PVA/SiO2-TiO2杂化电纺纤维膜的形态与性能

以正硅酸乙酯(TEOS)、钛酸四丁酯(TBT)和聚乙烯醇(PVA)为原料, 用溶胶凝胶法制备了PVA/(SiO2-TiO2)杂化纺丝液, 将其电纺成纤维膜. 红外光谱结果证实, PVA的羟基与TEOS和TBT水解后的羟基发生了缩合反应, 杂化电纺纤维膜以网络结构形式相结合; X射线衍射分析表明, 杂化电纺纤维膜的结晶度比纯PVA电纺纤维膜小; 扫描电镜表明, 随杂化纤维膜中无机相含量的增加, 纤维的直径不断增加, 纤维出现一定的弯曲和扭曲, 并伴有少量带状结构的纤维; 紫外-可见光谱结果表明, TiO2的引入增加了纤维膜的抗紫外性; TGA热分析结果表明, 杂化纤维膜的耐热性能优于纯PVA电纺纤维膜的; 耐水性和稳定性测试表明, 杂化纤维膜的耐水性和稳定性优于纯PVA和PVA/SiO2电纺纤维膜的.     

PVA/DTC纳米纤维的制备及对铅离子的吸附行为

通过高压静电纺丝技术制备了聚乙烯醇/聚乙烯亚胺(PVA/PEI)纳米纤维膜, 对纤维膜进行功能化使其转化为对重金属离子具有高络合能力的聚乙烯醇/二硫代氨基甲酸盐功能化聚乙烯亚胺(PVA/DTC)纳米纤维膜. 研究了PVA/PEI纳米纤维膜的交联和功能化以及PVA/DTC纤维膜对铅离子的吸附行为. 结果表明, 高压静电纺丝法可制备出纤维直径分布均匀、 形貌良好的纳米纤维膜, 且交联、 功能化后仍能保持蓬松纳米纤维状的网状结构. PVA/DTC纳米纤维膜对铅离子吸附速率快, 吸附量容量高, 且具有良好的再生吸附能力, 是一种潜在的重金属离子高效吸附材料.     

钯/聚乙烯醇纤维膜催化水相中的Heck偶联反应

通过静电纺丝和热交联技术、以聚乙烯醇( PVA)作为载体制备了一种电纺纤维膜负载型钯催化剂.利用扫描电镜(SEM)、能谱仪(EDS)和X射线光电子能谱(XPS)对其进行了表征.SEM结果显示:PdCl2的加入导致PVA纤维直径增加、形貌变差,而热交联过程可以减小纤维直径、改善纤维形貌.XPS表征则表明PVA可以还原pd...     

二氧化硅/聚乙烯醇杂化电纺纤维膜的制备与结构形态

用溶胶-凝胶(Sol-Gel)法制备了不同二氧化硅含量的PVA/SiO2杂化纺丝液,将其电纺成纤维膜.XRD结果表明,杂化电纺纤维膜的结晶度较纯PVA电纺纤维膜小;FTIR证实了PVA的羟基与正硅酸乙酯水解后的羟基发生了缩合反应,杂化电纺纤维膜是以网络结构形式相结合的;FESEM表明,PVA/SiO2质量比为4∶1时,纤维光滑,分散比较均匀.随着二氧化硅含量的增加,纤维直径变细,纺锤形珠节结构增多.加入金属盐NaCl和MgCl2后,纤维直径变细,圆形珠节增多.从理论上分析了纤维膜结构形态的形成机理.     

磷钼酸/聚苯乙烯/聚乙烯醇电纺纤维膜的制备及性能

采用静电纺丝法制备了磷钼酸/聚苯乙烯(PS)/聚乙烯醇(PVA)复合纤维,并将其模压成膜.利用红外光谱(IR)、扫描电子显微镜(SEM)及X射线能谱(EDX)等对复合纤维及其膜的结构与形貌进行表征,并对复合纤维膜的光催化性能、力学性能及在水中稳定性进行测试.结果表明,在复合纤维中磷钼酸的Keggin结构得到保持.PS与PVA质量比为1∶1时,复合纤维形貌最佳,表面光滑,直径较小且分布均匀,复合纤维的直径随着磷钼酸含量的增加而减小.将磷钼酸固载于复合纤维膜上比直接使用具有更高的光催化活性,光照25 min后接近98%的甲基橙降解;复合纤维膜易于回收再利用,5次重复使用后,复合纤维膜没有破损,磷钼酸损失较少,光催化性能无明显下降.复合纤维膜的强度随磷钼酸含量的增加先增大后减小,韧性随PVA含量的增加而增大,随磷钼酸含量的增加而减小.     

热压处理提升聚乙烯醇纳米纤维膜水稳定性的研究

通过静电纺丝技术制备了聚乙烯醇(PVA)纳米纤维膜,研究了热压处理的条件(温度、压力、时间)对提升PVA纤维膜水稳定性的影响。随着热压温度的增加,PVA纤维膜的水稳定性增强,红外测试显示,不同温度(50℃、100℃、155℃)热压处理,水稳定性增强的机理不同。扫描电镜照片及水稳定性测试表明,与单纯加热处理相比,热压处理可在较低温度下达到较高温度的效果,压力起到了协同作用。热压压力大于4MPa后,纤维膜的水稳定性无明显提升,热压时间对不同温度处理的PVA纤维膜的水稳定性影响有明显差异。综合考虑PVA的性能和水稳定性,最佳热压处理条件为100℃,4MPa,2min。     

聚乙烯醇明胶混合水溶液的静电纺丝

将聚乙烯醇与明胶混合水溶液进行静电纺丝,制备了聚乙烯醇与明胶混合超细纤维及其电纺膜,研究了混合纺丝液的组成对纺丝液的粘度、表面张力和电导率的影响,观察了纤维的微观形貌,并对电纺膜进行了差示扫描量热测定.结果表明:当混合液中明胶含量小于20 9/6时,静电纺丝可以稳定进行.随着明胶含量由5%逐渐增加至25%,混合超细纤维的平均直径先是由260nm逐渐下降至207 nm而后又逐渐增加至320 nm.明胶的含量低于15%时,不影响其混合电纺膜中PVA的结晶.     

大豆分离蛋白/聚乙烯醇的电纺研究

对大豆分离蛋白(SPI)/聚乙烯醇(PVA)的电纺进行了研究, 讨论了溶液性质和甘油的加入对SPI/PVA电纺纤维形貌的影响, 并对SPI/PVA电纺膜进行了成分分析和力学性能表征. 结果表明, 加入甘油可以提高SPI/PVA的可电纺性, 同时使SPI/PVA电纺膜的拉伸强度从不含甘油的(5.17±0.62) MPa下降到含有甘油的(1.67±0.21) MPa, 而伸长率呈增加趋势.     

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.     

同轴电纺超细纤维膜构建人工血管材料

以右旋糖酐(DEX)为芯、聚乙二醇-b-聚(L-丙交酯-co-ε-己内酯)(PELCL)为壳,经同轴电纺制备DEX/PELCL超细纤维膜。在该电纺纤维内芯分别负载血管内皮生长因子(VEGF)和血小板衍生生长因子(PDGF-bb),并以此构建双层超细纤维膜人工血管支架。4 w的释放结果表明,VEGF和PDGF-bb均表现出突释现象,含有肝素的VEGF样品释放量有所下降。大鼠腹主动脉移植实验表明,载有VEGF和PDGF-bb的超细纤维膜可以用于构建双层人工血管。     

Electrospun PVA Nanofibrous Membranes Reinforced with Silver Nanoparticles Impregnated Cellulosic Fibers: Morphology and Antibacterial Property

To enhance the mechanical and antibacterial properties of silver nanoparticle impregnated cellulosic fibers, carboxy-cellulose nanocrystals(CCNs) were grafted with chitooligosaccharide(COS), which was used as a stabilizer for silver nanoparticles (AgNPs). Nanofibrous membranes reinforced with silver nanoparticle impregnated cellulosic fibers(CCN-COS-AgNP) were prepared via electrospinning using polyvinyl alcohol(PVA) as a matrix. The effects of CCN-COS-AgNP contents on the morphology, surface composition, mechanical properties, and antibacterial performances of the prepared CCN-COS-AgNP/PVA membranes were examined. The addition of CCN-COS-AgNP certainly improved the mechanical properties and antibacterial performances of the PVA nanofibers. The tensile strength was significantly increased from 4.40 MPa to 8.60 MPa when 8% CCN-COS-AgNP(mass ratio) was introduced. When 10%(mass ratio) CCN-COS-AgNP was added, the nanofibers showed an excellent antibacterial activity for S. aureus(Staphylococcus aureus) and E. coli(Escherichia coli), with the maximum inhibition zones of 2.30 and 1.60 cm, respectively. Moreover, the 2%(mass ratio) CCN-COS-AgNP/PVA fibrous membrane showed 126% cell viability for mg63 human osteoblasts. The electrospun PVA membrane has great potential application in biomedical field.     

聚ε-己内酯/聚吡咯电纺膜的制备与性能

以吡咯(Py)和聚ε-己内酯(PCL)为原料、氯仿为溶剂,并掺杂一定量的十二烷基硫酸钠制备电纺膜,利用三氯化铁的氧化作用原位生成聚吡咯(PPy).对所得到的PCL/PPy电纺膜用红外光谱进行表征,在扫描电镜和透射电镜下观察纤维形貌,并测定力学性能和体积电阻率.结果表明,所生成的PPy以纳米粒子形式附着在电纺纤维表面,随着Py相对于PCL的质量百分含量由0增加到20%,PCL/PPy电纺膜的纤维直径从(730±341)nm逐渐下降至(325±84)nm;膜的拉伸模量和拉伸强度由不含Py的(25.7±0.8)MPa和(2.48±0.14)MPa分别增加至含有20%Py的(48.4±7.6)MPa和(5.05±0.59)MPa,断裂伸长率由(129±27)%下降至(86.2±9.1)%;体积电阻率降低了2～3个数量级.该PCL/PPy电纺纤维膜以期可作为电活性材料用于功能或生物医用领域.     

Deformation behavior of electrospun poly(L‐lactide‐co‐ε‐caprolactone) nonwoven membranes under uniaxial tensile loading

Biodegradable poly(L ‐lactide‐co‐ε‐caprolactone) copolymers with different L ‐lactide (LLA)/ε‐caprolactone (CL) ratios of 75/25 and 50/50 were electrospun into fine fibers. The deformation behavior of the electrospun membranes with randomly oriented structures was evaluated under uniaxial tensile loading. The electrospun membrane with a higher LLA content showed a significantly higher tensile modulus but a similar maximum stress and a lower ultimate strain in comparison with the membrane with a lower LLA content. The beaded fibers that formed in the membranes caused lower tensile properties. X‐ray diffraction and differential scanning calorimetry results suggested that the electrospun fine fibers developed highly oriented structures in CL‐unit sequences during the electrospinning process even though the concentration was only 25 wt %. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3205–3212, 2005     

A nanofibrous composite membrane of PLGA-chitosan/PVA prepared by electrospinning

Tissue engineering scaffolds produced by electrospinning feature a structural similarity to the natural extracellular matrix. In this study, poly(lactide-co-glycolide) (PLGA) and chitosan/poly(vinyl alcohol) (PVA) were simultaneously electrospun from two different syringes and mixed on the rotating drum to prepare the nanofibrous composite membrane. The composite membrane was crosslinked by glutaraldehyde vapor to maintain its mechanical properties and fiber morphology in wet stage. Morphology, shrinkage, absorption in phosphate buffered solution (PBS) and mechanical properties of the electrospun membranes were characterized. Fibroblast viability on electrospun membranes was discussed by MTT [3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide] assay and cell morphology after 7 days of culture. Results indicated that the PBS absorption of the composite membranes, no matter crosslinked or not, was higher than the electrospun PLGA membrane due to the introduction of hydrophilic components, chitosan and PVA. After crosslinking, the composite membrane had a little shrinkage after incubating in PBS. The crosslinked composite membrane also showed moderate tensile properties. Cell culture suggested that electrospun PLGA-chitosan/PVA membrane tended to promote fibroblast attachment and proliferation. It was assumed that the nanofibrous composite membrane of electrospun PLGA-chitosan/PVA could be potentially used for skin reconstruction.     

尿素/乙醇胺复配增塑聚乙烯醇性能的研究

采用尿素/乙醇胺为复合增塑剂,利用流延法制备了增塑改性的PVA膜.通过FTIR法研究了尿素/乙醇胺复合体系与PVA的相互作用,采用XRD、DSC考察了增塑改性PVA膜的结晶性能和热性能.研究结果表明,乙醇胺作为尿素的良溶剂,能有效抑制尿素从PVA基体中析出.由尿素、乙醇胺组成的复合增塑剂能破坏PVA分子中的氢键作用、降低PVA的结晶度和熔点,对PVA的增塑作用显著.增塑改性后的PVA膜在水中的溶胀率(DS)下降,溶失率(S)增加.力学性能测试表明增塑改性后的PVA膜拉伸强度(TS)降低,断裂伸长率(E%)提高.含30phr尿素/乙醇胺的PVA膜的拉伸强度、断裂伸长率分别为23.89MPa和542.88%.     

Preparation of electrospun chitosan/poly(vinyl alcohol) membranes

Electrospinning of chitosan from its solutions in 2% aqueous acetic acid was studied by adding poly(vinyl alcohol) (PVA) as a “guest” polymer. Properties of the chitosan/PVA solutions including viscosity, conductivity, and surface tension were measured, and effects of the polymer concentration, chitosan/PVA mass ratio and processing parameters (applied voltage, flow rate, capillary-to-collector distance) on the electrospinnability of chitosan/PVA were investigated. Analyses of scanning electron micrographs and transmission electron micrographs suggested that the chitosan/PVA ultrafine fibers were often obtained along with beads, and chitosan was located in the elctrospun fibers as well as in the beads. Uniform chitosan/PVA fibers with an average diameter of 99 ± 21 nm could be prepared from a 7% chitosan/PVA solution in 40:60 mass ratio. Results of Fourier transform infrared spectroscopy and X-ray diffraction demonstrated that there were possible hydrogen bonds between chitosan and PVA molecules, which could weaken the strong interaction in chitosan itself and facilitate chitosan/PVA electrospinnability. The electrospun chitosan/PVA membranes showed higher water uptake and would have potential applications in wound dressings.     

Synthesis and Characterization of Biodegradable Poly(ϵ-caprolactone)-b-Poly(L-lactide) and Study on Their Electrospun Scaffolds

A series of multi-block copolymers, poly(L-lactide)-b-poly (?-caprolactone) (PLLA-b-PCL) were synthesized. The first step of the synthesis consisted of the transesterification between the PLLA and 1,4-Butanediol, followed by the copolymerization of PLLA-diols and PCL, using isophorone diisocyanate (IPDI) as a coupling agent. The synthesized polymers were characterized by Fourier transform infrared (FTIR) spectra, differential scanning calorimetry (DSC) and wide angle X-ray diffraction (WAXD). PLLA/PCL block copolymers were electrospun into ultrafine fibers. The morphology of the electrospun fibrous scaffolds were investigated by Scanning Electron Microscopy (SEM). Results showed that the morphology and diameter of the fibers were affected by the electrospinning solution concentrationan and different weight ratio of PLLA/PCL. These electrospun PLLA-b-PCL fibrous membranes exhibited good flexibility and deformability. In comparison with the electrospun PLLA membrane, the electrospun fibrous membranes of PLLA-b-PCL demonstrated an enhanced elongation with still high tensile strength and Young's modulus to be beneficial for tissue engineering scaffolds.     

Immobilization of cellulase in nanofibrous PVA membranes by electrospinning

Electrospinning is a nanofiber-forming process by which either polymer solution or melt is charged to high voltages. With high specific surface area and porous structure, electrospun fibrous membranes are excellent candidates for immobilization of enzymes. In this paper, immobilization of cellulase in nanofibrous poly(vinyl alcohol) (PVA) membranes was studied by electrospinning. PVA and cellulase were dissolved together in an acetic acid buffer (pH 4.6) and electrospun into nanofibers with diameter of around 200 nm. The nanofibrous membranes were crosslinked by glutaraldehyde vapor and examined catalytic efficiency for biotransformations. The activity of immobilized cellulase in PVA nanofibers was over 65% of that of the free enzyme. Nanofibers were superior to casting films from the same solution for immobilization of cellulase. The activity of immobilized cellulase descended with ascending in enzyme loading efficiency and crosslinking time, which retained 36% its initial activity after six cycles of reuse.     

Carbendazim‐loaded electrospun poly(vinyl alcohol) fiber mats and release characteristics of carbendazim therefrom

Ultra‐fine poly(vinyl alcohol) (PVA) electrospun fiber mats containing carbendazim were successfully fabricated by electrospinning from the neat PVA solution containing carbendazim in various amounts based on the weight of PVA. The morphological appearance of both the neat and the carbendazim‐loaded electrospun PVA fibers were smooth and the incorporation of carbendazim in the neat PVA solution did not affect the morphology of the resulting fibers. The average diameters of the neat and the carbendazim‐loaded electrospun PVA fibers ranged between 155 and 160 nm. The chemical integrity of the as‐loaded carbendazim in the carbendazim‐loaded electrospun PVA fiber mats was intact as verified by the ¹H‐nuclear magnetic resonance spectroscopy. Thermal properties of the carbendazim‐loaded electrospun PVA fiber mats were analyzed by differential scanning calorimetry and thermogravimetric analysis. The release characteristics of the carbendazim‐loaded electrospun PVA mats were investigated by the total immersion method in distilled water at 30°C. The carbendazim‐loaded electrospun PVA mats exhibited greater amount of carbendazim released than the carbendazim‐loaded as‐cast films. Copyright © 2010 John Wiley & Sons, Ltd.