An evaluation of thermal plasmas in pyrometallurgy

The development of reliable, high powered plasma generators has resulted in many plasma processes being proposed as alternatives to existing pyrometallurgical technologies. This work evaluates the advantages and disadvantages of plasma systems by reviewing plasma generators, their integration with reactors and the process economics. Many plasma systems were shown to be technically and economically superior to existing technologies, but some of the plasma system advantages quoted in the literature were found to be impractical because of other system constraints. Process applications were limited by the power inputs available from plasma generators compared to AC electric furnaces. A series of trials were conducted where chromite and steelplant baghouse dusts were smelted in the Tetronics' 2.0 MW transferred arc/open bath reactor to confirm the operating characteristics of the plasma system and its economics. Chromite smelting was technical superior to submerged arc furnace technology, but the economics were unfavourable because of the limited power available from the water-cooled plasma torch and the high electrical energy consumption. A DC graphite electrode plasma furnace using preheated and prereduced chromite concentrates will compete economically with the submerged arc furnace. Ni, Cr and Mo were economically recovered from high alloy content steelplant dusts for recycling. Five Electric Arc Furnace dusts were smelted to produce a non-toxic residue and recover the contained zinc to an enriched zinc oxide product for recycling. It should be possible to condense the zinc vapour directly in a zinc splash condenser to increase the value of the product. Because of the limited power available from plasma generators, plasma processes will be most suitable for treating high and medium value materials such as Au, Pt, Mo, Ni, Ti, V, Cr etc at small production rates, heating metals in tundishes and ladles and remelting superalloy scrap. The treatment of environmentally hazardous waste materials is a particularly interesting application because of the additional financial incentives. Non-transferred arc plasma generators will be used for air and gas preheating in blast furnaces to reduce metallurgical coke consumptions.

Precipitation of chromium containing phases in aluminide coated nickel-base superalloy single crystals

The precipitation of chromium-containing phases, in both the B2 type β-phase coating matrix (nominally NiAl) and the substrate of high-activity-pack-aluminized single crystals of a nickel-base superalloy, is considered in this paper. An ‘edge-on’ transmission electron microscopy (TEM) technique is employed to examine the precipitation of M23X6, σ, α-Cr and other phases after coating and diffusion treatment and subsequent post-coating treatment at 850 and 950 °C. Initial precipitation is dominated by the formation of M23X6 in both the coating and substrate, however, in the case of single-crystal substrates the formation of this carbon-rich phase is not sustained. M23X6 precipitation is superceded by the formation of coherent precipitates of the α-Cr phase which effectively retains the basis but removes the superlattice of the β-matrix. Extensive precipitation of α-Cr has the effect of changing the balance of chromium to molybdenum in solution in the β-phase and further precipitation is dominated by Σ-phase intermetallics and other Cr-Mo-containing phases.

The chemistry of ceramic glazes

The development of ideas and theories concerning the structure of glazes, as one of the glassy materials, are reviewed in the general introduction. The raw materials and the manufacturing process for glazes are described (Chapter One). A number of new vanadyl(IV) dipyridylamine and tripyrldylamine complexes have been prepared, various spectroscopic techniques are used in the investigation of the vanadyl ion in a weak ligand field, the situation of those found in a glaze environment (Chapter Three). In glaze recipes containing silica, potash feldspar, china clay, MO(M= Ca, Sr, Sa, Ti and Zn) and NiO, the ligand field theory is used in the elucidation of the effect of M (in MO) on the absorption spectra and coordination behaviour of Ni(II) in glazes. The magnetic and visible spectral results are reviewed in terms of Dietzel's idea of field strength of M and also in terms of Shteinberg's theory of glaze structure. X-ray diffraction is used for the identification of various species that formed after the firing process of glazes (Chapter Four). In Chapter Five, [] Mossbauer spectroscopy, supplemented by E.S.R., X-ray and visible spectral measurements are used in the investigation of iron in a glaze composition similar to that used in Chapter Four. The Mossbauer results are used in following the influence of; M in MO (M= Sr, Ca and Ba), oxides of titanium(IV) and vanadium(V ), and firing conditions on the chemistry of iron. Generally the iron(II) and iron(III) in the fired glazes are in octahedral sites although there are a range of similar, though not identical environments. A quite noticable influence of M (in MO) on the resonance line width is seen. In one case evidence is found for iron(IV) in an iron/vanadium glaze. E.S.R. of vanadium containing glazes indicate that vanadium is present as V02+ in a highly distorted tetragonal environment .

The geochemistry of the sedimentary rocks of the Harlech Dome, North Wales

Bedrock geochemical analysis, coupled with detailed data analysis, was carried out on some 260 samples taken from two areas of 'the Harlech Dome, near Dolgellau, North Wales. This was done to determine if rocks from mineralised and non-mineralised areas could be distinguished, and to determine mineralisation types and wall rock alterations. The Northern Area, near Talsarnau, has no recorded mineralisation, while the Southern Area, near Bontddu, has been exploited for gold. The rocks sampled, in both areas, were from the Cambrian Gamlan Flags, Clogau Shales, Vigra Flags, later vein materials, and igneous intrusions. All samples were analysed, using a new rapid, atomic absorption spectrophotometric technique, for Si, AI, Fe, Cu, Ni, Zn, Pb, Sr, Hg, and Ba. In addition 60 samples were analysed by X-ray fluorescence for Mn, Ti, Ca, K, Na, P, Cr, Ce, La, S, Y , Rh, and Th. Total CO2 was determined, on selected samples, using a combustion technique. Elemental distributions, for each rock type, in each area, were· plotted, and means, standard deviations, and enrichment indices were calculated. Multivariate statistical analysis on the results distinguished a Cu-type mineralisation in the Northern area, and both Cu and Pb/Zn types in the Southern Area. It also showed the Northern Area to be less strongly mineralised than the Southern one in which both mineralisation types are associated with wall rock alteration. Elemental associations and trends due to sedimentary processes were distinguished from those related to mineralisation. Hg is related to mineralisation, and plots of factor scores, on the sampling grid, produced clusters of mineralisation related factors in areas of known mineralisation. A double Fourier Trend Analysis program, with a wavelength search routine, was developed and used to recognise sedimentary trends for Sr. Y., Rb, and Th. These trends were interpreted to represent areas of low pH and reducing conditions. They also indicate that the supply of sediment remained constant over Gamlan, Clogau, and Vigra times. The trend surface of Hg showed no association with rock type. It is shown that analysis of a small number of samples, for a carefully selected number of elements, with detailed data analysis, can provide more useful information than analysis of a large number of samples for many elements. The mineralisation is suggested to have been the result of water solutions leaching ore metals from the sedimentary rocks and redepositing them in veins.

Intragranular nucleation of austenite

The mechanism of intragranular nucleation of austenite in a duplex stainless steel (Fe-23.1 Cr-6.1 Ni-3.1 Mo-O.165 N-0.017 C, wt.%) weld metal and heat-affected zone (HAZ) has been examined. In the weld metal the acicular austenite is found to nucleate intragranularly on inclusions and subsequent plates form sympathetically resulting in a fine interlocked microstructure. Austenite plates adopt the Kurdjumov-Sachs orientation relationship with the ferrite matrix and grow with diffusion-controlled mechanism as evident from partitioning of substitutional alloying elements. At least one set of fine intrinsic dislocations on the austenite/ferrite interphase interfaces is observed suggesting that the boundaries are semi-coherent. The high cooling rates involved in the HAZ result in a supersaturated ferrite matrix where precipitation of intragranular austenite occurs as a result of reheating associated with subsequent passes. Austenite particles in the HAZ nucleate preferentially away from gain boundary austenite allotriomorphs indicating that intragranular precipitation is favoured by the supersaturated matrix.