The effects of solution properties and polyelectrolyte on electrospinning of ultrafine poly(ethylene oxide) fibers

The effects of solution properties and polyelectrolyte on the electrospinning of poly(ethylene oxide) (PEO) solutions were investigated. Ultrafine PEO fibers without beads were electrospun from 3, 4, 7 and 7 wt% PEO solutions in chloroform, ethanol, (dimethylformamide) DMF and water, respectively. At these concentrations, the values of [η]C were ∼10 for all solutions. The average diameters of PEO fibers were ranged from 0.36 to 1.96 μm. The higher the dielectric constant of solvent was, the thinner PEO fiber was. The average diameters of electrospun PEO fibers from PEO/water solutions were decreased and their distributions were narrowed by adding 0.1 wt% poly(allylamine hydrochloride) (PAH) and poly(acrylic acid sodium salt) (PAA) due to the increased charge density in solutions. The addition of PAH and PAA lowered the minimum concentration for electrospinning of a PEO/water solution to 6 wt%.     

Rheological properties of poly(ethylene oxide) aqueous solutions

This article describes the rheological properties of certain poly(ethylene oxide)s dissolved in water-based solvents. The experimental results show that the rheological properties in aqueous solutions are significantly affected by the solvent properties, which have been changed by the use of ethanol–water mixtures and electrolyte solutions and by the variation of the ambient pressure and temperature. The variation of the temperature and pressure is seen to change the polymer chain configuration and also the interactions of polymer segments with the solvent molecules. This gives rise to distinctive and apparently unusual rheological properties for these systems with the variation of the ambient temperature and pressure. The study generally illustrates that the rheology of these systems are, to a large degree, influenced by the hydrogen bonding in the solvent and between the solvent as well as the polymer. At a first-order level, the increase of the pressure and the temperature and also the addition of electrolytes, and the inclusion of an aqueous diluent, produce comparable effects. In essence, these changes seem to disrupt the hydrogen bonding structure in the solutions and, hence, the solvent quality in a comparable fashion. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 419–429, 1998     

Eudragit E100/poly(ethylene oxide) electrospun fibers for DNA removal from aqueous solution

The development of new strategies for production of low-cost deoxyribonucleic acid (DNA) adsorbents based on electrospun fibers of block copolymers [Eudragit E-100/poly(ethylene oxide) (PEO)] is a promising way for fast retrieval of free of degradation double-stranded DNA chains from aqueous solution. The adsorption takes place through electrostatic interaction between DNA and oppositely charged electrospun fibers that provide high surface area for DNA adsorption. The adsorption capacity observed for electrospun fibers of Eudragit E100/PEO (considering as target molecules the salmon sperm DNA) was in order of 44.31 mg g⁻¹, following the Langmuir model in a typical adsorption at solid/liquid interface (pseudo-second-order model), that characterizes the electrospun fibers as promising templates for removal of biologic components and further use in molecular biology techniques, as DNA amplification by polymerase chain reaction. The reuse and integrity of membranes after long period of adsorption were tested, confirming the potential of material as adsorbent. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47479.     

Electrospun ultrafine composite fibers from organic‐soluble chitosan and poly(ethylene oxide)

The ultrafine composite fibers had been successfully achieved by electrospinning of chloroform solutions of octadecyl chitosan (O‐CS) and poly(ethylene oxide) (PEO). The ultrafine composite fibers membranes were subjected to detailed analysis by Fourier‐transformed infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and water contact angle (WCA). The FTIR results confirmed that ultrafine composite fibers contained the two polymers. The SEM images showed that the morphology and diameter of the composite fibers were mainly affected by the weight ratio of O‐CS/PEO, the electric field strength, and the collection distance. The WCA data demonstrated that the composite fibers membranes performed a quite hydrophobic character. The special morphology of neck and porous structure was observed experimentally during electrospinning. The neck structure was due to the fibers elongated in the direction of stretching through the electric field, and the porous structure was decided by the competition between the phase separation and the fast evaporation rate of chloroform. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Corona discharge from electrospinning jet of poly(ethylene oxide) solution

Corona discharges from electrospinning jets were observed and photographed at the tip of the Taylor cone, and in a cylindrical region around the jet, a few millimeters below the tip. The corona discharge was also faintly visible to a dark adapted eye. At the position at which the cylindrical corona discharge became apparent, typical conditions were a jet diameter of 30 μm, an applied potential of 12 kV, and a calculated radial electric field of 400 kV/cm, The calculated electric field required to create a corona in air around a metal wire of the same diameter, calculated from Peek's empirical formula, was only about 200 kV/cm. The cross sectional shape of some segments of the electrospun fibers had two or three lobes. The lobes often separated, and formed smaller fibers.     

Fluorescent poly(p-phenylene vinylene)/poly(ethylene oxide) nanofibers obtained by electrospinning

Poly(p-phenylene vinylene) (PPV)/poly(ethylene oxide) (PEO) hybrid nanofibers were prepared by electrospinning a composite solution of PPV precursor/PEO in a mixture of ethanol and water, followed by thermal conversion. The precursor/PEO composite solutions were successfully electrospun into nanofibers with diverse helical, helical and linear, and helical bead-on-string morphologies by controlling the amount of aqueous PEO solution in a composite solution. Moreover, adding aqueous PEO solution to a precursor ethanol solution decreased the diameters of the fibers. The experimental data suggest that the viscosity, conductivity, and surface tension of the electrospinning solution are the main factors that influence the morphology of the fibers. Fourier transform infrared (FT-IR) and X-ray diffraction (XRD) investigations indicated that the PPV precursor reacts with PEO during thermal conversion. Ultraviolet–visible (UV-vis) and photoluminescence (PL) spectra of the PPV-PEO nanofibers exhibited appreciable blue shifts with the addition of PEO, which made it possible to fabricate nanofibers with fluorescence ranging from yellow-green to blue. These highly fluorescent PPV/PEO nanofibers with various morphologies are potentially interesting for many applications, such as micro- and nanooptoelectronic devices and systems.     

Fabrication of ultrafine fibers of poly(γ-glutamic acid) and its derivative by electrospinning

Poly(γ-glutamic acid) (PGA) was successfully electrospun by the addition of poly(ethylene glycol) (PEG) and Triton X-100 in its aqueous solution to produce the PGA non-woven mat of the ultrafine fibers. The average fiber diameter was in the range between 200 nm and 2 μm. The fiber mat was quickly soluble in water due to the large surface area of the fibers. The electrospinning of PGA butyl ester with the esterification degree of 61% in 1,1,1,3,3,3-hexafluoro-2-propanol gave the water-insoluble nanofiber mat.     

Synthesis of ultrafine poly(styrene‐maleic anhydride) and polystyrene fibers by electrospinning

Fiber formation from atactic polystyrene (aPS) and alternating poly(styrene‐maleic anhydride) (PSMA) synthesized by free radical polymerization (AIBN, 90°C, 4 h) were investigated by electrospinning from various solutions. aPS was soluble in dimethylformamide (DMF), tetrahydrofuran (THF), toluene, styrene, and benzene, whereas PSMA was soluble in acetone, DMF, THF, dimethylsulfoxide (DMSO), ethyl acetate, and methanol. aPS fibers could be electrospun from 15 to 20% DMF and 20% THF solutions, but not from styrene nor toluene. PSMA, on the other hand, could be efficiently electrospun into fibers from DMF and DMSO at 20 and 25%, respectively. Few PSMA fibers were, however, produced from acetone, THF, or ethyl acetate solutions. Results showed that solvent properties and polymer–solvent miscibility strongly influenced the fiber formation from electrospinning. The addition of solvents, such as THF, generally improved the fiber uniformity and reduced fiber sizes for both polymers. The nonsolvents, however, had opposing effects on the two polymers, i.e., significantly reducing PSMA fiber diameters to 200 to 300 nm, creating larger and irregularly shaped aPS fibers. The ability to incorporate the styrene monomer and divinylbenzene crosslinker in aPS fibers as well as to hydrolyze PSMA fibers with diluted NaOH solutions demonstrated potential for post‐electrospinning reactions and modification of these ultrafine fibers for reactive support materials. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation of photochromic poly(vinylidene fluoride-co-hexafluoropropylene) fibers by electrospinning

Photochromic poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-co-HFP) fibers were prepared by electrospinning from a solution of copolymer and ester-functionalized nitrospiropyran (SPEST) molecules. The surface and internal features of the electrospun (ES) fibers were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and wide-angle X-ray diffraction (WAXD). The strong segregation of fluorine-rich groups on the fiber surface, which occurs during and/or after the electrospinning process, is driven by the lower surface tension for fluorine-rich groups and leads to encapsulation of SPEST predominantly near the core of the fibers, as confirmed by both X-ray photoelectron spectroscopy (XPS) and dynamic water contact angle (CA) measurements. The photochromic behavior of the spiropyran is preserved in the polymeric fibers, as confirmed by steady-state absorption and emission spectroscopy. Both isomeric forms of the photochrome in SP-PVDF-co-HFP were emissive, an effect that is thought to be due to the steric and/or electrostatic restrictions on the ring-opening reaction imposed by the fiber.     

Efficient removal of cationic dyes from aqueous solutions using a modified poly(ethylene terephthalate) fibers adsorbent

ABSTRACT

A novel adsorbent was synthesized through functionalization of glycidyl methacrylate-g-poly(ethylene terephthalate) (GMA-g-PET) fibers with iminodiacetic acid (IDA) to give IDA-GMA-g-PET fibers. This adsorbent was then exploited for the removal of Malachite Green (MG) and Rhodamine B (RB) dyes. MG has shown faster adsorption kinetics and equilibrium was attained in 15 mins. and 90 mins. for MG and RB, respectively. IDA-GMA-g-PET fibers showed 100% removal efficiency for MG and RB dyes from the solutions having initial concentrations of 300 mg L^?1and 200 mg L^?1, respectively. Desorption conditions of dyes and reusability of the fibers were also investigated.     

Adsorption of hexavalent chromium from aqueous solutions using 4-vinyl pyridine grafted poly(ethylene terephthalate) fibers

Summary Sorption of hexavalent chromium ions from aqueous solution by 4- vinyl pyridine (4-VP) grafted poly(ethylene terephthalate) (PET) fibers was studied. The Influences of adsorption time, pH of solution and Cr(VI) concentration on the adsorbed amount were investigated. 30 minutes of treatment time was found to be sufficient to reach equilibrium. pH 3.0 was found as the optimum pH value in the process. The maximum adsorption capacity of the material (k_s) was found to be 263.16 mg g^-1. It was found that the reactive fibers are stable and regenerable by acid or base without losing their activity.     

Effect of evaporation and solidification of the charged jet in electrospinning of poly(ethylene oxide) aqueous solution

The electrospinning process uses electrical force to produce nanofibers. A charged droplet acquires a conical shape known as the Taylor cone and then becomes unstable. A charged jet emerges from the vertex and develops a spiral path due to the electrically driven bending instability, which makes it possible, in a small space, for the jet to elongate by a large amount and produce nanofibers. Evaporation and the associated solidification were identified as important factors that affect the diameter of electrospun nanofibers. In this study, the evaporation rate and solidification of the charged jet were controlled by varying the relative humidity during electrospinning of poly(ethylene oxide) from aqueous solution. As the relative humidity increased, the solidification process became slower, allowing elongation of the charged jet to continue longer and thereby to form thinner fibers. As the relative humidity increased from 5.1% to 48.7%, the diameter of the solidified fiber decreased from 253 nm to 144 nm. As the relative humidity increased above 50%, beads formed on the thinner fibers, indicating that the capillary instability occurred before the jet solidified. The vapor concentration of solvent is an effective electrospinning process control parameter of fiber diameter that also produces a systematic change in the development of beads on the fibers.     

Phase separation phenomena in aqueous solutions of amphiphilic poly(ethylene oxide) star polymers

Three- and four-armed star polymers with poly(ethylene oxide) arms capped with hydrophobic end-groups were synthesized from nonylphenoxypoly(ethylene glycol)s and well defined tri- and tetraisocyanates. The latter were hydrosilylation products of m-isopropenyl-,-dimethylbenzyl isocyanate (m-TMI). In aqueous solution the arm ends associate, and above a critical star concentration the mixture phase separates into a dilute phase and a condensed gel phase. Their respective polymer concentrations remain constant as long as the two phases coexist, their volume fractions being proportional to the total polymer concentration. Brookfield viscosity measurements confirm the formation of the gel phase which resembles an amphiphilic hydrogel. It exhibits a high affinity for hydrophobic compounds.     

Aggregate formation in poly(ethylene oxide) solutions

Static light scattering and viscosity measurements were performed on different molecular weight poly (ethylene oxide) to see the formation of aggregates in its dilute solutions. Viscosity measurements were carried out for PEO samples in water and methanol at 20–45°C and in chloroform at 20–30°C. Using Huggin's equation, the viscosity plots showed distinct upward curvature indicating the presence of aggregates in both PEO/H₂O and PEO/CH₃OH solutions The [η] values for PEO/H₂O and PEO/CH₃OH system were 2–4 times as large as observed for other linear flexible polymers in good solvents thus showing extensive coil swelling/aggregation. This is also apparent from the exponent a values of the Mark–Houwink–Sakurada equation. Light Scattering results using Zimm method showed that aggregation occurred in low molecular weight samples; however, in higher molecular weight samples there was a little evidence for aggregation both in water and methanol. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2578–2583, 2006     

Stability and phase behavior of the poly(ethylene oxide)-urea complexes prepared by electrospinning

The poly(ethylene oxide)-urea binary system forms a stable (α) complex that can be melt-quenched into a mixture of urea and a second (β) complex with a different stoichiometry. Our results confirm that this mixture is metastable, but that the β-α solid-solid transition is much slower than previously reported. In contrast with the melt-quenched mixture, we observe for the first time that the pure β complex, prepared by electrospinning, is thermodynamically stable up to its melting temperature. This melting is incongruent and leads to the formation of the crystalline α complex and liquid PEO. A phase diagram is drawn over the complete composition range and allows interpreting the formation of the various out-of-equilibrium mixtures observed experimentally. This work also demonstrates an interesting new possibility of electrospinning: the direct preparation of thermodynamically stable compounds that are otherwise inaccessible because of the formation of kinetically frozen products.     

Polyurethane networks based on poly(ethylene oxide)

A wide range of infinite urethane polymer networks were prepared from poly(ethylene glycol) (PEG) and hexamethylene diisocyanate (HMDI) using 1,1,1-tris-(hydroxymethyl) ethane (THME) as the cross-linking agent. The influence of temperature, cross-linking, and crystallinity on the swelling character of the hydrogel has been discussed. The toxicity of the network polymer by intravaginal implants in rats was studied. Implantation of the polymer did not result in alteration in behavior and feed intake or any pathological changes in the tissue. Vaginal fluids from the polymer-implanted rats or the polymer extract when inoculated on a listeria monocytogene culture plate were unable to inhibit the bacterial growth. © 1993 John Wiley & Sons, Inc.     

Preparation and characterization of poly(lactic acid)/poly(ethylene oxide) blend film: effects of poly(ethylene oxide) and poly(ethylene glycol) on the properties

Poly(lactic acid) (PLA) film plasticized with poly(ethylene oxide) (PEO) at various weight percentages (1–5 wt%) was prepared to improve the elongation, thus overcoming the inherent brittleness of the material. After optimization of the amount of PEO (4 wt%) through mechanical analysis, poly(ethylene glycol) (PEG), a well‐established plasticizer of PLA, was added (0.5–1.5 wt%) without hampering the transparency and tensile strength much, and again its amount was optimized (1 wt%). Neat PLA and PLA with the other components were solvent‐cast in the form of films using chloroform as a solvent. Improvement in elongation at break and reduction in tensile strength suggested a plasticizing effect of both PEO and PEG on PLA. Thermal and infrared data revealed that the addition of PEO induced β crystals in PLA. Scanning electron micrographs indicated a porous surface morphology of the blends. PEO alone in PLA exhibited the best optical clarity with higher percentage crystallinity, while PEG incorporation in PLA/PEO resulted in superior barrier properties. Also, the stability of the blends under a wide range of pH means prospective implementation of the films in packaging of food and non‐food‐grade products. © 2018 Society of Chemical Industry     

Turbulent friction reduction by aqueous poly(ethylene oxide) polymer solutions as a function of salt concentration

Turbulent friction reduction by high molecular weight poly(ethylene oxide) polymers has been examined in a series of salt solutions ranging from pure water to nearly theta solvent conditions. The effects of polymer homology and solvent character have been successfully analyzed under these conditions and relationships are proposed for the observed effects. The reduction in turbulent friction (drag reduction) has been catalogued through evaluation of the polymer intrinsic concentration—an index of drag reduction effectiveness. Plots of the reciprocal of the polymer intrinsic concentration versus salt molarity are approximately linear and are similar to the plots of intrinsic viscosity versus molarity reported by other workers. An attempt is made to graphically and numerically combine these results. The suggestion is advanced that those solvent properties which bring about decided conformational changes in these polymer molecules (as indexed by intrinsic viscosity effects) also affect, in an apparently analogous fashion, the turbulent friction reduction efficiencies of these molecules. The decreases in turbulent friction reduction resulting from the increasingly collapsed state of the polymer coil suggest the possibility of correlating friction reduction with changes in the polymer expansion factor α. On the basis of the limited data available, the suggestion is also made that drag reduction studies might best be made under theta solvent conditions where different polymer families might be more meaningfully compared in the absence of solvent effects.     

Behavior of aqueous solutions of poly(ethylene oxide-b-propylene oxide) copolymers containing a hydrotropic agent

The effect of the hydrotropic agent, sodium p-toluenesulfonate (NaPTS), was evaluated on the micelle formation process and on phase behavior of aqueous solutions containing poly(ethylene oxide-b-propylene oxide) (PEO–PPO) copolymers. We have studied monofunctional diblock copolymers coupled with hydrocarbons groups (R—PEO—PPO—OH and R—PPO—PEO—OH, where R length is linear C₄ and C_12–14). The critical micelle concentration (CMC) and critical micelle temperature (CMT) values of the aqueous copolymers solutions were obtained from both surface tension versus concentration plots and the dye solubilization method. The influence of the hydrocarbons groups length and PPO segment position in the structure of the copolymers were also analyzed. The same measures were obtained for the aqueous solutions of hydrotropic agent which, in turn, also presented molecular aggregation. The presence of the hydrotropic agent in the aqueous copolymers solutions altered the surface tension of these solutions and the occupied molecular area per copolymer molecule at air–water interface and CMC and CMT values of the copolymers. On the other hand, the aggregation points and the surface tension of the NaPTS solutions were dependent on the copolymer structure and composition. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2459–2468, 1998     

Crosslinking poly(ethylene oxide) in dilute solutions by gamma rays

A high molecular weight poly(ethylene oxide) is gelled by radiation from a ⁶⁰Co source. At concentrations of 0.25 to 1 wt-%, doses of 4.5 to 7.5 × 10⁴ rad cause gelation. The storage modulus of the gel formed increases linearly with additional dose to a plateau value and then remains constant during further irradiation. The does needed to reach the plateau, D_p in rads, and the plateau modulus G_p in dynes per square centimeter, are related to the concentration c, in weight per cent: D_p = 1.05 × 10⁶c and G_p = 1.75 × 10⁴c^2.5. The energy absorbed by the polymer per crosslink formed is about 80 ± 10 kcal/mol. The crosslink density produced by radiation is calculated from the measured modulus by using the theory of rubber elasticity. Both modulus and loss are measured in a special air-bearing, recording torsion pendulum with a coneplate geometry.