Characterization and antibacterial properties of Ag NPs doped nylon 6 tree-like nanofiber membrane prepared by one-step electrospinning

A hierarchically Ag/nylon 6 tree-like nanofiber membrane (Ag/PA6 TLNM) was fabricated by adding tetrabutylammonium chloride (TBAC) and silver nitrate (AgNO3) into spinning solution via one-step electrospinning. TBAC presented in PA6/formic acid (HCOOH) spinning solution was able to cause the formation of a tree-like structure due to its space steric structure and the increasing of solution conductivity. Electrospinning solvent acted as a reducing agent for in situ conversion of AgNO₃ into silver nanoparticles (Ag NPs) during the solution preparation. SEM, TEM, FT-IR XPS and XRD confirmed that Ag NPs were doped in the prepared nanofiber membrane successfully and the mechanical properties, pore size distribution and hydrophilicity of the membranes were investigated. The results showed that the tree-like structure improved the mechanical properties and hydrophilicity of the membrane while ensuring high specific surface area and small pore size. And the Ag/PA6 TLNM showed superior antibacterial properties against both E. coli and S. aureus compared with common Ag/PA6 nanofiber membranes (Ag/PA6 NMs). All of the results show that the Ag/PA6 TLNM would have potential applications in water purification.     

Preparation and Characterization of A Semi-interpenetrating Network Alkaline Anion Exchange Membrane

A series of semi-interpenetrating network (semi-IPN) anion exchange membranes (QCS/St-G_8-2-8, Quaternized chitosan/styrene-[maleic alkylene group diethyl bis (octyl dimethyl chloro/bromide), abbreviated as G_8-2-8] were prepared via in-situ polymerization by Styrene (St) and G_8-2-8 in QCS casting solution. During the process of in-situ polymerization, linear block polymers (St-G_8-2-8) of Styrene and G_8-2-8 was constructed, then was mixed with QCS casting solution, followed crosslinking the QCS by glutaraldehyde (GA). With the increasing content of linear block polymer, water uptake and swelling ratio of the composite membrane decreased; This kind of linear structure makes an order arrangement of quaternary ammonium groups which improves the OH? migration efficiency. At 70 °C, the M-30 composite membrane performs a high OH? conductivity of 8.20×10^-2 S·cm^-1, the methanol permeability is 3.23×10^-6 cm^-2·s^-1 which is still lower than Nafion 115 of 2.42×10^-6 cm^-2·s^-1, but M-30 shows a higher selectivity of 25.3 than Nafion 115 of 11.6. Furthermore, the membranes exhibited excellent thermal stability (≥150 °C), the tensile strength of the composite membrane is in the range of 14-25 MPa and elongation at break is in the range of 16-37 % at room temperature, as well as superior chemical stability in 1.0 M KOH solution for 250 h.     

A flexible nanocomposite membrane based on traditional cotton fabric to enhance performance of microbial fuel cell

A flexible and stretchable three-dimensional nanocomposite membrane based on traditional cotton fabric is a promising alternative for proton exchange membrane because it has the capability of transferring protons, is inexpensive, and also have higher current density compared to Nafion membranes in microbial fuel cells. The obtained results showed that the highest power and current of PVAc-g-PVDF-coated cotton fabric were 400±10 mW/m² and 92 mA/m², respectively. However, maximum generated power and current for Nafion-117 were 300±10 mW/m² and 60 mA/m², respectively. The highest proton conductivity of PVAc-g-PVDF-coated cotton fabric was (1.5±0.2)×10^-2 S/cm at 25 °C and lowest glucose permeability was (12±1)×10^-6 cm²/s after Mg²⁺ ions adsorption. Furthermore, the highest COD removal (85±3 %) and CE (11.2 %) were obtained from PVAc-g-PVDF-coated cotton fabric. The coated cotton fabric can provide a novel route for low-cost production of high-performance flexible proton exchange materials from the natural fabrics.     

Improvement of mechanical and electrical properties of poly(ethylene glycol) and cyanoresin based polymer electrolytes

Ionic conductivity and mechanical properties of a mixed polymer matrix consisting of poly(ethylene glycol) (PEG) and cyanoresin type M (CRM) with various lithium salts and plasticizer were examined. The CRM used was a copolymer of cyanoethyl pullulan and cyanoethyl poly(vinyl alcohol) with a molar ratio of 1:1, mixed plasticizer was ethylene carbonate (EC) and propylene carbonate (PC) at a volume ratio of 1:1. The conductive behavior of polymer electrolytes in the temperature range of 298∼338 K was investigated. The PEG/LiClO₄ complexes exhibited the highest ionic conductivity of ∼10⁻⁵ S/cm at 25°C with the salt concentration of 1.5 M. In addition, the plasticized PEG/LiClO₄ complexes exhibited improvement of ionic conductivity. However, their complexes showed decreased mechanical properties. The improvement of ionic conductivity and mechanical properties could be obtained from the polymer electrolytes by using CRM. The highest ionic conductivity of PEG/CRM/LiClO₄/(EC-PC) was 5.33×10⁻⁴ S/cm at 25°C.     

Electrospun in-situ hybrid polyurethane/nano-TiO<Subscript>2</Subscript> as wound dressings

By combining the organic-inorganic hybridization, wet phase inversion, and electrospinning, novel electrospun polyurethane (PU) membranes with in-situ generated nano-TiO₂ were prepared, which satisfied the requirements of an ideal wound dressing. The morphology of the PU-TiO₂ mats and the cross sectional morphologies of the membranes were characterized by a scanning electron microscopy (SEM). The average diameter of the individual fibers obtained from the solutions was 341±12 nm. SEM micrographs with higher magnification further showed that the in-situ generated TiO₂ particles were well-separated and dispersed homogeneously in the membranes. The average sizes of TiO₂ particles were increased from 31 to 57 nm, with the increase of nano-TiO₂ concentration. The water vapor transmission rates (WVTRs) of the membranes were in the range of 373.55–3121.86 g/m²·d and decreased gradually with the increase of nano-TiO₂ concentration. The water absorption of various PU membranes was in the range of 210.90–397.98 % which was enough to prevent wound beds from exudate accumulation. Shake flask testing indicated that the PU membrane exhibited antibacterial efficiency against Pseudomonas aeruginosa (Ps. aeruginosa) and Staphylococcus aureus (S. aureus) due to in-situ generated of nano-TiO₂. These electrospun nanofibrous membranes also had no toxic effect and showed good and immediate adherence to L929 cells.     

Decay of electrical conductivity in p-toluene sulfonate doped polypyrrole films

Long term performance of conductivity of p-toluene sulfonic acid (pTSA) doped electrochemically synthesized polypyrrole (PPy) films was estimated from accelerated aging studies between 80 °C and 120 °C. Conductivity decay experiments indicated that overall aging behavior of PPy films deviated from first order kinetics at prolonged aging times at elevated temperatures. However, an approximate value for the activation energy of the conductivity decay of PPy was calculated as E=47.4 kJ/mol, enabling an estimate of a rate constant of k=8.35×10⁻⁶/min at 20 °C. The rate of decrease of conductivity was not only temperature dependent but also influenced by the dopant concentration. A concentration of 0.005 M pTSA in the electrolyte resulted in a conductive film and when this film was exposed to 120 °C for a period of 40 h, the conductivity decayed to about 1/20 of its original value. The concentration of pTSA was increased to 0.05 mol/l and when the resulting film was aged in the same way, it showed a decrease in the conductivity to about 1/3 of its original value. Both microwave transmission and dc conductivity data revealed that highly doped films were considerably more electrically stable than lightly doped films. The dopant had a preserving effect on the electrical properties of PPy.     

Synthesis and characterization of boron doped alumina stabilized zirconia fibers

Boron doped PVA/Zr-Al acetate nanofibers were prepared by electrospinning using PVA as a precursor. The effect of calcination temperature on morphology and crystal structure was investigated at 250, 500, and 800 °C. The study also establishes the effect of boron doping on the morphology of PVA/Zr-Al acetate nanofibers at various calcination temperatures. The measurements showed that the conductivity, pH, viscosity and the surface tension of the hybrid polymer solutions have increased with boron doping. In addition, the fibers were characterized by FTIR, DSC, XPS, XRD and SEM techniques. The addition of boron did not only increase the thermal stability of the fibers, but also increased the average fiber diameters, which gave stronger fibers. The DSC results indicated that the melting temperature (Tm) of the fibers was increased from 256 to 270 °C with the addition of boron. XRD peak patterns showed that after further heat treatment at 800 °C, zirconia exists in two phases of tetragonal and monoclinic modifications. Moreover, alumina does not transform into the γ-Al₂O₃ and θ-Al₂O₃ phase at 800 °C. The SEM appearance of the fibers showed that the addition of boron resulted in the formation of crosslinked bright surfaced fibers.     

Preparation and antibacterial properties of nanocomposite fibers made of polyamide 6 and silver-doped hydroxyapatite

Nanocomposite fibers of polyamide 6 (PA6) and hydroxyapatite (HA) were prepared and doped with silver to investigate antibacterial activities due to good potential for textile modification. Nano-sized HA could be synthesized using agarose and ethanol as thickener and washing medium, respectively. The PA6/HA nanocomposite fibers could be doped with silver by dipping the fibers having HA in aqueous AgNO₃ solution containing 300 ppm of Ag ion for 1 min utilizing HA as a carrier to load silver through ion-exchange mechanism. It was found that silver was successfully doped to PA6/HA nanocomposite fibers from the EDS spectra. The nanocomposite fibers containing 3.3 wt% of HA after silver doping demonstrated such excellent antibacterial activities against K. pneumonia and E. coli that they are expected to serve as functional antibacterial materials in various application fields.     

Electrospun SiO<Subscript>2</Subscript>/PMIA nanofiber membranes with higher ionic conductivity for high temperature resistance lithium-ion batteries

The nanofiber membrane prepared by electrospinning has been widely applied in lithium-ion batteries. A powerful strategy for designing, fabricating and evaluating Poly-m-phenylene isophthalamide (PMIA) nanofiber membrane with SiO₂ nanoparticles was developed by electrospinning in this paper. The morphology, crystallinity, thermal shrinkage, porosity and electrolyte uptake, and electrochemical performance of the SiO₂/PMIA nanofiber membranes were investigated. It was demonstrated that the nanofiber membrane with 6 wt% SiO₂ possessed notable properties, such as better thermal stability, higher porosity and electrolyte uptake, resulting in higher ionic conductivity (3.23×10^-3 S·cm^-1) when compared with pure PMIA nanofiber membrane. Significantly, the SiO2/PMIA nanofiber membrane based Li/LiCoO₂ cell exhibited more excellent cycling stability with capacity retention of 95 % after 50 cycles. The results indicated that the SiO₂-doped PMIA nanofiber membranes had a potential application as separator in high temperature resistance lithium-ion batteries.     

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.     

The acid doping behavior of polybenzimidazole membranes in phosphoric acid for proton exchange membrane fuel cells

The acid doping behavior of poly(2,2′-(m-phenylene)-5,5′-bibenzimidazole) (PBI) membranes in aqueous phosphoric acid was studied at room temperature. It was found that doping phosphoric acid in the membrane obeyed a multimolecular layer absorption mechanism proposed in this work. Equation, i.e., 1/[L ^T ] _B =(1 − C ₀/17.5)/2.1, was presented to describe the relationship of the acid doping level of membranes and the concentration of the doping acid in a range of 2–14 mol L⁻¹. The acid doping kinetics as well as the influence of the doped acids on the conductivity and mechanical strength of the PBI membranes was investigated.     

Preparation and performance as PEM of sulfonated pre-oxidized nanofiber/SPEEK composite membrane

Building proton transfer channel is an important strategy to optimize the proton transfer process of the proton exchange membrane (PEM). In this work, sulfonated pre-oxidized nanofibers were prepared by solution blowing of polyacrylonitrile (PAN) nanofibers followed by pre-oxidization and sulfonating, and the nanofibers were composited with SPEEK to enhance its performance as PEM. The results of the proton conductivity verified that the employment of sulfonated pre-oxidized nanofibers improved the proton conductivity. Meanwhile, the introduction of the sulfonated pre-oxidized nanofibers realized the upgrades of the thermostability and water absorbency of the membrane, and led to the decrease of the swelling property and methyl alcohol’s permeability of the material. It is indicated that the composite membrane is promising materials for PEM fuel cells.     

Preparation of cellulose/multi-walled carbon nanotube composite membranes with enhanced conductive property regulated by ionic liquids

Cellulose/multi-walled carbon nanotubes (MWCNTs)- composite membranes applied in electrochemical and biomedical fields were prepared using 1-ethyl-3-methylimidazolium diethyl phosphate (EmimDEP) as solvent in this study. With the increasing of MWCNTs amount, the membrane conductivity increased, and the conductivity reached 9.1 S/cm as the mass ratio of MWCNTs to cellulose being 2:1. The additions of sodium dodecyl sulfate (SDS), 1-hexadecyl-3-methylimidazolium bromide (C₁₆mimBr) and 1-butyl-3-methylimidazolium tetrafluoroborate (BmimBF₄) efficiently improved the conductivity, mechanical property, and thermal stability by promoting the dispersion of MWCNTs. When the mass ratio of C₁₆mimBr to MWCNTs changed from 0 to 0.3:1, the conductivity increased from 0.08 S/cm to 0.14 S/cm, and the tensile strength increased from 13.3 MPa to 17.0 MPa. These results indicate that the binary ionic liquids (ILs) system can regulate the properties of the composite membranes, and is a feasible approach for preparing cellulose/MWCNTs composite membranes with enhanced properties.     

Carbon dioxide and methane gas permeations in thermally annealed and chemically cross-linked commercial polyimide hollow fiber membrane

Two types of modifications were performed on a commercial polyimide (PI) hollow fiber membrane for carbon dioxide (CO₂) and methane (CH₄) gas permeations. Thermal annealing was conducted between 50- and 200 °C while chemical cross-linking was performed using 0.1- to 1.0 wt% of N, (1-Naphthyl) ethylene-diamine dihydrochloride (NED). Membrane characterization revealed densification of the thermally annealed PIs. But formation of macrovoids was observed in PIs annealed near its glass transition temperature (207 °C). Fourier transform infrared spectroscopy confirmed the successful cross-linking of NED with PI. Highest CO₂ permeance was obtained from pristine PI (P/L=225 GPU) but it also had the lowest selectivity (α=72). The performances of thermally annealed (P/L=160–219 GPU, α=76–106), NED crosslinked (P/L=68–139 GPU, α=65–95) and thermally induced NED cross-linked (P/L=51-91 GPU, α=98–138) PIs varied according to modification conditions. Among the modified membranes, highest CO₂ permeance was obtained from thermally annealed PI at 100 °C (P/L=211GPU, α=106) while thermally induced NED cross-linked PI (100 °C, 0.5 wt% NED) exhibited the highest selectivity (P/L=91, α=138). Both modified membranes are the best candidates for CO₂/CH₄ separation.     

Electrical conductive and structural characterization of electrospun aligned carbon nanofibers membrane

In the paper, the membrane with aligned carbon nanofibers (CNFs) was prepared by electrospinning, stabilization and carbonization. The electrical conductivity of the membrane was examined. The effect of stabilization temperature and drum rotating speed on the conductivity of aligned CNFs membrane was discussed. The study on stabilization temperature showed that 250 °C was optimum parameter for preparing fibrous aligned CNFs membrane with uniform diameter, but 270 °C was benefit to fiber conglutination which could improve the electrical conductivity of the final CNFs membrane. The study on drum rotating speed showed that when drum rotating speed reached 2500 rpm, graphitic structures with parallel graphene sheets could be observed and 1000, 1500 and 2000 rpm CNFs membranes presented desirable conductivity with only 1.3 Ω·cm in the parallel directions and 2.0 Ω·cm in the perpendicular direction.     

Grafting of Triphenylmethyl Group onto Polyurethane and the Impact on the Shape Recovery and Flexibility at Extremely Low Temperature

The bulky and rigid triphenylmethyl group was grafted onto polyurethane (PU) to reduce the molecular attractions between hard segments and to improve the mobility of the PU chain under freezing conditions. The triphenylmethyl-grafted PU exhibited improvement in the cross-link density, solution viscosity, maximum tensile stress, shape recovery at 10 °C, and low temperature flexibility compared with the plain PU. The soft segment melting was not affected by the grafted triphenylmethyl group, whereas the soft segment crystallization disappeared with the increase of the triphenylmethyl group content. The glass transition temperature (T_g) increased with the increase of the triphenylmethyl group content. The rapid increase of the tensile strength and shape recovery at 10 °C resulted from the cross-linking effect, whereas the strain at break and shape retention at -25 °C slightly decreased with the increase of the triphenylmethyl group content. The triphenylmethylgrafted PU displayed an excellent low temperature flexibility even at -50 °C due to the improved mobility of the PU chain compared to ordinary PU.     

Preparation and properties of fibers produced from a cellulose/complex PA solvent system precipitating in diverse coagulants

Ethanol, as the first coagulation bath, and several common organic solvents, as well as aqueous solutions of NH₄Cl, NaHCO₃ and NaOH were explored and demonstrated to be adopted as the second coagulation bath for cellulose/phosphoric acid/tetraphosphoric acid (cellulose/complex PA solvent) solution to produce novel cellulose fibers by two-stage dry-wet spinning in a laboratory scale, and effect of coagulants, cellulose concentration, solvent concentration (P₂O₅ concentration) and coagulation temperature on crystal structure and properties of corresponding fibers were investigated. Surface morphology of regenerated fibers as-spun from different coagulants was observed by scanning electronic microscope (SEM), indicating that methanol and 8 wt% NaOH aqueous solution all rendered cellulose fibers relatively dense and smooth surface. X-ray diffraction (XRD) analysis showed that cellulose fiber precipitated from 8 wt% NaOH aqueous solution had pronounced characteristic peak of cellulose II than those of fibers precipitated from other coagulants, and highest crystallinity and orientation. Meanwhile, those two coagulants referred above also gave cellulose fibers relatively higher tensile strength under the same prerequisite. TGA curves exhibited that fibers were thermally stable produced from two salt aqueous solutions (8 wt% NH₄Cl and NaHCO₃) since they had the relatively higher onset decomposition temperatures. By evaluating the effect of cellulose concentration, P₂O₅ concentration and coagulation temperature on the structure and properties of asprepared fibers, it was preferable to produce cellulose fiber from a solution at 20 wt% cellulose concentration, 73 % P₂O₅ concentration, and coagulating in methanol at coagulation temperature of 60 °C at the second-stage.     

Porous Laponite/Poly(L-lactic acid) Membrane with Controlled Release of TCH and Efficient Antibacterial Performance

Fabrication of porous polymer membrane with controlled drug release and efficient antibacterial performances is of great interest in biomedical fields. In this study, Laponite (LAP) nanodisks were first used to encapsulate a model antibiotic drug, tetracycline hydrochloride (TCH). Then, drug-loaded LAP nanodisks with an optimized loading efficiency (85.3 %) were mixed with poly(L-lactic acid) (PLLA) polymer to form drug-loaded composite porous membrane via solvent coasting. The structure, morphology and swelling property of the porous membranes formed with varied solvent ratio of methylene dichloride (DCM) and dimethyl formamide (DMF) in the mixture solvent were characterized using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy and swelling test. In vitro drug release behavior, the cytotoxicity and the antibacterial activity of drug-loaded composite membranes were evaluated. Results showed that the TCH release was dependent on the physical structure of PLLA membrane and the presence of LAP nanodisks effectively weakened the initial burst release of TCH, and improved the sustained release property of porous PLLA membrane. The released TCH of TCH/LAP/PLLA_3:1 and TCH/LAP/PLLA_4:1 was 10.0 % and 5.3 % within initial 1 h, respectively. More importantly, the porous TCH/LAP/PLLA membrane was cytocompatible and displayed considerable antibacterial activity, solely associated with the loaded TCH drug, confirming its potential utility in wound dressings and tissue engineering.     

Thermal degradation studies of poly(o-anisidine) doped with 5-sulfosalicylic acid

Thermal decomposition of the solid state of poly(o-anisidine) (POAN) base (POAN-EB) and salt [doped with 5-sulfosalicylic (SSA) acid] (SSA-doped POAN) forms has been studied by thermogravimetric analysis (TGA) and differential thermal analysis (DTA) under non-isothermal conditions. The potential (PE) and optimum molecular geometric (OMG) energies of the repeating unit (tetramer form) of investigated matrix were calculated using molecular mechanics (MM+) calculations. These calculations (PE= −3.48×10⁹ and OMG=−122.72 kJ mol⁻¹) indicate that the optimum molecular geometric structure of this matrix is highly stable. The empirical formula of the doped polymer is best represented by [POAN-2SSA.n/6H₂O] and substantiate by elemental analysis and MM+ calculations. The full polymer decomposition and degradation were found to occur in three stages during the temperature increase. The decomposition activation energy (E _d) of both POAN base (POAN-EB) and its doped (SSA-doped POAN) were calculated by employing different approximations. The heating rate of decomposition and the frequency factor (k _o ) as well as kinetic parameters were calculated for doped or base form of this matrix. A remarkable heating rate dependence of the decomposition rate of the SSA-doped POAN matrix was observed.     

Copolymerization of benzyl methacrylate and a methacrylate bearing benzophenoxy and hydroxyl side groups: Monomer reactivity ratios,thermal studies and dielectric measurements

Statistical copolymers of 2-hydroxy-3-benzophenoxy propyl methacrylate (HBPPMA) and benzyl methacrylate (BzMA) in different feed ratios were synthesized by free radical copolymerization method at 60 °C in presence of AIBN initiator. The compositions of copolymer were estimated from ¹H-NMR technique. The monomer reactivity ratios of HBPPMA and BzMA were calculated as r₁ (r_HBPPMA)=0.51±0.076 and r₂ (r_BzMA)=1.07±0.140 for Kelen-Tüdos method, and was estimated as r₁=0.37±0.0006 and r₂=0.64±0.0485 according to Fineman Ross equation. The average values estimated from the two methods showed that monomer reactivity ratio of benzyl methacrylate was a slightly high in comparison to HBPPMA. The copolymer system showed an azeotropic point, which is equal to M _BzMA =m _BzMA =0.43. DSC measurements showed that the T_g’s of poly(HBPPMA) and poly(BzMA) were 84 °C and 73 °C, respectively. The T_g in the copolymer system decreased with increase in benzyl methacrylate content. The decomposition temperature of poly(BzMA) and poly(HBPPMA) occurs in a single stage at about 207 °C and 260 °C, respectively. Those of HBPPMA-BzMA copolymer systems are between decomposition temperatures of two homopolymers. The dielectric constant, dielectric loss factor and electrical conductivity were investigated depend on the frequency of the copolymers. The highest dielectric constants depending on all the studied frequencies were recorded for the poly(HBPPMA) and the copolymer containing the highest HBPPMA unit. The dielectric constant for P(HBPPMA) and P(BzMA) at 1 kHz are 6.56 and 3.22, respectively. Also, those of copolymer systems were estimated between these two values. Similarly, poly(HBPPMA) and copolymers, which are prepared under the same conditions show the dissipation factor and conductivity as well.