Preparation, crystallization, electrical conductivity and thermal stability of syndiotactic polystyrene/carbon nanotube composites

A homogeneous dispersion of multi-walled carbon nanotubes (MWCNTs) in syndiotactic polystyrene (sPS) is obtained by a simple solution dispersion procedure. MWCNTs were dispersed in N-methyl-2-pyrrolidinone (NMP), and sPS/MWCNT composites are prepared by mixing sPS/NMP solution with MWCNT/NMP dispersion. The composite structure is characterized by scanning electron microscopy and transmission electron microscopy. The effect of MWCNTs on sPS crystallization and the composite properties are studied. The presence of MWCNTs increases the sPS crystallization temperature, broadens the crystallite size distribution and favors the formation of the thermodynamically stable β phase, whereas it has little effect on the sPS γ to α phase transition during heating. By adding only 1.0 wt.% pristine MWCNTs, the increase in the onset degradation temperature of the composite can reach 20 °C. The electrical conductivity is increased from 10^{−10∼−16} (neat sPS) to 0.135 S m⁻¹ (sPS/MWCNT composite with 3.0 wt.% MWCNT content). Our findings provide a simple and effective method for carbon nanotube dispersion in polymer matrix with dramatically increased electrical conductivity and thermal stability.     

Horizontally aligned single-walled carbon nanotube field emitters fabricated on vertically aligned multi-walled carbon nanotube electrode arrays

Vertically aligned multi-walled carbon nanotube (MWCNT) arrays were fabricated on an anodic aluminum oxide membrane bonded to a Si wafer. After obtaining a protruding tip for the MWCNTs by etching away some oxide, they were used as electrodes in the fabrication of carbon nanotube field emitters. Long single-walled carbon nanotubes (SWCNTs) were spin coated on the MWCNT arrays of uniform height. Clean SWCNTs were suspended by attaching them to the tips of the vertically aligned MWCNT arrays. The spin coated SWCNTs function as emitters, while the MWCNT arrays function as electrodes. The field emission was greatly improved by coating gold on the MWCNT arrays and annealing at 400 °C. Our field emitter exhibits good field emission properties such as a low turn-on field (1.4 V/μm), high current density (122 mA/cm²), and good stability (55 h for 10% degradation of current density from 400 μA/cm²).     

Ultrahigh-shear processing for the preparation of polymer/carbon nanotube composites

Poly(vinylidene fluoride) (PVDF)/multiwalled carbon nanotube (MWCNT) composites were prepared using a novel ultrahigh-shear extruder by directly mixing MWCNT with PVDF in the molten state. A special feedback-type screw was used to obtain a high shear field and obtain a very uniform dispersion of the nanotubes in the polymer matrix under a higher screw rotation speed. Raman spectroscopy and scanning electron microscopy were used to determine the interaction and dispersion of nanotubes in the PVDF. The linear viscoelastic behavior and electrical conductivity of these composites were investigated. At low-frequencies, the storage shear modulus (G′) becomes almost independent of the frequency as nanotube loading increases, suggesting the onset of solid-like behavior in these composites. By plotting G′ vs. nanotube loading and fitting with a power-law function, we found that the rheological threshold of high-shear processed composites is about 0.96 wt% whereas that of low-shear processed composites is about 1.76 wt%. The electrical percolation threshold of high-shear processed composites is lower than that of low-shear processed composites.     

Characterization of conductive multiwall carbon nanotube/polystyrene composites prepared by latex technology

Conductive multiwall carbon nanotube/polystyrene (MWCNT/PS) composites are prepared based on latex technology. MWCNTs are first dispersed in aqueous solution of sodium dodecyl sulfate (SDS) driven by sonication and then mixed with different amounts of PS latex. From these mixtures MWCNT/PS composites were prepared by freeze-drying and compression molding. The dispersion of MWCNTs in aqueous SDS solution and in the PS matrix is monitored by UV–vis, transmission electron microscopy, electron tomography and scanning electron microscopy. When applying adequate preparation conditions, MWCNTs are well dispersed and homogeneously incorporated in the PS matrix. The percolation threshold for conduction is about 1.5 wt% of MWCNTs in the composites, and a maximum conductivity of about 1 S m⁻¹ can be achieved. The approach presented can be adapted to other MWCNT/polymer latex systems.     

Anisotropy of mesophase pitch-derived carbon foams

Carbon foams with uniform pore size were produced from mesophase pitch in a high-pressure chamber. The morphologies, crystal structure and mechanical properties of as-grown carbon foams, carbonized and graphitic foams were investigated. The microwave absorbing properties of carbon foam sandwich composites at 2-18 GHz were also examined. It was found that the extension of pores in the xz-plane direction (parallel to the direction of gravitational force) was larger than that in the xy-plane direction (perpendicular to the direction of gravitational force). The compressive strength and modulus of resultant foams in the xz-plane direction were higher than those in the xy-plane direction. Further, the reflection loss of the sandwich composites composed of xy-plane carbon foam slabs was lower than that of xz-plane composites. The results of this work showed that carbon foam was a kind of anisotropic material.     

Polystyrene composites containing crosslinked polystyrene‐multiwalled carbon nanotube balls

Crosslinked polystyrene‐multiwalled carbon nanotube (PS‐MWCNT) balls, which act as conductive microfillers, were prepared by the in situ suspension polymerization of styrene with MWCNTs and divinyl benzene (DVB) as a crosslinking agent. The diameters of the synthesized crosslinked PS‐MWCNT balls ranged from 10 to 100 μm and their electrical conductivity was about 7.7 × 10^?3 S/cm. The morphology of the crosslinked PS‐MWCNT balls was observed by scanning electron microscopy and transmission electron microscopy. The change in the chemical structure of the MWCNTs was confirmed by Raman spectroscopy and Fourier transform infrared spectroscopy. The mechanical and electrical properties of the PS/crosslinked PS‐MWCNT ball composites were investigated. It was found that the tensile strength, ultimate strain, Young's modulus, and impact strength of the PS matrix were enhanced by the incorporation of the crosslinked PS‐MWCNT balls. In addition, the mechanical properties of the PS/crosslinked PS‐MWCNT ball composites were better than those of the PS/pristine MWCNT composites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of confinement structure of Sn/C-C (MWCNTs) composite anode materials for lithium ion battery by carbothermal reduction

A composite anode material was prepared with confined tin into multiwall carbon nanotube by carbothermal reduction. The morphology and structure of Sn/C (nature graphite) and Sn/C-C (nature graphite + multiwall carbon nanotube) were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). It was revealed that the additive of MWCNT was a crucial factor to improve Sn /C composite anodes for cyclability and reversible capacity. Volume changes and morphological changes in Sn can be reduced by encasing MWCNT in a carbonaceous material that has sufficient flexibility to act as a buffer. Electrochemical performance test shows that the charge capacity of the Sn/C-C (NG + MWCNT) electrode in the fiftieth cycle was 400 mAh/g, which was higher than that of the Sn/C (NG) electrode. After 50 cycles, the retention of the Sn/C-C electrode and the Sn/C electrode was 80% and 63%, respectively.     

Biocompatible hyperbranched polyurethane/multi-walled carbon nanotube composites as shape memory materials

Multi-walled carbon nanotube (MWCNT)-based composites have been prepared by in situ technique using Mesua ferrea L. seed oil-based hyperbranched polyurethane (HBPU) as the matrix. The scanning electron microscope, transmission electron microscope and Fourier transform infrared spectroscopy analyses revealed good dispersion as well as interaction of MWCNT with the matrix. Remarkable recovery of shape to the extent of 98% was obtained after composite formation. More than 300% improvement in tensile strength was observed as compared to the pristine HBPU. Significant enhancement of thermal stability up to 275 °C was found even at low MWCNT loading (1 wt.%). Bacterial degradation of the composite films was tested using two strains of Pseudomonas aeruginosa, MTCC 7814 and MTCC 7815. The composites exhibited enhanced biodegradability as compared to the pristine polymer. The cytocompatibility test based on hemolysis of red blood cells showed that the material lacks cytotoxicity. The investigation indicates that the material has high potential as shape memory biomaterial.     

Spray deposited fluoropolymer/multi-walled carbon nanotube composite films with high dielectric permittivity at low percolation threshold

High performance perfluoro alkoxy (PFA) and chemical vapor deposition-grown multi-walled carbon nanotube (MWCNT) composite films with thicknesses of 30 μm were prepared using a scalable spray deposition technique. A homogeneous distribution of MWCNTs within the PFA matrix was confirmed by electron and optical microscopy. Dielectric and AC conductivity measurements showed a significant enhancement of dielectric permittivity for PFA/MWCNT films at low frequencies, and a very weak dependence of dielectric permittivity on temperature in the range 25-230 °C. Very low percolation threshold volume fractions of ca. 0.0043 and 0.0017 were attained for MWCNTs with two different aspect ratios, which have been explained by an inherent feature of spray route, a microcapacitor model and percolation theory. The combination of PFA/MWCNT composites and the spray deposition route provides a promising approach for the fabrication of industrial scale composite films with well-controlled dielectric properties for micro-electronic and high temperature applications.     

Mechanical performance of highly compressible multi-walled carbon nanotube columns with hyperboloid geometries

Multi-walled carbon nanotube (MWCNT) columns are formed from the frit compression of a random distribution of MWCNTs in a casting solvent; its drying led to the formation of hyperboloid geometry. Uniaxial loading of MWNT columns mimics an open-cell foam behaviour and possesses an expansion rate in excess of 250 mm min⁻¹ and an elastic modulus of 10-12 MPa, thus superior to conventional low-density flexible foams. Successive compression-expansion cycling within the Hookean region reveals a hysteresis loop in the stress-strain curve that stabilises at a final value of ε_F = 18%, but on contact with its casting solvent and subsequent drying, the sample can be regenerated to within ε_R = 6% according to a memory effect and is repeatable in successive stress cycles and solvent regeneration. The system was modelled for the macroscopic stress-strain behaviour of the MWCNT column to reveal the contributions of linear dependence, elasticity-plasticity and elasticity-plasticity with hardening, revealing good agreement with the stress-strain data. MWCNT columns should prove useful as an energy adsorbing device.     

Tin dioxide/carbon nanotube composites with high uniform SnO2 loading as anode materials for lithium ion batteries

SnO₂/multi-walled carbon nanotube (MWCNT) composites were prepared by the solvothermal method and subsequent heat treatment at 360 °C. The samples were characterized by field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), and transmission electron microscopy (TEM). Results on the higher SnO₂ content composite sample indicate that a uniform layer of SnO₂ nanocrystals with crystal size around 5 nm was deposited on the surface of the carbon nanotubes. The composite demonstrates a reversible lithium storage capacity of 709.9 mAh g⁻¹ at the first cycle and excellent cyclic retention up to 100 cycles as anode for lithium ion batteries.     

Synthesis and foaming of water expandable polystyrene-activated carbon (WEPSAC)

In this study, water acts as a co-blowing agent to support carbon dioxide (CO₂) in the extrusion foaming process of polystyrene (PS) to produce foams with very low density for thermal insulation applications. Herein, we report a simple suspension polymerization method to prepare water expandable polystyrene (WEPS) based on a PS/water containing activated carbon (AC) composite. AC pre-saturated with water was introduced into the styrene monomer to form a water-in-oil inverse emulsion without emulsifiers. Via suspension polymerization, water expandable PS/AC (WEPSAC) beads could be subsequently obtained. Low density PS foams (∼0.03 g/cc) were successfully produced in the CO₂ extrusion foaming process using WEPSAC. Because of lower foam density and better IR absorption due to the presence of water containing AC, WEPSAC foams provided a lower thermal conductivity than conventional talc reinforced PS foams.     

Preparation of phenolic-based carbon foam with controllable pore structure and high compressive strength

Phenolic-based carbon foams with controllable pore structure and high compressive strength were prepared by foaming of resin solution under the pressure of 4 MPa and then carbonizing. Results showed that the average pore size of carbon foam ranging from 20 to 180 nm can be controlled by changing the resin concentration. The nanometer pore structure resulted in significant improvement of compressive strength and thermal insulation properties of the carbon foams. Carbon foam with bulk density of 0.73 g/cm³, average pore size of 20 nm, compressive strength of 98.3 MPa and thermal conductivity of 0.24 W/mK was obtained.     

Sonochemical hybridization of carbon nanotubes with gold nanoparticles for the production of flexible transparent conducing films

We have demonstrated the fabrication of flexible, transparent, conducting multiwalled carbon nanotube (MWCNT)/gold nanoparticle hybrid films with improved optoelectronic properties by combining the ionic liquid-assisted sonochemical method (ILASM) for hybrid synthesis with the vacuum filtration (VF) method for thin film preparation. Au nanoparticles (NPs) with diameters of 10.3 ± 1.5 nm were uniformly distributed onto the sidewalls of MWCNTs through ILASM, and flexible, transparent, conducting films of Au/MWCNT hybrids (HBs) were reproducibly fabricated by the VF method. In particular, the sheet resistance of Au-MWCNT-HB films was more than 2-fold lower than the sheet resistance of pristine MWCNT films due to the well-interconnected three-dimensional nanotube network structure and the synergistic effect of hybridization of MWCNTs with Au-NPs.     

Positive temperature coefficient to resistively characteristics of polystyrene/nickel powder/multiwall carbon nanotubes composites

Positive temperature coefficient to resistivity (PTCR) characteristics of polystyrene (PS)/Ni‐powder (40 wt%) composites in the presence of multiwall carbon nanotubes (MWCNTs) has been investigated with reference to PS/carbon black (CB) composites. The PS/CB (10 wt%) composites showed a sudden rise in resistivity (PTC trip) at ≈110°C, above the glass transition temperature (T_g) of PS (T_g ≈95°C). Interestingly, the PTC trip temperature of PS/Ni‐powder (40 wt%)/MWCNT (0.75 phr) composites appeared at ≈90°C (below T_g of PS), indicating better dimensional stability of the composites at PTC trip temperature. The PTC trip temperature of the composites below the T_g of matrix polymer (PS) has been explained in terms of higher coefficient of thermal expansion (CTE) value of PS than Ni that led to a disruption in continuous network structure of Ni even below the T_g of PS. The dielectric study of PS/Ni‐powder (40 wt%)/MWCNT (0.75 phr) composites indicated possible use of the PTC composites as dielectric material. Dynamic mechanical analysis (DMA) and thermogravimetric analysis studies revealed higher storage modulus and improved thermal stability of PS/Ni‐powder (40 wt%)/MWCNT (0.75 phr) composites than the PS/CB (10 wt%) composites. POLYM. COMPOS., 33:1977–1986, 2012. © 2012 Society of Plastics Engineers     

Development of electrical conductivity with minimum possible percolation threshold in multi-wall carbon nanotube/polystyrene composites

A method is reported that involves the bulk polymerization of styrene monomer in the presence of multi-wall carbon nanotubes (MWCNTs) and polystyrene (PS) beads, for the preparation of MWCNT/PS conducting composites with a significantly lower (0.08 wt.% MWCNT) percolation threshold than previously reported. Thus, the conductivities of 7.62 × 10⁻⁵ and 1.48 × 10⁻³ S cm⁻¹ were achieved in the MWCNT/PS composites through homogeneous dispersion of 0.08 and 0.26 wt.% CNTs, respectively in the in situ polymerized PS region by using 70 wt.% PS beads during the polymerization. The extent of dispersion and location of the MWCNTs in the PS matrix has been investigated with a scanning and transmission electron microscopy. The conductivity of the composites was increased with increasing wt.% of the PS beads at a constant CNT loading, indicating the formation of a more continuous network structure of the CNTs in PS matrix.     

In vivo rat subcutaneous tissue response of binder-free multi-walled carbon nanotube blocks cross-linked by de-fluorination

Binder-free multi-walled carbon nanotube (MWCNT) blocks from fluorinated MWCNTs were prepared using thermal heating and a compression method in vacuo. The resulting carbon nanotube blocks are lighter than graphite, can be machined and polished, possess average bending strengths of 102.2 MPa, a bending modulus of 15.4 GPa, and moderate wettability. The binder-free MWCNT blocks possess good biocompatibility when tested in the subcutaneous tissue of rats in vivo, which were covered by thin granulation tissue, 40-70 μm in thickness, comprising a few lymphocytes, cell with large cytoplasmic spaces like fibroblasts and foreign-body giant cells. That is indicative of a slight inflammatory response than MWCNT/resin blocks and poly(methyl methacrylate). This material can potentially be employed as an alternative artificial hard tissue or internal bone plate that makes use of the properties of CNTs.     

Mechanical properties and electrical conductivity in a carbon nanotube reinforced silicon nitride composite

The influence of carbon nanotubes (CNTs) addition on basic mechanical, thermal and electrical properties of the multiwall carbon nanotube (MWCNT) reinforced silicon nitride composites has been investigated. Silicon nitride based composites with different amounts (1 or 3 wt%) of carbon nanotubes have been prepared by hot isostatic pressing. The fracture toughness was measured by indentation fracture and indentation strength methods and the thermal shock resistance by indentation method. The hardness values decreased from 16.2 to 10.1 GPa and the fracture toughness slightly decreased by CNTs addition from 6.3 to 5.9 MPa m^1/2. The addition of 1 wt% CNTs enhanced the thermal shock resistance of the composite, however by the increased CNTs addition to 3 wt% the thermal shock resistance decreased. The electrical conductivity was significantly improved by CNTs addition (2 S/m in 3% Si₃N₄/CNT nanocomposite).     

Electrochemical behavior of glassy carbon electrodes modified by multi-walled carbon nanotube/surfactant films in a buffer solution and an ionic liquid

The electrochemical behavior of glassy carbon (GC) electrodes coated with multi-walled carbon nanotube (MWCNT)/surfactant films was studied in an ionic liquid and a phosphate buffer solution (pH = 6.86), using cyclic voltammetry. The dispersion of MWCNTs in different media was investigated by scanning and transmission electron microscopy. Cast films of MWCNT/zwitterionic dodecyldimethylamine oxide on a GC electrode show a typical redox couple in phosphate buffer solution, which is better than that of MWCNT/anionic sodium dodecyl sulfate and cationic alkyltrimethylammonium bromide. However in the ionic liquid, 1-n-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF₆]), the GC electrode modified by MWCNT/cationic surfactant films shows a well-defined irreversible reduction of MWCNTs. The cyclic voltammograms clearly show that the surfactant hydrophilic group plays an important role in the electrochemical behavior of the MWCNTs. The electrolytes also have an important effect. In an ionic liquid, the strong binding of the ionic liquid cations with the MWCNTs may change the structure of the modified films and lead to changes of electrochemical behavior.     

Preparation of carbon nanofibers/carbon foam monolithic composite from coal liquefaction residue

Carbon nanofibers/carbon foam composites that are made by growing carbon nanofibers (CNFs) on the surface of a carbon foam (CF) have been prepared from coal liquefaction residues (CLR) by a procedure involving supercritical foaming, oxidization, carbonization, and catalytic chemical vapour deposition (CCVD) treatment. These new carbon/carbon composites were examined using SEM, TEM and XRD. The results show that the as-made CF has a structure with cell sizes of 300-600 μm. X-ray diffraction studies show that iron-containing contaminates are present in the CLR. However, these species may act as a catalyst in the CCVD process as established in the literature. After the CCVD treatment, the cell walls of CF are covered by highly compacted CNFs that have external diameters of about 100 nm and lengths of several tens of micrometers. This work may open a new way for direct and effective utilization of the CLR.