Synthesis and electrochemical capacitance of core-shell poly (3,4-ethylenedioxythiophene)/poly (sodium 4-styrenesulfonate)-modified multiwalled carbon nanotube nanocomposites

A noncovalent method was used to functionalize multiwalled carbon nanotubes with poly (sodium 4-styrene sulfonate). And then, the core-shell poly (3,4-ethylenedioxythiophene)/functionalized multiwalled carbon nanotubes (PEDOT/PSS-CNTs) nanocomposite was successfully realized via in situ polymerization under the hydrothermal condition. In the process, PSS served for not only solubilizing and dispersing CNTs well into an aqueous solution, but also tethering EDOT monomer onto the surface of CNTs to facilitate the formation of a uniform PEDOT coating. Fourier transform infrared spectroscopy (FT-IR) and transmission electron microscopy (TEM) were used to characterize the resultant PEDOT/PSS-CNTs. In addition, the PEDOT/PSS-CNTs nanocomposite (50 wt.% PEDOT) had a specific capacitance (SC) of 198.2 F g⁻¹ at a current density of 0.5 A g⁻¹ and a capacitance degradation of 26.9% after 2000 cycles, much better than those of pristine PEDOT and PEDOT/CNTs (50 wt.% PEDOT). The enhanced electrochemical performance of the PEDOT/PSS-CNTs nanocomposite (50 wt.% PEDOT) should be attributed to the high uniform system of the nanocomposite, resulting in the large surface easily contacted by abundant electrolyte ions through the three-dimensional conducting matrix.     

α-Pyrene polymer functionalized multiwalled carbon nanotubes: Solubility, stability and depletion phenomena

This paper presents a study on the stability of dispersions of multiwalled carbon nanotubes that are covered with α-pyrene functionalized polymers prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization and dispersed in different solvents. We find that a rather small amount of these polymers (M_polymer/M_CNT less than 0.1) is capable of stabilizing a high concentration of CNTs (up to 2500 mg/l) in solution. Another strong evidence for well-stabilized CNTs is the comparably low gel points of around 1 vol% of CNTs in solution. We find that adding the α-pyrene functionalized polymer to CNTs has two counter playing effects: on the one hand, increased surface coverage of the carbon nanotubes increases their solubility; on the other hand increased concentration of free polymer in the solution enhances the depletion forces between the nanotubes.     

Multiwall carbon nanotube supported poly(3,4-ethylenedioxythiophene)/manganese oxide nano-composite electrode for super-capacitors

MWCNT-PSS/PEDOT/MnO₂ nano-composite electrodes were fabricated by generating pseudo-capacitive poly(3,4-ethylenedioxythiophene) (PEDOT)/MnO₂ nano-structures on poly(styrene sulfonate) (PSS) dispersed multiwalled carbon nanotubes (MWCNTs). PSS dispersed MWCNTs (MWCNT-PSS) facilitated the growth of PEDOT and MnO₂ into nano-rods with large active surface area and good electrical conductivity. The ternary MWCNT-PSS/PEDOT/MnO₂ nano-composite electrode was studied for the application in super-capacitors, and exhibited excellent capacitive behavior between −0.2 V and 0.8 V (vs. saturated Ag/AgCl electrode) with high reversibility. Specific capacitance of the nano-composite electrode was found as high as 375 F g⁻¹. In contrast, specific capacitance of MWCNT-PSS/MnO₂ and MWCNT-PSS nano-composite electrodes is 175 F g⁻¹ and 15 F g⁻¹, respectively. Based on cyclic voltammetric studies and cycle-life tests, the MWCNT-PSS/PEDOT/MnO₂ nano-composite electrode gave a highly stable and reversible performance up to 2000 cycles. Our studies demonstrate that the synergistic combination of MWCNT-PSS, PEDOT and MnO₂ has advantages over the sum of the individual components.     

Dispersion effect of Cs-PW particles on multiwalled carbon nanotubes and their electrocatalytic activity on the reduction of bromate

Hybrid materials based on Cs-PW particles (Cs₃PW₁₂O₄₀) as the polyoxometalate were dispersed in CNTs matrices (multiwalled carbon nanotubes) with different oxidation degree. XRD, SEM, and EDS analyses confirmed the presence of Cs-PW particles in all hybrid materials, and revealed the influence of the CNTs oxidation degree on the dispersion of Cs-PW particles. Hybrids (CNT-S-50 and CNT-S-75) prepared with highly oxidized CNTs (CNT-S) showed the highest dispersion degree of Cs-PW (less segregation) with the best electrochemical behavior. The electrocatalytic properties were evaluated for the first time in the electroreduction of bromate ion, showing interesting results related with the concentration and dispersion degree of the hybrids components.     

Modified and unmodified multiwalled carbon nanotubes in high performance solution-styrene-butadiene and butadiene rubber blends

The outstanding properties of carbon nanotubes have generated scientific and technical interests in the development of nanotube-reinforced polymer composites. Therefore, we investigated a novel mixing approach for achieving a good dispersion of multiwalled carbon nanotubes (CNTs) in a rubber blend. In this approach the CNTs were incorporated into a 50:50 blend of solution-styrene-butadiene rubber and butadiene rubber. First, the CNTs were predispersed in ethanol and then this CNT-alcohol suspension was mixed with the rubber blend at elevated temperature. The rubber nanocomposites prepared by such method exhibit significantly enhanced physical properties already at very low nanotube concentrations. Additionally, we have analysed the dielectric and thermal properties of the compound. The high aspect ratio of the carbon nanotubes enabled the formation of a conductive percolating network in these composites at concentrations below 2 wt.%. In contrast to the electrical conduction behaviour, the thermal conductivity of the composites has not been influenced significantly by the presence of carbon nanotubes. Dynamic mechanical analysis indicates that the incorporation of CNTs affects the glass transition behaviour by reducing the height of the tan δ peak considerably. Above the glass transition temperature the storage modulus has been increased after incorporation of a small amount of CNTs. Finally, the ‘Payne effect’, an indication of filler-filler interactions, was observed at very low concentrations of CNT in the rubber matrix.     

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).     

Evaluation of mild acid oxidation treatments for MWCNT functionalization

Acidic oxidation methods have been widely reported as an effective method to purify and functionalize the surface of carbon nanotubes (CNTs). Although effective, the strong acids typically employed and the high sonication power used to disperse the nanotubes in the solution frequently cause nanotube damage, limiting their great potential as mechanical and electrical reinforcements. This work examines the use of HNO₃, H₂SO₄ and H₂O₂ at relatively low concentrations, short treatment times and low sonication power, in an attempt to achieve experimental conditions which efficiently functionalize the surface of multiwalled CNTs minimizing nanotube damage. A low power sonochemical treatment employing 3.0 M HNO₃ for 2 h followed by 2 h of identical treatment with H₂O₂ proved to be the most effective for this aim.     

A study of the electrical properties of carbon nanotube-NiFe2O4 composites: Effect of the surface treatment of the carbon nanotubes

Novel carbon nanotube-NiFe₂O₄ composite materials have been prepared for the first time by in situ chemical precipitation of metal hydroxides in ethanol in the presence of carbon nanotubes (CNTs) and followed by hydrothermal processing. The obtained composite powders were characterized using XRD, TEM and EDS. The effect of surface oxidation treatment of CNTs on their properties was investigated by FTIR, zeta potential and hydrodynamic radius distribution characterization. Electrical conductivity measurements show that surface oxidation treatment of CNTs can improve the electrical conductivity of the composites more pronouncedly than pristine CNTs do. With 10 wt.% addition of surface treated CNTs, the electrical conductivity is increased by 5 orders of magnitude. The surface oxidized CNTs are crucial for this significant increase in electrical conductivity, which provides strong adhesion between the nanotubes and the matrix to give a homogeneous carbon nanotube-NiFe₂O₄ composite.     

A treatment method to give separated multi-walled carbon nanotubes with high purity, high crystallization and a large aspect ratio

CNT agglomerates, prepared by catalytic chemical vapor deposition in a nano-agglomerate fluidized-bed reactor are separated and dispersed. The effects of shearing, ball milling, and ultrasonic and chemical treatments on the dispersing of the carbon nanotubes were studied using SEM, TEM/HRTEM and a Malvern particle size analyser. The resulting microstructures of the agglomerates and the efficiency of the different dispersion methods are discussed. Representative results of annealed CNTs are highlighted. The as-prepared CNT product exists as loose multi-agglomerates, which can be separated by physical methods. Although a concentrated H₂SO₄/HNO₃ (v/v=3:1) treatment is efficient in severing entangled nanotubes to enable their dispersion as individuals, damage to the tube-wall layers is serious and unavoidable. A high temperature annealing (2000 °C, 5 h) before the acid treatment (140 °C, 0.5 h) is recommended and can give well separated nanotubes with a high aspect ratio and 99.9% purity. These highly dispersed CNTs contain few impurities and minimal defects in their tube-bodies and will be of use in further research and applications.     

Pressureless sintering of carbon nanotube–Al2O3 composites

Alumina ceramics reinforced with 1, 3, or 5 vol.% multi-walled carbon nanotubes (CNTs) were densified by pressureless sintering. Commercial CNTs were purified by acid treatment and then dispersed in water at pH 12. The dispersed CNTs were mixed with Al₂O₃ powder, which was also dispersed in water at pH 12. The mixture was freeze dried to prevent segregation by differential sedimentation during solvent evaporation. Cylindrical pellets were formed by uniaxial pressing and then densified by heating in flowing argon. The resulting pellets had relative densities as high as ～99% after sintering at 1500 °C for 2 h. Higher temperatures or longer times resulted in lower densities and weight loss due to degradation of the CNTs by reaction with the Al₂O₃. A CNT/Al₂O₃ composite containing 1 vol.% CNT had a higher flexure strength (～540 MPa) than pure Al₂O₃ densified under similar conditions (～400 MPa). Improved fracture toughness of CNT–Al₂O₃ composites was attributed to CNT pullout. This study has shown, for the first time, that CNT/Al₂O₃ composites can be densified by pressureless sintering without damage to the CNTs.     

Influence of carbon nanotubes on thermal and electrical conductivity of zirconia-based composite

Carbon nanotubes (CNTs) are widely used in ceramic-matrix composites (CMC) as a filler. An individual carbon nanotube exhibits extremely high thermal conductivity, however, the influence of CNTs on the thermal conductivity of CMCs is moderate. In contrast, even a small quantity of CNTs significantly increases the electrical conductivity of CMCs. The present paper studies this contradictory influence for ZrO₂-CNTs composites with 3, 5, 10 and 20 vol% multi-wall carbon nanotubes (MWCNTs). Their thermal and electrical conductivity was studied by the laser flash method and electrochemical impedance spectroscopy. The analysis reveals that the moderate influence of MWCNTs on the thermal conductivity of composites originates from the similar thermal conductivity of MWCNTs in a bundle and zirconia. On the other hand, the substantial difference in the electrical conductivity of MWCNTs and zirconia leads to an exponential increase in the electrical conductivity of the ZrO₂-CNTs composite even with small additions of nanotubes.     

Improving the electrocapacitive properties of mesoporous CMK-5 carbon with carbon nanotubes and nitrogen doping

Nitrogen-containing carbon composite materials composed of mesoporous carbon CMK-5 and carbon nanotubes (CNTs) were prepared by the chemical vapor deposition method with Fe(NO₃)₃-impregnated SBA-15 as template and pyridine as the carbon precursor. The Fe nanoparticles confined in the channels of SBA-15 induced the formation of mesoporous carbon characteristic of CMK-5, whereas Fe particles homogeneously dispersed on the external surface of SBA-15 served as catalysts for CNTs growth. The contents of CNTs, the N doping level and the microstruture of the carbon composite were closely related to the initial Fe/Si atomic ratio in SBA-15 template. Incorporation of CNTs in the composite was found to substantially reduce the electric resistance, leading to the composite materials exhibiting excellent rate-performance. A maximum specific capacitance of 208 F/g and a power density of 10 kW/kg were achieved in 6.0 mol/L KOH aqueous electrolyte when these carbon composites were applied as supercapacitor electrodes. Moreover, the composite electrode also exhibited good electrochemical stability with no capacitance loss after 1000 cycles of galvanostatic charge-discharge process.     

The effect of carbon nanotubes on the rheology and electrical resistivity of polyamide 12/high density polyethylene blends

Different melt mixing sequences were applied to incorporate multiwalled carbon nanotubes (CNTs) into blends prepared from high density polyethylene (PE) and polyamide 12 (PA). Electron microscopy, rheology and electrical resistivity were used to characterize the morphology and microstructure. At a composition of 75PA/25PE, presence of CNT at the interface promoted by premixing the CNTs in the PE phase, resulted in finer phase morphology and a decrease in the resistivity of up to five decades relative to other mixing procedures used. At a composition of 25PA/75PE, premixing the CNT in the PA phase resulted in their segregation inside and around the PA domains and a four decade lower resistivity. Interestingly, compounds that yielded the lowest resistivity were also characterized by increased low frequency melt storage modulus (G′) which indicates the existence of a correlation between the two properties.     

Synthesis and characterization of multi-walled carbon nanotubes reinforced polyamide 6 via in situ polymerization

Polyamide 6 (PA6)/carbon nanotubes (PA6/CNTs) composites have been prepared by in situ polymerization of ε-caprolactam in the presence of pristine and carboxylated multi-walled carbon nanotubes (MWNT and MWNTCOOH). Viscosity measurements show that adding 0.5 wt% of carbon nanotubes (CNTs) does not affect the molecular weight of PA6. Compared with pure PA6, the yield strength of PA6/CNTs composites loaded with 0.5 wt% CNTs is almost unchanged, and the tensile strength is increased slightly. Dynamic mechanical analysis (DMA) demonstrates that both the storage modulus (E′) and glass transition temperature (T_g) of the PA6/CNTs composites increase, particularly for PA6/MWNTCOOH, indicating there is some chemical bonding between PA6 and MWNTCOOH. Scanning electron microscopy (SEM), transmission electron microscopy (TEM) and ultra small-angle X-ray scattering (USAXS) show that MWNT and MWNTCOOH are well dispersed in PA6 matrix. Comparison of the USAXS data with a stiff-rod model and wormlike rod model reveals that the CNTs are quite flexible, regardless the degree of chemical modification. Due to the flexibility of CNTs, mechanical properties of the PA6/CNTs composites are marginally enhanced.     

Effects of polarity and pH on the solubility of acid-treated carbon nanotubes in different media

The aggregation of acid-treated carbon nanotubes (CNTs) as a solid and their solubility in solvents of different polarity and in water of different pH were investigated as a function of acid treatment conditions. The CNTs were found to form solid hydrogen-bonded aggregates, with a higher content of COOH groups resulting in a denser aggregate. The untreated CNTs were non-polar in nature and could dissolve, or be easily dispersed, in non-polar or low polar solvents such as acetone and alcohols (methanol and ethanol), but precipitated from deionized water, a highly polar solvent. In contrast, the acid-treated CNTs dissolved or were well dispersed in the deionized water, but not in acetone or alcohols. The treated CNTs were insoluble in an aqueous solution of pH 0, but soluble in those of pH 4 and higher with their solubility monotonically increasing with pH up to pH 10. The considerable ionic bond strength between carboxylate anions and sodium cations could be a reason for a decrease of their solubility in an aqueous solution of pH 12.     

Selective growth of horizontally-oriented carbon nanotube bridges on patterned silicon wafers by electroless plating Ni catalysts

The main purpose of this research was to develop an Integrated Circuit compatible process to grow the horizontally-oriented carbon nanotubes (CNTs) across the trenches of the patterned Si wafer, which was produced by conventional photolithography technique. The selectivity of the process is based on the difference in electrical conductivity between amorphous silicon (a:Si) and silicon nitride (Si₃N₄), where the catalyst can be much easier deposited by electroless plating on the a:Si part of the pattern. The selectivity is also based on greater chemical reactivity of the catalyst with a:Si to form silicides, instead of with Si₃N₄. Furthermore, the Si₃N₄ barrier layer of the pattern was designed on top of the a:Si layer to guide the growth of CNTs in horizontal direction to bridge the trenches of the pattern. The as-deposited catalysts were examined by Auger electron spectroscopy (AES). The catalyst-coated pattern was pretreated in hydrogen plasma and followed by CNT growth in a microwave plasma chemical vapor deposition (MPCVD) system. The CNT bridges were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), and I–V measurements. Under the present deposition conditions, TEM and HRTEM examinations indicate that the deposited nanostructures are bamboo-like multiwalled carbon nanotubes (MWNTs) with a wall thickness of 2030 graphene layers. Electrical conductivity of the as-deposited MWNTs can be greatly improved by subjecting to 760 °C heat treatment under nitrogen atmosphere. The results demonstrate that the amounts of CNTs and bridges are tunable with the Ni catalyst plating time. Under the present experimental configuration and at a catalyst plating time of 20 s, countable numbers of bridges can be obtained, which are selectively and horizontally grown on the areas of the pattern with Ni catalyst. This process can be a step approaching the application of CNTs in electronic devices.     

Fischer–Tropsch synthesis over cobalt dispersed on carbon nanotubes-based supports and activated carbon

Carbon nanotubes (CNTs) and the ones grown on MgO and alumina are used as supports for cobalt catalyst in Fischer–Tropsch (FT) synthesis. Carbon nanotubes were synthesized by chemical vapor deposition of methane on 5.0 wt.% iron on MgO or alumina at 950 °C. The carbon nanotubes were characterized by SEM and TEM microscopy and Raman spectroscopy. Cobalt nitrate was impregnated onto the supports by impregnation, and the samples were dried and reduced in-situ at 400 °C for 12 h, and then FT synthesis was carried out in a fixed-bed reactor. The catalysts were characterized by BET surface area measurement, TPR and TPD. The effect of carbon nanotubes as cobalt support on CO conversion, product selectivity, and olefin to paraffin ratio of FT synthesis was investigated and compared with activated carbon as well as Al₂O₃, as a traditional support. The results revealed that the activity of the Co/CNT catalyst was improved by 22%, compared to the conventional Co/alumina catalysts. Also the cobalt supported on CNTs grown on MgO (Co/CNT–MgO) shows the highest selectivity to C₅₊ as the most desired FTS products. The C₅₊ selectivity enhancement was about 37, 34, 17, and 77% as compared to the Co/CNT, Co/alumina, Co/CNTs-alumina, and Co/activated carbon, respectively. Also the olefin/paraffin ratio on the Co/CNTs-MgO catalyst is about 7.7 times higher than the conventional cobalt catalysts. It seems that the degree of reduction of cobalt is higher when supported on CNTs than on alumina. This leads to higher FTS activity. Also, the particle size distribution of the cobalt is affected by the CNT–MgO support leading to higher C₅₊ selectivity.     

Preparation and properties of MoSi2 based composites reinforced by carbon nanotubes

Molybdenum disilicide (MoSi₂) based composites with various contents of carbon nanotubes (CNTs) were made by sintering in vacuum at 1500 °C for 1 h. Mechanical properties of these composites at room temperature revealed the addition of CNTs to have good hardening and toughening effect on the matrix. Especially when adding 6.0% CNTs by volume, the hardness and fracture toughness were improved respectively by about 25.3% and 45.7% compared to pure MoSi₂. Phase identification and microstructure of the samples were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HTEM). Multi-walled CNTs were found in the powders synthesized by self-propagating high temperature synthesis (SHS) and SiC phase existed in the sintering samples. Fine grain and the favorable effect of dispersed SiC particles resulted in a high hardness of the CNTs/MoSi₂ composite. The toughening mechanisms for the CNTs/MoSi₂ composites included crack deflection, crack micro-bridging, crack branching, crack bowing and fine-grain pullout.     

Preparation and characterization of carbon nanotube-promoted Co–Cu catalyst for higher alcohol synthesis from syngas

A cobalt–copper catalyst promoted by “herringbone-type” multiwalled carbon nanotubes (CNTs) was developed. This catalyst displayed excellent performance for higher alcohol synthesis (HAS) from syngas, with the (C_2–8-alc. + DME)-STY reached 760 mg/(g·h) under the reaction conditions of 5.0 MPa and 573 K, which was 1.78 times that of the CNT-free host, Co₃Cu₁. The addition of a minor amount of the CNTs to the Co₃Cu₁ host did not cause a marked change in apparent activation energy for the HAS, but led to an increase at the surface of the catalyst of the concentration of catalytically active Co-species, CoO(OH), a kind of surface Co-species related closely to the selective formation of the higher alcohols. Excellent adsorption performance of this kind of CNTs for H₂ generated a surface micro-environment with a high concentration of H-adspecies on the functioning catalyst, thus increasing the rate of surface hydrogenation reactions in the HAS. Moreover, synergistic action of the high surface-concentration H-adspecies with CO₂ in the feed-gas led to a greater inhibition for the WGS side-reaction. All these factors contribute considerably to an increase in the yield of alcohols.     

Nanocomposite films of poly(vinylidene fluoride) filled with polyvinylpyrrolidone‐coated multiwalled carbon nanotubes: Enhancement of β‐polymorph formation and tensile properties

To improve interactions between carbon nanotubes (CNTs) and poly(vinylidene fluoride) (PVDF) matrix, multiwalled CNTs (MWCNTs) were successfully coated with amphiphilic polyvinylpyrrolidone (PVP) using an ultrasonication treatment performed in aqueous solution. It was found that PVP chains could be attached noncovalently onto the nanotubes' surface, enabling a stable dispersion of MWCNTs in both water and N,N‐dimethylformamide. PVP‐coated MWCNTs/PVDF nanocomposite films were prepared by a solution casting method. The strong specific dipolar interaction between the PVP's carbonyl group (C?O) and the PVDF's fluorine group C?F₂ results in high compatibility between PVP and PVDF, helping PVP‐coated MWCNTs to be homogenously dispersed within PVDF. Fourier transform infrared and X‐ray diffraction characterization revealed that the as‐prepared nanocomposite PVDF films exhibit a purely β‐polymorph even at a very low content of PVP‐wrapped MWCNTs (0.1 wt%) while this phase is totally absent in the corresponding unmodified MWCNTs/PVDF nanocomposites. A possible mechanism of β‐phase formation in PVP‐coated MWCNTs/PVDF nanocomposites has been discussed. Furthermore, the tensile properties of PVDF nanocomposites as function of the content in PVP‐coated MWCNTs were also studied. Results shows that the addition of 2.0 wt% of PVP‐coated MWCNTs lead to a 168% increase in Young's modulus and a 120% in tensile strength. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers