesterenkonia xinjiangensis CCTCC AA001025

An endo-β-1,4-xylanase-encoding gene, xyn11NX, was cloned from Nesterenkonia xinjiangensis CCTCC AA001025 and expressed in Escherichia coli. The gene encoded a 192-amino acid polypeptide and a putative 50-amino acid signal peptide. The deduced amino acid sequence exhibited a high degree of similarity with the xylanases from Streptomyces thermocyaneoviolaceus (68%) and Thermobifida fusca (66%) belonging to glycoside hydrolase family 11. After purification to homogeneity, the recombinant Xyn11NX exhibited optimal activity at pH 7.0 and 55 °C and remained stable at weakly acidic to alkaline pH (pH 5.0–11.0). The enzyme was thermostable, retaining more than 80% of the initial activity after incubation at 60 °C for 1 h and more than 40% of the activity at 90 °C for 15 min. The K _m and V _max values for oat spelt xylan and birchwood xylan were 16.08 mg ml^?1 and 45.66 μmol min^?1 mg^?1 and 9.22 mg ml^?1 and 16.05 μmol min^?1 mg^?1, respectively. The predominant hydrolysis products were xylobiose and xylotriose when using oat spelt xylan or birchwood xylan as substrate.     

Facile fabrication of chitosan active film with xylan via direct immersion

Chitosan film was immersed in NaOH solution with xylan to simply prepare active chitosan/xylan film. FT-IR, XRD, FE-SEM, AFM and XPS were used to evaluate the effects of xylan on the structure and morphology of chitosan film, and a wide variety of material characteristics of the chitosan/xylan composite films were investigated. The results showed that the xylan chains entered into the gap of chitosan film and became nodules, leading to strong hydrogen bonds and electrostatic interactions between chitosan and xylan. Moreover, the introduction of xylan not only resulted in stronger crystallinity and a more compact structure of chitosan film, but also had an important effect on the properties of chitosan film. The tensile strength, breaking elongation and anti-ultraviolet performance of the chitosan/xylan films were improved greatly with the increasing concentration of xylan; the water vapor transmission rate, water absorption rate and oxygen barrier property of chitosan/xylan composite films were higher than those of chitosan film; chitosan/xylan composite films still showed hydrophobicity when the xylan concentration was more than 1 %. The chitosan/xylan composite film has more potential to be used as food packaging than pure chitosan film.     

The States,Diffusion, and Concentration Distribution of Water in Radiation‐Formed PVA/PVP Hydrogels

Abstract

Hydrogels with various compositions of polyvinyl alcohol (PVA) and poly(1‐vinyl‐2‐ pyrrolidinone) (PVP) were prepared by irradiating mixtures of PVA and PVP in aqueous solutions with gamma‐rays from ⁶⁰Co sources at room temperature. The states of water in the hydrogels were characterized using DSC and NMR T₂ relaxation measurements and the kinetics of water diffusion in the hydrogels were studied by sorption experiments and NMR imaging. The DSC endothermic peaks in the temperature range ?10 to +10°C implied that there are at least two kinds of freezable water present in the matrix. The difference between the total water content and the freezable water content was referred to as bound water, which is not freezable. The weight fraction of water at which only nonfreezable water is present in a hydrogel with F_VP=0.19 has been estimated to be g_H2O/g_Polymer=0.375. From water sorption experiments, it was demonstrated that the early stage of the diffusion of water into the hydrogels was Fickian. A curve‐fit of the early‐stage experimental data to the Fickian model allowed determination of the water diffusion coefficient, which was found to lie between 1.5×10^?11 m² s^?1 and 4.5×10^?11 m² s^?1, depending on the polymer composition, the cross‐link density, and the temperature. It was also found that the energy barrier for diffusion of water molecules into PVA/PVP hydrogels was ≈24 kJ mol^?1. Additionally, the diffusion coefficients determined from NMR imaging of the volumetric swelling of the gels agreed well with the results obtained by the mass sorption method.     

Mineral Supplementation Increases Erythrose Reductase Activity in Erythritol Biosynthesis from Glycerol by Yarrowia lipolytica

The aim of this study was to examine the impact of divalent copper, iron, manganese, and zinc ions on the production of erythritol from glycerol by Yarrowia lipolytica and their effect on the activity of erythrose reductase. No inhibitory effect of the examined minerals on yeast growth was observed in the study. Supplementation with MnSO₄·7H₂O (25 mg l^?1) increased erythritol production by Y. lipolytica by 14.5 %. In the bioreactor culture with manganese ion addition, 47.1 g l^?1 of erythritol was produced from 100.0 g l^?1 of glycerol, which corresponded to volumetric productivity of 0.87 g l^?1 h^?1. The addition of Mn²⁺ enhanced the intracellular activity of erythrose reductase up to 24.9 U g^?1 of dry weight of biomass (DW), hence, about 1.3 times more than in the control.     

Enhanced proton conductivity of polymer electrolyte membrane doped with titanate nanotubes

Nafion-titanate nanotubes composite membranes were prepared through a casting process. With the addition of 5 wt.%, the nanotubes were homogenously distributed in Nafion solution. The formed composite membrane showed a comparable mechanical strength to Nafion membrane. The proton conductivity of the composite membrane without external humidification is higher than that of the Nafion membrane, reaching 0.034 Scm^?1 and 0.01 Scm^?1 at 100 °C and 120 °C, respectively. The improved proton conductivity was attributed to the great water retention ability of the doped nanotubes.     

Characterization of Biodegradable Nanocomposite Films Prepared with Glutelin from Jatropha curcas L. by Response Surface Methodology and Infrared Spectroscopy

The water vapor permeability (WVP) and hardness of biodegradable nanocomposite films based on glutelin from Jatropha curcas L. were determined and the results were analyzed by response surface methodology (RSM). The effects of independent variables constituted by the plasticizer (glycerol), nanofiller (cloisite), and pH on the physical parameters were evaluated. The regression models obtained for each physical property adequately described the measurements used in the experimental design, with regression coefficients of 0.9513 and 0.9421 for WVP and hardness. The regression coefficients show that pH has the most significant effect on the WVP, whereas the cloisite content has the largest influence on the hardness of the nanocomposite film. Fourier transform infrared spectroscopy provided confirmation of the results obtained by RSM. Corroboration that the gluteline structure is in a similar form as the WVP and primarily influenced by pH was obtained using conventional and second derivative infrared spectra. However, the hardness of the film primarily depends on the cloisite content. This methodology may be useful for the design and elaboration of nanocomposite films based on J. curcas L. with specific barrier and mechanical properties.     

Graft Copolymerization of 2‐Acrylamido‐2‐methyl Propane Sulfonic Acid on Dimethyl Sulfoxide Pretreated Poly(Ethylene Terephthalate) Films Using Cerium Ammonium Nitrate as Initiator

Abstract

In this study, graft polymerization of 2‐acrylamido‐2‐methyl propane sulfonic acid (AMPS) on poly(ethylene terephthalate) (PET) films using cerium ammonium nitrate (CeAN) as an initiator was investigated. Before the polymerization reaction was carried out, films were swelled in dimethyl sulfoxide (DMSO) at 140°C for 1 h. The effect of polymerization temperature, time, initiator, and monomer concentrations on the graft yield were investigated. It was observed that the graft yield was initially increased with increasing temperature, monomer, and initiator concentrations; and then decreased. Graft yield was found to increase with increasing polymerization time up to 5 h, then remain constant. The effects of monomer and initiator inclusions on the grafting yield were also examined. Optimum conditions for grafting were found to be [AMPS] = 1.0 M, [Ce⁴⁺] = 1.5 × 10^?2 M, T = 85°C and t = 5 h. The rate of grafting was found to be proportional to the 0.1 and 0.4 powers of monomer and initiator concentrations, respectively. The overall activation energy for the grafting was calculated to be 11.4 kcal mol^?1. The effect of grafting on PET film properties such as intrinsic viscosity and water absorption capacity were determined. The grafted PET films were characterized with FTIR spectroscopy and scanning electron microscopy (SEM).     

Preparation of gelatin/poly(vinyl alcohol) film modified by methyl methacrylate and gamma irradiation

The properties of gelatin–polyvinyl alcohol (G–PVA) blend films were improved by methyl methacrylate (MMA) and γ irradiation for a practical viewpoint. The films were prepared by the casting method, modified by glycerol and MMA monomer, and their mechanical properties were also studied. The gelatin-based films were successfully prepared using γ irradiation (3.1 kGy) and gelatin: PVA = 97:3 (w/w) as optimized. Tensile properties of the films were studied and thermal properties of the films were characterized by thermogravimetric analysis and dynamic mechanical analysis pointed out that MMA treated both gelatin films, and G–PVA blend films showed less thermal degradation than untreated films. In addition, structural and morphological features of the gelatin-based films were examined by Fourier transform infrared and scanning electron microscopy, respectively. The ultimate results of the present study showed remarkable enhancement in tensile properties (> 40%) and a reduction in elongation at break of the films, thanks to the MMA addition and γ irradiation.     

Studies on bound water in poly(vinyl alcohol). Hydrogel by DSC and FT-NMR

The phase transition of water bound in poly(vinyl alcohol)(PVA) hydrogel was measured by differential scanning calorimetry. The cross-link density calculated from the swelling ratio of PVA hydrogel ranged from 3 × 10^?5 to 1 × 10^?3 according to the total dose of ⁶⁰Co γ-ray irradiation. From the enthalpy of melting, it was found that water in PVA gel can be classified into at least three groups; ca. 1–1.5 mol non-freezing water, 5–6 mol freezing bound water, and the rest free water, corresponding to each hydroxyl group of PVA. The characteristic properties of polymer hydrogel were attributed to the large number of molecules of freezing bound water in the network. The amount of free water depended markedly upon cross-link density; however, it was not apparent in PVA gel with cross-link density >2.0 × 10^?4. The decreases in the nuclear magnetic resonance relaxation times of water and PVA were related to the cross-link density and were found to level off at a cross-link density 2.0 × 10^?4.