Highly hydrophobic nanofibrous surfaces genearated by poly(vinylidene fluoride)

Lotus-leaf-like nanofibrous surfaces were prepared by electrospinning hydrophobic poly(vinylidene fluoride) (PVDF) from a mixed solvent of N,N-dimethylformamide (DMF) and acetone. PVDF fibrous mats with a bead-on-string morphology were generated because the nonpolar acetone decresed the viscosity of the PVDF solution and promoted the evaporation of the solution during electrospinning process. The morphology of the nanofibirous surface was examined by scanning electron microscopy. Micron-sized beads were introduced to the electrospun PVDF mats, resulting in enhanced hydrophobicity of the electrospun mats. The addition of a small amount (0.05 vol%) of acetic acid to the polymer solution effectively improved the bead-on-string morphology of the electrospun mats, and led to a higher water contact angle (WCA). The electrospun PVDF fibrous mat showed a maximum WCA of 148.5° due to the appropriate surface roughness.     

Tuning the properties of PVDF or PVDF-HFP fibrous materials decorated with ZnO nanoparticles by applying electrospinning alone or in conjunction with electrospraying

Novel composite nanofibrous materials of poly(vinylidene fluoride) (PVDF) or poly(vinylidene fluoride-cohexafluoropropylene) (PVDF-HFP) and ZnO nanoparticles were prepared by conjunction of electrospinning and electrospraying techniques. Simultaneous electrospinning of concentrated solution of PVDF or PVDF-HFP and electrospraying of suspension of ZnO in diluted PVDF or PVDF-HFP solution enable the preparation of materials consisting of fibers on which ZnO was deposited on the fibers’ surface (design type “on”). These fibrous materials were compared with materials consisting of PVDF or PVDF-HFP fibers in which ZnO was incorporated in the fibers (design type “in”) and which were obtained by one-pot electrospinning of a suspension of ZnO nanoparticles in concentrated PVDF or PVDF-HFP solution. The fiber morphology and the presence of ZnO “in” or “on” the fibers were observed by scanning electron microscopy (SEM) and by transmission electron microscopy (TEM). The effect of the used technique on the type, size and shape of the obtained structures was discussed. The fibrous mats were studied by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), X-ray diffraction (XRD), contact angle measurements and mechanical tests as well. It was found that the decoration of fibers with ZnO resulted in increase of their thermal stability and hydrophobicity. The microbiological tests showed that the materials of design type “on” possessed strong antibacterial activity against the pathogenic microorganism Staphylococcus aureus. The results suggest that, due to their antibacterial activity, the obtained composite materials are suitable for wound dressing applications.     

Superhydrophobic and Antibacterial Properties of Cotton Fabrics Treated with PVDF and nano-ZnO through Phase Inversion Process

Cotton fabrics exhibiting superhydrophobic and antibacterial properties were prepared through a non-solvent induced phase separation method using hydrophobic poly(vinylidene fluoride) (PVDF) and its hybrids with photocatalytic zinc oxide nanoparticles (nano-ZnO) as surface modifying agents for cotton fabric. The effects of coagulating medium and temperature on microstructural morphology and surface hydrophobictity of the cotton fabrics were investigated by FE-SEM observation and contact angle measurement. Superhydrophobic cotton fabrics exhibiting water contact angle higher than 150 ° could be obtained by coating the fabrics with solutions of PVDF and nano-ZnO followed by coagulation in ethanol as non-solvent. This phenomenon is considered to be originated from both chemically hydrophobic PVDF layer and physical micro- and nano-bumps formed on the surface of cotton fabric, which are essential requirements for Lotus effect. Moreover, antibacterial properties could be synergistically obtained by utilizing photocatalytic effect of nano-ZnO.     

One-step fabrication of high selective hollow fiber nanofiltration membrane module

A novel hollow fiber composite Nanofiltration (NF) membrane was fabricated by an improved preparation procedure. Using hollow fiber ultrafiltration (UF) membrane modules as the supporting modules, hollow fiber composite NF modules were fabricated by the one-step interfacial polymerization method. The effects of preparation conditions (such as concentration of the monomers, reaction time of monomers and ambient relative humidity, etc.) on the performance of the hollow fiber composite membranes were studied. When tested at 0.6 MPa, room temperature, the hollow fiber composite membrane had a rejection sequence of MgSO₄>Na₂SO₄>MgCl₂>NaCl and a permeate flux sequence of NaCl>Na₂SO₄> MgSO₄>MgCl₂. The nagative charge character of the membrane surface was examined by streaming potential methods. The effect of the surface electrolyte properties on the membrane separation performance was investigated. The morphologies of the hollow fiber composite Nanofiltration membranes were studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM).     

Carbon nanofiber/poly(vinylidene fluoride-hexafluoro propylene) composite films: The crystal structure and thermal properties with various drawing temperatures

Carbon nanofiber (CNF)/polyvinylidene fluoride-hexafluoro propylene (PVDF-HFP) composite film was prepared by solution casting and melt pressing. The resultant 2 % CNF/PVDF-HFP composite films were uniaxially drawn at 50 °C, 75 °C, and 100 °C, respectively. In the SEM images, the morphology of drawn CNF/PVDF-HFP composite film confirmed the orientation of the CNF and the polymer matrix. The WAXD results showed the coexistence crystal phase of PVDF-HFP. The drawn CNF/PVDF-HFP composite film demonstrates improved electrical properties. The DSC thermogram results indicated no change in the melting temperature but slightly increased crystallinity with increasing drawing temperature. Dynamic mechanical analysis and tensile test showed an improvement in the storage modulus and stress at a drawing temperature of 75 °C.     

Crystal structure and thermal properties of poly(vinylidene fluoridehexafluoropropylene) films prepared by various processing conditions

Poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP) films were prepared using either a melt pressing or solution casting methods. The resulting PVDF-HFP films were drawn uniaxially at various drawing temperatures and speeds. The mp-PVDF-HFP films were more transparent and had more drawability than the sc-PVDF-HFP films. The crystal form of the initial films was the alpha-phase (non polarity) of PVDF. The maximum draw ratio was 7.6. The mp-PVDF-HFP films were prepared at a drawing speed of 2500 %/min at 100 °C. With increasing drawing speed, the beta-phase (polarity) became the dominant phase of PVDF in mp-PVDF-HFP films. The thermal properties of the resulting PVDF-HFP films improved with increasing drawing temperature.     

Electrospun poly(tetrafluoroethylene) nanofiber membranes from PTFE-PVA-BA-H<Subscript>2</Subscript>O gel-spinning solutions

As a kind of high-performance fibers, PTFE fiber has been widely used in many fields because of its unique characteristics. In this study, the poly(tetrafloroethylene) (PTFE) nanofibers manufactured by electrospinning method was reported. The gel-spinning solution of poly(tetrafluoroethylene)/poly(vinyl alcohol)/boric acid (PTFE/PVA/BA), which was prepared by the gel process of the mixture of PTFE, PVA, BA and redistilled water, was electrospun to form PTFE/PVA/BA composite nanofibers. After calcinating, the PTFE nanofibers with diameters of 200 nm to 1000 nm were obtained. The fibers before and after calcinating were characterized by scanning electron microscopy (SEM), thermogravimetric analysis (TGA), X-ray diffraction (XRD), FT-IR spectrum analysis and X-ray photoelectron spectroscopy (XPS), respectively, and the mechanical and hydrophobic properties of the fibers were also investigated. The results showed that the PTFE nanofiber membranes could be electrospun effectively used the gel-spinning solution of PTFE/PVA/BA, and may realize the applications in the fields of high-temperature filtration, catalyst supports, battery separator and so on.     

Enhanced dielectric properties of electrospun titanium dioxide/polyvinylidene fluoride nanofibrous composites

Titanium dioxide/polyvinylidene fluoride (TiO₂/PVDF) composite was prepared by electrospinning process to enhance the dielectric properties for application as a gate insulator in organic thin-film transistors (OTFTs). Scanning electron microscopy, thermogravimetric analysis, and X-ray diffraction were employed to characterize the as-prepared samples, and then their dielectric constants were investigated by impedance analysis. The impedance results show that the dielectric constant of the electrospun TiO₂/PVDF nanofibers is higher than those of other samples, demonstrating that electrospun TiO₂/PVDF composite can be a proper candidate for gate insulators in OTFTs.     

Preparation and characterization of polysulfone membrane incorporating cellulose nanocrystals extracted from corn husks

Cellulose nanocrystals (CNCs) extracted from corn husks were used as additive to modify the hydrophilicity and anti-fouling properties of polysulfone (PSf) membrane. The PSf/CNCs blend membranes were prepared via an immersion phase inversion method. The influence of CNCs content on the morphology, structure, and performances of PSf membrane were carefully investigated by SEM, TG, DTG, DSC, break strength, elongation-at-break, Young modulus, contact angle and filtration experiment. The results showed that the isolated CNCs from corn husks were a promising additive for modifying the properties of PSf membrane. CNCs can improve mechanical property, thermal stability, hydrophilicity and anti-fouling performance of the pure PSf membrane. The PSf/CNCs blend membrane reached optimal properties at 2 wt% CNCs content, which was 2.76 and 1.57 times in pure water flux and FRR values respectively as compared to pure PSf membrane. Meanwhile, PSf-2 also can maintain a relatively high BSA rejection.     

Electrospun curcumin loaded poly(lactic acid) nanofiber mat on the flexible crosslinked PVA/PEG membrane film: Characterization and <Emphasis Type="Italic">in vitro</Emphasis> release kinetic study

Herein, a biodegradable and biocompatible composite comprising of support membrane based on crosslinked PVA/PEG film and curcumin loaded electrospun poly(lactic acid) (PLA) nanofiber mat is introduced. The membrane film was prepared from PVA/PEG blend followed by crosslinking with an optimum amount of citric acid, 15 wt.%. After then, PLA solutions with different curcumin content, 0-11 wt.%, were electrospinned on the prepared membrane substrate. The prepared film showed high water absorption, water vapor transmission rate and superior mechanical properties with improved elastic modulus, tensile strength and with an elongation of around 320 % with respect to the non-crosslinked one. Also, the scanning electron microscopy was revealed uniformly dispersed pores throughout the membrane film with a nearly narrow in size distribution centered at 36 μm. As well, a nanostructure porous morphology was found for the electrospun fibrous curcumin loaded PLA from the scanning electron microscopy micrographs and the average fiber diameter was decreased with curcumin content. In vitro drug release from the prepared flexible composite into the vertical diffusion cell was recorded by the measuring curcuminoids content using high performance liquid chromatography and drug release kinetic evaluations were revealed that the release pattern of all prepared samples, containing different content of curcumin, well fitted to the Higuchi’s model signifying diffusion-controlled release mechanism. As well, the determined release rate at the second release stages, i.e. steady state flux (J), was varied from 0.31 to 43.53 μg·cm^-2·h^-1 with increasing drug content from 1 to 11 wt.%. Regarding this results, this flexible composite by providing the moist environment along with miraculous healing properties of curcumin, can be potential candidate for transdermal drug delivery.     

Novel high flux nanofibrous composite membrane based on polyphenylsulfone thin barrier layer on nanofibrous support

A novel thin film nanofibrous composite (TFNC) polyphenylsulfone (PPSU) membrane was fabricated by casting a thin PPSU barrier layer on the surface of the electrospun nanofibrous PPSU support. Polyethylene glycol (PEG) 400 was applied in the electrospinning solution to prevent the penetration of coating solution into the support. The membrane morphology and filtration performance were investigated via scanning electron microscopy (SEM), and filtration of canned beans production wastewater, respectively. Atomic force microscopy (AFM) was utilized to evaluate the surface roughness of the membranes. Furthermore, the mechanical strength and thermal stability of the membranes were determined via tensile test and thermogravimetric analysis (TGA). Comparison of the TFNC membrane and the unsupported membrane prepared through the wet phase inversion method with almost equal rejection values indicated a 2.3 fold higher PWF using the former.     

Facile fabrication of PVAc-g-PVDF coating on surface modified cotton fabric for applications in oil/water separation and heavy metal ions removal

Selective separation is an effective method for the removal of heavy metal ions and waste oil from wastewater. Polyvinylidene fluoride (PVDF) was functionalized with polyvinyl acetate (PVAc) by in-situ polymerization, and novel PVAc-g-PVDF coating on surface modified cotton fabric were prepared. The contact angle (CA), pure water flux (PWF) and self-cleaning ability of coated cotton fabric were investigated in detail. In addition, the separation performance of coated cotton fabric was reflected by the removal of heavy metal ions in simulated wastewater. The results revealed that the PVAc-g-PVDF-coated cotton fabric was free of waste oil adhesion and was self-cleaning from waste oil in aqueous environment. Meanwhile, this coated cotton fabric can effectively separate oil/water mixtures with a high flux and high oil rejection, and was easily recycled for long-term use. More importantly, the heavy metal ions rejection ratio and adsorption capacity of cotton fabric were also improved with the addition of PVAc-g-PVDF coating. PVAc-g-PVDF-coated cotton fabric exhibited excellent rejection stability and reuse performances after several times fouling and washing tests. It can be expected that the present work will provide insight into a scaled-up fabrication process of PVAc-g-PVDF coating for purifying wastewater.     

Preparation and characterization of a novel nanofiltration membrane

In this study, poly[2-(N, N-dimethyl amino)ethyl methacrylate] (PDMAEMA) was prepared by bulk polymerization using AIBN as an initiator. Aqueous PDMAEMA solution was then purified by hollow fiber ultrafiltration membrane technology to remove oligomers. PDMAEMA/polysulfone (PSF) positively charged nanofiltration (NF) membrane was developed by interfacial polymerization by using PSF ultrafiltration membrane as the substrate, PDMAEMA aqueous solution as the coating solution and p-xylylene dichloride dissolved in n-heptane as the organic crosslinker. Effects of substrate material, concentration of monomer, pH value of PDMAEMA, coating time and crosslinking time were then carefully examined on the separation properties of the prepared NF membrane. Data suggested that the rejection rate of the composite NF membrane to 1 g/l of MgSO₄ was around 86.7 %, and the water flux was about 18.4 L·m⁻²·h⁻¹. Therefore, the developed NF membrane is suitable for rejection and desalination of alkaline dyes.     

Electrospun PU-PEG and PU-PC hybrid scaffolds for vascular tissue engineering

Produced via electrospinning, polyurethane (PU) scaffolds have always attracted the interest of medical applications due of their unique properties such as good adhesion, biocompatibility and excellent mechanical strength. However, the poor hydrophilicity and hemocompatibility of PU presented a problem during PU’s application in the manufacturing of biomedical materials. We hypothesized that the incorporation of polyethylene glycol (PEG) and phosphatidylcholine (PC) into electrospinning solution of PU could improve the cell affinity and hemocompatibility. This research focused on fabricating hybrid PU-PEG and PU-PC random/aligned scaffolds through electrospinning technique and comparing their properties as a potential biocompatible scaffold for vascular tissue engineering. PC was doped into a PU solution in order to prepare an electrospun scaffold through the electrospinning technology while crosslinked electrospun PUPEG hybrid scaffolds were fabricated by photoinduced polymerization. The contact angle dramatically decreased from 122.3±0.8° to 39.1±0.8° with doping of PC in electrospinning solution while it decreased from 122.3±0.8° to 41.6±0.8° with doping of PEG. Furthermore, the mechanical properties of PU scaffolds were altered significantly by the addition of PC. The hemolysis and cytocompatibility assays demonstrated that these composite scaffolds could potentially be used as a smalldiameter vascular graft.     

Facile Fabrication of Electrospun Silica Nanofibrous Membrane with Hydrophobic,Oleophilic and Breathable Performances

We report a simple and versatile method to prepare hydrophobic composite SiO₂ membrane. The electrospun SiO₂ membrane was selected due to its good flexibility and thermal stability. The hydrophobic SiO₂ membrane was succussfully prepared by simply evaporating a thin polydimethylsiloxane (PDMS) layer on the fiber surface. The characterization results show that the PDMS layer is too thin to be observed. The PDMS coating has no influence on the porous structure of the fibrous membrane, but imparts the good hydrophobicity and oleophilicity to the SiO₂ nanofibers. As demonstration, the hydrophobic SiO₂-PDMS membrane displays good oil absorption performance from the oil/water mixture, as well as filtration membrane for oil/water separation. Additionally, due to the proper pore size and hydrophobic surface, the SiO₂- PDMS membrane shows good waterproof performance and breathability at the same time.     

Water repellent cotton fabrics prepared by PTFE RF sputtering

A poly(tetrafluoroethylene) (PTFE) sputtering technique was employed to introduce water repellency onto the surfaces of commercial cotton fabrics. Sputtering power, time, and argon pressure were varied as processing parameters, when PTFE coatings were applied on the fabrics. Total 27 different samples were prepared to compare their water repellent properties, which were investigated by contact angle measurements. Morphology of the PTFE coatings were probed by scanning electron microscopy (SEM) and atomic force microscopy (AFM). Also, the extent of the coating was examined by X-ray photoelectron spectroscopy (XPS). Maximum hydrophobicity was obtained when PTFE coating was extensive enough to cover cotton fabrics almost completely, and the extensive coating was the roughest among the samples prepared in this study.     

Crystal structure and thermal properties of poly(vinylidene fluoride)-carbon fiber composite films with various drawing temperatures and speeds

PVDF-CF composite films were prepared using a melt pressing method. The PVDF-CF composite films were cut into rectangular shapes with a gauge length and width of 10 and 5 mm, respectively. The films were drawn using a universal testing machine equipped with a hot chamber. The drawing temperatures and speeds were 50∼150 °C and 100∼000 %/min, respectively. The crystal structure and physical properties of the resulting PVDF-CF films were investigated by wide angle X-ray diffraction, Fourier transform infrared spectroscopy, differential scanning calorimetry, dynamic mechanical analysis and scanning electron microscopy. The crystal form of the initial films was the 〈alpha〉 phase (non polarity, lamellar structure) of PVDF. The maximum draw ratio was 4.2. The drawn PVDF-CF films prepared at 100 °C were mainly the 〈beta〉 phase (polarity, fibrillar structure) of PVDF. With increasing drawing speeds, the 〈alpha〉 phase became the dominant phase of PVDF in the PVDF-CF films. The thermal properties of the PVDF-CF films improved with increasing drawing temperature, and the dynamic mechanical properties improved with increasing drawing speed.     

Preparation of electrospun affinity membrane and cross flow system for dynamic removal of anionic dye from colored wastewater

In this research, poly(vinyl alcohol) (PVA)/chitosan electrospun nanofibrous membrane (ENM) was prepared by electrospinning method in order to investigate its dye removal ability from colored wastewater. The morphology and average fiber diameter of the membranes were investigated by scanning electron microscopy (SEM), image analysis and atomic force microscopy (AFM). The chemical characterization was studied by Fourier transform infrared spectroscopy (FTIR). The permeability of the membranes was evaluated by measuring pure water flux (PWF). In order to investigate the performance of the prepared membranes they were used in the batch adsorption and membrane separation for dye removal from colored wastewater. The effect of pH, number of membranes and dye concentration on the dye removal ability of the ENM was investigated. Response surface methodology (RSM) was used to achieve multi-objective optimization and equations of adsorption capacity and breakthrough time regarding operating conditions. The results demonstrated the potential of using PVA/chitosan nanofiber membrane as a microfiltration (MF) membrane for dye removal. Moreover, the recoverability property of prepared membranes was noticeable.     

Fabrication of electrospun meta-aramid nanofibers in different solvent systems

Meta-aramid fibers were dissolved in four different solvent systems (DMAc, DMF, NMP, and DMSO) and two kinds of salts (LiCl and CaCl₂) were also introduced in this paper. Meta-aramid fibers had a limited solubility in above four solvents, however, fast dissolution could be obtained after adding a certain amount of salt (LiCl or CaCl₂). The concentration of salts was found to be an important role in affecting meltaging, dissolving time and viscosity of electrospun solution. Electrospun meta-aramid nanofibers mats were successfully prepared. A series of characterizations had been carried out by using SEM. The results shows the diameter of meta-aramid nanofibers ranging from 100 to 500 nm. The average diameter of the nanofibers increased with the concentration of meta-aramid fiber solution and the salt solution. A preferable morphology of meta-aramid nanofibers could be obtained under LiCl/DMAc system. While the electrospun nanofibers made in CaCl₂/DMAc solvent system had a better performance in thermal stability than that prepared in LiCl/DMAc system. Among the four kinds of prepared nanofibers, the nanofibersmat electrospun in LiCl/DMAc system with a concentration of meta-aramid solution at 11 wt% exhibit the best mechanical properties.     

A Study of Combining Elastin in the Chitosan Electrospinning to Increase the Mechanical Strength and Bioactivity

While electrospun chitosan membranes modified to retain nanofibrous morphology have shown promise for use in guided bone regeneration applications in in vitro and in vivo studies, their mechanical tear strengths are lower than commercial collagen membranes. Elastin, a natural component of the extracellular matrix, is a protein with extensive elastic property. This work examined the incorporation of elastin into electrospun chitosan membranes to improve their mechanical tear strengths and to further mimic the native extracellular composition for guided bone regeneration (GBR) applications. In this work, hydrolyzed elastin (ES12, Elastin Products Company, USA) was added to a chitosan spinning solution from 0 to 4 wt% of chitosan. The chitosan–elastin (CE) membranes were examined for fiber morphology using SEM, hydrophobicity using water contact angle measurements, the mechanical tear strength under simulated surgical tacking, and compositions using Fourier-transform infrared spectroscopy (FTIR) and post-spinning protein extraction. In vitro experiments were conducted to evaluate the degradation in a lysozyme solution based on the mass loss and growth of fibroblastic cells. Chitosan membranes with elastin showed significantly thicker fiber diameters, lower water contact angles, up to 33% faster degradation rates, and up to seven times higher mechanical strengths than the chitosan membrane. The FTIR spectra showed stronger amide peaks at 1535 cm⁻¹ and 1655 cm⁻¹ in membranes with higher concentrated elastin, indicating the incorporation of elastin into electrospun fibers. The bicinchoninic acid (BCA) assay demonstrated an increase in protein concentration in proportion to the amount of elastin added to the CE membranes. In addition, all the CE membranes showed in vitro biocompatibility with the fibroblasts.