The influence of oxygen impurities on the formation of AlN-Al composites by infiltration of molten Al-Mg

The influence of residual oxygen in nitrogen on the formation of AlN-Al matrix by reactive infiltration has been investigated. Increasing the oxygen content from 10 ppm upwards decreased the nitride content in the matrix from 64 to 6%, Based on the analysis of the availability of oxygen at the Al-melt/gas interface, three distinct scenarios have been proposed (i) at lowest values, oxygen does not interfere with either infiltration or nitridation reaction; (ii) at intermediate values, nitridation is suppressed, however infiltration continues; and (iii) at a critical upper value, the melt passivates without any infiltration. This phenomenon offers control of the AlN/Al ratio in the matrix and the possibility of creation of microstructural gradierits by the appropriate choice of gas mixtures. (C) 2002 Elsevier Science B.V. All rights reserved.

Influence of homogenization on the processing map for hot working of as-cast Mg-2Zn-1Mn alloy

Processing maps have been developed for hot deformation of Mg-2Zn-1Mn alloy in as-cast condition and after homogenization with a view to evaluate the influence of homogenization. Hot compression data in the temperature range 300-500degreesC and strain rate range 0.001-100 s(-1) were used for generating the processing map. In the map for the as-cast alloy the domain of dynamic recrystallization occurring, at 450degreesC and 0.1 s(-1) has merged with another domain occurring at 500degreesC and 0.001 s(-1) representing grain boundary cracking. The latter domain is eliminated by homogenization and the dynamic recrystallization domain expanded with a higher peak efficiency occurring at 500 degreesC and 0.05 s(-1). The flow localization occurring at strain rates higher than 5 s(-1) is unaffected by homogenization.

Temperature deformation behaviour of a Mg-0.8Al alloy

There is considerable interest currently in developing magnesium based alloys as replacements for aluminum alloys in automobile applications, due to their high specific strength as compared to aluminum alloys. However, the poor formability of magnesium alloys has restricted their applications; superplasticity can be utilized to form components with complex shapes. In the present study, the compressive deformation characteristics of a Mg-0.8 wt% Al alloy with an initial grain size of 19 +/- 1.0 mum have been studied in the temperature range of 623-673 K and at strain rates ranging from 10(-7) to 10(-3) s(-1). The stress exponent was observed to decrease with a decrease in stress. The results are analyzed in terms of the existing theoretical models for high temperature deformation. Furthermore, the potential for superplasticity in this alloy is explored, based on the mechanical and microstructural characteristics of the alloy.

Thermal cycling of Mg-MMCs

Creep resistant Mg alloy QE22 reinforced with maftec(R), saffil(R) or supertec(R) short fibres is cycled between room temperature and 308degreesC at different ramp rates in the longitudinal and transverse directions. From the careful analysis of the strain vs. temperature thermal cycling curves true material behaviour and artifacts from the dilatometer are deciphered. From this analysis true coefficient of thermal expansion and relaxation processes are deduced. Hysteresis at higher temperatures is attributed to the relaxation process, whereas hysteresis at low temperatures giving a tilt-ground shape to the thermal cycling curves is again an artifact due to the instrument. The change in ramp rate highlights this effect. Finally, the effect of thermal cycling on microstructure is examined.

D-MG Tradeoff and Optimal Codes for a Class of AF and DF Cooperative Communication Protocols

Cooperative relay communication in a fading channel environment under the orthogonal amplify-and-forward (OAF), non-orthogonal and orthogonal selection decode-and-forward (NSDF and OSDF) protocols is considered here. The diversity-multiplexing gain tradeoff (DMT) of the three protocols is determined and DMT-optimal distributed space-time code constructions are provided. The codes constructed are sphere decodable and in some instances incur minimum possible delay. Included in our results is the perhaps surprising finding that the OAF and NAF protocols have identical DMT when the time durations of the broadcast and cooperative phases are optimally chosen to suit the respective protocol. Two variants of the NSDF protocol are considered: fixed-NSDF and variable-NSDF protocol. In the variable-NSDF protocol, the fraction of time occupied by the broadcast phase is allowed to vary with multiplexing gain. In the two-relay case, the variable-NSDF protocol is shown to improve on the DMT of the best previously-known static protocol for higher values of multiplexing gain. Our results also establish that the fixed-NSDF protocol has a better DMT than the NAF protocol for any number of relays.

Achieving the D-MG and DMD Tradeoffs of MIMO fading channels

An overview of our recent results relating to the explicit construction of space-time block codes achieving the DMG tradeoff of the quasi-static fading channel is presented. The results include the explicit construction of D-MG optimal codes,generalization of perfect codes to any number of transmit antennas as well as optimal diversity-multiplexing-delay constructions for the MIMO ARQ Channel.

Gibbs energies of formation of intermetallic phases in the systems Pt Mg, Pt Ca and Pt Ba and some applications

The standard Gibbs energies of formation of platinum-rich intermetallic compounds in the systems Pt-Mg, Pt-Ca, and Pt-Ba have been measured in the temperature range of 950 to 1200 K using solid-state galvanic cells based on MgF2, CaF2, and BaF2 as solid electrolytes. The results are summarized by the following equations: ΔG° (MgPt7) = −256,100 + 16.5T (±2000) J/mol ΔG° (MgPt3) = −217,400 + 10.7T (±2000) J/mol ΔG° (CaPt5) = −297,500 + 13.0T (±5000) J/mol ΔG° (Ca2Pt7) = −551,800 + 22.3T (±5000) J/mol ΔG° (CaPt2) = −245,400 + 9.3T (±5000) J/mol ΔG° (BaPt5) = −238,700 + 8.1T (±4000) J/mol ΔG° (BaPt2) = −197,300 + 4.0T (±4000) J/mol where solid platinum and liquid alkaline earth metals are selected as the standard states. The relatively large error estimates reflect the uncertainties in the auxiliary thermodynamic data used in the calculation. Because of the strong interaction between platinum and alkaline earth metals, it is possible to reduce oxides of Group ILA metals by hydrogen at high temperature in the presence of platinum. The alkaline earth metals can be recovered from the resulting intermetallic compounds by distillation, regenerating platinum for recycling. The platinum-slag-gas equilibration technique for the study of the activities of FeO, MnO, or Cr2O3 in slags containing MgO, CaO, or BaO is feasible provided oxygen partial pressure in the gas is maintained above that corresponding to the coexistence of Fe and “FeO.”

Phase equilibria and thermodynamics of the system Dy-Mg-Cl at 1073 K

The phase relations in the system Dy–Mg–Cl at 1073 K have been established by isothermal equilibration and chemical analysis of quenched samples. Liquid Mg-rich alloy was found to be in equilibrium with molten DyCl2. Therefore, DyCl2 can be synthesized by reduction of MgCl2 with excess of metallic Dy at 1073 K. The Gibbs energy of formation of DyCl2 at 1073 K was evaluated by two different methods. From voltammetric determination of decomposition voltage, the upper limit for the standard Gibbs energy of formation of DyCl2 was estimated to be −505(±20) kJ mol−1. A value of −543(±10) kJ mol−1 was deduced from phase relations using Gibbs–Duhem integration. The value for the standard Gibbs energy of DyCl2 indicates that the Dy2+ ion has a potential capability for reducing TiCl4 to metal titanium. At the same time, Mg is a reductant for Dy3+ produced during the reduction of TiCl4. Thus, it is thermodynamically confirmed that reduction of TiCl4 by magnesium using a reaction mediator in the salt phase is feasible.

Solid state electrochemical sensor for monitoring Mg in Al refining process

Novel solid-state electrochemical sensors have been designed using the Mg2+ cation conductors incorporating novel solid-state reference electrodes for in-line monitoring of Mg in molten Al during the refining process and also for in-line monitoring of Mg content in molten Al in the alloying process. In this paper we report the preparation of Mg2+ ion conductors, MgAl2O4 and MgZr4(PO4)6, by the solid state ceramic synthesis route, measurement of their electrical properties using ac-impedance spectroscopy and application of the above cation conductors for designing novel electrochemical sensors for monitoring Mg dissolved in molten Al. The activation energy for Mg2+ ion conduction in MgAl2O4 is 2.08 eV and in MgZr4(PO4)6 is 1.7 eV, respectively. The sensors have been found to respond rapidly to change in Mg content in molten aluminium around 1000 K.

Evolution of sub-micron grain size and weak texture in magnesium alloy Mg-3Al-0.4Mn by a modified multi-axial forging process

This is the first successful attempt to produce simultaneously ultrafine grain size and weak texture in a single-phase magnesium alloy Mg-3Al-0.4Mn through an optimal choice of processing parameters in a modified multi-axial forging (MAF) process. An average grain size of similar to 0.4 mu m and a weak texture could be achieved. This has led to an increase in the strength as well as room-temperature ductility (55%). The plot of the yield loci shows a decrease in anisotropy after MAF. (C) 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Phase relations and Gibbs energies of spinel phases and solid solutions in the system Mg-Rh-O

Pure stoichiometric MgRh(2)O(4) could not be prepared by solid state reaction from an equimolar mixture of MgO and Rh(2)O(3) in air. The spinel phase formed always contained excess of Mg and traces of Rh or Rh(2)O(3). The spinel phase can be considered as a solid solution of Mg(2)RhO(4) in MgRh(2)O(4). The compositions of the spinel solid solution in equilibrium with different phases in the ternary system Mg-Rh-O were determined by electron probe microanalysis. The oxygen potential established by the equilibrium between Rh + MgO + Mg(1+x)Rh(2-x)O(4) was measured as a function of temperature using a solid-state cell incorporating yttria-stabilized zirconia as an electrolyte and pure oxygen at 0.1 MPa as the reference electrode. To avoid polarization of the working electrode during the measurements, an improved design of the cell with a buffer electrode was used. The standard Gibbs energies of formation of MgRh(2)O(4) and Mg(2)RhO(4) were deduced from the measured electromotive force (e.m.f.) by invoking a model for the spinel solid solution. The parameters of the model were optimized using the measured composition of the spinel solid solution in different phase fields and imposed oxygen partial pressures. The results can be summarized by the equations: MgO + beta -Rh(2)O(3) -> MgRh(2)O(4); Delta G degrees (+ 1010)/J mol(-1) = -32239 + 7.534T; 2MgO + RhO(2) -> Mg(2)RhO(4); Delta G degrees(+/- 1270)/J mol(-1) = 36427 -4.163T; Delta G(M)/J mol(-1) = 2RT(xInx + (1-x)In(1-x)) + 4650x(1-x), where Delta G degrees is the standard Gibbs free energy change for the reaction and G(M) is the free energy of mixing of the spinel solid solution Mg(1+x)Rh(2-x)O(4). (C) 2011 Elsevier B. V. All rights reserved.

Ultrahigh-temperature metamorphism from an unusual corundum plus orthopyroxene intergrowth bearing Al-Mg granulite from the Southern Marginal Zone, Limpopo Complex, South Africa

The Southern Marginal Zone of the Limpopo Complex is composed of granite-greenstone cratonic rocks reworked by a Neoarchean high-grade tectono-metamorphic event. Petrographic and mineral chemical characterization of an Al-Mg granulite from this zone is presented here. The granulite has a gneissic fabric with distinct Al-rich and Si-rich layers, with the former preserving the unusual lamellar (random and regular subparallel) intergrowths of corundum and symplectic intergrowth of spinel with orthopyroxene. The Al-rich layer preserves mineral assemblages such as rutile with orthopyroxene + sillimanite +/- A quartz, Al-rich orthopyroxene (similar to 11 wt%), spinel + quartz, and corundum in possible equilibrium with quartz, while the Si-rich layer preserves antiperthites and orthopyroxene + sillimanite +/- A quartz, all considered diagnostic of ultrahigh-temperature metamorphism. Application of Al-in-opx thermometry, ternary feldspar thermometry and construction of suitable pressure-temperature phase diagrams, compositional and model proportion isopleth results indicate P-T conditions as high as similar to 1,050-1,100 A degrees C, and similar to 10-12 kbars for the Al-Mg granulite. Our report of ultrahigh-temperature conditions is significant considering that the very high temperature was reached during decompression of an otherwise high-pressure granulite complex (clockwise P-T path), whereas most other ultrahigh-temperature granulites are linked to magma underplating at the base of the crust (counterclockwise P-T path).