Electrospinning and structural characterization of ultrafine poly(butylene succinate) fibers

Biodegradable ultrafine poly(butylene succinate) (PBS) fibers were continuously electrospun for the first time from PBS solutions in chloroform (CF)/2-chloroethanol (CE) (7/3, w/w), CF/CE (6/4, w/w), dichloromethane (DM)/CE (7/3, w/w), DM/CE (6/4, w/w), and CF/3-chloro-1-propanol (9/1, w/w). These mixed solvents had an appropriate evaporation rate for the continuous electrospinning of PBS. The ultrafine PBS fibers had very high crystallinity and their average diameters were in the range of 125-315 nm. The annealed ultrafine PBS fibers exhibited a lamellar stack morphology containing crystalline and amorphous layers.     

Mechanical and thermal properties of waste silk fiber‐reinforced poly(butylene succinate) biocomposites

This article reports the mechanical and thermal properties of poly(butylene succinate) (PBS) biocomposites reinforced with industrially available waste silk fibers, fabricated with varying fiber contents and lengths. The result indicates that use of waste silk fibers may be a potential as reinforcement for effectively improving the static and dynamic mechanical properties of a biodegradable polymer matrix resin, depending on the waste silk fiber content and length in the present biocomposite system. The “as‐separated” waste silk/PBS biocomposites showed the maximum tensile and flexural properties at a fiber loading of 40 wt %, and the “chopped” waste silk/PBS biocomposites showed the optimal strength and modulus with waste silk fibers of 12.7 mm length. The chopped waste silk fibers play a more contributing role in improving the mechanical properties of waste silk/PBS biocomposites than the as‐separated waste silk fibers at a fixed fiber loading. Above the glass transition temperature, the storage modulus of waste silk/PBS biocomposites was significantly greater than that of PBS resin, especially in the higher temperature region. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4972–4980, 2006     

Fabrication of discontinuous fibers of poly (N‐vinylpyrrolidone) containing metalloporphyrin molecules

This study described the preparation of discontinuous fibers of poly (N‐vinylpyrrolidone) (PVP) containing metalloporphyrin (Manganese (III) tetrakis (1‐methyl‐4‐pyridyl) porphyrin pentachloride) molecules using electrospinning method. SEM images showed that before adding the metalloporphyrin molecules, the electrospun nanofibers are straight and smooth, while after adding metalloporphyrin molecules into the PVP solutions, the SEM images clearly showed that there were two different types of fibers: the thinner fibrous phase and the thicker discontinuous fibers. The chemical composition of the resulting PVP/metalloporphyrin composite fibers was characterized by Fourier‐transform infrared (FTIR) and energy dispersive X‐ray (EDX) analysis. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 6017–6022, 2006     

Preparation of core/shell PVP/PLA ultrafine fibers by coaxial electrospinning

This study investigated the process feasibility and stability of core/shell structured bicomponent ultrafine fibers of poly(vinyl pyrrolidone) (PVP) and poly(D ,L ‐lactide) (PLA) by coaxial electrospinning. The morphological structure of the core/shell ultrafine fibers was studied by means of scanning electron microscopy, transmission electron microscopy, and X‐ray photoelectron spectroscopy. Results suggested that PVP/PLA core/shell ultrafine fibers with drawbacks could be produced from 6 or 8% PVP solutions (inner) in the mixture of N,N‐dimethlformamide (DMF) and ethanol and a 22% PLA solution (outer) in DMF and acetone when the flow rates of inner and outer fluids were 0.05 and 0.1 mL/h, respectively. The tensile modulus and tensile strength of the core/shell PVP/PLA membrane were dramatically lower than those of the electrospun PLA membrane, and its water uptake was twice more than that of the PLA membrane. Membranes made from the biodegradable core/shell ultrafine fibers could be potentially used in loading bioactive molecules for tissue regeneration. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 39–45, 2006     

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     

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     

Morphology of ultrafine polysulfone fibers prepared by electrospinning

Ultrafine fibers of bisphenol‐A polysulfone (PSF) were prepared by electrospinning of PSF solutions in mixtures of N,N‐dimethylacetamide (DMAC) and acetone at high voltages. The morphology of the electrospun PSF fibers was investigated by scanning electron microscopy. Results showed that the concentration of polymer solutions and the acetone amount in the mixed solvents influenced the morphology and the diameter of the electrospun fibers. The processing parameters, including the applied voltage, the flow rate, and the distance between capillary and collection screen, were also important for control of the morphology of electrospun PSF fibers. It was suggested that uniform ultrafine PSF fibers with diameter of 300–400 nm could be obtained by electrospinning of a 20 % (wt/v) PSF/DMAC/acetone (DMAC:acetone = 9:1) solution at 10–20 kV voltages when the flow rate was 0.66 ml h^?1 and capillary–screen distance was 10 cm. Copyright © 2004 Society of Chemical Industry     

Thermosensitive poly(n‐isopropylacrylamide) hydrogels bonded on cellulose supports

A two‐step initiation and polymerization process was developed for the preparation of two series of hydrogel–cellulose composites with distinctively different morphologies and swelling behaviors. Hydroentangled cotton cellulose fibers were optimally initiated in 20 mM aqueous ammonium cerium(IV) nitrate for 15 min and then polymerized in aqueous solutions of N‐isopropylacrylamide (NIPAAm) monomer and N,N′‐methylene bisacrylamide (BisA) crosslinker. The extents of hydrogels on the cellulose solids could be controlled by variations in the concentrations of the monomer and crosslinker as well as the NIPAAm/BisA solution‐to‐solid ratios. The two series of hydrogel–cellulose composites formed were hydrogel‐covered/filled cellulose (I) and cellulose‐reinforced hydrogel (II) composites. Series I composites were synthesized with NIPAAm/BisA solutions below the liquid saturation level of the cellulose; this led to pore structures (size and porosity) that depended on both the extent and swelling of the grafted hydrogels. Series II composites were polymerized in the presence of excessive NIPAAm/BisA solutions to produce cellulose solids completely encapsulated in the hydrogels. All the cellulose‐supported hydrogels exhibited lower extents of phase transition over a wider temperature range (28–40°C) than the free poly(N‐isopropylacrylamide) hydrogels (32°C). These findings demonstrate that hydrogels can be used to control the pore structure of cellulose and can be supported with cellulose fibers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 999–1006, 2003     

Influence of processing conditions on polymorphic behavior,crystallinity, and morphology of electrospun poly(VInylidene fluoride) nanofibers

The polymorphism and crystallinity of poly(vinylidene fluoride) (PVDF) membranes, made from electrospinning of the PVDF in pure N,N‐dimethylformamide (DMF) and DMF/acetone mixture solutions are studied. Influence of the processing and solution parameters such as flow rate, applied voltage, solvent system, and mixture ratio, on nanofiber morphology, total crystallinity, and crystal phase content of the nanofibers are investigated using scanning electron microscopy, wide‐angle X‐ray scattering, differential scanning calorimetric, and Fourier transform infrared spectroscopy. The results show that solutions of 20% w/w PVDF in two solvent systems of DMF and DMF/acetone (with volume ratios of 3/1 and 1/1) are electrospinnable; however, using DMF/acetone volume ratio of 1/3 led to blockage of the needle and spinning process was stopped. Very high fraction of β‐phase (～79%–85%) was obtained for investigated nanofiber, while degree of crystallinity increased to 59% which is quite high due to the strong influence of electrospinning on ordering the microstructure. Interestingly, ultrafine fibers with the diameter of 12 and 15 nm were obtained in this work. Uniform and bead free nanofiber was formed when a certain amount of acetone was added in to the electrospinning solution. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42304.     

Poly(lactic acid) biocomposites reinforced with ultrafine bamboo‐char: Morphology,mechanical, thermal,and water absorption properties

In this study, ultrafine bamboo‐char (BC) was introduced into poly(lactic acid) (PLA) matrix to improve mechanical and thermal properties of PLA based biodegradable composites. PLA/BC biocomposites were fabricated with different BC contents by weight. Uniform dispersion of BC in the PLA matrix and good interaction via physical and chemical interfacial interlocks were achieved. The maximum tensile strength and tensile modulus values of 14.03 MPa and 557.74 MPa were obtained when 30% BC was used. Impact strength of the biocomposite with 30% BC was increased by 160%, compared to that of pure PLA. DSC analysis illustrated that PLA/BC biocomposites had a better thermal property. Crystallization temperature decreased and maximal crystallinity of 30.30% was observed with 30% BC load. We did not notice significant thermal degradation differences between biocomposites with different BC loadings from TGA. Better water resistance was obtained with the addition of BC. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43425.     

Cellulose nanofibers prepared by the N‐methylmorpholine‐N‐oxide method

The process of electrospinning is very suitable for obtaining fibers with a diameter on a nanometer scale. Such fibers can be spun from almost all kinds of known polymers, copolymers, and polymer blends. In this work, we present cellulose nanofibers obtained by the electrospinning process from spinning dopes containing cellulose dissolved in an N‐methylmorpholine‐N‐oxide/water system. Under different electrospinning process conditions, cellulose fibers, a nonwoven fiber network, and a cellulose membrane were obtained. The fibers were examined with scanning electron microscopy. The diameters of the fibers were in the submicrometer range. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1855–1859, 2005     

Electrospinnability of poly(butylene succinate): Effects of solvents and organic salt on the fiber size and morphology

Submicrosized and nanosized fibers of polymers can be formed easily by electrospinning techniques. However, bead formation can occur if inappropriate solvent systems are used. In this study, we focused on investigating the effects of solvents and organic salt on the electrospinnability of poly(butylene succinate) (PBS). Electrospun PBS fibers were obtained from single‐solvent systems, that is, systems with chloroform (CF) or dichloromethane, at various concentrations (8–30% w/v). Discrete beads and beaded fibers were still found at every PBS concentration. In this study, the electrospinnability of the PBS solutions in CF were improved by the addition of methanol (MeOH) as a cosolvent and an organic salt [alkyl ammonium ethyl sulfate (AAES)]. The obtained fibers were smooth without any beads, and the diameters were affected by the amount of MeOH and the PBS concentration. The electrospinnability of PBS could be enhanced by the addition of a cosolvent with a high dielectric constant or organic salt (AAES). Moreover, the diameters of the electrospun PBS fibers decreased with increasing AAES concentration. We found that the presence of MeOH (30 vol %) and the addition of AAES caused an increase in the crystallinity of the PBS fibers. Therefore, we concluded that bead‐free ultrafine PBS fibers could be obtained through the addition of the cosolvent and the organic salt. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42716.     

Toward faster degradation for natural fiber reinforced poly(lactic acid) biocomposites by enhancing the hydrolysis-induced surface erosion

The poor and uncontrollable biodegradability of poly(lactic acid) (PLA)-based materials is one of the fundamental limitations for widening their applications. To regulate the degradation of PLA/ramie fiber biocomposites, the hydrophilicity of the composites was modified to attract more water attack by introducing water-soluble poly(ethylene glycol) (PEG). Analyses by characterization of sample size, weight loss and microstructure offered intensive information on the degradation behavior of PLA biocomposites. It was revealed that PEG indeed significantly enhanced the surface erosion process and thus facilitated the degradation rate. The biocomposite bar containing 15 wt% PEG completed degradation within 50 days, while only ~50 wt% mass lost for the control biocomposite sample without PEG. Morphological observation confirmed that PEG accelerated the penetration of outside water from the surface to the center driven by the diffusion-in process, which subsequently boosted the hydrolytic action of the PLA backbone ester groups. Our results indicated that the PEG induced water penetration governed the overall degradation kinetics. As a strong response to the degradation, the stiffness of the biocomposite bars suffered from drastic decrease while T _g varied in a climbing trend within the early stage. Microscopic examination of degradation solution formed during hydrolytic degradation of the PLA biocomposites suggested oligomers or lactic acid monomers were released to the solutions. It was of great interest to observe PEG dissolved in the alkaline solution speeded the ramie fibers breaking down to tiny fragments and cellulose macromolecules which further regenerated into cellulose aggregates in various fantastic appearances like coral-like leaves and pine needles. Our success in regulating the degradation of PLA biocomposites also provides an instructive approach for other PLA based materials.

Fabricating novel thermal crosslinked ultrafine fibers via electrospinning

In this article, we report the preparation of a kind of novel crosslinked ultrafine fiber by electrospinning of unsaturated polyester macromonomers (UPM) and subsequent thermal crosslinking. The UPM is prepared via a two‐step reaction with poly(2‐methyl‐1,3‐propyleneadipate) diol terminated (PMPA), isophorone‐diisocyanate (IPDI) and 2‐hydroxyethyl methacrylate (HEMA). Poly(3‐hydroxyl‐butyrate‐co‐3‐hydroxylvalerate) (PHBV) is chosen to improve the processability of the UPM. UPM/PHBV blend ultrafine fibers are successfully electrospun with a proper mass ratio of UPM to PHBV in dichloromethane solution. The fibers are thermally crosslinked after electrospinning. Measurement results indicate that the average diameter of the fibers is about 1 μm and the crosslinked fibers have good solvent‐stability and thermal‐stability. This novel fiber has potential applications in filtration and protective coating. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 107:2142–2149, 2008     

Electrospun Bead‐On‐String Hierarchical Fibers for Fog Harvesting Application

Quest for efficient fog harvesting methods has drawn immense attention in recent times. In this study, electrospinning is used to fabricate three different sets of membranes that are based on pristine poly(N‐isopropylacrylamide) (PNIPAM) fibers, pristine polyvinylidene fluoride (PVDF) fibers, and PNIPAM‐PVDF bead‐on‐string fibers. The wettability of these membranes is investigated as a function of temperature and the effect of their wettability on the fog collection efficiency is determined. Membranes based on pristine PNIPAM and pristine PVDF fibers are fabricated using conventional electrospinning and are shown to have a smooth surface morphology. On the other hand, PNIPAM‐PVDF bead‐on‐string fibers are fabricated using core–shell electrospinning. Water collection efficiency of the membranes is compared to investigate the influence of microstructures and wettability gradient on fog harvesting ability of the samples. Among the three samples, the bead‐on‐string hierarchical fibrous membrane demonstrates the highest fog harvesting rate of 1150 ± 28 mg cm⁻² h⁻¹ at 25 °C and 909 ± 31 mg cm⁻² h⁻¹ at 40 °C. Furthermore, the results demonstrate that the presence of microstructures on the nanofibers improve the fog harvesting efficiency of PNIPAM‐PVDF bead‐on‐string fibers.

     

Blend fibers of polyacrylonitrile and water‐soluble chitosan derivative prepared from sodium thiocyanate solution

A water‐soluble chitosan derivative of N‐(2‐hydroxy)propyl‐3‐trimethylammonium chitosan chloride (HTCC), synthesized by the reaction of chitosan and glycidyltrimethyl ammonium chloride, and polyacrylonitrile (PAN) were blended using 46% (w/w) NaSCN aqueous solution as a common solvent. The total polymer concentration of blend solution was fixed at 12% (w/w), and the relative composition of PAN/HTCC in the blend solution varied from 0/100 to 80/20 by weight. The PAN/HTCC blend fibers with the appropriate physical property were prepared by a wet spinning and drawing process. The effect of HTCC content on the structural change, miscibility, and ability to be dyed of the blend fibers was investigated. The optical and scanning electron microscopic observation gave no indication of phase separation up to 20% HTCC content. Differential scanning calorimetry and dynamic mechanical measurements of the blend fibers show single glass transition temperatures that increase with increasing blend ratio of HTCC. All the experimental results exhibit that the blends are miscible on the molecular scale. The blend fibers could be dyed with an acid dye. This enhanced ability of the blend fibers to be dyed with acid dyes could be useful for one‐step dyeing when mixed with other fibers, such as wool and nylon. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1620–1629, 2001     

Electrospinning of solvent‐resistant nanofibers based on poly(acrylonitrile‐co‐glycidyl methacrylate)

This article reports on the preparation of novel solvent‐resistant nanofibers by electrospinning of poly(acrylonitrile‐co‐glycidyl methacrylate) (PANGMA) and subsequent chemical crosslinking. PANGMA nanofibers with diameters ranging from 200 to 600 nm were generated by electrospinning different solutions of PANGMA dissolved in N,N‐dimethylformamide. Different additives were added to reduce the fiber diameter and improve the morphology of the nanofibers. The as‐spun PANGMA nanofibers were crosslinked with 27 wt % aqueous ammonia solution at 50°C for 3 h to gain the solvent resistance. Swelling tests indicated that the crosslinked nanofibers swelled in several solvents but were not dissolved. The weight loss of all the crosslinked nanofibrous mats immersed in solvents for more than 72 h was very low. The characterization by electron microscopy revealed that the nanofibrous mats maintained their structure. This was also confirmed by the results of the pore size measurements. These novel nanofibers are considered to have a great potential as supports for the immobilization of homogeneous catalysts and enzymes. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Hemodialysis membrane prepared from cellulose/N‐methylmorpholine‐N‐oxide solution. I. Effect of membrane preparation conditions on its permeation characteristics

Flat hemodialysis membranes were prepared from cellulose/N‐methylmorpholine‐N‐oxide (NMMO) solutions (dope) with different cellulose concentrations (6–8 wt %) by using a phase‐inversion method. The coagulant used was NMMO aqueous solution, of which the NMMO concentration and its temperature were varied in the range of 0 to 50 wt % and 5 to 60°C, respectively. The effects of these preparation conditions on the permeation characteristics, the ultrafiltration rate (UFR) of pure water, and sieving coefficient (SC) of dextran, were investigated. The decrease in cellulose concentration of the dope and the increases in both temperature and NMMO concentration of the coagulant gave a membrane with high UFR. Concerning the SC, the increase of the cellulose concentration and the decreases in both temperature and NMMO concentration gave a good result. Consequently, the membrane having the preferable UFR and SC as a hemodialysis membrane was obtained when the 8 wt % cellulose dope was coagulated in water at 5°C. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2302–2307, 2002     

Blend films of O‐carboxymethyl chitosan and cellulose in N‐methylmorpholine‐N‐oxide monohydrate

To introduce N‐methylmorpholine‐N‐oxide (NMMO) process to prepare antibacterial lyocell fiber, the blend films of O‐carboxymethyl chitosan (O‐CMCS) and cellulose were prepared. O‐CMCS in aqueous suspension with particles having a surface mean diameter of 2.24 μm was blended with cellulose in NMMO hydrate. The blend films with different O‐CMCS content were prepared with the blend solutions. SEM confirmed that O‐CMCS remained within the cellulose film in the particle. The mechanical properties of the blend films show little increased value when O‐CMCS was less 5%; however, it decreased sharply when O‐CMCS was over 8%. Thus, the optimum O‐CMCS content may give a good combination of antibacterial action and mechanical properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4601–4605, 2006     

Quick Polymerization from Electrospun Macroinitiators for Making Thermoresponsive Nanofibers

Thermoresponsive nanofibers by very fast grafting of N,N‐isopropylacrylamide (NIPAAm) from electrospun atom transfer radical polymerization (ATRP) macroinitiator are presented in this work. The heterogenous grafting of NIPAAm onto macroinitiator fibers could be done in few minutes, i.e., in less than 5 min. The procedure involved electrospinning of an ATRP macroinitiator and subsequent PNIPAAm grafting using “grafting from” technique. The ATRP Macroinitiator was based on a copolymer of methyl methacrylate (MMA) and 2‐hydroxyethyl methacrylate (HEMA). The growth of the PNIPAAm layer on electrospun fibers was followed by IR‐spectroscopy and SEM analysis. The temperature‐dependent‐phase transition was proven by contact angle measurements and could be shown on the same surface for many cycles.