Effect of electrospinning on the ferroelectric phase content of polyvinylidene difluoride fibers

Polyvinylidene difluoride (PVDF) fibers were prepared by electrospinning from dimethyl formamide (DMF) solutions. The effects of the electrospinning processing conditions on the formation of the alpha and beta phases of PVDF were studied using infrared spectroscopy and differential scanning calorimetry. We have shown that beta-phase PVDF fibers can be electrospun directly from a dimethyl formamide (DMF) solution with a maximum fraction of beta phase, F(beta)max, of 0.75. The fraction of beta phase is found to be greater for smaller-diameter fibers and those spun at an increased voltage.     

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.     

PHBV电纺纤维结构与形态的研究

利用电纺丝法制备了超细聚 β 羟基丁酸戊酸酯 (PHBV)纤维 ,通过扫描显微镜 (SEM)、差热分析(DSC)、宽角X射线衍射和偏振红外吸收光谱对产品进行了结构与形态的表征 .研究了纺丝过程中溶液浓度、电压和接收距离 3个参数对纤维形态的影响 .结果表明 ,溶液浓度是决定性的 ,只有高于一个定值才能获得单一的纤维产品 .与流延成型的PHBV相比 ,电纺丝具有较高的取向度和结晶度 .原因可能是 ,电场力下喷丝震荡过程中带来的拉伸作用从而引起分子链的规整排列     

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.     

Preparation,characterization, and properties of nanofibers based on poly(vinylidene fluoride) and polyhedral oligomeric silsesquioxane

Nanostructered nanofibers based on poly(vinylidene fluoride) (PVDF) and polyhedral oligomeric silsesquioxane (POSS) have been prepared by electrospinning process. The starting solutions were prepared by dissolving both the system components in the mixture N,N‐dimethylacetamide/acetone. The characteristics of the fiber prepared, studied by scanning electron microscopy, atomic force microscopy, and wide angle X‐ray diffraction, have been compared with those of PVDF fibers. Morphological characterization has demonstrated the possibility to obtain defect‐free PVDF/POSS nanofibers by properly choosing the electrospinning conditions, such as voltage, polymer concentration, humidity, etc. Conversely, in the case of fibers based on the neat polymer, it was not possible to attain the complete elimination of beads in the electrospun nanofibers. The different behavior of the two types of solutions has been ascribed to silsesquioxane molecules, which, without influencing the solution viscosity or conductivity, favor the formation of uniform structures by decreasing the system surface tension. Concerning POSS distribution in the fibers, the morphological characterization of the electrospun films has shown a submicrometric dispersion of the silsesquioxane. It is relevant to underline that cast films, prepared by the same solutions, have been found to be characterized by POSS aggregation, thus demonstrating a scarce affinity between the two‐system components. Indeed, the peculiar solvent evaporation of the electrospun solution, which is much faster than that occurring during the cast process, prevents POSS aggregation, thus leading to the formation of nanofibers characterized by a silsesquioxane dispersion similar to that present in solution. Finally, the presence of POSS improves the electrospun film mechanical properties. Copyright © 2011 John Wiley & Sons, Ltd.     

聚偏氟乙烯电纺膜及其电化学性能的研究

用电纺的方法制备了聚偏氟乙烯纳米纤维膜,它们具有多微孔结构,能够作为锂电池聚合物电解质.电纺中聚合物溶液的浓度对制备的电纺膜的结构形态有很大的影响,低浓度(10 wt%)时得到珠丝结构的膜,浓度15 wt%时则为纤维结构,而高浓度(18 wt%)时,电纺膜为交联的网状结构.用电纺法制备的聚偏氟乙烯纳米纤维微孔膜具有较高的孔隙率,而且它们与锂金属电极具有良好的界面稳定性;在25℃时吸液率最高可达340%,以这种膜制备的聚合物电解质室温电导率可达到1.57×10-3S.cm-1;由该电解质组装的扣式电池以0.5 mA.cm-2恒流充放电,25℃时50次循环后几乎无容量损失,具有良好的循环性能;即使60℃时,电池仍能保持良好的工作稳定性.     

聚乙二醇-b-聚乳酸的合成及其电纺形成超细纤维研究

为了提高聚乳酸的亲水性,以辛酸亚锡为催化剂、聚乙二醇单甲醚(mPEG)为大分子引发剂进行丙交酯(LLA)开环聚合,合成聚乙二醇-b-聚乳酸两嵌段共聚物(PELA).以红外光谱1、H核磁共振谱、接触角测试、差热扫描量热分析等方法对PELA的结构及性能进行表征.结果表明,通过调控mPEG与LLA的投料比可以控制PELA的相对分子质量,而随着mPEG组分含量或链长增加,共聚物亲水性增强,但其Tg、Tcc、Tm有所降低.由普通电纺制备PELA超细纤维,并分别由乳液电纺和同轴电纺得到以水溶性聚氧化乙烯(PEO)为芯、PELA为壳的芯/壳结构复合超细纤维(E-PEO/PELA和C-PEO/PELA).扫描电镜和透射电镜结果表明,PELA、E-PEO/PELA和C-PEO/PELA超细纤维形貌良好.随着PELA中mPEG含量的增加,电纺PELA纤维膜的吸水率增强,而由乳液电纺和同轴电纺制备的PEO/PELA芯/壳结构超细纤维膜,亲水性均好于PELA超细纤维膜.     

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     

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.     

核-壳结构壳聚糖/聚乙烯醇-聚碳酸亚丙酯超细纤维的制备

利用同轴电纺丝技术制备出具有核-壳结构的壳聚糖/聚乙烯醇-聚碳酸亚丙酯电纺丝纤维,考察了溶剂复配对成纤的影响,采用扫描电镜和透射电镜对纤维的形貌、结构、直径分布等进行了探索,并在优化的工艺条件下,将羟基磷灰石负载在内层结构中.研究表明,采用氯仿/N,N-二甲基甲酰胺(1/1)复配溶剂可有效避免聚合物溶液在喷丝口处的凝结现象.同单纺纤维相比,核壳结构的纤维直径分布较宽,纤维壳层和核层界限清晰;红外谱图分析证明羟基磷灰石可负载在纤维的核结构中.     

二氧化碳-环氧丙烷共聚物电纺纤维形貌研究

利用电纺丝技术制备了二氧化碳环氧丙烷共聚物超细纤维,研究了喷丝口电势、纺丝距离、浓度、溶剂等因素对纤维形貌、直径及均一性的影响.实验结果表明,利用电纺丝法可以制备直径在小于200nm到7μm二氧化碳环氧丙烷共聚物纤维;喷丝口电势和浓度对于共聚物电纺丝纤维是否形成串珠结构有重要影响;电势、距离和纺丝液浓度都对纤维直径及分散系数有较大影响,在一定范围内,随着喷丝口电势增加,纤维平均直径变大而分散系数变小;纺丝距离增大使得纤维平均直径变小,分散系数变大;浓度的增大使得纤维平均直径变大,分散系数变小;不同溶剂配制的溶液体系制备的电纺丝纤维形貌有很大差异,在二氯甲烷和丁酮的体系中,分别观察到了两组较为集中的直径分布.     

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.     

Electrospinning of Hyaluronic Acid (HA) and HA/Gelatin Blends

Summary: In the present study, electrospinning of hyaluronic acid (HA) and hyaluronic acid/gelatin (HA‐GE) blends in N,N‐dimethylformamide (DMF)/water‐mixed solvents have been investigated. When the volume ratio of DMF to water was in the range of 1.5–0.5, HA solutions could be electrospun into fibrous membranes successfully. The average diameter of HA fibers was about 200 nm. The HA‐GE composite nanofibrous membranes with varied HA/GE weight ratio in the range of 100/20–100/100 have also been successfully fabricated. The average diameter of HA‐GE fibers was in the range of 190–500 nm. The decrease in surface tension could promote fiber formation. Thus, an introduction of DMF that could decrease the surface tension distinctively, without significant change or increase in viscosity of the solution, could bypass the use of blowing‐assisted electrospinning. Our postulated picture is that the lower surface tension could help the ejection of stream with relatively high viscosity and reduce or prevent the droplet formation during the spinning process.

HA/GE (100/80) nanofibrous membrane produced by electrospinning.     

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.

     

PMMA/PVDF共混对PVDF的β相构型影响的研究

采用溶液法制备了不同含量的聚甲基丙烯酸甲酯/聚偏二氟乙烯(PMMA/PVDF)共混薄膜,利用傅立叶变换红外光谱(FTIR)、X射线衍射谱(XRD)、和差热分析法(DSC)对共混薄膜的结晶行为进行了分析。结果表明,共混物中PMMA的含量对PVDF的β相构型有明显影响:PMMA/PVDF=30/70共混物中β相含量最高。为提高PVDF薄膜的铁电性能提供了新的研究方法。     

溶剂对PVDF铸膜液相转化和微孔膜皮-亚两层结构的不同影响

采用皮-亚分步凝固成膜机理分析了3种不同溶剂对聚偏氟乙烯(PVDF)铸膜液相转化和膜结构的影响,采用浊度法测定铸膜液体系的热力学性质,沉淀速度采用光透射仪测定.结果显示,3种膜的皮层分相主要由热力学性质控制,均发生延时液固分相,生成了相互融合的球粒组成的致密皮层.3体系的亚层分相行为由动力学扩散过程控制;对于二甲基亚砜(DMSO)、N,N-二甲基乙酰胺(DMAc)体系亚层发生瞬时液液分相,结晶化对动力学过程影响小,表现为光透射曲线上分相时间t2短,生成了大孔结构为主的亚层,膜厚度、孔隙率和气通量均高、结晶度低;N,N-二甲基甲酰胺(DMF)体系亚层发生延时液液分相,结晶化对动力学过程影响大,t2长,生成蜂窝状孔结构亚层,其膜厚度、孔隙率和气通量较低,但膜的结晶度高.     

Investigation of nanomechanical and morphological properties of silane-modified halloysite clay nanotubes reinforced polycaprolactone bio-composite nanofibers by atomic force microscopy

There is remarkable interest in the fabrication of polymeric composite nano/micro-fibers by electrospinning for many applications ranging from bioengineering to water/air filtration. In almost all of these applications, the mechanical properties of both the polymer fibers and their assemblies, are significant. In this study, unmodified, 3-Glycidoxypropyltrimethoxysilane (GPTMS) or 3-Aminopropyltriethoxysilane (APTES) modified halloysite clay nanotube (HNT) reinforced polycaprolactone (PCL) nanofibers were successfully synthesized via the electrospinning. The morphology and mechanical features of the obtained electrospun fibers were investigated by atomic force microscopy (AFM) and AFM-based nanoindentation for single fibers in nanoscale, respectively. Besides, scanning electron microscopy and tensile strength tests were used to investigate whole fibrous structures in microscale. The AFMresults, accompanied by SEM and tensile strength, support the conclusion that silane-modification affected positively the morphology and mechanical characteristics of electrospun PCL nanofibers. Therefore, it was concluded that the morphological and mechanical features from the single fibers in the nanofiber mats were related to the whole fibrous structure.     

电纺聚氧化乙烯纤维的分散形态和结晶行为研究

将聚氧化乙烯(PEO)水溶液在不同的工艺条件下进行电纺,制备了PEO纤维.用SEM研究了纤维的分散形态;用DSC和XRD研究了纤维的结晶性能.电纺纤维分散形态是由浓度、电压、固化距离等因素综合作用的结果.其中,浓度是最关键的因素.降低溶液浓度,提高静电压和增加固化距离均会使纤维变细.电纺得到的纤维与原粉相比,电纺使纤维结晶度下降,理论上分析了可能的机理.     

ELECTROSPRAYING/ELECTROSPINNING OF POLY(y-STEARYL-L-GLUTAMATE):FORMATION OF SURFACES WITH SUPERHYDROPHOBICITY

Electrospraying/electrospinning of poly(y-stearyl-L-glutamate) (PSLG) was investigated on a series solutions with different concentrations in chloroform.Field emission scanning electron microscopy (FESEM) and attenuated total reflectance Fourier transform infrared spectroscopy (FT-IR/ATR) were used to characterize the morphology and structure of the electrosprayed/electrospun polypeptide mats.It was found that electrospraying of PSLG with concentrations lower than 16 wt% afforded beads,while microfibers could be electrospun at the concentration of 22 wt%.The hydrophobieity of the electrosprayed/electrospun PSLG mats was investigated with static water contact angle (WCA) and tilt angle measurements.It was demonstrated that the superhydrophobic surfaces of PSLG with WCAs and tilt angles in the ranges of 150°-170°and16.5°-4.2°,respectively,were obtained through electrospraying/electrospinning process.     

酚醛基电纺纤维的制备和分散形态研究

用电纺技术制备了酚醛纤维及碳纤维.用合成的甲阶酚醛(A-stage resol)和聚乙烯醇(PVA)在不同配比下进行电纺,然后经150℃固化处理1h,制得酚醛(PF)纤维.将PF和PVA质量比为1∶2的酚醛纤维在不同的温度下进行热处理,得到的纤维直径均小于200nm.用场发射扫描电镜(FESEM)观察并比较了纤维的直径和分散形态.用红外光谱(IR)证实了,在600℃下热处理后的酚醛纤维为碳纤维,分散形态最为理想.