Measurement of size‐dependent glass transition temperature in electrospun polymer fibers using AFM nanomechanical testing

The glass transition temperature (T_g) of individual electrospun polymer polyvinyl alcohol fibers of varying diameter was measured using atomic force microscopy (AFM) based nanomechanical thermal analysis. Indentation and bending of individual electrospun fibers using AFM allowed the calculation of the elastic modulus of the polyvinyl alcohol (PVA) fibers across a range of different temperatures. The elastic modulus of electrospun PVA fibers was observed to decrease significantly when passing through T_g, which allowed accurate determination of T_g. The T_g of electrospun PVA fibers was shown to decrease for smaller fiber diameters especially for fiber diameters below 250 nm. This size‐dependent glass transition behavior of electrospun PVA fibers is indicated as being due to polymer chain confinement. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Electrospinning of poly(ethylene-co-vinyl acetate)/clay nanocomposite fibers

Poly(ethylene-co-vinyl acetate)/clay nanocomposite fibers were fabricated using electrospinning. The fiber diameters were controlled by varying the polymer/chloroform concentration, which resulted in fibers with diameters ranging from 1 to 15 μm. The clay concentration was varied from 0.35 to 6.6 wt %. Scanning electron microscopy revealed that the fiber diameter increased with increasing clay concentration, whereas beading decreased. Transmission electron microscopy revealed a disruption of the spherulite structures by clay, which is consistent with heterogeneous nucleation. Shear modulus force microscopy indicated a reduction in melting point (T_m) with decreasing diameter for fibers thinner than 15 μm, which was confirmed by temperature dependent X-ray diffraction data. For fibers thinner than 8 μm, the presence of clay further enhanced the reduction of T_m. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2501–2508, 2009     

静电纺丝法制备聚甲醛纳米纤维

以六氟异丙醇为溶剂, 用静电纺丝的方法制备了聚甲醛纳米纤维. 利用场发射扫描电镜对纤维形貌进行了表征, 纤维的直径为0.3~1.2 μm. 讨论了溶液浓度、接收距离、电压和温度等纺丝参数对纤维形貌的影响. 用DSC方法对电纺纤维膜的结晶性能进行了研究, 并与溶液浇铸膜的进行了比较. 结果表明, 电纺纤维膜的熔点与溶液浇铸膜的相同, 与溶液的浓度无关, 但结晶度比溶液浇铸膜的低. 力学性能用拉伸试验进行了测试, 观察到很长的断裂伸长率.     

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.     

Aligned electrospun cellulose fibers reinforced epoxy resin composite films with high visible light transmittance

Uniaxially oriented cellulose nanofibers were fabricated by electrospinning on a rotating cylinder collector. The fiber angular standard deviation (a parameter of fiber orientation) of the mats was varied from 65.6 to 26.2^o by adjusting the rotational speed of the collector. Optically transparent epoxy resin composite films reinforced with the electrospun cellulose nanofibrous mats were then prepared by the solution impregnation method. The fiber content in the composite films was in the range of 5–30 wt%. Scanning electron microscopy studies showed that epoxy resin infiltrated and completely filled the pores in the mats. Indistinct epoxy/fiber interfaces, epoxy beads adhering on the fiber surfaces, and torn fiber remnants were found on the fractured composite film surfaces, indicating that the epoxy resin and cellulose fibers formed good interfacial adherence through hydrogen-bonding interaction. In the visible light range, the light transmittance was 88–92% for composite films with fiber loadings of 16–32 wt%. Compared to the composite films reinforced with 20 wt% randomly oriented fibers, the mechanical strength and Young’s modulus of the composite films reinforced with same amount of aligned fibers increased by 71 and 61%, respectively. Dynamical mechanical analysis showed that the storage moduli of the composite films were greatly reinforced in the temperature above the glass transition temperature of the epoxy resin matrix.     

Mechanical Properties of a Single Electrospun Fiber and Its Structures

Summary: A method to measure the Young's modulus of a single electrospun polyacrylonitrile (PAN) fiber is reported. The Young's modulus can be calculated from the force‐displacement curves obtained by the bending of a single fiber attached to an atomic force microscopy (AFM) cantilever. It is suggested that the high modulus of electrospun fibers is caused by the orientation of molecular chains, which is confirmed by wide‐angle X‐ray diffraction (WAXD) measurements. The communication will provide a basic understanding of the relationship between mechanical properties and structures of electrospun fibers.

A PAN fiber was attached to a contact mode cantilever to facilitate the measurement of force‐displacement curves and Young's modulus.     

Solvent and concentration effects on the properties of electrospun poly(ethylene terephthalate) nanofiber mats

This study describes the preparation and characterization of nanofibrous mats obtained by electrospinning poly(ethylene terephthalate) (PET) solutions in trifluoroacetic acid/dichloromethane (TFA/DCM). Special attention was paid to the effect of polymer concentration and solvent properties on the morphology, structure, and mechanical and thermal properties of the electrospun nonwovens. The results show that the spinnable concentration of PET solution in TFA/DCM solvents is above 10 wt %. Mats have nanofibrous morphology with fibers having an average diameter in the range of 200–700 nm (depending on polymer concentration and solvent composition) and an interconnected pore structure. Higher solution concentration favors the formation of uniform fibers without beads and with higher diameter. Morphology and fiber assembly changed with the solvent properties. Solvent mixtures rich in TFA, i.e., those with higher dielectric constant and lower surface tension, originated fibers with small diameter. However, due to the lower volatility, those solvent mixtures also produced more branched and crosslinking fibers, with less morphologic uniformity. Mechanical properties (Young's modulus, ultimate strength, and elongation at break) and thermal properties (glass transition, crystallization, and melting) have been studied for the PET electrospun nanomats and compared with those of the original polymer. Solvent effect on fiber crystallinity was not significant, but a complex effect was observed on the mechanical properties of the electrospun mats, as a consequence of the different structural organization of the fibers within the mat network. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 460–471, 2008     

Nanoporous structured submicrometer carbon fibers prepared via solution electrospinning of polymer blends

A facile means for obtaining submicrometer carbon fibers with a nanoporous structure is presented. A mixture of polyacrylonitrile (PAN) and a copolymer of acrylonitrile and methyl methacrylate (poly(AN-co-MMA)) in dimethylformamide was electrospun into submicrometer fibers with a microphase-separated structure. During the followed oxidation process, the copolymer domains were pyrolyzed, resulting in a nanoporous structure that was preserved after carbonization. The microphase-separated structure of the PAN/poly(AN-co-MMA) electrospun fibers, the morphology, and porous structure of both the oxidized and the carbonized fibers were observed with scanning electron microscopy and transmission electron microscopy. The carbon fibers have diameters ranging from several hundred nanometers to about 1 microm. The nanopores or nanoslits throughout the fiber surface and interior with diameters of several tens of nanometers are interconnected and oriented along the longitudinal axis of the fibers. This unique nanoporous morphology similar to the microphase-separated structure in the PAN/poly(AN-co-MMA) fibers is attributed to the rapid phase separation, solidification, as well as the stretching of the fibers during electrospinning. The pore volume and pore size distribution of the carbonized fibers were investigated by nitrogen adsorption and desorption.     

Mechanism of adhesion between polymer fibers at nanoscale contacts

Adhesive force exists between polymer nano/microfibers. An elaborate experiment was performed to investigate the adhesion between polymer nano/microfibers using a nanoforce tensile tester. Electrospun polycaprolactone (PCL) fibers with diameters ranging from 0.4-2.2 μm were studied. The response of surface property of electrospun fiber to the environmental conditions was tracked by FTIR and atomic force microscopy (AFM) measurements. The effect of temperature on molecular orientation was examined by wide angle X-ray diffraction (WAXD). The adhesive force was found to increase with temperature and pull-off speed but insensitive to the change of relative humidity, and the abrupt increase of adhesion energy with temperature accompanied by a reduced molecular orientation in the amorphous part of fiber was observed. Results show that adhesion is mainly driven by van der Waals interactions between interdiffusion chain segments across the interface.     

Thermal and mechanical properties of electrospun PMMA,PVC, Nylon 6, and Nylon 6,6

Poly(methyl methacrylate) (PMMA), poly(vinyl chloride) (PVC), Nylon 6, and Nylon 6,6 have been electrospun successfully. The nanofibers have been characterized by scanning electron microscopy (SEM), confirming the presence of bead free and fiber‐bead free morphologies. Thermogravimetric analysis (TGA) indicated differences between the thermal stability of PMMA nanofibers and PMMA powder. However, no significant differences were observed between the starting physical form (powder or pellet) of PVC, Nylon 6 and Nylon 6,6, and their corresponding electrospun nanofibers. Differential scanning calorimetry (DSC) demonstrated a lower glass transition temperature (T_g) and water absorption for PMMA electrospun nanofibers. Furthermore, electrospun Nylon 6 and Nylon 6,6 had a slight decrease in crystallinity. Tensile testing was performed on the electrospun nanofibers to obtain the Young modulus, peak stress, strain at break, and energy to break, revealing that the non‐woven mats obtained had modest mechanical properties that need to be enhanced. Copyright © 2007 John Wiley & Sons, Ltd.     

Study on morphology of electrospun poly(vinyl alcohol) mats

Submicron poly(vinyl alcohol) (PVA) fiber mats were prepared by electrospinning of aqueous PVA solutions in 6-8% concentration. Fiber morphology was observed under a scanning electron microscope and effects of instrument parameters including electric voltage, tip-target distance, flow rate and solution parameters such as concentration on the morphology of electrospun PVA fibers were evaluated. Results showed that, when PVA with higher degree of hydrolysis (DH) of 98% was used, tip-target distance exhibited no significant effect on the fiber morphology, however the morphological structure can be slightly changed by changing the solution flow rate. At high voltages above 10 kV, electrospun PVA fibers exhibited a broad diameter distribution. With increasing solution concentration, the morphology was changed from beaded fiber to uniform fiber and the average fiber diameter could be increased from 87 ± 14 nm to 246 ± 50 nm. It was also found that additions of sodium chloride and ethanol had significant effects on the fiber diameter and the morphology of electrospun PVA fibers because of the different solution conductivity, surface tension and viscosity. When the DH value of PVA was increased from 80% to 99%, the morphology electrospun PVA fibers was changed from ribbon-like fibers to uniform fibers and then to beaded fibers. The addition of aspirin and bovine serum albumin also resulted in the appearance of beads.     

Assessment of the parameters influencing the fiber characteristics of electrospun poly(ethyl methacrylate) membranes

This work evaluates the influence of electrospinning process parameters on the mean diameter and standard deviation of fiber diameters in electrospun poly(ethyl methacrylate) (PEMA). Processing conditions were selected using Taguchi’s statistical method. Oriented and unoriented electrospun mats with good mechanical properties were produced and demonstrated with tensile stress–strain diagrams. Differential scanning calorimetry (DSC) experiments showed that the polymer chains were forced into non-equilibrium conformations due to electrospinning. Enthalpic recovery during a heating scan is shown by an endothermic peak in the initial DSC heating scan that disappears in subsequent heating scans. An increase in the glass transition temperature with respect to PEMA films shows that the polymer is not equilibrated by heating above glass transition. Cell attachment was tested with MC3T3-E1 pre-osteoblastic cells cultured for short time periods on the electrospun mats. It is shown that the cells present less extended morphology with more diffuse perimetral focal adhesions than cells cultured on flat substrates. A tendency of cells to align in the direction of the substrate fibers in oriented electrospun membranes was also found.     

Influence of a mixing solvent with tetrahydrofuran and N,N‐dimethylformamide on electrospun poly(vinyl chloride) nonwoven mats

We evaluated the effects of the solvent composition with respect to the solution concentration, applied electric field, and tip‐to‐collector distance on the morphology of electrospun poly(vinyl chloride) (PVC) fibers. The solvent volume ratio was strongly correlated with the diameter of the electrospun fibers with respect to the other processing parameters. Electrospun PVC fibers dissolved in tetrahydrofuran (THF) had diameters ranging from 500 nm to 6 μm; those dissolved in N,N‐dimethylformamide (DMF) had an average diameter of 200 nm. The diameters of the electrospun fibers were obtained from narrow to broad distributions with the solvent composition. Also, the diameters of fibers electrospun from a mixed solvent of THF and DMF were less than 1 μm. The mechanical properties of electrospun PVC nonwoven mats depended on the fiber orientation and linear velocity of the drum surface. With increasing linear velocity of the drum surface, electrospun PVC fibers were arranged toward the machine direction, and the dimensions of the spiral path were shorter. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2259–2268, 2002     

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...     

以旋转竖直铜针为收集器静电纺制备PVP螺旋型纤维绳

以竖直旋转的细铜针为接收器,聚乙烯基吡咯烷酮(PVP)/无水乙醇质量分数为10%,电压25 kV,在不同的旋转速度下纺出了PVP螺旋纤维绳.当竖直细铜针固定不转时,纺丝纤维呈松散线状结构;竖直细铜针旋转速度加快,纤维形态由松散的螺旋缠绕向紧密缠绕的趋势变化,PVP纤维在纺丝针头和接收铜丝间静电库仑引力(垂直方向),纺出纤维间的库仑斥力(水平方向),以及铜针高速旋转力(切线方向)的三重作用下,最终制得PVP螺旋微米纤维绳.用扫描电子显微镜(SEM)对其进行表征.实验结果表明,接收器旋转速度和接收距离对多螺旋结构纤维的形貌有显著影响.讨论了螺旋纤维的形成机理.     

Effects of Solution Concentration,Emitting Electrode Polarity,Solvent Type,and Salt Addition on Electrospun Polyamide-6 Fibers: A Preliminary Report

Electrospinning is a process by which ultrafine fibers which have diameters in the range of tens of nanometers to less than ten of micrometers can be produced. This process utilizes expulsion of charges as a means to very thin fiber formation. In this short report, the effects of some of the influencing solution and process parameters (i.e. solution concentration, emitting electrode polarity, solvent type, and salt addition) on morphological appearance of electrospun polyamide-6 fibers were investigated based on visual observation of a series of scanning electron micrographs. It was found that all of the parameters studied played important roles in determining morphology and sizes of the fibers obtained.     

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。     

Polyaniline/poly(methyl methacrylate) coaxial fibers: The fabrication and effects of the solution properties on the morphology of electrospun core fibers

Electrically conductive polyaniline (PANi)/poly(methyl methacrylate) (PMMA) coaxial fibers were prepared through the chemical deposition of PANi onto preformed PMMA fibers via in situ polymerization. PMMA fibers were prepared as core materials via electrospinning. Spectral studies and scanning electron microscopy observations indicated the formation of PANi/PMMA coaxial fibers with a diameter of approximately 290 nm and a PANi layer thickness of approximately 30 nm. The conductivity of the PANi/PMMA coaxial fibers was significantly higher than that of electrospun fibers of PANi/poly(ethylene oxide) blends and blend cast films of the same PANi composition. To reproducibly generate uniform‐core polymer fibers, the organic solution properties that affected the morphology and diameter of the electrospun fibers were investigated. The polymer molecular weight, solution concentration, solvent dielectric constant, and addition of soluble organic salts were strongly correlated to the morphology of the electrospun fiber mat. In particular, the dielectric constants of the solvents substantially influenced both the fiber diameter and bead formation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3934–3942, 2004     

Electrospun EGNPs reinforced precursor carbon nanofibril composites by using RSM

Response surface methodology (RSM),based on five‐level, four variable Box‐Benkhen technique was investigated for modeling the average fiber diameter of electrospun polyacrylonitrile (PAN) nanofibers. The four important electrospinning parameters were studied including applied voltage (kV), Berry's number, deposition distance from nozzle to collector (cm), and spinning angle (? in degree). The measured fiber diameters were in a good agreement with the predicted results by using RSM technique. High‐regression coefficient between the variables and the response (R² = 87.74%) indicates excellent evaluation of experimental data by second‐order polynomial regression model. The optimum PAN average fiber diameters of 208 and 37‐nm standard deviation were collected at 19 kV, Berry's number = 10, 25^° spinning angle, and 16‐cm deposition distance. The PAN/N,N‐dimethylformamide (DMF) polymer solution with the optimum weight concentration (10 wt.%) was selected to study the effect of dispersing exfoliated graphite nanoplatelets (EGNPs) in PAN/DMF solution on the electrospun EGNP/PAN fibril composite diameter. Five different EGNPs weight concentrations (2, 4, 6, 8, and 10 wt.%) were dispersed in the optimized PAN/DMF polymer solution. Morphology of EGNPs/PAN fibril composites and its distribution were investigated by scanning electron microscopy (SEM) to show the minimum fiber diameter for the above‐mentioned 5 wt. % of EGNPs. A minimum fibril composite diameter of 182 nm was obtained at 10 wt.% of EGNPs. Morphological characteristics of electrospun fibers and their distribution were tested by Raman spectroscopy, SEM, differential light scattering, and high‐resolution transmission electron microscopy.     

The morphology and crystalline region distribution of polyacrylonitrile nanofibers prepared by electrospinning

The effects of electrospinning parameters in a wider range on the morphology and diameters of polyacrylonitrile (PAN) fibers are studied in detail. The fibers’ diameter increases from 288 to 3469 nm swiftly with the increasing PAN concentration. With the increasing voltage or prolonging gap distance, the diameter increases primarily and decreases later. The combined effects of surface tension, splitting and stretching, electric force, viscosity, and solvent volatilization are the main reasons. Ultrasonic etching method, Atomic force microscope (AFM), Scanning electron microscope (SEM) and X-ray diffraction (XRD) technology have been utilized to verify the nature structure of electrospun PAN fibers. Combining all the results, it is deduced that there are many grooves arranging nearly perpendicular to the fiber axis on the surface of electrospun PAN fibers. The thickness of relative ordered region is 40 to 190 nm and the thickness of amorphous region is 20 to 35 nm.