Reinforcement of electroactive characteristics in polyvinylidene fluoride electrospun nanofibers by intercalation of multi-walled carbon nanotubes

This research work reports on development and characterization of multi-walled carbon nanotube (MWCNT)-doped polyvinylidene difluoride (PVDF) nanofibers by the electrospinning method. PVDF is an extensively studied polymer both theoretically and experimentally due to its appealing ferroelectric, piezoelectric, and pyroelectric properties which strongly favors its promising applications in the development of micro/nanostructure devices. The foremost reason for its ferroelectric and piezoelectric behaviors has been attributed to its crystalline structure, specifically the presence of β-phase; however, the existence of the small percentage of β-phase in pristine PVDF limits its applications. To enhance the electroactive features in the PVDF, MWCNTs have been doped in it to prepare electrospun nanofibers, as electrospinning is a single-step approach. These nonwoven nanofibers were prepared at a DC voltage of 20 kV which were subsequently calcined at 100 °C for 12 h. The estimation of crystal structure and phase identification in these nanofibers have been determined by attenuated FT-IR and XRD, while the morphology, microstructure, mean diameter, and length have been examined by FE-SEM. The observed electrical conductivity, capacitance, permittivity (ε), conductivity (δ), and impedance (Z) in these samples have been tailored by doping a range of MWCNT contents and optimizing the experimental conditions.     

Nickel‐multiwalled carbon nanotubes/polyvinylidene fluoride composites with high dielectric permittivity

Composites with nickel particles coated multiwalled carbon nanotubes (Ni‐MWNTs) embedded into polyvinylidene fluoride (PVDF) were prepared by solution blending and hot‐press processing. The morphology, structure, crystallization behavior, and dielectric properties of composites were studied. The results showed that the crystallization of PVDF was affected by Ni‐MWNTs. With the increment of Ni‐MWNTs, the content of β‐phase in PVDF increased. The dielectric permittivity was as high as 290 at 10³ Hz when the weight fraction of Ni‐MWNTs was 10%. The results can be explained by the space charge polarization at the interfaces between the insulator and the conductor, and the formation of microcapacitance structure. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3746–3752, 2013     

Multiwall carbon nanotubes grown by thermocatalytic carbonization of polyacrylonitrile

A method is reported for the growth of multiwall carbon nanotubes (MWCNTs) using polyacrylonitrile as a solid carbon source and nanosized SiO₂ particles as catalyst. The nanotubes were grown either on a Si substrate or as a freestanding film at temperatures as low as 800 °C. The smallest measured inner diameter of the resultant MWCNTs is about 0.6 nm and therefore this method provides a new direction to prepare MWCNTs with very small inner diameter from solid carbon source.     

Synthesis of carbon nanotubes on carbon fibers by means of two-step thermochemical vapor deposition

The present study aimed at development of a method for synthesizing multi-walled carbon nanotubes (CNTs) on carbon paper substrates (CP) at densities as high as those so far reported for CNTs formed on quartz substrates. Applying conditions optimized for CNTs synthesis on quartz substrates, in which CP was heated at 1073 K, being placed parallel to the flow of m-xylene/ferrocene vapor, resulted in formation of extremely few deposits on CP. Forced vapor flow through the CP greatly improved the frequency and homogeneity of deposition of the Fe-bearing nanoparticles, but these became encapsulated by carbon and deactivated. The addition of H₂S to the vapor further enhanced nanoparticle deposition. Moreover, it enabled the subsequent formation of CNTs at densities as high as 2-6 × 10⁹ cm⁻². In order to realize such high population densities, it was found essential to perform CVD in a two-stage sequence commencing with nanoparticles deposition at 1073 K followed by the formation and growth of CNTs at 1273 K, with the H₂S concentration in the vapor phase optimized throughout within a range of 0.014-0.034 vol%.     

Synthesis of branched carbon nanotubes using copper catalysts in a hydrogen-filled DC arc-discharger

Branched multi-walled carbon nanotubes (b-CNTs) were deposited in a collar around the cathode in a DC arc-discharger in the presence of hydrogen and copper catalysts. Irrespective of the gas pressure or oxidation state of the catalysts, common morphologies (compartmentalization/segmentation, branching, partial metal filling) were observed when raw samples from the collar were analyzed by TEM. EDX confirmed the presence of metallic copper in the tips, in the branches and in the partially filled b-CNTs. These features have led to the proposal of a common growth model, in which reactions between metallic copper nanoparticles and gaseous carbon species that were formed in hydrogen, were used to rationalize the various CNT structures synthesised.     

Inorganic nanotubes reinforced polyvinylidene fluoride composites as low-cost electromagnetic interference shielding materials

Novel polymer nanocomposites comprising of MnO₂ nanotubes (MNTs), functionalized multiwalled carbon nanotubes (f-MWCNTs), and polyvinylidene fluoride (PVDF) were synthesized. Homogeneous distribution of f-MWCNTs and MNTs in PVDF matrix were confirmed by field emission scanning electron microscopy. Electrical conductivity measurements were performed on these polymer composites using four probe technique. The addition of 2 wt.% of MNTs (2 wt.%, f-MWCNTs) to PVDF matrix results in an increase in the electrical conductivity from 10^-16S/m to 4.5 × 10^-5S/m (3.2 × 10^-1S/m). Electromagnetic interference shielding effectiveness (EMI SE) was measured with vector network analyzer using waveguide sample holder in X-band frequency range. EMI SE of approximately 20 dB has been obtained with the addition of 5 wt.% MNTs-1 wt.% f-MWCNTs to PVDF in comparison with EMI SE of approximately 18 dB for 7 wt.% of f-MWCNTs indicating the potential use of the present MNT/f-MWCNT/PVDF composite as low-cost EMI shielding materials in X-band region.     

Synthesis and characterization of 3D double branched K junction carbon nanotubes and nanorods

Carbon nanobelts, highly branched carbon nanotubes (CNTs) and carbon nanorods (CNRs) were synthesized by the catalytic pyrolysis of acetylene using Fe-catalyst at different temperatures. The 3D double branched K junction and various 2D single branched Y, L, T junctions on CNTs and CNRs were characterized by SEM, TEM, and Raman spectroscopy. The bamboo shaped hollow interior of the K junction indicated a possible growth mechanism of the CNTs.     

Polypropylene fibers reinforced with carbon nanotubes

The strength properties of polypropylene fibers were enhanced with single‐wall carbon nanotubes (SWNTs). Solvent processing was used to disperse SWNTs in a commodity polypropylene. After the solvent was removed, the solid polymer was melt‐spun and postdrawn into fibers of unusual strength. For a 1‐wt % loading of nanotubes, the fiber tensile strength increased 40% (from 9.0 to 13.1 g/denier). At the same time, the modulus increased 55% (from 60 to 93 g/denier). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2079–2084, 2002     

Highly porous electrospun polyvinylidene fluoride (PVDF)-based carbon fiber

Porous poly(vinylidene fluoride) fibers were prepared by electrospinning from solutions in dimethylformamide, poly(ethylene oxide) (PEO) and water. The PVDF fiber mats were then converted into electrospun carbon fiber paper using a low temperature chemical stabilization treatment (“dehydrofluorination”) followed by carbonization at 1000 °C. The resulting self-supporting carbon fiber paper exhibits unusually high surface area, in excess of 380 m²/g as measured by the nitrogen adsorption method, and a hierarchical pore structure. The largest pores are formed by the interstices between fibers; intermediate-sized pores arise from liquid–liquid phase separation during electrospinning to form polymer-rich and solvent-rich domains within the fibers; the smallest pores form upon decomposition of the PEO during carbonization. The electrospun carbon paper performs well as an electrode for driving the redox chemistry of ferrocene/ferrocenium. This is attributed to the high surface area of the electrode and the ease of diffusion of the redox-active species within the porous structure. The ratio of the dehydrofluorination agent (1,8-diazabicyclo[5.4.0]undec-7-ene) to vinylidene fluoride during dehydrofluorination was found to be the key to retaining the as-spun pore morphology during carbonization. The structure and morphology were further characterized by Scanning Electron Microscopy, Energy Dispersive X-ray Spectroscopy, X-ray diffraction, and Raman spectroscopy.     

Facile preparation and properties of polyvinylidene fluoride dielectric nanocomposites via phase morphology control and incorporation of multiwalled carbon nanotubes conductive fillers

A novel PVDF dielectric nanocomposite was achieved by controlling phase morphology and incorporating conductive fillers simultaneously, and the mechanical, thermal, dielectric properties of the resultant dielectric nanocomposites were investigated. Mechanical analysis showed that incorporation of modified MWCNTs (MWCNTs-COOH) in the PVDF nanocomposites resulted in significant improvements on the tensile strength (T_s) and elasticity modulus (E_m). When the filler content was 12 wt%, the T_s of MWCNTs-COOH/PVDF could reach 64.6 MPa. XRD test showed that the addition of MWCNTs-COOH and MWCNTs promoted the formation of β-phase of PVDF. DMA analysis showed that the glass-transition temperature of the PVDF nanocomposites slightly increases on loading of original MWCNTs and this effect was more pronounced on loading MWCNTs-COOH. The dielectric property analysis showed that the original MWCNTs were more likely to form local conductive networks in the PVDF matrix, promoting the electron displacement polarization, and improving the dielectric constant. When the contents of MWCNTs was 12 wt%, the percolation threshold was obtained and the dielectric constant (ε′) reached 286, which was 36 times of pure PVDF. Our work provides a simple way to fabricate polymer blends with excellent dielectric performances, good mechanical properties as well as good processing capability but low cost. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48463.     

Effect of fiber size on structural and tensile properties of electrospun polyvinylidene fluoride fibers

We use electrospinning to obtain polyvinylidene fluoride (PVDF) fibers and demonstrate simultaneous improvements in β‐crystal microstructure and in tensile properties of fibers with reduction of their diameter. PVDF fibers with average diameters ranging from 70 to 400 nm are obtained by controlling the concentration of the polymer in the electrospinning solution. The amount of β‐crystals present is found to be greater for finer diameter fibers, yielding a maximum β‐phase fraction of 0.86 in the 70‐nm fibers. Moreover, the deformation behavior of the fibers reveals that the tensile modulus and strength improve with reductions in fiber size. Sharp increases in tensile properties are demonstrated when the size of the fibers is reduced below 175 nm. We attribute the enhanced concentration of β‐crystals and the tensile behavior of finer diameter fibers to the extensional forces experienced by the material during electrospinning. POLYM. ENG. SCI., 55:1812–1817, 2015. © 2014 Society of Plastics Engineers     

Development of lignin carbon fibers: Evaluation of the carbonization process

The use of lignin as a renewable resource for the production of less‐expensive carbon fibers has in recent years attracted great interest. In order to develop the strength properties, the stabilization and carbonization processes have to be optimized. For this reason, the process parameters during carbonization have here been studied on stabilized lignin fibers in the temperature interval from 300 to 1300 °C. The effects of temperature, heating rate, and straining of fibers during carbonization on the strength properties of carbon fibers were investigated. The heating rate, in the range from 1 to 40 °C/min, was shown to have no effect on the property development of the fibers. During carbonization with no load applied to the fibers, a shrinkage of 20% was noted. Counteracting the shrinkage by imposing a load on the fibers during the carbonization resulted in fibers with a greater stiffness. The tensile strength was not, however, affected by this loading. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43965.     

Synthesis and characterization of double-walled carbon nanotubes from multi-walled carbon nanotubes by hydrogen-arc discharge

Double-walled carbon nanotubes (DWNTs) were synthesized in a large scale by a hydrogen arc discharge method using graphite powders or multi-walled carbon nanotubes/carbon nanofibers (MWNTs/CNFs) as carbon feedstock. The yield of DWNTs reached about 4 g/h. We found that the DWNT product synthesized from MWNTs/CNFs has higher purity than that from graphite powders. The results from high-resolution transmission electron microscopy observations revealed that more than 80% of the carbon nanotubes were DWNTs and the rest were single-walled carbon nanotubes (SWNTs), and their outer and inner diameters ranged from 1.75 to 4.87 nm and 1.06 to 3.93 nm, respectively. It was observed that the ends of the isolated DWNTs were uncapped and it was also found that cobalt as the dominant composition of the catalyst played a vital role in the growth of DWNTs by this method. In addition, the pore structures of the DWNTs obtained were investigated by cryogenic nitrogen adsorption measurements.