Preparation and Characterization of Chemically Crosslinked Polyvinyl Alcohol/Carboxylated Nanocrystalline Cellulose Nanocomposite Hydrogel Films with High Mechanical Strength

Chemically crosslinked polyvinyl alcohol (PVA)/carboxylated nanocry-stalline cellulose (PVA/CNCC) nanocomposite hydrogel films were fabricated by film-casting of PVA/CNCC mixture solutions and subsequent thermal-curing of the PVA with the CNCC. Gel fractions of the hydrogel films were measured to confirm the occurrence of crosslinking. Morphologies of the hydrogel films were characterized by polarized light microscopy and scanning electron microscopy (SEM). Thermal properties, swelling behavior and mechanical properties of the hydrogel films were investigated to evaluate the influence of CNCC content (10～30% of PVA mass). Equilibrium water content of the hydrogel films was in the range of 40～49%. At swelling equilibrium, the hydrogel films could be stretched to 3～3.4 times their original length, and their tensile strength was in the range of 7.9～11.6 MPa. The results show that the PVA/CNCC nanocomposite hydrogel films were both extensible and highly tough.     

pH-Sensitive Poly(Vinyl Alcohol)/Sodium Carboxymethylcellulose Hydrogel Beads for Drug Delivery

A series of pH-sensitive hydrogel beads were prepared composed of poly(vinyl alcohol) (PVA) and sodium carboxymethylcellulose (CMC) by using Fe³⁺ crosslinking and freeze-thawing (FT) cycle techniques. The mixed solution of CMC and PVA was firstly crosslinked with Fe³⁺ to form beads and then subjected to freezing-thawing cycles for further crosslinking. The formation of hydrogel was confirmed by Fourier transform infrared spectroscopy (FTIR). The gelling rate in ferric solution and the swelling and pH-senstive properties of the hydrogel beads were investigated. The encapsulation efficiency and in-vitro release properties of beads were also evaluated using Bovine serum albumin as model drug. The pH sensitivity and the release rate increased with increasing CMC content. These results suggest that the PVA/CMC hgdrogel beads should be useful as pH-sensitive drug delivery systems for bioactive agents.     

Effects of the ZnSe concentration on the structural and optical properties of ZnSe/PVA nanocomposite thin film

This study investigated the effects of ZnSe nanoparticles (NPs) on the structural and (linear and nonlinear) optical properties of polyvinyl alcohol (PVA) thin film. Three samples of ZnSe NP-doped PVA thin films with different concentrations of ZnSe were produced on a glass substrate. The ZnSe NPs were synthesized by pulsed laser ablation of the ZnSe bulk target immersed in distilled water using a 1064 nm wavelength and a high frequency pulsed Nd:YAG laser. The optical bandgap energies of the films were extracted from their UV-Vis-NIR absorption spectra. The corresponding energy bandgaps of the nanocomposite films declined as the ZnSe NPs doping concentration increased. X-ray diffraction analysis was used to characterize the crystalline phases of the ZnSe/PVA nanocomposite films. The concentration-dependent nonlinear optical absorption and nonlinear refraction behaviors of the films after exposure to 532-nm nanosecond laser pulses were investigated using the Z-scan technique. The nonlinear absorption response of the films was positive when measured using an open aperture scheme, which was attributed to the two-photon absorption mechanism. In addition, the nonlinear refraction indices had a negative value and they increased as the concentration of ZnSe NPs in the films increased.     

Preparation and Properties of Polyvinyl Alcohol/Collagen Hydrogel

Hydrogel scaffolds based on poly(vinyl alcohol) (PVA) collagen films were prepared by a chemical cross-linking method. The effects of the contents of PVA and cross-linker on compressive strength and swelling ratio were studied, and the effect of the pH value of the immersion medium on the swelling ratio was also investigated. The results showed that the introduction of PVA improved the compressive strength of PVA/collagen hydrogel, and the swelling ratio of the hydrogel scaffold increased with increasing PVA content in the blends. With increasing cross-linker content, the swelling ratio decreased; however, the compressive strength increased. The swelling ratio of PVA/collagen scaffold increased when pH was decreased. In conclusion, swelling ratio and compressive strength in PVA/collagen blends can be controlled by variation of their contents, cross-linking agent content, and pH value.     

Thermo- and pH-responsive hydrogel-coated gold nanoparticles prepared from rationally designed surface-confined initiators

Gold nanoparticles (~40 nm in diameter) were encapsulated by a hydrogel overlayer generated by the free radical polymerization of N-isopropylacrylamide-co-acrylic acid (NIPAM-co-AA), which was promoted by a specifically designed radical initiator covalently anchored to the surface of the gold core. The size and morphology of the shell/core nanoparticles were characterized by scanning electron microscopy and transmission electron microscopy. In addition, the optical properties of the nanoparticles were characterized by UV–Visible spectroscopy. Separately, the particle size was evaluated as a function of temperature and pH using dynamic light scattering. The shell/core hydrogel nanoparticles undergo reversible volume changes in water at a lower critical solution temperature (LCST) of ~34 °C as well as at pH values between 3 and 4. The unique composition and properties of these shell/core hydrogel nanoparticles make them attractive for use as nanoscale drug-delivery vehicles.     

Characterization of Polyvinyl Alcohol/ZnO Nanocomposite Hydrogels for Wound Dressings

Polymeric hydrogels, as novel soft biomaterials, have found various applications in the medical field; for instance, as wound dressings and wound care management. In this study, in order to achieve wound dressings with improved properties, nanocomposite hydrogels using incorporation of nano zinc oxide (ZnO) in polyvinyl alcohol (PVA), were prepared by a freezing-thawing method. The effect of ZnO loading on the mechanical, structural, physical and antibacterial properties of the samples was investigated and the morphology of the prepared nanocomposite hydrogels was determined by field emission scanning electron microscopy (FESEM). The results of mechanical tests of the nanocomposite hydrogels, using compressive and hardness tests, indicated that by adding increasingly amounts of the ZnO nanoparticles, the mechanical properties of the nanocomposite hydrogels were improved. Structure-related properties of the hydrogels, such as swelling and gel fraction measurements, showed that the increase in ZnO content lead to a decrease in the swelling rate and increase in the gel fraction of the nanocomposites. Antibacterial and biocompatibility analysis revealed that, with increasing nano ZnO content, the antibacterial properties of the nanocomposite significantly increased and the cells viability rose, leading to slightly reduced toxicity. The results of this work indicated that the presence and quantity of added ZnO in the PVA hydrogels were very influential factors to obtain the desirable characteristics of wound dressings, such as absorbing the wound fluids and exudates, being biocompatible, anti-bacterial and nontoxic, and having mechanical stability and flexibility.     

Properties of nano-ZnO/poly(vinyl alcohol)/poly(ethylene oxide) composite thin films

A series of poly(vinyl alcohol)/nano-ZnO composites were prepared by dispersing nano-ZnO in aqueous solutions containing mixtures of the biodegradable polymers poly(vinyl alcohol) (PVA) and poly(ethylene oxide) (PEO), and composite thin films were prepared by casting. The introduction of nano-ZnO into PVA/PEO mixed solutions significantly decreased the resistivity of the solutions. Ultraviolet absorption, thermal behaviour and visco-elastic properties of the thin films were determined as a function of nano-ZnO content up to 15 wt%. Optimum film properties were obtained with 1 wt% nano-ZnO, higher proportions of nano-ZnO resulting in agglomeration of ZnO particles and deterioration in film properties. The Forouhi and Bloomer model was used for the modelling of ZnO thin films.     

Excellent UV absorption in spin-coated thin films of oleic acid modified zinc oxide nanorods embedded in Polyvinyl alcohol

The aim of the study is to investigate the optical properties of spin-coated, highly transparent nanocomposite films of oleic acid modified ZnO (Zinc oxide) nanorods embedded in Polyvinyl alcohol (PVA) matrix. Pristine and oleic acid (OA) modified ZnO nanorods have been prepared by wet chemical synthesis and are characterized by X-ray diffraction, FESEM, TEM and FT–IR spectroscopy techniques. The optical properties of ZnO/PVA films are studied using UV–visible absorption and Photoluminescence (PL) spectroscopy. The results show that the optical absorption of the films in the UV region is quite high and more than 95% absorption is observed in films prepared from OA modified ZnO nanorods. The excellent UV absorption at around 300 nm offers prospects of applications of these films as efficient UV filters in this wavelength region. The PL spectrum of pristine ZnO nanorods shows almost white light emission whereas OA modified ZnO nanorods have a more intense peak centered in the blue region. The PL emission of OA modified ZnO/PVA film shows appreciable increase in intensity compared to the film obtained with pristine ZnO. The surface modification of ZnO by the polymer matrix removes defect states within ZnO and facilitates sharp near band edge PL emission at 364 nm.     

Swelling and mechanical properties of radiation crosslinked Au/PVA hydrogel nanocomposites

Hydrogel nanocomposites of polyvinyl alcohol (PVA) filled with gold nanoparticles (Au NPs) were synthesised using gamma irradiation technique. Structural, optical, and morphological characterisation was performed using powder XRD, UV-vis, FESEM, and TEM techniques. Inclusion of Au NPs at the time of crosslinking may have reduced the binding sites of PVA matrix, which resulted in high-swelling capacity of Au/PVA hydrogel nanocomposites. The increase in mechanical stability of the Au/PVA hydrogel nanocomposites has been observed and it may be due to increase in the crystallinity percentage with increased Au NPs in PVA matrix. These nanocomposites may fulfil the increasing demand for multifunctional hydrogel with enhanced swelling and mechanical properties.     

Synthesis and characterization of CdS/PVA nanocomposite films

A series CdS/PVA nanocomposite films with different amount of Cd salt have been prepared by means of the in situ synthesis method via the reaction of Cd²⁺-dispersed poly vinyl-alcohol (PVA) with H₂S. The as-prepared films were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), ultraviolet-visible (UV-vis) absorption, photoluminescence (PL) spectra, Fourier transform infrared spectroscope (FTIR) and thermogravimetric analysis (TGA). The XRD results indicated the formation of CdS nanoparticles with hexagonal phase in the PVA matrix. The primary FTIR spectra of CdS/PVA nanocomposite in different processing stages have been discussed. The vibrational absorption peak of CdS bond at 405 cm⁻¹ was observed, which further testified the generation of CdS nanoparticles. The TGA results showed incorporation of CdS nanoparticles significantly altered the thermal properties of PVA matrix. The photoluminescence and UV-vis spectroscopy revealed that the CdS/PVA films showed quantum confinement effect.     

Effect of solvent on the characteristics of nanostructured composites of poly (1-naphthylamine) with poly (vinyl alcohol)

Efficient utilization of inherently conducting polymers in nano technological applications faces the challenge to assemble them into highly ordered structures which may yield novel properties. The present study reports for the first time the synthesis and characterization of nanostructured poly (1-naphthylamine) (PNA) dispersed polyvinyl alcohol (PVA) composites. The composites were prepared by loading PNA from 2 wt% to 10 wt% in PVA in aqueous as well as nonaqueous media. The composites were characterized by UV–visible spectroscopy, TEM, stress–strain studies, electrical conductivity measurements and moisture absorption studies under controlled humidity. A discrete but uniform distribution of nanoparticles was obtained in PNA/PVA composites synthesized in water having particle size between 5 and 30 nm. A self assembled network of nanostructured PNA particles was obtained in case of PNA/PVA composites synthesized in N-methylpyrolidone (NMP) with particle sizes between 10 and 65 nm. The variation in the nanostructured morphology of PNA particles in PVA matrix in the two cases resulted from the pronounced interaction of PVA with NMP through hydrogen bonding. This leads to the formation of a homogeneous matrix that facilitates the formation of a self assembled network of PNA nano particles. In case of PNA/PVA composites synthesized in water, lower affinity of PVA towards water was responsible for a discrete, agglomerate free distribution of PNA particles. We have found that the PNA/PVA nano composite synthesized in water exhibited good mechanical properties and electrical conductivity (8.1 × 10⁻¹ S/cm) as well as lowest moisture absorption (4 wt%) which holds potential for use in semiconductor and biomedical devices.     

Surface properties of UV-irradiated poly(vinyl alcohol) films containing small amount of collagen

The surface properties of poly(vinyl alcohol) (PVA) films in the presence of 1%, 3% and 5% of collagen before and after UV-irradiation have been studied by atomic force microscopy (AFM) and by contact angle measurements. PVA films have been obtained by solvent evaporation from water solution of PVA and PVA containing small amount of collagen. After drying, the samples were irradiated with UV light wavelength λ = 254 nm in air. Surface properties before and after UV-irradiation were observed using AFM. Contact angles of two liquids: diiodomethane (D) and glycerol (G) on polymeric films were measured at constant temperature using goniometer.The results have shown that the contact angle and the surface free energy for PVA films were altered by UV-irradiation. These alterations indicate photooxidation and an increase of polarity of the surface. The comparison of surface properties of PVA films and PVA containing collagen points out that collagen is more sensitive to photooxidation than PVA and PVA/collagen blends. PVA films containing collagen easier undergo photooxidation process with formation of new polar groups than pure PVA films.     

Preparation and Characterization of Poly(Vinyl Alcohol) (PVA)/SiO2, PVA/Sulfosuccinic Acid (SSA) and PVA/SiO2/SSA Membranes: A Comparative Study

Abstract

New organic–inorganic nanocomposites based on PVA, SiO₂ and SSA were prepared in a single step using a solution casting method, with the aim to improve the thermomechanical properties and ionic conductivity of PVA membranes. The structure, morphology, and properties of these membranes were characterized by Raman spectroscopy, small- and wide-angle X-ray scattering (SAXS/WAXS), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), water uptake (Wu) measurements and ionic conductivity measurements. The SAXS/WAXS analysis showed that the silica deposited in the form of small nanoparticles (～ 10?nm) in the PVA composites and it also revealed an appreciable crystallinity of pristine PVA membrane and PVA/SiO₂ membranes (decreasing with increasing silica loading), and an amorphous structure of PVA/SSA and PVA/SSA/SiO₂ membranes with high SSA loadings. The thermal and mechanical stability of the nanocomposite membranes increased with the increasing silica loading, and silica also decreased the water uptake of membranes. As expected, the ionic conductivity increased with increasing content of the SSA crosslinker, which is a donor of the hydrophilic sulfonic groups. Some of the PVA/SSA/SiO₂ membranes had a good balance between stability in aqueous environment (water uptake), thermomechanical stability and ionic conductivity and could be potential candidates for proton exchange membranes (PEM) in fuel cells.     

Microstructure and Thermal and Tensile Properties of Poly(vinyl alcohol) Nanocomposite Films Reinforced by Polyacrylamide Grafted Cellulose Nanocrystals

Abstract

Polyacrylamide grafted cellulose nanocrystals (CNC-g-PAM) were incorporated into poly(vinyl alcohol) (PVA) by a solution casting method to fabricate nanocomposite films with enhanced thermal and tensile properties. The microstructure and the thermal and tensile properties of the PVA/CNC-g-PAM nanocomposite films were investigated as a function of CNC-g-PAM content. Infrared spectroscopy corroborated the presence of hydrogen bonds between PVA and the PAM on the surface of the CNC. Polarized optical microscopy and scanning electron microscopy revealed good dispersion of the CNC-g-PAM in the PVA matrix and good interfacial compatibility. Accordingly, the initial degradation temperature of the nanocomposite films was elevated slightly compared to pristine PVA film. The glass transition temperature, melting temperature, and crystallinity of the PVA also varied slightly after the incorporation of the CNC-g-PAM. At both 0% and 50% RH, the nanocomposite films showed an obvious increase of elastic modulus, no apparent change of breaking strength and a drastic reduction of elongation at break with increasing CNC-g-PAM content.     

Polyvinyl Alcohol/Na-Montmorillonite Nanocomposite Hydrogels Prepared by Freezing–Thawing Method: Structural,Mechanical, Thermal,and Swelling Properties

Physically crosslinked nanocomposite hydrogels based on polyvinyl alcohol (PVA) containing Na-montmorillonite were prepared by the cyclic freezing–thawing method. The primarily exfoliated morphology of prepared nanocomposite hydrogels was confirmed by X-ray diffractometry (XRD) and transmission electron microscopy (TEM) as complementary techniques. It is shown that some interactions developed between the hydroxyl groups of PVA chains and Na-montmorillonite silicate layers in the nanocomposite hydrogels. Differential scanning calorimetry (DSC) results indicated some shifting in the glass transition temperature of the PVA hydrogel in the presence of the nanoclay. Swelling measurements showed that the swelling ratios of the nanocomposite hydrogels were increased either by decreasing the Na-montmorillonite content or by increasing the swelling medium temperature. Dynamic mechanical–thermal properties results showed higher storage modulus for nanocomposite hydrogels in temperature ranges both below and above 0°C. It was also found that the hardness of the nanocomposite hydrogels increased by increasing the nanoclay loading level.     

5,10,15,20-四-(4-十六烷基吡啶基)卟啉LB膜结构的研究

研究了两亲性卟啉５,１０,１５,２０－四－（４－十六烷基吡啶基）卟啉溴化物在气－液界面上的成膜性能,制备了其ＬＢ膜。用扫描隧道显微镜和ＵＶ－Ｖｉｓ光谱,荧光光谱,小角Ｘ射线衍射等实验方法研究了ＬＢ膜的形貌和卟啉大环分子在ＬＢ膜中的排列、取向和分子间的相互作用。结果表明,制备的ＬＢ膜结构均匀,性能稳定,在ＬＢ膜内,脂肪链并不是直立的,卟啉分子大环几乎平躺在基片上。     

Structural and magnetic properties of high magnetic moment electroplated CoNiFe thin films

CoNiFe alloy thin films deposited at various cobalt concentrations were galvanostatically electrodeposited on the pre-cleaned copper substrates. The effects of cobalt concentration on the structural, compositional, morphological, and magnetic properties of the films were investigated. X-ray diffraction patterns revealed that the deposited films possess polycrystalline in nature with mixed (fcc–bcc) cubic structure at optimized cobalt concentration. Microstructural properties of the films were calculated from predominant diffraction lines. The surface morphology and surface roughness were characterized using scanning electron microscopy and atomic force microscopy, respectively. EDAX results were revealed that the cobalt content increases as nickel content decreases whereas ferrous content initially increases and then eventually decreases in the CoNiFe alloy. VSM results show a higher value of saturation magnetization (4πM _s) above 2 T with coercivity 154 A/m for films deposited in the optimized deposition condition.     

Apatite formation on Poly (vinyl alcohol)-coated Poly (?-caprolactone) films by incubation in simulated body fluids

In this study, biodegradable poly (?-caprolactone) (PCL) films were coated with poly (vinyl alcohol) (PVA) and then incubated in a simulated body fluid 1.5SBF to prepare an apatite (HA)/PCL composite. It was found that the bone-like apatite formability of PCL was enhanced by PVA coating. The changes of surface properties induced by PVA coating were effective for apatite formation. The apatite formability increased with increasing coating amount. After 24 h incubation, apatite was formed on PVA-coated PCL film but hardly any apatite was found on uncoated PCL plate. The surface chemistry of the specimens was examined using XPS, FT-IR-ATR. The apatite formed was characterized by using SEM, TF-XRD, FT-IR, EDS. The apatite formed was similar in morphology and composition to that of natural bone. This indicated that simple PVA coating on PCL substrate could serve as a novel way to accelerated apatite formation via biomimetic method.     

含水量对PAM/PVA互穿网络水凝胶性能的影响

应用分子动力学方法对PAM/PVA互穿网络水凝胶体系进行研究.发现该水凝胶体系的内聚能密度、结合能随着水含量的增加而增加,即体系的稳定性更强.由静态力学性能分析发现随体系含水量的增加,弹性系数、工程模量以及延展性均减小.此外,通过对相关函数的分析,发现H₂O分子与其周围原子、官能团之间主要是通过氢键相互作用,形成氢键的强弱关系为O_water >O_PVA >O_PAM >N_PAM,与形成氢键的可能性(难易)关系一致.     

Study of enhanced red emission from Sm(Sal)3Phen ternary complexes in Poly Vinyl Alcohol film

In the present work, dinuclear complexes of salicylic acid (Sal) and 1,10-phenanthroline (Phen) were synthesized with different concentrations of Samarium ion (Sm³⁺) in Poly Vinyl Alcohol (PVA) polymer films and their structural and spectroscopic properties were investigated. Judd-Ofelt theory has been employed to estimate the several radiative parameters for SmCl₃ and Sm(Sal)₃Phen complex in PVA polymer film which are in fairly agreement between the experimental and the theoretical values supporting the J-O theory. Photoluminescence properties of the complex have been studied on 355 nm and 400 nm excitations in steady state as well as in time domain. On the basis of the UV-Vis absorption, FT-IR absorption, excitation, emission spectra and decay curves, spectroscopic properties of these films were studied and the photophysics involved was explained in terms of energy transfer and the RE encapsulation effect.