Fabrication of continuous nanofiber yarn using novel multi‐nozzle bubble electrospinning

A novel multi‐nozzle bubble electrospinning apparatus, including spinning unit, metering pump, constant flow pump, metal funnel and yarn winder, was designed for the preparation of continuous twisted polyacrylonitrile nanofiber yarns, and the principle of nanofiber yarn spinning was studied. An innovative spinning unit consisting of nozzle and air chamber was used to improve the production of nanofibers. Double conjugate electrospinning was developed using two pairs of oppositely charged spinning units to neutralize the charges. The effects of applied voltage, air flow rate, overall solution flow rate and funnel rotary speed on the fiber diameter, production rate and mechanical properties of the nanofiber yarns were analyzed. Nanofibers could be aggregated stably and bundled continuously, then twisted into nanofiber yarns uniformly at an applied voltage of 34 kV, air flow rate of 1200 mL min^?1 and overall solution flow rate of 32 mL h^?1. With an increase in the funnel rotary speed, the twist angle of the nanofiber yarns gradually increased when the take‐up speed was constant. The yarn tensile strength and elongation at break showed an increasing trend with increasing twist angle. Nanofiber yarns obtained using this novel method could be produced at a rate from 2.189 to 3.227 g h^?1 with yarn diameters ranging from 200 to 386 µm. Nanofiber yarns with a twist angle of 49.7° showed a tensile strength of 0.592 cN dtex^?1 and an elongation at break of 65.7%. © 2013 Society of Chemical Industry     

Tensile fatigue behavior of polyamide 66 nanofiber yarns

Nanofiber yarns with twisted and continuous structures have potential applications in fabrication of complicated structures such as surgical suture yarns, artificial blood vessels, and tissue scaffolds. The objective of this article is to characterize the tensile fatigue behavior of continuous Polyamide 66 (PA66) nanofiber yarns produced by electrospinning with three different twist levels. Morphology and tensile properties of yarns were obtained under static tensile loading and after fatigue loading. Results showed that tensile properties and yarn diameter were dependent on the twist level. Yarns had nonlinear time‐independent stress–strain behavior under the monotonic loading rates between 10 and 50 mm/min. Applying cyclic loading also positively affected the tensile properties of nanofiber yarns and changed their stress–strain behavior. Fatigue loading increased the crystallinity and alignment of nanofibers within the yarn structure, which could be interpreted as improved tensile strength and elastic modulus. POLYM. ENG. SCI., 55:1805–1811, 2015. © 2014 Society of Plastics Engineers     

Conjugate electrospinning of continuous nanofiber yarn of poly(L‐lactide)/nanotricalcium phosphate nanocomposite

The continuous nanofiber yarns of poly(L ‐lactide) (PLLA)/nano‐β‐tricalcium phosphate (n‐TCP) composite are prepared from oppositely charged electrospun nanofibers by conjugate electrospinning with coupled spinnerets. The morphology and mechanical properties of PLLA/n‐TCP nanofiber yarns are characterized by scanning electron microscope, transmission electron microscope, and electronic fiber strength tester. The results show that PLLA/n‐TCP nanofibers are aligned well along the longitudinal axis of the yarn, and the concentration of PLLA plays a significant role on the diameter of the nanofibers. The thicker yarn of PLLA/n‐TCP composite with the weight ratio of 10/1 has been produced by multiple conjugate electrospinning using three pairs of spinnerets, and the yarn has tensile strength of 0.31cN/dtex. A preliminary study of cell biocompatibility suggests that PLLA/n‐TCP nanofiber yarns may be useable scaffold materials. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Preparation and characterization of zein and zein/poly‐L‐lactide nanofiber yarns

Zein and zein/poly‐L ‐lactide (PLLA) nanofiber yarns were prepared by conjugate electrospinning using coupled spinnerets applied with two high electrical voltages of opposite polarities in this article. Structure and morphology of zein yarns were investigated by SEM and X‐ray diffraction. The results showed that zein yarn consisted of large quantity of fibers with diameters ranging from several hundreds nanometers to a few microns, and zein concentration played a significant role on the diameter of nanofibers in yarns. To improve mechanical property of nanofiber yarns, PLLA was then incorporated with zein. Zein/PLLA composite nanofiber yarns conjugate electrospun from solution with concentration of 7.5% (zein, w/v)/7.5% (PLLA, w/v) exhibited tensile strength of 0.305 ± 0.014 cN/dtex. The composite yarns showed better nanofiber alignment along the longitudinal axis. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Mechanical properties and morphology of hot drawn polyacrylonitrile nanofibrous yarn

In this study PAN nanofibrous yarn was produced by two‐nozzle conjugated electrospinning method. The nanofibrous yarns were drawn continuously in boiling water with drawing ratios of 1, 2, 3, and 4. The morphology of drawn yarns was investigated by scanning electron microscopy and tested for tensile properties as well as untreated yarn. The results showed that the nanofiber alignment in the yarn axis direction, the tensile strength, and tensile modulus of yarn increases as a result of drawing while the tensile strain and work of rapture decrease. X‐ray diffraction patterns of the produced yarns were analyzed as well. It was found that crystallinity index increases as the draw ratio increases. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The influence of solvent type and polymer concentration on the physical properties of solid state polymerized PA66 nanofiber yarn

We investigated the effects of two different solvent types and three solution concentrations on the electrospinning of solid state polymerized polyamide 66 (SSP PA66) nanofiber yarns. Nanofiber yarns were electrospun from SSP PA66 solutions in formic acid and formic acid/chloroform (3/1), using two oppositely metallic spinnerets system. Scanning electron microscopy (SEM) and X‐ray diffraction (XRD) were employed to characterize the morphology and properties of the nanofibrous yarns. Experimental results show that adding chloroform to formic acid as a binary solvent increases viscosity of polymer solution and the nanofibers diameter significantly. XRD patterns reveal that the presence of chloroform affects the crystallinity and the mechanical properties of the produced nanofibrous yarns. PA66 nanofiber yarn from 10 wt % formic acid/chloroform (3/1) solution was successfully electrospun with strength and modulus of 120.16 MPa and 1216.27 MPa respectively. It is also shown that the solution concentration has a significant effect on the modulus of the nanofibers yarns. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Continuous polymer nanofiber yarns prepared by self-bundling electrospinning method

Continuous polymer nanofiber yarns were manufactured by self-bundling electrospinning method. Compared with typical electrospinning setup, the special difference in this method was that a grounded needle tip was used to induce the self-bundling of polymer nanofibers at the beginning of electrospinning process. Four kinds of polymer self-bundling yarns, poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), polyacrylonitrile (PAN), poly(l-lactic acid) (PLLA) and poly(m-phenylene isophthalamide) (PMIA), were prepared successfully by using this self-bundling electrospinning method. Good alignment of polymer nanofibers in self-bundled yarns was confirmed by SEM observation. It was found out that the conductivity of the polymer solution was crucial to achieve stably continuous self-bundled fiber yarns. A possible mechanism for the self-bundling formation of align nanofiber yarn was proposed.     

Preparation and properties of the single‐walled carbon nanotube/cellulose nanocomposites using N‐methylmorpholine‐N‐oxide monohydrate

Single‐walled carbon nanotube (SWNT)/cellulose nanocomposite films were prepared using N‐methylmorpholine‐N‐oxide (NMMO) monohydrate as a dispersing agent for the acid‐treated SWNTs (A‐SWNTs) as well as a cellulose solvent. The A‐SWNTs were dispersed in both NMMO monohydrate and the nanocomposite film (as confirmed by scanning electron microscopy) because of the strong hydrogen bonds of the A‐SWNTs with NMMO and cellulose. The mechanical properties, thermal properties, and electric conductivity of the nanocomposite films were improved by adding a small amount of the A‐SWNTs to the cellulose. For example, by adding 1 wt % of the A‐SWNTs to the cellulose, tensile strain at break point, Young's modulus, and toughness increased ～ 5.4, ～ 2.2, and ～ 6 times, respectively, the degradation temperature increased to 9°C as compared with those of the pure cellulose film, and the electric conductivities at ? (the wt % of A‐SWNTs in the composite) = 1 and 9 were 4.97 × 10^?4 and 3.74 × 10^?2 S/cm, respectively. Thus, the A‐SWNT/cellulose nanocomposites are a promising material and can be used for many applications, such as toughened Lyocell fibers, transparent electrodes, and soforth. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Polyamide 6 nanofibrous nonwovens via electrospinning

Electrospinning of Polyamide 6 (PA 6) in 2,2,2‐trifluoroethanol (TFE) was investigated for the fabrication of nanofibrous nonwoven membranes useful for separation systems. The effects of solution characteristics such as concentration and conductivity as well as the effects of processing conditions such as relative humidity and applied potential on the resultant nonwoven fibers were studied. By changing the relative humidity of the electrospinning chamber and the conductivity of the solvent, it is possible to modulate the fiber's size and consequently the porosity of the mats. The morphology of the electrospun PA 6 nanofibers was observed by scanning electron microscopy. The mechanical properties of the nanofibers were also studied. The results showed that PA 6 nanofibers having a diameter ranging from 100 to 600 nm, has been successfully prepared. The electrospun PA 6 nanofiber mats show good mechanical properties, such as a high‐tensile strength (12 ± 0.2 MPa) and elongation (300% ± 50%). The strength of the web was high enough to use as filter without the need of any supporting matrix and could be applicable in the field of self‐supporting membranes. The X‐ray and DSC analyses of the PA 6 electrospun fibers show the presence of the γ‐form of PA 6 crystallite that is usually obtained in the condition where a high stress of the fibers is applied. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

丝素-聚己内酯纳米纤维膜的制备工艺

以六氟异丙醇(HFIP)为溶剂,采用静电纺丝技术制备丝素(SF)-聚己内酯(PCL)复合纳米纤维膜。采用热场发射扫描电镜、Image-Pro Plus图像分析和力学拉伸的方法表征了纳米纤维膜的结构与力学性能。通过设计的三因素四水平正交试验对复合纳米纤维膜的多个指标进行了分析,采取归一化数据处理及平均权重分配的方式量化了复合纳米纤维膜的品质,确定了共混复合纳米纤维膜制备的最优工艺参数,并且采用最佳工艺参数制备了SF-PCL复合纳米纤维膜,分析了其力学性能。结果表明:在溶质质量分数为6%、溶质SF与PCL质量比为3∶2、纺丝流速1.2 mL/h时,SF-PCL复合纳米纤维膜具有较好的品质;双轴拉伸时的破坏机制与单轴不同,其断裂应力和应变只是单轴时的一半左右,膜的力学性能表现为各向同性。     

Multiple conjugate electrospinning method for the preparation of continuous polyacrylonitrile nanofiber yarn

Continuous polyacrylonitrile nanofiber yarns were fabricated by the homemade multiple conjugate electrospinning apparatus, and the principle of yarn spinning was studied. The effects of the applied voltage, flow rate, spinning distance, and funnel rotary speed on the diameter and mechanical properties of nanofiber yarn were analyzed. The diameter of the nanofibers decreased with increasing applied voltage and the flow rate ratio of the positive and negative needles (F_P/F_N), whereas the diameter of nanofibers increased with increasing overall flow rate and needle distance between the positive and negative. Subsequently, the diameter of the yarns increased first and then decreased with increasing applied voltage, F_P/F_N, and needle distance. However, the diameters of the yarns increased dramatically and then remained stable with increasing overall flow rate. The nanofibers were stably aggregated and continuously bundled and then uniformly twisted into nanofiber yarns at an applied voltage of 20 kV, an overall flow rate of 6.4 mL/h, a needle distance of 18.5 cm, and an F_P/F_N value of 5:3. With increasing funnel rotary speed, the diameters of the nanofibers and yarns decreased, whereas the twist angle of the nanofiber yarns gradually enlarged. Meanwhile, an increase in the twist angle brought about an improvement in the yarn mechanical properties. Nanofiber yarns that prepared showed diameters between 70 and 216 μm. Nanofiber yarns with a twist angle of 65° showed a tensile strength of 50.71 MPa and an elongation of 43.56% at break, respectively. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40137.     

Fabrication and characterization of hollow nanofibrous PA6 yarn reinforced with CNTs

Core-sheath nanofibrous yarns were obtained through electrospinning of polyamide 6 (PA6) solution containing different concentrations of multi-wall carbon nanotubes (MWNTs) as sheath and PVA multifilament as the yarn core. By dissolving PVA, for obtaining conductive hollow nanofibrous PA6/MWNTs yarn, two types of porosity could be obtained including hollow central tube due to the structure of hollow yarn and nano-porous areas embedded in electrospun nanofibers. SEM results showed that the diameters of nanofibers were varying in the range of 103–145 nm obeying MWNTs concentrations and TEM results revealed that the MWNTs were embedded in nanofiber matrix as straight and aligned form. DSC analysis showed that electrospinning process caused the formation of less-ordered γ phase in nanofibers. The electrical conductivity of yarns increased from 10^?13 S m^?1 to 2.4?×?10^?6 S m^?1 with increasing the concentration of nanotubes from 0 wt.% to 7 wt.%.     

含银PA6纳米纤维的制备及抗菌性能研究

以次磷酸钠还原硝酸银制得银溶胶,按不同比例加入到质量分数为12%的聚己内酰胺(PA6)/甲酸溶液中,通过静电纺丝制备含银PA6纳米纤维毡,分析了纤维的表面形貌和抗菌性能。结果表明:当纤维中银质量分数为0.1%时,PA6纳米纤维对大肠杆菌的抑菌率达95%以上。扫描电镜和原子力显微镜分析表明,含银PA6纳米纤维比PA6纳米纤维平均直径稍粗,直径分布更集中,纤维直径为80～100 nm,但其表面有明显的褶痕,粗细节较多,不如PA6纳米纤维光滑。     

The influence of process parameters on the properties of electrospun PLLA yarns studied by the response surface methodology

Poly (l ‐lactide) (PLLA) fibrous yarns were prepared by electrospinning of polymer solutions in 2,2,2‐trifluoroethanol. Applying spinning from two oppositely charged needles the spontaneous formed triangle of fibers at a grounded substrate could be assembled into fibrous yarns using a device consisting of a take‐up roller and twister. The effect of processing parameters on the morphology, diameter and mechanical properties of PLLA yarns was investigated by the response surface methodology (RSM). This method allowed evaluating a quantitative relationship between polymer concentration, voltage, take‐up rate and distance between the needles' center and the take‐up unit on the properties of the electrospun fibers and yarns. It was found that at increasing concentrations up to 9 wt % uniform fibers were obtained with increasing mean diameters. Conversely, the fiber diameter decreased slightly when the applied voltage was increased. The take‐up rate had a significant influence on the yarn diameter, which increased as the take‐up rate decreased. The tensile strength and modulus of the yarns were correlated with these variables and it was found that the polymer concentration had the largest influence on the mechanical properties of the yarns. By applying the RSM, it was possible to obtain a relationship between processing parameters which are important in the fabrication of electrospun yarns. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41388.     

聚多巴胺改性静电纺EVOH–SO_3Li薄膜的热力性能

由静电纺丝技术制备的EVOH–SO_3Li纳米纤维薄膜的力学性能不高,为了改善薄膜的力学性能,采用多巴胺对EVOH–SO_3Li纳米纤维膜进行改性。通过宏观形貌观察、扫描电子显微镜、傅立叶变换红外光谱分析这三种测试方法相结合,表明多巴胺粘附在纳米纤维上,并在纤维膜上进行自聚形成聚多巴胺(PDA)。热失重分析结果表明,热失重为10%时PDA改性后的隔膜较未改性的EVOH–SO_3Li纯膜提高了67℃。拉伸性能测试结果表明,浸泡浓度为0.015 mol/L时,PDA改性后的隔膜拉伸强度比纯膜提高了11.89 MPa。PDA改性后薄膜的孔隙率有所下降但吸液率提升明显,最高达到了480%。     

Reversible Photochromic Nanofiber Membrane Containing Comb‐Like Poly(octadecyl acrylate) Nanoparticles Used for Ultraviolet Intensity Indicator

A novel reversible photo‐responsive polyvinyl alcohol (PVA)/polyethylenimine (PEI) electrospinning nanofiber membrane (NFM), assembled with photochromic nanoparticles containing spiropyran, is herein presented and the water resistance, mechanical properties as well as photochromic properties are investigated systematically. Here, glutaraldehyde, which can undergo a cross‐linking reaction with PVA/PEI, is selected as a cross‐linker to enhance water resistance and mechanical behavior of the NFM. Photochromic polymer nanoparticles are prepared using octadecyl acrylate as polymer matrix monomer through miniemulsion polymerization. Effect factors of the whole preparation process such as the PVA/PEI mass ratio, the amount of emulsifier, and the amount of photochromic nanoparticles added are regulated to obtain the optimal experimental parameters. The surface morphology and microstructure, water resistance, and mechanical properties of NFMs are studied by thermal field emission scanning electron microscopy, static water contact angle tester, and tensile universal testing machine, respectively. Furthermore, UV–vis spectrophotometer is employed to investigate the photochromic performance and fatigue resistance of NFMs. Overall, analyses reveal that the reversible photo‐responsive electrospinning NFM exhibit excellent photoresponsivity, photoreversibility, and fatigue resistance upon UV irradiation, thus showing promising application in the field of ultraviolet intensity indicator.     

Effect of spinning conditions on the mechanical properties of PA6/MWNTs nanofiber filaments

Carbon nanotube (CNT ) reinforced composite materials is a hot research issue now , but CNT/polymer composite nano-scale fibers still cannot be obtained readily, not mention to successfully prepare continuous CNTs/polymer composite nano-scale fiber filaments manufactured by electrospinning. In this paper, continuous filaments constructed of nano-scale PA6/MWNTs fibers in single-axis orientation were obtained by an improved wet-electrospinning technique. The effects of the concentrations of MWNTs, spinning speed and post-drawing on the mechanical properties of PA6/MWNTs nanofiber filaments were studied. The results show that when the concentrations of MWNTs is below 0.8 wt%, the increase of MWNTs content enhances the Young’s modules and breaking stress but reduces the breaking strain, while the breaking stress decreases when the MWNTs concentration exceeds 0.8 wt%. The Young’s modules and breaking stress increased as the spinning speed raised at the range of 1.8–9.0 m/min, but declined when the speed exceeded 9.0 m/min. The mechanical properties of the as-spun filaments can be improved by either dry or wet post-drawing, and the breaking stress of the wet post-drawn filaments was improved 2.64 times while that of the dry post-drawn filaments 2.28 times.     

Enhancement of interlaminar fracture toughness of carbon fiber–epoxy composites using polyamide‐6,6 electrospun nanofibers

In this study, carbon fiber–epoxy composites are interleaved with electrospun polyamide‐6,6 (PA 66) nanofibers to improve their Mode‐I fracture toughness. These nanofibers are directly deposited onto carbon fabrics before composite manufacturing via vacuum infusion. Three‐point bending, tensile, compression, interlaminar shear strength, Charpy impact, and double cantilever beam tests are performed on the reference and PA 66 interleaved specimens to evaluate the effects of PA 66 nanofibers on the mechanical properties of composites. To investigate the effect of nanofiber areal weight density (AWD), nanointerlayers with various AWD are prepared by changing the electrospinning duration. It is found that the electrospun PA 66 nanofibers are very effective in improving Mode‐I toughness and impact resistance, compressive strength, flexural modulus, and strength of the composites. However, these nanofibers cause a decrease in the tensile strength of the composites. The glass‐transition temperature of the composites is not affected by the addition of PA 66 nanofibers. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45244.     

Composite yarns fabricated from continuous needleless electrospun nanofibers

In this work, a spinning metal wire collector was employed to continuously collect polyacrylonitrile (PAN) nanofibers produced by a disc fiber generator and coil them around a polyethylene terephthalate (PET) yarn. The obtained composite yarns exhibited a core/shell structure (PET yarn/PAN nanofibers) with nanofibers orderly arranged on the surface of the PET yarn. The electric field analysis showed that the position of metal wire had insignificant effect on the formed electric field and high intensity electric field was formed at the disc circumferential area, which provided a constant electric field for the production of uniform nanofibers. The spinning solution, spinning speed of metal wire, and winding speed were found to play an important role in producing good quality nanofiber yarns, in terms of morphology, strength, and productivity. Pure nanofiber yarns were obtained after dissolving the core yarns in a proper solvent. This method has shown potential for the mass production of nanofiber yarns for industrial applications. POLYM. ENG. SCI., 54:1495–1502, 2014. © 2013 Society of Plastics Engineers     

Sea‐island polyurethane/polycarbonate composite nanofiber fabricated through electrospinning

Sea‐island polyurethane (PU)/polycarbonate (PC) composite nanofibers were obtained through electrospinning of partially miscible PU and PC in 3 : 7 (v/v) N,N‐dimethylformamide (DMF) and tetrahydrofuran (THF) mixture solvent. Their structures, mechanical, and thermal properties were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy, thermogravimetric (TG), and differential scanning calorimetry (DSC). The structures and morphologies of the nanofibers were influenced by composition ratio in the binary mixtures. The pure PC nanofiber was brittle and easy to break. With increasing the PU content in the PU/PC composite nanofibers, PU component not only facilitated the electrospinning of PC but improved the mechanical properties of PU/PC nanofibrous mats. In a series of nanofibrous mats with varied PU/PC composition ratios, PU/PC 70/30 showed excellent tensile strength of 9.60 Mpa and Young's modulus of 55 Mpa. After selective removal of PC component in PU/PC composite nanofibers by washing with acetone, the residual PU maintained fiber morphology. However, the residual PU nanofiber became irregular and contained elongated indents and ridges along the fiber surface. PU/PC composite fibers showed sea‐island nanofiber structure due to phase separation in the spinning solution and in the course of electrospinning. At PC content below 30%, the PC domains were small and evenly dispersed in the composite nanofibers. As PC content was over 50%, the PC phases became large elongated aggregates dispersed in the composite nanofibers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010