John Gisby

MTDATA - thermodynamic and phase equilibrium software from the National Physical Laboratory

Abstract In the past, the complexity of the chemical and phase equilibria established during many industrial processes has prevented the kind of in-depth understanding of their thermodynamics necessary for successful and efficient process control. Predictive thermochemistry, as embodied within MTDATA, makes such an understanding possible. MTDATA allows equilibria to be calculated for multicomponent systems of practical interest, containing many different types of phase, from critically assessed data for their component binary and ternary subsystems. Very complicated calculations can be undertaken with as many as thirty different components and 500 phases being considered simultaneously. A number of modules are incorporated for critically assessing, manipulating and retrieving the data, making various types of calculation and plotting binary, ternary, multicomponent, and predominance area diagrams. Facilities are also available for users to link the complexities of phase equilibrium calculations within MTDATA to their own software or to third party commercial software packages enabling users to simulate unit operations within an industrial plant or to integrate kinetic effects. Special derivatives of MTDATA are also now being developed to provide the sophisticated capabilities within MTDATA to non-expert users for special applications using carefully designed graphical user interfaces, which are both easy to use, and which provide output specifically designed for the particular industrial need.

The compound energy model for ionic solutions with applications to solid oxides

The application of the compound energy model to crystalline ionic phases is discussed and compared with the regular solution model. Its application to solutions with reciprocal reactions between cations on different sublattices is discussed with special reference to oxides. Examples are taken from various solutions between spinels, including cases with vacancies and interstitials. Problems connected with the choice of a state of reference for charged components in a multicomponent solution are addressed. This paper was presented at the International Phase Diagram Prediction Symposium sponsored by the ASM/MSD Thermodynamics and Phase Equilibria Committee at Materials Week, October21-23,1991, in Cincinnati, Ohio. The symposium was organized by John Morral, University of Connecticut, and Philip Nash, Illinois Institute of Technology.

Application of Metastable Phase Diagrams to Silicate Thin Films for Alternative Gate Dielectrics

Using the concept of metastable phase diagrams, we discuss the microstructure evolution during annealing of amorphous ZrO2–SiO2 and HfO2–SiO2 thin films for gate dielectric applications. These systems are characterized by a low solid solubility, a liquid miscibility gap and a kinetic barrier to the formation of the complex, crystalline silicate. We show that phase partitioning is expected for most compositions. Compositions within the metastable extensions of the spinodal are unstable and will spontaneously unmix in the amorphous phase upon heating. Hafnia- or zirconia-rich phases will subsequently crystallize to form HfO2 or ZrO2. Most compositions outside the metastable extensions of the liquid phase miscibility gap must phase separate above the crystallization temperature by nucleation of crystalline HfO2 or ZrO2 out of an amorphous silica-rich matrix. We present calculations of the metastable extensions of the miscibility gap and spinodal. The calculations predict that SiO2-rich compositions, investigated for gate dielectric applications, will show spinodal decomposition if they contain less than ~90 mol% SiO2 at the typical device processing temperature of 1000°C. Experimental studies of Hf-silicate films with three different compositions, between ~40 and 80 mol% HfO2 that lie inside and outside the miscibility gap, respectively, are presented. All three compositions show phase separation. Despite the different pathways of microstructure evolution, the final phase separated microstructures are similar. Experimental verification of the pathways that lead to these microstructures requires further studies.

Predictive thermochemistry and phase equilibria of slags

It is well understood that the efficient recovery of values by pyrometallurgical processing of ores requires control of the slag chemistry. In an effort to improve the understanding of slags, a thermodynamic database on subsystems of the CaO-MgO-Fe-O-Al2O3-SiO2 system has been generated through critical assessment of the literature. Data for connecting systems of specific industrial interest are being added. The data can be combined using well-established thermodynamic principles to make calculations on the multicomponent systems of practical interest. Following a description of the calculations, this article illustrates specific applications of thermodynamic modeling to the extraction of copper, nickel, and precious metals; zinc extraction; purification of pig iron; meltdown in nuclear reactors; hot corrosion; and pollution control.

MTDATA and the Prediction of Phase Equilibria in Oxide Systems: 30 Years of Industrial Collaboration

This paper gives an introduction to MTDATA, Phase Equilibrium Software from the National Physical Laboratory (NPL), and describes the latest advances in the development of a comprehensive database of thermodynamic parameters to underpin calculations of phase equilibria in large oxide, sulfide, and fluoride systems of industrial interest. The database, MTOX, has been developed over a period of thirty years based upon modeling work at NPL and funded by industrial partners in a project co-ordinated by Mineral Industry Research Organisation. Applications drawn from the fields of modern copper scrap smelting, high-temperature behavior of basic oxygen steelmaking slags, flash smelting of nickel, electric furnace smelting of ilmenite, and production of pure TiO2via a low-temperature molten salt route are discussed along with calculations to assess the impact of impurities on the uncertainty of fixed points used to realize the SI unit of temperature, the kelvin.

Liquidus slopes of impurities in ITS-90 fixed points from the mercury point to the copper point in the low concentration limit

A knowledge of the effect of impurities at the level of parts per million on the freezing temperature of very pure metals is essential for realisation of ITS-90 fixed points. New information has become available for use with the thermodynamic modelling software MTDATA, permitting calculation of liquidus slopes, in the low concentration limit, of a wider range of binary alloy systems than was previously possible. In total, calculated values for 536 binary systems are given. In addition, new experimental determinations of phase diagrams, in the low impurity concentration limit, have recently appeared. All available data have been combined to provide a comprehensive set of liquidus slopes for impurities in ITS-90 metal fixed points. In total, liquidus slopes for 838 systems are tabulated for the fixed points Hg, Ga, In, Sn, Zn, Al, Ag, Au, and Cu. It is shown that the value of the liquidus slope as a function of impurity element atomic number can be approximated using a simple formula, and good qualitative agreement with the existing data is observed for the fixed points Zn, Al, Ag, Au and Cu, but curiously the formula is not applicable to the fixed points Hg, Ga, In, and Sn. Some discussion is made concerning the influence of oxygen on the liquidus slopes, and preliminary calculations using MTDATA are discussed.

Thermodynamic modelling of phase equilibria in cement systems: multiple sublattice model for solids in equilibrium with non-ideal aqueous phase

Abstract The thermodynamics of the CaO–SiO2–H2O (C–S–H) gel phase present in cement systems has traditionally been modelled in terms of one or more stoichiometric solid phases. We present a model for the C–S–H gel phase based on non-ideal solution of ions and/or molecular species on a number of sublattices similar to that used extensively in National Physical Laboratory’s MTDATA software for modelling oxides and alloy phases. In application to the C–S–H system, aqueous phase compositions are represented within experimental uncertainties, and measured pH values are predicted exceptionally well although not included in the model parameterisation. Extensions to the base C–S–H model to account for the presence of Al2O3, modelling of the analogous M–S–H phase in MgO containing systems and an application to nuclear waste disposal technology where the portioning of uranium between the gel, aqueous and other phases is calculated, are also discussed.

Thermodynamic data to model the interaction between coolant and fuel in gen IV sodium cooled fast reactors

Understanding the behaviour of nuclear fuels in various environments is vital to the design and safe operation of nuclear reactors. While this is true if the reactor is operating within its design specification, it is even more so if accidents occur and the fuel is exposed to unexpected temperatures, pressures or chemical environments. It is clearly hazardous and costly to explore all such scenarios experimentally and therefore it is necessary to undertake modelling where possible using well-grounded theoretical approaches. This paper will show examples of where calculations of chemical and phase equilibria have been applied successfully to the long term storage of nuclear waste, phase formation during core meltdown and prediction of fission product release into the atmosphere. It will also highlight the development of thermodynamic data carried out during the European Metrology Research Project Metrofission required to model the potential interaction between the coolant, nuclear fuel, containment materials and atmosphere of a sodium cooled fast reactor.

Application of a Sub-lattice Model to Predictions of Cement Hydrate Chemistry

The incongruous dissolution of C-S-H gel is central to the performance of the chemical barrier in a deep geological disposal repository for nuclear wastes. Numerous thermodynamic models have been developed with which the dissolution of C-S-H gel may be simulated. One of the limitations in many of these models is their inflexibility in terms of incorporating additional chemical elements into the C-S-H gel structure. This chapter reports the application of a sub-lattice model for C-S-H gel, allowing for example, substitution of alumina, sulphate or heavy metals into the structure. Comparisons are drawn between the sub-lattice representation and other models, illustrating the inherent flexibility of this approach.

Purification of pigment grade titanium dioxide by processing in molten salts

Abstract An alternative method of purifying the mineral rutile (TiO2) is reported. This offers potential savings in process energy and reduced waste when compared with current technology. The work reported here focused on refining rutile sand (95%TiO2) containing transition metal oxides (Fe2O3, SiO2, ZrO2, Cr2O3, V2O5 and Al2O3), which impart a strong colour to the mineral concentrate. The objective was to remove the colour giving oxides to produce rutile of over 99% purity (which is white in colour). Complete dissolution in molten salt (alkali chloride–fluoride) at 750°C allowed electroseparation of the transition metals between a graphite anode and a stainless steel cathode. The voltage maintained across the cell ensured removal of transition metal ions from the solution, with minimal loss of titanium. In this process, dissolution of TiO2 was enhanced by partial replacement of chloride by fluoride in the melt to allow the complex ion TiF2−6 to dominate the titanium speciation. This had the additional advantage of minimising losses of Ti as volatile TiCl4.