Polyvinylidene fluoride-co-chlorotrifluoroethylene and polyvinylidene fluoride-co-hexafluoropropylene nanofiber-coated polypropylene microporous battery separator membranes

Nanofiber-coated polypropylene (PP) separator membranes were prepared by coating a Celgard® microporous PP membrane with electrospun polyvinylidene fluoride-co-chlorotrifluoroethylene (PVDF-co-CTFE) and PVDF-co-CTFE/polyvinylidene fluoride-co-hexafluoropropylene (PVDF-co-HFP) nanofibers. Three PVDF polymer solutions of varying compositions were used in the preparation of the nanofiber coatings. Two of the polymer solutions were PVDF-co-CTFE blends made using different types of PVDF-co-HFP copolymers. The PVDF-co-CTFE and PVDF-co-CTFE/PVDF-co-HFP blend nanofiber coatings have been found to have comparable adhesion to the PP microporous membrane substrate. The electrolyte uptakes and separator–electrode adhesion properties of nanofiber-coated membranes were evaluated. Both the electrolyte uptake and the separator–electrode adhesion were improved by the nanofiber coatings. The improvement in electrolyte update capacity is not only related to the gelation capability of the PVDF copolymer nanofibers, but also attributed to the increased porosity and capillary effect on nanofibrous structure of the electrospun nanofiber coatings. Enhancement of the separator–electrode adhesion was owing to the adhesion properties of the copolymer nanofiber coatings. Compared with the PVDF-co-CTFE/PVDF-co-HFP blend nanofiber coatings studied, the PVDF-co-CTFE coating was more effective in improving the electrolyte uptake and separator–electrode adhesion. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

Influence of solvents properties on morphology of electrospun polyurethane nanofiber mats

Segmented polyurethane (SPU) nanofiber mats were prepared by electrospinning technique using the combination of four different solvents viz. tetrahydrofuran, N,N′‐dimethyl formamide, N,N′‐dimethyl acetamide, and dimethyl sulfoxide. Morphology of the electrospun nanofibers was examined by field emission scanning electron microscope. Experimental results revealed that the morphologies of polyurethane nanofiber mats have been changed significantly with the solvent selection for the electrospinning. It was observed that the diameters and morphology of the SPU nanofibers were influenced greatly by the use of combination of solvents. The uniform polyurethane nanofibers without beads or curls could be prepared by electrospinning through the selection of combination of good conductive and good volatile solvent viz. 7.5 wt/v% of SPU in N,N′‐dimethyl formamide/tetrahydrofuran (30 : 70 v/v) solutions at 20 kV applied voltages and volume flow rate of 1 ml/min. On the basis of the results obtained from this investigation, it has been established that solvent selection is one of the driving factors for controlling the morphology of the polyurethane electrospun nanofiber mats. The well‐controlled morphology of electrospun polyurethane nanofiber mats could be useful for many potential industrial applications such as in biomedical, smart textiles, nanofiltration, and sensors. Copyright © 2013 John Wiley & Sons, Ltd.     

Plasma-Electrospinning Hybrid Process and Plasma Pretreatment to Improve Adhesive Properties of Nanofibers on Fabric Surface

Electrospun nanofiber mats are inherently weak, and hence they are often deposited on mechanically-strong substrates such as porous woven fabrics that can provide good structural support without altering the nanofiber characteristics. One major challenge of this approach is to ensure good adhesion of nanofiber mats onto the substrates and to achieve satisfactory durability of nanofiber mats against flexion and abrasion during practical use. In this work, Nylon 6 nanofibers were deposited on plasma-pretreated woven fabric substrates through a new plasma-electrospinning hybrid process with the objective of improving adhesion between nanofibers and fabric substrates. The as-prepared Nylon 6 nanofiber-deposited woven fabrics were evaluated for adhesion strength and durability of nanofiber mats by carrying out peel strength and flex resistance tests. The test results showed significant improvement in the adhesion of nanofiber mats on woven fabric substrates. The nanofiber-deposited woven fabrics also exhibited good resistance to damage under repetitive flexion. X-Ray photoelectron spectroscopy and water contact angle analyses were conducted to study the plasma effect on the nanofibers and substrate fabric, and the results suggested that both the plasma pretreatment and plasma-electrospinning hybrid process introduced radicals, increased oxygen contents, and led to the formation of active chemical sites on the nanofiber and substrate surfaces. These active sites helped in creating crosslinking bonds between substrate fabric and electrospun nanofibers, which in turn increased the adhesion properties. The work demonstrates that the plasma-electrospinning hybrid process of nanofiber mats is a promising method to prepare durable functional materials.     

Synthesis and properties of ZnO nanofibers prepared by electrospinning

ZnO nanofibers were prepared from zinc acetate/polyvinyl alcohol (PVA) by electrospun method. The morphological features, crystallinity, mechanical and optical properties of the ZnO nanofibers were studied. The results show the specific surface area of the ZnO nanofibers was influenced by the electrospun conditions. The specific surface area reached 389.7 m²g⁻¹ as the average diameter was 232 nm. The XRD date reveals the nanofibers consist of a single phase of well-crystallized ZnO with hexagonal structure. The elastic modulus of a single ZnO nanofiber was also characterized by nano-scale three-point bending test.     

Surface morphology and electrical properties of polyurethane nanofiber webs spray‐coated with carbon nanotubes

Multiwalled carbon nanotubes (MWNTs) were spray‐coated on electrospun polyurethane nanofiber webs for electrical conductive application. For the effective coating of MWNTs, hyperbranched polyurethane (HBPU) was used by blending with linear polyurethane, which was synthesized in the A₂ + B₃ approach using poly(ε‐caprolactone)diol, 4,4′‐methylene bis(phenylisocynate), and castor oil. SEM measurements showed that the MWNTs could be coated well along the surface of nanofibers when the HBPU was blended in the linear polyurethane nanofibers. Blending of HBPU in the nanofibers also affected the electrical conductivity of MWNT‐coated nanofiber webs. The low electrical resistance from 20 to 400 Ω/sq was obtained for MWNT‐coated nanofiber webs and their electrical resistance decreased with an increase of spraying frequency. As a potential application of MWNT‐coated nanofiber webs, the electrical heating effect because of applied voltage was demonstrated. Copyright © 2011 John Wiley & Sons, Ltd.     

基于荧光素的荧光纳米纤维的制备与表征

以电纺聚丙烯腈(PAN)纳米纤维为起始物, 经乙二胺改性后, 再利用Mannich反应将荧光素共价连接于PAN纳米纤维薄膜表面. 用荧光光谱、 扫描电镜和红外光谱进行了结构表征. 结果表明, 利用荧光素对静电纺丝薄膜表面进行修饰, 获得了很强的荧光信号, 证明了方法的可行性.     

溶胶凝胶法制备AZO包覆MgMn2O4及其电化学性能

通过X射线衍射(XRD)、扫描电镜(SEM)和充放电测试等方法研究了铝掺杂氧化锌(AZO)包覆对其材料结构、形貌以及电化学性能的影响。研究结果表明,AZO包覆能够引起Mn的平均价态发生一定程度的改变,同时能够显著地减少SEI电阻,从而有效地改善材料的动力学特性;同时,AZO包覆能够有效地遏制材料长循环导致的粉化问题,保持电极导电网络的连续性,进而提高了材料的长期循环稳定性。其中,包覆量为5%(w/w)的MgMn2O4材料200次循环后其可逆比容量仍可达590.3 mAh·g^-1,远高于未改性的MgMn2O4材料(295.9 mAh·g^-1)及文献报道的结果。     

磁控溅射中靶-基底距离与Si共掺对ZnO:Al薄膜性质的影响

使用射频磁控溅射, 在正方形石英衬底上沉积透明导电掺Al的ZnO(AZO)和Si共掺AZO(AZO:Si)薄膜. 系统研究了靶-基底距离(D_st)和Si共掺对AZO薄膜电学、光学性质的影响. 电阻率、载流子浓度和迁移率都强烈地依赖于靶-基底距离, 随着靶-基底距离的减少, 载流子浓度和迁移率都有显著的增加, 电导率也随之提高. 在靶-基底距离为4.5 cm处, 得到最低电阻率4.94×10^-4 Ω·cm, 此时的载流子浓度和迁移率分别是3.75×10²⁰ cm^-3和33.7 cm²·V^-1·s^-1. X射线光电子能谱(XPS)、X射线衍射(XRD)和边界散射模型被用于分析载流子浓度、迁移率和靶-基底距离的关系. 透射谱显示, 在可见-近红外范围内所有样品均有大于93%的平均透射率, 同时随着靶基距离的减少, 吸收边蓝移. AZO:Si表现出可与AZO相比拟的高电导和高透射光学特性, 但在热湿环境中却有着更好的电阻稳定性, 这在实际使用中很有意义.     

Fabrication of electrospun PVDF nanofibers with higher content of polar <Emphasis Type="Italic">β</Emphasis> phase and smaller diameter by adding a small amount of dioctadecyl dimethyl ammonium chloride

In this work, the effect of dioctadecyl dimethyl ammonium chloride (DDAC, a kind of alkyl ammonium salt) on polar β phase content and the diameter of electrospun PVDF nanofibers was investigated for the first time. Our experimental results show that the diameter of the electrospun PVDF nanofiber could be largely reduced and the content of polar β phase also become dominant immediately by just adding a little amount of DDAC. When the mass fraction of DDAC reached 4%, the content of polar β phase increased by about 39.1% compared with PVDF nanofibers without DDAC. Besides, the crystallinity of PVDF nanofibers also increased with the addition of DDAC. Based on the results, the possible mechanism of cooperative effect between electrospinning and DDAC on fiber diameter and formation of β phase in PVDF was discussed.     

Preparation of Polymer Nanofibers Containing Silver Nanoparticles by Using Poly(N‐vinylpyrrolidone)

Summary: Poly(N‐vinylpyrrolidone) (PVP) was used in two methods to prepare polymer nanofibers containing Ag nanoparticles. The first method involved electrospinning the PVP nanofibers containing Ag nanoparticles directly from the PVP solutions containing the Ag nanoparticles. N,N‐Dimethylformamide was used as a solvent for the PVP as well as a reducing agent for the Ag⁺ ions in the PVP solutions. In the second method, poly(vinyl alcohol) (PVA) aqueous solutions were electrospun with 5 wt.‐% of the PVP containing Ag nanoparticles. The Ag nanoparticles were evenly distributed in the PVA nanofibers. PVP containing Ag nanoparticles could be used to introduce Ag nanoparticles to other polymer nanofibers that are miscible with PVP.

TEM image of a PVA nanofiber electrospun with 5 wt.‐% of the PVP containing Ag nanoparticles.     

Developing new materials for paper-based diagnostics using electrospun nanofibers

The use of electrospun nanofibers as functional material in paper-based lateral flow assays (LFAs) was studied. Specific chemical features of the nanofibers were achieved by doping the base polymer, poly(lactic acid) (PLA), with poly(ethylene glycol) (PEG) and polystyrene_8K-block-poly(ethylene-ran-butylene)_25K-block-polyisoprene_10K-Brij76 (K3-Brij76) (KB). The LFAs were assembled such that the sample flowed through the nanofiber mat via capillary action. Initial investigations focused on the sustainable spinning and assembly of different polymer structures to allow the LFA format. Here, it was found that the base polymer poly(vinyl alcohol) (PVA), which was shown to function well in microfluidic biosensors, did not work in the LFA format. In contrast, PLA-based nanofibers enabled easy assembly. Three relevant features were chosen to study nanofiber-based functionalities in the LFA format: adsorption of antibodies, quantification of results, and nonspecific binding. In particular, streptavidin-conjugated sulforhodamine B (SRB)-encapsulating liposomes were captured by anti-streptavidin antibodies adsorbed on the nanofibers. Varying the functional polymer concentration within the PLA base enabled the creation of distinct capture zones. Also, a sandwich assay for the detection of Escherichia coli O157:H7 was developed using anti-E. coli antibodies as capture and reporter species with horseradish peroxidase for signal generation. A dose–response curve for E. coli with a detection limit of 1.9?×?10⁴ cells was achieved. Finally, functional polymers were used to demonstrate that nonspecific binding could be eliminated using antifouling block copolymers. The enhancement of paper-based devices using functionalized nanofibers provides the opportunity to develop a broad spectrum of sensitive and specific bioassays with significant advantages over their traditional counterparts.

Optimization of electrospun TiO2 nanofibers photoanode film for dye‐sensitized solar cells through interfacial pre‐treatment,controllable calcination,and surface post‐treatment

Dye‐sensitized solar cells (DSSCs) are generally viewed as next generation photovoltaic devices. Electrospun TiO₂ nanofibers (NFs) film can be used to construct photoanode for DSSCs. A systematic strategy to optimize such a novel photoanode material of DSSCs was elaborated in this paper. A main drawback of NFs photoanode is the poor adhesion of ceramic NFs film to its conductive glass substrate. This problem can be well solved by sandwiching a transition layer between the overlaid NFs film and the underlaid glass substrate through an interfacial spin‐coating pre‐treatment. After electrospinning, a controllable calcination is also indispensable for obtaining an ideal nanofibrous mat with good morphology and adhesion. The choice of calcination parameters including temperature, holding time, and heating rate was discussed in detail. In addition, a surface TiCl₄ post‐treatment can further improve adhesion as well as strength for the NFs photoanode film. And the performance of the resulting DSSCs will benefit from the TiCl₄ post‐treatment. Copyright © 2013 John Wiley & Sons, Ltd.     

Piezoelectric PVDF-TrFE nanocomposite mats filled with BaTiO3 nanofibers: The effect of poling conditions

BaTiO₃ nanofibers (BT NFs), prepared by electrospinning, were used as a filler for electrospun poly(vinylidene fluoride-co-trifluoroethylene) (PVDF-TrFE) nanocomposite mats. The phase structure and the effect of poling conditions on the piezoelectric properties of PVDF-TrFE/BT nanocomposites were investigated. The results showed an improved degree of crystallinity (78.6%) and a high β-crystal phase (up to 98.3%) in all electrospun samples, independent of the nanofiber content. The two-step poling method, applying electric fields of opposite polarity, led to significantly improved piezoelectric constants d₃₃ (−31.7 pC N⁻¹), strongly dependent on the added BaTiO₃ nanofibers. The inclusion of piezoelectric ceramic nanofibers into a polymer matrix, easily carried out by means of electrospinning, followed by an ad hoc optimized poling treatment, allowed to develop flexible materials with enhanced piezoelectric properties, potentially exploitable in innovative conversion systems used in wearable and sensing devices.     

Conducting core‐sheath nanofibers for electroactive shape‐memory applications

Conducting nanofibers coated with polypyrrole (PPy) and poly(3‐hexylthiophene) (P3HT) exhibiting core‐sheath structures were prepared by vapor‐phase polymerization of the conducting polymers on electrospun polyurethane nanofibers. The synthesis of the conducting polymers was confirmed by Fourier transform infrared spectroscopy and energy‐disperse X‐ray spectroscopy. The surfaces of the PPy‐coated nanofibers were slightly rough, while very smooth and regular surfaces were observed in the case of the P3HT‐coated nanofibers. The initial polymerization rate of PPy was higher than that of P3HT. In addition, the electrical conductivities of the core‐sheath structured nanofiber webs of both types increased with polymerization time. The maximum sheet conductivity of the PPy and P3HT‐coated nanofiber webs was 5 × 10^?3 S/cm and 1 × 10^?2 S/cm, respectively. The webs of the conducting core‐sheath structured nanofibers were effective in generating sufficient electrical heating necessary for harnessing these materials for electroactive shape‐memory‐based applications. Copyright © 2013 John Wiley & Sons, Ltd.     

Carbon nanofibers extracted from soot as a sorbent for the determination of aromatic amines from wastewater effluent samples

The isolation and characterization of carbon nanofibers from soot obtained by burning natural oil is reported. The fibers were extracted from the soot with tetrahydrofuran followed by sonication. The carbon nanofibers were mixed with poly(vinyl alcohol) and electrospun to get the nanofiber mat. The extraction ability of electrospun nanofibers for the separation and preconcentration of aromatic compounds such as 3-nitroaniline, 4-chloroaniline, 4-bromoaniline and 3,4-dichloroaniline were tested and efficiently evaluated using high performance liquid chromatography. Under optimized conditions, the method showed good linearity in a range of 0.5–50 μg L⁻¹ with correlation coefficient ranging from 0.989 to 0.998. High precision of the extraction with RSD values of 4.5–5.8% and low LOD value in a range of 0.009–0.081 μg L⁻¹ for all aniline compounds were achieved. The proposed microextraction method offers advantages such as easy operation, high recovery, fast extraction, minimal use of organic solvent and elimination of tedious solvent evaporation and reconstitution steps.     

Development of electrospun metallic hybrid nanofibers via metallization

The metallized hybrid nanofiber webs were prepared by using a combined technology of electrostatic spinning and metallization. The electrospun polyurethane (PU) nanofibers were metallized with different thicknesses of copper layer via metal vapor deposition technique. The thickness of the copper layer, which ranges from 10 to 100 nm, was monitored and controlled. The resultant metallized hybrid nanofiber webs were characterized using field emission scanning electron microscopy (FE‐SEM), wide angle X‐ray diffraction (WAXD), and thermogravimetric analysis (TGA). FE‐SEM images demonstrated that the nanoscaled copper layers are well deposited on the surface of the PU nanofibers. TGA result indicated that the thermal stability of the metallized hybrid PU nanofibers was dramatically enhanced due to the barrier effects of thin metallic copper layer. WAXD data confirmed that the crystalline copper layers were well deposited onto the PU nanofibers. Moreover, the mechanical properties of the metallized hybrid PU nanofiber webs were increased with increase in the thickness of deposited copper layer. Unlike the organic PU nanofiber webs, it was observed that the metallized hybrid PU nanofiber webs showed higher conductive properties depending on the thickness of the deposited copper layer. Copyright © 2009 John Wiley & Sons, Ltd.     

Electrospun Alginate Nanofibers with Controlled Cell Adhesion for Tissue Engineeringa

Alginate, a natural polysaccharide that has shown great potential as a cell scaffold for the regeneration of many tissues, has only been nominally explored as an electrospun biomaterial due to cytotoxic chemicals that have typically been used during nanofiber formation and crosslinking. Alginate cannot be electrospun by itself and is often co‐spun with poly(ethylene oxide) (PEO). In this work, a cell adhesive peptide (GRGDSP) modified alginate (RA) and unmodified alginate (UA) were blended with PEO at different concentrations and blending ratios, and then electrospun to prepare uniform nanofibers. The ability of electrospun RA scaffolds to support human dermal fibroblast cell attachment, spreading, and subsequent proliferation was greatly enhanced on the adhesion ligand‐modified nanofibers, demonstrating the promise of this electrospun polysaccharide material with defined nanoscale architecture and cell adhesive properties for tissue regeneration applications.

     

Antibacterial and wound healing properties of cellulose acetate electrospun nanofibers loaded with bioactive glass nanoparticles; in-vivo study

Bioactive glasses (BGs) have gained great attention owing to their versatile biological properties. Combining BG nanoparticles (BGNPs) with polymeric nanofibers produced nanocomposites of great performance in various biomedical applications especially in regenerative medicine. In this study, a novel nanocomposite nanofibrous system was developed and optimized from cellulose acetate (CA) electrospun nanofibers containing different concentrations of BGNPs. Morphology, IR and elemental analysis of the prepared electrospun nanofibers were determined using SEM, FT-IR and EDX respectively. Electrical conductivity and viscosity were also studied. Antibacterial properties were then investigated using agar well diffusion method. Moreover, biological wound healing capabilities for the prepared nanofiber dressing were assessed using in-vivo diabetic rat model with induced wounds. The fully characterized CA electrospun uniform nanofiber (100–200 nm) with incorporated BGNPs exhibited broad range of antimicrobial activity against gram negative and positive bacteria. The BGNP loaded CA nanofiber accelerated wound closure efficiently by the 10th day. The remaining wound areas for treated rats were 95.7?±?1.8, 36.4?±?3.2, 6.3?±?1.5 and 0.8?±?0.9 on 1st, 5th, 10th and 15th days respectively. Therefore, the newly prepared BGNP CA nanocomposite nanofiber could be used as a promising antibacterial and wound healing dressing for rapid and efficient recovery.

     

Electrospinning of polyvinylidene difluoride with carbon nanotubes: synergistic effects of extensional force and interfacial interaction on crystalline structures

Polyvinylidene difluoride (PVDF) solutions containing a very low concentration of single-walled carbon nanotubes (SWCNTs) and multiwalled carbon nanotubes (MWCNTs) of similar surface chemistry, respectively, were electrospun, and the nanofibers formed were collected using a modified rotating disk collector. The polymorphic behavior and crystal orientation of the nanofibers were studied using wide-angle X-ray diffraction and infrared spectroscopy, while the nanotube alignment and interfacial interactions in the nanofibers were probed by transmission electron microscopy and Raman spectroscopy. It is shown that the interfacial interaction between the SWCNTs and PVDF and the extensional force experienced by the nanofibers in the electrospinning and collection processes can work synergistically to induce highly oriented beta-form crystallites extensively. In contrast, the MWCNTs could not be well aligned along the nanofiber axis, which leads to a lower degree of crystal orientation.     

High strength electrospun polymer nanofibers made from BPDA-PDA polyimide

A series of high molecular weight PI precursors, poly(p-phenylene biphenyltetracarboxamide acid), were synthesized from 3,4,3′,4′-biphenyltetracarboxylic dianhydride (BPDA) and p-phenylenediamine (PDA) by using intense mechanical stirring at −15 to 0 °C for 48-72 h. The as-synthesized PI precursor solution was used to make BPDA/PDA polyimide thin films and electrospun nanofibers. IR, Ostward Viscometer, CMT-8102 Electromechanical Universal Testing Machine and scanning electron microscope (SEM) were used for the characterizations of the as-synthesized PI precursor, PI films and nanofiber sheets. The high molecular weight BPDA/PDA PI thin films and electrospun nanofiber sheets possess excellent mechanical properties of up to 900 MPa tensile strength with up to 18.0 GPa E-modulus and up to 210 MPa tensile strength with up to 2.5 GPa E-modulus, respectively.