Orthogonal design study on factors affecting the degradation of polylactic acid fibers of melt electrospinning

Melt electrospinning is a much simpler and safer method in the production of ultra-fine fibers compared with solution electrospinning. However, high-spinning temperature usually leads to serious degradation of polymer materials. In determining factors that affect the relative molecular mass of polylactic acid (PLA) fibers during melt electrospinning, an orthogonal design method was used to examine the influence of melting temperature, spinning distance, and species and content of antioxidants. Results showed that antioxidant content at the present three levels (i.e., 0.1%, 0.3%, and 0.5%) has the most considerable effect on the relative molecular mass of PLA fibers. Error analysis showed that changes in temperature, distance, and antioxidant content influence the experiment's results significantly. All interaction effects were larger than those of the single factor in the experimental results. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Efficient preparation of poly(lactic acid) nanofibers by melt differential electrospinning with addition of acetyl tributyl citrate

Poly(lactic acid) (PLA) nanofibers, as a biodegradable and environmentally friendly material, have potential applications such as biological medicine, efficient filter material, and so on. PLA nanofibers are usually prepared by solution electrospinning method with toxic solvents, such as chloroform, chloromethane, and N,N‐dimethyl formamide. In this work, PLA nanofibers were fabricated with a self‐designed melt differential electrospinning device, assisted by addition of nontoxic acetyl tributyl citrate (ATBC) and by airflow. Molecular dynamics simulations were performed to understand the experimental results. The results revealed that the fiber diameter decreased with increasing airflow velocity, and fibers with a diameter as small as 236 nm were obtained at the highest airflow velocity of 25 m/s (with 6 wt % of ATBC). Furthermore, a significantly accelerated falling speed of the jets of about 347 times of that without airflow was achieved at a flow rate of 25 m/s. These results demonstrated that the combination of adding ATBC and airflow assistance was a good strategy to achieve finer fibers with improved stability and efficiency, making it a promising way for mass green production of PLA nanofibers. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46554.     

Polymer melt differential electrospinning from a linear slot spinneret

Preparation of melt electrospun fibers with high efficiency and high productivity remains a big challenge. A polymer melt differential electrospinning system with linear slot spinneret (LSSP) was proposed in this work. Under a high electric field, multiple jets distributed at the tip of LSSP were self-organized from the polymer melt film with controlled thickness. The spinning parameters were investigated, and the electric filed between spinneret and collector was analyzed. The results showed that the interjet distance decreased significantly with the decrease of the thickness of polymer melt film and the Tayler cone size. The smallest average interjet distance of 1.9 mm with deviation of 0.5 mm was obtained under the condition of applied voltage of 45 kV, collecting distance of 9 cm, temperature of 250 °C, and slot thickness of 0.2 mm. The high output of 75.6 g/h was achieved and could be increased just by increasing the slot width. It was demonstrated that the proposed technology was a promising way to fabricate melt electrospun fibers with high efficiency. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48922.     

Solvent-resistant ultrafine nonwoven fibrous membranes by ultraviolet-assisted electrospinning of organo-soluble photosensitive polyimide resin

An ultraviolet-assisted electrospinning (UVAES) method was investigated to improve the solvent stability of soluble polyimide (PI) electrospun ultrafine fibrous membranes (UFMs) to assist in the development of fibrous polymeric materials with improved resistance to harsh environmental conditions and to expand the potential applications for such soft filaments. A preimidized soluble negative photosensitive polyimide (PSPI) was synthesized via an one-step thermal polycondensation from 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA) and 1,1′-bis(4-amino-3,5-dimethylphenyl)-1-(3′-trifluoromethylphenyl)methane (TFMDA). The PI resin was then fabricated into UFMs by both conventional electrospinning (ES) and UVAES with N,N-dimethylacetamide (DMAc) as the solvent. During spinning, photo crosslinking reaction occurred, accompanied by simultaneous micro-jets of PI-UV ultrafine fibers in the UVAES procedure. This created fibers that were thermally stable at higher than 500°C, reflection over 77% of the 457-nm- wavelength light, whiteness index (WI) higher than 83, and enhanced solvent resistance in DMAc. Generally speaking, compared with the PI UFMs fabricated by conventional ES procedure, the PI-UV UFMs obtained by the newly-developed UVAES procedure showed much superior solvent resistance, comparable thermal stability, slightly decreased optical reflectance and WI values, and reduced fiber diameters. These properties are of great value to future applications in microelectronics and wearable technology.     

Preparation and characterization of triangular hollow porous polyacrylonitrile fiber made by coaxial wet spinning

Hollow porous fiber with both hollow and mesoporous structural characteristics can play an important role in storage, adsorption, and other fields. Triangular hollow porous fiber was prepared by coaxial wet spinning in this paper. Polyacrylonitrile (PAN) and N-N dimethylformamide (DMF) were blended to get cortical solution. Polyvinylpyrrolidone (PVP) and DMF were blended to get core solution. Subsequently, coaxial triangular spinneret was adopted to inject solution into coagulation bath for double diffusion and obtain primary fiber. Then PAN-based triangular fiber with high porosity was prepared after washing and drying. Scanning electron microscopy, nitrogen physical adsorption instrument, thermogravimetric analyzer, and other instruments were used to test and characterize. The results show that the cross-section of the fiber is triangular and has a sense of luster. The hollow degree of the fiber is as high as 84.17%, and the sheath has three-level structure with multi-scale pore diameters, including micropores (200 μm), submicron pores (200 nm), and nanopores (20 nm). Through the range analysis of orthogonal experiment, it is found that the concentration of cortical solution is the main factor affecting the fiber tensile strength. When the concentration of cortical solution is 17%, the concentration of core solution is 10%, the flow rate ratio of cortical solution to core solution is 10:1, and the concentration of coagulation bath is 10%, the fiber tensile strength reaches 1.43 N/mm². The thermal insulation performance of fiber is better than that of silk, cotton and polyester. The results in this paper will provide an experimental foundation for the design and application of hollow porous profiled fibers.     

Recent development of centrifugal electrospinning

As a high‐output nanoscale fiber production method, centrifugal electrospinning (CES) has attracted increasing attention, and this has fostered its quick development. In this article, we review this technique and summarize its mechanism, characteristics, classification, and process equipment. Furthermore, we classify the effects of several CES process parameters on the fiber properties into three different categories. The mechanisms of these effects on the fiber characteristics are analyzed. Finally, the CES issues are summarized, and some strategic solutions and prospects are proposed. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44578.     

Modeling of melt electrospinning for semi-crystalline polymers

A comprehensive model for the stable jet region in electrospinning of crystallizing polymer melts has been presented. First, the conventional flow-induced crystallization (FIC) model by Ziabicki was coupled with the non-isothermal melt electrospinning model. The modeled initial jet profiles were compared to digitized experimental images of the stable Nylon-6 melt jet near the spinneret. The final jet diameters were also compared to the average thickness of collected fibers. The results were in good agreement with the flow visualization experiments for various melt temperatures and flow rates. The modeled crystallinity predictions were also in agreement with experimental data from collected fiber mats. Then, a new FIC model that can provide microstructure information, such as crystallite number density and average size, has been proposed and validated under isothermal and non-isothermal conditions in the bulk as well as in the confined geometry of the polymer melt jet in electrospinning. Nylon-6,6 was used as the model polymer in this crystallization study, and the results are in good agreement with the widely-used Ziabicki FIC model.     

电纺法制备TPU微/纳米纤维的研究进展

本文介绍了电纺热塑性聚氨酯(TPU)制备中所涉及熔融电纺法和溶液电纺法的研究现状,并综述了电纺TPU在医用支架材料、伤口敷料、锂电池电解质、形状记忆材料、吸声材料、压阻敏感性材料方面的应用研究进展。     

Reversibly thermochromic and high strength core-shell nanofibers fabricated by melt coaxial electrospinning

Recent years, phase change materials (PCMs) with potential to store and transform energy have attracted broad attention, especially in the field of thermal energy storage. However, the instability and leak proneness of PCMs limit their universal application. In this paper, core-shell fibers with 1-tetradecanol (TD) as core and poly(vinylidene fluoride) (PVDF) as shell were prepared via melt coaxial electrospinning method, and for improvement, the dye composed of crystal violet lactone (CVL) and bisphenol A (BPA) was added to the core to endow the fiber the function of reversible thermochromism. During the preparation process, it was found that the addition of NaCl could regulate the fiber morphology and strength its mechanical property. By adjusting the concentration of shell solution and the flow rate of core solution, the high-strength reversible thermochromic fibers were produced when polymer concentration was 24 wt% with a core feed rate of 0.4 ml/h. The latent heat of these fibers is up to 88.71 J/g. Besides, its color can change from blue to white when heated, and the transition temperature is around 38°C. And 100 thermal cycle tests of the fiber showed its strong thermal stability and thermochromic property.     

熔体静电纺丝纤维下落过程的DPD探索模拟

静电纺丝是目前唯一能够直接、连续制备聚合物纳米纤维的方法,为了深入了解熔体静电纺丝纤维下落过程中的变化情况,探索用耗散粒子动力学介观模拟方法创建了静电纺丝模拟体系,模拟出聚合物黏度对不同阶段纤维下落速度的影响,发现纤维下落速度增加到一个最大值时,又逐渐变小;还模拟了聚合物不同链长时纺丝纤维的下落形貌,发现随着链长增加,纤维下落速度逐渐减慢;最后研究了弹簧系数对下落过程中聚合物均方末端距的影响,均方末端距增加到一个最大值时,又逐渐变小。从介观模拟的角度对熔体静电纺丝纤维下落过程进行了模拟探索,对这一物理现象中的科学问题得到了更深层次的理解。     

Thermochromic core–shell nanofibers fabricated by melt coaxial electrospinning

Microcapsule/nanocapsule and encapsulation techniques have great potential for devices of functional materials. Also, electrospinning has attracted great attention for the fabrication of microstructures and nanostructures. The fluidity after melting limits the application of phase‐transformation thermochromic materials. In this study, with the melt coaxial electrospinning technique, a phase‐transformation thermochromic material was encapsulated in poly(methyl methacrylate) nanofibers. A device of this phase‐transformation thermochromic material was realized. With a poly(methyl methacrylate) shell with good optical transmission and a thermoresponsive core made of crystal violet lactone, bisphenol A, and 1‐tetradecanol core, the fibers had good thermal energy management, fluorescent thermochromism, and reversibility. The fabrication of thermochromic core–shell nanofibers has further potential in the preparation of temperature sensors with good fluorescence signals and body‐temperature calefactive materials with intelligent thermal energy absorption, retention, and release. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Emulsion‐electrospinning n‐octadecane/silk composite fiber as environmental‐friendly form‐stable phase change materials

The ultrafine n‐octadecane/silk composite fibers as form‐stable phase change materials were successfully developed by the emulsion‐electrospinning method. The effect of n‐octadecane content in the emulsion on the morphology and thermal energy storage capacity of the composite fibers were scientifically investigated. Scanning electron microscopy images show that the composite fibers display cylindrical shape with smooth surface and uniform diameter. Differential scanning calorimetry results demonstrate that the composite fibers exhibit reversible phase transition behavior, high thermal energy storage capacity, and good thermal reliability. Meanwhile, the composite fibers exhibit the capability to regulate their interior temperature as the ambient temperature alters according to the thermo‐infrared images. In addition, the composite fibers are friendly to the environment due to the biodegradability of silk. Therefore, the n‐octadecane /silk composite fibers have the great potential application of serving as form‐stable phase change materials for thermal energy storage and thermal regulation. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45538.     

High-efficiency preparation of polypropylene nanofiber by melt differential centrifugal electrospinning

Melt differential centrifugal electrospinning (MDCE) method is proposed by integrating the advantages of centrifugal spinning and melt differential electrospinning, including high efficiency, solvent-free, multiple jets formation from nozzle-less spinning system, and small diameter. A mathematical model of jet diameter in MDCE is established. An orthogonal experiment is carried out to explore the effects of main processing parameters on the average diameter and the diameter standard deviation of the prepared fibers. Ultimately, polypropylene (PP) nanofibers with an average diameter of 790 nm are successfully prepared in a higher flow rate of 124.26 g h⁻¹ than that of other methods. The X-ray diffraction and differential scanning calorimeter indicate that the introduction of high-voltage electrostatic field in centrifugal spinning contribute to the crystal orientation of the PP molecular chain. Therefore, tensile mechanical strength is enhanced as the increase of the loading voltage. MDCE may provide an efficient and eco-friendly method for nanofiber manufacturing in the future. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48299.     

Continuous aligned poly(meta‐phenylene isophthalamide) fibers via stable jet electrospinning

Continuous aligned poly(meta‐phenylene isophthalamide) (PMIA) fibers are first fabricated by Stable Jet Electrospinning (SJES) with a collection distance of 15 cm. The unfolded length of every single fiber is calculated to be several hundred to several thousand meters. Morphology analysis by field emission scanning electron microscopy (FE‐SEM) shows that these fibers are well arranged and uniformly distributed and their average fiber diameters decrease gradually with increasing collection speed. The effects of ambient temperature and humidity on the duration of stable jet are also discussed. Moderate temperatures and humidity are preferred for fabricating PMIA fibers with ultra‐long size. Besides, the changes of the thermal and crystalline properties of PMIA fibers are also investigated. The significant decline in crystallinity should be responsible for its decreased thermal property. Further improvements to its thermal and crystalline performance must be given consideration in future applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43690.     

Syndiotactic polypropylene nanofibers obtained from solution electrospinning process at ambient temperature

Fabrication of semicrystalline syndiotactic polypropylene (sPP) nanofibers by solution electrospinning was studied. It was found that sPP nanofibers with an average diameter of 230 nm were successfully fabricated via solution electrospinning with methylcyclohexane as solvent at room temperature (25°C). The obtained diameter was significantly thinner than the minimum diameter of 350 nm of PP fibers that were reported previously. It was also found that increasing viscosity of the sPP solution, which was customarily a useful way of fabricating noncrystalline thin fibers, was found ineffectual in producing thinner semicrystalline sPP fibers in our experiments. In fact, a careful selection of solvent by considering the evaporation rate and the specific viscosity could effectively lead to the fabrication of thinner sPP fibers by imposing proper elongation and preventing the sPP solution from gelation. The results could be applied to other semicrystalline polyolefins with similar gelation characteristics analogous to sPP to produce thinner nanofibers. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43238.     

Fabrication of superhydrophobic and self cleaning PVA-silica fiber coating on 304L SS surfaces by electrospinning

In this work superhydrophobic coating with self cleaning property is fabricated on 304L SS samples directly using a simple one step electrospinning process followed by silane treatment by using polyvinyl alcohol (PVA) and tetraethyl orthosilicate solution. A maximum water contact angle of 169.2° ± 2.1° is obtained at an electrospinning potential of 15 kV for 2 h, with a distance of 18 cm between the collector and needle. The hierarchical nanostructures thus formed on 304L SS composed of poly(vinyl alcohol)-silica microbeads and nanofibers. The surface morphologies are optimized by varying the electrospinning voltage, time, distance between needle and the collector and aging duration of the precursors. Attenuated total reflectance-infrared spectroscopy studies at different stages of preparation confirmed the presence of PVA/SiO₂ composite nanofibers deposited on the 304L SS surface. The reaction of SiO₂ nanofibers with hexamethyl disilazane resulted in the formation of Si O Si bonds that provided water repellent property. The developed SHP surface coating on 304L SS sample showed dynamic bouncing of water droplets and excellent self cleaning performance. The sample retained the SHP behavior in chloride solutions with different ionic strengths and pH.     

Investigation of nanoyarn preparation by modified electrospinning setup

Higher ordered structures of nanofibers, including nanofiber‐based yarns and cables, have a variety of potential applications, including wearable health monitoring systems, artificial tendons, and medical sutures. In this study, twisted assemblies of polyacrylonitrile (PAN), polyvinylidene fluoride trifluoroethylene (PVDF‐TrFe), and polycaprolactone (PCL) nanofibers were fabricated via a modified electrospinning setup, consisting of a rotating cone‐shaped copper collector, two syringe pumps, and two high voltage power supplies. The fiber diameters and twist angles varied as a function of the rotary speed of the collector. Mechanical testing of the yarns revealed that PVDF‐TrFe and PCL yarns have a higher strain‐to‐failure than PAN yarns, reaching 307% for PCL nanoyarns. For the first time, the porosity of nanofiber yarns was studied as a function of twist angle, showing that PAN nanoyarns are more porous than PCL yarns. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44813.     

Thermo‐rheological and interfacial properties of polylactic acid/polyethylene glycol blends toward the melt electrospinning ability

The electrospinning ability of PLA/PEG system at the melt state was investigated through the viscoelastic parameters obtained from dynamic shear and extensional rheometers. PLA and PEG were melt‐blended at various composition ratios. Effect of PEG concentration on the PLA thermal behavior was studied by the differential scanning calorimetry (DSC). According to DSC and wide‐angle X‐ray diffraction, the PLA crystallinity increased and the crystalline structure became more completed (α‐crystal form) in the presence of PEG. Viscoelastic parameters such as zero‐shear viscosity and relaxation time as an indication of elasticity were obtained. The results revealed enhanced polymer chain mobility and disentanglement ought to plasticizing effect of PEG. The critical content of PEG about 20–30 wt % at which the solid–liquid phase separation occurred was in good agreement with the viscoelastic properties. Hence, more than 20% PEG the elasticity diminished and the melt strength became zero. The interfacial tension of the PLA and PEG estimated through the rheological and morphological parameters evidenced the good miscibility of PLA/PEG system at the melt electrospinnig temperature. While the high viscose samples (η₀ > 1800 Pa/s) PLA and PLA/PEG (95/5) were not spinnable at the spinning temperature of 180 °C, blends containing 10–30% PEG were easily spun. The finest and continuous fiber mats were obtained by electrospinning of PLA/PEG (80/20) blend (d_f = 4.8 ± 0.8 μm). More than the critical concentration of PEG (Φ > 30%), lacking the elasticity suppressed the melt electro‐spinnability of PLA/PEG. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44120.     

Poly(vinylidene fluoride)/silica nanocomposite membranes by electrospinning

Poly(vinylidene fluoride) (PVDF)/silica nanocomposite membranes containing up to 30% silica were prepared by electrospinning using colloidal silica as the source of silica and dimethyl formamide as the solvent. The fiber morphology was observed by field emission scanning electron microscopy. The average fiber diameter is about 0.3 μm for PVDF/silica composite fibers having 10–30% silica. Silica nanoparticles were observed on all fiber surfaces with fairly good dispersion and distribution. Fourier transform infrared spectroscopy and differential scanning calorimeter were used to investigate the crystallization behavior of PVDF and showed that a mixture of α‐, β‐, and γ‐phase crystals was obtained with little content of α phase and all the PVDF/silica composite membranes have similar degree of crystallinity. Static water contact angle measurements were performed to investigate the surface wettability of the membranes. The mechanical properties were evaluated by tensile tests, showing strong reinforcement effect. The tensile modulus and tensile strength increase significantly when silica is present. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

熔体微分静电纺PBAT纤维膜的制备工艺研究

探究了聚己二酸对苯二甲酸丁二醇酯（PBAT）熔体静电纺性能,并研究了熔体微分静电纺工艺参数与PBAT纤维性能之间的关系。结果表明,随着纺丝温度的升高,纤维直径减小,纤维直径分布呈先减小后增大的趋势;随着纺丝电压的升高,纤维直径减小且分布均匀,纤维膜力学性能逐渐提高;当纺丝距离为9 cm,纺丝温度为260 ℃,纺丝电压为45 kV时,制备的纤维细度及均匀度最佳,其直径为4.31 μm,直径分布标准差为0.76,纤维膜拉伸强度为9.9 MPa、断裂伸长率为111.2 %。