Spinning Dope Research Articles

Influence of membrane morphology on characteristics of porous hydrophobic PVDF hollow fiber contactors for CO2 stripping from water

Wetting resistance and gas permeability are the main factors for membrane contactor applications, which can be optimized according to the membrane morphology. In present study, three different types of the membrane morphology were obtained via a dry–wet spinning technique. By measuring cloud point data and viscosity, the polymer dope composition was adjusted to produce the different morphologies. The membranes with large finger-like, small finger-like and almost sponge-like morphology were obtained. The plain PVDF membrane with large finger-likes morphology presented the higher N2 permeance, lower wetting pressure and larger mean pore size (0.08μm). By addition of phosphoric acid into the spinning dope, the prepared sponge-like morphology resulted in the high surface porosity with small pore sizes, which demonstrated good permeability and wetting pressure. It was found that the mean pore size measured by gas permeation method was approximately three times larger than those from FESEM examination. CO2 stripping from water was conducted through the gas–liquid membrane contactors. The membranes with smaller pore sizes and higher wetting pressure presented higher stripping performance. In conclusion, a structurally developed PVDF hollow fiber membrane for gas–liquid contactor applications can be achieved by controlling the membrane morphology.

Structure of silk by raman spectromicroscopy: From the spinning glands to the fibers

Raman spectroscopy has long been proved to be a useful tool to study the conformation of protein-based materials such as silk. Thanks to recent developments, linearly polarized Raman spectromicroscopy has appeared very efficient to characterize the molecular structure of native single silk fibers and spinning dopes because it can provide information relative to the protein secondary structure, molecular orientation, and amino acid composition. This review will describe recent advances in the study of the structure of silk by Raman spectromicroscopy. A particular emphasis is put on the spider dragline and silkworm cocoon threads, other fibers spun by orb-weaving spiders, the spinning dope contained in their silk glands and the effect of mechanical deformation. Taken together, the results of the literature show that Raman spectromicroscopy is particularly efficient to investigate all aspects of silk structure and production. The data provided can lead to a better understanding of the structure of the silk dope, transformations occurring during the spinning process, and structure and mechanical properties of native fibers.

The effect of phase inversion promoters on the structure and performance of polyetherimide hollow fiber membrane using in gas–liquid contacting process

Low molecular weight organic compounds were added to the spinning dope as phase inversion promoters and their effects on the structure of polyetherimide (PEI) hollow fibers as well as their performance as membrane contactor were investigated. Water, methanol, ethanol, glycerol and acetic acid were added individually to the solvent NMP to prepare a dope containing 15 wt% PEI, 4 wt% additive, 81 wt% NMP and hollow fiber membranes were fabricated via wet spinning method. The solution containing water as the additive had the lowest thermodynamic stability and highest viscosity, which yielded hollow fiber with a thin skin layer of high porosity and a sublayer with sponge-like structure. The four other polymer solutions were more stable thermodynamically and less viscous. Fast solvent/coagulant exchange yielded thick skin layers of lower porosity and sublayers of finger-like macrovoids. Among all fabricated follow fibers, adding methanol resulted in the highest absorption flux, which was ascribed to its high porosity and low tortuosity.

Bio-inspired capillary dry spinning of regenerated silk fibroin aqueous solution

To biomimic the spinning process of silkworm or spider, a capillary spinning equipment was applied to spin regenerated silk fibroin (RSF) fibers from RSF aqueous solutions in air. This equipment exhibits a wide processing window for various RSF aqueous solutions. The effects of pH, metal ions, RSF concentration and spinning parameters on the spinnability of the spinning dope and the mechanical properties of the obtained fibers were investigated. As a result, spinning dopes with a pH from 5.2 to 6.9 have good spinnability, especially for the dope with a pH of 6.0 and a Ca 2+ concentration of 0.3 M. The RSF concentration of this dope ranges from 44% to 48%. Under optimized conditions of our dry spinning experiments (L/D, 133; take-up speed, 30 mm/s), the obtained as-spun fiber has a breaking strength of 46 MPa, which can be improved up to 359 MPa after a preliminary post-drawing in 80 vol.% ethanol aqueous solution.

Exploring the Thermodynamic Aspects of Structure Formation During Wet-Spinning of Polyacrylonitrile Fibres

Wet-spun polyacrylonitrile fibres are the main precursor for high strength carbon fibres. The properties of carbon fibres strongly depend on the structure of the precursor fibre. Polyacrylonitrile fibres were spun from solutions with varying solvent/nonsolvent content and different draw ratios. Wet-spinning is an immersion precipitation process, thus thermodynamic affinity of spinning dope to the coagulation medium was considered as the driving force of phase-separation, while viscosity of the solution accounted for the resistive force against phase separation and growth of the nucleated voids. Thermodynamic affinity was estimated by modifying Ruaan’s theory and viscosity of the solution was assessed on-line by measuring flow rate and back pressure at the spinneret. Hence, the parameter X (thermodynamic affinity/viscosity) was introduced to predict the porous morphology of the fibres. Generally, an increase in X led to fibres with higher porosity. A combination of electron scanning microscopy (SEM), porosimetry and thermoporometry was applied to fully characterize microstructure of fibres. Based on image analysis of SEM micrographs and data obtained from thermoporometry and porosimetry fractions of dense polymer ligament, micrometer size voids (macrovoids) and nanometer size voids (nanovoids) were estimated. Increasing polymer content or nonsolvent content in the spinning dope caused an increase in the solution viscosity and resulted in fibres with lower porosity. Imposing drawing on the as-spun fibres further decreased the porosity. Drawing also shifted the size distribution of nanovoids toward smaller values.

Effect of elastomeric additives on fabrication and properties of filled fiber materials formed from polymer solutions

We have studied the effect of elastomer additives on the properties of spin dopes for obtaining filled fiber materials by aerodynamic spinning from polymer solutions. We have obtained laboratory samples of materials with different polyurethane content. We have analyzed the results of physicomechanical, sorption, and physical tests of these materials. We show that modification of filled fiber materials by introducing elastomeric additives has only an insignificant negative impact on the sorption properties and markedly improves their physicomechanical characteristics.

Posttreatment of the dry-spun fibers obtained from regenerated silk fibroin aqueous solution in ethanol aqueous solution

Abstract

Preparation and characterization of porous PVDF hollow fiber membranes for CO2 absorption: Effect of different non-solvent additives in the polymer dope

Different types of non-solvent additives were introduced into the polyvinylidene fluoride (PVDF) dope to investigate improvement of the hollow fiber membrane structure for CO2 absorption. Phase-inversion behavior of the PVDF dopes was studied using cloud points measurements. Glycerol, phosphoric acid, ethanol and polyethylene glycol (PEG-400) were used as non-solvent additives in the polymer dope. With addition of the additives, precipitation of the polymer dopes increased following the trend of phosphoric acid>glycerol>ethanol>PEG-400. From morphology examination, PEG-400, glycerol and phosphoric acid resulted in the membranes with almost sponge-like structure due to high viscosity of the spinning dopes. The low wetting resistance and high permeability of the plain PVDF and PVDF/ethanol membranes were attributed to the large finger-likes structure. Among the additives, glycerol provided the membranes with larger mean pore size (9.62nm). CO2 absorption by distilled water was conducted through the gas–liquid membrane contactors. The PVDF/glycerol membrane demonstrated higher CO2 absorption flux than the other membranes. At the absorbent flow rate of 280ml/min, CO2 flux of 7.8×10−4mol/m2s was achieved, which was approximately 30% higher than CO2 flux of the plain PVDF membrane. In conclusion, a developed membrane structure prepared by controlled phase-inversion process can be a promising alternative for CO2 capture in gas–liquid membrane contactors.

Characterization of surface-modified porous PVDF hollow fibers for refinery wastewater treatment using microscopic observation

Microscopic observation was made to investigate the surface structure of porous polyvinylidene fluoride hollow fiber membranes. Field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), and the Guerout–Elford–Ferry equation applied for pure water permeation rate were used to determine the average pore sizes. As well, surface roughness parameters and nodule sizes were determined by AFM. The observed unmodified and modified PVDF hollow fiber membranes were prepared by dry-jet wet spinning method from spinning dope mixtures containing 19 wt.% PVDF, 0.98 wt.% lithium chloride (LiCl.H 2O) and 0, 1.95, and 3.85 wt.% titanium dioxide (TiO 2). Significant difference of spun fibers surface morphology was observed between inner and outer surface by AFM and FESEM. Higher TiO 2 concentration formed rougher surfaces, increased average nodule sizes, and decreased the pore size, resulting in lower permeation flux. Pore size obtained from AFM was intermediate between FESEM and the method based on the Guerout–Elford–Ferry equation.

Properties of PVA/HfO2 Hybrid Electrospun Fibers and Calcined Inorganic HfO2 Fibers

New organic−inorganic hybrid fibers (polyvinyl alcohol (PVA)/HfO2) were prepared by an electrospinning method using DI water as a solvent. The HfO2−acetate nanoparticles could be loaded up to 80% by weight in PVA polymer to fabricate uniform PVA/HfO2 electrospun hybrid fibers. After annealing at 140 °C for 12 h, electrospun PVA/HfO2 fibers were stable when soaked in water. Calcination of these hybrid fibers at temperatures ranging from 450 to 700 °C resulted in the formation of pure inorganic HfO2 fibers with diameters ranging from 0.1 to 0.8 μm depending on the concentration of HfO2−acetate nanoparticles in the spinning dope. Fourier transform infrared spectroscopy and Raman spectroscopy techniques were used to investigate the crystal structures of the HfO2 fibers, which were confirmed by X-ray diffraction (XRD) results. XRD results showed the presence of both monoclinic and tetragonal crystal structures in the HfO2 fibers. The type and size of the crystals formed depended on the concentration of HfO2−acetate nanoparticles in the initial spinning dope and on the calcination temperature. In particular, the formation of stable tetragonal crystal structures in the as-spun hybrid fibers with lower concentration of HfO2 was achieved at lower temperature than the monoclinic-to-tetragonal transition temperature.

Electrospun nanosized cellulose fibers using ionic liquids at room temperature

Aiming at replacing the noxious solvents commonly employed, ionic-liquid-based solvents have been recently explored as novel non-volatile and non-flammable media for the electrospinning of polymers. In this work, nanosized and biodegradable cellulose fibers were obtained by electrospinning at room temperature using a pure ionic liquid or a binary mixture of two selected ionic liquids. The electrospinning of 8 wt% cellulose in 1-ethyl-3-methylimidazolium acetate medium (a low viscosity and room temperature ionic liquid capable of efficiently dissolving cellulose) showed to produce electrospun fibers with average diameters within (470 ± 110) nm. With the goal of tailoring the surface tension of the spinning dope, a surface active ionic liquid was further added in a 0.10 : 0.90 mole fraction ratio. Electrospun cellulose fibers from the binary mixture composed of 1-ethyl-3-methylimidazolium acetate and 1-decyl-3-methylimidazolium chloride ionic liquids presented average diameters within (120 ± 55) nm. Scanning electron microscopy, X-ray diffraction analysis, nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, and thermogravimetric assays were used as core methods to evaluate the structural integrity, morphology and crystallinity of the raw, electrospun, and regenerated samples of cellulose. Moreover, the photoluminescence spectra of both raw and electrospun fibers were acquired, and compared, indicating that the cellulose emitting centers are not affected by the dissolution of cellulose in ionic liquids. Finally, the use of non-volatile solvents in electrospinning coupled to a water coagulation bath allows the recovery of the ionic fluid, and represents a step forward into the search of environmentally friendly alternatives to the conventional approaches.

Exploring the effects of non-solvent concentration, jet-stretching and hot-drawing on microstructure formation of poly(acrylonitrile) fibers during wet-spinning

The simultaneous effects of non-solvent concentration in the spinning dope, jet-stretching and hot-drawing on porosity, morphology development and mechanical properties of wet-spun poly(acrylonitrile) fibers were studied. Addition of non-solvent to the spinning dope increased dope viscosity, the entanglement density of the polymeric solution and the number of entanglements per chain. Drawability of the as-spun fiber depended on the number of entanglements per polymer chain. Therefore, addition of non-solvent improved or spoiled drawability of the wet-spun fibers based on the concentration of the initial spinning dope. Hot-drawing and jet-stretching did not affect the fraction of nanovoids but shifted their size distribution towards smaller values. However, hot-drawing was more effective in reducing the overall porosity of the fibers in comparison with jet-stretching. Fiber tenacity increased when overall porosity decreased. Finally, strength-diameter correlation showed good agreement with the Griffith’s theory.

Simvastatin Release from Poly(lactide-co-glycolide) Membrane Scaffolds

Statins, a group of potent inhibitors of 3-hydroxy-3-methylglutaryl Coenzyme A reductase in cholesterol biosynthesis pathway, have been widely used as a cholesterol lowering drug. The plieotrophic effect of statins on bone metabolism in long-term usage has been begun to be studied during recent years and several in vitro and in vivo studies have demonstrated the ability of statins to promote expression of bone morphogenetic protein-2 (BMP-2), inhibition of osteoclast differentiation and reduction of osteoporotic fractures risk. The high liver specificity and low oral bioavailability of statins, leading to poor peripheral distribution, are the main obstacles to benefit anabolic effects of hydrophobic statins on bone formation. Therefore, developing new administration roots for direct delivery to achieve optimum concentration in the bone microenvironment is of interest. Here we present and compare two approaches of combining statins with bone tissue engineering scaffolds. Simvastatin was combined with a poly(lactide-co-glycolide) (PLGA) membrane scaffold for diffusion-controlled release by dissolving simvastatin (dis-sim) in the membrane casting dope, and for degradation-controlled release by covalently bonding saponifiedsimvastatin (sap-sim) to the PLGA in the spinning dope. Rheological and concentration-dependent membrane morphology changes were observed with saponifiedsimvastatin, suggesting ester bond cleavage and covalent bonding of the statin to the PLGA, but not with dissolved simvastatin. Dissolved simvastatin membranes showed a logarithmic decay release profile while the saponifiedsimvastatin membranes showed constant release. It can be concluded that the covalent bonding of simvastatinto PLGA scaffolds is showing potential for use as a controlled releasescaffold for bone tissue engineering.

Effect of additives concentration on the surface properties and performance of PVDF ultrafiltration membranes for refinery produced wastewater treatment

The aim of this study was to investigate the effect of pore-forming hydrophilic additives on the porous asymmetric polyvinylideneflouride (PVDF) ultrafiltration (UF) membrane morphology and transport properties for refinery produced wastewater treatment. PVDF ultrafiltration membranes were prepared via a phase inversion method by dispersing lithium chloride monohydrate (LiCl·H 2O) and titanium dioxide (TiO 2) nanoparticles in the spinning dope. The morphological and performance tests were conducted on PVDF ultrafiltration membranes prepared from a different additive content. The top surface and cross-sectional area of the membranes were observed using a field emission scanning electron microscope (FESEM) and energy dispersive X-ray (EDX) analysis. The surface wettability of porous membranes was determined by the measurement of a contact angle. The mean pore size and surface porosity were calculated based on the permeate flux. The results indicated that the PVDF/LiCl/TiO 2 membranes with lower TiO 2 nanoparticles loading possessed smaller mean pore size, more apertures inside the membrane with enhanced membrane hydrophilicity. LiCl·H 2O has been employed particularly to reduce the thermodynamic miscibility of dope which resulted in increasing the rate of liquid–liquid demixing process. The maximum flux and rejection of refinery wastewater using PVDF ultrafiltration membrane achieved were 82.50 L/m 2 h and 98.83% respectively at 1.95 wt.% TiO 2 concentration.

Effect of Raw Multi-Wall Carbon Nanotubes on Morphology and Separation Properties of Polyimide Membranes

Raw multi wall carbon nanotubes (r-MWCNTs) were embedded as fillers inside the polyimide (PI) matrix and PI/r-MWCNTs mixed matrix membranes were fabricated by the phase inversion method. The TEM images and permeation results using helium as test gas showed that r-MWCNTs were generally closed ended and acted as impermeable nano particles. Gas permeation tests using CO2 and CH4 showed that the addition of r-MWCNTs into the dope solution increased the CO2/CH4 separation factor while decreasing the carbon dioxide and methane permeances. When the r-MWCNTs content was increased from 0% to 6 wt.%, permeance of CO2 in the flat sheet mixed matrix membranes decreased from 9.15 GPU to 5.49 GPU and CO2/CH4 separation factor increased from 19.05 to 45.75. Identical to flat sheet mixed matrix membranes, the addition of 2 wt.% r-MWCNTs into a spinning dope increased the CO2/CH4 separation factor from 46.61 to 72.20. The glass transition temperature of the mixed matrix flat sheet membranes increased with an increase in the r-MWCNTs content. This implies a good segmental-level attachment between the two phases that forms a rigidified polymer region at the polymer/r–MWCNTs interface. FESEM images showed well dispersed r-MWCNTs in the polymer matrix at a loading of 2 wt% r-MWCNTs.

Effect of LiCl concentration in the polymer dope on the structure and performance of hydrophobic PVDF hollow fiber membranes for CO 2 absorption

Effect of lithium chloride (LiCl) concentration as non-solvent additive in the spinning dopes on the structure and CO 2 absorption performance of the polyvinylidene fluoride (PVDF) membranes was investigated. The hollow fiber membranes were prepared via a wet phase-inversion process and characterized in terms of gas permeability, wetting resistance, mass transfer resistance and overall porosity. The morphology study indicated that by increasing LiCl concentration in the spinning dope, the membrane structure changed from the finger-like to the sponge-like. In addition, by increasing LiCl concentration up to 4 wt.% a drastic decrease in the N 2 permeance and a significant increase in the wetting resistance were observed. CO 2 absorption by distilled water was conducted through the gas–liquid membrane contactors. Using LiCl in the spinning dopes, the CO 2 flux of the prepared membranes significantly improved. By introducing 2 wt.% LiCl, the PVDF membrane showed a CO 2 flux of approximately 60% higher than the plain PVDF membrane at the absorbent flow rate of 200 ml/min. It can be concluded that a porous hydrophobic hollow fiber membrane with improved structure can be a productive alternative for CO 2 absorption and separation through gas–liquid membrane contactors.

A comparative study on the structure and performance of porous polyvinylidene fluoride and polysulfone hollow fiber membranes for CO 2 absorption

Porous polyvinylidene fluoride (PVDF) and polysulfone (PSF) hollow fiber membranes were prepared via a wet spinning method. Glycerol was used as phase-inversion promoter additive in the spinning dopes. Cloud point diagrams of polymer/solvent–glycerol/water were obtained to study precipitation rate of the polymers solution. The membrane structure was compared in terms of morphology, gas permeation, critical water entry pressure, collapsing pressure, overall porosity, contact angle and mass transfer resistance. The cloud point diagrams confirmed a significant increase in the precipitation rate of the spinning dopes with addition of glycerol. The PSF membranes indicated more open cross-section structure with smaller pore sizes. However, the PVDF membranes illustrated an ultra thin outer skin layer with high permeability which resulted in significantly lower mass transfer resistance. Physical CO 2 absorption with distilled water was conducted through the gas–liquid membrane contactors. With addition of glycerol, the PVDF membrane demonstrated a structure with significantly higher CO 2 flux compared to the commercial asymmetric PVDF membrane. The CO 2 flux of 8.20 × 10 −4 mol/m 2 s was achieved by using the absorbent flow rate of 310 mL/min in the shell side of the membrane module. Therefore, using an improved hollow fiber membrane structure can be a promising alternative for CO 2 absorption and separation through membrane contactors.

Fabrication of DNA–magnetite hybrid nanofibers for water detoxification

DNA–magnetite hybrid nanofibers were fabricated by electrospinning a spin dope consisting of oleic acid coated magnetite nanoparticles and DNA–CTMA in ethanol/chloroform mixed solvent. The fabricated nanofibers exhibit superparamagnetic behaviour owing to embedded magnetite nanoparticles. It is demonstrated that these nanofibers can be used as effective detoxification materials in aqueous media as a combined result of DNA's affinity to both organic and inorganic toxicants, high surface area of the nanofibers and the fast and easy separation due to magnetite nanoparticles under external magnetic field. In addition to detoxification, these novel hybrid nanofibers have potential applications in many technological areas such as catalysis and drug delivery.

Study on the Mass Transfer Process in Pan Wet-Spinning

In order to reveal the formation mechanism in PAN wet-spinning process, the Magnifying Method was used to determine the mass transfer rate difference between solvent and coagulant by measuring the weight loss percent of the spinning dope at different interval in the coagulation bath. Then the effect of coagulation condition on and on structure and properties of as-spun fibers was discussed. It was found that increased along with hoist of the molecular volume of coagulants or the coagulation bath temperature but decreased with the increase of the dope solid content or coagulation bath concentration. When the coagulation condition was very moderate（high solid content, low bath temperature or high bath concentration）, the was smaller, the counter-diffusion took place slowly and peacefully, and sequentially an even and compact meshwork microstructure was obtained, thus the density and breaking tenacity of as-spun fibers increased gradually.

Hierarchical electrospun SiO 2 nanofibers containing SiO 2 nanoparticles with controllable surface-roughness and/or porosity

Herein we report that hierarchical electrospun SiO 2 nanofibers incorporated with SiO 2 nanoparticles with fiber diameters being ∼ 500 nm and particle sizes being tens of nanometers were developed through the combination of sol–gel process and electrospinning technique followed by high-temperature pyrolysis; and their morphologies and BET surface areas were examined. The study revealed that the pre-gelation of tetraethyl orthosilicate (TEOS) in spin dopes was important to achieve the morphological consistence of the electrospun precursor nanofibers and the resulting final SiO 2 nanofibers; additionally, SiO 2 nanoparticles appeared to be enriched on the fiber surface, while the surface-roughness and/or porosity of the nanofibers could be controlled through adjusting the incorporation amount of SiO 2 nanoparticles. The developed hierarchical electrospun SiO 2 nanofibers are expected to have important applications in composites (particularly dental composites) as well as catalyst support and adsorption.