The formation mechanisms of multi-wall carbon nanotubes over the Ni modified MCM-41 catalysts

Multi-wall carbon nanotubes (MWCNTs) were grown by thermal chemical vapor deposition (thermal CVD) of CH₄ by using Ni-MCM-41 as the catalyst. Methane pyrolysis has been performed in a quartz tube reactor over the catalyst surface to form carbon atoms via dehydrogenation process. The migration and rearrangement of the surface carbon atoms result in the formation of MWCNTs. Transmission electron microscope (TEM) and scanning electron microscope (SEM) were used to determine the morphologies and structures of CNTs, and Raman spectroscopy was exploited to analyze their purity with the relative intensity between the D-band (Disorder band) in the vicinity of 1,350 cm⁻¹ which is characteristic of the sp³ structure and G-band (Graphitic band) in vicinity of 1,580 cm⁻¹ which is characteristic of the sp² structure. In addition, the controlling factors of methane pyrolysis such as the catalyst composition; the reaction temperature, and the methane flow rate on the formation of MWCNTs were investigated to optimize the structure and yield of MWCNTs. SEM/TEM results indicate that the yield of the CNTs increases with increasing Ni concentration in the catalyst. The optimized reaction temperature to grow CNT is located between 640 and 670 °C. The uniform and narrow diameter MWCNTs form at lower flow rate of methane (∼30 sccm), and non-uniform in diameter and disorder structure of MWCNTs are observed at higher flow rate of methane. This is consistent with Raman analysis that the relative intensity of I _D/I _G increases with increasing methane flow rate. The formation mechanisms of the MWCNTs on the Ni-MCM-41 catalyst have been determined to be a Tip-Growth mode with a nanoscale catalyst particle capsulated in the tip of the CNT.     

Preparation and thermal properties of multiwalled carbon nanotube/polybenzoxazine nanocomposites

In this study, we prepared nanocomposites comprising multiwalled carbon nanotubes (MWCNTs) and polybenzoxazine (PBZ). The MWCNTs were purified through microwave digestion to remove most of the amorphous carbon and metal impurities. After purification, MWCNTs were treated with H₂SO₄/HNO₃ (3 : 1) to introduce hydroxyl and carboxyl groups onto their surfaces. Raman spectroscopy revealed the percentage of nanotube content improved after prolonged microwave treatment, as evidenced by the decrease in the ratio of the D (1328 cm^?1) and G (1583 cm^?1) bands. For the untreated MWCNTs, the I_D/I_G ratio was 0.56. After microwave treatment for 40 min, the value decreased to 0.29, indicating that the percentage of nanotube content improved. Dynamic mechanical analyses (DMAs) revealed that the storage moduli and the T_gs of the MWCNTs/PBZ nanocomposites were higher than that of the pristine PBZ. This is due to the nanometer‐scale MWCNTs restricting the motion of the macromolecular chains in the nanocomposites. Transmission electron microscopy (TEM) image revealed that the MWCNTs were well dispersed within the PBZ matrix on the nanoscale when the MWCNT content was less than 2.0 phr. The coefficient of thermal expansion (CTE) of the nanocomposites decreased on increasing the MWCNTs content. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

A simplified mathematical modeling for thermo-catalytic decomposition of methane over carbon black catalyst in a fluidized bed reactor

A mathematical model for thermo-catalytic decomposition of methane over carbon black catalysts in a fluidized bed was proposed. The simplified isothermal, uniform flow model was considered and implemented into a computer code to predict the reactor performance. The experiment of methane decomposition into hydrogen and carbon was carried out in a fluidized bed of I.D of 0.055 m and height of 1.0 m. The range of reaction temperature was 850–900 °C, gas velocity was 1.0–3.0 U _mf , and catalyst loading was 50–200 g. The reaction parameters for model equation were determined from the curve fittings and the comparison of experimental data with simulation results showed good agreement for fluidized bed reactor system. From the simulation results, the fluidized bed performance with different operating conditions were obtained, and this simple model can be used to predict the performance of a larger scale fluidized bed reactor and also in determining the optimum operating conditions.     

Parameter setting on growth of carbon nanotubes over transition metal/alumina catalysts in a fluidized bed reactor

This work investigates the synthesis of multilayered carbon nanotubes (CNTs) using the catalytic decomposition of acetylene at 700-850 °C over Fe- and Ni-supported Al₂O₃ catalysts in a fluidized bed reactor. Thermogravimetric analysis showed that the CNTs grown in a fluidized bed reactor have better thermal stability and higher production yield, compared to that in a fixed bed reactor. The CNT production yield increased with the growth temperature, and Fe-catalyst exhibited greater activity than Ni-catalyst in the formation of CNTs. According to Arrhenius plots, the apparent activation energies for the growth of CNTs were estimated to be 25.6 kJ/mol for Fe-catalyst and 65.6 kJ/mol for Ni-catalyst. The as-grown CNT products were characterized by high-resolution transmission electron spectroscopy, N₂ physisorption, Raman spectroscopy, and X-ray diffraction. After purification, the CNT products were of the multilayered type, which were composed of perfect graphene layers. The results of this study demonstrate that the fluidized bed technology favors the large-scale production of CNTs with uniformity and at low cost.     

Pulsed laser heating process of multi-walled carbon nanotubes film

The prepared multi-walled carbon nanotubes (MWCNTs) film was mounted on the holder and the film surface was flashed with a single pulse of Nd:YAG laser (λ = 532 nm) in the air. The dynamics of pulsed nanosecond laser heating process was simulated by the solution of the one-dimensional heat conduction equation. The finite element method (FEM) was applied to solve the equation. At the laser fluence of 1 J/cm² with Nd:YAG laser, the surface reached the maximum temperature 1503 °C at 13 ns. Moreover, the Raman spectroscopy of MWCNTs films before and after irradiation were measured. The intensity of the two characteristic Raman shifts I_D (defect-mode) and I_G (graphite-mode) was measured by the Raman spectroscopy. The maximum surface temperature was calculated and compared with the I_G/I_D ratio of MWCNTs film. The graphitization occurred on the sample after irradiation.     

Hydrogen production by catalytic decomposition of methane over carbon catalysts in a fluidized bed

A fluidized bed reactor made of quartz tube with an I.D. of 0.055 m and a height of 1.0 m was employed for the thermocatalytic decomposition of methane to produce CO₂ — free hydrogen. The fluidized bed was used for continuous withdrawal of the carbon products from the reactor. Two kinds of carbon catalysts — activated carbon and carbon black — were employed in order to compare their catalytic activities for the decomposition of methane in the fluidized bed. The thermocatalytic decomposition of methane was carried out in a temperature range of 800–925°C, using a methane gas velocity of 1.0–3.0 U _mf and an operating pressure of 1.0 atm. Distinctive difference was observed in the catalytic activities of two carbon catalysts. The activated carbon catalyst exhibited higher initial activity which decreased significantly with time. However, the carbon black catalyst exhibited somewhat lower initial activity compared to the activated carbon catalyst, but its activity quickly reached a quasi-steady state and was sustained over time. Surfaces of the carbon catalysts before and after the reaction were observed by SEM. The effect of various operating parameters such as the reaction temperature and the gas velocity on the reaction rate was investigated.     

The Influences of H2 Plasma Pretreatment on the Growth of Vertically Aligned Carbon Nanotubes by Microwave Plasma Chemical Vapor Deposition

The effects of H₂ flow rate during plasma pretreatment on synthesizing the multiwalled carbon nanotubes (MWCNTs) by using the microwave plasma chemical vapor deposition are investigated in this study. A H₂ and CH₄ gas mixture with a 9:1 ratio was used as a precursor for the synthesis of MWCNT on Ni-coated TaN/Si(100) substrates. The structure and composition of Ni catalyst nanoparticles were investigated using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The present findings showed that denser Ni catalyst nanoparticles and more vertically aligned MWCNTs could be effectively achieved at higher flow rates. From Raman results, we found that the intensity ratio of G and D bands (I _D/I _G) decreases with an increasing flow rate. In addition, TEM results suggest that H₂ plasma pretreatment can effectively reduce the amorphous carbon and carbonaceous particles. As a result, the pretreatment plays a crucial role in modifying the obtained MWCNTs structures.     

Effects of Gas Composition on Highly Efficient Surface Modification of Multi-Walled Carbon Nanotubes by Cation Treatment

High incident energy hydrogen and/or oxygen cations are generated by electron cyclotron resonance system, and then used to highly efficiently modify multi-walled carbon nanotubes (MWCNTs). The effects of various H₂/O₂ gas compositions on the modification process are studied. A systematic characterization method utilizing a combination of X-ray photoelectron spectroscopy (XPS), scanning electron microscopy, Raman spectroscopy, and thermogravimetric analysis (TGA) is used to evaluate the effects of various H₂/O₂ gas compositions on MWCNT functionalization. The Raman results show that the I _D/I _G ratio is directly affected by H₂ concentration in gas mixture, and the treatment applying a H₂/O₂ gas mixture with ratio of 40/10 (sccm/sccm) can yield the nanotubes with the highest I _D/I _G ratio (1.27). The XPS results suggest that the gas mixture with ratio of 25/25 (sccm/sccm) is most effective in introducing oxygen-containing functional groups and reducing amorphous carbon. The TGA suggests that the structural change of the treated nanotubes is marginal by this method with any gas condition.     

Multiwalled carbon nanotubes synthesis with high yield utilizing Pt/Al-MCM-41 via catalytic chemical vapour deposition technique

Multiwalled carbon nanotubes (MWNTs) were synthesized over Pt impregnated Al-MCM-41 catalyst by decomposition of acetylene and characterized by XRD and nitrogen sorption isotherm to study the mesophase nature of the material. The optimum temperature and flow rate of the carbon source for CNTs synthesis are 800 °C and 60 mL/min, respectively, within a short reaction period, typically 10 min. Moreover, longer reaction time (i.e. 30 min) favours the formation of more amorphous carbon. When the reaction time is reduced to less than 10 min, formation of amorphous carbon is greatly suppressed by the high yield of MWNTs (85%). The products obtained from the decomposition of acetylene over these catalysts were characterized by TGA, SEM, TEM and Raman spectroscopy. The TEM analysis reveals that CNTs are free from amorphous carbon, whereas Raman spectrum shows two prominent peaks at 1,327 and 1,594 cm⁻¹ as the tangential modes of CNTs. As a conclusion, Pt/Al-MCM-41 is an effective template for MWNTs synthesis using acetylene as a carbon source.     

Synthesis of multi-walled carbon nanotubes on ‘red mud’ catalysts

Red mud, a toxic waste product from bauxite processing, was used as a catalyst for the synthesis of multi-walled carbon nanotubes (MWCNTs) by fluidised bed chemical vapour deposition. The products were analysed using thermogravimetric analysis, Raman spectroscopy, and transmission electron microscopy. Using ethylene at 650 °C a MWCNT yield of 375% (with respect to Fe loading) was obtained. Carbon products were approximately 75% MWCNTs with an I_G/I_D ratio from Raman spectroscopy of 1.43. The production technique and reaction conditions used are conducive to large-scale CNT production, offering a potential value-added commercial use for red mud.     

Resonant Raman studies of tetrahedral amorphous carbon films

Resonant Raman scattering has been used to study the tetrahedral amorphous carbon films deposited by the filtered cathodic vacuum arc technique. The excitation wavelengths were 244, 488, 514 and 633 nm, corresponding to photon energies of 5.08, 2.54, 2.41 and 1.96 eV, respectively. In the visible Raman spectra only vibrational modes of sp²-bonded carbon (G and D peaks) are observed, while a wide peak (called the T peak) can be observed at approximately 1100 cm⁻¹ by UV-Raman spectra which is associated with the vibrational mode of sp³-bonded carbon. Both the position and the width of the G peak decrease almost linearly with increasing excitation wavelength, which is interpreted in terms of the selective ππ* resonant Raman scattering of sp²-bonded carbon clusters with various sizes. The G peak position in the UV-Raman spectra, the T peak position and the intensity ratios of I_D/I_G and I_T/I_G all exhibit maximum or minimum values at the carbon ion energy of 100 eV. The changes of these spectral parameters are discussed and correlated with the sp³ fraction of carbon atoms in the films.     

Characterization of epitaxial GaAs MOS capacitors using atomic layer-deposited TiO2/Al2O3 gate stack: study of Ge auto-doping and p-type Zn doping

Few-wall carbon nanotubes were synthesized by methane/acetylene decomposition over bimetallic Fe-Mo catalyst with MgO (1:8:40) support at the temperature of 900°C. No calcinations and reduction pretreatments were applied to the catalytic powder. The transmission electron microscopy investigation showed that the synthesized carbon nanotubes [CNTs] have high purity and narrow diameter distribution. Raman spectrum showed that the ratio of G to D band line intensities of I _G/I _D is approximately 10, and the peaks in the low frequency range were attributed to the radial breathing mode corresponding to the nanotubes of small diameters. Thermogravimetric analysis data indicated no amorphous carbon phases. Experiments conducted at higher gas pressures showed the increase of CNT yield up to 83%. M?ssbauer spectroscopy, magnetization measurements, X-ray diffraction, high-resolution transmission electron microscopy, and electron diffraction were employed to evaluate the nature of catalyst particles.     

Effects of Ni-catalyst characteristics on the growth of carbon nanowires

Carbon nanowires (CNWs) were grown on amorphous Ni thin film catalysts in a microwave plasma-enhanced chemical vapor deposition system under a methane and hydrogen gas mixture. The resulting CNWs were found to be polycrystalline but not amorphous as commonly found elsewhere. In general, a catalyst could be seen at the tip of each CNW. However, multiple CNWs grown from a single catalyst were also regularly observed. The use of amorphous Ni thin film catalyst also resulted in the formation of an interlayer between the CNWs and the substrate. The appearance of this interlayer, however, depends on the Ni film thickness. The carbon nanowires obtained were found to exhibit an unusual microstructure in that the basal planes were perpendicular to the wire axial direction. The Raman signatures of the CNWs consist of two peaks near 1322 cm⁻¹ (D-band) and 1578 cm⁻¹ (G-band), similar to that of carbon nanotubes. The broadening of the G-band peak was found to be greater than 60 cm⁻¹ and the I_D/I_G ratio was found to decrease with FWHM as in a-C:H.     

A novel catalytic process for cellulose gasification to synthesis gas

The catalytic gasification of cellulose to synthesis gas has been studied under mild conditions in a laboratory scale batch-feeding and fluidized bed reactor using air as a gasifying agent and Ar as a cellulose carrier from the feeder to catalyst bed under atmospheric pressure. Various types of support materials and supported metal catalysts have been investigated in this process. The flow conditions were 60 and 50 cm³ (STP)/min of air and Ar, 2 cm height of the fluidized bed and 0.7 s residence time of volatiles. From this investigation CeO₂ has been found as the best support and Rh/CeO₂ has been found as an excellent catalyst in the cellulose gasification at 823 K, which resulted in 100% C-conversion to gas. The use of Rh/CeO₂ catalyst in the secondary bed resulted in lower yield of CO and H₂.     

Catalytic Steam Reforming of Fast Pyrolysis Bio‐Oil in Fixed Bed and Fluidized Bed Reactors

Catalytic steam reforming of bio‐oil is an economically‐feasible route which produces renewable hydrogen. The Ni/MgO‐La₂O₃‐Al₂O₃ catalyst was prepared with Ni as active agent, Al₂O₃ as support, and MgO and La₂O₃ as promoters. The experiments were conducted in fixed bed and fluidized bed reactors, respectively. Temperature, steam‐to‐carbon mole ratio (S/C), and liquid hourly space velocity (LHSV) were investigated with hydrogen yield as index. For the fluidized bed reactor, maximum hydrogen yield was obtained under temperatures 700–800 °C, S/C 15–20, LHSV 0.5–1.0 h^–1, and the maximum H₂ yield was 75.88 %. The carbon deposition content obtained from the fluidized bed was lower than that from the fixed bed. The maximum H₂ yield obtained in the fluidized bed was 7 % higher than that of the fixed bed. The carbon deposition contents obtained from the fluidized bed was lower than that of the fixed bed at the same reaction temperature.     

SiC surface orientation and Si loss rate effects on epitaxial graphene

We have explored the properties of SiC-based epitaxial graphene grown in a cold wall UHV chamber. The effects of the SiC surface orientation and silicon loss rate were investigated by comparing the characteristics of each formed graphene. Graphene was grown by thermal decomposition on both the silicon (0001) and carbon (000-1) faces of on-axis semi-insulating 6H-SiC with a "face-down" and "face-up" orientations. The thermal gradient, in relation to the silicon flux from the surface, was towards the surface and away from the surface, respectively, in the two configurations. Raman results indicate the disorder characteristics represented by I_D/I_G down to < 0.02 in Si-face samples and < 0.05 in C-faces over the 1 cm² wafer surface grown at 1,450°C. AFM examination shows a better morphology in face-down surfaces. This study suggests that the optimum configuration slows the thermal decomposition and allows the graphene to form near the equilibrium. The Si-face-down orientation (in opposition to the temperature gradient) results in a better combination of low disorder ratio, I_D/I_G, and smooth surface morphology. Mobility of Si-face-down orientation has been measured as high as approximately 1,500 cm²/Vs at room temperature. Additionally, the field effect transistors have been fabricated on both Si-face-down and C-face-down showing an ambipolar behavior with more favorable electron conduction.     

Variations in the microstructure of carbon fibers prepared from liquefied wood during carbonization

After spinning by adding hexamethylenetetramine and the curing treatment, carbon fibers from liquefied wood (LWCFs) were prepared by direct carbonization. Microstructure change of LWCFs during carbonization is studied by X‐ray, Raman spectroscopy, and FTIR. Raman spectroscopy shows both the D peak at 1360 cm^?1 and the G peak at 1595 cm^?1 exist after 600°C, and a significant decrease is found in I_D/I_G during carbonization. X‐ray diffraction shows the crystallite size (L_c(002) and L_a(100)) of LWCFs firstly decreases before 800°C and then increases with heat treatment temperature (HTT) increasing, whereas the interlayer spacing (d₀₀₂) gradually decreases during carbonization. It is also found that the crystallite shape (L_a/L_c) and the degree of graphitization (G) all increase with increasing HTT. It is also found that structure of the precursor fibers from liquefied wood has been completely changed after carbonization. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Expansion characteristics of an anaerobic fluidized bed reactor with internal biogas production

More realistic dynamic bed‐expansion experiments using a three‐phase anaerobic fluidized bed reactor (AFBR) with and without internal biogas production were conducted for the establishment of correlation equations for the mean volume ratio of wakes to bubbles (k). A predictive model was also developed for the expansion characteristics of the three‐phase AFBR with internal biogas production. The predicted bed‐expansion heights (H_GLS) deviated by only ±10% from the experimental measurements for the three‐phase AFBR. According to the modeling results, if a three‐phase AFBR is loaded into a carrier with low specific gravity (dry density of carrier, ρ_md = 1.37 g cm^?3; wet density of carrier, ρ_mw = 1.57 g cm^?3) and operated at a high superficial liquid velocity (u_l = 4.0 cm s^?1), the ratio of H_GLS to H_LS at a high superficial gas velocity (u_g = 1.5 cm s^?1) can reach as high as 271%. A higher fluidized‐bed height has a greater effect on the bed‐expansion behavior because of the decrease in liquid pressure (surrounding gas bubbles) along the fluidized‐bed height. From parametric sensitivity analyses, H_GLS is most sensitive to the parameter reactor width (X), especially within a small ΔX/X₀ range of ±10%; sensitive to ρ_mw, diameter of the carrier, ρ_md and total mass of carrier and least sensitive to u_l, biofilm thickness and u_g. Copyright © 2005 Society of Chemical Industry     

Fluidization and coating of very dense powders by Fluidized Bed Chemical Vapour Deposition

The hydrodynamic behaviour of a very dense tungsten powder, 75 μm in median diameter and 19,300 kg/m³ in grain density, has been studied in a fluidized bed at room temperature using nitrogen and argon as carrier gas. Even if fluidization was achieved, the small bed expansion indicated that it was imperfect. Then, the fluidization was studied at 400 °C in order to investigate the feasibility of coating this powder by Fluidized Bed Chemical Vapour Deposition (FBCVD). In particular, the influence of the H₀/D ratio (initial fixed bed height to reactor diameter) on the bed thermal behaviour was analyzed. It appeared that at least 1.5 kg of powder (corresponding to a H₀/D ratio of 1.8) was necessary to obtain an isothermal bed at 400 °C. Finally, first results about alumina coatings on the tungsten powder by FBCVD from aluminium acetylacetonate are detailed. They show that for the quite low temperatures tested, the coatings are uniform on all bed particles and are formed of amorphous carbon containing alumina. This study demonstrates the efficiency to combine fluidization (instead of spouted bed) and CVD to coat such very dense powders.