Process development and characterization of spraying carbon nanofibers over fabrics for reinforcing polymer composites

Process development and characterization of spraying carbon nanofibers (CNF) over carbon fiber fabrics for reinforcing polymer composites are presented in this study. The molded composite structure consists of a high‐temperature polymer reinforced with carbon fiber fabrics sprayed with different dosages of carbon nanofibers. The materials were molded using vacuum assisted resin transfer molding process. Tensile testing and scanning electron microscopy (SEM) were used to characterize the molded materials. The results show that the tensile strength and modulus were both improved over the molded materials without CNF. Spraying CNF with a dosage of an 8 µg/mm² of the used fabrics helped to increase the tensile strength by 12%. The tensile modulus increased by 28% with a CNF dosage of 16 µg/mm². Uniform distribution of CNF was observed under SEM in the molded composites. POLYM. COMPOS., 35:1629–1635, 2014. © 2013 Society of Plastics Engineers     

Dispersion of soybean stock‐based nanofiber in a plastic matrix

The focus of this work is the study of the dispersion mechanism of soybean stock‐based nanofibers in a plastic matrix. The cellulose nanofibers were extracted from soybean stock by chemo‐mechanical treatments. These are bundles of cellulose nanofibers with a diameter ranging between 50 and 100 nm and lengths of thousands of nanometers. These nanofibers were characterized by atomic force microscopy and transmission electron microscopy. X‐ray diffraction studies showed that the soybean stock nanofibers had a relative percentage crystallinity of about 48%. Selective chemical treatments increased the cellulose content of soybean stock nanofibers from 41 to 61%. The matrix polymers used in this project were poly(vinyl alcohol) (PVA) and polyethylene (PE). The mechanical properties of nanofiber‐reinforced PVA film demonstrated a 4‐ to 5‐fold increase in tensile strength, as compared to the untreated fiber‐blend‐PVA film. One of the problems encountered in the use of nanoreinforcements lies in the difficulty in ensuring good dispersion of the filler in the composite material. Improved dispersion level of nanofibers within a thermoplastic was achieved by adding ethylene‐acrylic oligomer emulsion as a dispersant. In the solid phase of nanofiber‐blend‐PE composites, the compression‐molded samples showed that improved mechanical properties were achieved with coated nanofibers. Copyright © 2006 Society of Chemical Industry     

Development of a transparent PMMA composite reinforced with nanofibers

Core‐shell composite nanofibers with PA‐6 (Nylon‐6) as core and Poly (methyl methacrylate) (PMMA) as shell were fabricated by a coaxial electrospinning method, which were later made into nanofiber reinforced transparent composites through a hot press treatment. Morphological and structural characterizations for the composite nanofibers and the transparent composites were realized in terms of SEM, TEM, and FTIR techniques. The fiber reinforcement feature of the PA‐6 was demonstrated by the SEM photos of a composite sample fractured in liquid nitrogen. Through TGA and DSC tests, it was observed that thermal endurance and glass‐transition temperature of the nanofiber reinforced composites altered in variation with the contents of the reinforcing PA‐6. Experimental results indicated that the mechanical performance of the nanofiber reinforced transparent composites was obviously improved, and its transparency decreased a little with an increase in the PA‐6 content. As long as, however, a sacrifice of 10% in transparency was specified, an increment of more than 20% in the mechanical properties of the composites was achievable. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Electrospinning silica/polyvinylpyrrolidone composite nanofibers

Small diameter nanofibers of silica and silica/polymer are produced by electrospinning silica/polyvinylpyrrolidone (SiO₂/PVP) mixtures composed of silica nanoparticles dispersed in polyvinylpyrrolidone solutions. By controlling various parameters, 380 ± 100 nm diameter composite nanofibers were obtained with a high silica concentration (57.14%). When the polymer concentration was low, “beads‐on‐a‐string” morphology resulted. Nanofiber morphology was affected by applied voltage and relative humidity. Tip‐to‐collector distance did not affect the nanofiber diameter or morphology, but it did affect the area and thickness of the mat. Heat treatment of the composite nanofibers at 200°C crosslinked the polymer yielding solvent‐resistant composite nanofibers, while heating at 465°C calcined and selectively removed the polymer from the composite. Crosslinking did not change the nanofiber diameter, while calcined nanofibers decreased in diameter (300 ± 90 nm) and increased in surface area to volume ratio. Nanofibers were characterized by scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40966.     

Preparation and characterization of poly(vinyl alcohol) nanocomposites made from cellulose nanofibers

A method using a combination of ball milling, acid hydrolysis, and ultrasound was developed to obtain a high yield of cellulose nanofibers from flax fibers and microcrystalline cellulose (MCC). Poly(vinyl alcohol) (PVA) nanocomposites were prepared with these additives by a solution‐casting technique. The cellulose nanofibers and nanocomposite films that were produced were characterized with Fourier transform infrared spectrometry, X‐ray diffraction, thermogravimetric analysis, scanning electron microscopy, and transmission electron microscopy. Nanofibers derived from MCC were on average approximately 8 nm in diameter and 111 nm in length. The diameter of the cellulose nanofibers produced from flax fibers was approximately 9 nm, and the length was 141 nm. A significant enhancement of the thermal and mechanical properties was achieved with a small addition of cellulose nanofibers to the polymer matrix. Interestingly, the flax nanofibers had the same reinforcing effects as MCC nanofibers in the matrix. Dynamic mechanical analysis results indicated that the use of cellulose nanofibers (acid hydrolysis) induced a mechanical percolation phenomenon leading to outstanding and unusual mechanical properties through the formation of a rigid filler network in the PVA matrix. X‐ray diffraction showed that there was no significant change in the crystallinity of the PVA matrix with the incorporation of cellulose nanofibers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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     

芳纶纳米纤维增强聚乙烯醇复合膜的制备与性能

以芳纶纤维Kevlar@49为原料,在温和条件下制备了芳纶纳米纤维分散体(ANFS),并利用分散体制备了芳纶纳米纤维/聚乙烯醇(ANFs/PVA)复合膜。通过傅里叶红外光谱(FTIR)仪、差示扫描量热(DSC)仪、原子力显微镜(AFM)、扫描电子显微镜(SEM)、电子万能试验机及透光度/雾度测定仪等考察了复合膜的微观结构、热学、光学及力学性能。FTIR证明,复合膜中ANFs与PVA具有一定的分子间氢键作用,促进了ANFs在PVA基体中的分散。由AFM和SEM可以清晰观察到直径为20~30 nm的芳纶纳米纤维分散体,并且通过SEM观察到复合膜表面较为平整。当芳纶纳米纤维质量分数为6.0%时,复合膜的抗拉强度为17.86 MPa,断裂伸长率为442%;透光度为82.63%,雾度为27.56%;玻璃化温度,熔融温度和结晶温度分别为75.20、208.82和174.51℃,表明其透光性良好,力学和热学性能达到最佳。     

Synthesis of pH‐responsive crosslinked poly[styrene‐co‐(maleic sodium anhydride)] and cellulose composite hydrogel nanofibers by electrospinning

BACKGROUND: Stimuli‐sensitive materials show enormous potential in the development of drug delivery systems. But the low response rate of most stimuli‐sensitive materials limits their wider application. We propose that electrospinning, a technique for the preparation of ultrafine fibrous materials with ultrafine diameters, may be used to prepare materials with a fast response to stimuli. RESULTS: Poly[styrene‐co‐(maleic sodium anhydride)] and cellulose (SMA‐Na/cellulose) hydrogel nanofibers were prepared through hydrolysis of precursor electrospun poly[styrene‐co‐(maleic anhydride)]/cellulose acetate (SMA/CA) nanofibers. In the presence of diethylene glycol, the SMA/CA composite nanofibers were crosslinked by esterification at 145 °C, and then hydrolyzed to yield crosslinked SMA‐Na/cellulose hydrogel nanofibers. These nanofibers showed better mechanical strengths and were pH responsive. Their water swelling ratio showed a characteristic two‐step increase at pH = 5.0 and 8.2, with the water swelling ratio reaching a maximum of 27.6 g g^?1 at pH = 9.1. CONCLUSION: The crosslinked SMA‐Na hydrogel nanofibers supported on cellulose showed improved dimensional stability upon immersion in aqueous solutions. They were pH responsive. This new type of hydrogel nanofiber is a potential material for biomedical applications. Copyright © 2009 Society of Chemical Industry     

Effect of cellulose nanofibers and acetylated cellulose nanofibers on the properties of low‐density polyethylene/thermoplastic starch blends

The aim of this study was to evaluate the effect of cellulose nanofibers (CNFs) and acetylated cellulose nanofibers (ACNFs) on the properties of low‐density polyethylene/thermoplastic starch/polyethylene‐grafted maleic anhydride (LDPE/TPS/PE‐g‐MA) blends. For this purpose, CNFs, isolated from wheat straw fibers, were first acetylated using acetic anhydride in order to modify their hydrophilicity. Afterwards, LDPE/TPS/PE‐g‐MA blends were reinforced using either CNFs or ACNFs at various concentrations (1–5 wt%) with a twin‐screw extruder. The mechanical results demonstrated that addition of ACNFs more significantly improved the ultimate tensile strength and Young's modulus of blends than addition of CNFs, albeit elongation at break of both reinforced blends decreased compared with the neat sample. Additionally, biodegradability and water absorption capacity of blends improved due to the incorporation of both nanofibers, these effects being more pronounced for CNF‐assisted blends than ACNF‐reinforced counterparts. © 2018 Society of Chemical Industry     

Isolation of cellulose nanofibers from para rubberwood and their reinforcing effect in poly(vinyl alcohol) composites

In this article, we present an efficient method for isolating cellulose nanofibers from para rubberwood sawdust with a combination of chemical, mechanical, and ultrasonic treatments. The effects of the alkali concentration and treatment pathway on the cellulose structure and properties are discussed. The reinforcing efficiency of the resulting fibers on poly(vinyl alcohol) (PVA) composites was characterized. Field emission scanning electron microscopy and atomic force microscopy results revealed a well-organized network of the nanofibers with diameters in the range 20–80 nm and lengths of micrometer-scale dimensions. Fibers with a high crystallinity of 83% having a cellulose I structure were prepared by an isolation process involving a mild alkali solution and delignification before acid hydrolysis. Clear composite films with significant improvements in their modulus (by 100%) and strength (by 80%) were obtained by the addition of 7 wt % fiber. Strong interaction between the fibers and PVA was evident from dynamic mechanical analysis and differential scanning calorimetry. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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     

Crosslinked PVA nanofibers reinforced with cellulose nanocrystals: Water interactions and thermomechanical properties

Acid‐catalyzed vapor phase esterification with maleic anhydride was used to improve the integrity and thermo‐mechanical properties of fiber webs based on poly(vinyl alcohol), PVA. The fibers were produced by electrospinning PVA from aqueous dispersions containing cellulose nanocrystals (CNCs). The effect of esterification and CNC loading on the structure and solvent resistance of the electrospun fibers was investigated. Chemical characterization of the fibers (FTIR, NMR) indicated the formation of ester bonds between hydroxyl groups belonging to neighboring molecules. Thermomechanical properties after chemical modification were analyzed using thermal gravimetric analysis, differential scanning calorimetry, and dynamic mechanical analysis. An 80% improvement in the ultimate strength was achieved for CNC‐loaded, crosslinked PVA fiber webs measured at 90% air relative humidity. Besides the ultra‐high surface area, the composite PVA fiber webs were water resistant and presented excellent mechanical properties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40334.     

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     

Electrospinning of polymer nanofibers loaded with noncovalently functionalized graphene

Pristine graphene/polyvinyl alcohol (PVA) nanofibers were prepared by electrospinning an aqueous solution of polyvinylpyrrolidone‐stabilized graphene and PVA. This is the first report of electrospun nanofibers reinforced with dispersed pristine graphene. We examine the relationship between graphene loading and critical electrospinning parameters. Microscopy indicates uniform fiber formation and excellent graphene dispersion within the fiber. Rheological data indicates that the excellent level of graphene dispersion enhances the modulus of the polymer by 205%. We also find that the graphene significantly increases the fibers' thermal stability (increase of 15°C) and crystallinity (59% increase) above the baseline. In fact, the graphene may act as nucleating points for increased crystallinity. These graphene/polymer nanofibers have the potential to serve in a variety of applications, including electrodes, conductive wires, and biomedical materials. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Zein nanoparticle‐embedded electrospun PVA nanofibers as wound dressing for topical delivery of anti‐inflammatory diclofenac

Bioactive wound dressings from poly(vinyl alcohol) (PVA) and zein nanoparticles (NPs) loaded with diclofenac (DLF) were prepared successfully by the single jet electrospinning method. DLF‐loaded zein NPs with an average diameter of ～228 nm were prepared using anti‐solvent precipitation method. The formulation of zein:DLF 1:1 exhibited optimum encapsulation efficiency of 47.80%. The NPs were characterized by dynamic light scattering, zeta‐potential measurement, and differential scanning calorimetry. In vitro, drug release profiles of the DLF‐loaded zein NPs, and PVA–zein NPs were also studied within 120 h and showed the release efficiency of nearly 80% from zein NPs. A more controlled release of DLF was achieved by embedding the zein NPs in the PVA nanofibers. Fourier transform infrared spectroscopy was used to analyze possible interactions between different components of the fabricated dressings. The mechanical properties of the developed dressings were also evaluated using uniaxial tensile testing. Young's modulus (E) of the dressings decreased after inclusion of zein NPs within the PVA nanofibers. Moreover, fibroblast culturing experiments proved that the composite dressings supported better cell attachment and proliferation compared to PVA nanofibers, by exhibiting moderate hydrophilicity. The results suggested that the electrospun composite dressing of PVA nanofibers and zein NPs is a promising topical drug‐delivery system and have a great potential for wound healing application. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46643.     

Electrospun cellulose nanofiber reinforced soybean protein isolate composite film

This article presents the fabrication of cellulose nanofibrous mats (CNM) reinforced soybean protein isolate (SPI) composite with high visible light transmittance. The CNM was composed of cellulose nanofibers generated from electrospinning technique. The microstructure of the fractured surface of composite films was characterized by scanning electron microscopy (SEM). The light transmittance, mechanical properties, and swelling ratio of CNM/SPI composite were investigated in terms of CNM content in the composite. Because of the ultrafine diameter and superhigh length‐to‐diameter ratio of nanofibers, large amount of cellulose nanofibers fibers distribute in the SPI matrix to form an interpenetrating network (IPN) like composite material. It was found that strong interfacial interactions occurred at the cellulose nanofiber/SPI interfaces. The incorporation of 20 wt % cellulose nanofibers in the SPI matrix resulted in great improvement of mechanical strength and Young's modulus by respectively 13 and 6 times more than neat SPI film. More interestingly, this composite was translucent with light transmittance of over 75% at 700 nm. Furthermore, the swelling ratio of this IPN‐like CNM/SPI composite decreased from 106 to 22% as CNM content increased from 0 to 20 wt %. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and characterization of Bioglass®-based scaffolds reinforced by poly-vinyl alcohol/microfibrillated cellulose composite coating

The present work deals with the preparation and mechanical characterization of Bioglass^®-based porous scaffolds reinforced by a composite coating constituted by polyvinyl alcohol (PVA) and microfibrillated cellulose (MFC). Samples were produced by foam replication process, using a novel ethanol-based Bioglass^® slurry. The addition of PVA/MFC coating led to a 10 fold increase of compressive strength and a 20 fold increase of tensile strength in comparison with non-coated scaffolds. SEM observations of broken struts surfaces proved the reinforcing and toughening effect of the composite coating which were ascribed to crack bridging and fracture of cellulose fibrils. The mechanical properties of the coatings were investigated by tensile testing of PVA/MFC composite stripes. The stirring time of the PVA/MFC solution came out as a crucial parameter in order to achieve a more homogeneous dispersion of the fibers and therefore enhanced strength and stiffness.     

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     

Fabrication and characterization of electrospun Plantago major seed mucilage/PVA nanofibers

Electrospinning is a well-known technique for producing nanofibers using synthetic and natural polymers like mucilage. In this study, Plantago major Mucilage (PMM) was blended with polyvinyl alcohol (PVA) as a nontoxic adding agent, in order to produce electrospun nanofiber. Electrospinning parameters (voltage, tip-to-collector distance, feed rate, and PMM/PVA ratio) were optimized and solution properties were analyzed. The morphology of nanofibers was investigated using scanning electron microscopy (SEM), Fourier transform infrared (FTIR), X-ray diffraction (XRD), and Brunauer–Emmett–Teller (BET). Mechanical strength of nanofibers was determined, and cell viability on nanofibers was discussed by MTT assay. The results of SEM indicated that the PMM/PVA (50/50) nanofibers obtained with average diameter of 250 nm. Viscosity, electrical conductivity, and surface tension of PMM/PVA solution were 550 Cp, 575 μS/cm, and 47.044 mN/m, respectively. FTIR and XRD results verified the exiting PMM in produced nanofibers and no chemical reaction between PMM and PVA. Improvement in mechanical strength and cell viability of nanofibers by adding PMM to PVA nanofibers indicated the potential application of PMM-based nanofibers for medical and food industries. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47852.     

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.