Electrospinning short polymer micro-fibres with average aspect ratios in the range of 10–200

Ultra fine short fibres have a variety of applications. Short aligned fibres or a mixture of short and long fibres can reinforce brittle materials, alter the appearance, texture and durability of synthetic fibres, and adjust the strength, toughness and stiffness of a composite material. Among electrospun products, short fibres are usually produced by secondary processing of continuous as-spun fibres. However, this is not entirely straightforward or cost-effective due to the efficiency of the secondary process and the relatively low tensile strength of the electrospun ultrafine fibres. Besides, sub-micrometre size fibres with an average aspect ratio (AR) <200 have not been directly produced without further processing by changing collector geometry in electrospinning. Using a model polymer, polymethylsilsesquioxane (PMSQ), short micro-fibres with 10 < AR < 200 were electrospun directly in this work, i.e. without the need for a secondary process. The AR and particularly fibre length were shown to be strongly influenced by the solvent system used for electrospinning and the molecular weight ([`(M<sub>w</sub>)] \overline {{M_w}} ) of the polymer. When using PMSQ1 ([`(M_w)] \overline {{M_w}} =7500) in methanol instead of acetone, short fibres with AR <200 were produced instead of continuous fibres. Moreover, when [`(M_w)] \overline {{M_w}} of the polymer was decreased from 7500 (PMSQ1) to 4300 (PMSQ2), with all other conditions kept constant, significant reduction in the AR of the as-spun fibres was observed. Short fibres with average AR of 15 were produced from PMSQ2 solution in 3:2 v/v dimethylsulphoxide:2-nitropropane. The average AR of short fibres spun from PMSQ2 solution in 2:3 v/v methanol:propanol was 31. Also PMSQ1 in both of the above-mentioned binary solvent systems produced long continuous fibres with AR >3000 under the same spinning conditions.     

Electrospinning polymer blend of PLA and PBAT: Electrospinnability–solubility map and effect of polymer solution parameters toward application as antibiotic‐carrier mats

Electrospinning of a biodegradable polymer blend of poly(lactic acid) (PLA) and poly(butylene adipate‐co‐terephthalate) (PBAT) is reported for the first time. Effects of several solution parameters on electrospinning are explored, including types of single and binary solvents, binary solvent mixing ratio, polymer blend concentration, polymer blending ratio, and loading content of tetrabutyl titanate as a compatibilizer. An electrospinnability–solubility map of the PLA/PBAT blend is firstly developed for the facile selection of a suitable binary solvent system, thus simplifying the laborious, time‐consuming, trial‐and‐error process. A particular binary solvent system derived from good and non‐solvent serves as the most suitable medium for the successful preparation of homogeneous bead‐free electrospun PLA/PBAT nanofibers. It is revealed that the compatibilizer acts not only as a diameter size tuner for the PLA/PBAT fibers but also as a mechanical property enhancer for the immiscible PLA/PBAT electrospun mats. Moreover, the antibacterial activity of the drug‐loaded PLA/PBAT fibrous mats suggests their potential application as antibiotic‐carrier mats. Preparation of the composite mats comprising bead‐free fibers with an average size at sub‐micrometer scale is also demonstrated, additionally promoting the possibility of using the PLA/PBAT‐based electrospun mats as a matrix of various additives for a wide range of applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46486.     

Effects of solvent on structures and properties of electrospun poly(ethylene oxide) nanofibers

Poly(ethylene oxide) (PEO) nanofibers were prepared by electrospinning PEO solution with a mixed solvent of ethanol and deionized water. The results show that the mixed solvent system has noteworthy influences on structures and properties of electrospun PEO nanofibers, including molecular chain orientation, crystallinity degree, surface morphology, fiber diameter, diameter distribution, spinnability, and productivity. With increasing ethanol content in the mixed solvent, wrinkly morphologies appear on the surface of PEO nanofibers due to a high evaporation rate of ethanol during electrospinning process. The dielectric constant, dipole moment, conductivity, density, boiling point, and solubility parameter of the mixed solvent become lower with the ethanol content increasing. Besides, the hydrogen‐bonding interactions between PEO and solvents become weaker. As a result, PEO nanofibers with larger diameters, lower molecular chain orientation, and crystallinity degree are obtained. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45787.     

Electrospinning of uniform polystyrene fibers: The effect of solvent conductivity

By means of the electrospinning technique, micron- and nanofibers can be obtained from polymer solutions under a very high electrical field. A special challenge is to produce bead-free uniform fibers since any minor changes in the electrospinning parameters such as slight variations in the polymer solutions and/or electrospinning experimental parameters may result in significant variations in the final nanofiber morphology. Furthermore, it is often not trivial at all to obtain reproducible uniform electrospun nanofibers for the optimized electrospinning conditions. Here we report that the conductivity of the solvent is the key factor for the reproducible electrospinning of uniform polystyrene (PS) fibers from dimethylformamide (DMF) solutions. It is shown that even slight changes in the conductivity of the DMF solutions can greatly affect the morphology of the resulting electrospun PS fibers. Here, we have carried out a thorough and systematic study on the effect of solution conductivity on the electrospinning of bead-free polystyrene (PS) fibers when dimethylformamide (DMF) was used as the solvent. Interestingly, we found out that different grades of solvent as-received (DMF) from various suppliers have slightly different solution conductivities. Consequently, the polymer solutions prepared with the same PS concentration have different conductivities, which are shown to have significant changes on the morphology of the PS fibers resulting in beaded or bead-free uniform fibers when electrospun under the identical electrospinning conditions. Such as, bead-free PS fibers were obtained from PS solutions in the range of 20% (w/v) through 30% (w/v) depending on the DMF grade used. In brief, it was observed that solutions with a higher conductivity yielded bead-free fibers from lower polymer concentrations, which confirms that the solution conductivity plays a very significant role in producing bead-free uniform PS fibers.     

Physical and morphological characterisation of poly(L-lactide) acid-based electrospun fibrous structures: tunning solution properties

ABSTRACT

Poly(l-lactide) nano/micro fibres were produced using the electrospinning technique. The influence of solvent type and solution concentration on the morphology and structure of electrospun fibres were investigated. For this purpose, the electrospinning was performed using 2, 2, 2-trifluoroethanol (TFE) or dichloromethane (DCM) solvents at solution concentrations in a range of 5–9?wt-%. Morphological studies showed that versus DCM-based fibres with beaded structures and porous surface, when using TFE as a solvent, the uniform bead-free fibres with a smooth surface morphology were produced. Compared to DCM, the fibre diameter decreased using TFE as a solvent with lower vapour pressure while the crystallinity of the fibres increased. By increasing the solution concentration up to 9?wt-%, uniform fibres were produced with growing average diameters. Following these results, we conclude that varying the solution concentration and solvent type can modulate the final properties of electrospun fibres.     

The morphology,mechanical properties,and flammability of aligned electrospun polycarbonate (PC) nanofibers

The electrospinning of the polycarbonate (PC) solutions was performed for the variable electrospinning parameters such as polymer concentration, solvent composition, applied voltage, flow rate, and take‐up velocity in order to evaluate changes of morphology, mechanical properties, and flammability of the aligned PC nanofibers as a function of the electrospinning parameters. It was found that the ratio of THF/DMF solvent in the electrospinning parameters had a major effect on the spinnability and fiber morphology. Furthermore, it was confirmed that the mechanical properties were dependent upon the fiber morphology. The spinnability of the PC solutions with a lower THF ratio in THF/DMF solvent was poor. The aligned electrospun PC fiber with the best morphology was made in the range of polymer concentration of 22%, solvent ratio of 50:50 THF : DMF, applied voltage of 14 kV, flow rate of 0.050 ml/m, and a take‐up velocity of 7.3 m/s. The ultimate strength and initial modulus of the 80% drawn 22% PC fiber were 64 ± 2 MPa (commercial 55–75 MPa) and 1.9 ± 0.1 GPa. The heat release capacity (HRC) of the 22 and 25% PC fiber were 275 ± 27 J/g K and 198 ± 1 J/g K. It was found that the flame resistance of the electrospun PC nanofiber was superior to that of the PC raw material (HRC ～360 J/g K). POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

The morphology of electrospun polystyrene fibers

Electrospinning is a process of electrostatic fiber formation which uses electrical forces to produce polymer nanofibers from polymer solution. The electrospinning system consists of a syringe feeder system, a collector system, and a high power supplier. The important parameters in the morphology of electrospun polystyrene fibers are concentration, applied voltage, and solvent properties. Higher concentrations of the polymer solution form thicker fibers and fewer beads. When the concentration is 7 wt%, electrospun fibers have an average diameter of 340 nm, but as the concentration of PS increases to 17 wt%, the fiber diameter gradually thickens to 3,610 nm. The fiber morphology under different solvent mixture ratios and solvent mixtures has also been studied.     

Nanofibers from recycle waste expanded polystyrene using natural solvent

Summary A new recycling technique has been developed. In this method, EPS (expanded polystyrene), generally called Styrofoam, is dissolved with natural solvent, d-limonene and electrospun. This method can economically produce the nanofibers. The electrospinning process produces a nonwoven mat of long polymer fibers with diameters in the range of 10–500 nm and high surface areas per unit mass. PS (Polystyrene) polymer dissolved in different solvents such as THF (Tetrahydrofuran), DMF (Dimethylformaide), and DMAc (Dimethylacetamide) etc. may all be electrospun into nanofibers. These solvents cause environmental problem and difficulty of process handling. Natural solvent, d-limonene is used for dissolving PS. PS nanofibers are produced with PS solution using d-Limonene. This paper describes the use of polystyrene (PS) nanofibers electrospun from recycled EPS solution dissolved in d-limonene. The electrospun polystyrene nanofiber diameters vary from 300 to 900 nm, with an average diameter of about 700 nm.     

Morphology transition in electrospinning polymers by a dual‐capillary system

An experimental investigation of the fiber morphology change of fibers prepared by a dual‐capillary electrospinning system, operated in the cone‐jet mode, was carried out for poly(vinyl acetate) polymers of three molecular weights. The substrate morphology of the electrospun poly(vinyl acetate) could be changed significantly when the polymer's molecular weight, concentration, solvent, and outer liquid flow rate were varied. The onset of bead‐to‐fiber transition was determined by the critical chain overlap concentration. For solutions with a high concentration, the fiber diameter and surface were significantly affected by the physical properties of the solvents. To produce fibers of small diameter, electrospinning with a higher conductivity solution was desirable. On the other hand, a high‐conductivity solution needed to be avoided to keep the fiber uniform in diameter and smooth on the surface. The comparison of electrospun fibers produced by both single‐capillary and dual‐capillary systems was also addressed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

非良溶剂存在下静电纺PVDF和P(VDF-HFP)纤维的可纺性研究

将聚偏氟乙烯(PVDF)和聚偏氢氟乙烯-六氟丙烯共聚物[P(VDF-HFP)]分别溶解于良溶剂N,N-二甲基乙酰胺(DMAc)和非良溶剂丙酮(Act)的混合体系中(DMAc:Act体积比为3:7),用静电纺丝法制备两种超细纤维。考察了在非良溶剂存在的情况下两种溶液浓度和增比粘度(η8p)的依赖关系,测定了两种溶液中的缠结浓度(Ce)。结果表明,PVDF和[P(VDF-HFP)]两种溶液的浓度的对数和8p的对数在一定的浓度范围内存在线性关系,其Ce的质量分数分别为6．8％和4．8％;静电纺纤维经扫描显微镜观察表明,在缠结数评估失效情况下,Ce对两种含非良溶剂的高聚物溶液可纺性也具有半定量的评估作用。两种溶液浓度低于Ce时无法纺出纤维,主要形成聚合物液滴;Ce是电纺出珠状纤维的最小浓度,而纺出均一的无珠纤维溶液浓度为(2-2．5)Ce。     

“Dialdehyde Cellulose” Nanofibers by Electrospinning as Polyvinyl Alcohol Blends: Manufacture and Product Characterization

A nanofiber was obtained by electrospinning of “dialdehyde cellulose” (periodate-oxidized cellulose, DAC) and polyvinyl alcohol (PVA), using only water as the solvent. Celluloses of four different origins were fully oxidized with sodium periodate to water-soluble DAC. Aqueous solution of DAC showed inadequate spinnability regardless of the polymer concentration and the electrospinning conditions used. Addition of PVA improved the solution's viscoelasticity and, consequently, the solution's spinnability. We examined the effects of DAC/PVA composition and electrospinning parameters on fiber morphology. Highly homogeneous nanofibers were prepared from 1:1 up to 2:1 (weight) DAC/PVA blends while samples of lower viscosity or higher relative DAC contents resulted in continuous, beaded fiber networks. Characterization of the electrospun fabrics revealed a highly crosslinked DAC structure reinforced with PVA, strongly interacting through hemiacetal bonds and hydrogen bonding. Fluorescence labeling confirmed the presence of reactive aldehyde functionalities in the electrospun web. The versatile properties of DAC as reactive material can now be imparted on electrospun fiber and nanofiber material – which was not possible so far –further widening the application scope of this interesting cellulose derivative.     

Effect of blend composition on the morphology development of electrospun fibres based on PAN/PMMA blends

BACKGROUND: The aim of the work presented was to determine the morphology development and relevant change in fibre diameter of a binary polymer blend system during an electrospinning process. The size of the fibre diameter is one of the important factors determining the general properties of non‐woven mats formed from electrospun fibres. RESULTS: The morphology and diameter of electrospun polyacrylonitrile (PAN)/poly(methyl methacrylate) (PMMA) blends were investigated as a function of blend ratio using scanning electron microscopy. The diameter of the electrospun PAN/PMMA fibres decreased with increasing PMMA content up to 50 wt%, and then increased again with further increase of PMMA. After thermal treatment, the fibres shrank, and an irregularly shaped morphology was observed. CONCLUSION: The electrospinning of incompatible PAN/PMMA blends leads to a microphase‐separation morphology of fibres. A phase inversion occurs at a PMMA content of between 50 and 75 wt%. Due to the phase inversion, the fibre diameter shows a minimum value at the relevant composition. Copyright © 2008 Society of Chemical Industry     

萃取精馏分离乙酸甲酯-甲醇溶剂

用汽液平衡装置对萃取精馏分离乙酸甲酯-甲醇极性共沸体系的溶剂选择进行了实验研究.结果表明:被分离物系的分离效果随溶剂比(质量比)的增大而增大;二元混合溶剂(二甲基亚砜DMF+N,N-二甲基甲酰胺DMSO)和三元混合溶剂(N-甲基吡咯烷酮NMP+DMF+DMSO)的分离效果优于单一溶剂(DMF),且DMF和DMSO的摩尔...     

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

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

The effect of solvent dielectric properties on the collection of oriented electrospun fibers

A simple approach to electrospinning has been developed that enables the collection of polymer, ceramic, and multiphase composite fibers, in quantity, with a high degree of spatial orientation. It has been demonstrated that a careful choice of solvent effectively eliminates the onset of the characteristic “bending” instability that is commonly associated with the electrospinning process. This allows collection of spatially oriented submicron electrospun fibers on a rotating drum without the need for elaborate mechanical or electrostatic manipulation of the electrospinning jet and/or collection target (Deitzel, J. M.; Kleinmeyer, J. D. et al. Polymer 2001, 42, 8163, Zussman, E.; Theron, A.; et al. Appl Phys Lett 2003, 82, 973, and Li, D. Wang, Y. L.; et al. Nano Lett 2003, 3, 1167). Fibers have been electrospun from a series of model polyethylene oxide/CHCl₃ solutions with a range of conductivities. The experimental data confirms theoretical predictions that the onset of the bending instability is a function of the available “free” charge in the solution, which in turn is strongly influenced by the dielectric constant of the solvent. The results show that fiber orientation becomes random as the conductivity increases, indicating the need for the surface charge density to exceed a critical threshold in order for the bending instability to initiate. This method has been experimentally demonstrated with other low-dielectric constant solvents and other common polymer, ceramic, and composite materials. Furthermore, it has been demonstrated that fibers electrospun from these solutions can be mechanically drawn to submicron dimensions (∼ 200–500 nm) by controlling drum speed. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Transparent poly(methyl methacrylate‐co‐butyl acrylate) nanofibers

Nanofibers of n‐Butyl Acrylate/Methyl Methacrylate copolymer [P(BA‐co‐MMA)] were produced by electrospinning in this study. P(BA‐co‐MMA) was synthesized by emulsion polymerization. The structural and thermal properties of copolymers and electrospun P(BA‐co‐MMA) nanofibers were analyzed using Fourier transform infrared spectroscopy–Attenuated total reflectance (FTIR–ATR), Nuclear magnetic spectroscopy (NMR), and Differential scanning calorimetry (DSC). FTIR–ATR spectra and NMR spectrum revealed that BA and MMA had effectively participated in polymerization. The morphology of the resulting nanofibers was investigated by scanning electron microscopy, indicating that the diameters of P(BA‐co‐MMA) nanofibers were strongly dependent on the polymer solution dielectric constant, and concentration of solution and flow rate. Homogeneous electrospun P(BA‐co‐MMA) fibers as small as 390 ± 30 nm were successfully produced. The dielectric properties of polymer solution strongly affected the diameter and morphology of electrospun polymer fibers. The bending instability of the electrospinning jet increased with higher dielectric constant. The charges inside the polymer jet tended to repel each other so as to stretch and reduce the diameter of the polymer fibers by the presence of high dielectric environment of the solvent. The extent to which the choice of solvent affects the nanofiber characteristics were well illustrated in the electrospinning of [P(BA‐co‐MMA)] from solvents and mixed solvents. Nanofiber mats showed relatively high hydrophobicity with intrinsic water contact angle up to 120°. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4264–4272, 2013     

Fabrication and properties of elastic fibers from electrospinning natural rubber

Electrospinning natural rubber (NR) to get elastic nano-/microfibers has attracted much attention. Suitable solvent such as tetrahydrofuran (THF) was selected by considering solubility, toxicity, and electrospinning results. Dynamic light scattering testing was used to measure the hydrodynamic diameter (D_h) of the solutions with different solvents and the critical concentrations (C*) of NR/THF solution. For NR solutions with the same concentration from different solvents, the larger D_h the solution, the larger the electrospun fiber diameter. Stable electrospinning concentration window ranging from 25 to 50 g/L, which corresponds to 38 > [ŋ]C > 19, was identified. Mechanical properties of both electrospun NR fiber mats and single fibers were estimated from tensile testing. Fibrous mats with excellent elasticity at about 439 to 505% elongation were demonstrated; however, the elongation rate of single fibers was 44%. Electrospun fiber mats with high elasticity of NR materials can be potentially used in soft tissue engineering and strain sensor areas. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48153.     

Electrospinning of nanofibers from non-polymeric systems: polymer-free nanofibers from cyclodextrin derivatives

High molecular weight polymers and high polymer concentrations are desirable for the electrospinning of nanofibers since polymer chain entanglements and overlapping are important for uniform fiber formation. Hence, the electrospinning of nanofibers from non-polymeric systems such as cyclodextrins (CDs) is quite a challenge since CDs are cyclic oligosaccharides. Nevertheless, in this study, we have successfully achieved the electrospinning of nanofibers from chemically modified CDs without using a carrier polymer matrix. Polymer-free nanofibers were electrospun from three different CD derivatives, hydroxypropyl-β-cyclodextrin (HPβCD), hydroxypropyl-γ-cyclodextrin (HPγCD) and methyl-β-cyclodextrin (MβCD) in three different solvent systems, water, dimethylformamide (DMF) and dimethylacetamide (DMAc). We observed that the electrospinning of these CDs is quite similar to polymeric systems in which the solvent type, the solution concentration and the solution conductivity are some of the key factors for obtaining uniform nanofibers. Dynamic light scattering (DLS) measurements indicated that the presence of considerable CD aggregates and the very high solution viscosity were playing a key role for attaining nanofibers from CD derivatives without the use of any polymeric carrier. The electrospinning of CD solutions containing urea yielded no fibers but only beads or splashes since urea caused a notable destruction of the self-associated CD aggregates in their concentrated solutions. The structural, thermal and mechanical characteristics of the CD nanofibers were also investigated. Although the CD derivatives are amorphous small molecules, interestingly, we observed that these electrospun CD nanofibers/nanowebs have shown some mechanical integrity by which they can be easily handled and folded as a free standing material.     

Phase separation in polyetherimide/solvent/nonsolvent systems and membrane formation

Phase separation phenomena of polyetherimide (PEI)/solvent/nonsolvent systems were investigated by measuring their precipitation values over the temperature range from 20 to 50°C. The solvents used are N‐methyl‐2‐pyrrolidone (NMP), dimethylacetamide (DMAC), and dimethylformamide (DMF). Nine nonsolvents were employed including water, methanol, ethanol, 1‐propanol, 2‐propanol, acetic acid, propionic acid, ethylene glycol, and diethylene glycol. Based on the measured precipitation values, critical solubility parameters for PEI were calculated, and the partial solubility boundary for PEI was obtained in a two‐dimensional solubility parameter coordinate graph. The relationship between solvent strength and membrane structure was examined using PEI hollow‐fiber membranes prepared from binary polymer solutions containing NMP, DMAC, and DMF as solvents. Water was used both as internal and external coagulants. The cross‐sectional structure and gas permeation properties of these hollow fibers were examined. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1789–1796, 1999     

The influence of solvent type and polymer concentration on the physical properties of solid state polymerized PA66 nanofiber yarn

We investigated the effects of two different solvent types and three solution concentrations on the electrospinning of solid state polymerized polyamide 66 (SSP PA66) nanofiber yarns. Nanofiber yarns were electrospun from SSP PA66 solutions in formic acid and formic acid/chloroform (3/1), using two oppositely metallic spinnerets system. Scanning electron microscopy (SEM) and X‐ray diffraction (XRD) were employed to characterize the morphology and properties of the nanofibrous yarns. Experimental results show that adding chloroform to formic acid as a binary solvent increases viscosity of polymer solution and the nanofibers diameter significantly. XRD patterns reveal that the presence of chloroform affects the crystallinity and the mechanical properties of the produced nanofibrous yarns. PA66 nanofiber yarn from 10 wt % formic acid/chloroform (3/1) solution was successfully electrospun with strength and modulus of 120.16 MPa and 1216.27 MPa respectively. It is also shown that the solution concentration has a significant effect on the modulus of the nanofibers yarns. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012