Poly(vinyl alcohol)/Clay‐Based Nanocomposite Hydrogels: Swelling Behavior and Characterization

Polymer/clay composite hydrogels were prepared based on PVA hydrogels containing 3–10 wt.‐% MOM. Their microstructure and morphology were studied by FT‐IR, WAXS and SEM, whereas the interactions between MOM and PVA were evaluated by thermal analyses. The swelling ratios for the PVA/MOM hydrogels decrease with increasing MOM content. WAXS results indicate that MOM was intercalates, and DSC results show a strong interaction between PVA and MOM. This interaction results in a stable network, which is confirmed by the elastic modulus and the thermal decomposition behavior of the hydrogels. Therefore, MOM acts as a co‐crosslinker, improving the stability of the network.

     

Synthesis and Characterization of Poly(vinyl alcohol)/Poly(vinyl pyrrolidone)-Iodine Nanofibers with Poloxamer 188 and Chitosan

This study focuses on the fabrication of poly(vinyl alcohol)/ poly(vinyl pyrrolidone)-Iodine nanofibers via electrospinning. Electrospun fibers were characterized by FT-IR, DSC and SEM techniques. DSC results indicated that the thermal stability of nanofibers were improved after the addition of chitosan and poloxamer 188. SEM images showed that the spongiform structure is much more compact and fibrous in the case of added chitosan, with an average fiber diameter of 374 nm, whereas the addition of poloxamer 188 resulted in a more porous and beaded composition, with average fiber diameter of 489 nm.     

Nanostarch Reinforced with Chitosan/Poly (vinyl pyrrolidone) Blend for In Vitro Wound Healing Application

Nanostarch, which is inexpensive and environmentally abundant, has been used as filler to prepare biocompatible films. The bio-nanocomposites were synthesized by solution casting method. TEM analysis proves that the average particle size of the nanostarch is in the range of 20–40?nm. Thermal stability and cell viability of CS/PVP matrix were best enhanced at 1% of nanostarch loading. The antibacterial activity exhibited by CPS bio-nanocomposite against Staphylococcus aureus and Pseudomonas aeruginosa and synergistic effects of CPS such as barrier properties, swelling properties, and better blood compatibility make it a suitable material for in vitro wound healing application.     

Thermal and dynamic mechanical behavior of bionanocomposites: Fumed silica nanoparticles dispersed in poly(vinyl pyrrolidone), chitosan,and poly(vinyl alcohol)

Various bionanocomposites were prepared by dispersing fumed silica (SiO₂) nanoparticles in biocompatible polymers like poly(vinyl pyrrolidone) (PVP), chitosan (Chi), or poly(vinyl alcohol) (PVA). For the bionanocomposites preparation, a solvent evaporation method was followed. SEM micrographs verified fine dispersion of silica nanoparticles in all used polymer matrices of composites with low silica content. Sufficient interactions between the functional groups of the polymers and the surface hydroxyl groups of SiO₂ were revealed by FTIR measurements. These interactions favored fine dispersion of silica. Mechanical properties such as tensile strength and Young's modulus substantially increased with increasing the silica content in the bionanocomposites. Thermogravimetric analysis (TGA) showed that the polymer matrices were stabilized against thermal decomposition with the addition of fumed silica due to shielding effect, because for all bionanocomposites the temperature, corresponding to the maximum decomposition rate, progressively shifted to higher values with increasing the silica content. Finally, dynamic thermomechanical analysis (DMA) tests showed that for Chi/SiO₂ and PVA/SiO₂ nanocomposites the temperature of β‐relaxation observed in tanδ curves, corresponding to the glass transition temperature T_g, shifted to higher values with increasing the SiO₂ content. This fact indicates that because of the reported interactions, a nanoparticle/matrix interphase was formed in the surroundings of the filler, where the macromolecules showed limited segmental mobility. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermal and spectroscopic studies of poly(N‐vinyl pyrrolidone)/poly(vinyl alcohol) blend films

Poly(N‐vinyl pyrrolidone) (PVP) and poly (vinyl alcohol) (PVA) homopolymers and their blended samples with different compositions were prepared using cast technique and subjected to X‐ray diffraction (XRD) measurements, infrared (IR) spectroscopy, ultraviolet/visible spectroscopy, and thermogravimetric analysis (TGA). XRD patterns of homopolymers and their blended samples indicated that blending amorphous materials, such as PVP, with semicrystalline polymer, such as PVA, gives rise to an amorphous structure with two halo peaks at positions identical to those found in pure PVP. Identification of structure and assignments of the most evident IR ‐ absorption bands of PVP and PVA as well as their blends in the range 400–2000 cm^?1 were studied. UV–vis spectra were used to study absorption spectra and estimate the values of absorption edge, E_g, and band tail, E_e, for all samples. Making use of Coats‐Redfern relation, thermogravimetric (TG) data allowed the calculation of the values of some thermodynamic parameters, such as activation energy E, entropy ΔS^#, enthalpy ΔH, and free energy of activation ΔG^# for different decomposition steps in the samples under investigation. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Controlled Swelling of Poly(hydroxyethyl methacrylate) Hydrogels by Photochemical Grafting of Hydrophobic Acrylates

The photochemically induced grafting polymerization of various alkyl acrylates onto cross‐linked poly(hydroxyethyl methacrylate) (PHEMA) was performed to reduce the hydrophilicity of the swellable network. Butyl, 2‐ethylhexyl and lauryl acrylate were used as monofunctional monomers for increasing the hydrophobic character, whereas hexanediol diacrylate was used as a multifunctional monomer with the additional feature of forming networks. The various steps of the grafting procedure were examined sequentially so as to optimize the overall hydrophobing effect. The grafting yield was shown to depend primarily of PHEMA swelling in the considered ethanol/monomer mixture. In spite of their high specific hydrophobic character, alkyl monoacrylates were shown to be less efficient because of lower grafting yield. Grafting initiation by hydrogen abstraction with benzophenone or by homolytic cleavage of a hydroxyalkyl‐phenone resulted in comparable grafting yields even with monofunctional monomers. The hardness measured for the water swollen rubbery materials correlated well to the equilibrium water content.

Shore A hardness as a function of the swelling ratio in water at T = 22 °C for grafted and ungrafted PHEMA hydrogels (same samples as those described in Table 5 ).     

Swelling Characteristics of pH- and Thermo-Sensitive Crosslinked Poly(Vinyl Alcohol) Grafts

Grafting of N-isopropylacrylamide, NIPAAm, onto partially and fully hydrolyzed poly(vinyl alcohol–g-maleic anhydride), PVA–MA, was carried out in presence of ammonium persulfate as initiator. The crosslinked PVA–MA–NIPAAm copolymers were prepared in presence of different weight percentages of methylene bisacrylamide, MBA, as crosslinker and N,N,N,N′-tetramethylethylenediamine, TMEA, as accelerator. Crosslinked PVA–MA–NIPAAm copolymers were prepared at two different temperatures 5 and 55 °C. The structural features of these grafts were confirmed by ¹H NMR analysis. Solution behaviors of both PVA–MA and PVA–MA–NIPAAm were evaluated from viscosity measurements. The swelling ratios of the crosslinked polymers were measured at different temperatures and pH values. The phase transition of the crosslinked gels was measured from DSC analysis. Crosslinked PVA–MA–NIPAAm grafts show different pH and temperature sensitivity. The swelling behaviors of PVA–MA–NIPAAm were referred to formation of hydrogen bonding between amide and carboxylic groups and also to hydrophobic aggregation of NIPAAm grafts.     

Thermal characteristics of poly(vinyl alcohol) and poly(vinylpyrrolidone) IPNs

Interpenetrating polymer network (IPN) hydrogels based on poly(vinyl alcohol) (PVA) and 1‐vinyl‐2‐pyrrolidone (VP) were prepared by radical polymerization using 2,2‐dimethyl‐2‐phenylacetophenone (DMPAP) and methylene bisacrylicamide (MBAAm) as initiator and crosslinker, respectively. The thermal characterization of the IPNs was investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and dielectric analysis (DEA). Depressions of the melting temperatures of PVA segments in IPNs were observed with increasing VP content via the DSC. The DEA was employed to ascertain the glass transition temperature (T_g) of IPNs. From the result of DEA, IPNs exhibited two T_gs indicating the presence of phase separation in the IPN. The thermal decomposition of IPNs was investigated using TGA and appeared at near 270°C. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1844–1847, 2002     

Poly(vinyl alcohol) Based pH Responsive Semi-IPN Hydrogels: A Comparative Swelling Investigation

The semi-interpenetrating polymer network (IPN) hydrogels composed of poly(vinyl alcohol) (PVA) and random copolymers of poly(acrylamide-co-sodium methacrylate), poly(AAm-co-NMA); poly(acrylamide-co-potassium methacrylate), poly(AAm-co-KMA); poly(acrylamide-co-maleic acid), poly(AAm-co-MA) were prepared by conventional co-polymerization employing ammonium persulphate (APS)/N,N,N¹,N¹-tetraethylmethylenediamine (TMEDA) as redox initiating system in presence of N,N¹-methylenebisacrylamide (MBA) as a crosslinker. The swelling behavior of these semi-IPN hydrogels were compared in detail in various swelling media, including different pH, salt, and biological fluids.     

Effect of tacticity of poly(methyl methacrylate) on the miscibility with poly(vinyl pyrrolidone)

Isotactic, atactic, and syndiotactic poly(methyl methacrylates) (PMMA) (designated iPMMA, aPMMA, and sPMMA) with approximately the same molecular weight were mixed separately with poly(vinyl pyrrolidone) (PVP) primarily in chloroform to make three polymer blend systems. Differential scanning calorimetry (DSC) was used to study the miscibility of these blends. The results showed that the tacticity of PMMA has a definite impact on its miscibility with PVP. The aPMMA/PVP and sPMMA/PVP blends were found to be miscible because all the prepared films showed composition-dependent glass-transition temperatures (T_g). The glass-transition temperatures of the aPMMA/PVP blends are equal to or lower than weight average and can be qualitatively described by the Gordon–Taylor equation. The glass-transition temperatures of the other miscible blends (i.e., sPMMA/PVP blends) are mostly higher than weight average and can be approximately fitted by the simplified Kwei equation. The iPMMA/PVP blends were found to be immiscible or partially miscible based on the observation of two glass-transition temperatures. The immiscibility is probably attributable to a stronger interaction among isotactic MMA segments because its ordination and molecular packing contribute to form a rigid domain. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3190–3197, 2001     

Swelling behavior and cell viability of dehydrothermally crosslinked poly(vinyl alcohol) hydrogel grafted with N‐vinyl pyrrolidone or acrylic acid using γ‐radiation

To improve equilibrium water content, dehydrothermally crosslinked poly(vinyl alcohol) (PVA) hydrogel was grafted with N‐vinyl pyrrolidone (NVP) or acrylic acid (AA) monomer using γ‐radiation. Swelling behavior of the grafted hydrogels was studied in phosphate‐buffered saline, and cell viability was evaluated using fibroblast cells from mouse connective tissue. Equilibrium water content of AA‐ and NVP‐grafted PVA hydrogel ranged between 40–60% and 60–80%, respectively, depending on radiation dose and monomer concentration. For maximum degree of swelling, the optimum monomer concentration and radiation dose were 20% by weight and 20 kGy, respectively. Fibroblast cells seeded on NVP‐grafted hydrogel had an extended oval morphology while those seeded on AA‐grafted PVA had a rounded spherical morphology. These results support the use of NVP for grafting PVA to increase swelling and improve cell viability. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2862–2868, 2004     

Structural insights into a novel molecular‐scale composite of soluble poly(vinyl pyrrolidone) supporting uniformly dispersed nanoscale poly(vinyl pyrrolidone) particles

Structural insights into a novel, molecular‐composite poly(vinyl pyrrolidone) consisting of a soluble, film‐forming poly(vinyl pyrrolidone) (PVP) polymer and in situ formed, minute, crosslinked, nanoscale, insoluble poly [poly(vinyl pyrrolidone)] (PPVP) polymer particles are reported. A technique for determining the PVP molecular weight and PPVP weight fraction by gel permeation chromatography/multi‐angle light scattering (MALS) is described. Particle size studies by quasi‐elastic light scattering and field flow fractionation/MALS demonstrate that the nanoscale, insoluble polymer particles are nominally 370 and 325 nm in diameter, respectively. Rheological experiments on this dispersed system yield a complex macroscopic behavior. Atomic force microscopy images confirm a substantial heterogeneous nature for a film cast from this molecular‐composite material. Finally, this polymeric molecular composite in film form exhibits, among many other interesting properties, a dramatic enhancement in water resistance, as demonstrated by a simple image water resistance test for an ink‐jet printing application. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 734–741, 2003     

Poly(acrylic acid)–poly(vinyl alcohol) copolymers with superabsorbent properties

Biodegradable polyacrylates were produced by a series of novel copolymerization and/or crosslinking techniques using poly(vinyl alcohol) (PVA) moieties modified by the incorporation of olefinic structures. PVA was modified by a tosylation and/or detosylation reaction. The functionalized PVA was copolymerized and/or crosslinked with acrylic acid or its partially neutralized form to give crosslinked polyacrylates that could swell in water. Their swelling behavior was determined under load. Degradation studies were performed in α-chymotrypsin, trypsin, and papain solutions. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 817–829, 1998     

Fibrous membranes of cellulose acetate and poly(vinyl pyrrolidone) by electrospinning method: Preparation and characterization

Fibrous membranes of cellulose acetate (CA), poly(vinyl pyrrolidone) (PVP) and composite membranes of these polymers, were obtained by the electrospinning method. Using systematic method, the optimal conditions for preparation of fibrous membranes were found. Both CA and PVP a concentration of 8% weight was found. The CA was dissolved in a acetone:water solution, volume ratio 80 : 20 and the PVP is dissolved in ethanol:water solution, ratio volume 85 : 15. The flow rate for both polymers was 1.5 mL h^?1. The same applied voltage value and the distance between the needle and collection plate were for polymer both, 15 kV and 15 cm respectively. The morphology of fibrous membranes and composite membranes were evaluated by scanning electron microscopy (SEM). The CA fibers showed ribon morphology, while the PVP fibers were cilindric, in both cases with diameters in the micrometer range. Thermogravimetric analysis showed that CA had a complete degradation to 445°C, while the fibrous membranes PVP required a value of temperature for degradation of up to 571°C. Fibrous composite membrane PVP/CA/PVP shows a higher value of strain at break (%), and a lower value of tensile strength (MPa) compared to CA/PVP/CA. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and characterization of poly(vinyl alcohol)‐poly(vinyl pyrrolidone) blend: A biomaterial with latent medical applications

Aqueous solutions of poly(vinyl alcohol) and poly(vinyl pyrrolidone) are blended and films are produced by casting method with the further intention of being used as bio‐materials with latent medical application. Glutaraldehyde, 4,4′‐diazido‐2,2′‐stilbenedisulfonic acid disodium salt tetra‐hydrate are used as crosslinker agents, whereas lactic acid is the plasticizer in the blend. The obtained films are characterized by differential scanning calorimetry (DSC), mechanical properties, swelling and solubility behavior. DSC measurements show that the blends exhibit a single glass transition temperature indicating that they are miscible, even in the presence of the plasticizer and crosslinker agents. By the combination of all mentioned additives, a relevant enhancement of the swelling is observed, accompanied by a stabilization of the solubility during the tested time. Finally, mechanical properties show an appropriate performance in the studied parameters. As a consequence, the obtained films could be suitable for use as medium or long‐term implants. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

聚乙烯醇/膨润土杂化水凝胶的力学性能和溶胀行为

利用冷冻-解冻法制备了聚乙烯醇/膨润土杂化水凝胶. X射线衍射结果表明,膨润土以剥离形式分布在水凝胶基体中. 研究结果表明,与纯PVA5水凝胶相比,经过5个冷冻-解冻循环制备的含2%(w)膨润土的杂化水凝胶的拉伸模量、拉伸强度和断裂伸长率分别增加了44.0%, 74.2%和25.2%,而溶胀行为与5个循环的纯水凝胶相近. 含0.5%(w)膨润土的杂化水凝胶的拉伸模量和拉伸强度高于基体水凝胶,其在溶胀400 min时的溶胀度高于所有的样品.     

Thermal Decomposition of Polymer Mixtures Containing Poly(vinyl chloride)

Thermal decomposition of a series of 1 : 1 mixtures of typical polymer waste materials [polyethylene (PE), poly(propylene) (PP), polystyrene (PS), polyacrylonitrile (PAN), polyisoprene, poly(methyl methacrylate) (PMMA), polyamide‐6 (PA‐6), polyamide‐12 (PA‐12), polyamide‐6,6 (PA‐6,6), and poly(1,4‐phenylene terephthalamide) (Kevlar)] with poly(vinyl chloride) (PVC) was examined using thermal analysis and analytical pyrolysis techniques. It was found that the presence of polyamides and PAN promotes the dehydrochlorination of PVC, but PVC has no effect on the main decomposition temperature of polyamides. The hydrogen chloride evolution from PVC is not altered when other vinyl polymers or polyolefins are present. The thermal degradation of PAN is retarded significantly, whereas that of the other vinyl polymers is shifted to a slightly higher temperature in the presence of PVC. Among the pyrolysis products of PAN‐PVC mixture methyl chloride was found in comparable amount to the other gaseous products at 500°C pyrolysis temperature.     

Miscibility studies of hydroxypropyl cellulose/poly(vinyl pyrrolidone) in dilute solutions and solid state

The miscibility of hydroxypropyl cellulose (HPC) and poly(vinyl pyrrolidone) (PVP) blends in aqueous solutions was studied using viscosity, ultrasonic velocity, and refractive index techniques at 30°C. The interaction parameters ΔB, μ, and α calculated from viscosity using Sun and Chee methods indicated the miscibility of this blend. This was further confirmed by ultrasonic and refractive index results. The HPC/PVP blend films are prepared by solution casting method and are analyzed by differential scanning calorimetry, X-ray diffraction, Fourier transform infrared spectroscopy, and scanning electron microscopic techniques that confirmed the complete miscibility. This miscibility is due to the strong intermolecular H-bonding interactions between  OH groups of HPC and CO groups of PVP. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

A study of blending and complexation of poly(acrylic acid)/poly(vinyl pyrrolidone)

Poly(acrylic acid) (PAA) and poly(vinyl pyrrolidone) (PVP) were chosen to prepare polymer complex and blends. The complex was prepared from ethanol solution and the blends were prepared from 1-methyl-2-pyrrolidone solution. DSC results show that the T_gs of the PAA/PVP blends lie between those of the two constituent polymers, whereas T_g of the PAA/PVP complex is higher than both blends and the two constituent polymers. TGA results show that degradation temperature, T_d, of PAA increases upon adding PVP in the blend, but thermal stability of the complex is higher than that of the blends as reflected by the higher T_d. Both FTIR and high-resolution solid state NMR show strong hydrogen bonding between PAA and PVP by showing significant chemical shift. The T_1ρ(H) measurement shows that the homogeneity scale for the blend is at ∼20 Å and that for the complex is ∼15 Å.     

Anomalous thermally stimulated currents and space charge in poly(vinyl pyrrolidone)

To study the mechanisms of charge production and storage in poly(vinyl pyrrolidone) (PVP), short circuit thermally stimulated currents (TSCs) in solution‐grown PVP depolarized at 30, 50 and 80 °C with 25, 50 and 100 kV cm⁻¹ have been analysed in the temperature range 30–200 °C. By employing TSC measurements with a conventional ‘contact electrode’ two kinds of charges have been observed. An anomalous TSC flowing in the same direction as the charging current was observed for PVP thermoelectrets poled at 50 and 80 °C with 50 and 100 kV cm⁻¹. The TSCs for samples poled at different temperatures (30, 50 and 80 °C) with 25 kV cm⁻¹ have been found to be normal in the sense that the discharge current flows in the direction opposite to that of the charging current. The TSC thermograms have been found to be characterized by two peaks located at 60–70 °C and 160–170 °C. Various characteristics of thermograms have been explained in terms of the existence of heterocharge due to dipolar orientation and ionic homocharge drift, together with the injection of charge carriers from electrodes and their subsequent localization in surface and bulk traps. © 2000 Society of Chemical Industry