Morphology Tuning of Electrospun Liquid Crystal/Polymer Fibers

This paper elucidates the means to control precisely the morphology of electrospun liquid crystal/polymer fibers formed by phase separation. The relative humidity, solution parameters (concentration, solvent), and the process parameter (feed rate) were varied systematically. We show that the morphology of the phase‐separated liquid crystal can be continuously tuned from capsules to uniform fibers with systematic formation of beads‐on‐a‐string structured fibers in the intermediate ranges. In all cases, the polymer forms a sheath around a liquid‐crystal (LC) core. The width of the polymer sheath and the diameter of the LC core increase with increasing feed rates. This is similar to the results obtained by coaxial electrospinning. Because these fibers retain the responsive properties of liquid crystals and because of their large surface area, they have potential applications as thermo‐, chemo‐, and biosensors. Because the size and shape of the liquid‐crystal domains will have a profound effect on the performance of the fibers, our ability to precisely control morphology will be crucial in developing these applications.     

Design of a novel co‐electrospinning system with flat spinneret for producing helical nanofibers

A kind of biomimetic fibers of helical structures at nanoscale has attracted increasing interest. In this study, a novel co‐electrospinning setup with a designed flat spinneret, used for the fabrication of helical nanofibers, is reported in this study. Poly(m‐phenylene isophthalamide) (Nomex) and Thermoplastic polyurethane (TPU) are chosen as the two components in co‐electrospinning. To display the efficiency for producing helical fibers, a generally used core–shell needle spinneret is used for comparison. The effect of the uniformity of electric field distribution created by these two types of spinnerets on the jet motion and the resultant helical fibers is developed, with systematical simulation and experimental research. The results showed that the co‐electrospinning system with the newly designed flat spinneret can produce helical nanofibers efficiently. Compared with the needle spinneret, the flat spinneret created more uniform electric field, leading to better morphology and structure of the resultant helical fibers. In addition, an approach to achieve the scale‐up of this co‐electrospinning system is developed. This novel design is expected to provide a promising method to fabricate nanofiber materials with helical structures. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1496–1505     

Aligned and molecularly oriented semihollow ultrafine polymer fiber yarns by a facile method

In this work, aligned and molecularly oriented bone‐like PLLA semihollow fiber yarns were manufactured continuously from an optimized homogeneous polymer‐solvent‐nonsolvent system [PLLA, CH₂Cl₂, and dimethyl formamide (DMF)] by a single capillary electrospinning via self‐bundling technique. Here, it should be emphasized that the self‐bundling electrospinning technique, a very facile electrospinning technique with a grounded needle (which is to induce the self‐bundling of polymer nanofibers at the beginning of electrospinning process), is used for the alignment and molecular orientation of the polymer fiber, and the take‐up speed of the rotating drum for the electrospun fiber yarn collection is very low (0.5 m/s). PLLA can be dissolved in DMF and CH₂Cl₂ mixed solvent with different ratios. By varying the ratios of mixed solvent system, PLLA electrospun semihollow fiber with the porous inner structure and compact shell wall could be formed, the thickness of the shell and the size of inner pores could be adjusted. The results of polarized FTIR and wide angle X‐ray diffraction investigations verified that as‐prepared PLLA semihollow fiber yarns were well‐aligned and molecularly oriented. Both the formation mechanism of semihollow fibers with core‐shell structure and the orientation mechanism of polymer chains within the polymer fibers were all discussed. The as‐prepared self‐bundling electrospun PLLA fiber yarns possessed enhanced mechanical performance compared with the corresponding conventional electrospun PLLA fibrous nonwoven membranes. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1118–1125, 2010     

Polymer entanglement loss in extensional flow: Evidence from electrospun short nanofibers

High strain rate extensional flow of a semidilute polymer solution can result in fragmentation caused by polymer entanglement loss, evidenced by appearance of short nanofibers during electrospinning. The typically desired outcome of electrospinning is long continuous fibers or beads, but, under certain material and process conditions, short nanofibers can be obtained, a morphology that has scarcely been studied. Here we study the conditions that lead to the creation of short nanofibers, and find a distinct parametric space in which they are likely to appear, requiring a combination of low entanglement of the polymer chains and high strain rate of the electrospinning jet. Measurements of the length and diameter of short nanofibers, electrospun from PMMA dissolved in a blend of CHCl₃ and DMF, confirm the theoretical prediction that the fragmentation of the jet into short fibers is brought about by elastic stretching and loss of entanglement of the polymer network. The ability to tune nanofiber length, diameter and nanostructure, by modifying variables such as the molar mass, concentration, solvent quality, electric field intensity, and flow rate, can be exploited for improving their mechanical and thermodynamic properties, leading to novel applications in engineering and life sciences. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 1377–1391     

Different buckling regimes in direct electrospinning: A comparative approach to rope buckling

Understanding the dynamics of direct electrospinning is the key to control fiber morphologies that are critical for the development of new electrospinning methods and novel materials. Here, we propose the theory for direct electrospinning based on theories for (liquid) “rope coiling” and experimentally test it. For the experiments, the buckling of microscale liquid ropes formed from polymer solutions is studied systematically using three different electrospinning setups and for different polymer concentrations. We show that different buckling regimes exist, whose dynamics are governed by an interplay of electrical, inertial, and viscous forces, and that three different buckling regimes emerge depending on the dominant forces. For low polymer concentrations, we observe an inertial regime similar to that observed for viscous liquid ropes at high velocities. By increasing the polymer concentration and consequently decreasing the rope velocity, we enter an inertial‐electrical regime for which discontinuities occur in the buckling frequency as a function of applied voltage. These observations can be accounted for quantitatively by replacing the gravitational forces in viscous rope coiling theory with the electrical forces of our electrospinning experiment. Finally, for the highest polymer concentration, we observe a purely electrical regime for a solidified rope; this regime is well described by “elastic” rope coiling theory. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 451–456     

Shape recovery liquid crystal elastomer synthesized by melt‐polycondensation

A novel liquid crystal elastomer (LCE) synthesized by melt polymerization, which exhibits the capacity of shape memory, is reported here for the first time. The method of synthesize the shape memory LCE has been explored. A facile two‐step method to synthesize these anisotropic materials to realize reversible shape change behavior is reported. The first reaction is the addition of nematic liquid crystal molecules to form a kind of liquid crystal polymer. Subsequently, the polymer is crosslinked to trap the order of the liquid crystal into a crosslinked LCE. The LCE exhibits liquid crystalline behavior which has shape memory with excellent fixity and recovery. Its shape memory and actuating properties also have been studied. When reheating the LCE to 165 °C, the shape will recover. The main chains and crosslinked bonds of the LCE contain ester groups, which are sensitive to alkaline and acidic condition. It turns out that the LCE is intact under acidic condition, but it can be degraded under alkaline condition. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 389–394     

Novel antibacterial fibers of amphiphilic N‐halamine polymer prepared by electrospinning

As a significant role in subcategory of halogen antibacterial field, amphiphilic N‐halamine polymers show a promise as potential antimicrobials having a broad spectrum of microorganisms, long‐term stability, and renewal of their antibacterial properties. By controlling the process parameters, electrospinning has been well recognized as a versatile and effective method being capable of making fibers and could be easily engineered with desired pore size and porosity to enhance the antimicrobial properties. The amphiphilic N‐halamine P (ADMH‐MMA‐HEMA) terpolymer fibers showed efficient antimicrobial properties against both Gram‐positive and Gram‐negative bacteria within brief contact time. The result meant that the polymer fibers of macromolecular architecture with control of structural parameters such as hydrophobicity/hydrophilicity balance achievement improved antimicrobial activities via electrospinning technique. In vitro cytotoxicity study demonstrated that the polymer was biocompatible. As a result, the integration of amphiphilic antibacterial materials and the electrospinning technique provided us a feasible method to fabricate biocompatible antimicrobial products easily with low manufacturing cost and would be applied in many promising application areas.     

Effects of formulation variables on liquid‐crystal droplet size distributions in ultraviolet‐cured polymer‐dispersed liquid‐crystal cells

The size distributions of liquid‐crystal droplets in ultraviolet‐cured polymer‐dispersed liquid‐crystal cells have been studied with optical microscopy. It has been observed that (1) the relative masses of the liquid crystal and crosslinking agent determine the droplet size distribution for submicrometer droplet diameters and (2) only the liquid‐crystal mass fraction affects the droplet size distribution for diameters ranging from 1 to 4 μm. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1842–1848, 2005     

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.

     

Influence of solvents on the formation of ultrathin uniform poly(vinyl pyrrolidone) nanofibers with electrospinning

Although there have been many reports on the preparation and applications of various polymer nanofibers with the electrospinning technique, the understanding of synthetic parameters in electrospinning remains limited. In this article, we investigate experimentally the influence of solvents on the morphology of the poly(vinyl pyrrolidone) (PVP) micro/nanofibers prepared by electrospinning PVP solution in different solvents, including ethanol, dichloromethane (MC) and N,N‐dimethylformamide (DMF). Using 4 wt % PVP solutions, the PVP fibers prepared from MC and DMF solvents had a shape like a bead‐on‐a‐string. In contrast, smooth PVP nanofibers were obtained with ethanol as a solvent although the size distribution of the fibers was somewhat broadened. In an effort to prepare PVP nanofibers with small diameters and narrow size distributions, we developed a strategy of using mixed solvents. The experimental results showed that when the ratio of DMF to ethanol was 50:50 (w/w), regular cylindrical PVP nanofibers with a diameter of 20 nm were successfully prepared. The formation of these thinnest nanofibers could be attributed to the combined effects of ethanol and DMF solvents that optimize the solution viscosity and charge density of the polymer jet. In addition, an interesting helical‐shaped fiber was obtained from 20 wt % PVP solution in a 50:50 (w/w) mixed ethanol/DMF solvent. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3721–3726, 2004     

Liquid crystal fibers produced by using electrospinning technique

This paper investigates the electrospinning process of liquid crystalline polysiloxane with cholesterol as side chain (LCPC) and the influence on the morphology of the formed fibers by mixing LCPC solution with small-molecule liquid crystal, triethylamine, and poly(ethylene oxide)(PEO). The mechanical properties of single fibers were characterized by a novel approach. The results indicate that, under appropriate conditions, fine liquid crystal fibers can be obtained and the preferable mechanical properties can be achieved, especially after annealing. WXRD was used to investigate the orientation of polymer molecules in the formed fibers, suggesting that strong interaction exists between LCPC and PEO molecule in the resulting composite fibers, and polymer molecular tends to arrange regularly during electrospinning processing. This research work provides a new and facile method of using electrospinning to prepare liquid crystal fibers, which would be useful for designing the related high-performance materials.     

Dielectric relaxation spectroscopy and alignment behavior of a polymer‐dispersed liquid crystal and its component materials

The dielectric properties of a polymer‐dispersed liquid crystal (PDLC), a liquid‐crystal (LC) mixture (BL036), and three polymer matrices of PN314 containing different amounts of BLO36 were determined over a range of frequencies and temperatures and, for the LC and PDLC, over a range of voltages leading to homeotropic alignment of the LC. The overall dielectric relaxation process was a weighted sum of contributions from (1) the primary (δ) process in the LC arising from the motions of the dipoles about the short molecular axis and (2) dipole motions in the polymer matrix. The dielectric spectra were determined as a function of frequency, temperature, and, when appropriate, applied voltage. An equivalent electrical circuit was used as a working model to describe the dielectric behavior of the PDLC in the absence and presence of applied voltages. Agreement between the dielectric data and this model was achieved if a portion of the LC phase at the interface was assumed to be immobile. The director order parameter for the LC component in the PDLC was determined from dielectric measurements as the material was aligned homeotropically in an applied electric field. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 1173–1194, 2001     

Self-aligning liquid crystals in polymer composite systems

Soft composite materials combined with a holographic photopolymerization process are used for realizing an innovative switchable periodic structure made of slices of almost pure polymer alternated with films of well aligned nematic liquid crystals named POLICRYPS. It exhibits negligible scattering losses, while the effect of the spatial modulation of the refractive index (from polymer to nematic liquid crystal) can be switched on and off by applying a low (few V/μm) electric field. The diffractive properties of the POLICRYPS structure are characterized in terms of cell thickness, impinging probe angle and wavelength revealing a strong correlation between the diffraction efficiency and all the above mentioned parameters. These results are very attractive for many applications such as switchable Bragg gratings for telecom devices, phase modulators, and displays. Other advantages of the technology include absence of an alignment layer, absence of haze, robust structure, and inexpensive manufacturing. In addition, no special alignment layers are required. This is a unique opportunity and a big advantage compared to conventional liquid crystal devices. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 158–162     

Fabrication and characterization of zein-based nanofibrous scaffolds by an electrospinning method

Electrospun zein membranes were prepared using DMF as solvent. By changing the solution concentration, the electrospinning voltage and the distance between the spinneret and collector, nanofibrous meshes without bead defects could be obtained. In order to improve the mechanical strength of the hydrated zein meshes, core-shell-structured nanofibrous membranes with PCL as the core material and zein forming the shell were prepared by coaxial electrospinning. The core-shell structure of the composite fibers was confirmed by SEM characterization of the fibers, either extracted with chloroform to remove the inner PCL, or elongated to expose their cross-section. The composition and average diameter of the composite fibers could be modulated by the feed rate of the inner PCL solution. It was found that the core-shell fibrous membranes have similar wettability to the electrospun zein mesh. The presence of PCL in the fibers could significantly improve the mechanical properties of the zein membrane.     

Flat polymer ribbons and other shapes by electrospinning

In addition to round nanofibers, electrospinning a polymer solution can produce thin fibers with a variety of cross‐sectional shapes. Branched fibers, flat ribbons, ribbons with other shapes, and fibers that were split longitudinally from larger fibers were observed. The transverse dimensions of these asymmetric fibers were typically 1 or 2 μm, measured in the widest direction. A correlation of the branches and bends, observed in high‐frame‐rate videography of the electrified jets of polymer solutions from which the ribbons and branched fibers were produced, suggest that these phenomena occur at scales ranging from around 1 mm to 1 μm. The observation of fibers with these cross‐sectional shapes from a number of different kinds of polymers and solvents indicates that fluid mechanical effects, electrical charge carried with the jet, and evaporation of the solvent all contributed to the formation of the fibers. The influence of a skin on the jets of polymer solutions accounts for a number of the observations. The observed shapes can be used as guides for the extension of mathematical or computer‐generated models for the electrospinning process. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2598–2606, 2001     

Extension-Enhanced Conductivity of Liquid Crystalline Polymer Nano-Composites

Our aim here is to predict elongational flow-induced enhancements in thermal or electrical conductivity of liquid crystal polymer (LCP) nano-composites. To do so, we combine two classical mathematical asymptotic analyses: slender longwave hydro-thermo-dynamics for fibers and exact analysis of pure elongation of LCPs in solvents for bulk phases without boundary effects; and homogenization theory for effective properties of low volume-fraction spheroidal inclusions. Two implications follow: elongational flow dominates fiber free surface and thermal effects on electrical and thermal conductivity enhancements; and, there appears to be no sacrifice in enhancements by producing much higher radius, bulk fibers.     

Large‐scale aligned fiber mats prepared by salt‐induced pulse electrospinning

In this article, a new large‐scale aligned fiber mats formation method called salt‐induced pulse electrospinning was developed. By electrospinning salted solution in a humid environment, traditional continuous electrospinning changed into pulse electrospinning and aligned fibers were thus formed. The possible mechanisms for the occurrence of salt‐induced pulse electrospinning and the formation of fiber alignment were studied. The continuous electrospinning changing into the pulse electrospinning was due to the change of viscosity and conductivity of salted polymer solution in a wet electrospinning condition. Fishing net‐shaped whipping region of the electrospinning jet during pulse electrospinning process was considered as the key factor for the formation of fiber alignment. The mechanical properties of the aligned fiber mat increased significantly compared with that of the random fiber mat. This aligned fiber preparation method only requires a very low rotating drum speed as the receiver and can produce large‐scale aligned fiber mats for many applications. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Mass preparation of nanofibers by high pressure air‐jet split electrospinning: Effect of electric field

A novel electrospinning method using airflow, namely high pressure air‐jet split electrospinning, was proposed to fabricate polymer nanofibers with ultrahigh production rate. 7 wt % polyacrylonitrile spinning solution with a 0.157 Pa s viscosity was divided into micron size droplets by the filter screen in the front of the nozzle, and then these droplets were divided and split through high pressure airflow, which were drafted into nanofibers directly in the electric field and airflow field. In this study, the electric field distributions with different positive electrodes were simulated and their effect on fiber formation was investigated. The results show that electric field distribution and its intensity depended on electrodes area, a broader electric field distribution with a stronger intensity would bring about a larger cone angle of spraying jet region, at the same time, the contrast in the spray region enhanced. When the whole nozzle was charged, thinner fibers with about 170 nm could be prepared and the fiber production was 75.6 g/h. Compared with the conventional needle electrospinning, the throughput of nanofibers could be improved by thousands of times based on this novel electrospinning method. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 993–1001     

Ultrafine electrospun polyamide‐6 fibers: Effect of emitting electrode polarity on morphology and average fiber diameter

Electrostatic spinning or electrospinning is now a well‐known process for fabricating ultrafine fibers with diameters in the submicrometer down to nanometer range from materials of diverse origins. The polarity of the emitting electrode (i.e., the one that is in contact with the polymer solution or melt) can be either positive or negative. In the present contribution, the effects of emitting electrode polarity and some processing parameters (i.e., polyamide‐6 (PA‐6) concentration, molecular weight of PA‐6, electrostatic field strength, solution temperature, solvent type, and addition of an inorganic salt) on morphological appearance and average size of the as‐spun PA‐6 fibers were investigated. Scanning electron micrographs showed obvious morphological difference between the fibers obtained under positive and negative polarity of the emitting electrode. The main differences were that the cross section of the as‐spun PA‐6 fibers obtained under the negative electrode polarity was flat, while that of those obtained under the positive one appeared to be round and that the average size of the fibers obtained under the negative electrode polarity was larger than that of those obtained under the positive one. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3699–3712, 2005     

Preparation and properties of thermoresponsive and conductive composite fibers with core‐sheath structure

In this research, thermoresponsive and conductive fibers with core‐sheath structure were fabricated by coaxial electrospinning. For preparing the spinning sheath solution, poly‐(N‐isopropylacrylamide‐co‐N‐methylolacrylamide) (PNN) copolymer having thermoresponsive and cross‐linkable properties was synthesized by free‐radical polymerization using redox initiators; it was then mixed with the conductive poly(3,4‐ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) at different weight ratios in water. On the other hand, poly(butyl acrylate‐co‐styrene) (PBS) copolymer synthesized by emulsion polymerization was dissolved in chloroform and used as the spinning core solution. After electrospinning, the fibers were treated at 110 °C for 1 h to cross‐link the PNN portion in the sheath for strengthening the fibers. Well‐defined core‐sheath fibers were observed from SEM pictures; the outside and inside (core) diameters were 568 ± 24 and 290 ± 40 nm, respectively, as determined from TEM pictures. The fiber mats were further doped by DMSO to enhance their conductivity. For the fiber mat with the weight ratio of PEDOT:PSS/PNN at 0.20 in the sheath, its surface conductivity could reach 29.4 S/cm. In addition, the fiber mats exhibited thermoresponsive properties that both swelling ratio and electric resistance decreased with temperature. Furthermore, the fiber mats exhibited improved flexibility as evaluated via bending test. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1299–1307