Conductive polypyrrole nanofibers via electrospinning: Electrical and morphological properties

Conductive polypyrrole nanofibers with diameters in the range of about 70-300 nm were obtained using electrospinning processes. The conductive nanofibers had well-defined morphology and physical stability. Two methods were employed. Electrospun nanofibers were prepared from a solution mixture of polypyrrole (PPy), and poly(ethylene oxide) (PEO) acted as a carrier in order to improve PPy processability. Both the electrical conductivity and the average diameter of PPy nanofibers can be controlled with the ratio of PPy/PEO content. In addition, pure (without carrier) polypyrrole nanofibers were also able to be formed by electrospinning organic solvent soluble polypyrrole, [(PPy3)⁺ (DEHS)⁻]_x, prepared using the functional doping agent di(2-ethylhexyl) sulfosuccinate sodium salt (NaDEHS) [Jang KS, Lee H, Moon B. Synth Met 2004;143:289-94. [24]]. Electrospun blends of sulfonic acid (SO₃H)-bearing water soluble polypyrrole, [PPy(SO₃H)-DEHS], with PEO acting as a carrier, are also reported. The factors that facilitate the formation of electrical conduction paths through the electrospun nanofiber segments are discussed.     

Improved graphitization and electrical conductivity of suspended carbon nanofibers derived from carbon nanotube/polyacrylonitrile composites by directed electrospinning

Single suspended carbon nanofibers on carbon micro-structures were fabricated by directed electrospinning and subsequent pyrolysis at 900 °C of carbon nanotube/polyacrylonitrile (CNT/PAN) composite material. The electrical conductivity of the nanofibers was measured at different weight fractions of CNTs. It was found that the conductivity increased almost two orders of magnitude upon adding 0.5 wt.% CNTs. The correlation between the extent of graphitization and electrical properties of the composite nanofiber was examined by various structural characterization techniques, and the presence of graphitic regions in pyrolyzed CNT/PAN nanofibers was observed that were not present in pure PAN-derived carbon. The influence of fabrication technique on the ordering of carbon sheets in electrospun nanofibers was examined and a templating effect by CNTs that leads to enhanced graphitization is suggested.     

Stretching-induced orientation of polyacrylonitrile nanofibers by an electrically rotating viscoelastic jet for improving the mechanical properties

An additional centrifugal field applied to an electrostatic field in a novel electrospinning technique was proposed in this study. An additional centrifugal field can not only remove bending instability of electrically charged liquid jets during the electrospinning process but can also fabricate aligned and molecularly oriented nanofibers. The results indicated that combining a strong stretching force from an additional centrifugal field and an electrostatic field can be used to align polymer chains parallel to the nanofiber axis, producing polyacrylonitrile (PAN) nanofibers with superior molecular orientation and mechanical properties. The optimal stretching force of an electrically rotating viscoelastic jet was obtained from high-speed videography and dimensionless groups (Re, We, and Oh numbers) analysis. The dichroic ratio (D) was 0.78, and the chain orientation factor (f), measured via Polarized FT-IR was 0.21. These measurements indicated an increase in the molecular orientation for the fabricated PAN nanofibers via the optimal stretching force. The elastic modulus of PAN nanofibers with f = 0.21 was 6.29 GPa and 4.55 GPa when measured by atomic force microscopy (AFM) and nanoindenter experiments, respectively. These results demonstrated that superior mechanical properties of PAN nanofibers could be improved by conducting the proposed electrospinning technique. Furthermore, carbon nanofibers produced from the optimal PAN nanofibers through the proposed method could potentially be applied for the reinforcement of composites.     

Electrochemical properties of polypyrrole/sulfonted SEBS composite nanofibers prepared by electrospinning

The electrochemical behavior of electrospun polypyrrole (PPy)/sulfonated-poly(styrene-ethylene-butylenes-styrene) (S-SEBS) composite nanofibers was investigated, compared to PPy/poly(styrene-ethylene-butylenes-styrene) (SEBS) fibers prepared by a casting method. The electrospun PPy/S-SEBS (E-PSS) fibers were about 300 nm in average diameter, while PPy/SEBS composite (C-PS) prepared by a casting method showed the granular macroporous structure. The effect by both electrospinning and sulfonation results in higher electrochemical capacity due to the increase of doping level, high electrical conductivity, low interfacial resistance, and high reversibility by easy intercalation of Li ion. In addition, sulfonated SEBS induces higher elongation force to jet in the processing of electrospinning due to the role of dopant.     

Formation and characterization of core-sheath nanofibers through electrospinning and surface-initiated polymerization

Novel core-sheath nanofibers, composed of polyacrylonitrile (PAN) core and polypyrrole (PPy) sheath with clear boundary between them, were fabricated by electrospinning PAN/FeCl₃·6H₂O bicomponent nanofibers and the subsequent surface-initiated polymerization in a pyrrole-containing solution. By adjusting the concentration of FeCl₃·6H₂O, the surface morphology of PPy sheath changed from isolated agglomerates or clusters to relatively uniform thin-film structure. Thermal properties of PAN-PPy core-sheath nanofibers were also characterized. Results indicated that the PPy sheath played a role of inhibitor and retarded the complex chemical reactions of PAN during the carbonization process.     

Carbon nanotube/epoxy composites fabricated by resin transfer molding

Carbon nanotube (CNT)/epoxy composites with controllable alignment of CNTs were fabricated by a resin transfer molding process. CNTs with loading up to 16.5 wt.% were homogenously dispersed and highly aligned in the epoxy matrix. Both mechanical and electrical properties of the CNT/epoxy composites were dramatically improved with the addition of the CNTs. The Young’s modulus and tensile strength of the composites reach 20.4 GPa and 231.5 MPa, corresponding to 716% and 160% improvement compared to pure epoxy. The electrical conductivity of the composites along the direction of the CNT alignment reaches over 1 × 10⁴ S/m.     

Post-spinning modification of electrospun nanofiber nanocomposite from Bombyx mori silk and carbon nanotubes

Electrospinning is an effective procedure for fabricating submicron to nanoscale fibers from synthetic polymer as well as natural proteins. We successfully electrospun regenerated silk protein from cocoons of Bombyx mori to produce random as well as aligned fibers with diameter less than 100 nm. The fibers were characterized using field emission environmental scanning electron microscope (ESEM), Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy and wide angle X-ray diffraction (WAXD) studies. Post-spinning treatment with methanol and/or stretching and co-electrospinning with single walled carbon nanotubes (CNT) were carried out to alter the strength, toughness, crystallinity and conductivity of silk nanofibers. Addition of just 1% CNT along with post-spinning treatments resulted in 7-fold increase in the strength and 35-fold increase in the modulus of silk nanofibers. Raman spectroscopy confirmed that CNTs were incorporated in the silk fibers. FT-IR spectroscopy and WAXD studies proved that silk-CNT nanofibers had more crystallinity compared to silk nanofibers without CNT. Four-probe method demonstrated that silk-CNT nanofibers had 4 times higher electrical conductivity compared to silk nanofibers without CNT.     

Fabrication and characterization of magnetic cobalt ferrite/polyacrylonitrile and cobalt ferrite/carbon nanofibers by electrospinning

An electrospinning process was used to fabricate cobalt ferrite (CoFe₂O₄)-embedded polyacrylonitrile (PAN) nanofibers. Oleic acid-modified CoFe₂O₄ nanoparticles were dispersed in the PAN before spinning. The surface morphologies and structures of the nanofibers were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). SEM and TEM observation showed that the average diameter of the CoFe₂O₄/PAN nanofibers was 110 nm, and the magnetic CoFe₂O₄ nanoparticles were embedded in the PAN nanofibers. X-ray photoelectron spectroscopy was used to characterize the CoFe₂O₄/PAN and CoFe₂O₄/carbon nanofibers. Fiber magnetic properties were measured by vibrating sample magnetometry, showing that the saturation magnetization of the CoFe₂O₄/PAN nanofibers was 45 emu/g and that the fibers demonstrated superparamagnetic behavior.     

Preparation and characterization of coaxial halloysite/polypyrrole tubular nanocomposites for electrochemical energy storage

Halloysite nanotubes/polypyrrole (HNTs/PPy) nanocomposites with coaxial tubular morphology for use as electrode materials for supercapacitors were synthesized by the in situ chemical oxidative polymerization method based on self-assembled monolayer amine-functionalized HNTs. The HNTs/PPy coaxial tubular nanocomposites were characterized with transmission electron microscope (TEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), electrical conductivity measurement at different temperatures, cyclic voltammetry (CV), and galvanostatic charge-discharge measurements. The coaxial tubular nanocomposites showed their greatest conductivity at room temperature and a weak temperature dependence of the conductivity from 298 K to 423 K. A maximum discharge capacity of 522 F/g after correcting for the weight percent of the PPy phase at a current density of 5 mA cm⁻² in a 0.5 M Na₂SO₄ electrolyte could be achieved in a half-cell setup configuration for the HNTs/PPy composites electrode, suggesting its potential application in electrode materials for electrochemical capacitors.     

Novel polyimide-based electrospun carbon nanofibers prepared using ion-beam irradiation

This paper describes a novel study focused on preparing carbon nanofibers, with a narrow fiber diameter distribution, from a fluorinated polyimide using both electrospinning and ion-beam irradiation. We specifically focused on the effects of ion species and ion fluences on the electrical conductivity of the nanofiber. The nanofibers were successfully prepared in the diameter range from 340 nm to 1500 nm by varying the concentration of polyimide solution using electrospinning. The Raman spectrum of the ion-irradiated nanofiber included the two well-known D (1360 cm^?1) and G (1580 cm^?1) peaks, indicating that the nanofiber surface changed to a carbon-enriched material. The carbon nanofibers underwent a more ordered graphitic carbon structure with an increase in the ion fluence and the electrical conductivity of the nanofiber irradiated at 1 × 10¹⁶ ions/cm² of Ar⁺ was 0.18 S/cm. In addition, the electrical conductivities of the ion-irradiated nanofibers increased in the order, He⁺ < Ne⁺ < Ar⁺, which indicated that the amount of nuclear energy in the ion species had the most influence on the electrical conductivity. However, the higher electrical conductivity of the carbon nanofibers is required to realize their industrial applications. This paper is the first to address the properties of the electrical conductivity of the carbon nanfibers prepared by electrospinning and ion irradiation as a new approach.     

Molecular orientation and mechanical property size effects in electrospun polyacrylonitrile nanofibers

Electrospinning of polymeric solutions entails high jet velocities which could orient the polymer molecules along the jet direction. Polarized Fourier Transform IR spectroscopy (FTIR), Wide angle X-ray diffraction (WAXD) and Microelectromechanical System (MEMS)-based single nanofiber mechanical property experiments were employed to investigate the molecular orientation and crystallinity in electrospun polyacrylonitrile (PAN) nanofibers produced under different electrospinning conditions with diameters mainly varying between 100 and 300 nm. FTIR measurements with nanofibers fabricated at three different electrospinning distances, but under the same electric field intensity, revealed an enhanced molecular orientation only for the longest electrospinning distance. At long electrospinning distances the fiber solvent content is substantially reduced resulting in high viscosity, and, therefore, sustained shear stresses, which, in turn, allows for permanent molecular orientation. The orientation factors from polarized FTIR were in good agreement with the mechanical property trends obtained from individual nanofibers, where high elastic moduli and yield strengths were recorded from nanofibers with diameters smaller than 300 nm, which were fabricated at the longest electrospinning distance. WAXD studies on bundles of aligned PAN nanofibers showed small crystallinity which did not follow the trends in the mechanical properties and varied rather non-monotonically from 7%, for fibers spun at the shortest distance, to 17% for fibers spun at the longest distance used in this study.     

Structure and properties of polyacrylonitrile/single wall carbon nanotube composite films

Polyacrylonitrile (PAN)/single wall carbon nanotube (SWNT) composite films have been processed with unique combination of tensile strength (103 MPa), modulus (10.9 GPa), electrical conductivity (1.5×10⁴ S/m), dimensional stability (coefficient of thermal expansion 1.7×10⁻⁶/°C), low density (1.08 g/cm³), solvent resistance, and thermal stability. PAN molecular motion above the glass transition temperature (T_g) in the composite film is significantly suppressed, resulting in high PAN/SWNT storage modulus above T_g (40 times the PAN storage modulus). Rope diameter in the SWNT powder was 26 nm, while in 60/40 PAN/SWNT film, the rope diameter was 40 nm. PAN crystallite size from (110) plane in PAN and PAN/SWNT films was 5.3 and 2.9 nm, respectively. This study suggests good interaction between PAN and SWNT.     

Electrospun hydrophilic fumed silica/polyacrylonitrile nanofiber-based composite electrolyte membranes

Hydrophilic fumed silica (SiO₂)/polyacrylonitrile (PAN) composite electrolyte membranes were prepared by electrospinning composite solutions of SiO₂ and PAN in N,N-dimethylformamide (DMF). Among electrospinning solutions with various SiO₂ contents, the 12 wt% SiO₂ in PAN solution has highest zeta potential (−40.82 mV), and exhibits the best dispersibility of SiO₂ particles. The resultant 12 wt% SiO₂/PAN nanofiber membrane has the smallest average fiber diameter, highest porosity, and largest specific surface area. In addition, this membrane has a three-dimensional network structure, which is fully interconnected with combined mesopores and macropores because of a good SiO₂ dispersion. Composite electrolyte membranes were prepared by soaking these porous nanofiber membranes in 1 M lithium hexafluorophosphate (LiPF₆) in ethylene carbonate (EC)/dimethyl carbonate (DMC) (1:1 vol%). It is found that 12 wt% SiO₂/PAN electrolyte membrane has the highest conductivity (1.1 × 10⁻² S cm⁻¹) due to the large liquid electrolyte uptake (about 490%). In addition, the electrochemical performance of composite electrolyte membranes is also improved after the introduction of SiO₂. For initial cycle, 12 wt% SiO₂/PAN composite electrolyte membrane delivers the discharge capacity of 139 mAh g⁻¹ as 98% of theoretical value, and still retains a high value of 127 mAh g⁻¹ as 89% at 150th cycle, which is significantly higher that of pure PAN nanofiber-based electrolyte membranes.     

Effects of surrounding confinements of Si nanoparticles on Si-based anode performance for lithium ion batteries

We report herein the effects of various surrounding confinements of Si nanoparticles on the electrochemical performance of Si nanoparticles based anode for lithium ion batteries (LIBs). Three different types of surrounding confinements are incorporated onto or around the surface of Si nanoparticles: Si nanoparticles-embedded carbon nanofibers (Si@CNF) via electrospinning, carbon nitride encapsulated Si nanoparticles with core/shell structure (Si@CND), and binder enriched Si nanoparticles-based anode (Si@RBD). Morphology and microstructure of the samples are characterized using X-ray diffractometry, scanning electron microscopy, transmission electron microscopy, and the results were discussed in relation to the electrochemical performances. It is found that Si@CNF which has conducting hard surrounding confinements and Si@RBD exhibited high reversible specific capacity of 620 mA hg⁻¹ and 1200 mA hg⁻¹, up to 30th cycle, respectively. Meanwhile, Si@CND that has mechanically hard but poor electrical conductivity exhibits low specific capacity compared with the other two samples.     

Processing and properties of aligned multi-walled carbon nanotube/aluminoborosilicate glass composites made by sol-gel processing

We describe a novel sol-gel based approach for producing aluminoborosilicate glass composites containing continuous, aligned carbon nanotubes. The process involves the production of aligned carbon nanotubes (ACNT) via aerosol chemical vapour deposition (CVD), followed by infiltration of the ACNT with aluminoborosilicate sol. The advantages of this process are three fold: (1) aerosol CVD is an efficient method of producing clean, aligned arrays of CNTs, (2) sol-gel chemistry provides a simple route to infiltration of the ACNTs, and (3) carbon nanotube (CNT) agglomeration problems associated with CNT composites are circumvented. ACNTs (carpets) with heights of up to 4.4 mm were grown with areas of 10 mm × 20 mm for composite fabrication. The composite showed extensive pullout of the CNTs on a fracture surface and improved thermal and electrical conductivities of 16 Wm⁻¹ K⁻¹ and 5-8 × 10² S m⁻¹ respectively compared with only 1.2 W m⁻¹ K⁻¹ and 10⁻¹³ S m⁻¹ for the monolithic glass.     

Co-axial electrospinning with sodium thiocyanate solution for preparing polyacrylonitrile nanofibers

A modified co-axial electrospinning process including electrolyte solution as sheath fluid for preparing high quality polymer nanofibers is investigated. A series of polyacrylonitrile (PAN) nanofibers were fabricated utilizing the modified process with sodium thiocyanate solutions in N, N-dimethylacetamide (DMAc) as sheath fluids. Field-emission scanning electron microscopy results demonstrated that the sheath sodium thiocyanate solutions had significant influence on the quality of PAN nanofibers. High quality PAN nanofibers in terms of fiber diameters and their distributions, surface morphology and structure have been successfully produced. The diameters of nanofibers (D, nm) could be manipulated simply by adjusting the concentrations of sodium thiocyanate (C, mg ml^-1) in the sheath fluids with a scaling law of D = 324 C ^-0.1806. The mechanism about the influence of sodium thiocyanate solutions on the formation of PAN fibers is discussed and it is felt that co-axial electrospinning with electrolyte solution is a facile process for achieving high quality polymer nanofibers.     

Desirable electrical and mechanical properties of continuous hybrid nano-scale carbon fibers containing highly aligned multi-walled carbon nanotubes

The continuous highly aligned hybrid carbon nanofibers (CNFs) with different content of acid-oxidized multi-walled carbon nanotubes (MWCNTs) were fabricated through electrospinning of polyacrylonitrile (PAN) followed by a series of heat treatments under tensile force. The effects of MWCNTs on the micro-morphology, the degree of orientation and ordered crystalline structure of the resulting nanofibers were analyzed quantitatively by diversified structural characterization techniques. The orientation of PAN molecule chains and the graphitization degree in carbonized nanofibers were distinctly improved through the addition of MWCNTs. The electrical conductivity of the hybrid CNFs with 3 wt% MWCNTs reached 26 S/cm along the fiber direction due to the ordered alignment of MWCNTs and nanofibers. The reinforcing effect of hybrid CNFs in epoxy composites was also revealed. An enhancement of 46.3% in Young’s modulus of epoxy composites was manifested by adding 5 wt% hybrid CNFs mentioned above. At the same time, the storage modulus of hybrid CNF/epoxy composites was significantly higher than that of pristine epoxy and CNF/epoxy composites not containing MWCNTs, and the performance gap became greater under the high temperature regions. It is believed that such a continuous hybrid CNF can be used as effective multifunctional reinforcement in polymer matrix composites.     

Multi-wall carbon nanotubes coated with polyaniline

Multi-wall carbon nanotubes (CNT) were coated with protonated polyaniline (PANI) in situ during the polymerization of aniline. The content of CNT in the samples was 0-80 wt%. Uniform coating of CNT with PANI was observed with both scanning and transmission electron microscopy. An improvement in the thermal stability of the PANI in the composites was found by thermogravimetric analysis. FTIR and Raman spectra illustrate the presence of PANI in the composites; no interaction between PANI and CNT could be proved. The conductivity of PANI-coated CNT has been compared with the conductivity of the corresponding mixtures of PANI and CNT. At high CNT contents, it is not important if the PANI coating is protonated or not; the conductivity is similar in both cases, and it is determined by the CNT. Polyaniline reduces the contact resistance between the individual nanotubes. A maximum conductivity of 25.4 S cm⁻¹ has been found with PANI-coated CNT containing 70 wt% CNT. The wettability measurements show that CNT coated with protonated PANI are hydrophilic, the water contact angle being ∼40°, even at 60 wt% CNT in the composite. The specific surface area, determined by nitrogen adsorption, ranges from 20 m² g⁻¹ for protonated PANI to 56 m² g⁻¹ for neat CNT. The pore sizes and volumes have been determined by mercury porosimetry. The density measurements indicate that the compressed PANI-coated CNT are more compact compared with compressed mixtures of PANI and CNT. The relaxation and the growth of dimensions of the samples after the release of compression have been noted.     

Development of carbon nanofibers from aligned electrospun polyacrylonitrile nanofiber bundles and characterization of their microstructural, electrical, and mechanical properties

Carbon nanofibers with diameters of 200-300 nm were developed through stabilization and carbonization of aligned electrospun polyacrylonitrile (PAN) nanofiber bundles. Prior to the oxidative stabilization in air, the electrospun PAN nanofiber bundle was tightly wrapped onto a glass rod, so that tension existed during the stabilization. We also investigated several carbonization procedures by varying final carbonization temperatures in the range from 1000 to 2200 °C. The study revealed that: (1) with increase of the final carbonization temperature, the carbon nanofibers became more graphitic and structurally ordered; (2) the carbon nanofiber bundles possessed anisotropic electrical conductivities, and the differences between the parallel and perpendicular directions to the bundle axes were over 20 times; and (3) the tensile strengths and Young's moduli of the prepared carbon nanofiber bundles were in the ranges of 300-600 MPa and 40-60 GPa, respectively.     

Magnetic‐field‐assisted electrospinning highly aligned composite nanofibers containing well‐aligned multiwalled carbon nanotubes

Composite nanofiber meshes of well‐aligned polyacrylonitrile (PAN)/polyvinylpyrrolidone (PVP) nanofibers containing multiwalled carbon nanotubes (MWCNTs) were successfully fabricated by a magnetic‐field‐assisted electrospinning (MFAES) technology, which was confirmed to be a favorable method for preparation of aligned composite nanofibers in this article. The MFAES experiments showed that the diameters of composite nanofibers decreased first and then increased with the increase of voltage and MWCNTs content. With the increase of voltage, the degree of alignment of the composite nanofibers decreased, whereas it increased with increasing MWCNTs concentration. Transmission electron microscopy observation showed that MWCNTs were parallel and oriented along the axes of the nanofibers under the low concentration. A maximum enhancement of 178% in tensile strength was manifested by adding 2 wt % MWCNTs in well‐aligned composite nanofibers. In addition, the storage modulus of PAN/PVP/MWCNTs composite nanofibers was significantly higher than that of the PAN/PVP nanofibers. Besides, due to the highly ordered alignment structure, the composite nanofiber meshes showed large anisotropic surface resistance, that is, the surface resistance of the composite nanofiber films along the fiber axis was about 10 times smaller than that perpendicular to the axis direction. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41995.