Strong and ductile poly(vinyl alcohol)/graphene oxide composite films with a layered structure

We report the preparation of mechanically strong and ductile poly(vinyl alcohol)/graphene oxide (GO) composite films with a layered structure simply by vacuum filtration. The Young’s modulus and tensile yield strength of the composite film containing 3 wt.% GO were measured to be 4.8 GPa and 110 ± 7 MPa, respectively. Furthermore, it is flexible and exhibits a large elongation at break (36 ± 4%). The high mechanical properties of the composite films are mainly due to the homogeneous dispersion and alignment of GO sheets in the polymer matrix and strong interfacial interactions between both components.     

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.     

Uniaxial drawing of poly(vinyl alcohol)/graphene oxide nanocomposites

The unique potential of graphene oxide (GO) was exploited in the nanocomposites by a simple uniaxial drawing (up to three times) of poly(vinyl alcohol) (PVA)/GO nanocomposites with a small amount loading of GO. From X-ray diffraction images, the PVA crystallites were found to be oriented parallel to the drawn direction. At the same time, exfoliated GO platelets were found to be aligned parallel to the film surface. Compared with the properties of the as-cast nanocomposites, those of the uniaxially drawn nanocomposites were found to be remarkably enhanced. For the mechanical properties, not only Young’s modulus and tensile strength but also the toughness of the nanocomposites increased by the uniaxial drawing. It was revealed that 260% increase in toughness was achieved for the drawn nanocomposite with 1% w/w GO loading. Significant suppression of the swelling in water resulted in the excellent barrier properties against water, which exceeded that of the conventional high-barrier polymer, such as poly(vinylidene chloride). We revealed that this simple, fast and environmentally friendly process of uniaxial drawing exploits the excellent properties and high aspect ratio of GO in the nanocomposites.     

Thin polymer films based on poly(vinyl alcohol) containing graphene oxide and reduced graphene oxide with functional properties

In this article, the effect of the addition of graphene oxide (GO) and reduced graphene oxide (rGO) on the mechanical properties, thermal stability, and electrical conductivity of polyvinyl alcohol (PVA) has been investigated. Different weight percentages of nanofillers ranging from 0.5 to 5 wt% have been combined with PVA. The ultrasonic technique has been applied to disperse nanofillers in the PVA solution. The nanocomposite films have been prepared via solution casting technique and the dispersion of nanofillers into the PVA has been studied through optical microscopy. The microstructure, crystallization behavior, and interfacial interaction were characterized through X-ray diffraction and Fourier transform infrared spectroscopy. Differential scanning calorimetry (DSC) and thermogravimetric analysis have been applied to study the thermal properties of the prepared nanocomposites. The DSC results revealed that the crystallization temperature and melting temperature were enhanced in the presence of GO nanofiller. Besides, the tensile strength at break was improved along with the addition of GO; however, elongation at break for PVA/GO and PVA/rGO was diminished. Moreover, all specimens showed insulating behavior and the only sample was electrically conducting, which contain a high amount of rGO (5 wt%).     

Layer‐structured poly(vinyl alcohol)/graphene oxide nanocomposites with improved thermal and mechanical properties

Layer‐structured poly(vinyl alcohol)/graphene oxide nanocomposites in the form of films are prepared by simple solution processing. The structure and properties of these nanocomposites are studied using X‐ray diffractions, scanning electron microscopy, Fourier‐transform infrared spectroscopy, differential scanning calorimetry, and thermogravimetric analysis. The results indicate that graphene oxide is dispersed on a molecular scale and aligned in the poly(vinyl alcohol) matrix, and there exists strong interfacial interactions between both components, which are responsible for the significant improvement in the thermal and mechanical properties of the nanocomposites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Fabrication and characterization of poly(vinyl alcohol)/graphene oxide nanofibrous biocomposite scaffolds

Nanofibrous biocomposite scaffolds of poly(vinyl alcohol) (PVA) and graphene oxide (GO) were prepared by using electrospinning method. The microstructure, crystallinity, and morphology of the scaffolds were characterized through X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). The mechanical properties were investigated by tensile testing. Moreover, Mouse Osteoblastic Cells (MC3T3‐E1) attachment and proliferation on the nanofibrous scaffolds were investigated by MTT [3‐(4,5‐dimeth‐ylthiazol‐2‐yl)‐2,5‐diphenyl tetrazolium bromide] assay, SEM observation and fluorescence staining. XRD and FTIR results verify the presence of GO in the scaffolds. SEM images show the three‐dimensional porous fibrous morphology, and the average diameter of the composite fibers decreases with increasing the content of GO. The mechanical properties of the scaffolds are altered by changing the content of GO as well. The tensile strength and elasticity modulus increase when the content of GO is lower than 1 wt %, but decrease when GO is up to 3 and 5 wt %. MC3T3‐E1 cells attach and grow on the surfaces of the scaffolds, and the adding of GO do not affect the cells' viability. Also, MC3T3‐E1 cells are likely to spread on the PVA/GO composite scaffolds. Above all, these unique features of the PVA/GO nanofibrous scaffolds prepared by electrospinning would open up a wide variety of future applications in bone tissue engineering and drug delivery systems. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synergistic strengthening of composite films by crosslinking graphene oxide reinforcement and poly(vinyl alcohol) with dicarboxylic acids

High‐strength plastic materials with excellent biodegradability, non‐toxicity and economically wide availability are in high demand. Herein, we demonstrate graphene oxide (GO) composite of poly(vinyl alcohol) (PVA) as a potential bioplastic material by chemical crosslinking. For a potential bioplastic material, PVA has to be addressed for its high water absorbing capacity along with improvement in tensile strength and thermal stability. These issues were addressed by enhancing the interfacial binding between PVA and GO, covalent bonds between the two being introduced by crosslinking with dicarboxylic acids, namely succinic acid (SuA) and adipic acid (AdA). Crosslinking of neat PVA with dicarboxylic acids also resulted in enhanced swelling resistance and thermal stability. The greatest improvement in tensile strength and swelling resistance was observed for a GO crosslinked with diacids due to the synergistic effect of reinforcement and crosslinking. Improvements of 225 and 234% in the tensile strength of PVA (31.19 MPa) were observed for 5% GO–PVA samples crosslinked with 6.25 mmol AdA and 7.5 mmol SuA, respectively. For the same samples, water uptake was 44 and 29%, respectively, compared to the non‐crosslinked PVA (359%). © 2017 Society of Chemical Industry     

Effect of surface modification of graphene oxide on photochemical stability of poly(vinyl alcohol)/graphene oxide composites

Poly(vinyl alcohol) (PVA)/graphene oxide (GO) composites were prepared to improve the photochemical stability of PVA. The surface of GO was modified by oxyfluorination to introduce the polar functional groups on GO for the stronger interfacial interaction with PVA. The photochemical stability of PVA/oxyfluorinated-GO composites was evaluated by measuring the insoluble gel content after partial photodegradation of PVA under various UV irradiations. PVA/oxyfluorinated-GO composites showed the significant improvement in both the dispersion of GO in PVA matrix and the photochemical stability of PVA as the oxygen content increased in the oxyfluorination. The photochemical stability of composites had a close relation with the uniform distribution of GO in PVA matrix. The proper modification of GO by oxyfluorination showed the better photochemical stability for PVA/GO composites as compared to that of PVA/pristine GO composite.     

High‐strength biodegradable poly(vinyl alcohol)/fly ash composite films

We prepared biodegradable composite films of poly(vinyl alcohol) (PVA) and fly ash (FA) spanning 5, 10, 15, 20, and 25 wt % concentrations by casting aqueous solutions. The tensile strengths of the composite films were increased proportionally via the addition of FA. The strength of the film was enhanced by 193% with 20% FA compared to the neat PVA control. Further addition of FA deviated from the linear trend. The moduli of the composites also increased proportionally with FA addition to 212% at 20 wt % FA addition compared to the control. The percentage strain at break exponentially decreased with the addition of FA. In the dynamic mechanical behavior, the storage and loss moduli both increased with FA content. The tan δ peaks corresponding to the glass‐transition temperature shifted 5–10°C higher above the control sample (73°C). This shift was attributed to a reduction in the mobility of PVA segments because they were anchored by the FA surface. The reductions in mobility manifested in strong interfacial interactions were indicative of hydrogen bonding. Broadening and reduction in the intensities of the stretching and bending peaks of ? OH, ? CH and ? C?O of PVA in the Fourier transform infrared spectra were observed. This suggested that hydrogen bonding was active between the functional groups in the FA and PVA chains. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Physico-mechanical properties of poly (vinyl alcohol), poly (vinyl alcohol)/boric acid,and poly (vinyl alcohol) nanocomposites incorporated with amino-functionalized and pristine halloysite nanotubes films

Eco-friendly poly(vinyl alcohol) (PVA), PVA/boric acid, PVA/halloysite nanotubes (HNTs), and PVA/amino-functionalized HNTs (APTES-HNTs) films were fabricated by a solution casting technique. The samples were characterized by fourier transform infrared, X-ray diffraction, differential scanning calorimetry, scanning electron microscope, and energy-dispersive spectroscopy. The characterization results proved the chemical and physical interactions between the PVA and different additives. The viscoelastic behavior of the films was evaluated by DMA and creep analysis. The storage modulus, loss factor, and both α_α and β_β transitions affected by APTES-HNTs as a potential filler to form effective cross-links. APTES-HNTs existence enhanced creep-recovery beyond expectations. Tensile and impact strength were measured to understand samples' mechanical stability. PVA/APTES-HNTs and PVA/boric acid showed more yield behavior after the elastic limit. Furthermore, the subsequent rupture and impact strength were increased significantly compared with neat PVA and PVA/HNTs. The viscoelastic and mechanical behaviors were linked to each other by the area under Tanδ curve and the work of rupture and impact strength, which their linear correlation coefficient is statistically significant at 95% confidence limits. It seems that the presence of APTES-HNTs provides new cross-links, which altered (improved) the physico-mechanical properties of PVA, offering a bionanocomposite suitable for further applications. From the literature, possible explanations are provided for these observations.     

Citric acid crosslinking of poly(vinyl alcohol)/starch/graphene nanocomposites for superior properties

Polyvinyl(alcohol)/starch/graphene nanocomposites with enhanced properties were prepared by solution mixing and casting process with the aid of glycerol as plasticizer and citric acid (CA) as crosslinker. The dispersion of graphene in water was made by sonication prior to mixing it with PVA/starch solution. The effect of varying the concentration of CA crosslinker in PVA/starch nanocomposite with 0.5 wt% of graphene was studied in detail. The structural changes, properties and morphologies were characterized by different techniques. The FTIR results revealed that the crosslinking reaction enhanced the interaction between the hydroxyl groups in PVA and/or starch and the oxygen-containing groups present on the graphene sheets. The mechanical properties were also improved by the crosslinking reaction and reinforcing with graphene. The formation of PVA crystal from solution was interrupted to a large extent by the interface at the amorphous zone of polymers and also the crosslinks between the PVA and starch polymer chains. The total crystallinity of the system was found to decrease with increase in degree of crosslinking. There was a marked increase in the thermal stability as the blend system was crosslinked with CA. CA crosslinking produced compact bulk morphology and improved the homogeneity between PVA and starch. The results of this study illustrate that citric acid can be an effective crosslinker and/or compatibilizer in PVA/starch/graphene nanocomposites for improving properties, and for this reason it is a candidate to replace non-biodegradable plastic films in food packaging sector.     

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.     

Effect of graphene loading on thermomechanical properties of poly(vinyl alcohol)/starch blend

Polymer nanocomposites based on poly(vinyl alcohol) (PVA)/starch blend and graphene were prepared by solution mixing and casting. Glycerol was used as a plasticizer and added in the starch dispersion. The uniform dispersion of graphene in water was achieved by using an Ultrasonicator Probe. The composites were characterized by FTIR, tensile properties, X‐ray diffraction (XRD), thermal analysis, and FE‐SEM studies. FTIR studies indicated probable hydrogen bonding interaction between the oxygen containing groups on graphene surface and the –OH groups in PVA and starch. Mechanical properties results showed that the optimum loading of graphene was 0.5 wt % in the blend. XRD studies indicated uniform dispersion of graphene in PVA/starch matrix upto 0.5 wt % loadings and further increase caused agglomeration. Thermal studies showed that the thermal stability of PVA increased and the crystallinity decreased in the presence of starch and graphene. FE‐SEM studies showed that incorporation of graphene increased the ductility of the composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41827.     

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.     

Thermal processability and properties of highly filled poly(vinyl alcohol)/talc composite

Abstract

A highly filled PVA/talc composite was prepared through our invented thermal processing technology without using any coupling agent or compatibiliser. The results showed that compared with neat PVA, the melt temperature of the composite decreased and the degradation temperature increased, providing a big temperature window for thermal processing of PVA/talc composite. The composite melt exhibited shear thinning behaviour while its viscosity increased with increasing talc, still satisfied the requirement of thermal processing. The morphology analysis confirmed that talc was well dispersed in PVA, improving heat deflection temperature (HDT), tensile strength and modulus of PVA. When talc was 50 wt-%, the HDT, tensile strength and modulus of the composite were 115°C, 48 MPa, 1·23 GPa respectively, increased by 92, 16 and 150%, compared with PVA, and the elongation at break was 100% of the composite, confirming that the high filled PVA/talc composite was a novel PVA based material with excellent thermal and mechanical properties.     

Mechanical properties of borate crosslinked poly(vinyl alcohol) gels

Boric acid does not introduce crosslinks in poly(vinyl alcohol) solutions, but gelation does occur in the presence of cations. In this experimental study, the dynamic mechanical properties of these gels were determined using test-tube torsion pendulums and an air-bearing torsion pendulum. The modulus at a fixed concentration of polymer and boric acid increases with increasing sodium ion concentration up to the point where the atom ratio of sodium to boron reaches 1. Higher sodium concentrations do not increase the modulus. The log decrement, on the other hand, decreases with increasing sodium concentration continuously without reaching a plateau at the equal atom ratio. Log decrements as low as 0.02 can be measured. The storage modulus depends on the logarithm of borate concentration and on the 4.7 power of poly(vinyl alcohol) concentration. Only a very small portion of the borates in solution take part in effective crosslinks. The activation energy for breaking individual bonds in a function of temperature and the cation to boron ratios. At a fixed cation concentration, this activation energy is more negative with increasing amount of boron ions due to a transformation of monomeric crosslinks into polymeric crosslinks, so that the storage modulus which measures crosslink density decreases as a temperature rises.     

Synthesis and characterization of layer-aligned poly(vinyl alcohol)/graphene nanocomposites

Layer-aligned poly(vinyl alcohol)/graphene nanocomposites in the form of films are prepared by reducing graphite oxide in the polymer matrix in a simple solution processing. X-ray diffractions, scanning electron microscopy, Fourier-transform infrared spectroscopy, differential scanning calorimetry and thermogravimetric analysis are used to study the structure and properties of these nanocomposites. The results indicate that graphene is dispersed on a molecular scale and aligned in the poly(vinyl alcohol) (PVA) matrix and there exists strong interfacial interactions between both components mainly by hydrogen bonding, which are responsible for the change of the structures and properties of the PVA/graphene nanocomposites such as the increase in T_g and the decrease in the level of crystallization.     

Ionic liquid‐modified graphene/poly(vinyl alcohol) composite with enhanced properties

How to preserve the structure integrity of graphene while enhance its dispersion and compatibility in matrix attracts the attention of researchers in graphene/polymer nanocomposite field. In this paper, methacryloxyethyltrimethyl ammonium chloride (DMC), a kind of ionic liquids, was first used to non‐covalently functionalize graphene in the process of graphene oxide (GO) reduction. The as‐modified graphene (DMC‐rGO) was further incorporated into poly(vinyl alcohol) (PVA) matrix by solution casting technique to fabricate DMC‐rGO/PVA composites. The structure and properties of the obtained DMC‐rGO were investigated by X‐ray diffraction analysis (XRD), X‐ray Photoelectron Spectroscopy (XPS), Transmission Electron Microscope (TEM), Atomic force microscopy (AFM), and Raman test. The results showed that graphene could be successfully modified by DMC through ionic–π interaction and the structure integrity of the graphene could be reserved by this non‐covalently approach. Furthermore, after co‐reduction process, some hydroxyl groups were introduced into DMC‐rGO. In virtue of these intrinsic properties of DMC‐rGO, the fabricated DMC‐rGO/PVA composites exhibit considerable enhancements in mechanical properties and remarkable improvements in thermal stability, as well as the enhancement in electrical conductivity at low DMC‐rGO loading. This simple modification approach gives a new opportunity to improve the performances of graphene/polymer composites. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45006.     

Electromagnetic interference shielding properties of graphene quantum-dots reinforced poly(vinyl alcohol)/polypyrrole blend nanocomposites

Graphene quantum dots (GQDs) reinforced poly(vinyl alcohol) (PVA)/polypyrrole (WPPy) nanocomposite films with various GQDs loadings were synthesized using the versatile solvent casting method. The structural and morphological properties of PVA/WPPy/GQDs nanocomposite films were investigated by employing Fourier transform infrared spectroscopy, X-ray diffraction, and scanning electron microscopy. The thermogravimetric analysis revealed enhanced thermal stability of synthesized nanocomposites while enhanced dielectric properties were also observed. The maximum dielectric constant value for PVA/WPPy/GQDs nanocomposite films was observed to be ε = 6,311.85 (50 Hz, 150°C). The electromagnetic interference (EMI) shielding effectiveness (SE) of nanocomposite films was determined in the X-band (8–12 GHz) and Ku-band (12–18 GHz) frequency region. The EMI SE was found to be increased from 0.8 dB for the pure PVA film to 9.8 dB for the PVA/WPPy/GQDs nanocomposite film containing 10 wt% GQDs loading. The enhanced EMI shielding efficiency of nanocomposite films has resulted from the homogenous dispersion of GQDs in PVA/WPPy blend nanocomposites. Thus, the prepared nanocomposites are envisioned to utilize as a lightweight, flexible, and low-cost material for EMI shielding applications.