Nucleation and growth of Al2O3/metal composites by oxidation of aluminum alloys

The nucleation and growth mechanisms during high temperature oxidation of liquid Al-3% Mg and Al-3% Mg-3% Si alloys were studied with the aim of enhancing our understanding of a new composite fabrication process. The typical oxidation sequence consists of an initial event of rapid but brief oxidation, followed by an incubation period of limited oxide growth after which bulk Al2O3/Al composite forms. A duplex oxide layer, MgO (upper) and MgAl2O4 (lower), forms on the alloy surface during initial oxidation and incubation. The spinel layer remains next to the liquid alloy during bulk oxide growth and is the eventual repository for most of the magnesium in the original alloy. Metal microchannels developed during incubation continuously supply alloy through the composite to the reaction interface. During the growth process, a layered structure exists at the upper extremity of the composite, consisting of MgO at the top surface, MgAl2O4 (probably discontinuous), Al alloy, and finally the bulk Al2O3 composite containing microchannels of the alloy. The bulk oxide growth mechanism appears to involve continuous formation and dissolution of the Mg-rich oxides at the surface, diffusion of oxygen through the underlying liquid metal, and epitaxial growth of Al2O3 on the existing composite body. The roles of Mg and Si in the composite growth process are discussed.

Mechanistic Aspects of Nucleophilic Substitution at Half-Sandwich Metal Complexes

The hydrolysis reactions of organometallic ruthenium(II) piano-stool complexes of the type Ru-II(eta(6)-cymene)(L)Cl](0/+) (1-5, where L = kappa(1)- or kappa(2)-1,1-bis(diphenylphosphino)methane,1,1bis-(diphenylphosphino)methane oxide, kappa(1)-mercaptobenzothiazole) have been studied using density functional theory at the B3LYP level. In addition to considering a syn attack in an associative fashion, where the nucleophile approaches from the same side as the leaving group, we have explored alternative paths such as an anti attack in an associative manner, where the nucleophile attacks from the opposite side of the leaving group. During the anti attack, an intermediate is formed and there is a coordination mode change of the arene ring from eta(6) to eta(2) along with its rotation. When the intermediate goes to the product, the arene ring slips back from eta(2) to eta(6) coordination. This coordinated movement of the arene ring makes the associative anti attack an accessible pathway for the substitution process. Our calculations predict very similar activation barriers for both syn and anti attacks. In the dissociative path, the rate-determining step is the generation of a coordinatively unsaturated 16-electron ruthenium species. This turns out to be viable once solvent effects are included. The large size of the ancillary ligands on Ru makes the dissociative process as favorable as the associative process. Activation energy calculations reveal that although the dissociative path is favorable for kappa(1) complexes, both dissociative and associative processes can have significant contribution to the hydrolysis reaction in kappa(2) complexes. Once activated by hydrolysis, these complexes react with guanine and adenine bases of DNA. The thermodynamic stabilities of complexes formed with the nucleobases are also presented.

Electrobioleaching of base metal sulfides

Bioleaching of base metal sulfides, such as pyrite, chalcopyrite, and sphalerite, under the influence of applied direct current (DC) potentials is discussed. Contributions toward mineral dissolution from three effects, namely, galvanic, applied potential, and microbiological, are analyzed and compared. Sphalerite could be selectively bioleached in the presence of Thiobacillus ferrooxidans under an applied potential of -500 mV (SCE) from mixed sulfides containing sphalerite, pyrite, and chalcopyrite. Bacterial activity and growth were found to be promoted under electrobioleaching conditions. Probable mechanisms involved in the bioleaching of different sulfides under positive and negative applied potentials are discussed.

Combustion synthesis and properties of fine-particle rare-earth-metal zirconates, Ln2Zr2O7

Fine-particle rare-earth-metal zirconates, Ln2Zr2O7, where Ln = La, Ce, Pr, Nd, Sm, Gd and Dy having the pyrochlore structure have been prepared using a novel combustion process. The process employs aqueous solutions of the corresponding rare-earth-metal nitrate, zirconium nitrate and carbohydrazide/urea in the required molar ratio. When the solution is rapidly heated to 350–500 °C it boils, foams and burns autocatalytically to yield voluminous oxides. The formation of single-phase Ln2Zr2O7 has been confirmed by powder X-ray diffraction, infrared and fluorescence spectroscopy. The solid combustion products are fine, having surface areas in the range 6–20 m2 g–1. The cold-pressed Pr2Zr2O7 compact when sintered at 1500 °C, 4 h in air, achieved 99% theoretical density.

Large negative magnetoresistance and metal-insulator transition observed in MnO/C composite coatings grown on ceramic alumina by metalorganic chemical vapor deposition

MnO/C composite coatings were grown by the metalorganic chemical vapor deposition process on ceramic alumina in argon ambient. Characterization by various techniques confirms that these coatings are homogeneous composites comprising nanometer-sized MnO particles embedded in a matrix of nanometer-sized graphite. Components of the MnO/C composite coating crystalline disordered, but are electrically quite conductive. Resistance vs. temperature measurements show that coating resistance increases exponentially from a few hundred ohms at room temperature to a few megaohms at 30 K. Logarithmic plots of reduced activation energy vs. temperature show that the coating material undergoes a metal-insulator transition. The reduced activation energy exponent for the film under zero magnetic field was 2.1, which is unusually high, implying that conduction is suppressed at much faster rate than the Mott or the Efros-Shklovskii hopping mechanism. Magnetoconductance us. magnetic field plots obtained at various temperatures show a high magnetoconductance (similar to 28.8%) at 100 K, which is unusually large for a disordered system, wherein magnetoresistance is attributed typically to weak localization. A plausible explanation for the unusual behavior observed in the carbonaceous disordered composite material is proposed. (C) 2010 Elsevier Ltd. All rights reserved.

Enhancement in Bath Mixing and Plume area in a New Degassing Process - A Computational Fluid Dynamic Study

Reaction between the various species in slag and metal phase is usually mass transfer controlled. There have been continuous efforts to increase the reaction efficiency in slag-metal system, especially during decarburization of steel to produce the ultra low carbon steel (ULCS) in secondary steelmaking. It has been found that the surface reaction is a dominant factor in the final stage of decarburization. In the initial stage, the inner site reaction is major factor in the refining process. The mixing of bath affects the later reaction. However, the former reaction (surface reaction) is affected by the plume size area at the top of the metal surface. Therefore, a computational study has been made to understand the fluid dynamics of a new secondary steelmaking process called Revolutionary Degasser Activator (REDA) to study the bath mixing and plume area. REDA process has been considered as it is claimed that this process can reduce the carbon content in steel below 10ppm in a less time than the other existing processes such as RH and Tank degasser. This study shows that both bath mixing and plume area are increased in REDA process facilitating it to give the desired carbon content in less time. Qualitative comments are made on slag-metal reaction system based on this finding.

Heavy-metal removal using liquid membrane

Experiments have been conducted to obtain the optimum conditions of hydrogen ion concentration of feed and strip phases and concentration of the carrier ALAMINE 336, in the extraction of Cr(VI) and Hg(II) using two different types of liquid membranes-bulk liquid membrane and emulsion liquid membrane. Experiments have also been carried out to find the effect of metal loading and the effect of extraction time on metal flux.

Abrasive Jet Machining - Process variables and current applications

brusive Jet Machining (AJM) or Micro Blast Machining is a non-traditional machining process, wherein material removal is effected by the erosive action of a high velocity jet of a gas, carrying fine-grained abrasive particles, impacting the work surface. The AJM process differs from conventional sand blasting in that the abrasive is much finer and the process parameters and cutting action are carefully controlled. The process is particularly suitable to cut intricate shapes in hard and brittle materials which are sensitive to heat and have a tendency to chip easily. In other words, AJM can handle virtually any hard or brittle material. Already the process has found its ways Into dozens of applications; sometimes replacing conventional alternatives often doing jobs that could not be done in any other way. This paper reviews the current status of this non-conventional machining process and discusses the unique advantages and possible applications.

Microstructure evolution during solidification of DRMMCs (discontinuously reinforced metal matrix composites): State of art

Distribution of particle reinforcements in cast composites is determined by the morphology of the solidification front. Interestingly, during solidification, the morphology of the interface is intrinsically affected by the presence of dispersed reinforcements. Thus the dispersoid distribution and length scale of matrix microstructure is a result of the interplay between these two. A proper combination of material and process parameters can be used to obtain composites with tailored microstructures. This requires the generation of a broad data base and optimization of the complete solidification process. The length scale of soldification microtructure has a large influence on the mechanical properties of the composites. This presentation addresses the concept of a particle distribution map which can help in predicting particle distribution under different solidification conditions Future research directions have also been indicated.

Sub-micrometre spherical particles of TiO2, ZrO2, and PZT by nebulized spray pyrolysis of metal-organic precursors

Nebulized spray pyrolysis of metal-organic precursors in methanol solution has been employed to prepare powders of TiO2, ZrO2 and PbZr0.5Ti0.5O3 (PZT). This process ensures complete decomposition of the precursors at relatively low temperatures. The particles have been examined by scanning and transmission electron microscopy as well as X-ray diffraction. As prepared, the particles are hollow agglomerates of diameter 0.1-1.6 mu m, but after heating to higher temperatures the ultimate size of the particles comprising the agglomerates are considerably smaller (0.1 mu m or less in diameter) and crystalline.

Dendritic encapsulation of amino acid-metal complexes. Synthesis and studies of dendron-functionalized L-tyrosine-metal (Zn-II, Co-II) complexes

This paper describes the synthesis, characterization and studies of dendrimers possessing an amino acid-metal complex as the core. Using Frechet-type polyaryl ether dendrons, L-tyrosine-metal (Zn-II and Co-II) complex cored dendrimers of 0-4 generations were synthesized. The metal complexation of the tyrosine unit at the focal point of these dendrons took place smoothly, in excellent yields, even though the sizes of the dendrons increase as the generations advance. Spectrophotometric titrations with CoII metal ion confirmed the formation of a 2 : 1 dendritic ligand to metal complex and the existence of a pseudotetrahedral geometry at the metal centre is also inferred. Cyclic voltammetric studies of dendrimer-Co-II complexes showed that while the electron transfer of Co-II to Co-I was facile for generations 0-2, such a process was difficult with generations 3 and 4, indicating a rigid encapsulation of the metal ion centre by proximal dendron groups. Further reduction of Co-I to Co-0 and the corresponding oxidation processes appear to be limited by adsorption at the surfaces of the electrodes.

Comparison of CVD and MOCVD-grown Al2O3 coatings in the performance of cemented carbide cutting tool inserts

Low-pressure MOCVD, with tris(2,4 pentanedionato)aluminum(III) as the precursor, was used in the present investigation to coat alumina on to cemented carbide cutting tools. To evaluate the MOCVD process, the efficiency in cutting operations of MOCVD-coated tools was compared with that of tools coated using the industry-standard CVD process.Three multilayer cemented carbide cutting tool inserts, viz., TiN/TiC/WC, CVD-coated Al2O3 on TiN/TiC/WC, and MOCVD-coated Al2O3 on TiN/TiC/WC, were compared in the dry turning of mild steel. Turning tests were conducted for cutting speeds ranging from 14 to 47 m/min, for a depth of cut from 0.25 to 1 mm, at the constant feed rate of 0.2 mm/min. The axial, tangential, and radial forces were measured using a lathe tool dynamometer for different cutting parameters, and the machined work pieces were tested for surface roughness. The results indicate that, in most of the cases examined, the MOCVD-coated inserts produced a smoother surface finish, while requiring lower cutting forces, indicating that MOCVD produces the best-performing insert, followed by the CVD-coated one. The superior performance of MOCVD-alumina is attributed to the co-deposition of carbon with the oxide, due to the very nature of the precursor used, leading to enhanced mechanical properties for cutting applications in harsh environment.

Surfactant-mediated Synthesis of Functional Metal Oxide Nanostructures via Microwave Irradiation-assisted Chemical Synthesis

Nanostructured materials have attracted considerable interest in recent years due to their properties which differ strongly from their bulk phase and potential applications in nanoscale electronic and optoelectronic devices. Metal oxide nanostructures can be synthesized by variety of different synthesis techniques developed in recent years such as thermal decomposition, sol-gel technique, chemical coprecipitation, hydrothermal process, solvothermal process, spray pyrolysis, polyol process etc. All the above processes go through a tedious synthesis procedure followed by prolonged heat treatment at elevated temperature and are time consuming. In the present work we describe a rapid microwave irradiation-assisted chemical synthesis technique for the growth of nanoparticles, nanorods, and nanotubes of a variety of metal oxides in the presence of an appropriate surfactant, without the use of any templates The method is simple, inexpensive, and helps one to prepare nanostructures in a very simple way, and in a very short time, measured in minutes. The synthesis procedure employs high quality metalorganic complexes (typically -diketonates) featuring a direct metal-to-oxygen bond in its molecular structure. The complex is dissolved in a suitable solvent, often with a surfactant added, and the solution then subjected to microwave irradiation in a domestic microwave oven operating at 2.45 GHz frequency with power varying from 160-800 W, from a few seconds to a few minutes, leading to the formation of corresponding metal oxides. This method has been used successfully to synthesize nanostructures of a variety of binary and ternary metal oxides such as ZnO, CdO, Fe2O3, CuO, Ga2O3, Gd2O3, ZnFe2O4, etc. There is an observed variation in the morphology of the nanostructures with the change of different parameters such as microwave power, irradiation time, appropriate solvent, surfactant type and concentration. Cationic, anionic, nonionic and polymeric surfactants have been used to generate a variety of nanostructures. Even so, to remove the surfactant, there is either no need of heat treatment or a very brief exposure to heat suffices, to yield highly pure and crystalline oxide materials as prepared. By adducting the metal complexes, the shape of the nanostructures can be controlled further. In this manner, very well formed, single-crystalline, hexagonal nanorods and nanotubes of ZnO have been formed. Adducting the zinc complex leads to the formation of tapered ZnO nanorods with a very fine tip, suitable for electron emission applications. Particle size and their monodispersity can be controlled by a suitable choice of a precursor complex, the surfactant, and its concentration. The resulting metal oxide nanostructures have been characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, FTIR spectroscopy, photoluminescence, and electron emission measurements.

Synthesis of cnt-metal oxide nano-composite electrode materials for supercapacitator by low-pressure mocvd

Homogeneous composite thin films of Fe2O3-carbon nanotube were synthesized in a novel, single-step process by metalorganic chemical vapor deposition (MOCVD) using ferric acetyl acetonate as precursor. The deposition of composite takes place in a narrow range of CVD conditions, beyond which the deposition either multiwall carbon nanotubes (MWNTs) only or hematite (α-Fe2O3) only takes place. The composite film formed on stainless steel substrates were tested for their supercapacitive properties in various aqueous electrolytes.

Effect of ester chemical structure and peptide bond conformation in fragmentation pathways of differently metal cationized cyclodepsipeptides

Fragmentation behavior of two classes of cyclodepsipeptides, isariins and isaridins, obtained from the fungus Isaria, was investigated in the presence of different metal ions using multistage tandem mass spectrometry (MS(n)) with collision induced dissociation (CID) and validated by NMR spectroscopy. During MS(n) process, both protonated and metal-cationized isariins generated product ions belonging to the identical `b-ion' series, exhibiting initial backbone cleavage explicitly at the beta-ester bond. Fragmentation behavior for the protonated and metal-cationized acyclic methyl ester derivative of isariins was very similar. On the contrary, isaridins during fragmentation produced ions belonging to the `b' or/and the `y' ion series depending on the nature of interacting metal ions, due to initial backbone cleavages at the beta-ester linkage or/and at a specific amide linkage. Interestingly, independent of the nature of the interacting metal ions, the product ions formed from the acyclic methyl ester derivative of isaridins belonged only to the `y-type'. Complementary NMR data showed that, while all metal ions were located around the beta-ester group of isariins, the metal ion interacting sites varied across the backbone for isaridins. Combined MS and NMR data suggest that the different behavior in sequence specific charge-driven fragmentation of isariins and isaridins is predetermined because of the constituent beta-hydroxy acid residue in isariins and the cis peptide bond in isaridins.