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By J. E. Dutrizac

"The end of an era in zinc metallurgy took place on July 31, 1976 when the horizontal retort furnaces of the National Zinc Company in Bartlesville, Oklahoma were permanently shut down (1) . For more than a century, horizontal retorting had been the most common method of producing zinc in the United States; it was a thriving industry in many parts of that country, especially in the natural gas belts of Oklahoma and Texas. With the Bartlesville closure, yet another metallurgical process has become an object of historical interest for North American metallurgists. Although shrouded in controversy, the origins of zinc metallurgy seem to date back at least 2000 years. Pyrometallurgical methods with carbon reductants are capable of producing zinc from oxidic zinc ores, but only above the boiling point of the metal. Although slow cooling results in re-oxidation of the zinc vapour by air or carbon monoxide, quenching yields liquid zinc; some form of rapid cooling, either accidental or intentional, was likely used by ancient metallurgists to liquify the metal. Zinc metal found in Athenian objects of the Roman era was likely of accidental origin. The Romans employed brass extensively for coins and ornaments(2) , and this was intentionally produced by the calamine process whereby oxidic zinc ores were added to molten copper under strongly reducing conditions. Zinc appears to have been known in China and India as early as 1000-1300 A.D., and was probably smelted commercially in those countries from the 14th century. Although the early metallurgical procedures were probably inefficient, they were able to produce zinc metal in significant amounts. The large heaps of zinc residues with clay retorts bear testimony to an early smelting industry of impressive magnitude. It is estimated that the heaps at Zawar, India alone represent the extraction of 100 000 tons of metallic zinc(2) In the 1730s the smelting of oxidic zinc ores was developed in England using a vertical retort method. In 1788 a British patent was granted for making zinc from zinc blends (ZnS) by roasting the ore in a coalfired reverberatory furnace, mixing the calcine with charcoal and smelting the mixture with suitable zinc condensation. The English process was very energy intensive, however, and early in the 19th century the Belgians developed a horizontal retort process for the reductiondistillation of zinc that was more fuel efficient. This technique was gradually developed into what came to be known as the Belgian process, the forerunner of the ""modern"" horizontal retort furnace."

Jan 1, 1999

By Richard D. Miller

The helium resources base of the United States was estimated by the U.S. Bureau of Mines (Bureau) to be 894.6 Bcf as of January 1, 1989. These resources are divided into four categories in decreasing degree of assurance of their existence: (1) helium in storage and in proved natural gas reserves, 282.4 Bcf, (2) helium in probable natural gas resources, estimated at 237.7 Bcf, (3) helium in possible natural gas resources, estimated at 263.1 Bcf and (4) helium in speculative natural gas resources, estimated at 111.4 Bef. These helium resources are further divided into depleting and nondepleting, with the helium in storage being in a classification. The depleting resources are those associated with natural gasfields that are, or will be produced for the natural gas they contain. Almost all of the helium in potential (probable, possible and speculative) natural gas resources is included in this classification. These depleting resources are estimated to contain 775 Bcf of the total helium resource base. Helium resources contained in nondepleting natural gas resources, i.e., those in shut-in, abandoned, or otherwise nonproducing natural gas fields, are estimated to total 84 Bcf There is 35 Bcf of helium in storage in the Federal Government-owned Cliffside Gasfield near Amarillo, TX.

Jan 1, 1990

By Julio Cezar de Sousa Zorzi

Aços com teor de Mn entre 15% e 30% apresentam ductilidade excepcionalmente alta para sua elevada resistência mecânica, devido à ocorrência de transformação de fases (efeito TRIP) e/ou à formação de maclas de deformação (efeito TWIP) na microestrutura predominantemente austenítica. A adição de Mn ajuda a manter a austenita até a temperatura ambiente, evitando a sua decomposição após o recozimento aplicado depois da laminação a frio. O objetivo desse estudo foi avaliar o efeito da temperatura de recozimento na microestrutura e nos valores de propriedades mecânicas de um aço com 17% de Mn, por meio de simulações piloto das etapas de processamento industrial utilizando dilatômetro e simulador termomecânico do Centro de Pesquisa da Usiminas. Observou-se que o aumento na temperatura de encharque durante o ciclo térmico de recozimento contínuo promoveu a reversão completa da martensita a’ para austenita. Além disso, a alteração desse parâmetro praticamente não afetou o limite de resistência e o alongamento total do aço, embora tenha reduzido significativamente o limite de escoamento.

Jul 30, 2018

By Morris Muskat

In preparing a well for pumping, observations are often made of the fluid level in the well bore or bottom-hole pressures at various times before equilibrium has set in. From a qualitative point of view one may immediately infer that if the rise in the bottom-hole pressure or fluid level is rapid the permeability of the sand about the well bore is large, and converse conclusions may be drawn if the rise is slow. However, a more quantitative estimate will give additional information of value, as will be shown in this paper. To derive such an estimate we may proceed as follows. Let h be the fluid height, above the sand face, at time t, and let yo be the average density of the fluid that enters the bore. The bottom-hole pressure, for a fluid height h will therefore be p = rogh, neglecting, of course, the friction drop in the well bore, while the fluid is rising, as may be justifiably done for most pumping wells. If a is the free area of the open-flow string—assumed to be uniform— the rate of production from the sand during the rise of fluid will be: where the last part of the equation merely indicates that, in general, the production rate Q must be considered as a function of the back pressure, and is determined by it alone. In fact, equation 1 shows that if the rate of rise of the pressure or fluid level is determined as a function of the height of rise, or p, for a number of values of the latter, this functional relation between Q and p will be immediately given. Conversely, if we know this functional relation, the rate of increase of p or h may be predicted, or, by observing the rate of rise of p or h some of the constants of the sand may be determined. Thus we may approximate the production from a well in a pumping state by that of a dead

Jan 1, 1937

Coking coals are very much in demand on a world wide basis, particularly the higher rank coking coals, which form an important part of many coking blends and which represent the smallest portion of the world'scoking coal reserves. Conventional coke oven plants, using these coals, will predominate at least until the next century.Blending schemes for conventional coking require definition of the basic properties of coals so that the factors influencing the carbonization behaviour may be assessed. Several concepts, which are relatively simple, ate available to help promote a better understanding of the bask factors controlling -coke strength and are also useful in suggesting possible lines to follow in the blending of coals for coking.The interpretation of carbonization behaviour and coke structure in terms of petrographically defined coal rank and type provide a basis for planning and exploitation of coal Teserves. The optimum parameters for coking are suggested as follows.1. Type- Vitrinite content (% m.m.f. by volume) 55 ± 5%2. Rank- Mean maximum reflectance of vitrinite 1.30 ± O.10% Carbon content of vitrinite (% d.m.m.f.) 87·5 ± 1·0%The value of a coal should be assessed in relation to all its possible uses in blends. This is a more realistic and productive approach, as compared with considering coals only in relation to the results of blending with"good" coking coals. Blending schemes have been outlined to assist in the assessment of the blend potential of coals of all ranks and types.Reserves of higher rank coking coals in N.S.W. are very limited and should be conserved by blending with the low rank coking coals, of which there are large reserves.Examination of blending theories in relation to N.S.W. coals suggest that blends in the broad categories of minimal downgrading of the higher rank N.S.W. cok...

Jan 1, 1972

By Aloys H. Wohlrab

[THE conditions that govern the selection of a suitable type of detachable bit for the small isolated mine, for rock work and tunnel contracting and for the large mine are quite dissimilar, therefore intelligent recommendation of a particular make of detachable bit must involve consideration of many factors. Small, isolated mines may find advantageous a detachable bit that a larger mine cannot afford to use, because of more efficient conventional steel sharpening and steel-distribution practice, but a small mine may of be able to adopt the practice of larger mines because of necessary capital expendites for equipment for detachable-bit sharpening and shanking. The perfect detachable bit, suitable for all conditions, has n yet been developed. CONVENTIONAL DRILL BIT IN USE That drilling speed increases as the hit gauge decreases is well known, but since small-hole drilling is the exception rather than the rule the rate of such increase is probably not so generally recognized. Tests married out by Holman Brothers Limited1 with 7/8-in. show that when bit sizes are reduced from. 1 ½ in. 1 3/8 in., and 1 3/16 in., to 1 3/8 in., 1¼ in., and it' in., respectively, the volume of the hole is15 per cent less and the drilling speed 4q per cent higher. Recent tests by the United States Bureau of Mines2,3in hard, uniform basalt showed that a reduction in average gauge from 2.077 to 1.826 in., a difference of 0.251 in., gave an increased drilling speed of 65 per cent. The limits to which a drill hole may be extended depend upon the loss in gauge. Since the conventional bit with 5° and 14° clearances did not possess sufficient reaming edge to permit the smaller gauge changes that were required for small-hole drilling, experiments were made in bit construction with a view to correcting this deficiency. This resulted in the adoption of the full reaming cross bit (having full Carr characteristics) by some mines.4 In order to drill holes having a minimum taper from the collar to the bottom of the hole, full reaming center-hole cross bits with 90° cutting angles, 5° and I4° wing tapers, forged on 7/8-in. quarter-octagon drill rods, are used in the conventional drill-steel practice at Hollinger. In the steel shop close attention is given to the condition of the dies and dollies, which, combined with a rigid inspection of the finished bit, ensures as nearly a perfect bit as can be forged economically. Shop practices and costs have been discussed in earlier papers.5,6 The method by which the radii for the special dies used for forging bits of different gauge diameter are obtained so that the points and reaming edges cut circles of the same diameter has been discussed by Hibbert.7 REQUIREMENTS FOR DETACHABLE BIT FOR HOLLINGER Under these circumstances, it was apparent that it would be difficult to introduce a detachable bit that could successfully compete with the conventional bit already in]

Jan 1, 1942

By D. H. Ryan, B. Abdul, M. Pernechele, E. Asselin

Hydrometallurgical processing of sulphide concentrates at medium temperature (150°C) produces residues, which contain valuable metals (Cu, Ni) as well as sulphur and iron bearing minerals and phases. The low solubility of iron during the medium temperature processing of sulphide ores can favour the formation of poorly crystalline, nano-scale iron oxide/oxyhydroxide phases. A better understanding of the formation and structure of these iron precipitates may elucidate key factors that would ultimately result in lower valuable metal losses and more stable leach residues. Residues from two medium temperature leach processes were characterized by Mössbauer Spectroscopy. Some portions of the Mössbauer Spectrum were suspected to be linked to jarosite but could not be positively identified as such. There was a broad range of disorder and substitution present in the material and solely attributing it to jarosite proved difficult. Various synthetic jarosites with Cu substitution were precipitated for Mössbauer analysis. These were then characterized by Quantitative X-Ray Diffraction (QXRD), Scanning Electron Microscopy (SEM), Inductively Coupled Plasma Mass Spectroscopy (ICP-MS) and Mössbauer Spectroscopy. The Mössbauer Spectra of the synthetic jarosites is compared with that of the residues from medium temperature (150°C) sulphide concentrate leaching.

Jan 1, 2014

By Brendan Reilly, Jon Isaacson, Paul McDermott

Kenny/Shea JV is constructing the water intake tunnel for the new Elm Road Generating Station, a supercritical coal-fired power plant in Oak Creek, Wisconsin, being built by Bechtel Power Corporation. The intake tunnel system consists of a temporary mining shaft, pump house and intake channel riser shafts, and four lakebed intake shafts. An 8.33 m diameter, 2,800 m long TBM mined rock tunnel is being constructed to connect the shafts. The intakes are located 2.4 kilometers offshore in Lake Michigan. The shafts and tunnel are being constructed in glacial tills and Silurian Dolomite. The estimated tunnel completion is December 2007.

Jan 1, 2007

By Rubén Ossandon, Diego Venegas

La presente investigación describe la caracterización de una de las zonas de alteración hidrotermal de El Laco, denominada Zona Steam Heated del sector SE (ZSH-SE) con respecto al cima del Volcán El Laco, además de apoyar el modelo mixto magmático-hidrotermal.

May 1, 2008

By F. Keller, E. H. Dix

The use of magnesium as an alloying element in aluminum alloys has been limited, in general, to comparatively small quantities. In duralumin-type, strong aluminum alloys, magnesium is present to the extent of 35 to 3/4 per cent. and various grades of Magnalite and the "Y" alloy of the National Physical Laboratory of England contain up to 1 1/2 per cent. In this country small quantities of aluminum alloy sheet containing 4 per cent. magnesium are produced commercially. All commercial aluminum contains sufficient silicon to convert a portion of the magnesium added to the compound Mg2Si. It is well known that the solubility of both magnesium and magnesium-silicide decrease with decrease in temperature. It is, therefore, impossible to separate the age-hardening effect of the magnesium-silicide from that of magnesium, except by the use of aluminum of such high purity that the silicon content is negligible. The present paper is the fifth l, 2, 3, 4 of a series from the laboratories of the Aluminum Co. of America reporting the results of investigations of the equilibrium relations in aluminum-rich alloys made from the high-purity aluminum manufactured by this company. 5 Previous Investigations A number of investigations have been made of the constitution of the complete aluminum-magnesium system and several determinations made

Jan 1, 1929

Atlas Copco Wagner launched its ST1010 Scooptram load haul dumper. The ST1010 replaces the company’s Wagner ST-1000 Scooptram. The improvements to the Wagner ST1010 include increased reliability, ease of maintenance and driver comfort or ergonomics. The ST1010 has been redesigned and has added several new features and options not offered in the earlier model. These include anew boom design with side stops. Heavy reinforcements to the bogie offer better protection against the harsh working conditions in underground mining and tunneling. An auto lube system has also been added as has paint-on grip tread to reduce slips and falls during maintenance checks or repair work. Other features include a heavy-duty, auxiliary-fan motor, an isolated transverter, remote diagnostic pressure taps, a bolt-on battery box, raised air-intake, improved fuel-filter access for easier maintenance, larger wear-bars around the engine tub, and smaller, higher output batteries

Jan 1, 2000

By M. L. Requa

This paper is abstracted from the report of the Appraisement Committee of the Independent Oil Producers' Agency, of which the writer was Chairman. The other members of the committee were M. V. McQuigg and R. S. Haseltine. To Thomas Cox, engineer in charge of the investigation, and to his efficient staff of assistants, is due the credit for the detail work necessary in carrying out the plan of the Committee. It treats only of the valuation of the lands, wells, and piping, without going into details of equipment and other features. It was recognized, early in the operation, that the value of oil lands was the value of oil ,to be extracted and marketed, less the costs attendant thereon. Referring this back to the costs in cents per barrel, it became obvious that surface improvements, absolutely necessary in the production of oil, from wells then drilled, had no separate and independent value aside from the value of the land, but that any excess equipment, not necessary for the production of oil from present wells, such as drilling tools, well casing, etc., should be given a present condition value. In valuing the properties of the Independent Oil Producers' Agency, the Committee has considered the following facts: 1. That from each property there will ultimately be produced a certain total quantity of oil. 2. That in the production of that oil a certain total quantity of money will be expended. 3. That a certain total amount of money will be received from the oil. 4. That the total net receipts will be the total gross receipts less the cost of development and production. 5. That the present value of the net receipts must be such an amount that when invested by a purchaser it will be returned with 8 per cent, interest additional during the life of the property. The initial procedure consisted in making a general reconnaissance of the entire district in which the property was located and determining the lithological and structural conditions underlying the area. The data obtained from each individual tract comprised the logs of all the wells

Jan 1, 1918

By Ralph Hultgren, Haim H. Chiswik

In recent years considerable attention has been devoted to the development of new commercial uses for silver, chiefly because of lowered prices and large stocks of the metal. This has led to increased interest in the phase diagrams of silver alloys. The silver-lead diagram is reported' to be of the simple eutectie type, but no measurements of the solubility of lead in silver have been made. The solubility of silver in lead has been estimated2 from diffusion experiments and resistance measurements to vary with temperature from 0.09 to 0.18 atomic per cent (0.05 to 0.10 weight per cent). Silver-rich silver-lead alloys have recently been recommended as high-strength bearing metals3 The silver-bismuth diagram is similar.' The solubility of bismuth in silver. has been estimated to be about 5.5 weight per cent on the basis of X-ray work.4 Matthiessen6 found a solubility of silver in bismuth from 0.25 to 0.50 per cent by conductivity measurements. Silver and thallium form the same type of diagram,' with no data on their mutual miscibilities. We have studied the first two of these diagrams by X-ray methods, verifying their main features and determining the solubilities of lead and bismuth in silver at several temperatures. We also determined the solubility of thallium in silver at one temperature. The solubilities of silver in lead and in bismuth were found to be too low to be detectable. Materials and Methods Mallinckrodt precipitated silver, analytical reagent, was used. Maximum impurities listed on the label were: chloride, 0.005 per cent; copper, 0.001; iron, 0.002; other heavy metals (as Pb), 0.002; and sulphate (SO³), 0.05. The lattice constant was found to be a0 = 4.0782 $., in good agreement with the value of Jette and Foote,6 a0 = 4.0779 A., for

Jan 1, 1940

By Shuvranshu K. Rout, Anup K. Mandal, Biswajit Das, Manos De

"To adopt new technology advancement in Steel Plant, there is a requirement of shifting of operation process from Coke Wet Quenching (CWQ) to Coke Dry Quenching (CDQ). New CDQ chamber foundation with deep basement and underground conveyor tunnel are to be constructed in an operating plant where heavy foundations and structures are located in close proximity. Furthermore, the existing CWQ system will be in operation during new underground construction and erection. Challenges to deep excavation of tunnel and chamber foundation consist of non-uniform ground condition, prevent washing out of soil from bottom of existing foundations, stability of existing nearby structures, presence of large number of underground utilities, ensuring safe underground workplace to construction resources engaged in new construction work along with project schedule and budget constraints. A combination methods involving use of soil nailing, soil grouting, contiguous bored pile and micro pile had been adopted for protection of excavation sides as well as existing structures. Each side of excavation in different stretches were analysed during design as well as construction stages. The use of combination of all techniques in a single brown field project in context of the nature of site constraints and safety issues made this a unique project.INTRODUCTIONSteel Industry is one of the backbones of industrial growth of any developing country like India. Due to increasing land prices most of the steel plants in India are expanding within their existing plant facilities. In addition to that, there is demand of adoption of new technology for future expansion projects to set new benchmarks with global standards.The property owner had earlier installed a Coke Wet Quenching (CWQ) for their Coke Plant. Now, there is a requirement from process department to proceed with Coke Dry Quenching (CDQ). To facilitate the CDQ within the existing CWQ which will be in operation is the main challenge for the property owner. The second challenge is the limited space for underground construction and subsequent equipment erection within the stipulated time frame.From a geotechnical prospective, the project team had uncertainty and reservations in their mind about the construction methodology. Therefore, the role of three “C”: ‘Consultant’-‘Client’- ‘Contractor’ and their combining brainstorming is essential to freeze a working plan for achieving the goal. In this paper, only the excavation support systems for underground foundation structures have been highlighted in the context of solving geotechnical problems."

Jan 1, 2017

By J. Y. Hwang, M. L. Jeong, R. C. Greenlund

Various aluminum-smelting by-products from three production sources were received and characterized. The waste materials were tested for compound identification and environmental acceptance. A coarse metallic aluminum recovery test using an Eddy Current separator (ECS) was performed using two different Circuit configurations. White dross performed equally well with either Circuit, while black dross processing shows significant difference on the separation results. It was found that ECS technology was effective for particle sizes down to 6-10 mesh.

Jan 1, 2001

By L. F. Elkins

Water coming into wells with bottom water present in the Fosterton field, when their oil recovery was only 0.1 to 1.5 per cent of oil in place below the lowest perforation, confirms lack of shale barriers to vertical flow which also are not apparent in cores and electric logy. Low contrast of vertical and horizontal permeability, high mobility ratio betweerz oil and water zone and pos.rible rate effects due to gravity Combine to prevent easy analysis of water invasion pattern and efficiency by analogy or intuition. Theoretical analysis of performance including these factors using a new direct nurnerical .solution of potential distribution in a network led to unanticapted indications that water would under-run the entire oil reservoir with low volumetric coverage if supplied through natural influx or peripheral water injecfion below the oil-water contact. An unusual pattern of water injection is to he adopted in this recently unitized pool to provide more uniform water flooding in that two-thirds of the oil reservoir not underlain by bottom wafer. INTRODUCTION The Fosterton field, Southwestern Saskatchewan, Canada, was discovered in Jan., 1952. It produces at a depth of 3,100 ft from a pinch-out of the Roseray sand at the Lower Cretaceous-Jurassic unconformity. The field, covering 2,500 acres, contains 54 wells on 40-acre spacing. Development was essentially complete in June, 1954, but significant production did not start until May, 1955, when a pipeline outlet became available. Within one year rapid in- creases in gas-oil ratio and early encroachment of water created operating problems in the down-structure eastern half of the field and raised serious questions about reservoir performance and ultimate recovery. This paper describes the unusual behavior of water encroachment—on both well and reservoir bases—and the analyses made to interpret it. The field was unitized July 1, 1958, for water flooding. A somewhat unconventional

By P M. Hancock

The West Coast contains one of the world's giant placer gold deposits with production since the 1860s totalling some six million ounces (present day value NZ$ 3.6 billion). The deposits have been worked variously by hand, ground sluicing, hydraulicking and/or elevating, blocking out, deep leading and bucketline dredging. Since the sharp gold price rise of 1979 - 1980 gold production has increased steadily (in spite of the closure of the Kaniere dredge) to some 30 000 ounces (933 kg) in 1984. Production is primarily from some 100 medium scale mining, operations treating 50 - 200 000 m3 of auriferous late Pleistocene fluvial gravels year. In spite of their economic value the deposits remain only poorly investigated and many fundamental questions relating to the origin and formation of the deposits remain unanswered. This paper attempts to describe the geology of the deposits and outline a genetic model for their formation, and then discusses some of the economic aspects and current limitations and opportunities of the growing alluvial gold mining industry of the region.

Jan 1, 1985

By H. A. Kuhn

THE Pittsburg coal field in western Pennsylvania, is conceded to be the most important in the world. To measure its importance it is necessary to understand the extent of its service in the various industries of the country. Probably 90 per cent. of the pig iron manufactured in the United States up to the present time has been made by using coke manufactured from the Pittsburg coal seam in western Pennsylvania. This coal field is the foundation on which the city of Pittsburg rests and is the reason for the great growth of the iron industry in the Pittsburg district. Iron ore is brought to this district, not because Pittsburgh is a. natural location, over other locations, for the iron and steel industry-as its position places the manufacturer at the mercy of the railroads-but the ore is brought 1,100 miles to meet the fuel. It can be said that the illuminating-gas industry in the United States has used this coal exclusively to the same extent that the pig-iron maker has used it. It may be also said that 20 to 25 per cent. of the fuel used on railroads in the United States conies from this coal field. The Pittsburg coal field is unquestionably the center of the industrial population of the United States, for in addition to the industries of the district and those closely adjoining, it has tributary to it all the cities and industries along the Great Lakes and practically all of Canada with the exception of the extreme western and eastern ends. It supplies the industries and population west of Duluth and Superior many hundreds of miles. This coal is floated down the Ohio and Mississippi rivers, supplying the towns en route, and is delivered in New Orleans, a distance of 2,200 miles, for approximately SO to 90 c. per ton transportation cost. It is delivered on the docks of Superior and Duluth at a cost of transportation 50 c. a ton less than the cost of transporting the same coal from Pittsburg to a local consumer in Philadelphia. With other Appalachian coals it has large markets east and along the seaboard, especially for byproduct-coke making and the illuminating-gas industry. It is considered the premier railroad fuel of the world on account of the fact that this coal in a given-sized locomotive will probably haul more cars than any other coal in the

Jan 10, 1914

By D. R. Mathews

The solubility of carbon in electrorefined vanadium was determined to be approximately 0.27 wt pct at the eutectic temperature 1,650° C and 0.03 wt pct at 700° C. The tensile strength and hardness of vanadium increased with car-bon content to the solubility limit, but this effect was small, probably because of the narrow solubility range. Between the solubility limit and 0.3 weight-percent carbon, the second phase had essentially no strengthening effect in vanadium. The second phase, observed metallographically at the grain boundaries and within the grains, was shown by autoradiography to contain high-carbon concentrations. This second phase was identified as VgC by X-ray analysis. The VgC in the grain boundaries contributed largely to the poor cold-and-hot workability of vanadium-carbon alloys. Increased concentrations of V2C occurred at the grain boundaries of the high-carbon alloy ingots as a result of homogenization at 1,600° C for 1 hour. Alloy ingots containing more than 0.36 wt pet carbon (a calculated 2.9 wt pct VaC) following homogenization, cracked severely and failed by intergranular fracture upon swaging at 900° C.

Jan 1, 1965

By John Henderson

FOR some time now the most commonly accepted description of liquid silicate structure has been the "discrete ion" theory, proposed originally by Bockris and owe.' This theory is that when certain metal oxides and silica are melted together, the continuous three dimensional silica lattice is broken down into large anionic groups, such as sheets, chains, and rings, to form a liquid containing these complex anions and simple cations. Each composition is characterized by "an equilibrium mixture of two or more of the discrete ions",' and increasing metal oxide content causes a decrease in ion size. The implication is, and this implication has received tacit approval from subsequent workers, that these anions are rigid structures and that once formed they are quite stable. The discrete ion theory has been found to fit the results of the great majority of structural studies, but in a few areas it is not entirely satisfactory. For example it does not explain clearly the effect of temperature on melt structure,3 nor does it allow for free oxygen ions over wide composition ranges, the occurrence of which has been postulated to explain sulfur4 and water5 solubility in liquid silicates. In lime-silica-alumina melts the discrete ion theory is even less satisfactory, and in particular the apparent difference in the mechanism of transport of calcium in electrical conduction8 and self-diffusion,' and the mechanism of the self-diffusion of oxygen8 are very difficult to explain on this basis. By looking at melt structure in a slightly different way, however, a model emerges that does not pose these problems. It has been suggested5" that at each composition in a liquid silicate, there is a distribution of anion sizes; thus the dominant anionic species might be Si3,O9 but as well as these anions the melt may contain say sis0:i anions. Decreasing silica content and increasing temperature are said9 to reduce the size of the dominant species. Taking this concept further, it is now suggested that these complexes are not the rigid, stable entities originally envisaged, but rather that they exist on a time-average basis. In this way large groups are continually decaying to smaller groups and small groups reforming to larger groups. The most complete transport data 8-10 available are for a melt containing 40 wt pct CaO, 40 wt pct SiO2, and 20 wt pct Al2O3. Recalculating this composition in terms of ion fractions and bearing in mind the relative sizes of the constituent ions, Table I, it seems reasonable to regard this liquid as almost close packed oxygens, containing the other ions interstitially, in which regions of local order exist. On this basis, all oxygen positions are equivalent and, since an oxygen is always adjacent to other oxygens, its diffusion occurs by successive small movements, in a cooperative manner, in accord with modern liquid theories." Silicon diffusion is much less favorable, firstly because there are fewer positions into which it can move and secondly, because it has the rather rigid restriction that it always tends to be co-ordinated with four oxygens. Silicon self-diffusion is therefore probably best regarded as being effected by the decay and reformation of anionic groups or, in other words, by the redistribution of regions of local order. Calcium self-diffusion should occur more readily than silicon, because its co-ordination requirements are not as stringent, but not as readily as oxygen, because there are fewer positions into which it can move. There is the further restriction that electrical neutrality must be maintained, hence calcium diffusion should be regarded as the process providing for electrical neutrality in the redistribution of regions of local order. That is, silicon and calcium self-diffusion occur, basically, by the same process. Aluminum self-diffusivity should be somewhere between calcium and silicon because, for reasons discussed elsewhere,' part of the aluminum is equivalent to calcium and part equivalent to silicon. Consider now self-diffusion as a rate process. The simplest equation is: D = Do exp (-E/RT) [I] This equation can be restated in much more explicit forms but neither the accuracy of the available data, nor the present state of knowledge of rate theory as applied to liquids justifies any degree of sophistication. Nevertheless the terms of Eq. [I] do have significance;12 Do is related, however loose this relationship may be, to the frequency with which reacting species are in favorable positions to diffuse, and E is an indication of the energy barrier that must be overcome to allow diffusion to proceed. For the 40 wt pct CaO, 40 wt pct SiO2, 20 wt pct Al2O3, melt, the apparent activation energies for self-diffusion of calcium, silicon, and aluminum are not significantly different from 70 kcal per mole of diffusate,' in agreement with the postulate that these elements diffuse by the same process. For oxygen self-diffusion E is about 85 kcal per mole,' again in agreement with the idea that oxygen is transported,

Jan 1, 1963