Effect of metal chlorides on the sintering and densification of hydroxyapatite adsorbent

This work is part of a series of studies dealing with the evaluation of the effects of major elements of solid waste, especially metallic oxides, nitrates, sulfates, and chlorides, on the sintering and the densification of calcium hydroxyapatite (Ca-HAP) adsorbent. The effects of chloride salts of potassium (KCl) and zinc (ZnCl2) on sintering and densification of Ca-HAP were studied using surface area reduction and shrinkage measurements. The addition of KCl (2% w/w) activated the sintering process by bringing a swift reduction in surface area and lowering the densification temperature. However, a low final densification was achieved. Increasing the amount of this additive to 10% w/w further lowered the final densification and lowered the densification temperature of hydroxyapatite by 150 degrees C. On the other hand, the addition of 2 wt % of ZnCl2 deactivated the sintering process by slowing down the densification process and raising the densification temperature. However, the reduction of surface area was comparable to that of Ca-HAP. The densification rate contained two or more rate maxima indicating the additives (salts) bring multiple speeds in the densification process.

Precipitation induced densification in a sintered Al-Zn-Mg-Cu alloy

It is demonstrated that slow cooling to 200 degrees C from a high sintering temperature (620 degrees C) reduces porosity in an Al-8Zn-2.5Mg-1Cu powder compact when compared to isothermal sintering at the higher temperature for a longer time. The reduction in porosity is attributed to shrinkage associated with removal of solute from the aluminium solid solution and heterogeneous precipitation of the eta phase (MgZn2), particularly onto pore surfaces. (c) 2006 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Reactivity of chars and carbons: New insights through molecular modeling

A new model proposed for the gasification of chars and carbons incorporates features of the turbostratic nanoscale structure that exists in such materials. The model also considers the effect of initial surface chemistry and different reactivities perpendicular to the edges and to the faces of the underlying crystallite planes comprising the turbostratic structure. It may be more realistic than earlier models based on pore or grain structure idealizations when the carbon contains large amounts of crystallite matter. Shrinkage of the carbon particles in the chemically controlled regime is also possible due to the random complete gasification of crystallitic planes. This mechanism can explain observations in the literature of particle size reduction. Based on the model predictions, both initial surface chemistry and the number of stacked planes in the crystallites strongly influence the reactivity and particle shrinkage. Its test results agree well with literature data on the air-oxidation of Spherocarb and show that it accurately predicts the variation of particle size with conversion. Model parameters are determined entirely from rate measurements.

On the use of trace additions of Sn to enhance sintered 2xxx series Al powder alloys

The mechanical properties of a typical sintered aluminium alloy (Al-4.4Cu-0.8Si-0.5Mg) have been improved by the simultaneous use of trace additions of Sn, high sintering temperatures and modified heat treatments. Tin increases densification, but the Sn concentration is limited to less than or equal to 0.1wt% because incipient melting occurs during solution treatment at higher Sn levels. A sintering temperature of 620 degrees C increases the liquid volume over that formed at the conventional 590 degrees C sintering temperature. However, the higher sintering temperature results in the formation of an embrittling phase which can be eliminated if solution treatment is incorporated into the sintering cycle (a modified TS heat treatment). These conditions produce a tensile strength of 375 MPa, an increase of nearly 20% over the unmodified alloy. (C) 1999 Elsevier Science S.A. All rights reserved.

α′ phase stability in Nd-Li-sialon systems

The formability and stability of the alpha-sialon (alpha') phase was investigated in multi-cation Nd-Li-sialon systems. Four samples were prepared, ranging from a pure Nd-sialon to a pure Li-sialon, with two intermediate samples being prepared with either lithium or neodymium replacing the other alpha'-stabilising additive by 20 eq.%, as to maintain an equivalent design composition in all samples. After sintering, all samples were subsequently heat treated up to 192 h at 1450 and 1300 degreesC. While significant quantities of the beta'-sialon (beta' phase were found in most samples, the high-lithium Li-Nd-sialon sample was found to be almost pure a' phase after sintering. Furthermore, the long-term stability of the a' phase on heat treatment was also found to be superior in both multi-cation samples than in either of the single-alpha'-stabilising-cation samples. This is thought to be related to improved retention of the lithium in the multi-cation systems, as much of the lithium was found to volatilise during sintering in the neodymium-free sample. (C) 2002 Elsevier Science Ltd. All rights reserved.

Hydrophobicity of Templated Silica Xerogels for Molecular Sieving Applications

Silica xerogels were prepared by a sol-gel process catalyzed by acid with tetraethylorthosilicate, and using an organic covalent ligand template (methyltriethoxysilane) or a noncovalent template C6 surfactant (triethylhexylammonium bromide). The influence of hydrotreatment on the structure of templated xerogels is examined in terms of surface area, micropore volume, average pore size, and pore size distribution, and compared against a blank xerogel (nontemplated). The role of surface functional groups was evaluated using Si-29 nuclear magnetic resonance. The structural integrity of the xerogel was maintained to a large extent in samples that had a high contribution of Q(4) species (siloxane groups). Xerogel matrix densification occurred when there was a large concentration of Q(3) and Q(2) species (silanol groups), which also were responsible for increased hydrophilicity. The templated xerogels resulted in up to a 25% concentration of methyl functional groups (T-3 and T-2 species), leading to hydrophobic xerogels. The best results in terms of structural integrity and hydrophobicity were obtained with templated xerogels prepared with the C6 surfactant. The results in this study suggest that surfactant-enhanced condensation reactions lead to structures with a high contribution of Q(4) groups, which are not susceptible to water attack, but are strong enough to oppose matrix densification during rehydration.

Characterisation of templated xerogels for molecular sieve application

This paper presents the results of the characterisation of templated silica xerogels as precursor material for molecular sieve silica membranes for gas separation. The template agent integrated in the xerogel matrix is a methyl ligand covalently bended to the siloxane network in the form of methyltriethoxysilane (MTES). Several surface and microstructural characterisation techniques such as TGA, FTIR, NMR, and nitrogen adsorption have been employed to obtain information on the reaction mechanisms involved in the sol-gel processing of such molecular sieves. The characterisation results show the effects of processing parameters such as heat treatment temperature, and the concentration of the covalently bonded template on the development of the pore structure. It was found that calcination temperature significantly enhanced the condensation reactions thus resulted in more Si-O-Si groups being formed. This was also confirmed with the data of FTIR characterisation showing enhanced silicon bands at higher heat treatment temperatures. As a result of the promoted densification and shrinkable pore network the micropore volume also reduced with increasing methyl ligand molar ratio. However, the mean pore diameter does not change significantly with calcination temperature. While the contribution of the templates towards controlling pore size is less precise, increasing the methyl ligand molar ratio results in the broadening of the pore size distribution and lower pore volume. Higher template concentration induces the collapse of the xerogel matrix due to capillary stress promoting dense xerogels with low pore volume (C) 2001 Elsevier Science B.V. All rights reserved.

Freeform fabrication of aluminum metal-matrix composites

A series of metal-matrix composites were formed by extrusion freeform, fabrication of a sinterable aluminum alloy in combination with silicon carbide particles and whiskers, carbon fibers, alumina particles, and hollow flyash cenospheres. Silicon carbide particles were most successful in that the composites retained high density with up to 20 vol% of reinforcement and the strength approximately doubles over the strength of the metal matrix alone. Comparison with simple models suggests that this unexpectedly high degree of reinforcement can be attributed to the concentration of small silicon carbide particles around the larger metal powder. This fabrication method also allows composites to be formed with hollow spheres that cannot be formed by other powder or melt methods.

Finite, three-dimensional adsorbed phase growth in activated carbon mesopores

The role of PACs (primary adsorption centers) in the mesopore (i.e., transport) region of activated carbons during adsorption of polar species, such as water, is unclear. A classical model of three-dimensional adsorption on finite PACs is presented. The model is a preliminary, theoretical investigation into adsorption on mesopore PACs and is intended to give some insight into the energetic and physical processes at work. Work processes are developed to obtain isotherms and three-dimensional sorbate growth on PACs of varying size and energetic characteristics. The work processes allow two forms of adsorbed phase growth: densification at constant boundary and boundary growth at constant density. Relatively strong sorbate-sorbent interactions and strong surface tension favor adsorbed phase densification over boundary growth. Conversely, relatively weak sorbate-sorbent interactions and weak surface tension favor boundary growth over densification. If sorbate-sorbate interactions are strong compared to sorbate-sorbent interactions, condensation with hysteresis occurs. This can also give rise to delayed boundary growth, where all initial adsorption occurs in the monolayer only. The results indicate that adsorbed phase growth on PACs may be quite complex.

Variation of the crystalline structure of coal char during gasification

The variation of the crystallite structure of several coal chars during gasification in air and carbon dioxide was studied by high-resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD) techniques. The XRD analysis of the partially gasified coal chars, based on two approaches, Scherrer's equation and Alexander and Sommer's method, shows a contradictory trend of the variation of the crystallite height with carbon conversion, despite giving a similar trend for the crystallite width change. The HRTEM fringe images of the partially gasified coal chars indicate that large and highly ordered crystallites exist at conversion levels as high as 86%. It is also demonstrated that the crystalline structure of chars can be very different although their pore structures are similar, suggesting a combination of crystalline structure analysis with pore structure analysis in studies of carbon gasification.

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.

Synthesis and characterization of nano-hetero-structured dy doped CeO2 solid electrolytes using a combination of spark plasma sintering and conventional sintering

Doped ceria (CeO2) compounds are fluorite-type oxides that show oxide ionic conductivity higher than yttria-stabilized zirconia in oxidizing atmosphere. As a consequence of this, considerable interest has been shown in application of these materials for low (500 degrees-650 degrees C) temperature operation of solid oxide fuel cells (SOFCs). To improve the conductivity in dysprosium (Dy) doped CeO2, nano-size round shape particles were prepared using a coprecipitation method. The dense sintered bodies with small grain sizes (< 300 nm) were fabricated using a combined process of spark plasma sintering (SPS) and conventional sintering (CS). Dy-doped CeO2 sintered body with large grains (1.1 mu m) had large micro-domains. The conductivity in the sintered body was low (-3.2 S/cm at 500 degrees C). On the other hand, the conductivity in the specimens obtained by the combined process was considerably improved. The micro-domain size in the grain was minimized using the present process. It is concluded that the enhancement of conductivity in dense specimens produced by the combined process (SPS+CS) is attributable to the microstructural changes within the grains.

Sintering of maraging steel with phosphorous additions

The aim Of this study was to develop a steel powder system for rapid tooling applications. The properties required are rapid densification, dimensional precision. high mechanical strength and corrosion resistance. To this end. the densification and microstructural development of a loose packed 200 grade maraging steel powder sintered with ferrophosphorous additions was examined. Liquid initially formed from a reaction of the Fe3P and carbon, which was a residue of the polymeric binder used to shape the powder compact. This liquid caused a burst of sintering which ceased as the liquid dissipated. On further heating, a phosphorous rich supersolidus liquid appeared at triple points and grain boundaries leading to rapid densification and a sintered density of 98%.