The role of the gas species on the formation of carbon nanotubes during thermal chemical vapour deposition

In this paper, we investigate the several roles that hydrogen plays in the catalytic growth of carbon nanotubes from the point of view of gas species, catalyst activation and subsequent interaction with the carbon nanotubes. Carbon nanotubes and nanofibres were grown by thermal chemical vapour deposition, using methane and a mixture of hydrogen and helium, for a range of growth temperatures and pre-treatment procedures. Long, straight carbon nanotubes were obtained at 900?°C, and although the growth yield increases with the growth temperature, the growth shifts from nanotubes to nanofibres. By introducing a helium purge as part of the pre-treatment procedure, we change the gas chemistry by altering the hydrogen concentration in the initial reaction stage. This simple change in the process resulted in a clear difference in the yield and the structure of the carbon nanofibres produced. We find that the hydrogen concentration in the initial reaction stage significantly affects the morphology of carbon fibres. Although hydrogen keeps the catalyst activated and increases the yield, it prevents the formation of graphitic nanotubes.     

Chlorinated crosslinked adsorbents

High crosslinked copolymers based on poly(ethylstyrene-co-divinylbenzene), bead shaped, have chlorinated, resulting in adsorbents with a high content of chlorine (45.0% Cl). The chlorination process of the copolymer beads (0.40–0.80 mm in diameter) was carried out in 1,2-dichloroethane in the presence of a Friedel–Crafts catalyst (AlCl₃, FeCl₃), at 5–40°C, yielding yellow beads without any cracks and good mechanical strength. The chlorination degree of the samples is high because each vinyl aromatic unit contains 1.8–2.2 chlorine atoms. The chlorinated copolymer samples were used to retain Cephalosporine C from standard solutions comparatively with commercial adsorbents (Amberlite XAD-4 Rohm, Haas Co.; SP-206/7, Mitsubishi Kasai Corp., Japan). © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1579–1587, 1998     

Development of a stability intelligent control system for turning

This paper presents a stability control system based on a new strategy, with application in turning. It works by permanent assessment of the system operating point position relative to the stability limit, and process parameter permanent, in-process modification such as this point is always placed in the stable domain zone that gives the highest process performance. In the case of turning, here approached: (1) this zone is the stability limit proximity; (2) the system operating point position is determined by assessing a cutting force monitored signal feature; and (3) this position is changed by modifying the cutting edge setting angle, the feed rate, and the cutting speed, as it follows: when the risk of overpassing the stability limit is imminent, the setting angle is increased, followed by a feed rate diminishing and then by a worked piece rotation speed reduction, while immediately after surpassing the risk, the three variables modification is reversed, this way the chatter onset being permanently avoided and the performance kept in every moment at the highest possible level. The system was experimentally implemented on a transversal lathe. The results of tests on dedicatedly designed specimens are showing a machining productivity significant increase, in conditions of a stable cutting process. The system is simple, and it can be easily added to the existing CNC machine tools, without important modifications.     

Heavy Metal Removal and Neutralization of Acid Mine Waste Water ‐ Kinetic Study

The influence of the apatite on the efficiency of neutralization and on heavy metal removal of acid mine waste water has been studied. The analysis of the treated waste water samples with apatite has shown an advanced purification, the concentration of the heavy metals after the treatment of the waste water with apatite being 25 to 1000 times less than the Maximum Concentration Limits admitted by European Norms (NTPA 001/2005). In order to establish the macro‐kinetic mechanism in the neutralization process, the activation energy, Ea, and the kinetic parameters, rate coefficient of reaction, k_r, and k_t were determined from the experimental results obtained in “ceramic ball‐mill” reactor. The obtained values of the activation energy Ea >> 42 kJ mol^?1 (e.g. Ea = 115.50 ± 7.50 kJ mol^?1 for a conversion of sulphuric acid η_H2SO4 = 0.05, Ea = 60.90 ± 9.50 kJ mol^?1 for η ^H2SO4 = 0.10 and Ea = 55.75 ± 10.45 kJ mol^‐1 for η ^H2SO4 = 0.15) suggest that up to a conversion of H2SO4 equal 0.15 the global process is controlled by the transformation process, adsorption followed by reaction, which means surface‐controlled reactions. At a conversion of sulphuric acid η ^H2SO4 > 0.15, the obtained values of activation energy Ea < 42 kJ mol^‐1 (e.g. Ea = 37.55 ± 4.05 kJ mol^‐1 for η ^H2SO4 = 0.2, Ea = 37.54 ± 2.54 kJ mol^‐1 for η ^H2SO4 = 0.3 and Ea = 37.44 ± 2.90 kJ mol^‐1 for η ^H2SO4 = 0.4) indicate diffusion‐controlled processes. This means a combined process model, which involves the transfer in the liquid phase followed by the chemical reaction at the surface of the solid. Kinetic parameters as rate coefficient of reaction, kr with values ranging from (5.02 ± 1.62) 10‐4 to (8.00 ± 1.55) 10‐4 (s^‐1) and transfer coefficient, kt, ranging from (8.40 ± 0.50) 10‐5 to (10.42 ± 0.65) 10‐5 (m s^‐1) were determined.     

Expedient Immobilization of TEMPO by Copper‐Catalyzed Azide‐Alkyne [3+2]‐Cycloaddition onto Polystyrene Resin

TEMPO was readily grafted by copper(I)‐catalyzed azide‐alkyne cycloaddition onto polystyrene. Starting with commercially available Merrifield resin (4.3 mmol/ g) almost quantitative loading of TEMPO onto the polymer was achieved (≥ 4 mmol/ g). The so obtained PS‐CLICK‐TEMPO allowed the oxidation of alcohols to aldehydes with bleach or molecular oxygen as the terminal oxidant with high yields and selectivity in multiple cycles without loss of activity.     

On the preparation of porous crosslinked poly(ethylene dimethacrylate esters): Polymers and copolymers

Macroreticular polymers and copolymers based on poly(ethylene glycol dimethacrylate esters) possessing a permanent porosity (white opaque beads, 40–60% porosity, 354 m²/g, the apparent density less than 1.060 g/mL, etc.) were prepared. The influence of the porogen thermodynamic quality and its weight fraction used in the polymerization mixture on the bead structure was also studied. The porous structure of the matrices was investigated and proved by SEM analyses, the N₂ adsorption (BET) method, etc. The thermal degradation mechanism of the macroreticular beads based on dimethacrylate esters shows that the thermal stability of samples depends on the monomer structure, i.e., the chain length between the two vinyl groups. © 1996 John Wiley & Sons, Inc.     

Controlled growth-reversal of catalytic carbon nanotubes under electron-beam irradiation

The growth of carbon nanotubes from Ni catalysts is reversed and observed in real time in a transmission electron microscope, at room temperature. The Ni catalyst is found to be Ni3C and remains attached to the nanotube throughout the irradiation sequence, indicating that C most likely diffuses on the surface of the catalyst to form nanotubes. We calculate the energy barrier for saturating the Ni3C (2-13) surface with C to be 0.14 eV, thus providing a low-energy surface for the formation of graphene planes.