Preparation and properties of PVA/PVP hydrogels containing chitosan by radiation

Radiation can induce chemical reactions to modify polymers even when they are in the solid state or at a low temperature. Radiation crosslinking can be easily adjusted by controlling the radiation dose and is reproducible. The finished product contains no residuals of substances required to initiate the chemical crosslinking, which can restrict its application possibilities. In these studies, hydrogels for wound dressing were made from a mixture of chitosan and polyvinyl alcohol (PVA)/poly‐N‐vinylpyrrolidone (PVP) by freezing and thawing, gamma‐ray irradiation, or combined freezing and thawing and gamma‐ray irradiation. The physical properties of the hydrogel, such as gelation, water absorptivity, and gel strength, were examined to evaluate the usefulness of the hydrogels for wound dressing. The PVA/PVP composition was 60:40, PVA/PVP–chitosan ratio was in the range 9:1–7:3, and the concentration of, PVA/PVP–chitosan as a solid was 15 wt %. A mixture of PVA/PVP–chitosan was exposed to gamma irradiation doses of 25, 35, 50, 60 and 70 kGy to evaluate the effect of irradiation dose on the physical properties of hydrogels. Water‐soluble chitosan was used in these experiment. The physical properties of the hydrogels, such as gelation and gel strength, were higher when the combination of freezing and thawing and irradiation were used rather than just freezing and thawing. The PVA/PVP–chitosan composition and irradiation dose had a greater influence on swelling than gel content. Swelling percent increased as the composition of chitosan in PVA/PVP–chitosan increased. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1787–1794, 2002     

Phase separation and morphology in polymer modified colloids

The morphology of films of sterically stabilised polystyrene particles, PS, with added free poly(vinyl alcohol), PVA, and poly(vinyl pyrrolidone), PVP, was investigated with scanning electron microscopy and correlated to the phase behaviour and interactions. In the case of the PS/PVP system exhibiting depletion phase separation, large polymer domains (ca. 7 μm) were present in the solid state when free polymer concentration exceeded ca. 13%. This concentration was well within the two-phase region of the phase diagram. Similar polymer domains were also observed for the homogeneous system PS/PVA. The surface of the films was sealed at free polymer concentrations of ca. 20% and ca. 40% for PVP/PS and PVA/PS, respectively. The final film morphology reflects non-equilibrium conditions arising from the increase in system viscosity due to particle close packing and continuous phase thickening by the free polymer. In the case of PS/PVP systems, incomplete depletion phase separation and phase demixing and prevention of particle restabilisation gives rise to large free polymer domains in the final film. Bridging flocculation was argued to be responsible for the large polymer domains, some with internal structure, observed with the PVA/PS systems.     

Electrically conductive bioplastics based on chitosan,polyvinyl alcohol,polyvinyl pyrrolidone,and plant extract nanoparticles for detecting Rhizopus stolonifer on tomato fruit

This work aimed to manufacture bioplastics with mechanical and electrical properties for monitoring the Rhizopus stolonifer growth in tomato fruit packaging. Bioplastics were based on chitosan/polyvinyl alcohol (Ch/PVA), chitosan/polyvinyl pyrrolidone (Ch/PVP), and nanoparticles (NPs) of plant extracts at 10% and 30% of concentrations. Bioplastics were exposed to tomato inoculated with R. stolonifer for 6 d at 25°C. Water vapor permeability (WVP), mechanical properties, FTIR, UV–vis, morphology, electrical resistance of bioplastics, and the NPs size were assessed. In bioplastics added with plant extracts, 1.5 times more WVP than in the control group (18–35 gs⁻¹m⁻¹Pa⁻¹) were quantified. Ch/PVA bioplastic showed 51% more tensile strength, 44% more elongation at break, and 40% more Young's modulus than Ch/PVP, regardless of the plant extract. The electrical resistance in Ch/PVA bioplastics with 30% mushroom extract and 10% radish allowed the differentiation between inoculated (10⁹–10¹⁰ Ω) and non-inoculated tomatoes (10¹⁰–10¹¹ Ω). The FTIR assay confirmed the presence of each compound used in the bioplastic, and UV–vis confirmed phenols at 300 nm. The NPs measured less than 50 nm. Only Ch/PVA with 30% mushroom and 10% radish can be useful to monitor fungi in tomatoes based on their electrical behavior.     

Sustainable conducting polymer composites: study of mechanical and tribological properties of natural fiber reinforced PVA composites with carbon nanofillers

ABSTRACT

Ball milled jute fiber (JF) was added to Polyvinyl Alcohol (PVA)/20 wt.% multi-layer graphene (MLG) composites in various proportions (0, 5, 10, 15 and 20 wt.%) to prepare sustainable and biodegradable conducting polymer composites. Also, PVA/17.5wt.%MLG/2.5wt.%MWCNT/20wt.% JF composite was prepared for comparison purpose. A dynamic mechanical analysis of the composites was conducted to analyze their viscoelastic nature. The electrical conductivity of the composites was measured to study their suitability for various applications. Jute reinforcement increased the electrical conductivity of PVA/MLG nanocomposites. The PVA/20wt.%JF/17.5wt.%MLG/2.5wt.%MWCNT hybrid composite had the highest electrical conductivity of 3.64 × 10^?4 S/cm among all the composites prepared. Multilayered structures of the hybrid composite films were made by hot-pressing, and their effectiveness in electromagnetic interference shielding was tested. The shielding effectiveness of the composites decreased with jute addition. The wear resistance of PVA/MLG/JF composites increased with an increase in the jute content up to an optimum value of 10 wt.%, and then it started deteriorating.     

Poly(vinyl alcohol)/chitosan oligosaccharide blend submicrometer fibers prepared from aqueous solutions by the electrospinning method

Submicrometer fibers of poly(vinyl alcohol) (PVA) and chitosan oligosaccharide [COS; i.e., (1→4)‐2‐amino‐2‐deoxy‐β‐D ‐glucose] were prepared by an electrospinning method with aqueous solutions with polymer concentrations of 7.5–15 wt %. Scanning electron microscopy, Fourier transform infrared, X‐ray diffraction, differential scanning calorimetry, and thermogravimetric analysis were used to characterize the morphology and properties of the PVA/COS fibers. The PVA/COS mass ratio, the total polymer concentration, and processing parameters such as the applied voltage and capillary‐to‐collector distance played important roles in controlling the fiber morphology. Fourier transform infrared and X‐ray diffraction data demonstrated that there were possibly hydrogen bonds between COS and PVA molecules that weakened the interactions in COS and improved the electrospinnability of PVA/COS. Moreover, with a higher percentage of COS in the PVA/COS blend fibers, superior thermal stability could be obtained. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and characterization of chitosan/poly(vinyl alcohol) blend fibers

Chitosan and poly(vinyl alcohol) blend fibers were prepared by spinning their solution through a viscose‐type spinneret at 25°C into a coagulating bath containing aqueous NaOH and ethanol. The influence of coagulation solution composition on the spinning performance was discussed, and the intermolecular interactions of blend fibers were studied by infrared analysis (IR), X‐ray diffraction (XRD), and scanning electron micrograph (SEM) and by measurements of mechanical properties and water‐retention properties. The results demonstrated that the water‐retention properties and mechanical properties of the blend fibers increase due to the presence of PVA in the chitosan substract, and the mechanical strength of the blends is also related to PVA content and the degree of deacetylation of chitosan. The best mechanical strength values of the blend fibers, 1.82 cN/d (dry state) and 0.81 cN/d (wet state), were obtained when PVA content was 20 wt % and the degree of deacetylation of chitosan was 90.2%. The strength of the blend fibers, especially wet tenacity could be improved further by crosslinking with glutaraldehyde. The water‐retention values (WRV) of the blend fibers were between 170 and 241%, obviously higher than pure chitosan fiber (120%). The structure analysis indicated that there are strong interaction and good miscibility between chitosan and poly(vinyl alcohol) molecular resulted from intermolecular hydrogen bonds. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2558–2565, 2001     

Preparation of KOH‐doped PVA/PSSA Solid Polymer Electrolyte for DMFC: The Influence of TiO2 and PVP on Performance of Membranes

The development of low cost alkaline anion solid exchange membranes requires high ionic conductivity, low liquid uptake, strong mechanical properties and chemical stability. PVA/PSSA blends cross‐linked with glutaraldehyde and decorated with titanium dioxide nanoparticles introduce advantages relative to the pristine membrane of PVA and PVA/PVP membranes due to their improved electrical response and low methanol uptake/ swelling ratio allowing their use in alkaline direct methanol fuel cells.     

Miscibility study of polymer blends composed of semirigid thermotropic liquid crystalline polycarbonate,poly(vinyl alcohol), and chitosan

Miscibility of binary and ternary polymer blends composed of thermotropic liquid crystalline polycarbonate (LCPC), poly(vinyl alcohol) (PVA), and chitosan was investigated by viscosity method, FTIR spectrum, and scanning electron microscope techniques. Effect of addition of chitosan as a compatibilizer on miscibility and morphology of binary LCPC/chitosan and PVA/chitosan and ternary LCPC/PVA/chitosan polymer blends was discussed. These measurements indicated that addition of chitosan into the blends of LCPC with PVA leads to an increase of miscibility and a formation of clear fibril structures on fractured surfaces, which are due to intermolecular hydrogen‐bonding interaction between LCPC, PVA, and chitosan chains. It was suggested that side‐chain hydroxy group of PVA and amino and hydroxy groups of chitosan play an important role in the formation of miscible phase and improvement of morphology in binary and ternary blends composed of LCPC, PVA, and chitosan. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1616–1622, 2004     

Facile fabrication of PVA composite fibers with high fraction of multiwalled carbon nanotubes by gel spinning

Poly(vinyl alcohol) (PVA) composite fibers with high fraction of multiwalled carbon nanotubes (MWCNTs) were prepared by gel spinning process. Here, a modified process was introduced to prepare concentrated PVA/MWCNTs/DMSO spinning dope, and to attain good dispersion of MWCNTs in the fibers. The final composite fibers were studied by thermogravimetric analyzer (TGA), Fourier transform infrared spectrometer (FTIR), Raman spectroscopy, differential scanning calorimetry (DSC), and WAXD analysis. The total content of MWCNTs in PVA composite fibers, from 5 to 30 wt%, was confirmed by TGA analysis. FTIR and Raman measurements demonstrated the existence of strong hydrogen interaction between MWCNTs and PVA matrix. SEM images of composite fibers showed smooth surface, regular cross‐section shape and good dispersion of MWCNTs in the fibers. DSC analysis showed that the crystallinity first increased and then decreased with the increase of MWCNTs contents. It can be concluded that low concentration of MWNCTs can act as nucleation sites for crystallization of PVA component, and large amount of MWCNTs may impede the crystallization of PVA component. The WAXD analysis results indicated that the crystal orientation of the PVA component in PVA composite fibers is almost identical at the same drawn ratio. Polarized Raman analysis indicated a small increase in MWCNTs orientation for the composite fibers. The mechanical properties tests showed that the composite fibers exhibit significant improvement in tensile strength and modulus as compared to the neat PVA fibers. The composite fibers also showed sustained growth in electrical conductivity. POLYM. ENG. SCI., 58:37–45, 2018. © 2017 Society of Plastics Engineers     

Alkaline solid polymer electrolyte membranes based on structurally modified PVA/PVP with improved alkali stability

Novel alkaline solid polymer electrolyte membranes that can conduct anions (OH⁻) have been prepared from poly(vinyl alcohol)/poly(vinylpyrrolidone) (PVA/PVP) by blending and chemical cross-linking, followed by doping in aqueous KOH solution. The physicochemical properties of these membranes have been studied in detail by FTIR, TG, and SEM analyses. The ionic conductivity was found to be greatly dependent on the concentration of KOH and the interpenetrated PVP in the PVA matrix. A maximum conductivity of up to 0.53 S cm⁻¹ at room temperature was achieved for PVA/PVP in a mass ratio of 1:0.5 after doping in 8 m aqueous KOH solution. The membrane showed perfect alkaline stability without losing its integrity even upon exposure to 10 m KOH solution at up to 120 °C. Scanning electron micrographs revealed a highly ordered microvoid structure uniformly dispersed on the membrane surface with a pore size of ca. 200 nm after heat-curing, which imparted the membrane with good liquid electrolyte (KOH) retention ability. FTIR spectra showed that these high ionic conductivities may be attributed to the presence of excess free KOH in the polymer matrix in addition to KOH bound to the polymer. Almost constant, highly stable, ionic conductivity while maintaining mechanical integrity was retained at room temperature for more than one month.     

Electrical conductivity and Joule heating of polyacrylonitrile/carbon nanotube composite fibers

Carbon nanotube (CNT) can exhibit electrical conductivity and introduce electric current into polymer. Using dry-jet-wet spin technology, polyacrylonitrile (PAN)/CNT composite fibers with 15 wt% and 20 wt% of CNT content were fabricated. The electrical conductivity of PAN/CNT fibers was enhanced by the annealing process at different temperatures and changed with time. These fibers could also respond to stretching, and the electrical conductivity decreased by 50% when the elongation reached 3%. In addition, electrical current can induce Joule heating effect and thermally transform PAN/CNT composite fibers. With the application of various electrical currents up to 7 mA at a fixed length, conductivity was enhanced from around 25 S/m to higher than 800 S/m, and composite fibers were stabilized in air. The temperature of composite fibers can increase from room temperature to several hundreds of degree Celsius measured by an infra-red (IR) microscope. Joule heating effect can also be estimated according to one-dimensional steady-state heat transfer equation, which reveals the temperature can be high enough to stabilize or carbonize fibers. As a result, this research provides a new idea of heating fabrics for thermal regulation, and a new approach for stabilizing and carbonizing PAN-based carbon fibers.     

Electrical and optical properties of a polyblend electrolyte

A potassium ion conducting polyblend electrolyte based on polyvinyl pyrrolidone (PVP)+polyvinyl alcohol (PVA) complexed with KBrO₃ was prepared using solution cast technique. The electrical conductivity increased with increasing dopant concentration. Optical absorption studies were made in the wavelength range (200-600 nm) on pure (PVP+PVA) and KBrO₃ doped (PVP+PVA) films. The absorption edge was observed at 5.13 eV for undoped (PVP+PVA) while it ranged from 4.88 to 5.0 eV for differently KBrO₃-doped samples. The direct band gaps for undoped and KBrO₃ doped (PVP+PVA) films were found to be, respectively, 5.05 and 4.95, 4.86 and 4.90 eV while the indirect band gaps were 5.03 and 4.88, 4.79 and 4.83 eV, respectively. The absorption edge and the band gaps moved towards lower energies as the dopant concentration was increased up to 20 wt% of the dopant. For further increase in dopant concentration these values started increasing again. This is explained in terms of formation of charge transfer complexes between the dopant and the host matrix. The thermal properties of these films were investigated with differential scanning calorimetry (DSC). The variation in film morphology is examined by scanning electron microscopic examination.     

A redox‐mediator‐doped gel polymer electrolyte applied in quasi‐solid‐state supercapacitors

Methylene blue (MB) redox mediator was introduced into polyvinyl alcohol/polyvinyl pyrrolidone (PVA/PVP) blend host to prepare a gel polymer electrolyte (PVA‐PVP‐H₂SO₄‐MB) for a quasi‐solid‐state supercapacitor. The electrochemical properties of the supercapacitor with the prepared gel polymer electrolyte were evaluated by cyclic voltammetry, galvanostatic charge–discharge, electrochemical impedance spectroscopy, and self‐discharge measurements. With the addition of MB mediator, the ionic conductivity of gel polymer electrolyte increased by 56% up to 36.3 mS·cm^?1, and the series resistance reduced, because of the more efficient ionic conduction and higher charge transfer rate, respectively. The electrode specific capacitance of the supercapacitor with PVA‐PVP‐H₂SO₄‐MB electrolyte is 328 F·g^?1, increasing by 164% compared to that of MB‐undoped system at the same current density of 1 A·g^?1. Meanwhile, the energy density of the supercapacitor increases from 3.2 to 10.3 Wh·kg^?1. The quasi‐solid‐state supercapacitor showed excellent cyclability over 2000 charge/discharge cycles. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39784.     

Convenient approach to making nanocomposites based on a chitosan–poly(vinyl pyrrolidone) polymer matrix and a graphene nanofiller

Conducting, mechanically durable, elastic nanocomposite films were prepared with chitosan (CS) as the polymer matrix, graphene obtained from highly exfoliated graphite as the nanofiller, and poly(vinyl pyrrolidone) (PVP) as the stabilizer of the graphene sheets. The maximum graphene content in the composites without a loss of uniformity and other useful properties increased up to 4.0 wt %. The resulting composites were characterized by scanning electron microscopy, Raman spectroscopy, X‐ray diffraction analysis, mechanical testing, and electrical conductivity testing to determine the effects of the addition of graphene on the morphology and mechanical and electrical properties of the CS–PVP–graphene nanocomposite films. In this study, we took an approach to making nanocomposites from the perspectives of green chemistry, environmental protection, regenerative medicine, and low cost. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45038.     

Synthesis and characterization of hybrid polymeric networks (HPN) based on polyvinyl alcohol/chitosan

The aims of this study are the preparation of hybrid polymer network (HPN) hydrogels with slight differences in their hydrophilic balance and evaluate the influence of the chemical composition on the HPN for application as solid polymeric electrolytes (SPEs). A hydrogels series of polyvinyl alcohol (PVA)/chitosan (CHI) were prepared using glutaraldehyde as crosslinking agent. The hydrogels were characterized by Fourier transformed infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), swelling ratio (SR) and electrochemical impedance spectroscopy (EIS). For sample with higher chitosan in the HPN the PVA crystallization was decreased and HPN with higher PVA content presented an increased swelling ratio. The electrochemical impedance studies demonstrated that the ionic conductivity of PVA/CHI HPN films depend on their composition and it is higher as the PVA content in hydrogel was diminished.     

Electrical conductivity of LTA‐zeolite in the presence of poly(vinyl alcohol) and poly(vinyl pyrrolidone) polymers

In this work we studied the electrical behavior of Linde type A zeolite (K⁺) in the presence of two polymers, poly(vinyl alcohol) (PVA) and poly(vinyl pyrrolidone) (PVP), with excellent film forming properties. Homogeneous composite thin films of PVA/LTA‐zeolite and PVP/LTA‐zeolite were prepared with different zeolite concentrations. The current?voltage (I?V) characteristics of the composites were measured at different applied voltages. The results show that the conductivity properties are composition‐ratio‐dependent and are also related to the type of polymers. Moreover, a well‐defined step‐like change was detected in the I?V curve of PVP/LTA‐zeolite at very high applied voltage. © 2013 Society of Chemical Industry     

A study on polymer blend electrolyte based on PVA/PVP with proton salt

Proton-conducting polymer blend electrolytes based on PVA–PVP–NH₄NO₃ were prepared for different compositions by solution cast technique. The prepared films are investigated by different techniques. The XRD study reveals the amorphous nature of the polymer electrolyte. The FTIR and laser Raman studies confirm the complex formation between the polymer and salt. DSC measurements show decrease in T _g with increasing salt concentration. The ionic conductivity of the prepared polymer electrolyte was found by ac impedance spectroscopy analysis. The maximum ionic conductivity was found to be 1.41 × 10^?3 S cm^?1 at ambient temperature for the composition of 50PVA:50PVP:30 wt% NH₄NO₃ with low-activation energy 0.29 eV. The conductivity temperature plots are found to follow an Arrhenius nature. The dielectric behavior was analyzed using dielectric permittivity (ε*) and the relaxation frequency (τ) was calculated from the loss tangent spectra (tan δ). Using this maximum ionic conducting polymer blend electrolyte, the primary proton battery with configuration Zn + ZnSO₄·7H₂O/50PVA:50PVP:30 wt% NH₄NO₃/PbO₂ + V₂O₅ was fabricated and their discharge characteristics studied.     

静电纺丝PBT/PVA复合膜的制备及性能研究

以三氟乙酸和二氯甲烷为混合溶剂,采用静电纺丝法制备聚对苯二甲酸丁二酯(PBT)/聚乙烯醇(PVA)复合膜。用旋转粘度计和电导率仪测定溶液的黏度和电导率,用扫描电子显微镜、拉伸和水接触角测试PBT/PVA不同比例对纤维膜的形貌、力学和亲水性能的影响。结果表明,随着PVA比例的增加,混合溶液的黏度逐渐增大,而电导率先增大后减小;当PBT/PVA的比例为90/10时,纳米纤维的平均直径最小,为323 nm,而其纳米纤维膜的力学性能与纯PBT纤维膜相比显著提高,拉伸强度、弹性模量和断裂伸长率分别增加了213%,260%和57%;PVA的加入改善PBT纤维的亲水性,制备出力学性能优异且亲水的PBT/PVA纤维膜。     

Structural characterization of hydrophilic polymer blends/montmorillonite clay nanocomposites

The nanocomposite films comprising polymer blends of poly(vinyl alcohol) (PVA), poly(vinyl pyrrolidone) (PVP), poly(ethylene oxide) (PEO), and poly(ethylene glycol) (PEG) with montmorillonite (MMT) clay as nanofiller were prepared by aqueous solution casting method. The X‐ray diffraction studies of the PVA–x wt % MMT, (PVA–PVP)–x wt % MMT, (PVA–PEO)–x wt % MMT and (PVA–PEG)–x wt % MMT nanocomposites containing MMT concentrations x = 1, 2, 3, 5 and 10 wt % of the polymer weight were carried out in the angular range (2θ) of 3.8–30°. The values of MMT basal spacing d₀₀₁, expansion of clay gallery width W_cg, d‐spacing of polymer spherulite, crystallite size L and diffraction peak intensity I were determined for these nanocomposites. The values of structural parameters reveal that the linear chain PEO and PEG in the PVA blend based nanocomposites promote the amount of MMT intercalated structures, and these structures are found relatively higher for the (PVA–PEO)–x wt % MMT nanocomposites. It is observed that the presence of bulky ester‐side group in PVP backbone restricts its intercalation, whereas the adsorption behavior of PVP on the MMT nanosheets mainly results the MMT exfoliated structures in the (PVA–PVP)–x wt % MMT nanocomposites. The crystallinities of the PEO and PEG were found low due to their blending with PVA, which further decreased anomalously with the increase of MMT concentration in the nanocomposites. The decrease of polymer crystalline phase of these materials confirmed their suitability in preparation of novel solid polymer nanocomposite electrolytes. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40617.     

PVP与PVA对原位聚合导电聚苯胺薄膜的影响

分别以水溶性高分子聚乙烯吡咯烷酮(PVP)和聚乙烯醇(PVA)为稳定剂,采用苯胺的分散聚合体系,在玻璃基片上原位沉积了表面光滑均匀、亚微米厚度的导电聚苯胺薄膜,改善了导电聚苯胺的加工性能。研究了薄膜的形貌、厚度及电导率。结果表明:聚苯胺薄膜表面光滑,黏附一些胶体粒子,以PVP为稳定剂制备的聚苯胺薄膜表观质量好于以PVA为稳定剂得到的聚苯胺薄膜,表面更加光洁致密;不同稳定剂影响聚苯胺薄膜厚度及性能,在其他实验条件相同的情况下,以PVA为稳定剂制备的聚苯胺薄膜厚度及电导率均高于以PVP为稳定剂制备的聚苯胺薄膜厚度和电导率。