High flux ultrafiltration membranes based on electrospun nanofibrous PAN scaffolds and chitosan coating

Conventional ultrafiltration (UF) or nanofiltration (NF) filters for water treatments are based on porous membranes, typically manufactured by the phase immersion method. The torturous porosity in these membranes usually results in a relatively low flux rate. In this study, we demonstrated a new type of high flux UF/NF medium based on an electrospun nanofibrous scaffold (e.g. polyacrylonitrile, PAN) coupled with a thin top layer of hydrophilic, water-resistant, but water-permeable coating (e.g. chitosan). Such nanofibrous composite membranes can replace the conventional porous membranes and exhibit a much higher flux rate for water filtration. The interconnected porosity of the non-woven nanofibrous scaffold can be controlled partially by varying the fiber diameter (from about 100 nm to a few micrometers) through the electrospinning processing. The example membrane, containing an electrospun PAN scaffold with an average diameter from 124 to 720 nm and a porosity of about 70%, together with a chitosan top layer having a thickness of about 1 μm, although not yet fully optimized, exhibited a flux rate that is an order magnitude higher than commercial NF membranes in 24 h of operation, while maintaining the same rejection efficiency (>99.9%) for oily waste-water filtration.     

Processing and characterization of electrospun poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) nanofibrous membranes

Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx) nanofibrous membranes were first fabricated via electrospinning from chloroform (CHCl₃) or CHCl₃/dimethylformamide (DMF) polymer solutions. The electrospinning conditions such as the polymer concentration, the solvent composition, and the applied voltage were optimized in order to get smooth and nano-sized fibers. The crystalline structure, the melting behaviors and the mechanical properties of the obtained nanofibrous membranes were characterized. With pure CHCl₃ as the solvent in the electrospinning process, the finest smooth PHBHHx fibers were about 1 μm in diameter. When DMF is added to CHCl₃ as a co-solvent, the conductivity and volatility of the solution increased and reduced, respectively, and the electrospinnability of the polymer solution increased as a result. The averaged diameters of PHBHHx fibers could be reduced down to 300-500 nm when the polymer concentration was kept at 3 wt%, the ratio of DMF/CHCl₃ was maintained at 20/80 (wt%), and the applied voltage was fixed at 15 kV during electrospinning. WAXD and DSC results indicated that the crystallization of the PHBHHx nanofibers was restricted to specific crystalline planes due to the molecular orientation along the axial direction of the fibers. The crystallization behaviors of the electrospun nanofibers were significantly different from that of the cast membranes because of the rapid solidification and the one-dimensional fiber size effect in the electrospinning process. Mechanically, the electrospun PHBHHx nanofibrous membranes were soft but tough, and their elongation at break averaged 240-300% and could be up to 450% in some cases. This study demonstrated how the size of electrospun PHBHHx fibers could be reduced by adding DMF in the solvent and gave a clue of the presence of oriented molecular chain packing in the crystalline phase of the electrospun PHBHHx fibers.     

Crosslinking of the electrospun gelatin nanofibers

Gelatin (Gt) nanofibers have been prepared by using an electrospinning process in a previous study. In order to improve their water-resistant ability and thermomechnical performance for potential biomedical applications, in this article, the electrospun gelatin nanofibers were crosslinked with saturated glutaraldehyde (GTA) vapor at room temperature. An exposure of this nanofibrous material in the GTA vapor for 3 days generated a crosslinking extent sufficient to preserve the fibrous morphology tested by soaking in 37 °C warm water. On the other hand, the crosslinking also led to improved thermostability and substantial enhancement in mechanical properties. The denaturation temperature corresponding to the helix to coil transition of the air-dried samples increased by about 11 °C and the tensile strength and modulus were nearly 10 times higher than those of the as-electrospun gelatin fibers. Furthermore, cytotoxicity was evaluated based on a cell proliferation study by culturing human dermal fibroblasts (HDFs) on the crosslinked gelatin fibrous scaffolds for 1, 3, 5 and 7 days. It was found cell expansion took place and almost linearly increased during the course of whole period of the cell culture. The initial inhibition of cell expansion on the crosslinked gelatin fibrous substrate suggested some cytotoxic effect of the residual GTA on the cells.     

Effect of suspension medium on the electrophoretic deposition of hydroxyapatite nanoparticles and properties of obtained coatings

The suspensions of hydroxyapatite (HA) nanoparticles were prepared in different alcohols. The zeta potential of HA nanoparticles was the highest in butanolic suspension (65.65 mV) due to the higher adsorption of RCH₂OH₂⁺ species via hydrogen bonding with surface P3OH group of HA. Electrophoretic deposition was performed at 20 and 60 V/cm for different times. Deposition rate was faster in low molecular weight alcohols due to the higher electrophoretic mobility of HA nanoparticles in them. The coating deposited from butanolic suspension had the highest adhesion strength and corrosion resistance in SBF solution at 37.5 °C. The surface of this coating was covered by apatite after immersion in SBF solution for 1 week.     

Chitin and chitosan nanofibers: electrospinning of chitin and deacetylation of chitin nanofibers

An electrospinning method was used to fabricate chitin nanofibous matrix for wound dressings. Chitin was depolymerized by gamma irradiation to improve its solubility. The electrospinning of chitin was performed with 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) as a spinning solvent. Morphology of as-spun and deacetylated chitin (chitosan) nanofibers was investigated by scanning electron microscopy. Although as-spun chitin nanofibers had the broad fiber diameter distribution, most of the fiber diameters are less than 100 nm. From the image analysis, they had an average diameter of 110 nm and their diameters ranged from 40 to 640 nm. For deacetylation, as-spun chitin nanofibous matrix was chemically treated with a 40% aqueous NaOH solution at 60 or 100 °C. With the deacetylation for 150 min at 100 °C or for 1day at 60 °C, chitin matrix was transformed into chitosan matrix with degree of deacetylation (DD) ∼85% without dimensional change (shrinkage). This structural transformation from chitin to chitosan was confirmed by FT-IR and WAXD.     

Fabrication and characterization of poly(l-lactic acid) 3D nanofibrous scaffolds with controlled architecture by liquid-liquid phase separation from a ternary polymer-solvent system

Poly(l-lactic acid) (PLLA) three-dimensional (3D) scaffold with macro/micropores and nanofibrous structure was fabricated by phase separation from a ternary PLLA/dioxane/water system. The pore size was mainly determined by the coarsening effects in the phase separation process, while the nanofibrous structure was due to the formation of PLLA microcrystallite domains in the gelation process. Increasing the gelation temperature or the content of water in the mixed solvent system, the pore size definitely increased and macropores up to 300 μm were observed. However, coalescence of nanofibers occurred, even platelet-like structure appeared at gelation temperatures higher than 12 °C or the proportion of water exceeded 12%. X-ray diffraction (XRD) and Differential Scanning Calorimetry (DSC) analyses demonstrated that the crystallinity degree increased with increasing the gelation temperature or the non-solvent volume ratio in the mixed system. Moreover, the results indicated that α′ was mainly corresponding to the nanofibers structure, while α crystal was detected in the platelet-like structure. Scanning electron micrograph (SEM) and methyl thiazolyl tetrazolium (MTT) assays indicated that the nanofibrous scaffold provided a better attachment and viability of MSCs (rat derived mesenchymal stem cells) than the platelet-like scaffold.     

Facile preparation and separation performances of cellulose nanofibrous membranes

Ultrafiltration (UF) is a size selective pressure‐driven membrane separation process increasingly required for high efficient water treatment and suspended solids removal in many industrial applications. This study examined the morphology of as‐prepared cellulose nanofibers and then utilized the nanofibers dispersion to fabricate nanofibrous nanoporous membranes with potential wide applications in various fields including water treatment. The nanofibers were prepared using a simple and powerful mechanical high intensity ultrasonication following a pre‐chemical treatment of α‐cellulose. The cellulose nanofibers’ morphology, crystallinity, and yield were found to be influenced by pre‐chemical treatment. Cellulose nanofibrous membranes were fabricated from cellulose nanofibers dispersion on a porous support. A nanoporous structure with an extensive interconnected network of fine cellulose nanofibers was formed on the support substrate. The resulting membranes exhibited typical and high‐efficient UF performances with high water fluxes of up to 2.75 10³ L/m²/h/bar. The membranes also displayed high rejections for ferritin and 10 nm gold nanoparticles with a reactive surface area capable of rapidly decolorizing methylene blue from its aqueous solution. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43544.     

High strength antibacterial membranes consisted of nanofibrous chitosan immobilized silver nanoparticles

Chitosan (CS) has biocompatibility and biodegradability, but the bulk CS hydrogel/membranes with its poor strength and limited antibacterial property could not satisfy the practical application. Here green dissolving/regeneration and in situ reduction strategy was combined to construct high strength antibacterial CS membranes. First nanofibrous CS hydrogels were constructed through dissolving CS in LiOH/KOH/urea aqueous system via freezing–thawing process followed regeneration. Then, Ag NPs were immobilized along CS nanofibers through in situ reductions of Ag + by the NH₂ group of CS. The obtained NCM-Ag composite dry membranes are easy for storing and can quick switch to nanofibrous hydrogels as absorbing water. Size of Ag NPs can be controlled to very small until 2 nm by concentration and limited space network. Fourier transform infrared spectroscopy and X-ray photoelectron spectrometer indicated the forceful grasp ability of CS nanofibers to Ag NPs for a stable binding, mechanical property was enhanced over 100Mpa as the nanofibrous structure and chain linked by Ag coordination. The NCM-Ag membranes had excellent antibacterial activities against both Staphylococcus aureus and Escherichia coli. Moreover, such nanofibrous CS membrane exhibited good adhesive ability to tissues. Combining all these properties, NCM-Ag membranes would be potential as antibacterial adhesion barrier to accelerate wound healing.     

Influence of Post-Treatment with 75% (v/v) Ethanol Vapor on the Properties of SF/P(LLA-CL) Nanofibrous Scaffolds

In order to improve the water-resistant ability of silk fibroin (SF) and SF/P(LLA-CL) blended nanofibrous scaffolds for tissue engineering applications, 75% (v/v) ethanol vapor was used to post-treat electrospun nanofibers. SEM indicated that the treated SF and SF/P(LLA-CL) nanofibrous scaffolds maintained a nanofibrous structure and possessed good water-resistant ability. Characterization of (13)C CP-MAS NMR clarified that 75% (v/v) ethanol vapor could induce SF conformation from random coil or α-helix to β-sheet. Although the water contact showed that treated SF/P(LLA-CL) blended nanofibrous scaffolds were hydrophobic, the water uptake demonstrated that their hydrophilicity was greatly superior to those of pure P(LLA-CL) nanofibrous scaffolds. Furthermore, the treated SF/P(LLA-CL) nanofibrous scaffolds, both in dry state and wet state, could retain good mechanical properties. Therefore, 75% (v/v) ethanol vapor treatment might be an ideal method to treat SF and SF/P(LLA-CL) nanofibrous scaffolds for biomedical applications.     

Synthesis and characterization of high molecular weight perfluorocyclobutyl-containing polybenzimidazoles (PFCB-PBI) for high temperature polymer electrolyte membrane fuel cells

High molecular weight perfluorocyclobutyl-containing polybenzimidazoles (PFCB-PBI) were synthesized from 4,4′-((1,2,3,3,4,4-hexafluorocyclobutane-1,2-diyl)bis(oxy))dibenzoic acid (PFCB diacid) and 3,3′,4,4′-tetraaminobiphenyl (TAB) in phosphorous pentoxide/methanesulfonic acid (PPMA). PPMA was used as a reaction medium to replace PPA due to the higher monomer solubility. High molecular weight polymer was achieved via optimization of the monomer/solvent ratio, polymerization temperature, and polymerization time. The resulting polymer showed good thermal and chemical stability. Several different phosphoric acid doping membrane preparation processes were investigated. Conventional DMAc solvent casting and direct-casting of the PBI/PPMA solution did not produce sufficiently strong membranes to fabricate into MEAs. A modified PPA process was developed that produced improved membranes. The mechanical properties of these membranes were low compared to other PBI membranes; however, they were sufficiently strong to fabricate into membrane electrode assemblies and tested in single cell fuel cells under various conditions. The polymer dissolved in phosphoric acid at temperatures above 140 °C, which limited the operation of fuel cells below 140 °C. The maximum power densities of fuel cells operated with these membranes were similar to meta-PBI membranes prepared by the conventional casting process and lower than para-PBI membranes prepared by the PPA process.     

Preparation of chitosan bicomponent nanofibers filled with hydroxyapatite nanoparticles via electrospinning

Chitosan (CS) bicomponent nanofibers with an average diameter controlled from 100 to 50 nm were successfully prepared by electrospinning of CS and poly(vinyl alcohol) (PVA) blend solution. Finer fibers and more efficient fiber formations were observed with increased PVA contents. On this contribution, a uniform and ultrafine nanofibrous CS bicomponent mats filled with hydroxyapatite (HA) nanoparticles were successfully electrospun in a well devised condition. An increase in the contents of HA nanoparticles caused the conductivity of the blend solution to increase from 1.06 mS/cm (0 wt % HA) to 2.27 mS/cm (0.5 wt % HA), 2.35 mS/cm (1.0 wt % HA), respectively, and the average diameter of the composite fibers to decrease from 59 ± 10 nm(0 wt % HA) to 49 ± 10 nm (0.5 wt % HA), 46 ± 10 nm (1.0 wt % HA), respectively. SEM images showed that some particles had filled in the nanofibers whereas the others had dispersed on the surface of fibers, and EDXA results indicated that both the nanoparticles filled in the nanofibers and those adhered to the fibers were HA particles. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Thiol-modified cellulose nanofibrous composite membranes for chromium (VI) and lead (II) adsorption

Oxidized cellulose nanofibers (CNF), embedded in an electrospun polyacrylonitrile (PAN) nanofibrous scaffold, were grafted with cysteine to increase the adsorption capability for chromium (VI) and lead (II). Thiol-modified cellulose nanofibers (m-CNF) were characterized by titration, FT-IR, energy dispersive spectroscopy (EDS) and SEM techniques. Static and dynamic Cr(VI) and Pb(II) adsorption studies of m-CNF nanofibrous composite membranes were carried out as a function of pH and of contact time. The results indicated these membranes exhibited high adsorption capacities for both Cr(VI) (87.5 mg/g) and Pb(II) (137.7 mg/g) due to the large surface area and high concentration of thiol groups (0.9 mmol of –SH/gram m-CNF). The morphology and property of m-CNF nanofibrous composite membranes was found to be stable, and they could be used and regenerated multiple times with high recovery efficiency.     

Porous hydroxyapatite ceramics by ice templating: Freezing characteristics and mechanical properties

Ice templating produces porous hydroxyapatite (HA) scaffolds with a lamellar morphology and aligned channels when using aqueous HA slurries. We investigated the freezing characteristics of HA slurries with regard to the pore structures of the porous HA scaffolds. We found that by increasing the cooling rate, the lamellar spacing decreased. The average lamellar spacing is about 785.7 μm at a cooling rate of 1.3 °C/min. The porous geometry changes from lamella and well aligned channels to a partial dendrite and partially aligned cavities with a decrease in the initial nucleation temperature and an increase in the degree of supercooling. Additionally, we determined the relationship between compressive strength and porosity. The compressive strength of the porous HA scaffolds reach 6.7 MPa at a porosity of 64% and the lamellar spacing is about 124 μm.     

Polysulfone ionomers for proton-conducting fuel cell membranes: 2. Sulfophenylated polysulfones and polyphenylsulfones

Polysulfones and polyphenylsulfones having pendant phenyl groups with sulfonic acid units have been prepared by lithiation of the respective polymer, followed by reaction with 2-sulfobenzoic acid cyclic anhydride. The resulting ionomers were cast into membranes and properties such as thermal stability, ion-exchange capacity, water sorption and proton conductivity were evaluated. These membranes proved to have a high thermal stability, with a decomposition temperature between 300 and 350 °C, and a high proton conductivity, 60 mS/cm at 70 °C for a polyphenylsulfone with 0.9 sulfonic acid group per repeating unit measured at 100% relative humidity. Moreover, some of the membranes endured immersion in water at temperatures ranging from 20 to 150 °C without swelling extensively, and therefore kept their mechanical stability under these conditions. It was also shown that these membranes retained a high conductivity up to 150 °C under humidifying conditions. The combination of properties make these membranes potential candidates for fuel cells operating at temperatures above 100 °C.     

Modeling and optimization of sulfonated poly (ether ether ketone) nanofibrous proton exchange membranes with response surface methodology

The morphological control of proton conductive nanofibrous mat used in proton exchange membranes (PEMs) is a key issue to improve proton conductivity of PEMs. In this study, response surface methodology (RSM) was utilized to investigate the morphological characterizations of electrospun sulfonated poly (ether ether ketone) (SPEEK) nanofibrous membranes. The effects of electrospinning parameters namely solution concentration, applied voltage and tip to collector distance were studied on the average diameter, its standard deviation and the degree of alignment of SPEEK nanofibers. The adequacy of the response surface models was verified by the validation experiments. Optimized conditions were obtained to meet the desired status of collecting more uniform and finer nanofibers with improved alignment. After obtaining the significant factors and optimal test level, an additional optimization was conducted at different take‐up speeds to fabricate high‐grade aligned nanofibers. The resultant nanofibers had the diameter of 107 ± 22 nm at the optimum point which was in good agreement with the predicted response values. The highest degree of alignment was yielded at the take‐up speed of 8.8 m/s with the maximum second‐order orientation parameter of 0.869. Electrochemical spectroscopy analysis showed that the aligning of proton conductive nanofibers improved in‐plane proton conductivity about 67%. POLYM. ENG. SCI., 2017. © 2017 Society of Plastics Engineers     

Enhanced simulated solar sono-photocatalytic performance and antibacterial activities of ZnO/NiO heterojunction nanofibrous membranes

ZnO/NiO heterojunction nanofibrous membranes with different Zn/Ni molar ratios were successfully prepared via electrospinning. The microstructures of the nanofibers were characterized by using scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy. The ZnO/NiO heterojunction nanofibrous membranes showed superior photocatalytic performance on Congo red, particularly under ultrasonic action and simulated solar irradiation. The degradation of Congo red could reach 100% after 40 min with a high degradation constant of 0.064 min^?1. Additionally, the catalyst maintained high photocatalytic activity over five cycles. Furthermore, the heterojunction nanofibrous membranes had good antibacterial effects on Escherichia coli and Staphylococcus aureus with an inhibition zone width of above 8 mm. The generation of superoxide free radical and hydroxyl free radicals played important roles for the heterojunction nanofibrous membranes. This work is significant for studying the potential applications of nanofibers in waste water remediation.     

Electrospinning of chitosan-poly(ethylene oxide) blend nanofibers in the presence of micellar surfactant solutions

Nanofibers were fabricated by electrospinning a mixture of cationic chitosan and neutral poly(ethylene oxide) (PEO) at a ratio of 3:1 in aqueous acetic acid. Chitosan ((1 → 4)-2-amino-2-deoxy-β-d-glucan) is a multifunctional biodegradable polycationic biopolymer that has uses in a variety of different industrial applications. Processing conditions were adjusted to a flow rate of 0.02 ml/min, an applied voltage of 20 kV, a capillary tip-to-target distance of 10 cm and a temperature of 25 °C. To further broaden the processing window under which nanofibers are produced, surfactants of different charge were added at concentrations well above their critical micellar concentrations (cmc). The influence of viscosity, conductivity and surface tension on the morphology and physicochemical properties of nanofibers containing surfactants was investigated. Pure chitosan did not form fibers and was instead deposited as beads. Addition of PEO and surfactants induced spinnability and/or yielded larger fibers with diameters ranging from 40 nm to 240 nm. The presence of surfactants resulted in the formation of needle-like, smooth or beaded fibers. Compositional analysis suggested that nanofibers consisted of all solution constituents. Our findings suggest that composite solutions of biopolymers, synthetic polymers, and micellar solutions of surfactants can be successfully electrospun. This may be of significant commercial importance since micelles could serve as carriers of lypophilic components such as pharmaceuticals, nutraceuticals, antimicrobials, flavors or fragrances thereby further enhancing the functionality of nanofibers.     

Tough organogels based on polyisobutylene with aligned porous structures

Macroporous gels with aligned porous structures were prepared by solution crosslinking of butyl rubber (PIB) in cyclohexane at subzero temperatures. Sulfur monochloride was used as a crosslinker in the organogel preparation. The reactions were carried out at various temperatures between 20 and −22 °C as well as at various freezing rates. The structure of the gel networks formed at −2 °C consists of pores of about 100 μm in length and 50 μm in width, separated by polymer domains of 10-20 μm in thickness. The aligned porous structure of PIB gels indicates directional freezing of the solvent crystals in the direction of the temperature gradient. The size of the pores in the organogels could be regulated by changing the freezing rate of the reaction solution. The results suggest that frozen cyclohexane templates are responsible for the porosity formation in cyclohexane. In contrast to the regular morphology of the gels formed in cyclohexane, benzene as a crosslinking solvent produces irregular pores with a broad size distribution from micrometer to millimeter sizes due to the phase separation of PIB chains at low temperatures. Macroporous organogels prepared at subzero temperatures are very tough and can be compressed up to about 100% strain without any crack development. The gels also exhibit superfast swelling and deswelling properties as well as reversible swelling-deswelling cycles in toluene and methanol, respectively.     

P123对聚醚砜纳米纤维膜结构和性能的影响

通过静电纺丝法制备了聚醚砜(PES)/聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物(P123,PEO₂₀PPO₇₀PEO₂₀,M_a=5800)纳米纤维膜,考察了P123含量对纺丝液的黏度和表面张力的影响,以及对所制备的纳米纤维膜的结构和性能的影响。实验结果表明:P123含量从3%(质量)增至9%时,其纺丝液的黏度由300 mPa·s增至1000 mPa·s,表面张力在36.5～37.8 mN·m^-1范围内;P123改性的PES纳米纤维直径约为360 nm,分布均匀,其表面也比较光滑,取向趋于一致;此外,该纳米纤维膜具有良好的机械性能和耐溶胀性能,较大的比表面积(>39 m²·g^-1),孔隙率,可用作催化剂载体。     

In vitro biodegradable and mechanical performance of biphasic calcium phosphate porous scaffolds with unidirectional macro-pore structure

In this study, porous biphasic calcium phosphate (BCP) scaffolds were fabricated by a freeze–gel casting technique using a tertiary-butyl alcohol (TBA) based slurry. After sintering, unidirectional macropore channels of scaffolds aligned regularly along the TBA ice growth direction were tailored simultaneously with micropores formed in the outer wall of the pore channels. The synthesized porous BCP scaffolds (two different sintering temperatures) exhibit compressive strength of 46.8 MPa for 43.0% porosity and 33.1 MPa for 45.9% porosity, respectively. After immersion in Hank's balanced salt solution (HBSS) for 1, 2, 4, 8 weeks, a precipitation started to be formed with individual small granules on the scaffolds surface. In the case of BCP scaffolds sintered at 1200 °C, β-TCP were slowly degraded with increasing the immersing time; on the other hand, α-TCP (from BCP scaffolds sintered at 1300 °C) was extremely degraded within 1 week of immersing. This behavior could be due to a fast hydrolysis (dissolution–reprecipitation) as a phase transformation from α-TCP to brushite or apatite compared to the β-TCP. After immersion in HBSS, overall the compressive strength of the scaffolds reduced by the gradual degradation in biological environment solution. This behavior is consistent with the degradation behavior of scaffolds after immersion in HBSS.