Piezoelectric and Electrostatic Properties of Electrospun PVDF‐TrFE Nanofibers and their Role in Electromechanical Transduction in Nanogenerators and Strain Sensors

Piezo‐ and ferroelectric nanofibers of the polymer poly(vinylidenefluoride) (PVDF) have been widely employed in strain and pressure sensors as well as nanogenerators for energy harvesting. Despite this interest, the mechanism of electromechanical transduction is under debate and a deeper knowledge about relevant piezoelectric or electrostatic properties of nanofibers is crucial to optimize transduction efficiency. Here poly(vinylidenefluoride‐trifluoroethylene) nanofibers at different electrospinning conditions are prepared. Macroscopic electromechanical response of fiber mats with microscopic analysis of single nanofibers performed by piezoelectric and electrostatic force microscopy are compared. The results show that electrospinning favors the formation of the piezoelectric β‐phase in the polymer and leads directly to piezoelectric properties that are comparable to annealed thin films. However, during electrospinning the electric field is not strong enough to induce direct ferroelectric domain polarization. Instead accumulation of triboelectric surface charges and trapped space charge is observed in the polymer that explain the electret like macroscopic electromechanical response.     

Aerosol filtration performance of nanofibrous mats produced via electrically assisted industrial-scale solution blowing

Highly efficient polyamide 6 (PA6)-based nanofibrous air filter media was developed for particulate matter (PM) removal in the ambient atmosphere. The PA6 nanofibrous mats exhibited 85% PM0.3 capture performance at a cost of 164 Pa pressure drop when the multiple-nozzle solution blowing system was set to 8 m/h fabric winding speed. However, an increase in the winding speed at a constant feeding rate lowered the filtration efficiency to 62% due to the less amount of nanofibrous mats collected on the substrate. The application of electrical field at the same parameters allowed us to produce a filter media having FFP3-level filtration performance, which means 99% PM0.3 capture performance. This was attributed to a fine fiber diameter (116 nm), higher solidity value (0.149), and lower average pore size (2.28 μm). These results show that the electrically assisted solution blowing provides a feasible route for the production of high-quality nanofibrous filter media.     

Influence of oxygen plasma treatment parameters on poly(vinylidene fluoride) electrospun fiber mats wettability

Electrospun poly(vinylidene fluoride) (PVDF) fiber mats find applications in an increasing number of areas, such as battery separators, filtration and detection membranes, due to their excellent properties. However, there are limitations due to the hydrophobic nature and low surface energy of PVDF. In this work, oxygen plasma treatment has been applied in order to modify the surface wettability of PVDF fiber mats and superhydrophilic PVDF electrospun membranes have been obtained. Further, plasma treatment does not significantly influences fiber average size (∼400 ± 200 nm), morphology, electroactive β-phase content (∼80–85%) or the degree of crystallinity (X_c of 42 ± 2%), allowing to maintain the excellent physical–chemical characteristics of PVDF. Plasma treatment mainly induces surface chemistry modifications, such as the introduction of oxygen and release of fluorine atoms that significantly changes polymer membrane wettability by a reduction of the contact angle of the polymer fibers and an overall decrease of the surface tension of the membranes.     

Preparation of the chitosan containing nanofibers by electrospinning chitosan–gelatin complexes

Electrospinning is an interesting technique, which provides a facile and an effective mean in producing nonwoven fibrous materials; however, for producing nanofibers, investigation of the electrospinning conditions is very important. In this study, chitosan, gelatin, and their polyelectrolyte complexes (PECs) were electrospun to prepare nonwoven nanofibrous mats. The concentrations of chitosan and gelatin solutions and electric field (kV/cm) were optimized. The solutions were then blended in different ratios (0–100%) to get electrospun nanofibrous mats. Solution concentration and electric field showed pronounced effect on the electrospinnability and fiber diameter of these systems. Mostly large beads coexisted with the fibers were observed for chitosan at 1 wt% solution concentration, which then showed good electrospinnability at 2 wt% (nanofiber diameter was 145 and 122 nm at 15 and 20 kV/10 cm, respectively), whereas gelatin showed no electrospinnability below 15 wt% solution concentration and a homogenous fibers network at 15 wt% (149 nm at 20 kV/10 cm). The morphology and diameter of chitosan–gelatin PEC nanofibers varied with the chitosan/gelatin ratio. The crystallinity of chitosan was also observed to reduce with electrospinning and addition of gelatin. POLYM. ENG. SCI. 50:1887–1893, 2010. © 2010 Society of Plastics Engineers     

Poly(butylene terephthalate) electrospun/melt‐blown composite mats for white blood cell filtration

In this research, poly(butylene terephthalate) (PBT) electrospun nanofibrous mats were prepared for white blood cell (WBC) filtration after the blood was collected from donors. The feasibility of using PBT electrospun mats used as WBC filtration materials was studied. The average fiber diameter and mean pore diameter of the PBT electrospun mats were much lower than those of melt‐blown mats, and such properties were found to be beneficial for the functions of filtration and cell absorbency. A layer of PBT electrospun mats was added before the exit of filter; this formed a kind of compound material with different pore diameters and fibers diameters in the direction of blood flow. The WBC filtration efficiency of the newly designed filter and a traditional filter were also compared. The results show that filters with electrospun PBT fibers reduced the number of WBCs to 10⁴/L, whereas the remaining WBCs after flow through the traditional filter was about 10⁵L^?1. The existence of electrospun fibers increased the filtration resistance at the same time, and this led to a longer filtration time. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Electrospinning of antibacterial poly(vinylidene fluoride) nanofibers containing silver nanoparticles

Poly(vinylidene fluoride) (PVDF) nanofibrous mats containing silver nanoparticles were prepared by electrospinning. The diameter of the nanofibers ranged between 100 and 300 nm, as revealed by scanning electron microscopy. The silver nanoparticles were dispersed, but some aggregation was observed with transmission electron microscopy. The content of silver nanoparticles incorporated into the PVDF nanofibrous mats was determined by inductively coupled plasma and X‐ray photoelectron spectroscopy. The antibacterial activities of the samples were evaluated with the colony‐counting method against Staphylococcus aureus (Gram‐positive) and Klebsiella pneumoniae (Gram‐negative) bacteria. The results indicate that the PVDF nanofibrous mats containing silver nanoparticles showed good antibacterial activity compared to the PVDF nanofiber control. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Electret characteristics of melt-blown polylactic acid fabrics for air filtration application

Polylactic acid (PLA) is a biodegradable and biocompatible polymer. Melt-blown PLA electret fabrics have become attractive materials for air filter applications. Its filtration performance mainly depends on the electrostatic effect originating from electrets. How to improve their electret behavior and then to enhance their filtration efficiency has always been challenging. In this article, three melt-blown PLA fabrics with different morphological or crystal structure are made from different process conditions or ingredient. The electrets are formed by means of corona charging technology. Their crystalline and morphological structure was analyzed, and filtration performance was measured. Their charge-trapping feature was studied by thermal stimulating discharge technology. The results proved that the air filtration efficiency of three melt-blown samples improved a lot when electrets were formed. Different crystalline structures of PLA fabrics will result in differences in their electret charge-trapping feature. The PLA fabrics with semi-crystalline characteristics display a regular charge-trapped level distribution and amorphous structure hints the diversity of charge-trapped levels. The deference in filtration resistance is mainly ascribed to the different fiber diameters and their distributions. More narrow distribution of fiber diameter leads to more compact fabrics and to higher filtration resistance. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48309.     

Electrostatic Capture Efficiency Enhancement of Polypropylene Electret Filters with Barium Titanate

This study reports on the effects of BaTiO₃—a high dielectric constant additive—addition on charging and filtration properties of meltblown polypropylene (PP) electret filters. Since electrostatic capture efficiency of electret filters is mainly dependent on electrical forces, surface potential and aerosol filtration properties were analyzed and compared. Due to quasi-permanent nature of electret property, stability of charging and filtration performance was also investigated via following an isothermal charge decay procedure. Addition of BaTiO₃ did not alter fiber morphology significantly. Particularly, the stability of electrostatic filtration performance was found to be promising with the addition of BaTiO₃. Possible microstructural changes after addition of BaTiO₃ were investigated via wide angle X-ray diffraction. Changes in crystal structure of PP upon addition of BaTiO₃ did not deteriorate electrostatic properties.

Copyright 2015 American Association for Aerosol Research     

Preparation of antibacterial biocompatible polycaprolactone/keratin nanofibrous mats by electrospinning

Keratin-based materials are widely used in biomedical applications due to excellent biocompatibility and biodegradability. In this study, keratin was extracted from waste wool fibers and blended with polycaprolactone (PCL) to produce PCL/keratin nanofibrous mats by electrospinning. The electrospun PCL/keratin nanofibrous mats were chlorinated in diluted sodium hypochlorite solution to endow antibacterial properties. The prepared nanofibrous mats were characterized by scanning electron microscopy, X-ray photoelectron, and Fourier infrared spectroscopy. The effect of the chlorination time on the active chlorine loading of the mats was investigated. The chlorinated PCL/keratin nanofibrous mats with 0.78 ± 0.009 wt% active chlorine displayed potent antibacterial activity against Gram-positive Staphylococcus aureus (ATCC 6538) and Gram-negative Escherichia coli O157:H7 (ATCC 43895) with 6.88 and 6.81 log reductions, respectively. It was found that the mats were compatible with mouse fibroblast cells (L929). The chlorinated PCL/keratin nanofibrous mats might find promising applications in the biomedical field.     

Sustained release of CIP from TiO2-PVDF/starch nanocomposite mats with potential application in wound dressing

Electrospinning is an economical and alluring method to fabricate wound dressing mats from a variety of natural and synthetic materials. In this study, polyvinylidene fluoride (PVDF) and starch composite mats containing ciprofloxacin (CIP) loaded on titanium dioxide nanoparticles (TiO₂) were prepared. Fourier Transform Infrared spectra of CIP, synthesized TiO₂ NPs, TiO₂/CIP, and PVDF/starch composite mats are analyzed. Scanning electron microscopy images revealed that the fiber diameter of PVDF nanofibers thickens by increasing starch, which varies between 180 nm and 550 nm. Strain at break of PVDF, starch, PVDF/starch (2:1 w:w; P2S1), PVDF/starch (1:1 w:w; P1S1), PVDF/starch (1:2 w:w; P1S2), and nanofibers were 103 ± 11, 3 ± 0.6, 27 ± 4, 52 ± 5.2, 7.7 ± 1%, respectively. Based on strain at break and young modulus, P2S1 was selected as a suitable candidate for wound dressing to which load TiO₂/CIP as a bioactive agent. The release rate of CIP showed that about 40% of the drug is released in the first 2 days. Furthermore, the antibacterial activity of dressings was investigated using Escherichia coli and Staphylococcus aureus microorganisms and zones of clearance were obvious around the specimen on the agar plate. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48916.     

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.     

Optimization of electro-blown polysulfone nanofiber mats for air filtration applications

Durable, robust, and hydrophobic air filtration media was produced via electro-blow spinning (EBS) technique using polysulfone (PSU) due to its superior properties. To our knowledge, this is the first optimization study of PSU nanofiber production via EBS technique for air filtration applications. Concentration, air pressure, and voltage were determined as independent variables for the optimization based on “smaller is the better” approach of Taguchi Design of Experiment. The optimized values which supplied the smallest average fiber diameter (AFD) possible were obtained as 13 wt% PSU, 3 bar, and 7.5 kV. The AFD of the sample obtained from the confirmation experiment was calculated as 105 ± 34 nm. Surface morphologies, porosity values, and wettability behaviors of the samples were investigated by using scanning electron microscopy, gravimetric method, and water contact angle measurements, respectively. PSU nanofiber mats exhibited superhydrophobic behavior (water contact angle values up to 159.8°) which is important for various separation processes. Samples prepared at different deposition times (15, 30, 45, and 60 min) were investigated in terms of particle capture efficiency and pressure drop. The 0.3 μm particle filtration efficiency was found to be 98.09% at an expense of 202 Pa pressure drop which would be suitable for various respiratory and HVAC filter applications.     

Electrospun PVDF/MWCNT/OMMT hybrid nanocomposites: preparation and characterization

Electrospinning technique was employed to prepare neat PVDF, nanoclay-PVDF and carbon nanotube (MWCNT)-PVDF nanocomposites, and nanoclay-carbon nanotube-PVDF hybrid nanocomposites. A mixture of dimethyl formamide/acetone (60/40) was used to fluidize the polymer and nanofillers. Electrospinning process was conducted under optimized conditions. Maximum modification was achieved at 0.15 wt% nanofiller. Rheological measurements on the prepared solutions revealed decreased material functions in the presence of nanoclay, whereas the rheological properties of MWCNT-PVDF solution did not show any significant reduction compared with those of neat PVDF solution. The behaviors of the hybrid nanocomposite solutions, though dependent on their composition and their material functions, increased with MWCNT concentration. These differences, together with variations in electrical properties of nanoclay and MWCNT, led to changes in morphology of the fiber during electrospinning process. Under electrospinning conditions designed for neat PVDF solution, mats with beads and with the highest fiber diameter were produced. Meanwhile, incorporation of both nanoclay and MWCNT into the solutions resulted in bead-free fibers with thinner diameter. Fourier transformed infrared spectrophotometry (FTIR) and X-ray diffractometry (XRD) were used to measure the β-phase crystalline content in electrospun mats. Complete agreement was found between the FTIR and XRD results. The lowest and highest β-phase contents were obtained for neat PVDF mat and hybrid nanocomposite mat containing 0.1 wt% clay, respectively. The mixing procedure of nanofillers and the PVDF solution was also found to be important. In case of hybrid nanocomposites, more β-crystals were formed when the nanoclay was first mixed in the absence of MWCNT.     

Electrospun ultrathin nylon fibers for protective applications

Electrospun nylon 6 fiber mats were deposited on woven 50/50 nylon/cotton fabric with the motive of making them into protective material against submicron‐level aerosol chemical and biological threats. Polymer solution concentration, electrospinning voltage, and deposition areal densities were varied to establish the relationships of processing‐structure‐filtration efficiency of electrospun fiber mats. A high barrier efficiency of greater than 99.5% was achieved on electrospun fiber mats without sacrificing air permeability and pressure drop. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and characterization of microporous sodium poly(aspartic acid) nanofibrous hydrogel

A novel biodegradable sodium poly(aspartic acid) (PASP) hydrogel with microporous structure was manufactured using electrospun polysuccinimide (PSI) nanofibers. PSI is the intermediate of sodium PASP and could be electospun into nanofibers easily. Firstly, PSI nanofibers were prepared from PSI/N, N-dimethylformamide solution. Then the PSI nanofibrous mats were crosslinked and hydrolyzed to obtain biodegradable microporous sodium PASP nanofibrous hydrogels. The chemical structures, morphologies and pore sizes of PSI nanofibrous mats and microporous sodium PASP nanofibrous hydrogels were investigated. Moreover, the properties of PSI electrospinning solutions, and the swelling ratio and biodegradability of sodium PASP hydrogels were also examined. The results showed that the swelling ratio of microporous sodium PASP nanofibrous hydrogels achieved to 21.0–24.3 g/g and were obviously higher than that of the sodium PASP casting film, reporting a swelling ratio of only 4.6 g/g. When the microporous sodium PASP nanofibrous hydrogel was immersed in water, it exhibited quick absorption and morphological robustness. The microporous sodium PASP nanofibrous hydrogel showed 83 wt% weight loss after 7 days of trypsin catalyzed biodegradation, and the SEM analysis demonstrated the significant morphology change of the microporous sodium PASP nanofibrous hydrogel during the biodegradation.     

纳米纤维膜在空气净化中的应用研究进展

面向空气净化的应用需要,开发高效净化材料已成为研究热点之一,其中具有相互连贯孔结构的纳米纤维膜在高效空气净化领域展示出巨大的应用前景。对于纳米纤维膜对空气净化效果的评估指标通常包括过滤效率和过滤阻力。本文介绍了串珠、蛛网和复合等结构纳米纤维膜的研究进展,分析了驻极式纳米纤维膜在高效除尘方面的应用现状,探讨了银纳米颗粒和半导体金属氧化物改性纳米纤维膜在抗菌和除有机易挥发性气体等多功能性空气净化中的应用可行性,指出了高效低阻、功能化是纳米纤维膜用于空气净化领域的研究重点。并提出今后应高度关注多污染物对纳米纤维空气净化膜性能的影响,深入研究具有多功能协同作用的纳米纤维空气净化膜,以期获得更广泛的应用。     

Effect of spinning temperature and blend ratios on electrospun chitosan/poly(acrylamide) blends fibers

We report the formation of non-woven fibers without bead defects by electrospinning blend solutions of chitosan and polyacrylamide (PAAm) with blend ratios varying from 75 wt% to 90 wt% chitosan using a modified electrospinning unit wherein polymer solutions can be spun at temperatures greater than ambient up to 100 °C. Electrospinning at elevated temperature leads to further expansion of the processing window, by producing fibers with fewer defects at higher chitosan weight percentage in the blends. Effects of varying blend ratios, spinning temperatures, and molecular weights on fiber formation were studied and optimum conditions for formation of uniform non-woven fiber mats with potential applications for air and water filtration were obtained. Uniform bead-less fiber mats with fiber diameter as low as 307 ± 67 nm were formed by spinning 90% chitosan in blend solutions at 70 °C.     

PET/CA根须状蓬松纳米纤维复合膜的制备及其烹饪油烟过滤性能

为有效净化烹饪油烟，采用共溶剂静电纺丝技术，通过调控聚酯（PET）和醋酸纤维素（CA）的共混比，制备根须状蓬松纳米纤维复合膜。借助扫描电子显微镜、接触角测试仪及自动滤料测试系统等分析所制备纤维膜的微观形貌、表面润湿性及油烟过滤性能。结果表明：所制备的8:2纳米纤维复合膜成形良好，具有明显的根须状结构，直径集中在根须100nm和根冠300nm左右；且堆积蓬松，孔隙率、堆积密度分别达93.85±1.71%、0.023±0.008；水接触角154±1°，油从初始接触角84°到吸收为0°仅需2s，具有特殊表面润湿性；模拟烹饪油烟过滤测试表明：过滤效率达92%，过滤压降仅为36Pa，且经20次循环测试后其过滤效率基本不下降，仍保持在91%以上；在100 min连续过滤测试后，其过滤效率仍大于90%，过滤阻力规律性缓慢上升，满足烹饪油烟过滤的需求。     

Dust Collection by a Fiber Bundle Electret Filter in an MVAC System

Electret filters are composed of thin, electrically charged fibers that are often utilized in industrial fields that require high collection efficiency with low flow resistance. A bundle-type electret filter in the Mechanical Ventilation and Air-Conditioning (MVAC) system of a Metro-subway was characterized in this study. The particle penetration and pressure drop parameters were examined under a filtration velocity ranging from 0.5 to 2.5 m/s. Particle penetration increased significantly in the early stages of filtration, but then became steady. The filter quality, which is a useful index of the filtration performance incorporating pressure drop and filtration efficiency, was evaluated for the test filters. The fiber bundle filter demonstrated a higher filter quality than the mechanical filter or the general panel-type electret filter with a small drop in pressure even at a high filtration velocity. In addition, the three dimensional structure and high electrostatic charge of the fiber bundle filter would enable a long retention time and constant level of pressure drop throughout the filtration.     

A review of cement-based materials as electroceramics

The dielectric behavior of unpoled cured cement-based materials enables these materials to serve as electroceramics. The behavior entails the DC polarization (apparent DC electrical resistivity increase), permittivity (AC polarization, capacitance measurement) and DC electret (permanent electric dipole, voltage measurement). The dielectric behavior is not derived from functional admixtures such as the perovskite ceramics. The polarization involves charge-carrier polarization, with the carriers being primarily the ions in the pore solution. Dipolar polarization associated with the polar water molecules plays a minor role. Silica fume, if present, decreases the permittivity, partly due to the pore refinement. A polymer admixture, if present, increases the permittivity, with significant polarization resulting from the cement-polymer interface. Carbon fiber, if present, affects the electronic and ionic conduction, with the fiber’s ozone treatment promoting the ionic conduction and enhancing the permittivity. As the water/cement ratio increases, the permittivity increases, but the DC polarization decreases. The DC polarization occurs faster and more significantly than the subsequent depolarization. This reflects the electret, which discharges upon short circuiting (as in capacitor discharge) and subsequently charges back upon open circuiting. The temperature increases the permittivity or the electret’s electric field, whereas tension decreases the same, enabling capacitance-based/voltage-based self-sensing of temperature and stress/strain.