Electrospinning of ultrafine cellulose acetate fibers: Studies of a new solvent system and deacetylation of ultrafine cellulose acetate fibers

Electrospinning of cellulose acetate (CA) in a new solvent system and the deacetylation of the resulting ultrafine CA fibers were investigated. Ultrafine CA fibers (∼2.3 μm) were successfully prepared via electrospinning of CA in a mixed solvent of acetone/water at water contents of 10–15 wt %, and more ultrafine CA fibers (0.46 μm) were produced under basic pH conditions. Ultrafine cellulose fibers were regenerated from the homogeneous deacetylation of ultrafine CA fibers in KOH/ethanol. It was very rapid and completed within 20 min. The crystal structure, thermal properties, and morphology of ultrafine CA fibers were changed according to the degree of deacetylation, finally to those of pure cellulose, but the nonwoven fibrous mat structure was maintained. The activation energy for the deacetylation of ultrafine CA fibers was 10.3 kcal/mol. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 5–11, 2004     

Electrospinning of ultrafine PVDF/PC fibers from their dispersed solutions

Dispersed solutions of poly(vinylidene fluoride) (PVDF)/polycarbonate (PC) in the mixed solvent of N,N‐dimethylformamide (DMF)/tetrahydrofuran (THF) were used to electrospin in order to discuss the relationship between the properties of the polymer dispersions and the morphology of the obtained ultrafine fibers. With the changes of the mass ratio of PVDF/PC, the relative molecular mass of PVDF, and the volume ratio of DMF/THF, the morphology and the microstructure of the prepared PVDF/PC ultrafine fibers altered in accord with the viscosity, surface tension, and conductivity of the PVDF/PC dispersions. When the PVDF/PC mass ratio varied from 9/1 to 5/5, the ability of the polymer chain entanglement in PVDF/PC dispersion decreased as to the lower relative molecular mass of PC and higher chain rigidity, which lead to the formation of the beaded fibers together with the distinct core/shell structure. Similar phenomenon was also found when the lower molecular mass of PVDF was used instead of a higher one. Though the change of DMF/THF volume ratio did not specifically contribute to the properties of PVDF/PC dispersions, the accelerated evaporation and solubility of the mixed solvent by the THF amount increasing was feasible to generate the uniform fibrous morphology and the distinct core/shell structure. © 2009 Wiley Periodicals, Inc.J Polym Sci Part B: Polym Phys 48: 372–380, 2010     

Electrospinning of Collagen Nanofiber Scaffolds from Benign Solvents

Nanofiber scaffolds of collagen have been fabricated via electrospinning using benign solvent systems as a replacement for 1,1,1,3,3,3 hexafluoro‐2‐propanol. Simple binary mixtures of phosphate‐buffered saline and ethanol have been found to be highly effective for electrospinning. FTIR spectra suggest that the triple helical structure of collagen was conserved after dissolution and electrospinning. Crosslinking of the electrospun collagen scaffolds was achieved with standard methods.

     

Electrospinning of Chitosan

Summary: An electrospun nonwoven fabric of a cationic polysaccharide, chitosan, was successfully prepared. The present study focuses on the effect of the electrospinning solvent and the chitosan concentration on the morphology of the resulting nonwoven fabrics. The solvents tested were dilute hydrochloric acid, acetic acid, neat formic acid and trifluoroacetic acid. As the chitosan concentration was increased, the morphology of the deposition on the collector changed from spherical beads to interconnected fibrous networks. The addition of dichloromethane to the chitosan‐TFA solution improved the homogeneity of the electrospun chitosan fiber. Under optimized conditions, homogenous (not interconnected) chitosan fibers with a mean diameter of 330 nm were prepared.

Effects of the coexisting dichloromethane (MC) in the prespun chitosan‐TFA solution on the morphology of the electrospun chitosan fibers. The volume ratio of TFA:MC was 70:30 (×5 000).     

Poly(dicyclopentadiene) Submicron Fibers Produced by Electrospinning

Summary: We have used the process of electrospinning to produce fibers of poly(dicyclopentadiene) with diameters on the submicron scale. The material, formed from a monomer‐catalyst solution, polymerized in flight during the electrospinning process. Fibers were collected over trenches etched in silicon and the Young's moduli were measured using an atomic force microscope to measure force‐displacement curves. The resulting values of Young's moduli are larger than typical values for bulk polymer material.

SEM image of suspended PDCPD fiber.     

Colloid‐Electrospinning: Fabrication of Multicompartment Nanofibers by the Electrospinning of Organic or/and Inorganic Dispersions and Emulsions

Solution‐, melt‐, and co‐axial electrospinning are well‐known methods for producing nano‐ and microfibers. The electrospinning of colloids (or colloid‐electrospinning) is a new field that offers the possibility to elaborate multicompartment nanomaterials. However, the presence of colloids in the electrospinning feed further complicates theoretical predictions in a system that is dependent on chemical, physical, and process parameters. Herein, we give a summary of recent important results and discuss the perspectives of electrospinning of colloids for the synthesis and characterization of multicompartment fibers.     

Electrical bending instability in electrospinning visco‐elastic solutions

The electrical bending instability in charged liquid jets is the phenomenon determining the process of electrospinning. A model of this phenomenon is lacking however, mostly due to the complicated interplay between the viscosity and elasticity of the solution. To investigate the bending instability, we performed electrospinning experiments with a solution of polyethylene oxide in water/ethanol. Using a fast camera and sensitive multimeter, we deduced an experimental dispersion relation describing the helix pitch length as a function of surface charge. To understand this relation, we developed a theoretical model for the instability for a wide range of visco‐elastic materials, from conducting to nonconducting. The theoretical dispersion relation shows good agreement with the experimental results. Using the new model, we find that the elastic tension in the visco‐elastic threads plays an important role in triggering the instability. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1036–1042     

Electrospinning through the prism of time

Electrospinning is a versatile and flexible technique for the preparation of ultrafine fibers. The present study aims to provide a comprehensive overview of electrospinning, as a complex technique, its evolution toward the high-throughput techniques, including the basic principles, parameters influencing the fibers production process, methods applied to solve the alignment difficulties, commonly used polymers and solvents, and the applications of the electrospun materials. We begin with an insight into the history of electrospinning, followed by its theoretical background and typical apparatus. Then, its renaissance over the past two decades as a powerful technology for the production of nanofibers suitable for industrial scale is presented. Afterward, we briefly discuss the applications of electrospun fibers, including use in different fields of industry, energy harvesting/conversion/storage, photonic and electronic devices, as well as biomedical applications. In the end, we also offer perspectives on the challenges and new directions for developments in electrospinning.     

Electrospinning of poly(vinylidene fluoride)/dimethylformamide solutions with carbon nanotubes

For conductive carbon nanotube (CN)/polymer composite fibers to be obtained, CNs were incorporated into poly(vinylidene fluoride) (PVDF) in dimethylformamide (DMF) solutions and electrospun to form CN/PVDF fiber mats. The thinnest fiber was 70 nm thick. The percolation threshold for the insulator‐to‐conductor transition was 0.003 wt % CN for CN/PVDF/DMF solutions, 0.015 wt % CN for CN/PVDF spin‐coated films, and 0.04 wt % CN for CN/PVDF electrospun fiber mats. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1572–1577, 2003     

Electrospinning of poly(ethylene-co-vinyl acetate)/clay nanocomposite fibers

Poly(ethylene-co-vinyl acetate)/clay nanocomposite fibers were fabricated using electrospinning. The fiber diameters were controlled by varying the polymer/chloroform concentration, which resulted in fibers with diameters ranging from 1 to 15 μm. The clay concentration was varied from 0.35 to 6.6 wt %. Scanning electron microscopy revealed that the fiber diameter increased with increasing clay concentration, whereas beading decreased. Transmission electron microscopy revealed a disruption of the spherulite structures by clay, which is consistent with heterogeneous nucleation. Shear modulus force microscopy indicated a reduction in melting point (T_m) with decreasing diameter for fibers thinner than 15 μm, which was confirmed by temperature dependent X-ray diffraction data. For fibers thinner than 8 μm, the presence of clay further enhanced the reduction of T_m. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2501–2508, 2009     

Multicomponent Phase Change Microfibers Prepared by Temperature Control Multifluidic Electrospinning

Multicomponent phase change microfibers, which can storage and release thermal energy in a stepwise manner, are firstly prepared through a facile one‐step multifluidic compound‐jet electrospinning with temperature control. The multiresponsive effect benefits from a special multichannel tubular microstructure that could controllably encapsulate different phase change materials into the channels independently. Aside from the fabrication of multicomponent phase change microfibers, the melt multifluidic compound‐jet electrospinning is promising for applications related to microencapsulation and multifunctional material fields.

     

Polymorphism Control of Poly(vinylidene fluoride) through Electrospinning

Polymorphism control of PVDF has been realized through electrospinning. PVDF fibrous membranes with fiber diameter in the range of 100 nm to several micrometers were produced by electrospinning and the crystal phase of electrospun PVDF fibers can be adjusted at the same time. Through the control of electrospinning parameters such as the solvent, electrospinning temperature, feeding rate, and tip‐to‐collector distance, PVDF fibrous membranes containing mainly α‐ or β‐ or γ‐phase could be fabricated successfully.

     

Transport properties of water in hydroxypropyl methylcellulose

The relation between the self-diffusion coefficient, D_self, of water and the free volume hole size, V_h, has been investigated in a hydroxypropyl methylcellulose (HPMC)-water system in the water content range 0.08-0.36 w/w, at room temperature. Furthermore, the thermal properties of the water in the HPMC-water system, as measured with differential scanning calorimetry (DSC) and the tensile storage, E′, and tensile loss, E″, moduli, of the HPMC-water systems, as determined with dynamic mechanical analysis (DMA), have been probed. Pulsed-field gradient nuclear magnetic resonance (PFG NMR) was used to measure the D_self of water and positron annihilation lifetime spectroscopy (PALS) was used to measure the ortho-Positronium (o-Ps) lifetime in the HPMC-water system. The glass transition temperature of the HPMC was found to be reduced by the water to room temperature in the water content range 0.10-0.15 w/w. The relation between ln D_self of water and the inverse free volume hole size of the HPMC-water system was non-linear. Furthermore, the PALS measurements showed that molecular water co-existed with water clusters in the HPMC-water system.     

Melt Dispersion and Electrospinning of Non‐Functionalized Multiwalled Carbon Nanotubes in Thermoplastic Polyurethane

Nanoscale fibers with embedded, aligned, and percolated non‐functionalized multiwalled carbon nanotubes (MWCNTs) were fabricated through electrospinning dispersions based on melt‐compounded thermoplastic polyurethane/MWCNT nanocomposite, with up to 10 wt.‐% MWCNTs. Transmission electron microscopy indicated that the nanotubes were highly oriented and percolated throughout the fibers, even at high MWCNT concentrations. The coupling of efficient melt compounding with electrospinning eliminated the need for intensive surface functionalization or sonication of the MWCNTs, and the high aspect ratio as well as the electrical and mechanical properties of the nanotubes were retained. This method provides a more efficient technique to generate one‐dimensional nanofibers with aligned MWCNTs.

     

Thermal extrusion of cellulose using hydroxypropyl methylcellulose

Cellulose - Hydroxypropyl methylcellulose (HPMC), a cellulose derivative, is highly water soluble, viscoelastic, and thermoplastic. However, the thermoplasticity of HPMC has not yet been studied in...     

Photocrosslinkable Liquid Crystal Main‐Chain Polymers: Thin Films and Electrospinning

For mechanical actuators, a response to external stimuli is required. Main‐chain liquid crystal elastomers (MCLCEs) show high response to changes in temperature especially in the vicinity of a phase transition. Most of these crosslinked materials were synthesized in a one‐step reaction which leads to a macroscopically aligned elastomer. Up to now only macroscopic samples have been prepared. We are presenting a new approach which allows us to prepare thin films as well as aligned fibers. First a liquid crystalline main‐chain polymer with a photoactive moiety was synthesized, which was oriented by a mechanical field and photocrosslinked. The thin films show exceptional mechanical properties such as large temperature‐dependent changes in length and a nonlinear stress–strain relation. To obtain fibers, we used the electrospinning process from solution with in situ UV curing. We obtained crosslinked fibers with a uniform alignment of the nematic director.

     

Fabrication of CdS Nanorods in PVP Fiber Matrices by Electrospinning

Summary: A controlled fabrication of rod‐like nanostructures of cadmium sulfide (CdS) incorporated into polymer fiber matrices has been developed by an electrospinning method. Here, poly(vinyl pyrrolidone) (PVP) was used as a polymer capping reagent, utilizing the interactions of cadmium ions with the carbonyl groups in the PVP molecules. The formation of CdS nanorods inside the PVP was carried out via the reaction of Cd²⁺ with H₂S. SEM images showed that the electrospun films of PVP/CdS are composed of fibers with a diameter between 100 and 900 nm. TEM proved that most of the CdS nanorods are incorporated in the PVP fibrous film. The diameter of the rod is about 50 nm and the length is from 100 to 300 nm.

TEM image of the CdS nanorods formed in the PVP fibrous film.     

Electrospinning and cutting of ultrafine bioerodible poly(lactide‐co‐ethylene oxide) tri‐ and multiblock copolymer fibers for inhalation applications

Triblock copolymers made up of poly(ethylene oxide) (PEO) and polylactide (PLA) were synthesized and converted to fibers by the electrospinning process. A two‐step in situ‐synthesis in bulk was applied to extend PLA‐PEO‐PLA triblock copolymers with relatively short block length and low molecular weight in order to obtain electrospinnable materials. DL‐lactide was polymerized to the hydroxyl chain ends of PEO via the stannous octoate route. Hexamethylene diisocyanate (HDI) was added as chain extender in the second step, leading to poly(ether‐ester‐urethane) multiblock copolymers. The materials were electrospun from solutions in chloroform. Different concentrations and voltages were analyzed. The ether and ester blocks were varied in their block length and their effects on the fiber morphology was studied. Variations in the electrical conductivity of the chloroform solutions were investigated by adding triethyl benzyl ammonium chloride (TEBAC) in different amounts. Finally, with high quality electrospun PLA‐PEO‐PEO triblock copolymer fibers mechanical cutting was possible. Copyright © 2009 John Wiley & Sons, Ltd.     

静电纺丝制备荧光导电双功能复合纳米纤维及其表征

采用静电纺丝技术将导电聚苯胺(PANI)和铕/铽稀土配合物掺杂到高分子基质聚乙烯吡咯烷酮(PVP)中,制备出荧光导电复合纳米纤维。用扫描电镜(SEM)、荧光光谱仪(FL)、宽频介电松驰谱仪对荧光导电复合纳米纤维的性能进行分析,结果显示,在270nm紫外光激发下,铕系列与铽系列复合纳米纤维分别发出红光和绿光。同时,复合纳米纤维的电导率可以达到1.18×10~(-6) S/cm,两种复合纳米纤维同时具有优异的荧光性能及良好的导电功能。