Chemical and structural induced ductile-to-brittle transition in electrospun silica nanofiber membranes

Electrospun silica nanofiber membranes show a high potential in many advanced environmental applications. However, little is known about their mechanical performance which could be a limiting factor for further innovation. It is shown in this work that silica nanofiber membranes have a completely different deformation behavior compared to conventional polymeric/thermoplastic nanofiber membranes, resulting from their significant differences in chemical and physical properties such as fiber interactions and porosity. Furthermore, storage at room temperature initiates remarkable changes in failure mechanisms, depending on the storage humidity, which can be accelerated via a thermal treatment. These changes are linked to the structural changes of the membrane resulting from its chemical reactivity towards moisture in the air. Additional interactions and crosslinks are observed, leading to fiber shrinkage and rearrangement. As a result, more contact points are created between nanofibers, creating additional friction forces and, as such, a complete shift in mechanical properties towards a stronger, stiffer, and more brittle material (tensile strength of 14.0 ± 3.8 MPa vs. 3.1 ± 0.4 MPa and failure strain of 0.9 ± 0.2% vs. 24.2 ± 1.0%). The silica nanofiber membranes thus allow mechanical tunability via altering the storage or treatment conditions.     

完全生物降解塑料PLA/PPC合金的结构与性能研究

利用机械共混法,将聚乳酸(PLA)与聚丙撑碳酸亚丙酯(PPC)熔融共混,制备了完全生物降解塑料PLA/PPC合金,并用FTIR、流变仪等手段研究了其结构、力学性能和流变性能。结果表明该共混体系具有良好的相容性、力学性能和熔体流动性,PLA与PPC之间存在着较强的相互作用,PPC的加入使体系拉伸强度下降幅度不大,断裂伸长率升高到23.8%,比纯PLA提高近20倍。共混体系的黏度亦随着PPC的加入逐渐增大,PLA/PPC(50/50)体系的黏流活化能为37.1kJ/mol,同时在一定的温度范围内,提高切应力也会使体系黏度下降。     

紫外线吸收剂在PLA/PBAT生物降解薄膜中的应用

通过挤出共混造粒、吹塑成型工艺制备出了聚乳酸(PLA)/聚对苯二甲酸-己二酸丁二醇酯(PBAT)完全生物降解薄膜。研究了一种二苯甲酮类紫外线吸收剂对PLA/PBAT薄膜抗紫外老化的作用。采用万能拉力试验机、紫外-可见吸光光谱仪、差示扫描量热法(DSC)对PLA/PBAT薄膜在紫外老化过程中的性能进行了测试和表征。结果表明,选择的紫外线吸收剂能有效减缓PLA/PBAT薄膜在老化过程中力学性能的下降。紫外老化更易发生在薄膜的无定型区,该紫外线吸收剂能明显降低薄膜在老化过程中结晶度的变化。同时,添加该紫外线吸收剂能大幅度降低薄膜在紫外老化过程中产生的凝胶含量。     

聚乳酸/聚乙烯醇纳米纤维的制备及结构

以二甲基亚砜为溶剂,制备不同配比的聚乳酸(PLLA)和聚乙烯醇(PVA)的混合溶液,静电纺丝制得PLLA/PVA纳米纤维。采用红外光谱仪、原子力显微镜等对PLLA/PVA纳米纤维结构与性能进行了表征。结果表明:PLLA/PVA纳米纤维中PVA上的羟基与PLLA上的羰基形成了氢键,PLLA与PVA之间存在一定的相互作用,但PLLA/PVA纳米纤维存在相分离现象;混合溶液的PLLA质量分数为11%,PVA质量分数为8%时可以得到较好的PLLA/PVA纳米纤维,但PVA质量分数为6%时出现液滴及珠丝,PVA质量分数为4%时,不能制得纳米纤维。     

Characterization of CS/PVA/GO electrospun nanofiber membrane with astaxanthin

Tissue engineering has been widely used in regenerative medicine and tissue engineering scaffolds have become a new research direction for periodontal regenerative repair. We aim to develop a biological scaffold material that can support host immunity and promote periodontal regeneration. In this paper, chitosan (CS)/polyvinyl alcohol (PVA)/graphene oxide (GO)/astaxanthin (ASTA) nanofibers membranes were prepared by electrospinning. The nanofibers were characterized by scanning electron microscopy, infrared spectroscopy, mechanical testing, antibacterial testing and cytotoxicity testing. The CS/PVA/GO/ASTA nanofiber membrane had favorable micro-morphology, good mechanical properties and no cytotoxicity. This preliminary study demonstrates that the CS/PVA/GO/ASTA nanofiber membrane can be used for in vivo and in vitro experiments related to periodontal regeneration. The related mechanism of periodontal regeneration will be evaluated in future studies.     

Understanding polymorphism formation in electrospun fibers of immiscible Poly(vinylidene fluoride) blends

Effects of electric poling, mechanical stretching, and dipolar interaction on the formation of ferroelectric (β and/or γ) phases in poly(vinylidene fluoride) (PVDF) have been studied in electrospun fibers of PVDF/polyacrylonitrile (PAN) and PVDF/polysulfone (PSF) blends with PVDF as the minor component, using wide-angle X-ray diffraction and Fourier transform infrared techniques. Experimental results of as-electrospun neat PVDF fibers (beaded vs. bead-free) showed that mechanical stretching during electrospinning, rather than electric poling, was effective to induce ferroelectric phases. For as-electrospun PVDF blend fibers with the non-polar PSF matrix, mechanical stretching during electrospinning again was capable of inducing some ferroelectric phases in addition to the major paraelectric (α) phase. However, after removing the mechanical stretching in a confined melt-recrystallization process, only the paraelectric phase was obtained. For as-electrospun PVDF blend fibers with the polar (or ferroelectric) PAN matrix, strong intermolecular interactions between polar PAN and PVDF played an important role in the ferroelectric phase formation in addition to the mechanical stretching effect during electrospinning. Even after the removal of mechanical stretching through the confined melt-recrystallization process, a significant amount of ferroelectric phases persisted. Comparing the ferroelectric phase formation between PVDF/PSF and PVDF/PAN blend fibers, we concluded that the local electric field-dipole interactions were the determining factor for the nucleation and growth of polar PVDF phases.     

Morphological and rheological characterization of multi-walled carbon nanotube/PLA/PBAT blend nanocomposites

Biodegradable poly (lactic acid) (PLA)/poly (butyleneadipate-co-butyleneterephthalate) (PBAT)/multi-walled carbon nanotube (MWNT) polymer blend nanocomposites were prepared by using a laboratory-scale twin-screw extruder. Fractured surface morphology of the polymer blend/MWNT nanocomposites were examined via SEM. Furthermore, cross sectioned samples obtained using an ultramicrotome was observed via TEM. In addition, effects of both MWNT reinforcement and phase affinity of MWNT on thermal and rheological properties of the PLA/PBAT blends were investigated by TGA and rotational rheometer. Immiscible PLA/PBAT blend with MWNT nanocomposites showed two-step thermal degradation. The onset temperature of thermal degradation started in the PLA much earlier than in the PBAT. Nonetheless, based on TGA data, it was found that the MWNT enhanced thermal property of the PLA/PBAT blend/MWNT nanocomposites. Rheological properties revealed that both shear and complex viscosities showed unique shear thinning behavior due to selectively localized MWNT dispersion state.     

Morphology, polymorphism behavior and molecular orientation of electrospun poly(vinylidene fluoride) fibers

The morphology, polymorphism behavior and molecular orientation of electrospun poly(vinylidene fluoride) (PVDF) fibers have been investigated. We found that electrospinning of PVDF from its N,N-dimethylformamide/acetone solutions led to the formation of β-phase. In contrast, only α- and γ-phase was detected in the spin-coated samples from the same solutions. In the aligned electrospun PVDF fibers obtained using a rotating disk collector, the β-phase crystallites had a preferred orientation along the fiber axis. The degree of orientation did not, however, vary significantly with the speed of the rotation disk collector, and the β-phase was also not significantly enhanced with the increase in the rotation speed or the decrease in the size of spinnerets. These facts indicated that the orientation was likely to be caused by Columbic force rather than the mechanical and shear forces exerted by the rotating disk collector and spinnerets. The Columbic force may induce local conformational change to straighter TTTT conformation, and hence promote the β-phase. The addition of 3 wt.% of tetrabutylammonium chloride (TBAC) into the polymer solutions effectively improved the morphology of the electrospun fibers, and led to almost pure β-phase in the fibers. With spin coating, PVDF-TBAC did not, however, show any strong β-phase diffraction peak. The synergistic β-enhancement effect of TBAC and electrospinning is possibly due to the fact that while TBAC could induce more trans conformers, electrospinning promotes parallel packing, and hence inter-chain registration.     

Stress-induced structural changes in electrospun polyvinylidene difluoride nanofibers collected using a modified rotating disk

By attaching separate, parallel electrodes onto a rotating disk collector, well aligned electrospun polyvinylidene difluoride (PVDF), PVDF/carbon nanotube nanocomposite and vinylidene fluoride-trifluoroethylene copolymer nanofibers are directly deposited onto flat substrates forming relatively large, uniform and compact fibrous thin films. The attachments alter the electric-field distribution on the rotating disk, which fosters the fanning of the nanofibers, while the electric field between the separate electrodes and the mechanical force exerted by the rotational disk facilitate the alignment. X-ray diffraction and infrared spectroscopic studies show that the specific environment and force fields created on the modified rotating disk cause the electrospun fibers being effectively stretched to form highly oriented β-form crystallites with slightly reduced inter-chain distance. They also lead to slight increases in crystallinity and crystal size. A mechanism is proposed to account for the structural alteration induced by the modified rotating disk collector. Ferroelectricity of the aligned electrospun PVDF fibrous thin films is also demonstrated.     

Apparatus for preparing electrospun nanofibers: designing an electrospinning process for nanofiber fabrication

Nanofibers are widely used in a range of material applications, such as filter media, biosensors, military protective coatings, three‐dimensional tissue scaffolds, composites, drug delivery, wound dressings and electronic devices. To fabricate nanofibers with desired physical and chemical functions, a variety of electrospinning processes have been introduced using specially designed collectors, microelectromechanical system (MEMS) nozzle tips and auxiliary electrodes to stabilize the spin jets. However, the development of new electrospinning processes continues in the search for ‘tailor‐made’ nanofibers, in which parameters such as the fiber orientation and three‐dimensional structure are ultimately controllable. This paper discusses recently suggested electrospinning methods that are designed to impart specific functionality. It also details the correlations between applied processing parameters and the obtained physical properties of electrospun fibers. Finally, future design directions are suggested for developing an electrospinning apparatus capable of producing optimally structured nanofibers. Copyright © 2007 Society of Chemical Industry     

溶剂对电纺聚酯纳米纤维可纺性的影响

利用静电纺丝法制备聚酯(PET)纳米纤维,选择苯酚和四氯乙烷,三氟乙酸,三氟乙酸和二氯甲烷3种溶剂分别溶解PET切片进行静电纺丝,通过扫描电子显微镜(SEM)对纤维表面形态进行观察,结果表明:三氟乙酸和二氯甲烷混合溶剂溶解PET制备的电纺纤维较好。使用视频光学接触角测定仪测试PET电纺纤维膜与其流延膜的接触角,通过分析两者表面结构,证明PET电纺纤维膜能产生较强的疏水功能。     

Chemical crosslinking and biophysical properties of electrospun hyaluronic acid based ultra-thin fibrous membranes

Hyaluronic acid (HA) ultra-thin fibrous membranes by electrospinning technology had been fabricated successfully by our group. However, these HA fibrous membranes dissolve and decompose rapidly in water. In this study, chemical crosslinking of HA and HA based ultra-thin fibrous membranes was studied in detail. It was found that the chemically crosslinked pure HA ultra-thin fibrous membranes with 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) as the crosslinking agent did not show an obvious improvement in the water-resistance. However, by simply adding and changing the gelatin content, the degradation time of the HA based fibrous membranes could be effectively adjusted from one week to several months. That is with the increase in gelatin content, the water-resistance of the HA/gelatin bi-component membranes could be increased greatly. The crosslinked HA/gelatin bi-component membranes were evaluated in vitro by seeding with mouse embryonic fibroblasts (3T6-Swiss Albino). The results showed that the HA/gelatin fibrous membranes were cytocompatible and suitable for cell viability. However, cells were hard to attach and grow on the HA based membranes. Thus, the HA/gelatin fibrous membranes with controllable degradation rate could have good potential applications in the anti-adhesion and wound dressing fields.     

Structure, mechanical properties and degradation behaviors of the electrospun fibrous blends of PHBHHx/PDLLA

Blends of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx) and poly(d,l-lactic acid) (PDLLA) with different ratios were fabricated into fibrous membranes by electrospinning processes. Suggested by DSC, WAXD, and SAXS results, the molecular chains of PHBHHx and PDLLA were partially mixed in the amorphous phase, PDLLA didn’t affect the growth of PHBHHx crystalline phase, and PDLLA was excluded from PHBHHx lamella stacks, i.e. in form of interstack segregation, in the blend fibrous matrix. The mechanical properties of the electrospun fibrous membranes depended on the orientation of fibers in the membranes. The electrospun membranes had higher elongation; furthermore, the tensile strength and modulus of the fibers within the membranes were higher than the corresponding cast membranes. As the content of PDLLA increased, the electrospun fibrous membranes of the blends showed higher elongation and lower tensile modulus due to the decreased number of lamellae. According to the change of molecular weight distribution, both PHBHHx and PDLLA portions in the electrospun blend membranes followed bulk erosion and PDLLA degraded faster than PHBHHx during the degradation process. The morphology change of the electrospun fibrous blends during the hydrolytic degradation indicated that the degradation behaviors were strongly influenced by the miscibility and the structural phase segregation of PHBHHx/PDLLA blend in the electrospun fibers.     

Reducing electrospun nanofiber diameter and variability using cationic amphiphiles

One major limitation of the electrospinning technique for generating polymer fibers is the large average diameter and the broad diameter variability of electrospun fibers. Improved methods of controlling fiber diameter and variability will have implications for many applications ranging from filtration to cell and tissue engineering. Here we report an effective method of reducing the diameter and variability of fibers prepared from three different polymers, poly(ethersulfone), poly(caprolactone), and poly(caprolactone-co-ethyl ethylene phosphoester), by doping polymer solutions with a positively charged amphiphile, octadecyl rhodamine (R18) or octadecyltrimethylammonium bromide (OTAB) at 5000:1 to 20:1 of polymer to amphiphile weight ratio. This is due to the combined effect of field-driven surface partitioning of positively charged amphiphiles and surface tension reduction. This method of diameter reduction can be applied easily without modifying the electrospinning setup or changing the polymer-solvent system.     

Evaluation of electrospun nanofiber pore structure parameters

Nanofibers produced by electrospinning method are widely used for drug delivery, as tissue scaffolding materials and filtration purposes where specific pore characteristics are required. For continued growth in these areas, it is critical that the nanofibers be properly designed for these applications to prevent failure. Most of the current methods only provide an indirect way of determining pore structure parameters and contain inherent disadvantages. In this study, we developed a novel image analysis method for measuring pore characteristics of electrospun nanofiber webs. Five electrospun webs with different pore characteristics were analyzed by this method. The method is direct, very fast, and presents valuable and comprehensive information regarding pore structure parameters of the webs. Two sets of simulated images were generated to study the effects of web density, fiber diameter and its variations on pore characteristics. The results indicated that web density and fiber diameter significantly influence the pore characteristics, whereas the effect of fiber diameter variations was insignificant.     

Effects of hard and soft components on the structure formation,crystallization behavior and mechanical properties of electrospun poly(l-lactic acid) nanofibers

The effects of multi-wall carbon nanotubes (MWCNTs) and poly(ethylene oxide) (PEO) on the structure formation, morphology, crystallization behavior and mechanical property of electrospun poly (l-lactic acid) (PLLA) nanofiber mats were investigated by field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), differential scanning calorimeter (DSC) and mechanical test. If incorporate hard filler, MWCNTs into electrospun PLLA nanofiber, the crystallinity, chain orientation, and crystallization behaviors were almost not influenced by the MWCNTs content owing to the MWCNTs mainly acted as impeding the crystal growth and chain diffusion. If incorporate small content of soft and miscible component, PEO (10 wt%) into the electrospun PLLA and PLLA/MWCNTs nanofibers, the crystallinity and crystallization rate of PLLA in nanofibers were obviously enhanced. The synergistic effect of PEO and MWCNTs in PLLA nanofibers was observed during melt-crystallization behaviors of PLLA/MWCNTs fibers. Based on those results, we found that the chain mobility is an important factor to influence the structure formation and crystallization behaviors in the electrospun nanofibers. Our results indicated that the structure and properties of electrospun nanofibers could be optimized by compounding with hard inorganic filler and soft polymer components.     

电纺纳米纤维增强聚合物复合材料的研究进展

与作为填料的普通纤维相比,通过静电纺丝所得纳米纤维(简称电纺纳米纤维)的长径比及比表面积较大,相对于基体材料具有较大的模量和韧性,对聚合物基体有较好的力学增强效果;电纺纳米纤维在复合材料中应力集中程度低、与聚合物基体间界面结合较好。加入电纺纳米纤维可以提高复合材料的性能,如拉伸及弯曲强度、模量,抗冲击性能等都有较大提高。电纺纳米纤维在聚合物基体中的分散及其与基体间的界面黏结等问题有待进一步研究和改善。     

Biodegradable multiblock PEO/PLA thermoplastic elastomers: molecular design and properties

Given the need for highly flexible biodegradable polymers, a series of poly(ethylene oxide)/poly(l-lactic acid) (PEO/PLA) (PELA) multiblock poly(ether-ester-urethane)s, were synthesized and characterized. The first step of the synthesis consisted of the ring-opening polymerization of l-lactide, initiated by the hydroxyl terminal groups of the PEO chain, followed by the chain extension of these PLA-PEO-PLA triblocks, using hexamethylene diisocyanate (HDI). The trimers comprised PEO segments in the 1000-10,000 molecular weight range, with the length of each PLA block covering the 200-10,000 interval. DSC and X-ray analyses revealed that, depending on their composition, amorphous matrices, monophasic crystalline materials and copolymers comprising two crystalline phases, were generated. The multiblock copolymers synthesized exhibited superior mechanical properties, with ultimate tensile strength values around 30 MPa, Young's moduli as low as 14 MPa and elongation at break values well above 1000%. Because of their phase segregated morphology, most of these multiblock copolymers displayed remarkable mechanical properties also when fully hydrated, with typical UTS values around 9 MPa.     

Effects of poly (vinyl alcohol) (PVA) content on preparation of novel thiol-functionalized mesoporous PVA/SiO2 composite nanofiber membranes and their application for adsorption of heavy metal ions from aqueous solution

Thiol-functionalized mesoporous poly (vinyl alcohol)/SiO₂ composite nanofiber membranes and pure PVA nanofiber membranes were synthesized by electrospinning. The results of Fourier transform infrared (FTIR) indicated that the PVA/SiO₂ composite nanofibers were functionalized by mercapto groups via the hydrolysis polycondensation. The surface areas of the PVA/SiO₂ composite nanofiber membranes were >290 m²/g. The surface areas, pore diameters and pore volumes of PVA/SiO₂ composite nanofibers decreased as the PVA content increased. The adsorption capacities of the thiol-functionalized mesoporous PVA/SiO₂ composite nanofiber membranes were greater than the pure PVA nanofiber membranes. The largest adsorption capacity was 489.12 mg/g at 303 K. The mesoporous PVA/SiO₂ composite nanofiber membranes exhibited higher Cu²⁺ ion adsorption capacity than other reported nanofiber membranes. Furthermore, the adsorption capacity of the PVA/SiO₂ composite nanofiber membranes was maintained through six recycling processes. Consequently, these membranes can be promising materials for removing, and recovering, heavy metal ions in water.     

原位反应增容制备可生物降解PLA/PCL复合材料

基于原位反应增容原理制备了一种可生物降解的聚乳酸(PLA)/聚己内酯(PCL)共混材料。探究了PLA/PCL不同配比及相容剂乙烯-丙烯酸丁酯-甲基丙烯酸缩水甘油酯(EBA-GMA)(8份)对增韧效果的影响,目的是研究设计一种增韧效果最佳的PLA/PCL/EBA-GMA可降解材料。并采用平板流变仪、傅里叶红外光谱仪(FTIR)、扫描电子显微镜(SEM)及差示扫描量热法(DSC)对其反应机理、微观形貌及热性能进行了表征。结果表明,在不加相容剂时,PLA/PCL(80/20)能取得最好的增韧效果;加入8份相容剂后,PLA/PCL(85/15)的缺口冲击强度达75.4 kJ/m^2,增韧效果最好。