Effect of copper sulfate pentahydrate on the structure and properties of poly(vinyl alcohol)/graphene oxide composite films

Poly(vinyl alcohol) (PVA)/graphene oxide (GO)/copper sulfate pentahydrate (CuSO₄·5H₂O) composite films were prepared by the solution casting method, and the effect of CuSO₄·5H₂O on the structure and properties of the PVA/GO composites was investigated. Fourier transform infrared (FTIR) analysis proved the crosslinking interaction between CuSO₄·5H₂O and the ? OH group of PVA. The crystallinity of the composite films increased first and then decreased. For the composite films, the tensile strength, Young's modulus, and yield stress values improved with increasing CuSO₄·5H₂O, whereas the elongation at break decreased compared with that of the neat PVA/GO composite film. The thermogravimetric analysis (TGA) and derivative thermogravimetry (DTG) patterns of the PVA/GO/CuSO₄·5H₂O composite films showed that the thermal stability decreased; this was consistent with the TGA–FTIR analysis. A remarkable improvement in the oxygen‐barrier properties was achieved. The oxygen permeability coefficient was reduced by 60% compared to that of the neat PVA/GO composite film. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44135.     

The optical properties of PVA/TiO2 composite nanofibers

The electrospun nanofibers emerge several advantages because of extremely high specific surface area and small pore size. This work studies the effect of PVA nanofibers diameter and nano‐sized TiO₂ on optical properties as reflectivity of light and color of a nanostructure assembly consisting polyvinyl alcohol and titanium dioxide (PVA/TiO₂) composite nanofibers prepared by electrospinning technique. The PVA/TiO₂ composite spinning solution was prepared through incorporation of TiO₂ nanoparticles as inorganic optical filler in polyvinyl alcohol (PVA) solution as an organic substrate using the ultrasonication method. The morphological and optical properties of collected composites nanofibers were highlighted using scanning electron microscopy (SEM) and reflective spectrophotometer (RS). The reflectance spectra indicated the less reflectance and lightness of composite with higher nanofiber diameter. Also, the reflectance and lightness of nanofibers decreased with increasing nano‐TiO₂ concentration. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation of poly(vinyl alcohol)/poly(acrylic acid)/TiO2/carbon nanotube composite nanofibers and their photobleaching properties

The composite nanofibers of poly(vinyl alcohol) (PVA)/poly(acrylic acid) (PAAc)/titanium(IV) oxide (TiO₂) were prepared by electrospinning for a novel photocatalytic treatment of waste water. To improve the photoelectronic properties of PVA/PAAc/TiO₂ composite nanofibers, carbon nanotubes (CNTs) were used as an additive. The TiO₂ and CNTs were immobilized in the PVA/PAAc hydrogels as electrospun nanofibers for an easier recovery after the wastewater treatment. The improved efficiency of pollutant dye removal was observed at pH 10 due to the pH-sensitive swelling behavior of the PVA/PAAc/TiO₂/CNTs composite nanofibers. The photocatalytic activity of TiO₂ was improved noticeably by applying electric field to the CNTs-embedded composite nanofibers.     

Preparation of well‐dispersed reduced graphene oxide and its mechanical reinforcement in polyvinyl alcohol fibre

The current work reports the preparation and characterization of polyvinyl alcohol (PVA) composite fibres reinforced with graphene reduced from graphene oxide (GO) by using oligomeric proanthocyanidin (OPC) as a reductant. After reduction, most of the oxygen‐containing groups were removed from the GO and reduced graphene oxide (rGO) was prepared. As a result of combined OPC as a dispersant, rGO could be well dispersed in a dimethyl sulfoxide/H₂O mixed solvent and in PVA matrix, and the PVA/rGO dispersion was wet spun followed by hot drawing to prepare continuous PVA/rGO composite fibres. The PVA/rGO composite fibres exhibited a significant enhancement of mechanical properties at low rGO loadings; in particular the tensile strength and Young's modulus of the 2.0 wt% rGO and PVA composite fibre increased to 244% and 294% respectively relative to neat PVA fibre. Moreover, the storage modulus (?10 °C) and T_g increased to 300% and 7.2 °C, respectively. © 2016 Society of Chemical Industry     

Facile preparation and characterization of poly(vinyl alcohol)/chitosan/graphene oxide biocomposite nanofibers

Poly(vinyl alcohol) (PVA)/chitosan (CS)/graphene oxide (GO) biocomposite nanofibers have been successfully prepared using aqueous solution by electrospinning. CS colloidal gel in 1% acetic acid can be changed to homogeneous solution by using electron beam irradiation (EBI). The uniform distributions of GO sheets in the nanofibers were investigated by field emission scanning electron microscopy (FESEM) and Raman spectroscopy. FESEM images illustrated that the spread single GO sheet embedding into nanofibers was formed via self-assembly of GO sheet and PVA/CS chains. And the average diameters of the biocomposite nanofibers decreased (200, 173, 160 and 123 nm) with increasing the contents of GO (0.05, 0.2, 0.4 and 0.6 wt%). Raman spectra verified the presence of GO in the biocomposite nanofibrous mats. The mechanical properties of as-prepared materials related with GO contents. It revealed that the highest tensile strength was 2.78 MPa, which was 25% higher than that of neat PVA/CS nanofibers. Antibacterial test demonstrated that the addition of GO to PVA/CS nanofiber had great ability to increase inhibition zone till 8.6 mm. Overall, these features of PVA/CS/GO nanofibers which were prepared by eco-friendly solvent can be a promising candidate material in tissue engineering, wound healing and drug delivery system.     

Fabrication and characteristics of graphene oxide/nanocellulose fiber/poly(vinyl alcohol) film

Poly(vinyl alcohol) (PVA), PVA/nanocellulose fiber (CNF), and PVA/CNF/graphene oxide (GO) films were prepared simply by casting stable aqueous mixed solutions. FTIR investigation indicated that hydrogen bonding existed between the interface of GO and PVA‐CNF. Scanning electron microscopy and X‐ray diffraction analysis showed that GO was uniformly dispersed in PVA‐CNF matrix. Introducing CNF into PVA caused a significant improvement in tensile strength, and further incorporating GO into PVA/CNF matrix led to a further increase. The tensile strength of the neat PVA film, PVA/CNF composite, and PVA/CNF/GO film (0.6 wt % GO) was 43, 69, and 80 MPa, respectively. Moreover, when incorporating 8 wt % CNF into PVA matrix, O₂ permeability and water absorption decreased from 13.36 to 11.66 cm³/m²/day and from 164.2% to 98.8%, respectively. Further adding 0.6 wt % GO into PVA/CNF matrix resulted in a further decrease of permeability and water absorption to 3.19 cm³/m²/day and 91.2%, respectively. Furthermore, for all composite samples, the transmittance of visible light was higher than 67% at 800 nm. CNF and GO‐reinforced PVA with high mechanical and barrier properties are potential candidates for packaging industry. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45345.     

Preparation of atactic poly(vinyl alcohol)/silver composite nanofibers by electrospinning and their characterization

Poly(vinyl alcohol) (PVA)/silver composite nanofibers were successfully prepared by the electrospinning method. Water‐based colloidal silver in a PVA solution was directly mixed without any chemical or structural modifications into PVA polymer fibers to form organic–inorganic composite nanofibers. The ratio of silver colloidal solution to PVA played an important role in the formation of the PVA/silver composite nanofibers. We prepared two different atactic PVA/silver nanocomposites with number‐average degrees of polymerization of 1700 and 4000 through electrospinning with various processing parameters, such as initial polymer concentration, amount of silver colloidal solution, applied voltage, and tip‐to‐collector distance. The PVA/silver composite nanofibers were characterized by field emission scanning electron microscopy and transmission electron microscopy (TEM). TEM images showed that silver nanoparticles with an average diameter of 30–50 nm were obtained and were well distributed in the PVA nanofibers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effects of poly (vinyl alcohol) (PVA) content on preparation of novel thiol-functionalized mesoporous PVA/SiO2 composite nanofiber membranes and their application for adsorption of heavy metal ions from aqueous solution

Thiol-functionalized mesoporous poly (vinyl alcohol)/SiO₂ composite nanofiber membranes and pure PVA nanofiber membranes were synthesized by electrospinning. The results of Fourier transform infrared (FTIR) indicated that the PVA/SiO₂ composite nanofibers were functionalized by mercapto groups via the hydrolysis polycondensation. The surface areas of the PVA/SiO₂ composite nanofiber membranes were >290 m²/g. The surface areas, pore diameters and pore volumes of PVA/SiO₂ composite nanofibers decreased as the PVA content increased. The adsorption capacities of the thiol-functionalized mesoporous PVA/SiO₂ composite nanofiber membranes were greater than the pure PVA nanofiber membranes. The largest adsorption capacity was 489.12 mg/g at 303 K. The mesoporous PVA/SiO₂ composite nanofiber membranes exhibited higher Cu²⁺ ion adsorption capacity than other reported nanofiber membranes. Furthermore, the adsorption capacity of the PVA/SiO₂ composite nanofiber membranes was maintained through six recycling processes. Consequently, these membranes can be promising materials for removing, and recovering, heavy metal ions in water.     

Preparation of a Cu(II)-PVA/PA6 Composite Nanofibrous Membrane for Enzyme Immobilization

PVA/PA6 composite nanofibers were formed by electrospinning. Cu(II)-PVA/PA6 metal chelated nanofibers, prepared by the reaction between PVA/PA6 composite nanofibers and Cu²⁺ solution, were used as the support for catalase immobilization. The result of the experiments showed that PVA/PA6 composite nanofibers had an excellent chelation capacity for Cu²⁺ ions, and the structures of nanofibers were stable during the reaction with Cu²⁺ solution. The adsorption of Cu(II) onto PVA/PA6 composite nanofibers was studied by the Langmuir isothermal adsorption model. The maximum amount of coordinated Cu(II) (q_m) was 3.731 mmol/g (dry fiber), and the binding constant (K_l) was 0.0593 L/mmol. Kinetic parameters were analyzed for both immobilized and free catalases. The value of V_max (3774 μmol/mg·min) for the immobilized catalases was smaller than that of the free catalases (4878 μmol/mg·min), while the K_m for the immobilized catalases was larger. The immobilized catalases showed better resistance to pH and temperature than that of free form, and the storage stabilities, reusability of immobilized catalases were significantly improved. The half-lives of free and immobilized catalases were 8 days and 24 days, respectively.     

Antibacterial electrospun chitosan/poly(vinyl alcohol) nanofibers containing silver nitrate and titanium dioxide

Chitosan/poly(vinyl alcohol) (PVA) nanofibers with antibacterial activity were prepared by the electrospinning of a chitosan/PVA solution with a small amount of silver nitrate (AgNO₃) and titanium dioxide (TiO₂). Nanofibers with diameters of 270–360 nm were obtained. The yield of low‐viscosity chitosan (LCS)/PVA nanofibers was higher than that of high‐viscosity chitosan (HCS)/PVA, and the water content of the HCS/PVA nanofibers and the LCS/PVA nanofibers were 430 and 390%, respectively. The nanofibers developed in this study exhibited antibacterial activities of 99 and 98% against Staphylococcus aureus and Escherichia coli, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Surface properties,thermal, and mechanical characteristics of poly(vinyl alcohol)–starch‐bacterial cellulose composite films

Nanocomposite films for food packaging applications were developed using bacterial cellulose (BC) nanofibers in different amount in a poly(vinyl alcohol)/starch (PVA/St) matrix. In search of a better method to reduce the harmful ingredients in food packaging, the cellulose nanofibers were obtained by the mechanical defibrillation of BC pellicles thus avoiding the addition of chemicals in the final packaging material. Improved mechanical performances were obtained starting from just 1% BC nanofibers in PVA/St. Atomic force microscopy images showed a uniform dispersion of BC nanofibers on the surface of nanocomposites. A twofold increase of both tensile strength and modulus was obtained for 2 wt % BC in the composite. BC nanofibers have greatly improved the barrier properties of PVA/St matrix, a twofold increase of water vapor permeability being obtained for only 2 wt % BC nanofibers in the composite film. PVA/St/2BC was proposed as a high potential material for food packaging applications. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45800.     

Preparation of graphene oxide/carboxymethyl chitosan/polyvinyl alcohol composite nanofiber membranes by electrospinning for heavy metal adsorption

In this paper, a graphene-oxide/carboxymethyl-chitosan/polyvinyl-alcohol (GO/CMC/PVA) composite nanofiber membrane was prepared by electrospinning and cross-linking with glutaraldehyde (GA) to improve the water resistance. The composite nanofiber membrane can be used in the field of heavy metal adsorption. The membrane was characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray diffraction. The effects of GO concentration, adsorption time, and initial concentration of heavy-metal ion (Ni²⁺, Cu²⁺, Ag⁺, and Pb²⁺) solution on the adsorption performance of the fiber membranes were investigated. The results showed that the addition of GO can reduce the diameter of nanofibers. GO, CMC, and PVA exhibited good compatibility, and the intermolecular hydrogen bonding improved. The addition of GO also improved the crystalline properties of the composite fiber membrane. In the optimal cross-linking condition, GA was saturated by steam cross-linking for 6 h. The introduction of GO improved the adsorption capacity of the membrane for heavy metals in water. The utmost adsorption capacities for Ni²⁺, Cu²⁺, Ag⁺, and Pb²⁺ were 262.1, 237.9, 319.3, and 413.6 mg/g when using the cross-linked composite fiber membranes, respectively. The results of adsorption kinetics and thermodynamics showed that the adsorption process accorded with the pseudo-second-order kinetic model and Langmuir–Freundlich isotherm model.     

Fabrication and characterization of chitosan/poly(vinyl alcohol) electrospun nanofibrous membranes containing silver nanoparticles for antibacterial water filtration

Electrospun nanofibrous membranes (ENMs) were fabricated based on chitosan/poly(vinyl alcohol) (CS/PVA) with a 70/30 mass ratio containing silver nanoparticles (AgNPs) via the electrospinning method. AgNPs were produced on the surface of CS/PVA nanofibers by adding AgNO₃ to a CS/PVA blend solution as a silver rendering component. The presence of AgNPs in the polymer blend solution was detected by UV spectrophotometry. The morphology of nanofibers before and after cross-linking with glutaraldehyde was investigated by the field emission scanning electron microscopy. The formation and size distribution of AgNPs onto the surface of nanofibers were observed by transmission electron microscopy and confirmed by energy dispersing X-ray spectroscopy. As-spun and cross-linked CS/PVA nanofibers revealed a smooth surface with diameters ranging from 58 to 73 nm and 95 to 109 nm, respectively. The effect of AgNP formation on the chemical structure of nanofibers was explored by Fourier transform infrared spectroscopy. Static and dynamic antibacterial filtration efficiencies of CS/PVA ENMs, containing differing amounts of AgNO₃, have been tested against Escherichia coli, a gram negative bacterium. The antibacterial assessment results exhibited a significant increase in both static and dynamic antibacterial filtration efficiencies of the prepared CS/PVA ENMs by addition of AgNO₃ as a bactericidal agent.     

Graphene oxide reinforced polyvinyl alcohol/polyethylene glycol blend composites as high-performance dielectric material

Novel flexible dielectric composites composed of polyvinyl alcohol (PVA), polyethylene glycol (PEG), and graphene oxide (GO) with high dielectric constant and low dielectric loss have been developed using facile and eco-friendly colloidal processing technique. The structure and morphology of the PVA/PEG/GO composites were evaluated using Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, UV-vis spectroscopy (UV-vis), X-ray diffraction (XRD), scanning electron microscopy (SEM), and atomic force microscopy (AFM). The dielectric behavior of PVA/PEG/GO composites was investigated in the wide range of frequencies from 50 Hz to 20 MHz and temperature in the range 40 to 150 °C using impedance spectroscopy. The dielectric constant for PVA and PVA/PEG (50/50) blend film was found to be 10.71 (50 Hz, 150 °C) and 31.22 (50 Hz, 150 °C), respectively. The dielectric constant for PVA/PEG/GO composite with 3 wt% GO was found to be 644.39 (50 Hz, 150 °C) which is 60 times greater than the dielectric constant of PVA and 20 times greater than the dielectric constant of PVA/PEG (50/50) blend film. The PVA/PEG/GO composites not only show high dielectric constant but also show low dielectric loss which is highly attractive for practical applications. These findings underline the possibilities of using PVA/PEG/GO composites as a flexible dielectric material for high-performance energy storage applications such as embedded capacitors.     

Electrospun polyvinyl alcohol/waterborne polyurethane composite nanofibers involving cellulose nanofibers

TEMPO‐oxidized cellulose nanofibers (TOCNs) were used as nanofillers in this work. Composite nanofibers of polyvinyl alcohol (PVA)/waterborne polyurethane (WPU) reinforced with TOCNs were produced by electrospinning. The reinforcing capability of TOCNs was investigated by tensile tests. Scanning electron microscopy (SEM), X‐ray diffraction, and thermogravimetry analyses were also carried out in order to characterize the appearance, crystallinity, and reinforcing effect of the cellulose nanofibers. SEM results showed that PVA/WPU/TOCNs composite nanofibers presented a highly homogeneous dispersion of TOCNs. The reinforced composites had about 44% increase in their mechanical properties with addition of only 5 wt % of TOCNs while about 42% decrease in elongation at break. The TOCNs reinforced composite nanofibers were more thermally stable than pure PVA/WPU nanofibers. The development of crystalline structure in the composite fibers was observed by XRD. Since PVA, WPU, and TOCNs are hydrophilic, non‐toxic, and biocompatible, and therefore, these nanocomposite nanofibers could be used for tissue scaffolding, filtration materials, and medical industries as wound dressing materials. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41051.     

Poly (vinyl alcohol)/graphene oxide nanocomposite films and hydrogels prepared by gamma ray

ABSTRACT

Poly (vinyl alcohol)/graphene oxide (PVA/GO) gamma irradiated nanocomposite films and hydrogels were prepared. In composite films, GO was initially irradiated by gamma ray in order to improve interactions between GO and PVA. The film containing 1?wt-% GO was very strong where tensile modulus and tensile yield strength were 45 and 115% higher than those of pure PVA. In the second set of experiments PVA/GO hydrogels were made by irradiating PVA/GO suspensions by gamma ray at various doses. It was an interesting finding that GO increased the gel portion of hydrogels through contribution of H-bonds between PVA and GO. The hydrogels prepared at 20?kGy had remarkable water swelling ratio that reached as high as 20 at water temperature of 80°C. The hydrogel metal ion adsorption capability was tested on Cu²⁺ ions. It was shown that the GO contributed significantly to the adsorption capacity of PVA hydrogels.     

Novel composite nanofibers based on polyamide 66/graphene oxide- grafted aliphatic- aromatic polyamide: preparation and characterization

New polyamide 66/graphene oxide (GO)-grafted aliphatic-aromatic polyamide (polyamide-imide) (PAI) (PA66/GOF) composites nanofibers were successfully prepared via electrospinning method for the first time. An polyamide imide (PAI) was synthesized using polycondensation reaction from a dicarboxylic acid and a diamine based on 4,4′-(4,4′-isopropylidenediphenyl-1,1′-diyldioxy) dianiline, and characterized by ¹HNMR and FTIR. Morphological, structural, thermal and mechanical characteristics of the nanocomposite fibers were investigated by means of SEM, TEM, WAXD, DMTA and TGA techniques. Composites nanofibers of PA66/GO, PA66/PAI and PA66/GOF with smooth surface, uniform structure as well as with diameter ranging from 195 to 784 nm were obtained. The GO incorporation caused a reduction in the nanofibers diameters. The TEM images showed that the GO was well dispersed in the PA66 nanofibers without significant aggregation. An approximately 10 °C temperature increase in the glass transition temperature of PA66 was achieved by addition of 0.5 wt% of PAI, resulting from aliphatic-aromatic structure of PAI. By the TGA results, an increase about 40 °C was observed in the thermal stability of PA66/PAI composite nanofibers in comparison with that of pure PA66 nanofibers.     

Radiation synthesis of graphene oxide/composite hydrogels and their ability for potential dye adsorption from wastewater

A high yield of graphene oxide (GO) was chemically synthesized from graphite powder utilizing adjusted Hummer's method. The contents of acidic functional groups in GO were determined using potentiometric titration. Composite hydrogels dependent on graphene oxide/poly(2-acrylamido-2-methylpropanesulfonic acid)/polyvinyl alcohol (GO/PAMPS/PVA) were synthesized utilizing a ⁶⁰Co gamma irradiation source at different doses. The synthesized graphene oxide and composite hydrogels were portrayed via X-ray diffraction, thermogravimetric analysis, and Fourier transform infrared analysis. The morphology of composite hydrogels was characterized by scanning electron microscope. The gel % and swelling % for the prepared hydrogel demonstrated that the swelling % of hydrogel increased with raising AMPS content. Whereas the increment of GO and increasing the irradiation dose lead to a reduction in the swelling %. The influences of pH, GO percentage, initial dye concentration, the adsorbent dosage, contact time, and temperature on the adsorption of basic blue 3 dye were evaluated and the adsorption capacity was 194.6 mg/g at optimum conditions; pH = 6, GO/PAMPS/PVA composite hydrogels with 5 wt% of GO, initial dye concentration = 200 mg/L, adsorbent dose = 0.1 g, solution volume = 50 mL after 360 min at room temperature (25°C). The adsorption of dye onto the GO/PAMPS/PVA composite hydrogels follows Pseudo-second-order adsorption kinetics, fits the Freundlich adsorption isotherm model.     

Preparation and antibacterial activity of polyvinyl alcohol/regenerated silk fibroin composite fibers containing Ag nanoparticles

Polyvinyl alcohol (PVA)/regenerated silk fibroin (SF)/AgNO₃ composite nanofibers were prepared by electrospinning. A large number of nanoparticles containing silver were generated in situ and well‐dispersed nanoparticles were confirmed by transmission electron microscopy (TEM) intuitionally. Ultraviolet (UV)‐visible spectroscopy and X‐ray diffraction (XRD) patterns indicated that nanoparticles containing Ag were present both in blend solution and in composite nanofibers after heat treatment and after subsequent UV irradiation. By annealing the nanofibers, Ag⁺ therein was reduced so as to produce nanoparticles containing silver. By combining heat treatment with UV irradiation, Ag⁺ was transformed into Ag clusters and further oxidized into Ag₃O₄ and Ag₂O₂. Especially size of the nanoparticles increased with heat treatment and subsequent UV irradiation. This indicated that the nanoparticles containing silver could be regulated by heat treatment and UV irradiation. The antimicrobial activity of heat‐treated composite nanofibers was evaluated by Halo test method and the resultant nanofibers showed very strong antimicrobial activity. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Fabrication of superhydrophobic and self cleaning PVA-silica fiber coating on 304L SS surfaces by electrospinning

In this work superhydrophobic coating with self cleaning property is fabricated on 304L SS samples directly using a simple one step electrospinning process followed by silane treatment by using polyvinyl alcohol (PVA) and tetraethyl orthosilicate solution. A maximum water contact angle of 169.2° ± 2.1° is obtained at an electrospinning potential of 15 kV for 2 h, with a distance of 18 cm between the collector and needle. The hierarchical nanostructures thus formed on 304L SS composed of poly(vinyl alcohol)-silica microbeads and nanofibers. The surface morphologies are optimized by varying the electrospinning voltage, time, distance between needle and the collector and aging duration of the precursors. Attenuated total reflectance-infrared spectroscopy studies at different stages of preparation confirmed the presence of PVA/SiO₂ composite nanofibers deposited on the 304L SS surface. The reaction of SiO₂ nanofibers with hexamethyl disilazane resulted in the formation of Si O Si bonds that provided water repellent property. The developed SHP surface coating on 304L SS sample showed dynamic bouncing of water droplets and excellent self cleaning performance. The sample retained the SHP behavior in chloride solutions with different ionic strengths and pH.