Electrospinning preparation of a graphene oxide nanohybrid proton‐exchange membrane for fuel cells

Proton‐exchange membrane (PEM) is a core component of fuel cells that provides a channel for proton migration and transport. Prevailing PEMs fabricated using well‐established casting techniques have several limitations such as low proton conductivity, high fuel permeability, and poor stability. To overcome these shortcomings, this article introduces a graphene oxide (GO)‐based nanohybrid Nafion nanofiber membrane prepared using a facile electrospinning technique. On the one hand, electrospinning nanofibers provide efficient transport paths for protons, which tremendously enhance the proton conductivity. On the other hand, GO doping in PEM improves the self‐humidification, stabilities (mechanical, thermal, and chemical), and proton conductivity and reduces the fuel permeability. In this research, nanofiber membranes were obtained from Nafion solutions containing 0, 0.1, and 0.2 wt % GO via electrospinning. The morphology, structure, mechanical properties, proton conductivity, water uptake, and swelling properties of the membranes were studied. The results demonstrated that the comprehensive performance of PEM was significantly improved. The new findings may promote the wide application of PEM fuel cells. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46443.     

PVDF/TiO2/graphene oxide composite nanofiber membranes serving as separators in lithium-ion batteries

Improving the electrochemical properties of membranes in lithium-ion batteries (LIBs) is very important. Many attempts have been made to optimize ionic conductivity of membranes. The aim of this study was fabricating composite nanofiber membranes of poly(vinylidene fluoride) (PVDF), containing titanium dioxide (TiO₂) and graphene oxide (GO) nanoparticles to use in LIBs as separators. The morphology, crystallinity, porosity, pore size, electrolyte uptake, ionic conductivity, and electrochemical stability of the membranes were investigated using scanning electron microscopy, wide-angle X-ray diffraction, Fourier transform infrared spectroscopy, electrochemical impedance spectroscopy, and linear sweep voltammetry. The electrolyte uptake and ionic conductivity of the PVDF/TiO₂/GO composite nanofiber membranes containing 2 wt % GO were 494% and 4.87 mS cm⁻¹, respectively, which were higher than those of the other fabricated membranes as well as the commercial Celgard membrane. This could be attributed to the increased porosity, larger surface area, and higher amorphous regions of the PVDF/TiO₂/GO composite nanofiber membranes as a result of the synergistic effects of the nanoparticles. In this work, suitable optimized membranes with greater electrochemical stability compared with the other membranes were presented. Also, it was demonstrated that the incorporation of the TiO₂ and GO nanoparticles into the PVDF nanofiber membranes led to a porous structure where the electrolyte uptake enhanced. These properties made these membranes promising candidates for being used as separators in LIBs. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48775.     

Coupling hybrid of graphene oxide and layered zirconium phosphonate to enhance phenolic resin–based friction materials

A two‐dimensional (2D) heterogeneous coupling nanoparticle composed of graphene oxide and zirconium phosphonate (GO‐ZrP) was synthesized layer by layer in a self‐assembly manner. A rigid layer of zirconium phosphonate can inhibit the curling of graphene oxide and then improve its dispersion. The GO‐ZrP was then applied to phenolic resin–based friction materials by blending and hot pressing to improve their friction properties. The results show that the phenolic resin–based friction materials modified by GO‐ZrP possess excellent tribological, mechanical, and thermal properties. Also, the specific wear rate of the material decreased nearly fivefold with the optimal loading, while the friction coefficient was basically stable. Synergistic effects between GO and ZrP nanosheets provide good prospects for the application of 2D nanofillers in friction materials. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46543.     

Electrospun PAN–GO composite nanofibers as water purification membranes

Varying amounts of exfoliated graphene oxide (GO) are systematically incorporated into nanoscale polyacrylonitrile (PAN) fibers via an electrospinning method. Subsequent treatment of the PAN–GO composite nanofibers under a moderate temperature and high pressure leads to the formation of membrane sheets with enhanced mechanical properties. scanning electron microscope, Fourier transform infrared spectroscopy, and contact angle measurements confirm the successful incorporation of the GO into the PAN nanofiber membranes whose diameter, porosity, and pore size are notably influenced by the amount of the GO content. These composite membranes also exhibit a gradual reduction in the water contact angle as a function of the hydrophilic GO content, resulting in a beneficial property for water purification. In addition, the proper integration of GO into the PAN nanofibers improves the protein rejection rate and water flux during the filtration process, which indicates the possibility of utilizing these types of composite membranes in water treatment systems. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45858.     

High antibacterial performance of electrospinning silk fibroin/gelatin film modified with graphene oxide-sliver nanoparticles

In this study, graphene oxide-sliver nanoparticle (GO-AgNP) composite was synthesized in situ with GO as the raw material. Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy, and scanning electron microscopy were used to characterize the composite, the spherical Ag particles with a diameter of about 36 nm were well deposited on the surface of GO nanosheets without serious agglomeration, and the antibacterial properties of the composites were also tested. Moreover, the silk fibroin (SF)/gelatin (GT) electrospun nanofiber film was prepared by electrospinning, and the structure of the SF nanofiber film was observed using a Fourier transform infrared spectrometer, X-ray diffractometer, and scanning electron microscope. The TGA curves indicated that the total weight loss rate of SF nanofibers at 400°C was significantly higher than that of SF/GT composite nanofibers (74.72% for pure SF, 62.37% for SF/GT nanocomposites). Finally, the GO-AgNP composite was combined with electrospinning SF film, which resulted in the decrease in surface roughness from 393.5 ± 123.7 nm to 109.9 ± 24.43 nm and the decrease in contact angle from 82.48° to 54.78°. Besides, the GO-AgNP composites enhanced the antibacterial performance of SF film greatly, which was conducive to its application in biological tissue engineering. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47904.     

Performance enhancement of polylactide by nanoblending with POSS and graphene oxide

We report the effect of filler modification on the properties of polylactide (PLA)‐based nanocomposites, where graphene oxide (GO) nanosheets and polyhedral oligomeric silsesquioxane (POSS) nanocages are employed as nanofillers. The organically treated nanofillers are termed as GO‐functionalized and POSS‐functionalized. The synthesis of the nanocomposites was carried out via in situ ring‐opening polymerization of lactic acid (LA). The following four naocomposite systems were prepared, characterized, and compared to achieve a better understanding of structure‐property relationship (1) PLA/GO‐functionalized, (2) PLA/POSS‐functionalized, (3) PLA/physical mixture of GO‐functionalized and POSS‐functionalized, and (4) PLA/GO‐graft‐POSS (with eight hydroxyl groups). As revealed by the thermal and mechanical (nanoindendation) characterization, that the nanocomposites having a combination of GO and POSS as nanofiller, either as physical mixture of GO‐functionalized and POSS‐functionalized or as GO‐graft‐POSS, is far more superior as compared with the nanocomposites having individually dispersed nanofillers in the PLA matrix. Observed enhancement is attributing to the synergistic effect of the nanofillers as well as better dispersion of the modified‐fillers in the matrix. POLYM. COMPOS., 35:118–126, 2014. © 2013 Society of Plastics Engineers     

Characterization of CS/PVA/GO electrospun nanofiber membrane with astaxanthin

Tissue engineering has been widely used in regenerative medicine and tissue engineering scaffolds have become a new research direction for periodontal regenerative repair. We aim to develop a biological scaffold material that can support host immunity and promote periodontal regeneration. In this paper, chitosan (CS)/polyvinyl alcohol (PVA)/graphene oxide (GO)/astaxanthin (ASTA) nanofibers membranes were prepared by electrospinning. The nanofibers were characterized by scanning electron microscopy, infrared spectroscopy, mechanical testing, antibacterial testing and cytotoxicity testing. The CS/PVA/GO/ASTA nanofiber membrane had favorable micro-morphology, good mechanical properties and no cytotoxicity. This preliminary study demonstrates that the CS/PVA/GO/ASTA nanofiber membrane can be used for in vivo and in vitro experiments related to periodontal regeneration. The related mechanism of periodontal regeneration will be evaluated in future studies.     

Preparation and characterization of antifouling and antibacterial polysulfone ultrafiltration membranes incorporated with a silver–polydopamine nanohybrid

A silver–polydopamine (Ag–PDA) nanohybird was used to produce polysulfone (PSf) ultrafiltration membranes with excellent antifouling and antibacterial properties. First, the catechol functional groups of polydopamine (PDA) helped with the in situ immobilization of silver (Ag) nanoparticles (<10 nm) on the PDA sphere surface; this led to the formation of the Ag–PDA nanohybrid. Then, Ag–PDA/PSf hybrid membranes were prepared via the phase‐inversion method, and the influence of Ag–PDA loading on the hybrid membrane properties was systematically investigated. When the content of Ag–PDA was 0.5 wt %, the hybrid membrane achieved optimal separation performance, including a dramatically increased pure water flux and a well‐maintained bovine serum albumin rejection. Furthermore, the Ag–PDA/PSf hybrid membranes presented a significantly enhanced protein‐fouling resistance and a good antibacterial activity. These improvements were attributed to the unique structure and properties of the Ag–PDA nanohybrid because of the synergistic effect of the hydrophilic PDA substrate and well‐distributed Ag nanoparticles. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46430.     

Sulfonated graphene oxide‐doped proton conductive membranes based on polymer blends of highly sulfonated poly(ether ether ketone) and sulfonated polybenzimidazole

Simultaneously improving the proton conductivity and mechanical properties of a polymer electrolyte membrane is a considerable challenge in commercializing proton exchange membrane fuel cells. In response, we prepared a new series of miscible polymer blends and thus the corresponding crosslinked membranes based on highly sulfonated poly(ether ether ketone) and sulfonated polybenzimidazole. The blended membranes showed more compact structures, due to the acid‐base interactions between the two constituents, and improved mechanical and morphological properties. Further efforts by doping sulfonated graphene oxide (s‐GO) forming composite membranes led to not only significantly elevated proton conductivity and electrochemical performance, but also better mechanical properties. Notably, the composite membrane with the filler content of 15 wt % exhibited a proton conductivity of 0.217 S cm^?1 at 80 °C, and its maximum power density tested by the H₂/air single PEMFC cell at room temperature reached 171 mW cm^?2, almost two and half folds compared with that of the native membrane. As a result, these polymeric membranes provided new options as proton exchange membranes for fuel‐cell applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46547.     

Pervaporation of toluene and iso‐octane through poly(vinyl alcohol)/graphene oxide nanoplate mixed matrix membranes: Comparison of crosslinked and noncrosslinked membranes

Removal of aromatic compounds from fuel is an essential requirement in new environmental policies. In the present study, poly(vinyl alcohol)/graphene oxide (GO) mixed matrix membranes were prepared and applied to the separation of toluene from iso‐octane by pervaporation, considering the similarity and interaction between graphene and aromatics. The effects of crosslinking and GO content on separation efficiency have been investigated in detail. Owing to the high affinity of GO with toluene through s and π bonds, the selectivity of the membranes was increased by incorporating a low amount of GO. The results also indicated that noncrosslinked membranes have higher selectivity and permeation flux due to higher crystallinity and also have lower mechanical properties. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45853.     

Influences of hybrid carbon nanofillers on structures and electrical properties of sulfonated poly(1,3,4‐oxadiazole)‐based composite films

Sulfonated poly(1,3,4‐oxadiazole) (sPOD)‐based composite films, including 10 wt % hybrid carbon nanofillers composed of different weight ratios of multiwalled carbon nanotube (MWCNT) and graphene sheets, were manufactured via an efficient ultrasonication‐assisted solution mixing and casting. Fourier transform infrared (FTIR) spectra of the composite films confirmed the existence of specific interactions between sPOD backbone and MWCNT or graphene sheet. Transmission electron microscopic (TEM) images of cross sections of the composite films showed that 2‐dimensional (2D) graphene sheets formed an anisotropically oriented structure in the sPOD matrix film, but they are randomly dispersed owing to the introduction of 1‐dimensional (1D) MWCNT. Accordingly, the electrical resistivity of the composite films decreased largely from ～10³ Ω cm to ～10¹ Ω cm with the increment of the relative MWCNT content in hybrid carbon nanofillers due to the synergistic bridging effect. Thus, sPOD‐based composite films with 10 wt % hybrid carbon nanofillers exhibited high performance in electric heating by attaining rapid temperature responsiveness, high electric power efficiency, and stable maximum temperatures under given applied voltages. It was also revealed that the hybrid composite films were operationally stable over a long‐term stepwise electric heating experiment. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44499.     

Ultrasmall Ag nanocrystals supported on chitosan/PVA nanofiber mats with bifunctional properties

Bifunctional nanofiber mats consisting of chitosan (CS), poly(vinyl alcohol) (PVA), and silver nanocrystals (Ag NCs) have been fabricated by a facile electrospinning method. The formation and presence of Ag NCs supported on CS/PVA nanofibers are confirmed by ultraviolet‐visible spectroscopy and X‐ray diffraction. The morphology of the samples is characterized by transmission electron microscopy and scanning electron microscopy. The prepared Ag NCs/CS/PVA nanofiber mats show pronounced antibacterial activity against Escherichia coli and excellent filtration property for suspended particulate matter (SPM) particles. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46504.     

Mechanical characterization of high‐performance graphene oxide incorporated aligned fibroporous poly(carbonate urethane) membrane for potential biomedical applications

In this article, we report the development of graphene oxide (GO) reinforced electrospun poly(carbonate urethane) (PCU) nanocomposite membranes intended for biomedical applications. In this study, we aimed to improve the mechanical properties of PCU fibroporous electrospun membranes through fiber alignment and GO incorporation. Membranes with 1, 1.5, and 3% loadings of GO were evaluated for their morphology, mechanical properties, crystallinity, biocompatibility, and hemocompatibility. The mechanical properties were assessed under both static and dynamic conditions to explore the tensile characteristics and viscoelastic properties. The results show that GO presented a good dispersion and exfoliation in the PCU matrix, contributing to an increase in the mechanical performance. The static mechanical properties indicated a 55% increase in the tensile strength, a 127% increase in toughness for 1.5 wt % GO loading and the achievement of a maximum strength reinforcement efficiency value at the same loading. Crystallinity changes in membranes were examined by X‐ray diffraction analysis. In vitro cytotoxicity tests with L‐929 fibroblast cells and percentage hemolysis tests with fresh venous blood displayed the membranes to be cytocompatible with acceptable levels of hemolytic characteristics. Accordingly, these results highlight the potential of this mechanically improved composite membrane's application in the biomedical field. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41809.     

Mixed Matrix PVDF/Graphene and Composite‐Skin PVDF/Graphene Oxide Membranes Applied in Membrane Distillation

This work elucidates the influence of graphene (G) and graphene oxide (GO) content on the desalination performance and scaling characteristics of G/polyvinylidene fluoride (G/PVDF) mixed matrix and GO/PVDF composite‐skin membranes, applied in a direct contact membrane distillation process (DCMD). Inclusion of high quality, nonoxidized, monolayered graphene sheets as polymer membrane filler, and application of a novel GO/water‐bath coagulation method for the preparation of the GO/PVDF composite films, took place. Water permeability and desalination tests via DCMD, revealed that the optimal G content was 0.87 wt%. At such concentration the water vapor flux of the G/PVDF membrane was 1.7 times that of the nonmodified reference, while the salt rejection efficiency was significantly improved (99.8%) as compared to the neat PVDF. Similarly the GO/PVDF surface‐modified membrane, prepared using a GO dispersion with low concentration (0.5 g/L), exhibited twofold higher water vapor permeate flux as compared to the neat PVDF, but however, its salt rejection efficiency was moderate (80%), probably due to pore wetting during DCMD. The relatively low scaling tendency observed for both G and GO modified membranes is primarily attributed to their smoother surface texture as compared to neat PVDF, while scaling is caused by the deposition of calcite crystals, identified by XRPD analysis. POLYM. ENG. SCI., 59:E262–E278, 2019. © 2018 Society of Plastics Engineers     

A Study on Poly(vinyl alcohol-co-ethylene)-graft-Polystyrene Reinforced with Two Functional Nanofillers

A facile route was adopted to graft polystyrene on poly(vinyl alcohol-co-ethylene) matrix. Poly(vinyl alcohol-co-ethylene)-graft-polystyrene (PVAE-g-PS) was then reinforced with two types of nanofillers, i.e., graphene oxide (GO) and nanodiamond functional graphene oxide (GO-ND). PVAE-g-PS/GO and PVAE-g-PS/GO-ND nanocomposite series reinforced with 0.1—5 wt.% nanofiller were fabricated by solution processing. Structure of nanofillers and composite was confirmed by FTIR. FESEM imaging revealed that nanodiamond functional GO platelets were fully incorporated into matrix. TGA demonstrated enhanced stability of PVAE-g-PS/GO-ND nanomposites containing GO-ND. Similarly, UL 94 and electrical conductivity measurement of GO-ND-based system were found to be superior compared to one of copolymer/GO.     

A thin film composite membrane supported by a hydrophilic poly(vinyl alcohol‐co‐ethylene) nanofiber membrane: Preparation,characterization, and application in nanofiltration

In this study, a fabricated hydrophilic poly(vinyl alcohol‐co‐ethylene) (PVA‐co‐PE) nanofiber membrane was used as the middle support layer to prepare thin film composite (TFC) membranes for nanofiltration. The effects of the supporting nonwoven layer, grams per square meter (GSM) of nanofiber, reaction time, heat treatment, monomer concentration, operating pressure, and pH value on the separation performance of the TFC membranes were analyzed. These results show that the TFC membranes prepared with the PVA‐co‐PE nanofiber membrane can be used to filtrate different metal ions. For NaCl, Na₂SO₄, CaCl₂, CuCl₂, CuSO₄, and methyl orange solutions, the rejection rates of the TFC membrane with nonwoven polyester as the supporting layer and a nanofiber GSM of 12.8 g/m² are 87.9%, 93.4%, 92.0%, 93.1%, 95.8%, and 100%, respectively. This indicates the potential application of the PVA‐co‐PE nanofiber membrane in the preparation of nanofiltration and reverse‐osmosis TFC membranes. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46261.     

Preparation of polyimide/siloxane‐functionalized graphene oxide composite films with high mechanical properties and thermal stability via in situ polymerization

An effective approach to prepare polyimide/siloxane‐functionalized graphene oxide composite films is reported. The siloxane‐functionalized graphene oxide was obtained by treating graphene oxide (GO) with 1,3‐bis(3‐aminopropyl)‐1,1,3,3‐tetra‐methyldisiloxane (DSX) to obtain DSX‐GO nanosheets, which provided a starting platform for in situ fabrication of the composites by grafting polyimide (PI) chains at the reactive sites of functional DSX‐GO nanosheets. DSX‐GO bonded with the PI matrix through amide linkage to form PI‐DSX‐GO films, in which DSX‐GO exhibited excellent dispersibility and compatibility. It is demonstrated that the obvious reinforcing effect of GO to PI in mechanical properties and thermal stability for PI‐DSX‐GO is obtained. The tensile strength of a composite film containing 1.0 wt% DSX‐GO was 2.8 times greater than that of neat PI films, and Young's modulus was 6.3 times than that of neat PI films. Furthermore, the decomposition temperature of the composite for 5% weight loss was approximately 30 °C higher than that of neat PI films. © 2015 Society of Chemical Industry     

Synergistic effect of α‐ZrP and graphene oxide nanofillers on the gas barrier properties of PVA films

Two types of 2D nanofillers, α‐zirconium phosphate (α‐ZrP) and graphene oxide (GO), were synthesized and incorporated into poly(vinyl alcohol) (PVA) with 1 wt % loading level at various α‐ZrP:GO (Z:G = 5:1, 2:1, 1:1, 1:2, and 1:5) ratios. The resulting nanocomposites were tested for barrier properties by casting films from solution. The structure and morphology of α‐ZrP and GO were characterized by Fourier‐transform infrared spectroscopy, atomic force microscope, scanning electron microscopy, transmission electron microscopy, and X‐ray diffraction, which demonstrated successful preparation of exfoliated α‐ZrP and GO. The physical characteristics of the nanocomposite films, including thermal, mechanical, and gas barrier properties were investigated. The results indicated that the tensile strength, Young's modulus, and elongation at break of the PVA nanocomposite films with Z:G hybrid nanofiller improved compared to neat PVA. The glass transition temperature, melting temperature, and crystallinity also increased. Consequently there appears to be a synergistic effect with these two types of nanofillers that formed a specific macro structure of a “wall.” This macrostructure resulted in excellent O₂ gas barrier properties with the PVA/Z:G‐5:1 nanocomposite films having the best performance. The of the PVA/Z:G‐5:1 nanocomposite decreased from 1.835 × 10^?16 to 0.587 × 10^?16 cm³ cm cm^?2 s^?1 Pa^?1 compared with neat PVA. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46455.     

Interface engineering for the improvement of mechanical and thermal properties of covalent functionalized graphene/epoxy composites

Functionalized reduced graphene oxide (GO)/epoxy composites are fabricated through solution mixing. GO is functionalized using 3‐amino‐1,2,4‐triazole (TZ) in presence of potassium hydroxide (KOH). KOH is expected to serve dual role as catalyst for nucleophilic addition reaction between GO and TZ, and also as reducing agent. The grafting of TZ moiety on GO is confirmed by Fourier transform infrared spectroscopy, X‐ray diffraction, and thermogravimetric analysis. The prepared composites show remarkable improvement in mechanical and thermal stability. The fracture toughness of the composites (critical stress intensity factor, K_IC) achieved from single edge notched bending testing is improved by ～111% against pure epoxy at 0.1 wt % loading of TZ functionalized GO. Further, the tensile strength and Young's modulus are improved by ～30.5% and 35%, respectively. Thermal stability of the composites as investigated by thermogravimetric analysis showed 29 °C rise in onset degradation temperature for 0.1 wt % TZ functionalized GO incorporated composite. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46124.     

Mechanical reinforcement of electrospun water‐soluble polymer nanofibers using nanodiamonds

Optimization of the mechanical properties is necessary in the applications of electrospun nanofibrous matrices. In this work, mechanical reinforcement of electrospun nanofiber membranes of water‐soluble polymer by the incorporation of commercial nanodiamonds (NDs) was studied. Through an ND/poly(vinyl alcohol) (ND/PVA) model system, it is demonstrated that 155% improvement of Young's modulus, 89% increase in tensile strength, and 336% elevation in energy to break are achieved by the addition of only 2 wt% ND. Fourier transform infrared spectroscopy results suggest the existence of molecular interactions between NDs and PVA matrix, which contributes to the effective load transfer from the polymer matrix to the fillers. However, higher level of ND addition (>2 wt%) aggravates the agglomeration of nanofillers in PVA matrix and offsets the reinforcing effect, as ND agglomerates may act as flaws in composite nanofibers. Furthermore, NDs have optimizing effect on the morphology of ND/PVA nanofibers through increasing the conductivity of the electrospinning solution. Therefore, ND nanofillers possess the potential to improve the mechanical performance of water‐soluble polymer‐based nanofiber membranes. POLYM. COMPOS., 34:1735–1744, 2013. © 2013 Society of Plastics Engineers