Electronic structure methods applied to gas-carbon reactions

A review is given on the fundamental studies of gas-carbon reactions using electronic structure methods in the last several decades. The three types of electronic structure methods including semi-empirical, ab initio and density functional theory, methods are briefly introduced first, followed by the studies on carbon reactions with hydrogen and oxygen-containing gases (non-catalysed and catalysed). The problems yet to solve and possible promising directions are discussed. (C) 2002 Elsevier Science Ltd. All rights reserved.

Zr-Laponite pillared clay-based nickel catalysts for methane reforming with carbon dioxide

Zr-Laponite pillared clays were prepared and used as supports of nickel catalysts for the methane reforming reaction with carbon dioxide to synthesis gas. The structural and textural characteristics of supports and catalysts were systematically examined by N-2 adsorption/desorption and X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmission electron spectroscopy (TEM) techniques. The catalytic performance and carbon deposition were investigated. It is found that Zr-Laponite pillared clays are promising catalyst supports for carbon dioxide reforming of methane. The pore structure and surface properties of such supports greatly affect the catalytic behaviors of catalysts derived. Carbon deposition on catalysts was also affected by the property and structure of supports. The sintering of nickel metal and zirconia was another factor responsible for catalyst deactivation. This new-type nickel supported catalyst Ni/Zr-Laponite(8), with well-developed porosity, gave a higher initial conversion and a relatively long-term stability, and is therefore a promising catalyst for potential application to carbon dioxide reforming of methane to synthesis gas. (C) 2002 Elsevier Science B.V All rights reserved.

Immobilization of aluminum chloride on MCM-41 as a new catalyst system for liquid-phase isopropylation of naphthalene

A great deal of effort has been made at searching for alternative catalysts to replace conventional Lewis acid catalyst aluminum trichloride (AlCl3). In this paper, immobilization of AlCl3 on mesoporous MCM-41 silica with and without modification was carried out. The catalytic properties of the immobilized catalyst systems for liquid-phase isopropylation of naphthalene were studied and compared with those of H/MCM-41 and H/mordenite. The structures of the surface-immobilized aluminum chloride catalysts were studied and identified by using solid-state magic angle spinning nuclear magnetic resonance (MAS NMR), Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), nitrogen adsorption, and X-ray diffraction (XRD) techniques. The catalytic activity of the immobilized catalysts was found to be similar to that of acidic mordenite zeolite. A significant enhancement in the selectivity of 2,6-diisopropylnaphthalene (2,6-DIPN) was observed over the immobilized aluminum chloride catalysts. Immobilization of aluminum chloride on mesoporous silica coupled with surface silylation is a promising way of developing alternative catalyst system for liquid-phase Friedel-Crafts alkylation reactions. (C) 2002 Elsevier Science B.V. All rights reserved.

Designing biostable polyurethane elastomers for biomedical implants

The chemical structure, synthesis, morphology, and properties of polyurethane elastomers are briefly discussed. The current understanding of the effect of chemical structure and the associated morphology on the stability of polyurethanes in the biological environments is reviewed. The degradation of conventional polyurethanes appears as surface or deep cracking, stiffening, and deterioration of mechanical properties, such as flex-fatigue resistance. Polyester and poly( tetramethylene oxide) based polyurethanes degrade by hydrolytic and oxidative degradation of ester and ether functional groups, respectively. The recent approaches to develop polyurethanes with improved long-term biostability are based on developing novel polyether, hydrocarbon, polycarbonate, and siloxane macrodiols to replace degradation-prone polyester and polyether macrodiols in polyurethane formulations. The new approaches are discussed with respect to synthesis, properties and biostability based on reported in vivo studies. Among the newly developed materials, siloxane-based polyurethanes have exhibited excellent biostability and are expected to find many applications in biomedical implants.

Mechanical alloying of MoSi2 with ternary alloying elements. Part 1: Experimental

Phase evolution during the mechanical alloying of Mo and Si elemental powders with a ternary addition of Al, Mg, Ti or Zr was monitored using X-ray diffraction. Rietveld analysis was used to quantify the phase proportions. When Mo and Si are mechanically alloyed in the absence of a ternary element, the tetragonal C11b polymorph of MoSi2 (t-MoSi2) forms by a self-propagating combustion reaction. With additional milling, the tetragonal phase transforms to the hexagonal C40 structure (h-MoSi2). The mechanical alloying of Al, Mg and Ti additions with Mo and Si tend to promote a more rapid transformation of t-MoSi2 to h-MoSi2. In high concentrations, the addition of these ternary elements inhibits the initial combustion reaction, instead promoting the direct formation of h-MoSi2. The addition of Zr tends to stabilise the tetragonal phase.

Mechanical alloying of MoSi2 with ternary alloying elements. Part 2 - computer simulation

A computer model of the mechanical alloying process has been developed to simulate phase formation during the mechanical alloying of Mo and Si elemental powders with a ternary addition of Al, Mg, Ti or Zr. Using the Arhennius equation, the model balances the formation rates of the competing reactions that are observed during milling. These reactions include the formation of tetragonal C11(b) MOSi2 (t-MoSi2) by combustion, the formation of the hexagonal C40 MoSi2 polymorph (h-MoSi2), the transformation of the tetragonal to the hexagonal form, and the recovery of t-MoSi2 from h-MoSi2 and deformed t-MoSi2. The addition of the ternary additions changes the free energy of formation of the associated MoSi2 alloys, i.e. Mo(Si, Al)(2), Mo(Mg, Al)(2), (Mo, Ti)Si-2 (Mo, Zr)Si-2 and (Mo, Fe)Si-2, respectively. Variation of the energy of formation alone is sufficient for the simulation to accurately model the observed phase formation. (C) 2003 Elsevier B.V. All rights reserved.

Transmission electron microscopy sample preparation technique for sintered alloys

Powder metallurgy alloys are typically inhomogeneous with a significant amount of porosity. This complicates conventional transmission electron microscopy sample preparation. However, the use of focused ion beam milling allows site specific transmission electron microscopy samples to be prepared in a short amount of time. This paper presents a method that can be used to produce transmission electron microscopy samples from an Al-Cu-Mg PM alloy. (C) 2003 IoM Communications Ltd. Published by Maney for the Institute of Materials, Minerals and Mining.

Sintering of freeformed maraging steel with boron additions

This paper describes the sintering of an 18Ni(350) maraging steel with additions of boron, with the aim of producing high hardness rapid tooling. Reaction of the boron with the alloying elements in the maraging steel resulted in the formation of a Mo- and Ti-rich borides. The former melted at similar to1220degreesC, providing a liquid phase for enhanced sintering. Although densification could occur regardless of the boron content, especially at high temperature, 0.4% B was required to produce a near full density component. The formation of the various borides depleted the matrix of critical age hardening elements. However, by altering the starting powder composition to compensate for this, hardness close to the wrought alloy has been achieved. This hardness was comparable to a common die casting tool steel. Examples of dies produced using selective laser sintering (SLS) are also shown. (C) 2003 Elsevier B.V. All rights reserved.

Rapid manufacturing of aluminum components

A manufacturing technique for the production of aluminum components is described. A resin-bonded part is formed by a rapid prototyping technique and then debound and infiltrated by a second aluminum alloy under a nitrogen atmosphere. During thermal processing, the aluminum reacts with the nitrogen and is partially transformed into a rigid aluminum nitride skeleton, which provides the structural rigidity during infiltration. The simplicity and rapidity of this process in comparison to conventional production routes, combined with the ability to fabricate complicated parts of almost any geometry and with high dimensional precision, provide an additional means to manufacture aluminum components.

The effect of resin type on the sintering of freeformed maraging steel

The role of the resin type on the sintering of maraging steel with boron additions has been investigated. Two different resins were added to the steel mixture and their subsequent debinding was evaluated and sintering responses compared with that of a resin-free alloy. The two resins used, nylon and a mixture of phenolic resin and synthetic wax, possessed different debinding behaviour, with the latter causing significant carbon contamination of the parts. This caused the formation of a Ti-Mo carbide, depleting the matrix of these elements. Consequently, the microstructure consisted of the equilibrium Fe-Fe2B eutectic, as well as a Mo-rich boride. The liquid phase also appeared to contain significant amounts of carbon, which lowered the temperature at which the liquid formed, resulting in high density occurring at a much lower temperature. When nylon was used as the binder, a similar sintering response to the resin-free alloy was observed. (C) 2002 Published by Elsevier Science B.V.

On the sintering of uncompacted, pre-alloyed Al powder alloys

The effect of the addition of elemental Mg, Sri and Pb on the sintering of impressed prealloyed 2124 and 6061 powder has been investigated. Despite being sintered at a temperature that resulted in similar to20 vol.% liquid phase, high density was possible only upon the addition of similar to1% elemental Mg as well as trace amounts of Sri or Pb. Additions of Mg facilitated oxide disruption, while Sri and Pb segregated to the liquid phase, where they reduced the liquid's surface tension, thus improving sintering. (C) 2002 Elsevier Science B.V. All rights reserved.

Modulation of the antibody response by Porphyromonas gingivalis and Fusobacterium nucleatum in a mouse model

Successive immunization of mice with Fusobacterium nucleatum and Porphyromonas gingivalis has been shown to modulate the specific serum IgG responses to these organisms. The aim of this study was to investigate these antibody responses further by examining the IgG subclasses induced as well as the opsonizing properties of the specific antibodies. Serum samples from BALB/c mice immunized with F. nucleatum (gp1-F), P. gingivalis (gp2-P), P. gingivalis followed by F. nucleatum (gp3-PF) F. nucleatum followed by P. gingivalis (gp4-FP) or saline alone (gp5-S) were examined for specific IgG1 (Th2) and IgG2a (Th1) antibody levels using an ELISA and the opsonizing properties measured using a neutrophil chemiluminescence assay. While IgG1 and IgG2a subclasses were induced in all immunized groups, there was a tendency towards an IgG1 response in mice immunized with P. gingivalis alone, while immunization with F. nucleatum followed by P. gingivalis induced significantly higher anti-P. gingivalis IgG2a levels than IgG1. The maximum light output due to neutrophil phagocytosis of P. gingivalis occurred at 10 min using nonopsonized bacteria. Chemiluminescence was reduced using serum-opsonized P. gingivalis and, in particular, sera from P. gingivalis-immunized mice (gp2-P), with maximum responses occurring at 40 min. In contrast, phagocytosis of immune serum-opsonized F. nucleatum demonstrated peak light output at 10 min, while that of F. nucleatum opsonized with sera from saline injected mice (gp5-S) and control nonopsonized bacteria showed peak responses at 40 min. The lowest phagocytic response occurred using gp4-FP serum-opsonized F. nucleatum. In conclusion, the results of the present study have demonstrated a systemic Th1/Th2 response in mice immunized with P. gingivalis and/or F. nucleatum with a trend towards a Th2 response in P. gingivalis-immunized mice and a significantly increased anti-P. gingivalis IgG2a (Th1) response in mice immunized with F. nucleatum prior to P. gingivalis. Further, the inhibition of neutrophil phagocytosis of immune serum-opsonized P. gingivalis was modulated by the presence of anti-F. nucleatum antibodies, while anti-P. gingivalis antibodies induced an inhibitory effect on the phagocytic response to F. nucleatum.

Hydrogen economy options for Australia

Global concerns over the effects of current carbon dioxide (CO2) emissions have lead to extensive research on the use of hydrogen as a potential energy carrier for a lower emissions society. Hydrogen can be produced from both fossil and renewable energy sources. The hydrogen economy, in which hydrogen will be a carrier of energy from renewable sources, is a long-term development and any increasing demand for hydrogen will probably be covered initially from fossil sources. Technologies for hydrogen generation from renewable energies are being explored, whereas technologies for hydrogen production from fossil fuels have to a certain extent reached maturity. This paper addresses the major hydrogen generation processes and utilisation technology (fuel cells) currently available for the move from a fossil fuelsbased economy to a hydrogen economy. In particular, it illustrates the applicability of different hydrogen sources using Australia as an example.