静电纺丝法制备复合纳米材料

经由溶胶-凝胶法过程,应用静电纺丝机原理,以聚乙烯醇(PVA)和无机盐(LiMn2O4)为前驱物,制备出了含有LiMn2O4无机组分的复合纳米纤维,为复合无机纳米纤维的制备方式供给了一条新的思路。实验中系统地研究了PVA的浓度对其所形成的纤维描摹特征的影响。PVA水溶液用于纺丝的最好质量分数约为8.0%。在实验过程中,随着PVA质量分数的渐渐增加,其所形成纤维的直径也随之渐渐增大,而溶液的黏度也在逐步增大,这就使得溶剂挥发变得越来越难,小液珠的表面难以构成理想的"泰勒锥",电压过小,样品溶液无法纺丝,在针头处成水滴状落在针头下方。电压过大则会在纤维丝上呈现念珠形态,阻碍样品电纺时的形貌。实验表明,在施加18kV的高电压,默认机器的其它设定条件下,依托不同质量分数的PVA溶液可制备出三种不同的纤维。     

静电纺丝法制备Y2O3纳米纤维与表征

采用静电纺丝法制备了PVA/Y(NO3)3复合纳米纤维,在适当的温度下进行热处理,得到Y2O3纳米纤维. 利用XRD,SEM,TG-DTA,FTIR等现代分析手段对样品进行了表征. XRD分析表明,PVA/Y(NO3)3复合纤维为无定型,焙烧温度在600 ℃以上得到晶态单相的Y2O3纳米纤维,属于立方晶系,空间群为Ia3. SEM分析表明,PVA/Y(NO3)3复合纤维表面光滑,平均直径为110 nm. 焙烧温度对Y2O3纳米纤维的形成有重要影响. 600 ℃焙烧得到的Y2O3纳米纤维的平均直径约50 nm,900 ℃焙烧得到的Y2O3纳米纤维由纳米颗粒堆积而成,部分已断裂. TG-DTA和FTIR分析表明,PVA,Y(NO3)3以及水分在600 ℃以上时完全分解挥发,最终样品为晶态单相的Y2O3纳米纤维.     

静电纺丝制备醋酸纤维素复合纳米纤维的研究进展

静电纺丝技术就是通过带电聚合物溶液或熔体的喷射来制备纳米纤维,是一种制备纳米纤维材料简单有效的技术。醋酸纤维素(CA)易溶于有机溶剂,常作为纤维素的替代材料应用于静电纺丝领域。本文总结了近年来国内外采用静电纺丝技术制备CA复合纳米纤维的研究新进展,重点介绍了CA/CNTs复合纳米纤维、CA/金属粒子复合纳米纤维、CA/金属氧化物复合纳米纤维、CA基载药复合纳米纤维、CA/PAN复合纳米纤维、CA/PVA复合纳米纤维、CA/CS复合纳米纤维等CA复合纳米纤维的研究进展以及潜在的应用领域。     

静电纺丝法制备三维聚二甲基硅氧烷纳米通道

利用静电纺丝技术构建了新型三维纳米通道系统。 在不同质量分数的聚苯乙烯（PS：Mw=1.3×105）溶液中加入一定量十二烷基磺酸钠（SDS）,于不同电压下进行静电纺丝。 所得纤维在90 ℃加热粘连后,形成三维聚苯乙烯纳米网络模板,然后于聚二甲基硅氧烷(PDMS)预聚体（含10%交联剂）灌注进入上述模板并交联形成网络复合材料,再用二硫化碳超声除去聚苯乙烯纤维。 采用扫描电子显微镜、透射电子显微镜对纤维模板形貌和纳米通道进行了表征。 结果表明,质量分数为10%的PS溶液加入0.5%SDS,在20 kV电压下进行静电纺丝,得到直径为150 nm的纤维。 SDS的加入对纺丝纤维具有平滑作用,使得粘连的纤维模板更易去除,形成的三维纳米通道直径约160 nm,与纤维模板直径一致。 该类型纳米通道可以应用于医学药物载体、纳流控芯片等众多领域。     

磁场辅助静电纺有序聚丙烯腈纳米纤维的研究

磁场辅助静电纺丝方法能够制备有序纳米纤维,但是其参数之间的匹配关系很少被研究。本文通过正交实验,对影响磁场辅助静电纺丝制备聚丙烯腈纳米纤维的四个工艺参数(溶液浓度、磁铁间距、纺丝电压和注射速度)在3个水平上进行优化筛选。以纤维直径大小、均匀度和纤维有序度为考察目标,同时考虑溶液浓度、磁铁间距与纺丝电压这三个因素之间的两两交互作用,结合极差分析、方差分析,发现溶液浓度是影响纤维直径和均匀度的高度显著因素,溶液浓度和纺丝电压的交互作用对直径均匀度有显著影响,纺丝电压是影响纤维有序度的显著因素。     

静电纺微量串珠纤维复合滤料的制备及过滤性能探究

以聚偏氟乙烯(PVDF)为原材料,以PET熔喷非织造布为接收基材,通过静电纺丝技术制备了微量串珠纤维复合滤料,利用扫描电子显微镜(SEM)观察纺丝液浓度、纺丝电压、纺丝距离对纤维形貌的影响,并研究了静电纺丝时间对复合滤料过滤性能的影响。结果表明,工艺参数最优组合为:纺丝液质量分数20%,纺丝电压38 kV和纺丝距离25 cm,并且各纺丝时间的复合滤料样品都表现出极高的过滤效率和较低的过滤阻力,综合考虑,优选纺丝时间为5min时,复合滤料可达到最佳的过滤性能。     

ZnO纳米纤维的静电纺丝及其光催化性能的研究

以聚乙烯醇溶液为络合剂与醋酸锌反应制得前驱体溶液,采用静电纺丝法制备PVA/Zn(Ac)2复合纳米纤维,经过高温煅烧得到直径为100 nm的ZnO纳米纤维,采用差热-热重分析、红外光谱分析、X射线粉末衍射分析及扫描电镜等手段对其进行了表征.光催化降解酸性品红溶液的实验结果表明,太阳光照65 min使质量浓度为45 mg/L酸性品红水溶液的脱色率达93%;另外,重复使用ZnO纳米纤维4次之后,其光催化降解率仍能达到70%以上.这充分说明ZnO纳米纤维具有良好的光催化性能.     

CUR-CAP/PLGA纳米静电纺丝纤维膜的制备和活性研究

采用静电纺丝的方法制备了不同质量分数的CUR-CAP/PLGA复合静电纺丝纤维膜,并通过扫描电子显微镜、红外光谱、单晶X射线衍射进行表征,并用四唑盐MTT比色法测定其对成纤维细胞增殖的影响.表征结果表明:所合成的复合静电纺丝纤维膜的直径具有纳米结构,复合薄膜中,3种物质很好的混合在一起,没有发生化学键的结合.细胞实验检测结果显示,CUR-CAP/PLGA复合膜有助于细胞在其表面的生长及增殖,当姜黄素的质量分数为3%、氯霉素的质量分数为1%时效果最佳.     

恩诺沙星分子印迹纳米纤维膜的制备及性能

通过沉淀聚合法制备了恩诺沙星（ENRO）分子印迹聚合物（MIPs）微球,将其添加到聚乙烯醇（PVA）溶液中,采用静电纺丝技术制备了恩诺沙星分子印迹纳米纤维膜（MINFMs）. 利用扫描电子显微镜（SEM）研究了纺丝液浓度、纺丝电压及接收距离对MINFMs纤维直径及表面形貌的影响,从溶胀性、孔隙率、吸附容量及吸附选择性等几个方面对印迹膜的性能进行了评价. 结果表明,在环境温度25 ℃、相对湿度 40%~50%、MIPs加入量8%（质量分数）、PVA质量分数7%、纺丝电压15 kV和接收距离25 cm的条件下,得到的MINFMs的纤维形态良好,纤维平均直径为180 nm. MINFMs的溶胀度和孔隙率分别为136.76%和33.42%,均大于非印迹纳米纤维膜（NINFMs）. 动力学吸附性能结果显示,MINFMs在300 min后吸附基本达到平衡,且明显高于NINFMs的吸附量;Scatchard分析结果表明,在所研究的浓度范围内MINFMs对模板ENRO的结合位点是等价的,其离解平衡常数（K_d）与最大表观结合量（Q_max）分别为505.817 mg/L和3.862 mg/g. 与环丙沙星（CIP）和氧氟沙星（OFL）相比,MINFMs对ENRO表现出更强的特异性吸附能力.     

静电纺丝法制备PVP螺旋纤维及其机理研究

研究了电纺丝聚乙烯吡咯烷酮螺旋纤维的形成条件, 在9kV的电压下, 由于溶液质量分数的增加(12%-24%), 纤维形态呈现出直线→螺旋→折叠→无序的变化趋势; 在质量分数为20%时, 随着纺丝电压的增加, 纤维形态呈现出折叠→螺旋→无序的变化趋势, 同时对螺旋纤维的形成机理进行了讨论, 在纺丝过程中纤维束所带静电荷之间的库仑斥力是形成螺旋纤维的直接动力.     

金纳米棒负载的静电纺丝纤维的制备及其表面增强拉曼光谱性能

为简单有效地制备高活性表面增强拉曼光谱(Surface-enhanced Raman Spectroscopy,SERS)基底。本文采用静电纺丝聚乙烯醇(PVA)/聚丙烯酸(PAA)纳米纤维为支撑材料,通过直接浸泡的方法,利用金纳米棒与电纺纤维之间的静电力,使纳米棒在纤维表面自组装,得到了性能优异的SERS基底。通过透射电子显微镜、扫描电子显微镜对金纳米棒以及不同状态下的电纺纤维的形貌进行表征,结果表明,金纳米棒均匀且密集地负载在纤维表面。通过设置不同的浸泡时间确定了金纳米棒组装平衡的时间为12 h,并通过调控纺丝时间和金纳米棒的浓度发现随着纺丝时间和金纳米棒浓度的增加,复合纤维膜SERS增强效果随之提升。该复合纤维膜具有优异的SERS均匀性,并且能够检测到浓度低至10~(-10)mol/L的4-氨基苯硫酚的存在。     

Stabilization of electrospun poly(vinyl alcohol) nanofibrous mats in aqueous solutions

<正>The stability ofpoly(vinyl alcohol)(PVA) nanofibrous mats in water media was improved by post-electrospinning treatments.Bifunctional glutaraldehyde(GA) in methanol was used as a crosslinking agent to stabilize PVA nanofiber,but fiber twinning was observed frequently,and the highly porous structure of PVA nanofibrous mats was destroyed when the crosslinked fiber was soaked in water.To overcome this shortcoming,chitosan(CS) was introduced into the PVA spinning solution to prepare PVA/CS composite nanofibers.Their treatment in GA/methanol solution could retain the fiber morphology of PVA/CS nanofibers and porous structure of PVA/CS nanofibrous mats even if they were soaked in aqueous solutions for 1 month.Scanning electron microscopy(SEM),X-ray diffraction(XRD),thermal gravimetric analysis(TGA) and differential scanning calorimetry(DSC) were applied to characterize the physicochemical structure and thermal properties of PVA nanofibers.It was found that the water resistance of PVA nanofibrous mats was enhanced because of the improvement of the degree of crosslinking and crystallinity in the electrospun PVA fibers after soaking in GA/methanol solution.     

不同分子量聚丙烯腈的制备及其高压静电纺丝研究

采用DMSO/H2O混合溶剂法制备了5种不同分子量的PAN,并以PAN为原料,DMF为溶剂,配成纺丝溶液,通过高压静电纺丝技术制备超细纤维毡(UFFM)。研究表明,相同单体组成和浓度、相同反应条件情况下,通过聚合制备PAN,随着混合溶剂中水含量的增加,生成的PAN粘均分子量相应增加,其转化率也增加。聚合所得的不同分子量PAN的热重分析显示,随着PAN分子量的增加,热重曲线的剧烈失重区会越来越明显,剧烈失重区的失重率也呈增加的趋势;高压静电纺丝研究发现,PAN-4和PAN-5纺丝溶液由于分子量过高而不可纺;另外,研究还发现,较高的纺丝电压有利于纤维直径的减小,但相应的纺丝稳定性减小,导致纤维直径分布的离散度增加。     

In situ growth of ZnO nanocrystals from solid electrospun nanofiber matrixes

Porous fiber membranes consisting of 1D assemblies of ZnO nanocrystal-supported poly(vinyl alcohol) (PVA) nanofibers are described. These hybrid nanofiber membranes were assembled by first electrospinning a ZnO precursor-containing PVA aqueous solution. Subsequently, the electrospun composite nanofibers were submerged in a basic ethanol solution. As a result, ZnO precursors in solid PVA matrixes were hydrolyzed to generate ZnO crystals residing on the fiber surfaces. Photoluminescence spectroscopy analysis demonstrated the as-hydrolyzed fiber membranes possess white luminescence. Furthermore, the ZnO-encapsulated PVA nanofibers were prepared by directly electrospinning a ZnO nanocrystal-containing PVA solution as the contrast of the as-hydrolyzed hybrid nanofibers. The surface photovoltage spectroscopy (SPS) confirmed that the as-hydrolyzed hybrid fiber membranes had a strong SPS response, but the directly spun fiber membranes did not have any SPS response. This can be attributed to the favorable structure of the hydrolyzed hybrid nanofibers, that is, the surface residence of ZnO permits ZnO crystals to make direct contact with ITO electrodes to transfer the photogenerated electron originating from ZnO to ITO electrodes. By contrast, the transfer of the photogenerated electron is limited by PVA matrixes in the directly spun fiber system.     

Nanofibers of LiMn2O4 by electrospinning

Through sol-gel processing and electrospinning technique, extrathin fibers of poly(vinyl alcohol) (PVA)/lithium chloride/manganese acetate composite fibers were prepared. After calcination of the above precursor fibers at 600 degrees C, the spinel lithium manganese oxide (LiMn2O4) nanofibers, with a diameter of 100-200 nm, were successfully obtained. The fibers were investigated by TG-DTA, XRD, FT-IR, and SEM, respectively. The results showed that the crystalline phase and morphology of the fibers were largely influenced by the calcination temperature.     

Control of diameter,morphology, and structure of PVDF nanofiber fabricated by electrospray deposition

Poly(vinylidene fluoride) (PVDF) nanofibers were prepared by electrospray deposition (ESD). To control the diameter, morphology, and structure of PVDF nanofibers, some parameters were investigated, such as polymer concentration, nozzle‐to‐ground collector distance, feeding rate of the polymer solution, and applied voltage. The fabricated fiber was 80–700 nm in diameter. The increase in the polymer concentration caused an increase in the polymer viscosity and fiber diameter. At low polymer concentration (5 wt %), polymer nanoparticles were formed. An increase in applied voltage will increase the fiber diameter. Variation in the nozzle‐to‐ground collector distance did not result in significant changes in the fiber diameter. Increase in the feeding rate of the polymer solution decreased the fiber diameter. Differential scanning calorimetry (DSC) and wide angle X‐ray diffraction (WAXD) measurements showed that the melting point and total crystallinity were decreased. Fourier transform infrared spectroscopy (FTIR) measurement revealed that ESD process induced the formation of the oriented β‐phase PVDF structures. It was also demonstrated that the addition of hydrofluorocarbon solvent to polymer solution remarkably enhanced the formation of β‐phase crystalline structure of PVDF nanofiber. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 779–786, 2006     

Preparation and characterization of high‐molecular‐weight atactic poly(vinyl alcohol)/sodium alginate/silver nanocomposite by electrospinning

High‐molecular‐weight poly(vinyl alcohol) (PVA)/sodium alginate (SA)/ silver nanocomposite was successfully prepared via electrospinning technique. Water‐based colloidal silver in a PVA/SA blend solution was directly mixing without any chemical and structural modifications into PVA/SA matrix to form an organic‐metallic nanocomposite. The effect of the addition of silver colloidal solution on the PVA/SA/silver nanocomposite was investigated through a series of experiments varying molecular weight of PVA and electrospinning processing parameters such as concentration of PVA solution, PVA/SA blend ratio, applied voltage, and tip‐to‐collector distance. In the case of PVA with number‐average degree of polymerization of 1700, by increasing the amount of SA in spinning solution, the morphology was changed from fine uniform fiber to beaded fiber or bead‐on‐string fiber structure. Increase of the amount of silver colloidal solution resulted in higher charge density on the surface of ejected jet during spinning, thus more electric charges carried by the electrospinning jet. As the charge density increased, the diameter of the nanocomposites became smaller. Transmission electron microscopy images showed that the dense silver nanoparticles were well separately dispersed in PVA/SA matrix. Energy‐disperse X‐ray analysis indicated that carbon, oxygen, natrium, and silver were the principle element of PVA/SA/silver nanocomposite. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1916–1926, 2009     

PVA/GA/β-CD纳米纤维的制备及染料吸附性能

利用静电纺丝技术,以六氟异丙醇(HFIP)和水为溶剂,制备了环糊精(β-CD)含量为70%(质量分数)的聚乙烯醇(PVA)/β-CD纳米纤维,并经戊二醛(GA)交联处理得到了可用于染料吸附的PVA/GA/β-CD纳米纤维.通过红外光谱和扫描电子显微镜研究了交联反应前后纳米纤维组成和形貌的变化;考察了PVA/GA/β-CD纳米纤维对7种水溶性染料的吸附性能.结果表明,PVA/GA/β-CD纳米纤维对孔雀石绿、甲基紫和刚果红的吸附效果较好,最大吸附量分别为124.71,121.14和127.39 mg/g,4次吸附-解吸附循环后,染料去除率仍保持80%左右,在染料废水处理中具有良好的应用前景.     

Oxymatrine Loaded Cross-Linked PVA Nanofibrous Scaffold: Design and Characterization and Anticancer Properties

This study focuses on the fabrication, characterization and anticancer properties of biocompatible and biodegradable composite nanofibers consisting of poly(vinyl alcohol) (PVA), oxymatrine (OM), and citric acid (CA) using a facile and high-yield centrifugal spinning process known as Forcespinning. The effects of varying concentrations of OM and CA on fiber diameter and molecular cross-linking are investigated. The morphological and thermo-physical properties, as well as water absorption of the developed nanofiber-based mats are characterized using microscopical analysis, energy dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, differential scanning calorimetry, and thermogravimetric analysis. In vitro anticancer studies are conducted with HCT116 colorectal cancer cells. Results show a high yield of long fibers embedded with beads. Fiber average diameters range between 462 and 528 nm depending on OM concentration. The thermal analysis results show that the fibers are stable at room temperature. The anticancer study reveals that PVA nanofiber membrane with high concentrations of OM can suppress the proliferation of HCT116 colorectal cancer cells. The study provides a comprehensive investigation of OM embedded into nanosized PVA fibers and the prospective application of these membranes as a drug delivery system.     

PVA微晶交联和SA/PAA双网络协效增强增韧SA纤维

为了提高海藻酸钠(SA)纤维的断裂强度和断裂伸长率, 以丙烯酸(AA)为化学交联组分, SA为离子交联组分, 聚乙烯醇(PVA)为微晶交联组分, 采用湿法纺丝和冻融循环方法制备含有PVA微晶交联点和海藻酸钠/聚丙烯酸(SA/PAA)双网络结构的海藻酸钠/聚丙烯酸/聚乙烯醇(SA/PAA/PVA)复合纤维. 通过流变性能、 力学性能、 红外光谱、 X射线衍射仪(XRD)和扫描电子显微镜(SEM)测试研究了交联剂N,N-亚甲基双丙烯酰胺(MBA)含量和PVA微晶交联对SA/PAA/PVA纺丝原液和复合纤维的结构与性能的影响. 结果表明, 当MBA质量分数为0.5%时, 纺丝原液的损耗模量(G″)最小, 可纺性最好, 复合纤维的断裂强度达到2.83 cN/dtex, 断裂伸长率达到9.38%, 比再生SA纤维分别提高了15.98%和38.96%; PVA冷冻之后形成微晶交联点并且PAA和PVA已经复合到体系中; PAA和PVA的加入提高了复合纤维的结晶度; 复合纤维的表面形貌趋于光滑和规整, 纤维断面更加致密.