The influence of oxidation with nitric acid on the preparation and properties of active carbon enriched in nitrogen

The effect of oxidation by 20% nitric acid on the properties and performance of active carbons enriched with nitrogen by means of the reaction with urea in the presence of air has been studied. The study has been made on demineralised orthocoking coal and the carbonisates obtained from it at 600 or 700 °C, subjected to the processes of nitrogenation, oxidation and activation with KOH in different sequences. The amount of nitrogen introduced into the carbon with the aid of urea has been found to depend on the stage at which the process of nitrogenation was performed. The process of oxidation of the demineralised coal and the active carbon obtained from the former has been found to favour nitrogen introduction into the carbon structure. In the process of nitrogenation of the carbonisates the amount of nitrogen introduced has inversely depended on the temperature of carbonisation. The modifications of the processes permitted obtaining materials of different textural parameters, different acid-base character of the surface and different iodine sorption capacity.     

HPHT Synthesis of Different Shape Coarse-Grain Diamond Single Crystals

Synthesis of coarse-grain diamond crystals is studied in a China-type SPD6× 1670T cubic high-pressure apparatus with high exact control system. To synthesize high quality coarse-grain diamond crystals, advanced indirect heat assembly, powder catalyst technology and optimized synthesis craft are used. At last, three kinds of coarse- grain diamond （about 0.85 mm） single crystals with hexahedron, hex-octahedron and octahedron are synthesized successfully under HPHT （about 5.4 GPa, 1300-1450℃）. The growth characters of different shape crystals are discussed. The results and techniques might be useful for the production of coarse-grain diamonds.     

Effect of Carbon Source with Different Graphitization Degrees on the Synthesis of Diamond

Using three kinds of graphites with different graphitization degrees as carbon source and Fe-Ni alloy powder as catalyst, the synthesis of diamond crystals is performed in a cubic anvil high-pressure and high-temperature apparatus （SPD-6 × 1200）. Diamond crystals with perfect hexoctahedron shape are successfully synthesized at pressure from 5.0 to 5.5GPa and at temperature from 1570 to 1770K. The synthetic conditions, nucleation, morphology, inclusion and granularity of diamond crystals are studied. The temperature and pressure increase with the increase of the graphitization degree of graphite. The quantity of nucleation and granularity ofdiamonds decreases with the increase of graphitization degree of graphite under the same synthesis conditions. Moreover, according to the results of the M6ssbauer spectrum, the composition of inclusions is mainly Fe3 C and Fe-Ni alloy phases in diamond crystals synthesized with three kinds of graphites.     

Influence of activated carbon surface acidity on adsorption of heavy metal ions and aromatics from aqueous solution

Adsorption of toxic heavy metal ions and aromatic compounds onto activated carbons of various amount of surface C-O complexes were examined to study the optimum surface conditions for adsorption in aqueous phase. Cadmium(II) and zinc(II) were used as heavy metal ions, and phenol and nitrobenzene as aromatic compounds, respectively. Activated carbon was de-ashed followed by oxidation with nitric acid, and then it was stepwise out-gassed in helium flow up to 1273 K to gradually remove C-O complexes introduced by the oxidation. The oxidized activated carbon exhibited superior adsorption for heavy metal ions but poor performance for aromatic compounds. Both heavy metal ions and aromatics can be removed to much extent by the out-gassed activated carbon at 1273 K. Removing C-O complexes, the adsorption mechanisms would be switched from ion exchange to Cπ-cation interaction for the heavy metals adsorption, and from some kind of oxygen-aromatics interaction to π-π dispersion for the aromatics.     

HPHT Synthesis of High-Quality Diamond Single Crystals with Micron Grain Size

High-quality diamond single crystals with micron grain size are synthesized with a new high-pressure and high-temperature （HPHT） synthesis technique in a cubic anvil high pressure apparatus. Morphology of the synthesized diamonds is observed by a scanning electron microscope （SEM）. The samples are characterized using laser Raman spectra. The results show that the new synthesis technique improves the nucleation of diamond greatly, and diamond single crystals with perfect morphology and micron grain size are successfully synthesized, with the average grain size of about 6μm. This work provides a new synthesis technique to implement industrialization of high-quality diamond single crystals with super-fine grain size, and paves the way for future development.     

Diamond coating deposition by synergy of thermal and laser methods—A problem revisited

Diamond coatings were deposited by synergy of the hot filament CVD method and the pulse TEA CO₂ laser, in spectroactive and spectroinactive diamond precursor atmospheres. Resulting diamond coatings are interpreted relying on evidence of scanning electron microscopy as well as microRaman spectroscopy. Thermal synergy component (hot filament) possesses an activating agent for diamond deposition, and contributes significantly to quality and extent of diamond deposition. Laser synergy component comprises a solid surface modification as well as the spectroactive gaseous atmosphere modification. Surface modification consists in changes of the diamond coating being deposited and, at the same time, in changes of the substrate surface structure. Laser modification of the spectroactive diamond precursor atmosphere means specific consumption of the precursor, which enables to skip the deposition on a defined substrate location. The resulting process of diamond coating elimination from certain, desired locations using the CO₂ laser might contribute to tailoring diamond coatings for particular applications. Additionally, the substrate laser modification could be optimized by choice of a proper spectroactive precursor concentration, or by a laser radiation multiple pass through an absorbing medium.     

AFM investigation on surface evolution of amorphous carbon during ion-beam-assisted deposition

Hydrogen-free amorphous carbons (a-C) have been prepared on mirror-polished Si(1 1 1) wafers through thermally evaporated C₆₀ with simultaneous bombardments of Ne⁺ ions. The time evolution of film surfaces has been characterized by atomic force microscopy (AFM) at two temperatures of 400 and 700 °C, respectively. Based on the topography images and the root-mean-square (rms) roughness analysis, it is found that the a-C surfaces present roughening growth at the initial stage. With increasing growth time, the cooperative nucleation of the islands and pits appears on the surfaces, suggesting three-dimensional growth, and then they continue to evolve to irregular mounds at 400 °C, and elongated mounds at 700 °C. At the steady growth stage, these surfaces further develop to the structures of bamboo joints and ripples corresponding to these two temperatures, respectively. It is believed that besides ion sputtering effect, the chemical bonding configurations in the amorphous carbon films should be taken into considerations for elucidating the surface evolutions.     

Electroless deposition of copper and fabrication of copper micropatterns on CVD diamond film surfaces

Electroless deposition of copper on as-grown and amino-modification diamond substrates was investigated. The compact and uniform copper films were successfully electrolessly deposited on as-grown and amino-modification diamond substrates after activation by Pd/Sn colloid nanoparticles. The adhesion interaction between copper films and diamond substrates was roughly estimated by the ultrasonic treatment. The results showed the higher adhesion interaction between copper films and amino-modification diamond substrates than that between the copper films and as-grown diamond substrates due to the greater attractive force between the Pd/Sn colloid nanoparticles and amino-modified diamond surface. The favorable copper micropatterns were successfully constructed on diamond film surfaces by means of the catalyst lift-off method and the copper lift-off method. Furthermore, the electrochemical behavior of copper-modified boron-doped diamond (BDD) was studied for glucose oxidation in 0.2 M sodium hydroxide solution by using cyclic voltammetry, and the result indicated that copper-modified BDD exhibited high catalytic activity to electrochemical oxidation of glucose in alkaline media.     

On Room-Temperature Inversion of EPR Signals of P1 Centre in Synthetic Diamond

Room-temperature inversion of EPR absorption signals of P1 centre in synthetic diamond is studied by the transient nutation technique. Use of the bichromatic field, consisting of a transverse microwave field and longitudinal radio frequency field, allows to investigate the dynamics of P1 centres in the same field configuration as in cw EPR spectrometers. It is shown that the annealing decreases the P1 centre concentration and, respectively, increases the spin-spin relaxation time. As a result, the periodic inversion （nutation） of the P1 centre absorption signal is observed longer. It is assumed that the P1 centre signal inversion, which was previously observed by cw EPR, might be caused by the Bloch-Siegert effect in the bichromatic field.     

Characterization of soft-X-ray detectors fabricated with high-quality CVD diamond thin films

We have characterized the performance of soft-X-ray detectors fabricated with undoped and B-doped homoepitaxial diamond layers of high quality which were grown on a commercially available type Ib (1 0 0) substrate by means of a high-power microwave-plasma chemical-vapor-deposition (CVD) method. The signal currents of the diamond-based detectors with thin TiN electrodes formed vertically (along the homoepitaxial growth direction) were measured at room temperature as a function of the applied voltage, V_a, for irradiations of 500-1200 eV soft-X-ray beams ranging from ≈6 × 10⁹ to ≈1 × 10¹¹ photons/s. The deduced apparent quantum efficiencies increased with the increasing V_a and reached to 2.5 × 10³ at V_a = 60 V. As expected from the device structure, the detector performance depended only very slightly on the applied magnetic field up to 10 T. The excellently high sensitivities attained for soft-X-ray photons are discussed in relation to carrier amplification mechanisms which invested the above diamond detectors.     

High-Rate Growth and Nitrogen Distribution in Homoepitaxial Chemical Vapour Deposited Single-crystal Diamond

High rate （〉 50 μm/h） growth of homoepitaxial single-crystal diamond （SCD） is carried out by microwave plasma chemical vapour deposition （MPCVD） with added nitrogen in the reactant gases of methane and hydrogen, using a polyerystalline-CVD-diamond-film-made seed holder. Photolumineseenee results indicate that the nitrogen concentration is spatially inhomogeneous in a large scale, either on the top surface or in the bulk of those as-grown SCDs. The presence of N-distribution is attributed to the facts： （i） a difference in N-incorporation efficiency and （ii） N-diffusion, resulting from the local growth temperatures changed during the high-rate deposition process. In addition, the formed nitrogen-vacancy eentres play a crucial role in N-diffusion through the growing crystal. Based on the N-distribution observed in the as-grown crystals, we propose a simple method to distinguish natural diamonds and man-made CVD SCDs. Finally, the disappearance of void defect on the top surface of SCDs is discussed to be related to a filling-in mechanism.     

Effects of Radius and Orientation of Single-Walled Carbon Nanotubes on Their Nonlinear Tensile Deformation Behaviour

By capturing the atomic information and reflecting the behaviour governed by a nonlinear potential function, an analytical molecular mechanics approach is applied to establish the constitutive relation for single-walled carbon nanotubes （SWCNTs）. The nonlinear tensile deformation curves of zigzag and armchair nanotubes with different radii are predicted, and the elastic properties of these SWCNTs are obtained. A conclusion is made that the nanotube radius has little effect on the mechanical behaviour of SWCNTs subject to simple tension, while the nanotube orientation has larger influence.     

Micromachining and surface processing of the super-hard nano-polycrystalline diamond by three types of pulsed lasers

Laser beam micromachining was applied to super-hard nano-polycrystalline diamond (NPD) synthesized by the direct conversion of graphite at high pressure and high temperature. Three types of pulsed lasers were tested: nanosecond near-infrared, nanosecond near-ultraviolet, and femtosecond near-infrared lasers. The latter two were also applied for synthetic single crystal of diamond to compare the results with those of the NPD. It was demonstrated that the nanosecond near-infrared laser was the most efficient device for rough shaping of the NPD, while the ultraviolet and femtosecond lasers give satisfactory results for precise surface finishing of it. The properties of the laser-processed surfaces were analyzed by scanning and transmission electron microscopy, laser scanning microscopy, and micro Raman spectroscopy. These analyses demonstrated that the three types of lasers play different and complementary roles, and that their combination is the best suitable solution for micromachining of the hardest diamond into any desired shapes.     

Laser treatment of white China surface

The surface of gloss fired porcelain with and without raw glaze coating was radiated by a CO₂ laser working at 10.6 μm, a choice resulted from spectroscopic studies of suspensions made of China. The shine of the untreated sample was defined as the distribution of micro-droplets on the surface. The surface alterations due to laser heating were classified by the diameter of the completely melted surface, the ring of the surface at the threshold of melting, and the size of microscopic cracks. The diameter of the laser treated area was in the range of 3 mm, while the incident laser power and the duration of laser heating were varied between 1 and 10 W and 1-8 min, respectively. The different stages of surface modifications were attributed primarily to the irradiating laser power and proved to be rather insensitive to the duration of the treatment. We have found a range of parameters under which the white China surface coated with raw glaze and followed by laser induced melting exhibited very similar characteristics to the untreated porcelain. This technique seems prosperous for laser assisted reparation of small surface defects of unique China samples after the firing process.     

Optical and electrical properties of different oriented CVD diamond films

Due to different oriented diamond films having different properties, in this paper optical and electrical properties of different oriented diamond films have been investigated. The measured results indicate diamond films are of high quality and the properties of the (0 0 1)-oriented diamond film are better than those of the (1 1 1)-oriented one. Refractive index and extinction coefficient of (0 0 1)-oriented diamond film in the wavelength range of 2.5-12.5 μm is 2.391 and in the order of 10⁻⁵, respectively. And for the (1 1 1)-oriented one it is 2.375 and in the order of 10⁻⁴. The dark current of the (0 0 1)-oriented diamond film is 33.7 nA under an applied electric field of 100 kV/cm. The resistivity of the (0 0 1)-oriented diamond film obtained is about 2.33 × 10¹⁰ Ω cm. The current of (0 0 1)-oriented diamond film is almost no change with the time testing.     

Finite Element Analysis of Convection in Growth Cell for Diamond Growth Using Ni-Based Solvent

Thermal-electricaJ-fluid coupled finite element analyses are performed in the model of the growth cell in a high-pressure and high-temperature （HPHT） cubic apparatus in which the large diamond crystal can be grown by using Ni-based solvent with temperature gradient method （TGM）. The convection in the Ni-based solvent with different thicknesses at 1700-1800 K is simulated by finite element method （FEM）. The experiments of diamond crystal growth are also carried out by using Ni-based solvent at 5.7GPa and 1700-1800K in a China-type cubic high pressure apparatus （CHPA）. The simulation results show that the Rayleigh number in the solvent is enhanced obviously with the increasing solvent thickness. Good quality diamond single crystal cannot be grown if the Rayleigh number in the solvent is too high.     

Dependence of Limited Growth Rate of High-Quality Gem Diamond on Growth Conditions

The growth rate of diamond has been investigated for a long time and researchers have been attempting to enhance the growth rate of high-quality gem diamond infinitely. However, it has been found according to previous research results that the quality of diamond is debased with the increase of growth rate. Thus, under specific conditions, the growth rate of high-quality diamond cannot exceed a limited value that is called the limited growth rate of diamond. We synthesize a series of type Ib gem diamonds by temperature gradient method under high pressure and high temperature （HPHT） using the as-grown {100} face. The dependence of limited growth rate on growth conditions is studied. The results show that the limited growth rate increases when synthetic temperature decreases, also when growth time is prolonged.     

The effect of hydrogen peroxide on polishing removal rate in CMP with various abrasives

The effect of hydrogen peroxide in chemical mechanical planarization slurries for shallow trench isolation was investigated. The various abrasives used in this study were ceria, silica, alumina, zirconia, titania, silicon carbide, and silicon nitride. Hydrogen peroxide suppresses the polishing of silicon dioxide and silicon nitride surfaces by ceria abrasives. The polishing performances of other abrasives were either unaffected or enhanced slightly with the addition of hydrogen peroxide. The ceria abrasives were treated with hydrogen peroxide, and the polishing of the work surfaces with the treated abrasive shows that the inhibiting action of hydrogen peroxide is reversible. It was found that the effect of hydrogen peroxide as an additive is a strong function of the nature of the abrasive particle.     

Formation of Mixture of A and C Centres in Diamond Synthesized with Fe90Ni10-C-High-Content Additive NaN3 by HPHT

Very rich nitrogen concentration with the dominant C centres and some A centres are found in diamonds grown from a Fe90Ni10-C-high-content NaN3 additive system. The concentrations of C centres rapidly increase with increasing content of NaN3 additive, while the concentrations of A centres increase slowly. The total nitrogen concentration tends to increase rapidly with increasing content of NaN3 additive when the content of NaN3 is below 0.7 wt%. However, the total concentration of nitrogen in the diamonds increases slowly when the content of NaN3 is further increased up to 1.0 wt%, and the total nitrogen average concentration are calculated to be around 2230ppm for most of the analysed synthetic diamonds. Eurthermore, the nitrogen impurities in different crystal sectors of the diamonds are inhomogeneously distributed. The nitrogen impurities in the diamonds in [111] zones are incorporated more easily than that in [100].     

A New Dopant of NaN3 for High-Concentration-Nitrogen Diamond Synthesized by HPHT

Nitrogen is successfully doped in diamond by adding sodium azide （NaN3 ） as the source of nitrogen to the graphite and iron powders. The diamond crystals with high nitrogen concentration, 1000-2200ppm, which contain the same concentrations of nitrogen with natural diamond, have been synthesized by using the system of iron-carbon- additive NAN3. The nitrogen concentrations in diamond increase with the increasing content of NAN3. When the content of NaN3 is increased to 0.7-1.3 wt. %, the nitrogen concentration in the diamond almost remains in a nitrogen concentration range from 1250ppm to 2200ppm, which is the highest value and several times higher than that in the diamond synthesized by a conventional method without additive NaN3 under high pressure and high temperature （HPHT） conditions.