Preparation of novel organic‐inorganic nanoporous membranes

In this study, the water permeability, the rejection property of sucrose and glucose, the fouling property of humic acid as the foulant for a novel porous fluorinated polyimide membrane made by combining the ion irradiation and plasma treatment have been reported. First, an asymmetric polyimide membrane with a defect‐free and thin skin layer was prepared, then ions on the skin layer were irradiated and the ion‐irradiated layer was treated by plasma to form nanopores in the layer. The asymmetric polyimide membranes with a defect‐free skin layer were irradiated with 50 keV He⁺ at 1 × 10¹⁵ ions/cm², and the irradiated polyimide surfaces were treated by Ar glow discharge. The porous polyimide membrane showed a high water flux and excellent rejection properties and fouling resistance when compared with NTR‐7250, which is commercially available. These findings indicated that the pore size formed on the porous polyimide membrane was effectively controlled by the plasma treatment time and the skin layer thickness. Copyright © 2005 John Wiley & Sons, Ltd.     

Preparation of Water‐Absorbing Polyacrylonitrile Nanofibrous Membrane

Summary: Hydrophilic acrylic nanofibers were prepared from alkaline hydrolysis of hydrophobic polyacrylonitrile (PAN) nanofibers. Water contact angle, pore volume, and liquid retention capacity of PAN nanofibrous membranes were measured to determine their dependence on hydrolysis parameters such as base concentration, temperature, and time. Vertical water retention capacity of hydrolyzed PAN nanofibrous membrane could reach as large as 200 times of that of original membrane.

Fiber twinning in post‐hydrolyzed PAN nanofibrous membrane.     

Membrane formation mechanism and permeation properties of a novel porous polyimide membrane

The transport properties of a novel porous fluorinated polyimide membrane fabricated by a wet phase inversion process were studied with a stirred dead‐end filtration cell. The porous membrane‐forming solvents were tetrahydrofuran (THF), acetone, N,N‐dimethylacetamide (DMAc), N‐methylpyrrolidone (NMP), N,N‐dimethylformamide (DMF), and dimethylsulfoxide (DMSO). The phase separation phenomena in a ternary system of polyimide/solvent/water were investigated from cloud point curves by a titration method and binary interaction parameters. Solvent–water demixing in the system has been found to play very important roles in determining the structure and surface morphology of the polyimide membrane. The porous fluorinated polyimide membranes showed pore sizes from 4 to 500 nm and permeation properties from ultrafiltration to a microfiltration range. In this study, we particularly focused on fouling of the polyimide membranes, because fouling decreases the flux and increases the resistance. Interestingly, the porous polyimide membrane showed excellent water flux recovery after water cleaning compared with that of the polyethersulfone (PSf) membrane, which suggest that for a 6FDA‐6FAP membrane, the protein–membrane and protein–protein interaction was not so strong compared with those in a PSf membrane. Copyright © 2002 John Wiley & Sons, Ltd.     

Morphological Characterization of Electrospun Nano-Fibrous Membranes of Biodegradable Poly(L-lactide) and Poly(lactide-co-glycolide)

Hydrophobic biodegradable polyesters, poly(L-lactide) (PLLA) and poly(lactide-co-glycolide) (PLGA), were electrospun on different types of collectors to induce morphological changes in the nanofibrous membrane. On the metal collector smooth nonwoven membranes were obtained for both PLLA and PLGA, while on the water reservoir the surface of the membranes became rough due to shrinkage and slow charge dissipation. When NaCl was added to water to enhance the conductivity, the roughness of the membrane surface was changed, yet the shrinkage remained relatively unchanged. The crystallization of PLLA electospun material on the metal plate was suppressed because of the rapid solvent evaporation, however, upon annealing above the glass transition temperature for 24 hr the PLLA membrane became crystallized. When electrospun on the water reservoir, the PLLA membrane remained amorphous. Crystalline PLLA was obtained by electrospinning on the methanol reservoir due to the swelling of nanofibers by methanol.     

Carbon Nanotube‐Adsorbed Electrospun Nanofibrous Membranes of Nylon 6

Summary: A simple and mass‐producible method was developed to densely assemble multiwalled carbon nanotubes (MWNTs) onto electrospun nylon 6 nanofibrous membranes. The process consists of dispersing the acid‐treated MWNTs in surfactant solutions or organic solvents, and dipping the nanofibrous membranes in the resulting dispersion for only 60 seconds, followed by the extraction of the surfactants in pure water and drying. The conductivity of the MWNT‐adsorbed nanofibrous membranes ranges from 2.2 × 10⁻² to 1.5 × 10⁻¹ S · cm⁻¹, as determined by the four probe method, which implies that the MWNTs are adsorbed uniformly and densely along the nanofibrous membranes. Furthermore, the results suggest that there is a strong interaction between the acid‐treated MWNTs and nylon 6. We also investigate the amount of MWNTs present in the membranes using thermogravimetric analysis.

SEM images of the non‐woven fibrous nylon 6 membranes after dip‐coating in a dispersion of the MWNTs in surfactant‐containing water.     

Obtainment of Aromatic Polyimide Nanofibers and Materials on Their Basis for Cell Technologies

Nanofibers with a diameter of 100–300 nm are obtained by electroformation of solutions of polyamide acid based on 3,3′,4,4′-biphenyltetracarboxylic acid dianhydride and o-toluidine in an N,N-dimethylacetamide/ benzene solvent mixture. Thermal treatment of nanofibrous polyamide acid material leads to the formation of nanofibers of aromatic polyimide with a diameter of 100–200 nm. The temperature of the beginning of thermal decomposition of polyimide nanofibers in an argon atmosphere is 537°C. SEM images show that the material based on aromatic polyimide nanofibers preserves its elastic properties even at the temperature of liquid nitrogen. The obtained material is characterized by the absence of cytotoxicity: human fibroblasts cultivated on it are characterized by high proliferative activity.     

Crosslinked PVAL nanofibers with enhanced long‐term stability prepared by single‐step electrospinning

We present a single‐step route for the preparation of crosslinked poly(vinyl alcohol) (PVAL) nanofibers where a conventional electrospinning setup can be used. The simple crosslinking chemistry and the fast and easily applicable technique is an important step towards large‐scale production. In contrast to conventional systems, the PVAL crosslinker solution exhibited no increase in viscosity during storage and can therefore be used even after long shelf‐times before electrospinning. In addition, the crosslinked nanofibrous mats exhibited a gel content of almost 100%, indicating complete crosslinking; they did not dissolve in water, and no PVAL was found in the aqueous extract. The E‐moduli of the nanofibrous mats before and after water immersion could be measured by an intermodulation atomic force microscopy technique. A denser nanofibrous texture with enhanced mechanical properties can be observed after long‐term water immersion. Copyright © 2012 John Wiley & Sons, Ltd.     

γ-Al2O3柔性纳米纤维膜的制备及机械性能

以氯化铝和异丙醇铝为原料, 水和乙醇为溶剂, 通过溶胶凝胶结合静电纺丝法制备了柔性γ-Al2O3纳米纤维膜.表征了纤维膜的形貌和机械性质, 并研究了纤维膜的形成过程.组成纤维膜的纤维直径均匀, 平均直径188 nm, 纤维由粒径在15~30 nm的纳米颗粒组成且表面光滑.制备的纤维膜具有较好的柔性及抗拉强度(1.01 MPa).     

Novel compaction resistant and ductile nanocomposite nanofibrous microfiltration membranes

Despite promising filtration abilities, low mechanical properties of extraordinary porous electrospun nanofibrous membranes could be a major challenge in their industrial development. In addition, such kind of membranes are usually hydrophobic and non-wettable. To reinforce an electrospun nanofibrous membrane made of polyethersulfone (PES) mechanically and chemically (to improve wettability), zirconia nanoparticles as a novel nanofiller in membrane technology were added to the nanofibers. The compressive and tensile results obtained through nanoindentation and tensile tests, respectively, implied an optimum mechanical properties after incorporation of zirconia nanoparticles. Especially compaction resistance of the electrospun nanofibrous membranes improved significantly as long as no agglomeration of the nanoparticles occurred and the electrospun nanocomposite membranes showed a higher tensile properties without any brittleness i.e. a high ductility. Noteworthy, for the first time the compaction level was quantified through a nanoindentation test. In addition to obtaining a desired mechanical performance, the hydrophobicity declined. Combination of promising properties of optimum mechanical and surface chemical properties led to a considerably high water permeability also retention efficiency of the nanocomposite PES nanofibrous membranes. Such finding implies a longer life span and lower energy consumption for a water filtration process.     

Supercritical Carbon Dioxide‐Treated Electrospun Poly(vinylidene fluoride) Nanofibrous Membranes: Morphology,Structures and Properties as an Ionic‐Liquid Host

A reverse‐barrier technique is used to enable the treatment of electrospun poly(vinylidene fluoride) nanofibrous membranes with supercritical carbon dioxide. The treatment induces the formation of nanopores and extended‐chain β crystallites of small lateral dimensions in the nanofibers. It also creates interfiber junctions, resulting in a remarkable improvement in mechanical properties of the membranes. The treated membranes are able to retain their shape very well after loading with an ionic liquid (IL). The ionic conductivity of the IL‐loaded membrane is very close to that of the neat IL.

     

γ-Al2O3柔性纳米纤维膜的制备及机械性能

以氯化铝和异丙醇铝为原料, 水和乙醇为溶剂, 通过溶胶凝胶结合静电纺丝法制备了柔性γ-Al₂O₃纳米纤维膜. 表征了纤维膜的形貌和机械性质, 并研究了纤维膜的形成过程. 组成纤维膜的纤维直径均匀, 平均直径188 nm, 纤维由粒径在15~30 nm的纳米颗粒组成且表面光滑. 制备的纤维膜具有较好的柔性及抗拉强度(1.01 MPa).     

Electrospinning process using field‐controllable electrodes

For the production of uniaxially oriented nanofibers and a three‐dimensional, biodegradable scaffold consisting of nanosized fibers, an electrospinning process was modified with a cylindrical auxiliary electrode that was connected to a spinning nozzle to stabilize the initially spun solution and a parallel‐plate electrode as a collector generating an alternating‐current electric field for collecting spun jets. With the complex electric field in the electrospinning process, biodegradable poly(ε‐caprolactone) nanofibers were stacked on a thin, dielectric substrate covering the electrode according to a predetermined design. The degree of orientation of spun nanofibers to the field direction of a target electrode was highly dependent on the applied frequency and field strength of the target electrode. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1426–1433, 2006     

Nanofibrous mats with bird’s nest patterns by electrospinning

Electrospun material with bio-inspired ordered architectures and patterns is very interesting,yet remains a challenge.We report here that nanofibrous mats with bird’s nest patterned structures can be directly electrospun from chlorinated polypropylene solutions doped with an ionic liquid.The solution viscosity and the ionic liquid content are two dominant factors to influence the topological morphology of the nanofibrous mats.The patterned structures can be further modulated by the collection time of electrospinning,the humidity of environment and the design of collector.We suggest the electrostatic repulsion between the residual charges of the mat surface and the upcoming nanofibers plays a key role in the formation of the bird’s nest patterns.     

Synthesis and characterization of a novel polyurethane/polypyrrole‐p‐toluenesulfonate (PU/PPy‐pTS) electroactive nanofibrous bending actuator

Electroactive actuators based on conductive polymers currently have attracted a great deal of attention. In this study, a nanofibrous structure of polypyrrole (PPy) was used to fabricate an electroactive bending actuator. For this purpose, polyurethane/PPy (PU/PPy) nanofibrous bending actuator was fabricated through the combined use of electrospinning and in‐situ chemical polymerization. The response surface methodology (RSM) was considered to find the optimal electrospinning conditions for producing PU nanofibers with the minimum diameter. The in‐situ chemical polymerization method was then used to prepare a conductive layer of PPy on the surface of optimum electrospun nanofibers with p‐toluenesulfonate (pTS) as the dopant. The coated nanofibers were used in the fabrication of PU/PPy‐pTS nanofibrous bending actuator. The morphology and electrical, thermal, electrochemical, and electrochemomechanical properties of the fabricated actuator were investigated. By using optimum conditions of electrospinning, PU nanofibers were obtained with a diameter of 221 nm. The results showed that the produced PU/PPy‐pTS nanofibers enjoy good thermal stability and have an electrical conductivity of about 276.34 S/cm. The obtained cyclic voltammetric and dynamo‐voltammetric responses showed that the dominant mechanism of actuation in the fabricated PU/PPy‐pTS nanofibrous actuator is the exchange of perchlorate anions with a partial exchange of lithium cations in 1M lithium perchlorate electrolyte solution. The fabricated actuator was capable of undergoing 141° reversible angular displacement during a potential cycle. The results demonstrated that, given high porosity, large specific surface area, flexibility, and desirable electrical properties, PU/PPy nanofibrous electroactive actuator provides a lot of potential for developing artificial muscle applications.     

Electrospun nanofibrous membranes embedded with aerogel for advanced thermal and transport properties

The primary purpose of cold weather clothing is to shield the wearer from the extremities of the external environment. The thermal properties of nanofibers and their potential applications have tremendous scope and application in this area. The objective of this study was to investigate the mechanisms of heat transfer through fibrous insulation where the fiber diameter was less than 1 μm. Electrospinning process was used to produce flexible polyurethane and polyvinylidene fluoride nanofibers embedded with silica aerogel. The thermal and transport behavior of the samples was evaluated, and results were statistically analyzed. Presence of aerogel particles were confirmed through microscopic examination. Thermal behavior was investigated by using thermogravimetric analysis and differential scanning calorimetry. The results showed that the polyvinylidene fluoride nanofibrous membranes embedded with aerogel obtained a good thermal stability with lower weight loss than polyurethane nanofibrous membranes. The glass transition and melting point was not affected by the aerogel content in the layers, validating that polymers are not miscible. The increase in duration of electrospinning led to higher web thickness, which resulted in considerable decrease in air permeability. Considerable improvement of thermal insulation was observed by increasing the number and the weight per unit area of both nanofibrous membranes. The results confirmed increase in thermal insulation by embedding silica aerogel in nanofibrous membranes. With reference to the results, it could be concluded that nanofibers embedded with aerogel are good for thermal insulation in cold weather conditions. Thermal insulation battings incorporating nanofibers could possibly decrease the weight and bulk of current thermal protective clothing.     

Green,ultrafine cellulose-based porous nanofibrous membranes for efficient heavy metal removal through incorporation of chitosan by various electrospinning ways

Rapid global industrialization has worsened the heavy metal contamination of aquatic ecosystems globally. In this study, green, ultrafine cellulose-based porous nanofibrous membranes for efficient heavy metal removal were obtained by incorporating chitosan (CS) and using conventional and core–shell electrospinning ways. The relationship between the parameters of the electrospinning solution, the micro-morphology and porosity, the chemically active sites, the thermal stability, and the adsorption performance of the biocomposite nanofibrous membranes were analyzed. The adsorption effects of the copper ions, including the initial concentration, solution pH, and interaction time, were investigated. The results show that the average diameters of the conventional and core–shell ultrafine nanofibers with 50% and 30% CS loading are 56.22 nm and 37.28 nm, respectively. The core–shell cellulose acetate (CA)/CS biocomposite nanofibrous membranes showed the weaker thermal stability with a 48.2 °C lower maximum thermal decomposition temperature and induced the surface aggregation of more copper ions compared to the conventional one. A more uniform distribution of the chemical adsorption sites is obtained by conventional single-nozzle electrospinning than by core–shell electrospinning, which effectively promotes the adsorption performance of copper ions and decreases the surface shrinkage of the nanofibrous membranes during adsorption. The 30% CS conventional nanofibrous membranes at an aqueous solution pH of 5 showed the optimum adsorption capacity of copper ions (86.4 mg/g). The smart combination of renewable biomass with effective chemical adsorption sites, electrospinning technology that produces an interwoven porous structure, and an adsorption method with low cost and facile operation shows a promising prospect for water treatment.

     

Carbon nanotube and carbon nanorod-filled polyacrylonitrile electrospun stationary phase for ultrathin layer chromatography

The application of carbon nanotube or nanorod/polyacrylonitrile (PAN) composite electrospun nanofibrous stationary phase for ultrathin layer chromatography (UTLC) is described herein. Multi-walled carbon nanotubes (MWCNTs) and edge-plane carbon (EPC) nanorods were prepared and electrospun with the PAN polymer solution to form composite nanofibers for use as a UTLC stationary phase. The analysis of laser dyes demonstrated the feasibility of utilizing carbon nanoparticle-filled electrospun nanofibers as a UTLC stationary phase. The contribution of MWCNT or EPC in changing selectivity of the stationary phase was studied by comparing the chromatographic behavior among MWCNT–PAN plates, EPC–PAN plates and pure PAN plates. Carbon nanoparticles in the stationary phase were able to establish strong π–π interactions with aromatic analytes. The separation of five polycyclic aromatic hydrocarbons (PAHs) demonstrated enhanced chromatographic performance of MWCNT-filled stationary phase by displaying substantially improved resolution and separation efficiency. Band broadening of the spots for MWCNT or EPC-filled UTLC stationary phases was also investigated and compared with that for pure PAN stationary phases. A 50% improvement in band dispersion was noted using the MWCNT based composite nanofibrous UTLC plates.     

Preparation and properties of photochromic bacterial cellulose nanofibrous membranes

The photochromic bacterial cellulose (BC) nanofibrous membranes containing 1′,3′,3′-trimethyl-6-nitrospiro(2H-1-benzopyran-2,2′-indoline) (NO₂SP) were successfully prepared by surface modification of BC nanofibers with spiropyran photochromes, and their physical and photochromic properties were characterized. The FTIR spectra indicated the interaction between BC and NO₂SP which leads to the uniform dispersion of NO₂SP in the nanofibrous membrane. SEM results demonstrated that the introduction of NO₂SP maintains the nanofibrous network structure of BC. UV/vis spectrometry of the resulting BC-NO₂SP revealed that the membranes show reversible photochromic property by changing their color from colorless to pink forming a merocyanine structure upon UV irradiation, and returning back again to colorless spiropyran structure by visible light. The contact angle of the BC-NO₂SP with water was found to be reversibly regulated due to the reversible isomerization of the spiropyran moieties in BC-NO₂SP. The result indicates that the surface modification with spiropyran photochromes expands new applications of BC nanofibers and such photochromic nanofibers with excellent photosensitivity have great potentials for sensitive displays, biosensors and other optical devices.     

Fluorescent conjugated dendrimers with fluorinated terminal groups: nanofiber formation and electroluminescence properties

Two conjugated dendrimers with fluorinated terminal groups have been designed and synthesized. Dendrimer TP1 exhibits nanofibrous self-assembly ability accompanied by an unusual blue-shifted emission from nanofibers, and TP2 shows efficient electroluminescence property in single-layer organic light-emitting diodes (OLEDs).     

Preparation and applications of novel fluoroalkyl end‐capped oligomers/polyimide/silica nanocomposites

Fluoroalkyl end‐capped acrylic acid, N,N‐dimethylacrylamide, N‐(1,1‐dimethyl‐3‐oxobutyl)acrylamide and vinyltrimethoxysilane oligomers reacted with polyamic acid possessing trimethoxysilyl groups under alkaline conditions to yield the corresponding fluoroalkyl end‐capped oligomers/polyamic acid/silica nanocomposites. These isolated fluorinated composite powders were found to afford nanometer size‐controlled fine particles with a good dispersibility and stability in water and traditional organic solvents. We succeeded in preparing new fluoroalkyl end‐capped oligomers/polyimide/silica nanocomposites by the imidization of fluorinated polyamic acid silica nanocomposites through the stepwise heating at 110 and 270°C under air atmosphere conditions. These fluorinated polyimide/silica nanocomposites thus obtained were applied to the surface modification of glass and poly(methyl methacrylate) (PMMA) to exhibit good hydro‐ and oleo‐phobic characteristics imparted by fluoroalkyl groups in the composites on their surface. In addition, the surface morphology of the modified glass treated with these fluorinated nanocomposites were analyzed by using FE‐SEM and DFM. Copyright © 2011 John Wiley & Sons, Ltd.