Fabrication and superhydrophobicity of fluorinated carbon fabrics with micro/nanoscaled two-tier roughness

Superhydrophobic carbon fabric with micro/nanoscaled two-tier roughness was fabricated by decorating carbon nanotubes (CNTs) onto microsized carbon fibers, using a catalytic chemical vapor deposition and subsequent fluorination surface treatment. The superhydrophobic surfaces are based on the regularly ordered carbon fibers (8-10 μm in diameter) that are decorated by CNTs with an average size of 20-40 nm. The contact angle of water significantly increases from 148.2 ± 2.1° to 169.7 ± 2.2° through the introduction of CNTs. This confirms that the wettability of carbon fabric changes from hydrophobicity to superhydrophobicity due to structural transformation. This finding sheds light on how the two-tier roughness surface induces superhydrophobicity of rough surfaces, and how the presence of CNTs reduces the area fraction of a water droplet in contact with the carbon surface with two-tier roughness.     

Vertically aligned carbon nanotube arrays grown on a lamellar catalyst by fluidized bed catalytic chemical vapor deposition

Large amount of vertically aligned carbon nanotube (CNT) arrays were grown among the layers of vermiculite in a fluidized bed reactor. The vermiculite, which was 100-300 μm in diameter and merely 50-100 μm thick, served as catalyst carrier. The Fe/Mo active phase was randomly distributed among the layers of vermiculite. The catalyst shows good fluidization characteristics, and can easily be fluidized in the reactor within a large range of gas velocities. When ethylene is used as carbon source, CNT arrays with a relatively uniform length and CNT diameter can be synthesized. The CNTs in the arrays are with an inner diameter of 3-6 nm, an outer diameter of 7-12 nm, and a length of up to several tens of micrometers. The as-grown CNTs possess good alignment and exhibit a purity of ca. 84%. Unlike CNT arrays grown on a plane or spherical substrate, the CNT arrays grown in the fluidized bed remain their particle morphologies with a size of 50-300 μm and the good fluidization characteristics were preserved accordingly.     

Iron catalyst supported on carbon nanotubes for Fischer-Tropsch synthesis: Effects of Mo promotion

Our studies on the application of carbon nanotubes (CNTs) as support have shown that iron catalysts supported on CNTs are active and selective catalysts for Fischer-Tropsch synthesis (FTS). However, these catalysts experienced deactivation as a result of active site agglomerations. In order to control the agglomeration of active site, which is an important step in developing a novel catalyst supported on carbon-based supports, the effects of Mo promotion on deactivation behavior of iron catalysts supported on CNTs were studied. In this work the properties and catalytic performance of unpromoted iron catalysts were compared with a promoted catalyst with different Mo contents (0.5, 1, 5, and 12 wt%). Based on TEM and XRD analyses, promotion of the catalysts with Mo resulted in production of smaller metal particles compared to the unpromoted iron catalyst. According to XRD analysis, Mo species were deposited in their amorphous structure. TPR analyses showed that addition of Mo increased reduction temperature significantly. Based on TEM and XRD analyses, the particle size of the iron oxides in the unpromoted catalyst increased from 16 to 25 nm under FT operating conditions, while the particle size of the iron oxide in the Mo promoted catalysts (∼12-14 nm) did not change noticeably under the same operating conditions. Activity, selectivity and stability of the unpromoted and Mo promoted catalysts showed that addition of 0.5-1 wt% Mo resulted in a more stable catalyst. Higher contents of Mo (5 and 12 wt%) decreased the activity of the catalysts due to catalytic site coverage and lower extent of reduction. Mo promotion (0.5-12 wt%) increased the selectivity of the catalysts toward lighter hydrocarbons. The promotion of the iron catalyst with 0.5 wt% of Mo stabilized the activity of the catalyst with minimal increase (2%) in methane selectivity.     

Investigation of turbulence modulation in solid–liquid suspensions using parallel competing reactions as probes for micro-mixing efficiency

The Bourne and the Villermaux competitive reaction chemistries were applied to study the effects of suspended particles on the yield of an undesired product and hence to infer their effects on local dissipation rates. Two-phase micro-mixing experiments were carried out in a 1 l stirred vessel, agitated by a pitched-blade turbine, using four particle size ranges: 70–100, 250–300, 700–750 and 1000 μm. Experiments were carried out with up to 1.75 vol% particles in the Bourne scheme and 3 vol% in the Villermaux scheme. Both reaction schemes gave qualitatively similar results, although stronger effects of added particles were obtained with the Bourne chemistry. The effect of 700–750 μm particles could not be distinguished from experimental error, but the other size ranges gave increased by-product yields and suppressed the dissipation rates. These results confirmed earlier two-phase PIV observations: smaller particles (70–100 and 250–300 μm) gave maximum suppression at ∼1 vol%. Above this volume fraction, the level of suppression decreased and in some cases turbulence augmentation occurred, indicating that particle concentration, as well as size, is an important factor.     

Significance of surface moisture removal on triboelectrostatic beneficiation of fly ash

The gas transport, triboelectrostatic beneficiation of coal combustion fly ash into carbon-rich and ash-rich products was studied relative to the effect of ash surface moisture. Increasing the humidity to which the ashes from American and Italian coal-fired utilities were exposed under process and ambient conditions affected carbon and ash separability. The effect of humidity and particle surface moisture became more important as particle size decreased: particles greater than 75 μm in diameter were nearly unaffected whereas particles smaller than 45 μm experienced up to a four-fold change in their separability upon changing their surface moisture contents. Although particle size influences the moisture adsorption, which in turn affects tribocharging, the decrease in adhesive forces between carbon and ash from otherwise intractable clusters during drying also may be a factor influencing triboelectrostatic beneficiation performance.     

Adsorption of lipopolysaccharide on carbon sieves

Adsorption of lipopolysaccharide, LPS, on carbon sieves Carboxen 1003 and Carboxen 1010 has been studied. LPS adsorption kinetics is initially faster on smaller size (1-10 μm) particles of predominantly microporous Carboxen 1010 compared to Carboxen 1003 (150-200 μm) particles. However, the adsorption capacity of micro/meso/macroporous Carboxen 1003 by LPS is higher than that of Carboxen 1010 since the former carbon has wider pores that can accommodate large lipopolysaccharide molecules or their agglomerates. Carboxen 1010 probably adsorbs LPS mainly on the external (macropore) surface.     

Process intensification of particle separation by lift force in arc microchannel with bifurcation

The present study demonstrates a novel hydrodynamic lift force sieving attained in an arc microchannel with a bifurcation at the downstream end. The fluorescent polystyrene particles with diameter of 10 or 20 μm are dispersed in water or NaCl aqueous solutions so that the particles are completely neutrally buoyant, lighter or denser relative to medium. The slurry is fed into the arc microchannel whose radius, width and depth are 20 mm, 200 and 150 μm, respectively. The fluorescent trajectories of flowing particles are recorded at the bifurcation. It is found that the 20-μm particle is sharply focused to an equilibrium position somewhat distant from the outer wall regardless of the given density difference. As a result, all 20-μm particles report to the outer branch of bifurcation. On the other hand, the 10-μm particles dispersed mostly across the channel width are always recovered from the both branches. The results imply that the arc microchannel with a bifurcation will intensify the process of particle separation since the particles completely neutrally buoyant as well as denser and lighter particles can be simultaneously separated or classified without membrane. Finally, a separation process in a series of arc channels is proposed and the process efficiencies are discussed.     

Carbon nanotube growth mechanism switches from tip- to base-growth with decreasing catalyst particle size

The growth of carbon nanotubes by a plasma assisted catalytic chemical vapor deposition was investigated using cobalt, nickel and iron catalyst particles of different sizes. For the three catalysts examined, it was shown that the growth mode switches from “tip-growth” for large particles (>>5 nm) to “base-growth” for smaller ones (<5 nm). While single-walled nanotubes and those with few walls (typically <7 walls) grow from their base, larger multi-walled nanotubes are fed with carbon via their tips which support the catalyst particle. A growth scenario involving two different pathways for carbon diffusion is proposed in order to explain the change in growth mode.     

Colloidal poly(styrene-co-butyl acrylate)/multi-walled carbon nanotubes nanocomposite by heterocoagulation in aqueous media

Colloidal nanocomposite particles were prepared by heterocoagulation of carbon nanotubes (CNTs) dispersion stabilized by cationic hexadecyltrimethylammonium bromide (CTAB) and negatively charged poly(styrene-co-butyl acrylate), P(St-co-BA), latex prepared by conventional emulsion polymerization in aqueous medium with the aid of a flocculant, polyaluminium chloride (PAC), at elevated temperature above the T_g of P(St-co-BA). The hybrid nanocomposite particles were prepared by a simple procedure consisting of mixing two dispersions, particle growth, and stabilization steps. The effects of the surface properties of CNTs, molecular weight of latex polymer, types of flocculants and its optimum concentration were investigated. At a well-controlled condition, the spherical or potato-like particles in the size range of 10-100 μm were achieved. After film formation of the nanocomposite particles, it was able to confirm that CNTs were uniformly distributed without agglomeration in the matrix, resulting in the percolation at a low concentration of CNTs.     

Synthesis of nitrogen-doped horn-shaped carbon nanotubes by reduction of pentachloropyridine with metallic sodium

Nitrogen-doped horn-shaped carbon nanotubes (CNTs) have successfully been prepared by reducing pentachloropyridine with metallic sodium at 350 °C. A typical CNT has an open-end diameter of ∼2 μm, a close-end diameter of ∼0.3 μm, a wall thickness of ∼30 nm, and a length up to 8 μm. TEM observation indicates that the CNTs account for ∼30% of the products, and the rest is solid and hollow carbon nanospheres (CNSs) with a diameter of about 50-290 nm. Elemental analysis shows that the N/C atomic ratio of the carbon nanostructures is about 0.0208. XRD and HRTEM measurements reveal that the CNTs are amorphous. To understand the growth process and refine the growth condition, various control experiments have been finished. At last, a sodium-catalysis-reduction solid-liquid-solid growth mechanism of the CNTs has been suggested on the basis of the experiments.     

Density measurement of size selected multiwalled carbon nanotubes by mobility-mass characterization

We employ a combination of gas phase particle mobility and mass methods to make the first absolute density measurement of gas phase grown carbon nanotubes (CNTs). The approach combines a tandem differential mobility analyzer and aerosol particle mass analyzer in series to achieve two steps of electrical mobility classifications of the CNTs and one of mass classification. In the first mobility classification step a stream of monodisperse catalytic particles was produced by pulsed laser ablation. These mobility-classified catalysts seeded the aerosol growth of CNTs, where were directly passed to a second electrical mobility classification step which allows classification of the diameter-controlled CNTs in length. These diameter- and length-classified CNTs were finally introduced into the aerosol particle mass analyzer to measure their mass distribution. We found that the condensed phase density of CNTs was 1.74 ± 0.16 g/cm³ for two different groups of CNTs with diameters of ∼15 and ∼22 nm. This value is lower (about 3 sigma) than for graphite, and about 1 sigma lower than the average value for density measurements for carbon black.     

Prediction of carbon nanotube growth success by the analysis of carbon-catalyst binary phase diagrams

The growth of carbon nanotubes (CNTs) was attempted using a vapor-phase CVD method, and a wide variety of transition metals, in the form of metallocenes and chlorides, were used as potential growth catalysts. Well-aligned mats of multi-walled carbon nanotubes were observed in samples catalyzed with iron, nickel, and cobalt. Nanotube lengths could be varied between 3 μm and 3 mm, and diameters ranged from 20 nm to 60 nm. X-ray diffraction, energy dispersive X-ray spectroscopy, and Mossbauer spectroscopy were used to determine the compositions of the nanotube products. None of the other elements studied, consisting of Cr, Mn, Zn, Cd, Ti, Zr, La, Cu, V, and Gd, were able to successfully catalyze the growth of CNTs. A study was performed of the respective metal-carbon binary phase diagrams to understand why the catalytic ability of different elements varied. Successful catalysts had carbon solubility limits of 0.5 wt.% to 1.5 wt.% carbon, followed closely by nanotube growth through graphite precipitation. Unsuccessful catalysts were found to have either nearly zero carbon solubility, or to form numerous intermediate carbides, making it difficult for the diffusion required for graphite precipitation to occur. These findings were then used to look for other potential CNT catalysts by examining the phase diagrams of a wide variety of metals.     

Formation of carbon nanotubes through ethylene decomposition over supported Pt catalysts and silica-coated Pt catalysts

Ethylene decomposition was performed over supported Pt catalysts to fabricate composites of Pt metal nanoparticles and carbon nanotubes (CNTs). All supported Pt catalysts (Pt/carbon black, Pt/CNT, Pt/MgO, Pt/Al₂O₃ and Pt/SiO₂) showed catalytic activity for ethylene decomposition at 973 K to form CNTs. Pt metal particles were found at tips of CNTs. These results indicate that Pt metal particles have catalytic activity for growth of CNTs through hydrocarbon decomposition. A broad range (5-50 nm) of CNT diameters were formed from the use of supported Pt metal catalysts although Pt metal particles in the catalysts before ethylene decomposition were relatively uniform in size (2-5 nm). These results imply that Pt metal particles in the catalysts aggregated during ethylene decomposition at 973 K. Aggregation of Pt metal particles in catalysts during ethylene decomposition could be suppressed by covering catalysts with silica layers that were a few nanometers thick. Silica-coated Pt catalysts showed high activity for ethylene decomposition to form CNTs with uniform diameters (8-10 nm) despite the uniform coverage of Pt metal particles with silica layers.     

Enhanced electron emission from functionalized carbon nanotubes with a barium strontium oxide coating produced by magnetron sputtering

Carbon nanotubes (CNTs) were functionalized with a surface coating using magnetron sputter deposition. The CNT samples used were prepared by plasma enhanced chemical vapor deposition and were vertically aligned to the surface of the tungsten substrate. A thin layer of barium strontium oxide approximately 100 nm in thickness was deposited on their surface using magnetron sputtering. The oxide coating was uniform, covering the whole surface of the CNTs and significantly lowered the work function while preserving the geometry. The resulting oxide coated CNTs had a work function of 1.9 eV and a field enhancement factor of 467, which led to a significant improvement in both field and thermionic emission. Compared to uncoated CNTs, the field emission was increased by a factor of two, while the thermionic emission increased by more than four orders of magnitude. At 4.4 V/μm, a field emission current of 23.6 μA was obtained from an emitting surface of 0.012 cm². Similarly, at 1.1 V/μm and 1221 K, a thermionic emission current of 14.6 mA was obtained.     

Preparation of submicron-sized RDX particles by rapid expansion of solution using compressed liquid dimethyl ether

Cyclotrimethylenetrinitramine (RDX) was precipitated to submicron-sized particles with spherical morphology by the rapid expansion from supercritical solution (RESS). Compressed liquid dimethyl ether (DME) was used as a solvent for the RDX. This study examined the influence of extraction temperature (293-333 K), extraction pressure (8-20 MPa) and size of orifice nozzle (50, 100, 200, and 250 μm) on the size and morphology of the RDX particles in the RESS process. The precipitated RDX particles were characterized by using the following instruments: field emission scanning electron microscope (FE-SEM), image analyzer, powder X-ray diffraction (PXRD), Fourier transform infrared (FT-IR) spectroscopy, and differential scanning calorimetry (DSC). The precipitated RDX particles showed granular and spherical morphologies, submicron-sized particles, and narrow particle size distributions. The mean particle size of the precipitated RDX ranged from 2.48 to 0.36 μm, and the crystallinity of the precipitated RDX decreased. The enthalpy change for the exothermic decomposition of the precipitated RDX (ΔH = 714.4 J/g) was much higher than that of the original RDX (ΔH = 381.5 J/g).     

The use of camphor-grown carbon nanotube array as an efficient field emitter

Three-dimensional growth of well-aligned high-purity multiwall carbon nanotubes (CNTs) is achieved on silicon, nickel-coated silicon and cobalt-coated silicon substrates by thermal decomposition of a botanical carbon source, camphor, with different catalyst concentrations. Field emission study of as-grown nanotubes in a parallel-plate diode configuration suggests them to be an efficient emitter with a turn-on field of ∼1 V/μm (for 10 μA/cm²) and a threshold field of ∼4 V/μm (for 10 mA/cm²). Maximum current density lies in a range of 20-30 mA/cm² at 5.6 V/μm with significant reversibility. Prolonged stability test of camphor-grown CNT emitters suggests a life time of ∼5 months under continuous operation. A new feature, metal-assisted electron emission from CNTs, has been addressed. Isolated nanotubes used as a cold cathode in a field emission microscope reveal the pentagonal emission sites and hence the atomic structure of the nanotube tips.     

Field emission properties of carbon nanotubes synthesized by capillary type atmospheric pressure plasma enhanced chemical vapor deposition at low temperature

Carbon nanotubes (CNTs) were grown using a modified atmospheric pressure plasma with NH₃(210 sccm)/N₂(100 sccm)/C₂H₂(150 sccm)/He(8 slm) at low substrate temperatures (?500 °C) and their physical and electrical characteristics were investigated as the application to field emission devices. The grown CNTs were multi-wall CNTs (at 450 °C, 15-25 layers of carbon sheets, inner diameter: 10-15 nm, outer diameter: 30-50 nm) and the increase of substrate temperature increased the CNT length and decreased the CNT diameter. The length and diameter of the CNTs grown for 8 min at 500 °C were 8 μm and 40 ± 5 nm, respectively. Also, the defects in the grown CNTs were also decreased with increasing the substrate temperature (The ratio of defect to graphite (I_D/I_G) measured by FT-Raman at 500 °C was 0.882). The turn-on electric field of the CNTs grown at 450 °C was 2.6 V/μm and the electric field at 1 mA/cm² was 3.5 V/μm.     

Computational modelling of the impact of particle size to the heat transfer coefficient between biomass particles and a fluidised bed

The fluid-particle interaction and the impact of different heat transfer conditions on pyrolysis of biomass inside a 150 g/h fluidised bed reactor are modelled. Two different size biomass particles (350 μm and 550 μm in diameter) are injected into the fluidised bed. The different biomass particle sizes result in different heat transfer conditions. This is due to the fact that the 350 μm diameter particle is smaller than the sand particles of the reactor (440 μm), while the 550 μm one is larger. The bed-to-particle heat transfer for both cases is calculated according to the literature. Conductive heat transfer is assumed for the larger biomass particle (550 μm) inside the bed, while biomass-sand contacts for the smaller biomass particle (350 μm) were considered unimportant. The Eulerian approach is used to model the bubbling behaviour of the sand, which is treated as a continuum. Biomass reaction kinetics is modelled according to the literature using a two-stage, semi-global model which takes into account secondary reactions. The particle motion inside the reactor is computed using drag laws, dependent on the local volume fraction of each phase. FLUENT 6.2 has been used as the modelling framework of the simulations with the whole pyrolysis model incorporated in the form of User Defined Function (UDF).     

Synthesis of carbon nanotubes over gold nanoparticle supported catalysts

The synthesis of carbon nanotubes (CNTs) through the catalytic decomposition of acetylene was carried out over gold nanoparticles supported on SiO₂-Al₂O₃. Monodispersed gold nanoparticles with 1.3-1.8 nm in diameter were prepared by the liquid-phase reduction method with dodecanethiol as protective agent. The carbon products formed after acetylene decomposition consist of multi-walled carbon nanotubes with layered graphene sheets, carbon nanofilaments (CNFs), and carbon nanoparticles encapsulating gold particles. The observed CNTs have outer diameters of 13-25 nm under 850 °C. The influence of several reaction parameters, such as kind of carriers, reaction temperature, gas flow rate, was investigated to search for optimum reaction conditions. The CNTs were observed at a relatively low temperature (550 °C). The silica-alumina carrier showed higher activity for the formation of CNTs than others used in the screening test. With increasing temperature, the CNTs showed cured structures having thick diameters and inside compartments. When Au content on the support was over 5 wt.%, the gold nanoparticles coagulated to form large ones >20 nm in diameter and became encapsulated with graphene layers after decomposition of acetylene.     

Pulsed laser deposition-assisted patterning of aligned carbon nanotubes modified by focused laser beam for efficient field emission

Patterned carbon nanotube (CNT) arrays have been synthesized on patterned substrates created via pulsed laser deposition (PLD) of the precursor catalyst films with a mask. Arrays of CNTs in square and hexagonal patterns with tube lengths of 8 μm and 16 μm were created on silicon or quartz substrates, respectively. Using the method of laser cutting, as-grown CNT patterns were pruned by focused He-Ne laser beam. It is found that after pruning, CNTs tend to cluster together and form welded junctions. The comparison of field emission properties of CNTs before and after pruning shows that laser modification of CNT morphologies effectively enhanced the emission currents.