Morphology, structure and properties of conductive PS/CNT nanocomposite electrospun mat

The morphologies and properties of Polystyrene (PS)/Carbon Nanotube (CNT) conductive electrospun mat were studied in this paper. Nanocomposite fibers were obtained through electrospinning of PS/Di-Methyl Formamide (DMF) solution containing different concentrations and types of CNTs. The dispersion condition of CNTs was correlated to morphologies and properties of nanocomposite fibers. A copolymer as an interfacial agent (SBS, Styrene-butadiene-styrene type) was used to modify the dispersion of CNTs in PS solution before electrospinning. The results showed that the presence of the copolymer significantly enhances CNT dispersion. The fiber diameters varied between 200 nm and 800 nm depending on CNT type, polymer concentration and copolymer. The final morphological study of the fibers showed that CNT addition caused a decrease in beads formation along fiber axis before percolation threshold. However, addition of CNTs above percolation increased the beads formation, depending on the dispersion condition. The presence of SBS modified the dispersion, reduced the fiber diameter and the number of bead structures. Electrical conductivity measurements on nanocomposite mats of 15-300 μm in thickness showed an electrical percolation threshold around 4 wt% MWCNT; while the samples containing SBS showed higher values of conductivities below percolation compared to the samples with no compatibilizer. Enhancement in mechanical properties was observed by the addition of CNTs at concentrations below percolation.     

不同溶剂对静电纺聚乳酸纳米纤维形态结构的影响

以聚乳酸（PLA）为原料,分别用三种不同的溶剂制得三种纺丝液并采用静电纺丝法,制备了聚乳酸纳米纤维。探讨了溶剂、电压、溶液质量分数对纤维形貌和直径的影响。结果表明,溶剂是决定PLA超细纤维形成的关键因素,三氯甲烷（CHC l3）与二甲基甲酰胺（DMF）混合溶剂（体积比为9∶1）是PLA静电纺丝较为理想的溶剂。在PLA质量分数为6%、极距15 cm、电压25 kV,流量2.5 mL/h的工艺条件下,可制备直径为1 200 nm左右的PLA纤维。     

Electrospun PLA/PCL fibers with tubular nanoclay: Morphological and structural analysis

Biodegradable polymers are good candidates for a wide range of applications in tissue engineering and drug delivery because of their biocompatibility, their degradation, mechanical properties, and offer a sustained release of encapsulated drugs. The electrospun polymer nanofibrous materials can be used as carriers for hydrophobic and hydrophilic drugs. This research work focused on poly(lactic acid) (PLA) and blends of PLA with poly (ε‐caprolactone) (PCL) that are reinforced with different concentrations of halloysite nanotubes (HNTs) and various cosolvents for electrospinning including chloroform : acetone, chloroform : methanol, and dichloromethane (DCM) : N,N, dimethylformamide (DFM). The fibers produced from the DCM : DMF system without HNTs were more uniform resulting in smaller fiber diameters as compared to the chloroform: methanol system due to the increased solution conductivity. The addition of HNT nanoparticles produced electrospun fibers with large diameters because the viscosity of the solution increased. Cosolvent was important in determining fiber diameters because it strongly influenced the solution viscosity and conductivity. HNTs had relatively small impact on the growth of a crystalline morphology in PCL–HNT composites. The solvent mixture of chloroform : methanol was better for PLA‐based systems since PLA was found to have slightly higher crystallinity and larger enthalpy value indicating the improved structural orderness in the PLA polymer matrix. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Poly(lactic acid) fibers obtained by solution blow spinning: Effect of a greener solvent on the fiber diameter

Poly(lactic acid) (PLA) fibers has been obtained by solution blow spinning (SBS) using different solvents, however most of them are toxic and can be dangerous to human health or cause harm to the environment. Therefore, this work aimed to evaluate the use of dimethyl carbonate (DMC), a greener solvent, on the production of PLA fibers by SBS using surface response analysis to evaluate and compare the influence of three solvents (chloroform, DMC, and 1,1,1,3,3,3‐hexafluoro‐2‐propanol, HFP) in the average fiber diameter. Scanning electron microscopy (SEM) was used to analyze the fiber morphology and different ranges of fiber diameter was observed when varying the solvents (chloroform: 260–970 nm; DMC: 240–650 nm; and HFP: 220–470 nm). Regression analysis showed the polymer concentration was significant for all solvents and the air pressure was significant when using chloroform and HFP. Regardless of the air pressure, increasing the PLA concentration increased the average fiber diameters for all solvents. Chloroform and HFP indicated a tendency of reduction on the average fiber diameter when the air pressure was decreased, however this behavior was not observed for DMC. It was also observed that the standard deviation indicated to be more affected by the polymer concentration than by the air pressure. The results also indicated that lower surface tension and viscosity can reduce fiber thickness. All solvents showed to be feasible to produce PLA fibers by SBS and DMC can be used to produce PLA fibers with an affordable price using a greener process. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43379.     

Electrospinning of uniform polystyrene fibers: The effect of solvent conductivity

By means of the electrospinning technique, micron- and nanofibers can be obtained from polymer solutions under a very high electrical field. A special challenge is to produce bead-free uniform fibers since any minor changes in the electrospinning parameters such as slight variations in the polymer solutions and/or electrospinning experimental parameters may result in significant variations in the final nanofiber morphology. Furthermore, it is often not trivial at all to obtain reproducible uniform electrospun nanofibers for the optimized electrospinning conditions. Here we report that the conductivity of the solvent is the key factor for the reproducible electrospinning of uniform polystyrene (PS) fibers from dimethylformamide (DMF) solutions. It is shown that even slight changes in the conductivity of the DMF solutions can greatly affect the morphology of the resulting electrospun PS fibers. Here, we have carried out a thorough and systematic study on the effect of solution conductivity on the electrospinning of bead-free polystyrene (PS) fibers when dimethylformamide (DMF) was used as the solvent. Interestingly, we found out that different grades of solvent as-received (DMF) from various suppliers have slightly different solution conductivities. Consequently, the polymer solutions prepared with the same PS concentration have different conductivities, which are shown to have significant changes on the morphology of the PS fibers resulting in beaded or bead-free uniform fibers when electrospun under the identical electrospinning conditions. Such as, bead-free PS fibers were obtained from PS solutions in the range of 20% (w/v) through 30% (w/v) depending on the DMF grade used. In brief, it was observed that solutions with a higher conductivity yielded bead-free fibers from lower polymer concentrations, which confirms that the solution conductivity plays a very significant role in producing bead-free uniform PS fibers.     

Preparation of fibers with nanoscaled morphologies: Electrospinning of polymer blends

The aim was to prepare fibers with diameters below the micrometer range characterized by specific bulk morphologies and surface topologies. Such materials are of interest for various applications including reinforcement, sensors or filtration as well as the formation of functional tubes by the use of fiber templates. We were able to manufacture highly structured submicrometer fibers by electrospinning from ternary solutions using polylactide (PLA) and polyvinylpyrrolidone (PVP) as polymer model components. Co‐continuous phase morphologies resulted from phase separation processes taking place during fiber formation. In a subsequent step, specific surface topologies or fine pores were generated by selective removal of one of the components.     

Electrospinning polycaprolactone dissolved in glacial acetic acid: Fiber production,nonwoven characterization,and In Vitro evaluation

The electrospinning of polycaprolactone (PCL) dissolved in glacial acetic acid and the characterization of the resultant nonwoven fiber mats is reported in this work. For comparison purposes, PCL fiber mats were also obtained by electrospinning the polymer dissolved in chloroform. Given the processing parameters chosen, results show that 14 and 17 wt % PCL solutions are not viscous enough and yield beaded fibers, 20 and 23 wt % solutions give rise to high quality fibers and 26 wt % solutions yield mostly irregular and fused fibers. The nonwoven mats are highly porous, retain the high tensile strain of PCL, and the fibers are semicrystalline. Cells adhere and proliferate equally well on all mats, irrespective of the solvent used in their production. In conclusion, mats obtained by electrospinning PCL dissolved in acetic acid are also a good option to consider when producing scaffolds for tissue engineering. Moreover, acetic acid is miscible with polar solvents, which may allow easier blending of PCL with hydrophilic polymers and therefore achieve the production of electrospun nanofibers with improved properties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41068.     

Lignin-based carbon fibers: Carbon nanotube decoration and superior thermal stability

Lignin-based carbon fibers (CFs) decorated with carbon nanotubes (CNTs) were synthesized and their structure, thermal stability and wettability were systematically studied. The carbon fiber precursors were produced by electrospinning lignin/polyacrylonitrile solutions. CFs were obtained by pyrolyzing the precursors and CNTs were subsequently grown on the CFs to eventually achieve a CF–CNT hybrid structure. The processes of pyrolysis and CNT growth were conducted in a tube furnace using different conditions and the properties of the resultant products were studied and compared. The CF–CNT hybrid structure produced at 850 °C using a palladium catalyst showed the highest thermal stability, i.e., 98.3% residual weight at 950 °C. A mechanism for such superior thermal stability was postulated based on the results from X-ray diffraction, Raman spectroscopy, scanning and transmission electron microscopy, and electron energy loss spectroscopy analyses. The dense CNT decoration was found to increase the hydrophobicity of the CFs.     

Multifunctional porous membranes with antibacterial properties

Abstract

The paper describes the results of research on obtaining porous membranes produced from polylactide fibers (PLA) by electrospinning, additionally modified with gentamicin antibiotic (GM) at the stage of preparing a spinning solution to provide bactericidal properties. Both solid (1^oPNF) and porous (2^oPNF 3^oPNF) polymer fibers were obtained, and the control of fiber porosity was achieved using various solvent systems: dichloromethane (DCM), dimethylformamide (DMF), chloroform (CHL) and dimethyl sulfoxide (DMSO). Three types of fibers differing in morphology (fiber diameter) and mean pore size were obtained. Physicochemical properties of porous and solid drug-containing fibers were examined, determining their surface free energy (SFE) and wetting angle (CA), and the effectiveness of modification with the drug was confirmed in spectroscopic studies (FTIR-ATR). Antibacterial activity of the prepared drug-modified nonwovens was confirmed by the disk diffusion method against Gram-negative Escherichia coli bacteria strain. The results of tests have shown that depending on the type of solvents used at the electrospinning stage, porous fibers can be obtained from polylactide. The addition of gentamicin affected antibacterial properties, and the pore size determined the rate of drug release monitored by the ion coupled plasma method (ICP).     

Morphology transition in electrospinning polymers by a dual‐capillary system

An experimental investigation of the fiber morphology change of fibers prepared by a dual‐capillary electrospinning system, operated in the cone‐jet mode, was carried out for poly(vinyl acetate) polymers of three molecular weights. The substrate morphology of the electrospun poly(vinyl acetate) could be changed significantly when the polymer's molecular weight, concentration, solvent, and outer liquid flow rate were varied. The onset of bead‐to‐fiber transition was determined by the critical chain overlap concentration. For solutions with a high concentration, the fiber diameter and surface were significantly affected by the physical properties of the solvents. To produce fibers of small diameter, electrospinning with a higher conductivity solution was desirable. On the other hand, a high‐conductivity solution needed to be avoided to keep the fiber uniform in diameter and smooth on the surface. The comparison of electrospun fibers produced by both single‐capillary and dual‐capillary systems was also addressed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

静电纺聚乳酸纳米纤维的制备及其孔结构调控

为了调控聚乳酸(PLA)纳米纤维的孔结构,采用静电纺丝技术,以PLA母粒为原料,三氯甲烷(CF)和N,N-二甲基甲酰胺(DMF)按一定比例混合的溶液为溶剂,制备了平均直径在1.37μm的PLA纳米纤维,并对其结构进行表征。结果表明,PLA纳米纤维的平均直径随着纺丝液中CF含量、聚合物浓度、环境湿度的增加而增大;随纺丝电压和灌注速度的增大而呈减小的趋势。同时,环境湿度对纤维表面孔结构有显著影响。随着湿度的增加,纤维表面孔的分布密度增加,且形状由圆形转变为椭圆形。此外,与表面光滑的PLA纳米纤维(2.4 m²/g)相比,所制备的PLA多孔纤维的比表面积提升了10倍(24.0 m²/g)。     

Multiwalled carbon nanotube/polysulfone composites: Using the Hildebrand solubility parameter to predict dispersion

Polysulfone composites were prepared by solution casting, using various types of treated carbon nanotubes (CNTs) at loadings of up to 5 wt%. The CNT types tested were: as‐received, acid treated, OCA surfactant, OCA functionalized and Poly(methyl methacrylate) functionalized nanotubes prepared using both as‐received and acid treated CNT. The treatment types investigated were selected based upon their solubility parameters and on the results of previous studies. The treated CNTs, CNT/solvent dispersions and the final composite samples were characterised using Fourier Transform Infrared Spectroscopy (FTIR), thermal analysis, Transmission Electron Microscopy (TEM), Ultraviolet‐Visible (UV‐vis) spectroscopy, optical microscopy, electrical conductivity and tensile testing. It was observed that the all the treatments studied improved the stability of CNT in the solvent. Of the CNT types studied, composites containing OCA functionalised CNT displayed the lowest percolation threshold (3 wt%) and highest mechanical performance. While the use of Hildebrand solubility parameters is useful in indentifying promising CNT treatments, their use can not fully predict CNT dispersion behaviour and composite performance. It is also critical to consider the influence of any treatments on CNT length and residual solvent levels. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Increasing the electrical conductivity of carbon nanotube/polymer composites by using weak nanotube-polymer interactions

A weak interaction between carbon nanotubes (CNTs) and polymers was found to reduce polymer-wrapping on CNT surface, decrease the contact resistance between CNTs, and increase the electrical conductivity of their composites. Thermodynamic properties such as surface energy of components, filler-polymer interactions, and wettability of carbon/polymer systems were analyzed. It was found that the graphitized CNTs filled polyoxymethylene (POM) system exhibits the weakest CNT-polymer interaction among all the investigated systems and a poor wettability. Consequently, the graphitized CNT/POM composites possess a high electrical conductivity and a low percolation threshold of 0.5 wt.% CNT loading, which is associated with the weak CNT-polymer interaction, low contact resistance between CNTs, good connectivity of CNT networks, and high crystallinity of POM in the composites. The results obtained imply that high-performance composites with optimal CNT-network structures can be designed and fabricated by fully considering the surface properties of components and CNT-polymer interactions.     

The effect of carbon nanotube aspect ratio and loading on the elastic modulus of electrospun poly(vinyl alcohol)-carbon nanotube hybrid fibers

The reinforcement effect of carbon nanotubes (CNTs) has been examined as a function of their loading and aspect ratio in poly(vinyl alcohol) (PVA) based hybird fibers. Lignosulfonic acid sodium salt (LSA) was used to disperse CNTs to produce consistently high CNT loaded PVA-LSA-CNT hybrid fibers using an electrospinning process. The elastic modulus of individual fibers was measured using atomic force microscopy. The presence of CNTs significantly increased the average elastic modulus of PVA-LSA-CNT fibers compared to PVA-LSA fibers. The elastic modulus, however, exhibited no fiber diameter dependency. Transmission electron microscopy (TEM) was used to determine the loading and the aspect ratio of CNTs in each hybrid fiber. The CNT loading in PVA-LSA-CNT fibers varied widely due to non-uniform CNT dispersion and displayed no relationship with the elastic modulus. Our results also demonstrated that the average value of CNT aspect ratio significantly affected the elastic modulus of the hybrid fibers. Such a result was in agreement with theoretical prediction in which the stress transfer efficiency in a composite matrix is strongly dependent on the CNT aspect ratio.     

The effects of processing parameters on the morphology of PLA/PEG melt electrospun fibers

Electrospinning of a polymer melt is an ideal technique to produce highly porous nanofibrous or microfibrous scaffolds appropriate for biomedical applications. In recent decades, melt electrospinning has been known as an eco‐friendly procedure as it eliminates the cytotoxic effects of the solvents used in solution electrospinning. In this work, the effects of spinning conditions such as temperature, applied voltage, nozzle to collector distance and collector type as well as polyethylene glycol (PEG) concentration on the diameter of melt electrospun polylactic acid (PLA)/PEG fibers were studied. The thermal stability of PLA/PEG blends was monitored through TGA and rheometry. Morphological investigations were carried out via optical and scanning electron microscopy. Based on the results, blends were almost stable over the temperature range of melt electrospinning (170 ? 230 °C) and a short spinning time of 5 min. To obtain non‐woven meshes with uniform fiber morphologies, experimental parameters were optimized using ANOVA. While increasing the temperature, applied voltage and PEG content resulted in thinner fibers, PEG concentration was the most influential factor on the fiber diameter. In addition, a nozzle to collector distance of 10 cm was found to be the most suitable for preparing uniform non‐woven PLA/PEG meshes. At higher PEG concentrations, alterations in the collector distance did not affect the uniformity of fibers, although at lower distances vigorous bending instabilities due to polarity augmentation and viscosity reduction resulted in curly fibrous meshes. Finally, the finest and submicron scale fibers were obtained through melt electrospinning of PLA/PEG (70/30) blend collected on a metallic frame. © 2017 Society of Chemical Industry     

原子层沉积氧化锌功能化碳纳米管织物及其光催化特性

以二乙基锌和去离子水为前驱体,利用原子层沉积(ALD)在自支撑碳纳米管(CNT)织物上沉积氧化锌(ZnO)对其进行了功能化;考察了ALD沉积过程中功能化织物的微观形貌、晶型结构、表面性质及光催化性能.实验结果表明,ZnO最初在CNTs表面生长为纳米颗粒,随ALD循环次数的增加,逐渐形成包覆CNTs的保形生长层,改变AL...     

Study on the preparation of hyperbranched polyethylene fibers and hyperbranched polyethylene composite fibers via electrospinning

This contribution mainly studied the preparation of hyperbranched polyethylene (HBPE) fibers and HBPE/multiwalled carbon nanotube (MWCNT) composite fibers via electrospinning for the first time. Firstly, the effects of solvents, solution concentration, voltage, and rotating speed of collector on the morphology of HBPE fibers were studied. Among the factors, solvent type, concentration, and voltage showed notable influence on the morphology of HBPE fibers. HBPE has an excellent dispersion effect on CNT in organic solvents. Through ultrasonic dispersion, the HBPE solutions with dispersed MWCNT were obtained. Then HBPE/MWCNT composite fibers were obtained with different contents of MWCNT via electrospinning. The effects of voltage and working distance on the morphology of HBPE/MWCNT composite fibers were investigated. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42517.     

Multiscale fiber‐reinforced composites prepared by vacuum‐assisted resin transfer molding

Carbon nanotube (CNT)/aramid fiber epoxy composites were produced using a new manufacturing method proposed in this study. The rheological and morphological experiments of the CNT/PEO nanocomposites indicates that the PEO nanocomposites have a good dispersion state of the CNTs. The flexural mechanical properties of the aramid fiber/CNT epoxy composites were measured. The CNTs dispersed in the epoxy resin between the aramid fibers were observed using field emission scanning electron miscroscope (FESEM). It was found that the flexural properties of the multiscale fiber‐reinforced composites were higher than those of aramid fiber/epoxy composites. POLYM. COMPOS., 28:458–461, 2007. © 2007 Society of Plastics Engineers.     

Charge storage of electrospun fiber mats of poly(phenylene ether)/polystyrene blends

Nonwoven fiber mats composed of poly(phenylene ether) (PPE) and polystyrene (PS) blends were prepared by electrospinning of PPE/PS solutions in a mixture of chloroform and hexafluoroisopropanol. The blends showed higher electrospinnability and led to thinner fibers (200 nm–1.3 μm) than the pure components, because of a proper balance of electrical conductivity and interaction with the electrospinning solvent. The charge retention of the electrospun fibers was evaluated and related to the blend composition and the electret properties of the components. It was found that the nonwoven mats were able to retain up to 60% of the initial surface potential after several days of annealing at temperatures as high as 140°C, which is markedly higher than the charge retention of corona‐charged compact films. The capability of the electrospinning technique, to inject charges into the bulk of the material and to orientate the dipoles of the PPE phase in the field direction at the same time, was related to the good surface potential stability of the PPE/PS electrospun fiber mats. The possibility of creating thin PPE/PS fibers with excellent charge retention capabilities makes these materials ideal candidates for electret filter and sensing applications. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Noncovalent functionalization of carbon nanotubes with maleimide polymers applicable to high-melting polymer-based composites

As novel carbon nanotube (CNT) dispersants are effective not only for obtaining stable CNT-dispersed solutions but also for high-melting polymer/CNT composites, we synthesized maleimide polymers (MIPs) using N-substituted maleimide for imparting physical adsorption on the CNT surfaces and high heat resistance. The MIPs showed strong physical adsorption on various CNT surfaces and good solubility in a wide variety of organic solvents, and acted as excellent CNT dispersants in these substances. The MIPs on the CNT surfaces were very stable at high temperatures (?∼300 °C) required for melt mixing using high-melting polymers. The addition of MIP-adsorbed CNTs (CNT/MIPs) to poly(1,4-phenylenesulfide) (PPS) as a high-melting polymer was, therefore, very effective for dispersing CNTs and improving the physical properties of the resulting PPS/CNT/MIP composites, in comparison with the PPS/CNT composites. Even at a low CNT loading (1 vol%), the storage modulus of the PPS/CNT/MIP composites increased drastically. Furthermore, thermal conductivity of the PPS/CNT/MIP composites also improved, in comparison with the PPS/CNT composites. These results are considered to be due to an increase of interactions between the CNT and PPS matrices, caused by the stable formation of MIPs on the CNT surfaces.