Fabrication and characterization of electrospun titania nanofibers

Titania (TiO₂) nanofibers were fabricated by electrospinning three representative spin dopes made of titanium (IV) n-butoxide (TNBT) and polyvinylpyrrolidone (PVP) with the TNBT/PVP mass ratio being 1/2 in three solvent systems including N,N-dimethylformamide (DMF), isopropanol, and DMF/isopropanol (1/1 mass ratio) mixture, followed by pyrolysis at 500 °C. The detailed morphological and structural properties of both the as-electrospun precursor nanofibers and the resulting final TiO₂ nanofibers were characterized by SEM, TEM, and XRD. The results indicated that the precursor nanofibers and the final TiO₂ nanofibers made from the spin dopes containing DMF alone or DMF/isopropanol mixture as the solvent had the common cylindrical morphology with diameters ranging from tens to hundreds of nanometers, while those made from the spin dope containing isopropanol alone as the solvent had an abnormal concave morphology with sizes/widths ranging from sub-microns to microns. Despite the morphological discrepancies, all precursor nanofibers were structurally amorphous without distinguishable phase separation, while all final TiO₂ nanofibers consisted of anatase-phased TiO₂ single-crystalline grains with sizes of approximately 10 nm. The electrospun TiO₂ nanofiber mat is expected to significantly outperform other forms (such as powder and film) of TiO₂ for the solar cell (particularly dye-sensitized solar cell) and photo-catalysis applications.     

Fabrication and characterization of electrospun mullite nanofibers

Continuous mullite (3Al₂O₃·2SiO₂) nanofibers were fabricated by a sol-gel electrospinning technique. The detailed crystallization development and micromorphological evolution of both the as-electrospun nanofibers and the sintered mullite nanofibers were investigated. Results indicated that the spinnability and micromorphological evolution of mullite nanofibers are largely dependent on the viscosity η of the mullite sol, which can be adjusted by polyvinylprrolidone (PVP) content. Mullite nanofibers with common cylindrical morphology and diameters ranging from 400 nm to 800 nm could be obtained easily and rapidly when PVP content is ranged from 5 wt.% to 8 wt.%. High purity polycrystalline mullite nanofibers with diameters of about 200 nm were obtained after sintering at 1200 °C for 2 h. All sintered nanofibers consisted of single crystalline grains with size of approximately 100 nm.     

两种有机黏土与PA6复合纳米纤维的结构与热稳定性的比较

通过简单的溶液混合及静电纺丝的方法制备了含有两种不同有机黏土的聚酰胺6(PA6)复合纳米纤维.首先将有机黏土分散在N,N-二甲基甲酰胺(DMF)中,PA6溶解于甲酸中,然后将两种溶液进行充分混合后制得静电纺丝液,最后通过静电纺丝来制备PA6复合纳米纤维.通过XRD、XPS、SEM和TGA分别对纯PA6纳米纤维和两种复合纳米纤维的结构、形貌和热稳定性进行表征与比较.XRD和XPS的研究结果表明,黏土层在复合纳米纤维中分散均匀.TGA的分析表明,由于有机黏土的隔热作用,PA6复合纳米纤维在700℃时的热稳定性和残余量都比PA6纳米纤维的高.并且,硅酸盐晶格上铁离子的作用使得PA/Fe-OMT复合纳米纤维的残余量也明显高于PA/Na-OMT复合纳米纤维.     

Self-assembly of graphene onto electrospun polyamide 66 nanofibers as transparent conductive thin films

A simple method was developed to assemble graphite oxide (GO) densely onto electrospun (ES) polyamide 66 (PA66) nanofibrous membranes, used as a guide for the deposition of graphene nanosheet (GNS) conductive networks for preparing transparent conductive thin film (TCF). The main advantage of this technique by comparison with previous methods is that graphene does not form a uniform coating, but a percolated conductive network, when guided by PA66 nanofiber templates. A low surface coverage of the transparent substrate by GNS resulted in high transmittance. Polyvinylpyrrolidone-stabilized GO (PVP-GO) was prepared as a modifier for improving the adsorption to the nanofibers. The resulting PVP-GO material could adsorb well on PA66 nanofibers due to stronger hydrogen bonds. Hence, a lower sufficient concentration of PVP-GO (0.050 wt%) solution was required than that for GO solution (0.100 wt%) to fabricate a complete conductive path through a possible enriched adsorption process. For TCF applications, a reduction step is essential because as-deposited GO is non-conductive. In this work, we reduced GO to GNS by a combination of chemical reduction and thermal annealing. The TCF optical transmittance also could be improved after thermal annealing at 350?°C above the PA66 melting point. Light scattering by PA66 nanofibers was found as the main cause of reduced transmittance. A fused film, obtained after electrospinning PA66 solution for 120 s, and immersing in 0.050 wt% PVP-GO solution, exhibits a surface resistance of 8.6 × 103 Ω/square, while maintaining 88% light transmittance.     

Surface-confined synthesis of silver nanoparticle composite coating on electrospun polyimide nanofibers

A methodology for fabricating hierarchical nanostructures by surface-confined synthesis of silver nanoparticles on electrospun polyimide nanofibers is reported. Through surface-confined imide cleavage at the dianhydride domain via immersion in an aqueous KOH solution, potassium polyamate coatings of accurately defined thickness are formed (at a rate of 25 nm h(-1) ). By utilizing the ion-exchange capability of the polyamate resin, silver ions are introduced through immersion in an aqueous AgNO3 solution. Subsequent reduction of the metal ion species leads to the formation of nanoparticles at the fiber surface. Two modes of reduction, chemical and thermal, are investigated in the report, each leading to distinct morphologies of the nanoparticle coatings. Via thermal reduction, a composite surface layer consisting of monodisperse silver nanoparticles (average diameter 5.2 nm) embedded in a re-imidized polyimide matrix is achieved. In the case of chemical reduction, the reduction process occurs preferentially at the surface of the fiber, leading to the formation of silver nanoparticles anchored at the surface, though not embedded, in a polyamic acid matrix. By regulating the modification depth, control of the particle density on the fiber surface is established. In both reduction approaches, the polyimide nanofiber core exhibits maintained integrity.     

Fabrication and characterization of electrospun CdS-OH/polyacrylonitrile hybrid nanofibers

CdS-OH/polyacrylonitrile (PAN) hybrid nanofibers with strong photoluminescence and photocatalytic hydrogen production efficiency were synthesized by one-step co-electrospinning for the first time. The suspension of CdS-OH nanoparticles (size: 5 nm) in N,N-dimethylformamide (DMF) was mixed with PAN/DMF solutions to make spinning solutions, followed by electrospinning to make CdS-OH/PAN hybrid nanofibers. Their morphology and structure were characterized by SEM, TEM, XRD and fluorescence spectrophotometer. TEM and XRD measurements proved that the crystallographic structure of CdS-OH nanoparticles is identical to that of CdS. The CdS-OH nanoparticles were evenly distributed in PAN nanofibers of 320 nm in diameter. Thermogravimetrical analysis demonstrated that hybrid nanofibers were more thermally stable than neat PAN nanofibers. The hybrid nanofibers displayed excellent photoluminescent property. Additionally, they showed good photocatalytic hydrogen production efficiency with a rate of 13.5 μmol/h g fiber containing 60 mg of CdS-OH nanoparticles.     

High performance polyimide composite films prepared by homogeneity reinforcement of electrospun nanofibers

Highly aligned polyimide (PI) and PI nanocomposite fibers containing carbon nanotubes (CNTs) were produced by electrospinning. Scanning electron microscopy showed the electrospun nanofibers were uniform and almost free of defects. Transmission electron microscopy indicated that the CNTs were finely dispersed and highly oriented along the CNT/PI nanofiber axis at a relatively low concentration. The as-prepared well-aligned electrospun nanofibers were then directly used as homogeneity reinforcement to enhance the tensile strength and toughness of PI films. The neat PI nanofiber reinforced PI films showed good transparency, decreased bulk density and significantly improved mechanical properties. Compared with neat PI film prepared by solution casting, the tensile strength and elongation at break for the PI film reinforced with 2 wt.% CNT/PI nanofibers were remarkably increased by 138% and 104%, respectively. The significant increases in the overall mechanical properties of the nanofibers reinforced polyimide films can be ascribed to good compatibility between the electrospun nanofibers and the matrix as well as high nanofiber orientation in the matrix. Our study demonstrates a good example for fabricating high performance and high toughness polyimide nanocomposites by using this facile homogeneity self-reinforcement method.     

Nano-epoxy resins containing electrospun carbon nanofibers and the resulting hybrid multi-scale composites

For the first time, electrospun carbon nanofibers (ECNFs, with diameters and lengths of ∼200 nm and ∼15 μm, respectively) were explored for the preparation of nano-epoxy resins; and the prepared resins were further investigated for the fabrication of hybrid multi-scale composites with woven fabrics of conventional carbon fibers via the technique of vacuum assisted resin transfer molding (VARTM). For comparison, vapor growth carbon nanofibers (VGCNFs) and graphite carbon nanofibers (GCNFs) were also studied for making nano-epoxy resins and hybrid multi-scale composites. Unlike VGCNFs and GCNFs that are prepared by bottom-up methods, ECNFs are produced through a top-down approach; hence, ECNFs are more cost-effective than VGCNFs and GCNFs. The results indicated that the incorporation of a small mass fraction (e.g., 0.1% and 0.3%) of ECNFs into epoxy resin would result in substantial improvements on impact absorption energy, inter-laminar shear strength, and flexural properties for both nano-epoxy resins and hybrid multi-scale composites. In general, the reinforcement effect of ECNFs was similar to that of VGCNFs, while it was higher than that of GCNFs.     

Fabrication and characterization of three-dimensional PMR polyimide composites reinforced with woven basalt fabric

A PMR polyimide composite reinforced with three-dimensional (3D) woven basalt fabric is fabricated for medium high temperature applications. The PMR polyimide matrix resin is derived from 4,4′-methylenediamine (MDA), diethyl ester of 3,3′,4,4′-oxydiphthalic (ODPE) and monoethyl ester of Cis-5-norbornene-endo-2,3-dicarboxylic acid (NE). The rheological properties of the PMR polyimide matrix resin are investigated. Based on the curing reaction of the PMR type polyimide and the rheological properties, an optimum two-step fabrication method is proposed. The three dimensional fabric preforms are impregnated with the polyimide resin in a vacuum oven at 70 °C for 1 h followed by removing the solvent and pre-imidization. The composites are then consolidated by an optimized molding procedure. Scanning electron microscopy analysis shows that needle shaped voids are generated in yarns and the void volume fraction is 4.27%. The decomposition temperature and the temperature at 5% weight loss of the composite post-cured at 320 °C for 24 h are 440 °C and 577 °C, respectively. The dielectric constant and the dielectric loss of the composite are measured by circular cavity method at 7–12 GHz. The tensile strength and the modulus in the warp direction of the composite are 436 MPa and 22.7 GPa. The composite shows a layer-by-layer fracture mode in three-point bending test. The flexure strength and modulus in the warp direction of the composite are 673 MPa and 27.1 GPa, respectively.     

Synthesis and characterizations of Pt nanorods on electrospun polyamide-6 nanofibers templates

We report on the synthesis of platinum (Pt) nanorods by using ultrafine polyamide-6 nanofibers templates produced via electrospinning technique. These ultrafine polyamide-6 nanofibers can be utilized as the templates for growing Pt nanorods after modifying them optimally by plasma passivations. The morphological, structural, optical and electrical properties of the template assisted Pt nanorods were studied by field-emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HR-TEM), X-ray diffraction (XRD), photoluminescence (PL) and current–voltage (I–V) characteristics. The ability to fabricate the ultrafine size controlled Pt nanorods on polyamide-6 templates with optimized growth parameters in real time can be utilized for the variety of technological applications. Therefore, it is possible to obtain high quality with size control Pt nanorods. Once obtaining the high quality metal nanorods on polymer templates, the same can be adapted for the electronic device fabrication.     

Preparation and properties of polyamide 6 thermal conductive composites reinforced with fibers

The majority of inorganic particles-filled thermal conductive composites highlight thermal conductivity in detriment of mechanical properties. In this work, magnesium hydroxide (Mg(OH)₂), alumina (Al₂O₃) and flake graphite-filed polyamide 6 (PA6) composites prepared by twin-screw extruder, were reinforced with carbon and glass fibers separately. Effects of fiber type and content on thermal conductivity, mechanical properties and heat deflection temperature (HDT) of the PA6-based composites were investigated. The results showed that the thermal conductivity of the composites improved with increasing carbon fiber content, while decreased slightly with glass fiber loading. Furthermore, strength, modulus and HDT of the PA6-based composites increased with the increase of fiber content. The reinforcing effects of the two fibers on the thermal and mechanical properties of the composites were compared and interpreted in this paper. By incorporating simultaneously high thermal conductive fillers and high-strength fibers, the combined composites hold a good potential in heat dissipation applications.     

Crystallization and thermal properties of polyamide 6 composites filled with different nanofillers

The aim of this research is mainly to study the melting and crystallization behavior of polyamide 6 (PA6) when interacting with different nanofillers. The results show that the addition of nanofillers causes the increase of the peak temperature (T_p) during crystallization, which can be explained by the nucleation effect of the nanofiller. For PA6 and nanocomposites, the α crystal is the dominant crystalline phase. However, the γ form crystal appeared in PA6 containing montmorillonite (MMT) and SiO₂, while the crystallization did not appear in the composites with carbon nanotube (CNTs). For the PA6/CNTs nanocomposites, the length and surface properties of CNTs also had an effect on the crystallization of PA6. Although there are more -COOH groups on the surface of CNTs1^#, the crystallization degree of PA6/CNTs1^# is the lowest. The area of the melting peak of CNTs3^# is relatively large for a shorter size. The crystal-particle distribution is also varied for different dimensions of CNTs treated using three methods and the width of the melting peak of PA6/CNTs3^# is the largest.     

In vitro evaluation of electrospun gelatin–glutaraldehyde nanofibers

The gelatin–glutaraldehyde (gelatin–GA) nanofibers were electrospun in order to overcome the defects of ex-situ crosslinking process such as complex process, destruction of fiber morphology and decrease of porosity. The morphological structure, porosity, thermal property, moisture absorption and moisture retention performance, hydrolytic resistance, mechanical property and biocompatibility of nanofiber scaffolds were tested and characterized. The gelatin–GA nanofiber has nice uniform diameter and more than 80% porosity. The hydrolytic resistance and mechanical property of the gelatin–GA nanofiber scaffolds are greatly improved compared with that of gelatin nanofibers. The contact angle, moisture absorption, hydrolysis resistance, thermal resistance and mechanical property of gelatin–GA nanofiber scaffolds could be adjustable by varying the gelatin solution concentration and GA content. The gelatin–GA nanofibers had excellent properties, which are expected to be an ideal scaffold for biomedical and tissue engineering applications.     

Fabrication and characterization of polyamide 6-functionalized graphene nanocomposite fiber

Graphene oxide was prepared by the Hummers’ method and then functionalized with 4-substituted benzoic acid via “direct Friedel–Crafts” acylation in a mild reaction medium of polyphosphoric acid/phosphorous pentoxide (P₂O₅). Raman spectroscopy, differential scanning calorimetry, thermo-gravimetric analysis, and transmission electron microscopy were used to characterize the resultant structure. The results show that 4-substituted benzoic acid functionalized graphene (FG) sheets were achieved without pretreatment of oxidation. Polycaprolactam (PA6)-FG composites were prepared by in situ polymerization of ε-caprolactam in the presence of FG. Nanocomposite fiber with 0.01–0.5?wt% content of FG was prepared with a piston spinning machine and hot-roller drawing machine. A significant enhancement of mechanical properties of the PA6-FG composites’ fiber is obtained at low graphene loading; that is, a 29?% improvement of tensile strength and a three times increase of Young’s modulus are achieved at a graphene loading of only 0.1?wt%. The “graft-from” methodologies pave the way to prepare graphene-based nanocomposites of condensation polymers with promising performance and functionality.     

聚酰胺6/氧化石墨烯复合材料的制备及其性能

为研究氧化石墨烯对聚酰胺6的相容性和力学性能的影响,以天然鳞片石墨为原料,采用改良的Hummers方法制备氧化石墨烯,用氯化亚砜将其活化得到酰氯修饰氧化石墨烯,再与氨气反应制备氨基化氧化石墨烯,采用原位聚合法制备出聚酰胺6/氧化石墨烯复合材料,利用扫描电子显微镜对其进行表征分析,通过在甲酸中的分散实验研究该材料的相容性,并利用拉伸实验测试其力学性能.结果表明:聚酰胺6成功以化学键形式键接到氨基化氧化石墨烯表面;氧化石墨烯在聚酰胺6基体中呈现均匀稳定分散;氧化石墨烯均匀分散于甲酸中,其在甲酸中的相容性得到了明显改善;氨基化氧化石墨烯质量分数为0.1%时,聚酰胺6/氧化石墨烯的拉伸强度和杨氏模量分别达到133和736 MPa.     

Fabrication and characterization of electrospun Ag doped TiO2 nanofibers for photocatalytic reaction

Titanium dioxide is one of the best semiconductor photocatalysts available for photocatalytic reaction of dye pollutants. To prevent the recombination caused by the relatively low photocatalytic efficiency, Ag doped TiO₂ nanofiber was prepared by electrospinning method. The photocatalysts (pure TiO₂ nanofiber and Ag doped TiO₂ nanofiber) were characterized by FE-SEM, XRD, XPS, and PL analysis. These photocatalysts were evaluated by the photodecomposition of methylene blue under UV light. Ag doped TiO₂ nanofiber was found to be more efficient than pure TiO₂ fiber for photocatalytic degradation of methylene blue. The photocatalytic degradation rate was applied to pseudo-first-order equation. The degradation of Ag doped TiO₂ nanofiber was significantly higher than the degradation rate of pure TiO₂ nanofiber. Activation energy was calculated by applying Arrhenius equation from the rate constant of photocatalytic reaction. The activation energies for the pure TiO₂ nanofibers calcined at 400 and 500 °C were 16.981 and 12.187 kJ/mol and those of Ag doped TiO₂ nanofibers were 18.317 and 7.977 kJ/mol, respectively.     

Hybrid multi-scale composites developed from glass microfiber fabrics and nano-epoxy resins containing electrospun glass nanofibers

In this study, hybrid multi-scale composites were developed from glass microfiber fabrics (GFs) and nano-epoxy resins containing electrospun glass nanofibers (EGNFs). The hypothesis was that, through dispersing a small amount of EGNFs into epoxy resin, mechanical properties (particularly out-of-plane mechanical properties) of the resulting hybrid multi-scale composites would be significantly improved. The composites were fabricated by the technique of vacuum assisted resin transfer molding (VARTM). The interlaminar shear strength, flexural properties, impact absorption energy, and tensile properties of the composites were evaluated, and the results were compared to those acquired from GFs/epoxy composite as well as GFs/epoxy composites containing chopped glass microfibers (GMFs); additionally, the reinforcement and/or toughening mechanisms were investigated. The study revealed that the nano-epoxy resin with 0.25 wt.% of EGNFs resulted in substantial improvements on mechanical properties of the resulting hybrid multi-scale composites.     

Sub-nanomolar sensing of ionic mercury with polymeric electrospun nanofibers

Ethyl cellulose (EC) based electrospun nanofibers were exploited for sub-nanomolar level optical chemical sensing of ionic mercury. An azomethine ionophore was used as Hg (I) and Hg (II) sensing material. Ethyl cellulose nanofibers with varying amounts of the ionic liquid; 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIMBF₄) were prepared and characterized. The nanofibers were fabricated by electrospinning technique. The offered chemosensor allow determination of mercury ions in a large linear working range between 1.0 × 10⁻¹⁰ and 1.0 × 10⁻⁴ mol L⁻¹. Limit of detection was found to be 0.07 nM which makes this technique alternative to cold-vapor atomic absorption spectrometry (CV-AAS), flame emission methods and to inductively coupled plasma-mass spectrometry (ICP-MS).     

Fabrication of mineralized electrospun PLGA and PLGA/gelatin nanofibers and their potential in bone tissue engineering

Surface mineralization is an effective method to produce calcium phosphate apatite coating on the surface of bone tissue scaffold which could create an osteophilic environment similar to the natural extracellular matrix for bone cells. In this study, we prepared mineralized poly(d,l-lactide-co-glycolide) (PLGA) and PLGA/gelatin electrospun nanofibers via depositing calcium phosphate apatite coating on the surface of these nanofibers to fabricate bone tissue engineering scaffolds by concentrated simulated body fluid method, supersaturated calcification solution method and alternate soaking method. The apatite products were characterized by the scanning electron microscopy (SEM), Fourier transform-infrared spectroscopy (FT-IR), and X-ray diffractometry (XRD) methods. A large amount of calcium phosphate apatite composed of dicalcium phosphate dihydrate (DCPD), hydroxyapatite (HA) and octacalcium phosphate (OCP) was deposited on the surface of resulting nanofibers in short times via three mineralizing methods. A larger amount of calcium phosphate was deposited on the surface of PLGA/gelatin nanofibers rather than PLGA nanofibers because gelatin acted as nucleation center for the formation of calcium phosphate. The cell culture experiments revealed that the difference of morphology and components of calcium phosphate apatite did not show much influence on the cell adhesion, proliferation and activity.