Enhanced ferroelectric phase content of polyvinylidene difluoride fibers with the addition of magnetic nanoparticles

Polyvinylidene difluoride (PVDF) fibers with continuously dispersed ferrite (Ni 0.5Zn 0.5Fe 2O 4) nanoparticles were prepared by electrospinning from dimethyl formamide (DMF) solutions. The effects of the electrospinning processing conditions and nanoparticle loading on the formation of the alpha, beta, and gamma phases of PVDF were studied using infrared spectroscopy and differential scanning calorimetry. The amount of the ferroelectric beta and gamma phases present in the fibers was found to increase with increased nanoparticle loading. We have shown that the formation of PVDF phases with extended chain conformations can be enhanced by the addition of a well-dispersed nanoparticle phase. At increased nanoparticle loadings, the alpha phase is completely converted to the more extended beta and gamma phases.     

EFFECT OF GAS FLOW RATE ON CRYSTAL STRUCTURES OF ELECTROSPUN AND GAS-JET/ELECTROSPUN POLY(VINYLIDENE FLUORIDE) FIBERS

The effect of gas flow rate on crystal structures of electrospun and gas-jet/electrospun poly(vinylidene fluoride) (PVDF) fibers was investigated.PVDF fibers were prepared by electrospinning and gas-jet/electrospinning of its N,N-dimethylformamide (DMF) solutions.The morphology of the PVDF fibers was investigated by scanning electron microscopy (SEM).With an increase of the gas flow rate,the average diameters of PVDF fibers were decreased.The crystal structures and thermal properties of the PVDF fibers w...     

Poly(methyl methacrylate)/silica nanocomposite fibers by electrospinning

Uniform poly(methyl methacrylate) (PMMA)/silica nanocomposite fibers containing up to 20 wt % silica were prepared by electrospinning. The electrospun solutions were prepared by mixing a solution of PMMA in dimethyl formamide (DMF) with colloidal silica in methyl ethyl ketone (MEK). The average fiber diameter decreases from 2.49 μm to 1.69 μm when 20 wt % silica is incorporated as a result of considerably increased solution conductivity, although the solution viscosity increases significantly, which should result in opposite effect. Thinner fibers (down to 350 nm) can be obtained by changing DMF/MEK proportion and by the addition of an ammonium salt. Nano‐sized silica particles (10–40 nm) distributes homogeneously in the fibers, as revealed by transmission electron microscopy. Furthermore, the incorporation of silica nanoparticles can change the thermal properties and surface wettability of the fiber mats. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1211–1218, 2009     

采用静电纺丝/非溶剂致相分离制备聚丙烯腈多孔超细纤维的研究

以聚丙烯腈/二甲基亚砜/N,N'-二甲基甲酰胺三元体系为纺丝液、3℃水浴为接收介质,通过静电纺丝制备了具有纳米孔结构的静电纺聚丙烯腈多孔超细纤维.探讨了溶剂比例、接收介质、聚丙烯腈浓度、纺丝电压及接收距离等因素对纤维直径和表面孔隙率的影响.结果表明最佳制备条件为混合溶剂质量比1∶1、纺丝电压16 kV、聚丙烯腈浓度15 wt%、接收距离5 cm、纺丝速率0.7 mL/h、环境温度25℃、相对湿度40%～70%.在此条件下得到的聚丙烯腈多孔超细纤维直径在420～490 nm,平均直径468 nm,表面孔隙率3.4%,纤维内部形成大量孔径为8～30 nm的孔结构,且孔径分布均匀,孔形状相对一致.N2吸附脱附测试表明,聚丙烯腈多孔纤维的BET比表面积达43.86 m2/g,是相同直径无孔聚丙烯腈纤维比表面积理论值的6倍.通过研究聚丙烯腈/(二甲基亚砜+N,N'-二甲基甲酰胺)/水的三元相图,提出非溶剂致相分离是主要成孔机理.     

Fabrication of Electrospun PVDF Nanofibers with Higher Content of Polar β Phase and Smaller Diameter by Adding a Small Amount of Dioctadecyl Dimethyl Ammonium Chloride

In this work,the effect of dioctadecyl dimethyl ammonium chloride(DDAC,a kind of alkyl ammonium salt) on polar β phase content and the diameter of electrospun PVDF nanofibers was investigated for the first time.Our experimental results show that the diameter of the electrospun PVDF nanofiber could be largely reduced and the content of polar β phase also become dominant immediately by just adding a little amount of DDAC.When the mass fraction of DDAC reached 4%,the content of polar β phase increased by about 39.1% compared with PVDF nanofibers without DDAC.Besides,the crystallinity of PVDF nanofibers also increased with the addition of DDAC.Based on the results,the possible mechanism of cooperative effect between electrospinning and DDAC on fiber diameter and formation of β phase in PVDF was discussed.     

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     

原生纤维素静电纺丝的调控

通过电纺非溶剂调控的纤维素溶液, 制备出纤维素电纺纤维. 在N,N-二甲基乙酰胺(DMAc)-氯化锂(LiCl)溶解纤维素体系中, 以DMAc和N,N-二甲基甲酰胺(DMF)作为非溶剂, 添加到高浓度的纤维素溶液中制备电纺溶液. 考察添加非溶剂对纤维素溶液性质和电纺纤维形貌的影响. 结果表明, 添加非溶剂有助于提升纤维素溶液的可纺浓度, 获得分散性较好的电纺纤维, 其中DMF效果最好. 添加非溶剂降低了纤维素溶液的黏度, 使纤维素溶液可纺浓度提高; 添加非溶剂改变了电纺溶液的稳定性, 获得了分散良好的纳米纤维, 从而有助于纤维素射流在电纺过程中快速固化成型.     

Process optimization and empirical modeling for electrospun polyacrylonitrile (PAN) nanofiber precursor of carbon nanofibers

Ultrafine fibers were spun from polyacrylonitrile (PAN)/N,N-dimethyl formamide (DMF) solution as a precursor of carbon nanofibers using a homemade electrospinning set-up. Fibers with diameter ranging from 200 nm to 1200 nm were obtained. Morphology of fibers and distribution of fiber diameter were investigated varying concentration and applied voltage by scanning electric microscopy (SEM). Average fiber diameter and distribution were determined from 100 measurements of the random fibers with an image analyzer (SemAfore 5.0, JEOL). A more systematic understanding of process parameters was obtained and a quantitative relationship between electrospinning parameters and average fiber diameter was established by response surface methodology (RSM). It was concluded that concentration of solution played an important role to the diameter of fibers and standard deviation of fiber diameter. Applied voltage had no significant impact on fiber diameter and standard deviation of fiber diameter.     

Microfluidic fabrication of β-phase enriched poly(vinylidene fluoride) microfibers toward flexible piezoelectric sensor

β-phase enriched piezoelectric poly(vinylidene fluoride) (PVDF) films/fibers are often prepared by high-energy costing methods, including mechanical stretching, high-electric field or electrospinning. In this study, PVDF piezoelectric microfibers, for the first time, were prepared by microfluidic spinning technology. The β-phase enriched PVDF microfibers with various diameters could be easily obtained inside the microfluidic channel due to the mass transfer induced phase inversion of the inner PVDF solution. The influence of diameter of the fibers, PVDF concentration of the inner phase and water content of the outer phase on the β-phase content and crystallinity degree of the obtained fibers was studied in detail. The obtained β-phase enriched fiber was weaved into meshes. Flexible piezoelectric fabrics were then developed based on these meshes, and further used as in-situ and real time human motion monitoring. This simple and effective strategy provides a promising microfluidic spinning technique toward the development of functional microfibers and wearable piezoelectric sensors, which may also give some implies for the industrial wet-spinning of piezoelectric PVDF fibers in the future.     

Fabrication of electrospun PVDF nanofibers with higher content of polar <Emphasis Type="Italic">β</Emphasis> phase and smaller diameter by adding a small amount of dioctadecyl dimethyl ammonium chloride

In this work, the effect of dioctadecyl dimethyl ammonium chloride (DDAC, a kind of alkyl ammonium salt) on polar β phase content and the diameter of electrospun PVDF nanofibers was investigated for the first time. Our experimental results show that the diameter of the electrospun PVDF nanofiber could be largely reduced and the content of polar β phase also become dominant immediately by just adding a little amount of DDAC. When the mass fraction of DDAC reached 4%, the content of polar β phase increased by about 39.1% compared with PVDF nanofibers without DDAC. Besides, the crystallinity of PVDF nanofibers also increased with the addition of DDAC. Based on the results, the possible mechanism of cooperative effect between electrospinning and DDAC on fiber diameter and formation of β phase in PVDF was discussed.     

Thermal properties and structure of electrospun blends of PVDF with a fluorinated copolymer

We report the structure and thermal properties of blends comprising poly(vinylidene fluoride) (PVDF) and a random fluorinated copolymer (FCP) of poly(methyl methacrylate)‐random‐1H,1H,2H,2H‐perfluorodecyl methacrylate, promising membrane materials for oil–water separation. The roles of processing method and copolymer content on structure and properties were studied for fibrous membranes and films with varying compositions. Bead‐free, nonwoven fibrous membranes were obtained by electrospinning. Fiber diameters ranged from 0.4 to 1.9 μm, and thinner fibers were obtained for PVDF content >80%. As copolymer content increased, degree of crystallinity and onset of degradation for each blend decreased. Processing conditions have a greater impact on the crystallographic phase of PVDF than copolymer content. Fibers have polar beta phase; solution‐cast films contain gamma and beta phase; and melt crystallized films form alpha phase. Kwei's model was used to model the glass transition temperatures of the blends. Addition of FCP increases hydrophobicity of the electrospun membranes. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 312–322     

Membranes of epitaxial-like packed, super aligned electrospun micron hollow poly(l-lactic acid) (PLLA) fibers

Novel epitaxial-like packed, super aligned, mono-layered hollow fibrous membranes were prepared by co-axial electrospinning technology. PLLA pellets were dissolved in solvent mixture of dichloromethane and dimethyl formamide (DCM/DMF = 9:1) to prepare sheath solution dope with various concentrations (from 8 to 19 wt.%). Aqueous solution of poly-ethylene glycol (PEG) was used as core solution dope. During the electrospinning process, dope concentrations and feed rate ratios were adjusted, separately, to evaluate the formation of resulting membranes. With lower shell solution concentration (from 8 to 15 wt.%), the collected, flattened film showed arrangement of lower order. A stood-up film was clearly seen when concentration increased to 17 wt.% and higher. As the collecting time went longer, these fibers piled up and eventually, stood up as a thin film from the surface of collector. Increasing flow rate ratio (FRR) also resulted similar outcomes and verify the cause of this phenomenon. After washing with water, scanning electron microscopy (SEM) revealed sheets of mono-layered, micron-sized hollow fiber arrays which were well aligned and tightly packed, just like the epitaxial growth of some semiconducting materials. These perfectly aligned and tightly packed hollow fiber arrays can be considered as highly anisotropic scaffolds that mimic tissue structures, such as nerve tissue, vascular structure as well as other application.     

Controlling the surface structure,mechanical properties,crystallinity, and piezoelectric properties of electrospun PVDF nanofibers by maneuvering molecular weight

Polyvinylidene fluoride (PVDF) is a significant polymer in the formation of nanofiber webs via the electrospinning technique. In this paper, three PVDF-wrinkled fiber webs with different molecular weights (M_Ws) (180000, 275000, and 530000) were generated via the electrospinning method by using tetrahydrofuran/N,N-dimethylformamide at the solvent ratio of 1:1 as a mixed solvent. The formation mechanism of the wrinkled electrospun PVDF fibers is demonstrated. Furthermore, the relationships between the M_W and the surface structure, mechanical properties, crystalline phases, and piezoelectric properties of electrospun PVDF fibers are comprehensively investigated. The results reported that the surface structure, mechanical properties, crystalline phases, and piezoelectric properties of wrinkled electrospun PVDF fibers can be affected intensely by maneuvering the M_W. We believe this study can be served as a good reference for the effect of M_W on the morphology and properties of electrospun fibers.     

多孔Fe_2O_3纳米纤维用于高容量长寿命锂空气电池催化剂

采用静电纺丝技术,以乙酰丙酮铁[Fe(C5H7O2)3]、聚乙烯吡咯烷酮(PVP)和二甲基甲酰胺(DMF)为原料,制备了由Fe2O3纳米颗粒组成的高比表面积的多孔纳米纤维,并成功应用于锂氧气电池用催化剂.Fe2O3纳米颗粒为反应提供了充足的活性位点,提高了电池容量;而三维网状结构为反应物及产物提供了足够的反应及储存空间,避免了对电极孔道堵塞的问题,从而达到了锂空气电池长循环的目的.     

Crystallization kinetics of poly(ethylene oxide) confined in semicrystalline poly(vinylidene) fluoride

Polymer blends based on poly(vinylidene fluoride) (PVDF) and poly(ethylene oxide) (PEO) have been prepared to analyze the crystallization kinetics of poly(ethylene oxide) confined in semicrystalline PVDF with different ratios of both polymers. Both blend components were dissolved in a common solvent, dimethyl formamide. Blend films were obtained by casting from the solution at 70 °C. Thus, PVDF crystals are formed by crystallization from the solution while PEO (which is in the liquid state during the whole process) is confined between PVDF crystallites. The kinetics of crystallization of the confined PEO phase was studied by isothermal and nonisothermal experiments. Fitting of Avrami model to the experimental DSC traces allows a quantitative comparison of the influence of the PVDF/PEO ratio in the blend on the crystallization behavior. The effect of melting and further recrystallization of the PVDF matrix on PEO confinement is also studied. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 588–597     

Effect of coagulant temperature and composition on surface morphology and mass transfer properties of cellulose acetate hollow fiber membranes

Cellulose acetate (CA) hollow fibers were spun via the dry‐jet wet spinning technique under various external coagulant compositions and temperatures. The surface morphology of the resulting hollow fiber was examined using field emission scanning electron microscopy (FESEM) and tapping mode atomic force microscopy (TMAFM). The pure water permeability (PWP) and the retention of dextran of the hollow fiber were also measured. The results showed that both the temperature and composition can affect greatly the surface morphology and hence the permeation performance of hollow fiber membranes when the temperature was over 55°C and the dimethyl formamide (DMF) content was higher than 15%. The on‐line draw ratio increased with the coagulant temperature and DMF content (in the range of 0 to 10%) in the external coagulant. The ultimate tensile strength also increased when the fibers were coagulated in 5–10% DMF and at 70°C. The PWP increased with the DMF content in the coagulant and the coagulant temperature. The retention of dextran decreased with the increase of the DMF content in the coagulant and the coagulant temperature. Copyright © 2005 John Wiley & Sons, Ltd.     

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     

静电纺制备纳米孔结构聚乳酸(PLLA)超细纤维

采用静电纺丝法制备了孔径为40～150 nm的PLLA纳米孔结构超细纤维,纳米孔不仅分布在纤维表面,而且存在于纤维内部.通过扫面电镜观察了纤维表面形貌.探讨了混合溶剂二氯甲烷/N,N-二甲基甲酰胺的比例、PLLA浓度、电场强度对PLLA纤维纳米孔大小、分布密度、深度的影响.结果表明通过调节PLLA溶液性质和纺丝参数,PLLA纤维的表面形貌可以在3种状态即光滑无孔、疏浅凹坑、密集深孔之间可控.二氯甲烷/N,N-二甲基甲酰胺比例为1∶4,PLLA浓度9%,电场强度1 kV/cm,环境温湿度分别为30℃和52%,静电纺丝所得PLLA超细纤维表面孔洞直径为150 nm,孔洞分布密集.纳米孔PLLA纤维形成的主要机理是由于静电纺丝过程中溶剂的快速挥发引起纤维表面温度急剧降低导致热致相分离而产生多孔结构.PLLA纤维膜的疏水性与纤维表面孔洞结构密切相关,纤维膜接触角最高可达146.6°.由于PLLA纤维的多孔结构,这种高疏水性的PLLA纤维膜能够快速、大量地吸油,90 s内吸收柴油达到90 g/g,25 min内可以达到145 g/g.     

酞菁锌高效催化以二氧化碳、含氢硅烷和有机胺为原料合成甲酰胺类衍生物

目前为了有效地利用好CO2,主要策略有以下几种:(1)"水平途径"——无价态及能量变化,譬如生成尿素、环状碳酸酯、聚碳酸酯及噁唑烷酮类衍生物等;(2)"垂直途径"——有价态及能量变化,譬如直接加氢转化成碳一产品(甲酸、甲醛、甲醇、甲烷)等;(3)"对角线途径"——有价态及能量变化,即结合石油化工原料将CO2还原生成醇、醚、羧酸、亚胺、酰胺、酯等系列高附加值的精细有机化工产品.其中以二氧化碳和含氢硅烷为原料,通过有机胺的N-甲酰化反应合成甲酰胺类衍生物符合绿色化学和可持续发展的要求.基于仿生催化CO2分子活化的基本理论,我们借鉴强极性的有机溶剂可有效活化硅氢键的性质,创新性地将廉价易得的酞菁锌(ZnPc)作为类酶催化剂,并以化学计量的N,N'-二甲基甲酰胺(DMF)为添加剂,构成组分新颖并高效绿色的类酶协同催化体系,实现了在温和反应条件下高效高选择性地合成甲酰胺类衍生物.研究发现:以苯硅烷作为还原剂,当加入0.5 mol%ZnPc和2 mmol DMF,在25℃和0.5 MPa下仅需反应6 h,可得到收率为99%的N-甲基甲酰苯胺.更值得注意的是,当以更易得的聚甲基氢硅烷(PMHS)为还原剂时,加入5 mol%ZnPc和1 mL DMF,在80℃和1 MPa下反应8 h,N-甲基甲酰苯胺的收率也高达99%.实验结果表明:添加剂DMF可以通过溶剂化和强极性作用高效活化含氢硅烷中的Si?H键,然后具有亲电性的金属活性中心能够稳定氢负离子生成高活性锌氢中间体.即ZnPc/DMF之间的协同催化作用能够促进氢化物从含氢硅烷转移到CO2分子,进而有利于CO2分子的高效活化.综上所述,利用类酶催化剂反应专一性的特点,通过有机胺的N-甲酰化反应,实现了以CO2和含氢硅烷为原料在温和条件下甲酰胺类衍生物的绿色高效合成.这对于设计和开发更加高效的催化体系具有一定的指导作用和借鉴意义.     

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.