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.     

Carbon nanotube/boehmite-derived alumina ceramics obtained by hydrothermal synthesis and spark plasma sintering (SPS)

Preparation, structure and properties of hydrothermally treated carbon nanotube/boehmite (CNT/γ-AlOOH) and densification with spark plasma sintering of Al₂O₃ and CNT/Al₂O₃ nanocomposites were investigated. Hydrothermal synthesis was employed to produce CNT/boehmite from an aluminum acetate (Al(OH)(C₂H₃O₂)₂) and multiwall-CNTs mixture (200 °C/2 h.). TEM observations revealed that the size of the cubic shape boehmite particles lies around 40 nm and the presence of the interaction between surface functionalized CNTs and boehmite particles acts to form ‘nanocomposite particles’. Al₂O₃ and CNT/Al₂O₃ compact bodies were formed by means of spark plasma sintering (SPS) at 1600 °C for 5 min using an applied pressure of 50MPa resulting in the formation of stable α-Al₂O₃ phase and CNT–alumina compacts with nearly full density. It was also found that CNTs tend to locate along the alumina grain boundaries and therefore inhibit the grain coarsening and cause inter-granular fracture mode. The DC conductivity measurements reveal that the DC conductivity of CNT/Al₂O₃ is 10^?4 S/m which indicate that there is a 4 orders of magnitude increase in conductivity compared to monolithic Al₂O₃. The results of the microhardness tests indicate a slight increase in hardness for CNT/Al₂O₃ (28.35 GPa for Al₂O₃ and 28.57 GPa for CNT/Al₂O₃).     

Enhanced production of benzyl alcohol in the gas phase continuous hydrogenation of benzaldehyde over Au/Al2O3

Exclusive hydrogenation of benzaldehyde to benzyl alcohol in gas phase continuous operation (393–413 K, 1 atm) was achieved over Au/Al₂O₃, Au/TiO₂ and Au/ZrO₂. Synthesis of Au/Al₂O₃ by deposition–precipitation generated a narrower distribution (2–8 nm) of smaller (mean = 4.3 nm) Au particles relative to impregnation (1–21 nm, mean = 7.9 nm) with increased H₂ uptake under reaction conditions and higher benzaldehyde turnover. Switching reactant carrier from ethanol to water resulted in a significant enhancement of selective hydrogenation rate over Au/Al₂O₃ with 100% benzyl alcohol yield, attributed to increased available reactive hydrogen. This response extends to reaction over Au/TiO₂ and Au/ZrO₂.     

Single stage production of carbon nanotubes using microwave technology

Carbon nanotubes (CNTs) were produced by gas phase single stage tubular microwave chemical vapor deposition (TM–CVD) using ferrocene as a catalyst and acetylene (C₂H₂) and hydrogen (H₂) as precursor gasses. The effect of the process parameters such as microwave power, radiation time, and gas ratio of C₂H₂/H₂ was investigated. The CNTs were characterized using scanning and transmission electron microscopy (TEM), and by thermogravimetric analysis (TGA). Results reveal that the optimized conditions for CNT production were 900 W reaction power, 35 min radiation time, and 0.6 gas ratio of C₂H₂/H₂. TEM analyses revealed that the uniformly dispersed vertical alignment of multiwall carbon nanotubes (MWCNTs) have diameters ranging from 16 to 23 nm. The TGA analysis showed that the purity of CNT produced was 98%.     

The effect of TiO2 particle size on the characteristics of Au–Pd/TiO2 catalysts

The nanocrystalline TiO₂ materials with average crystallite sizes of 9 and 15 nm were synthesized by the solvothermal method and employed as the supports for preparation of bimetallic Au/Pd/TiO₂ catalysts. The average size of Au–Pd alloy particles increased slightly from sub-nano (< 1 nm) to 2–3 nm with increasing TiO₂ crystallite size from 9 to 15 nm. The catalyst performances were evaluated in the liquid-phase selective hydrogenation of 1-heptyne under mild reaction conditions (H₂ 1 bar, 30 °C). The exertion of electronic modification of Pd by Au–Pd alloy formation depended on the TiO₂ crystallite size in which it was more pronounced for Au/Pd on the larger TiO₂ (15 nm) than on the smaller one (9 nm), resulting in higher hydrogenation activity and lower selectivity to 1-heptene on the former catalyst.     

Suppression of resist contamination during photolithography on carbon nanomaterials by a sacrificial layer

To suppress photoresist residues on carbon nanotubes (CNTs) resulting from photolithography, CNTs are covered by a sacrificial layer during photolithography. Using aluminum oxide (Al₂O₃) deposited by low temperature atomic layer deposition as the sacrificial layer, the fabricated suspended CNT field-effect transistors exhibit low on-state resistances as low as 91 kΩ and low gate hysteresis of 0.5 V in ambient air. The effectiveness of this technique in suppressing residues on CNTs was affirmed by atomic force microscopy, scanning electron microcopy, and micro Raman spectroscopy. The etchants of Al₂O₃, hydrofluoric acid and phosphoric acid, were found not to cause defects in CNTs while removing the sacrificial Al₂O₃ layer. With the protection of the Al₂O₃ layer, oxygen plasma ashing can be performed without causing further defects in CNTs, and the minimum thickness was determined to be between 9 nm and 17 nm. This simple and effective approach can be easily implemented in different resist-based lithography processes to fabricate carbon nano-devices that are free of resist residues.     

The effect of carbon nanotubes on the sintering behaviour of zirconia

The sintering behaviour and activation energy of Y₂O₃ partially stabilised ZrO₂ and ZrO₂–CNT (0.5 and 2 vol%) composites was determined using spark plasma sintering (SPS) under isothermal conditions. The sintering activation energy for the Y₂O₃ partially stabilised ZrO₂ was found to be 456 kJ/mol. The addition of 2 vol% CNTs reduced the sintering activation energy to 172 kJ/mol. The significant reduction of the activation energy with the addition of only 2 vol% CNTs is attributed to the formation of a percolating network of CNTs providing a lower energy diffusion pathway. The sintering mechanism was found to be grain boundary diffusion for all samples suggesting that the presence of CNTs does not change the sintering mechanism but does lower the activation energy for the rate limiting step in the sintering process.     

Co-production of hydrogen and multi-wall carbon nanotubes from ethanol decomposition over Fe/Al2O3 catalysts

The co-production of hydrogen and carbon nanotubes (CNTs) from the decomposition of ethanol over Fe/Al₂O₃ at different temperatures and feeding rates of ethanol was investigated systematically. The results indicated that Fe/Al₂O₃ was a quite active catalyst for the co-production of hydrogen and CNTs and that its activity and stability depended strongly on the Fe loading. Among all catalysts tested, 10 mol% Fe/Al₂O₃ was the most effective catalyst based on the ratio of hydrogen production, the total H₂ yield, and the quality of the CNTs formed. The efficiency of hydrogen production from ethanol decomposition over 10 mol% Fe/Al₂O₃ reached a maximum of ∼80% at 800 °C and the yield of CNTs with well-oriented growth and uniform diameter was 141%. In addition, the reaction of hydrogen and CNTs co-produced from ethanol decomposition was proposed.     

Carbon nanotube/carbon nanofiber growth from industrial by-product gases on low- and high-alloy steels

The growth of carbon nanotubes (CNTs) on sheet metal surfaces (including low- and high-alloyed steel and Ni-plated steel) has been explored using a mixture of CO, CO₂, and H₂ as the precursor feedstock in a thermal chemical vapor deposition process. The influence of various experimental parameters such as the reactor temperature, reaction time, and precursor composition on the yield, purity, and dimensions of the CNTs has been elucidated. Addition of CO₂ during CNT growth leads to higher carbon deposition rates, especially for low- and high-alloyed steel. The diameters of the obtained CNTs range from 12 to 300 nm at carbon deposition rates of ～0.3 mg cm^?2 min^?1. The CNTs are observed to be uniformly distributed and adhered firmly to the substrates. The experimental conditions for CNT growth on sheet metal surfaces are very similar to concentrations and temperatures of a typical effluent stream of the steel industry. This process thus holds potential to harness waste gases to fabricate CNT-based coatings that impart added functionality to sheet metals, while further reducing the carbon footprint of steel plants.     

Simple fabrication of strongly coupled cobalt ferrite/carbon nanotube composite based on deoxygenation for improving lithium storage

An easy method to synthesize a strongly coupled cobalt ferrite/carbon nanotube (CoFe₂O₄/CNT) composite with oxygen bridges between CoFe₂O₄ and reduced carbon nanotubes (CNTs) by calcining the precursor material was reported. The precursor was prepared by an electrostatic self-assembly of the exfoliated Co(II)Fe(II)Fe(III)-layered double hydroxide (CoFeFe-LDH) nanosheets and acid treated CNTs. The deoxygenation effect of ferrous ion (Fe²⁺) in CoFeFe-LDH nanosheets on the oxygen-containing groups of acid treated CNTs was investigated by X-ray photoelectron spectroscopy (XPS) measurement. After thermal conversion, the obtained CoFe₂O₄ was bonded to the reduced CNTs through Metal–O–C (oxygen bridge), which was characterized by XPS, Fourier transform infrared spectroscopy, and Raman spectroscopy. When applied as an anode for lithium-ion battery, the CoFe₂O₄/CNT composite exhibited a low resistance of charge transfer and Li-ion diffusion, good cycle performance, and high rate capability. At a lower current density of 0.15 A·g⁻¹, a specific discharge capacity of 910 mA·h·g⁻¹ was achieved up to 50 cycles. When current density was increased to 8.8 A·g⁻¹, the CoFe₂O₄/CNT composite still delivered 500 mA·h·g⁻¹.     

Chemical oxidation of residual carbon from ZnAl2O4 powders prepared by combustion synthesis

The removal of carbon residue from ZnAl₂O₄ nanopowders by annealing at 500–800 °C leads to a decrease of specific surface area from 228.1 m²/g to 47.6 m²/g. At the same time, the average crystallite size increased from 5.1 nm to 14.9 nm. In order to overcome these drawbacks, a new solution for removing the carbon residue has been suggested: chemical oxidation using hydrogen peroxide. In terms of carbon removal, a H₂O₂ treatment for 8 h at 107 °C proved to be equivalent to a heat treatment of 1 h at 600 °C. The benefits of chemical oxidation over thermal oxidation were obvious. The specific surface area was much larger (188.1 m²/g) in the case of the powder treated with H₂O₂. The average crystallite size (5.8 nm) of ZnAl₂O₄ powder treated with H₂O₂ was smaller than the crystallite size (8.2 nm) of the ZnAl₂O₄ powder annealed at 600 °C.     

Thermal transport phenomena and limitations in heterogeneous polymer composites containing carbon nanotubes and inorganic nanoparticles

An Off-Lattice Monte Carlo model was developed to investigate effective thermal conductivities (K_eff) and thermal transport limitations of polymer composites containing carbon nanotubes (CNTs) and inorganic nanoparticles. The simulation results agree with experimental data for poly(ether ether ketone) (PEEK) with inclusions of CNTs and tungsten disulfide (WS₂) nanoparticles. The developed model can predict the thermal conductivities of multiphase composite systems more accurately than previous models by taking into account interfacial thermal resistance (R_bd) between the nanofillers and the polymer matrix, and the nanofiller orientation and morphology. The effects of (i) R_bd of CNT–PEEK and WS₂–PEEK (0.0232–115.8 × 10⁻⁸ m²K/W), (ii) CNT concentration (0.1–0.5 wt%), (iii) CNT morphology (aspect ratio of 50–450, and diameter of 2–8 nm), and (iv) CNT orientation (parallel, random and perpendicular to the heat flux) on K_eff of a multi-phase composite are quantified. The simulation results show that K_eff of multiphase composites increases when the CNT concentration increases, and when the R_bd of CNT–PEEK and WS₂–PEEK interfaces decrease. The thermal conductivity of composites with CNTs parallel to the heat flux can be enhanced ∼2.7 times relative to that of composites with randomly-dispersed CNTs. CNTs with larger aspect ratio and smaller diameter can significantly improve the thermal conductivity of a multiphase polymer composite.     

Thermodynamics and regeneration studies of CO2 adsorption on multiwalled carbon nanotubes

Multiwalled carbon nanotubes (CNTs) were fabricated and modified by 3-aminopropyl-triethoxysilane (APTS) solutions to study thermodynamics and regeneration of CO₂ adsorption from gas streams. The CO₂ adsorption capacities of CNTs and CNT(APTS) decreased with temperature indicating the exothermic nature of adsorption process while the thermodynamic analysis gave low isosteric heats of adsorption, which are typical for physical adsorption. The cyclic CO₂ adsorption on CNT(APTS) showed that the adsorbed CO₂ could be effectively desorbed via thermal treatment at 120 °C for 25 min while the adsorbed CO₂ due to physical interaction could be effectively desorbed via vacuum suction at 0.145 atm for 30 min. If a combination of thermal and vacuum desorption was conducted at 120 °C and 0.145 atm, the time for effectively desorbing CO₂ could be further shortened to 5 min. The adsorption capacities and the physicochemical properties of CNT(APTS) were preserved during 20 cycles of adsorption and regeneration. These results suggest that the CNT(APTS) can be stably employed in prolonged cyclic operation and they are thus possibly cost-effective sorbents for CO₂ capture from flue gases.     

Activity and deactivation of Au/Al2O3 catalyst for low-temperature CO oxidation

Au/Al₂O₃ catalyst was investigated with respect to its activity for low-temperature CO oxidation. The activity changes of the catalyst were examined after separate treatment in the following different atmosphere: (i) O₂ + N₂ + CO; (ii) O₂ + N₂ heated above 100 °C and (iii) O₂ + N₂ + H₂O vapor. The results show that each of the treatments above may deactivate the catalyst to the different degree. The deactivation by CO oxidation is mainly due to the accumulation of carbonate-like species on the catalyst surface. The addition of H₂O vapor may inhibit the deactivation effectively. The removal of hydroxyl groups at active sites during heating may be responsible for the deactivation by thermal treatment. These two kinds of deactivations are reversible. The irreversible deactivation by H₂O vapor treatment is mainly caused by the growth of gold particles size.     

High performance electrochemical H2O2 sensor based on MWCNT thin films fabricated by novel electron beam evaporation

High quality multi-walled carbon nanotubes (MWCNT) were grown by electron beam evaporation (EBE) under a high vacuum of 10⁻⁶ mtorr. The influence of deposition thickness on the orientation, morphology and vibrational bands of MWCNT films fabricated on tantalum (Ta) substrate was discussed. XRD patterns of the film revealed the presence of (002) preferential plane of carbon. Raman spectral analysis show the G-band Raman feature corresponding to high frequency E₂g of first order mode, suggesting that CNTs were composed of crystalline carbon. SEM image of 200 nm thick MWCNT film shows well shaped homogenous fine nanotubes of length ~300 nm and diameter ~70 nm with high purity. The electrochemical performance of the MWCNTs/Ta electrodes was studied by cyclic voltammetry. The sensor prepared with optimum thickness can detect H₂O₂ in the wide range covering 5 µM to 0.025 mM, with the detection limit as low as 0.09 µM. The results demonstrate that the fabrication of MWCNTs/Ta electrode by EBE is a very interesting and useful approach, likely to be a focus of upcoming research efforts in electrochemical sensing.     

Enhanced field emission properties from titanium-coated carbon nanotubes

The effect of titanium (Ti) coating over the surface of carbon nanotubes (CNTs) on field emission characteristics was investigated. Vertically aligned CNTs were grown by inductively-coupled plasma-enhanced chemical vapor deposition (ICP-CVD). In order to reduce the screening effect of electric field due to densely packed CNTs, as-grown CNTs were partly etched back by DC plasma of N₂. Ti with various thicknesses from 5 nm to 150 nm was coated on CNTs by a sputtering method. Since thick Ti coating with thickness of 100 nm or more resulted in the shape of a metal post by merging an individual CNT in a bundle, it was inadequate to a field emission application. On the other hand, thin Ti-coated CNTs with thickness of 10 nm or less showed a lower turn-on field, a higher emission current density, and improved emission uniformity compared with pristine CNTs. The improved emission performance was mainly attributed to the low work function of Ti and the reliable and lower resistance contact between CNTs and substrates.     

Effect of particle size,heating rate and CNT addition on densification,microstructure and mechanical properties of B4C ceramics

Monolithic B₄C ceramics and B₄C–CNT composites were prepared by spark plasma sintering (SPS). The influence of particle size, heating rate, and CNT addition on sintering behavior, microstructure and mechanical properties were studied. Two different B₄C powders were used to examine the effect of particle size. The effect of heating rate on monolithic B₄C was investigated by applying three different heating rates (75, 150 and 225 °C/min). Moreover, in order to evaluate the effect of CNT addition, B₄C–CNT (0.5–3 mass%) composites were also produced. Fully dense monolithic B₄C ceramics were obtained by using heating rate of 75 °C/min. Vickers hardness value increased with increasing CNT content, and B₄C–CNT composite with 3 mass% CNTs had the highest hardness value of 32.8 GPa. Addition of CNTs and increase in heating rate had a positive effect on the fracture toughness and the highest fracture toughness value, 5.9 MPa m^1/2, was achieved in composite with 3 mass% CNTs.     

Hierarchical carbon nanotube membrane with high packing density and tunable porous structure for high voltage supercapacitors

We reported the fabrication of a hierarchical carbon nanotube (CNT) membrane by using the 90% granulated double- or triple-walled CNTs and 10% 100 μm long multiwalled CNTs as the linker. The membrane with packing density of 420 kg/m³, excellent electrical conductance and good mechanical strength, functioned as both the electrode and current collector and allowed the weight ratio of CNTs increased up to 45–50% based on the weight of CNT, electrolyte and separator. The granulated double or triple walled CNTs, by the aggregation at high temperature etching using CO₂, simultaneously exhibited high surface area and tunable pore structure and high pore volume, and were favorable for the ion transport of organic electrolyte, due to the effect of opening cap or side wall by the CO₂. The CNT membrane electrode, exhibited the capacitance of 57.9 F/g and the energy density of 35 W h/kg, as operated at 4 V.     

The performance of CNT as catalyst support on CO oxidation at low temperature

A carbon nanotube (CNT) was used as catalyst support impregnated with transition metal cobalt for CO oxidation at low temperature. Catalyst properties were analyzed by X-ray powder diffractometer (XRD), X-ray photoelectron spectrometer (XPS), and transmission electron microscope (TEM). Analytical results for TEM and XRD demonstrated that cobalt particles were highly dispersed on the carbon nanotube (20–30 nm) with nanosized cobalt particles (10–15 nm). These investigations indicated that Co/CNT generates about 99% of the high activity for CO conversion at 250 °C and thermally stability that is superior to Co/activated carbon (AC). The optimum reaction conditions for CO conversion were O₂ concentration 3%, operation temperature 250 °C, CO concentration 5000 ppm, and space velocity 156,000 h⁻¹. At 250 °C, CO may act as a reductant for NO reduction over Co/CNT in the presence of oxygen, whereas CO/NO = 2.5 showed that maximum NO reduction was 30%. Under H₂ rich conditions, the optimum reaction temperature for CO conversion was under 300 °C, and performance of CO₂ selectivity was better at 200 °C than 250 °C as the oxygen concentration increased.     

Optimization of carbamazepine removal in O3/UV/H2O2 system using a response surface methodology with central composite design

This study used an ozone/ultraviolet/hydrogen peroxide (O₃/UV/H₂O₂) system to remove carbamazepine (CBZ) from water using a second-order response surface methodology (RSM) experiment with a five-level full-factorial central composite design (CCD) for optimization. The effects of both the primary and secondary interactions of the photocatalytic reaction variables, including O₃ concentration (X₁), H₂O₂ concentration (X₂), and UV intensity (X₃), were examined. The O₃ concentration significantly influenced CBZ and total organic carbon (TOC) removal as well as total inorganic nitrogen ion production (T-N) (p < 0.001). However, CBZ, TOC removal, and T-N production were enhanced with increasing O₃ and H₂O₂ concentrations up to certain levels, and further increases in O₃ and H₂O₂ resulted in adverse effects due to hydroxyl radical scavenging by higher oxidant and catalyst concentrations. UV intensity had the most significant effect on T-N production (p < 0.001). Complete removal of CBZ was achieved after 5 min. However, only 34.04% of the TOC and 36.99% of T-N were removed under optimal concentrations, indicating formation of intermediate products during CBZ degradation. The optimal ratio of O₃ (mg L^? 1): H₂O₂ (mg L^? 1): UV (mW cm^? 2) were 0.91:5.52:2.98 for CBZ removal, 0.7:18.93:12.67 for TOC removal, and 0.94: 4.85:9.03 for T-N production, respectively.