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By L. D. Stamp

In view of the comprehensive accounts which have appeared in recent years of the oil fields of Burma, Assam and the Punjab,' this brief account will be restricted to an outline recapitulation of the position of the fields and a note on progress and developments in the last two or three years. It is actually peculiarly difficult to give an account of recent developrnents in the oil fields of the Indian Empire. The companies naturally are compelled to make a return to the Government of India of oil produced. These figures are published annually (about 10 months later) for each administrative district (which may include more than one field) where oil is produced, in the Annual Review of the Mineral Production of India (Records of the Geological Survey of India). Some details of recent developments may be given in the Annual Report of the Geological Survey of India (also published in the Records), but otherwise the companies tend to preserve a policy of extreme secrecy. Some of the smaller companies usually publish wellhead production month by month in order to encourage their shareholders when such figures are encouraging, but the larger companies do not necessarily even give figures of production in their annual reports to shareholders. Occasionally details of new tests, new machinery, and so on, leak out through the daily or weekly press in India, but, except for generalized official statements, no details :ire available as to the number of new wells, depths, wells abandoned, or other figures which are common property in other parts of the world. In the country itself the geologists preserve the utmost secrecy, and at times quite a serious system of espionage is developed. Of recent years there has been a slight tendency towards the pooling of experience, but actually the Indian Empire, particularly of course Burma, where there is a

Jan 1, 1933

By D. A. Flanagan, B. L. Landrum, P. B. Crawford, B. C. Norwood

Herern is described a heat conduction model which has been developed to predict the pressure distribution within a reservoir being subjected to rrnsteady-state depletion. Although potentiometric models have been widely used to study reservoir pressure distribution, their application is limited to the study of steady-state cases. Electrical analyzers may be used to study unsteady-state phenomena, but their application and simulation have certain limitations. Much of the now accepted theory of unsteady-state fluid flow in porous media has evolved from previous heat conduction knowledge. An analogy between the flow of fluid in an unsymmetrical reservoir and con-duct ion of heat in a similarly shaped unsymmetrical metal plate is made to show adaptability of the hear conduction principle to transient reservoir cases. A description of the model and necessary instrumenrarion is included. Data show influence of well location on pressure distribution during unsteady-state deple[ion. Application of results is made to a hypothetical reservoir and to a reservoir located in an irregular aquifer. INTRODUCTION Development of methods for predicting behavior of petroleum reservoirs has resulted partially from adaptation of electrical and thermal flow concepts to the flow of fluids through porous media. Extensive investigation of electrical and thermal flow problems has resulted in mathematical solutions applicable to many reservoir problems. The relative ease of measuring electrical flow has brought wide acceptance of the use of the potentiometric model to study certain field problems. Potentiometric models are restricted to the study of steady-state conditions because of the instantaneous response of electrical flow to changes in the applied potential. The electrical reservoir analyzer has been one of our most useful instruments for studying certain phases of unsteady-state behavior1. Other than approximation techniques, no method exists for determining pressure distribution in an irregular reservoir during primary depletion. Heat flow, like fluid flow, is inherently transient. The model described here was developed to use this transient nature of heat flow, measurable in the laboratory, to simulate transient flow of fluids in the porous medium of the reservoir above the bubble point. A metal plate shaped like the reservoir to be studied was heated by a "well" source. Temperature increase in the plate is analogous to pressure decline in the field if the field is being depleted, or pressure increase if fluid is being injected. This study is intended to determine the feasibility of using the transient nature of the heat flow to study the transient behavior of fluid flow. It is hoped that this new technique will aid in the understanding of one of the more complex phases of reservoir engineering. THE FLUID FLOW-HEAT CONDUCTION ANALOGY The similarity of the equations which describe the flow of fluids through a porous medium and the conduction of heat through a solid is well known2. Rate of flow of fluids is given by Darcy's law3. while the rate of flow of heat is given by Fourier', (I,, - KA 4T........(2) Combining Eq. 1 with the equation of continuity for a compressible liquid", i.e.,results in Expressing y in terms of the compressibility, i.e., pr = peey ,..........(5) and by expanding the exponential and neglecting higher orders of cp one can obtain

By W. H. Blauvelt

The technical and engineering problems in the manufacture of coke are today the problems of the byproduct oven. Except in a few special localitics, practically no beehive ovens have been built in the United States for the last 5 or 6 years except as renewals of old plants, and during these years the total number of beehive ovens in existence has been steadily falling. On the other hand, the number of byproduct ovens has increased from 4624 in 1911 to a total of about 7660 in operation at the end of 1917; with 2800 building, this makes a total of about 10,460 which will be in operation in 1918, or shortly thereafter. Preliminary Government estimates place the total production of coke for 1917 at 56,600,000 tons, the largest tonnage in the history of the industry. Of this 34,000,000 tons, or 60 per cent., was beehive, and 22,-600,000 tons, or 40 per cent., was byproduct coke. Some time in 1918 the production of byproduct coke should pass the beehive output, and when the byproduct ovens now building are completed the total byproduct capacity will be about 40,000,000 tons of coke per annum, which is over 70 per cent. of the record-breaking total coke production of 1917. The reasons for these changes in the coking industry are familiar to all of us, and need not be discussed here. Improvement in Oven Design Since the byproduct oven was brought to this country from Europe, in 1892, it has been radically improved, and from the point of view of American metallurgical practice it is safe to say that the American ovens arc superior to those of Europe. The points of superiority are mainly those of larger units and larger output per unit, and the greater extent to which labor-saving machinery has been introduced. The increased output is largely due to the use of silica refractory material, which permits higher heats and shorter coking time than are employed in Europe. The modern American oven will carbonize commercially more than 20 tons of coal per day, and contrary to the European idea that slower

Jan 1, 1920

By J. Blodget Britton

To the question, "Do the Pennsylvania anthracites contain phosphorus ?" asked at the last meeting of the Institute during the discussion on the metallurgical value of Western lignites, I can now give a definite answer. Through the kindness of a gentleman connected with the Philadelphia and Reading Railroad, and another connected with one of the principal ironworks on the Lehigh, there was sent to the Iron-masters' Laboratory a number of samples of the coals now largely shipped from the Schuylkill and Lehigh regions. Seventeen of these I examined for their contents of ash and phosphorus, and obtained results as follows

Jan 1, 1873

By John R. Anderson, Michael B. Bever

Carbon may affect the alloys of copper in several ways. Provided an alloying element does not oxidize preferentially, even minute quantities of carbon dissolved in liquid alloys of high copper content will form insoluble carbon oxide gases under oxidizing conditions. Gas porosity in castings of high-copper alloys can originate in this way. In certain alloys of low copper content carbon may have considerable solubility and may be an effective deoxidizer. In these alloys carbon will tend to suppress porosity. Carbon that is dissolved in the molten alloy is likely to be retained in the solidified metal. The effects of carbon on the physical properties of the metal are determined by the form in which it is present. Depending on the alloying elements and also on the cooling rate, carbon may precipitate as graphite, may form a carbide or may remain in solid solution on cooling. As solid copper does not dissolve a measurable amount of carbon, a carbon-bearing solid solution can occur only if the copper is alloyed with a large excess of an element that forms such a solution. The effect of graphite or of carbides on the properties of an alloy will depend on the size and distribution of the precipitated particles. As Hensel pointed out in discussion,' the formation of an alloy carbide may interfere with the age-hardening properties of a copper alloy. One would also expect that the presence of carbides or of graphite will under certain conditions promote corrosion or high-temperature failure in nonferrous alloys. Since carbon has an effect on the soundness of castings and affects the structure and behavior of solid copper alloys, its solubility in the liquid alloys is of practical importance. The isothermal change of carbon solubility with alloy composition is of interest from a theoretical standpoint. The binary alloys of copper with manganese and with nickel are used industrially and serve as a base for more complex alloys. The solubility of carbon in each of these metals is known, but its solubility in their alloys has not been determined. Earlier Data The solubility of carbon in molten pure copper is about o.oooi pct at II00°C and 0.0004 pct at 1475°C.l Various authors2""6 have published data on the solubility of carbon in molten manganese. There is agreement on a value of about 6.7 pct in the temperature range r2170 to 1245°c This solubility value corresponds to the formula Mn3C. It increases very little with increasing temperature. Corson7 states that carbon is soluble in copper-manganese alloys and that the

Jan 1, 1947

While the production of this state has not realized the early hopes that this coal would replace eastern coal on the Pacific Coast, it has been steady though small. Nearly all of the tonnages given are from Goodyear's, The Coal Mines of the Western Coast of the U. s., a carefully com- piled and accurate account of the development of the industry along the Pacific. [ ]

Jan 1, 1942

By I. Cadoff, E. Miller, K. Komarek

Jan 1, 1960

By O. N. Carlson, K. E. Solie

The brittle-ductile transition temperatures of single and poly crystalline chromium metal were studied as a function of nitrogen concentration and chromium nitride distribution. It was observed that In recent years there has been an increasing interest in chromium-base alloys for high-temperature applications. The principal disadvantages, however, have been the difficulties of fabrication and the design problems associated with a material of such limited ductility. Various studies have been the effects noted in the poly crystalline material are essentially reversed in the single crystals. These observations are discussed in terms of existing theories for the brittleness of chromium. conducted recently directed toward a determination of the cause of this brittleness and to find ways for minimizing its effects. Allen et al.,' Wain Abrahamson and rant,' and weaver4 have carried out studies on the effects of interstitial impurities on the brittle-ductile transition of chromium metal of various degrees of purity. These investigations have shown that oxygen has little or no effect on the transition temperature of chromium in all conditions studied but that carbon increases the transition temperature under all conditions tested. Nitrogen was found to increase the transition temperature in the wrought condition and in the quenched or cast conditionS but reportedly has no effect in the furnace-cooled condition.

Jan 1, 1964

"Butte originated as a placer mining camp. The first gold discovery was made in the year 1864, near what is now Main Street. Placer mining was vigorously prosecuted along Silver Bow Creek and in Missoula, Buffalo, Town and Parrot gulches for a period of five years, at the end of which time, in 1870, the camp was practically deserted. In the meantime, the quartz veins so prominently traceable over the hillsides were located, the first location being made by W. L. Farlin and called the Black Chief claim, and later restaked as the Travona. Reasoning from the presence of the gold placers, free-milling gold ores were eagerly looked for by the early prospectors. Claims covering the great Rainbow and other silver lodes were located in the sixties. The presence of valuable silver ores in these veins caused the staking out of many claims, believed to be valuable only for silver, but which later proved to be enormous copper producers.Treatment of these early discovered rich ores was first attempted in arrastres. Later, stamp mills were built. The Centennial dropping 10 stamps, was the first, and in 1875 Mr. Farlin built the Dexter 10-stamp mill, intro¬ducing chloridizing-roasting. More successful processes were soon introduced and several large mills built, among which were the Alice, Lexington, Silver Bow, Moulton and Bluebird, in all representing a total of 290 stamps. The silver mining industry reached its zenith in 1887 and declined rapidly in the early nineties, following the sudden drop in the price of silver in 1892.During this period of silver mining activity the business of copper mining was making rapid strides. Development of the veins, located as silver veins, had uncovered copper ore in many instances. There was great activity in ""claim staking'' in the years from 1871 to 1879, during which period most of the claims covering the present productive copper area were located."

Jan 1, 1913

By John Hays, Hammond

IT is both a pleasure and an honor to be a guest of the Institute and I thank you, Mr. President and fellow-members, for giving. me the opportunity of meeting you this evening. My esteemed friend, President Smith, has requested me to do a bit of "reminiscing" as to the earlier years of my career as a mining engineer, which has now covered a period of fifty years. Let me reassure you by promising that my narrative will not include all the experiences I have had over that long period. You will, I trust, pardon what might seem egotistical but I do not see how a personal narrative could well be otherwise.

Jan 1, 1928

By R. W. Mancantelli, J. R. Woodward

IN 1947 a large low grade deposit of uranium was located in the northwest corner of Saskatchewan, in the Beaverlodge property of Eldorado Mining & Refining Ltd. Most of the values occur as thin seams and as coatings on other minerals, and the ore, which is light and friable, is not amenable to the usual gravity methods of concentration. The acid leaching process developed to retreat the company's Port Radium tailings was also impractical, as the percentage of carbonates is high and the percentage of sulphides relatively low. Construction of the mill building and installation of equipment, both scheduled for 1952, awaited selection of a satisfactory ore dressing process on or before Oct. 1, 1951. An extensive research program on dressing of ores from the Ace mine therefore was undertaken by the Mines Branch in Ottawa, a research team at the University of British Columbia, and an ore dressing group at the company's Port Hope refinery. Pilot plant operations were conducted at the Ottawa plant of Sherritt Gordon Mines Ltd. under the general direction of C. S. Parsons, consultant on metallurgy and ore dressing for Eldorado. In mid-September, having compared results of the several research programs, Dr. Parsons recommended a process employing a carbonate or basic leach. He reported that, while the chemistry of the process had been proved, engineering of the flowsheet was incomplete, and he suggested that under normal conditions further pilot plant work at the Ace mine might be profitable. However, since this would involve a delay of 12 to 18 months in bringing the property into operation, he recommended that design of the concentrator proceed immediately. Concentrator capacity was determined by two considerations: 1) the amount of ore then available and 2) the expectation that continued improvements would be made in the ore dressing process as a result of the intensive research being carried out by the Mines Branch of the Department of Mines and Technical Surveys. As these improvements could affect both the chemistry and the en-

Jan 1, 1956

By Harold B. Goldman, Don Reining

The sand and gravel industry is the largest nonfuel mineral industry in the nation. In 1981, the production of sand and gravel totaled 755 million tons valued at $2.3 billion. California, which leads the nation with more than 110 million tons, together with Alaska, Texas, Michigan, and Ohio, account for 36% of the total production in the nation (Table 1). In commercial usage, sand applies to rock or mineral fragments ranging in size from particles retained on a No. 200 sieve (0.074 mm openings) to those passing a No. 4 sieve (4.76 mm openings). Gravel consists of rock or mineral fragments larger than 4.76 mm, ranging up to 88.9 mm (3 ½ -in.) maximum size. The construction industry consumes 97% of the sand and gravel produced; the remainder is sand used for specialized products such as glass (see the chapter on "Silica and Silicon"). Utilization The building industry uses sand and gravel chiefly as aggregate in portland cement concrete, mortar, and plaster; the paving industry uses sand and gravel in both asphaltic mixtures and portland cement concrete. Aggregate is commonly designated as the inert fragmental material which is bound into a conglomerate mass by a cementing material such as portland cement, asphalt, or gypsum plaster. Portland Cement Concrete Aggregates Portland cement concrete consists of sand and gravel surrounded and held together by hardened portland cement paste. Concrete mixes commonly contain 15-20% water, 7-14% cement, and 66-78% aggregate. Sand and gravel used as concrete aggregate have to meet many requirements (Goldman, 1956). Premature deterioration of concrete has been traced in many instances to the use of unsuitable aggregates. Asphaltic Aggregate Asphaltic mixtures used predominantly for paving consist of combinations of sand, gravel, and mineral filler (material finer than 0.003 in.), uniformly coated and mixed with asphalt produced in the refining of petroleum. Except for the addition of mineral filler, sand and gravel used as asphaltic aggregate must meet the same general physical requirements as materials used for portland cement concrete aggregate. General Requirements of Aggregates Construction aggregate has many requirements that are difficult to meet if only unprocessed material from natural deposits is used. Suitable material is composed of clean, uncoated, properly shaped particles which are sound and durable. Soundness and durability are terms used to denote the ability of aggre- [ ]

Jan 1, 1983

By T. M. Geffen, F. F. Craig

Laboratory model flow tests have been made to simulate field conditions of partial pressure rnaintenance by dispersed gas drive on rocks having sandstone-type porosity. In this production method there is a significant saturation gradient between injection and production wells. A means of calculating relative permeability characteristics. from partial pressure rnaintenance flow tests has been developed. This method takes into account the saturation gradient. These kg/ko characteristics are identical to those for solution and external gas drives. This method of calculation, which has been proved experimentally, has limitations; however, it is valid for cases likely to be encountered in field prediction of partial pressure maintenance performance. The production performance of a hypothetical reservoir has been calculated for several different injection programs, involving both full and partial pressure maintenance. Results indicate that the maxinum oil recovery by these gas injection programs is obtained by full pressure mainte- nance at the original bubble point. Correspondingly lower oil recoveries are obtained by postponing gas injection and/or by reducing the degree of pressure maintenance. INTRODUCTION Dispersed gas injection is an important method of recovering additional oil beyond that obtainable by pressure depletion alone. The injected gas acts as a source of additional energy to displace oil from the rock formation as well as to retard oil shrinkage in the reservoir. In practice, gas injection is usually started after the reservoir pressure has fallen below the original bubble point. For various reasons sufficient gas is generally not injected to completely maintain the pressure in the reservoir. So, injecting gas at a declining reservoir pressure results in a combined external and solution gas drive. These two oil displacement processes are characterized by different gross saturation distributions in the reservoir. The external gas drive, like all frontal drive processes, inherently results in an oil saturation which increases from the injection wells to the producing wells. In the solution gas drive there is essentially a uniform oil saturation throughout the reservoir, provided the field is being depleted uniformly. It has been customary to predict oil recovery performance under partial pressure maintenance by a method which does not take into account the saturation gradient1. It has been shown2 that neglecting the presence of a saturation gradient can cause considerable error. It is the purpose of this paper to develop and present an improved method of predicting partial pressure maintenance performance of reservoirs including, where necessary. the effects of well arrangement. From the laboratory standpoint, this problem involves the measurement of the basic flow behavior (relative permeability characteristics) under partial pressure maintenance conditions. Recent research- as shown that for rocks having sandstone-type porosity, the relative permeability characteristics are identical for solution gas drive and complete pressure maintenance external gas drives. Since both solution and external drives have the same basic flow behavior, it was speculated that partial pressure maintenance, being a combination of the two, would also

Jan 1, 1957

By Herbert A. Stein, John B. Murdock

Perlite is a natural volcanic glass which expands into an insulation material upon the application of heat. This paper discusses the operating characteristics of eight different types of furnaces for the expansion of perlite. It also includes a section on the theory of perlite expansion which serves as the basis for the authors' analysis of the furnaces.

Jan 1, 1950

BLAMEY STEVENS, Nogales, Ariz. (written discussion *).-This subject should be approached boldly from the purely physical standpoint. There are usually many known ways of making chemical deposits of any particular mineral and probably many more ways that are still unknown. With-physical-effects; .however, there-are, in-general, only one or two, or possibly three, ways that will pass muster before the physicist, when he realizes the geological conditions to be harmonized with the physical ones. Let us consider the second way that Mr. Taber describes: "It (the mineral matter transported in solution) may enter along a fracture, bedding plane, or similar passage, and, as it is deposited, force the wall rock apart, thus making room, for the growing vein," because it is the one Mr. Taber chooses for the great bulk of metalliferous veins. By "forcing the wall rock apart" Mr. Taber indicates that he means that the process of crystallization or-solidification of the mineral in the vein forces the walls apart. To prove this, he offers a great variety of geological evidence, which, from the physical standpoint, is entirely superficial. From the geological standpoint the evidence is the best to be had, but it is entirely negative and one single grain of really positive evidence will entirely offset it. Suppose it be granted that there is a considerable force of crystallization. It is well known among physicists that, other circumstances being equal, the crystal would rather form where it does not have to exert that pressure; or, to be more exact, where it is not necessary for the crystal to

Jan 12, 1918

Jan 1, 1949

The beginning of Colorado's mining industry is linked on one side with that of the Appalachian districts and on the other side with that of California, because the first discoveries were made by pioneers when on their way from Georgia to California. In the summer of 1849 a party of seven Georgians were taking a herd of thoroughbred horses across the continent to the Pacific coast. They reached Camp Lyon, on the Arkansas river, in October, and, meeting James Dempsey, a Government guide, they were persuaded by him that it was too late to cross the mountains that season. His advice was accepted, and, moving northward, they established a winter camp at the junction of Cherry creek with the Platte, close to the site of the city of Denver. Upon a sand-bar, lining the south side of the river, they built two cabins. During the closing months of 1849 they prospected the alluvial banks of Cherry creek, but they made no attempt to penetrate into the mountain canyons, near them, westward, for fear of the Indians.* They found gold in several places along Cherry creek, and particularly at a spot 16 miles up the stream from their camp. From the feathers of the wild geese that they shot they obtained quills in which they placed their gold-dust. This party of Georgians consisted of Dr. L. J. Russell and his brother, Green Russell, also A. T. Lloyd, G. W. Kiker, and P. H. Clark. Early in 1850 they crossed the main range of the Rocky Mountains by the Bridger pass and went on to California. They mined near Downieville, and were successful. Occasionally mention was made by them of the gold

Jan 1, 1932

By H. A. Shaw, H. G. G. Whitton

This paper describes the use of the electric-arc furnace for the production of tough-pitch, horizontal cast copper shapes and the production of copper anodes from tank house anode scrap. This installation is the only one of its kind in the United States. SINCE the initial use of electric-arc furnaces for refined copper melting on a commercial scale at Copper Cliff in 1936, this type of melting has been of extreme interest to everyone in any way connected with copper casting and fabricating. Early in 1948, Kennecott Copper Corp. decided to build an electrolytic copper refinery at Garfield, Utah. One of the major decisions to be made at that time was the type of furnace to be used for melting cathodes for casting into refined copper shapes and for melting anode scrap for the production of anodes. Based on the results obtained from arc furnaces by the Tnternational Nickel Co. of Canada, at Copper Cliff, and by the American Smelting and Refining Co., at Baltimore, coupled with certain important economic factors such as having an adequate amount of relatively cheap power available at the Magna Central Power Plant, high cost of poles and oil in the Salt Lake District, and the lack of natural gas at that time, the final decision was to install electric-arc furnaces rather than the standard type of rever-beratory furnaces. Experience has shown certain parts of the original installation to have been inadequate or in need of modification. Although the present status of arc-furnace melting at the Utah Refinery is far from perfect, nevertheless substantial progress has been made. At the Utah refinery, copper is melted in three 15-ft diam, size "M" Lectromelt furnaces, two of which are used for melting cathodes and one for remelting anode scrap. Each furnace is energized from a 13,800-225 v, 3-phase, 60-cycle, 6000-kva (at 40°C rise) oil-immersed water-cooled transformer. Auxiliary equipment for each refined copper furnace includes a charging machine, launders, ladle, 40 ft diam Walker-type casting wheel, bosh, and inspection conveyor. The anode furnace differs in that it is charged by hand from an elevated platform and the anodes are picked off the 24-ft diam casting wheel by a takeoff hoist and loaded directly into specially designed trailers, Figs. 1 and 2. Electrical Equipment Electric power to operate the arc furnaces is generated at the Kennecott-owned Magna Central Power Station two miles distant and transmitted to the Refinery outdoor substation at 44,000 v. At this point it is stepped down to 13,800 v and carried through concrete-lined underground tunnels to the switchgear and then to the primary side of the furnace transformers. The power is conducted from the Y-connected secondary bus bars of the transformer to the electrode arms by means of 22 flexible copper cable conductors per phase. Each cable has a cross-sectional area of 1,750,000 circular mils, giving a total area of 38,500,000 circular mils per phase. The power is carried from these cables to the three individual electrode holders by means of water-cooled copper bus tubing. The electrode clamps are incorporated in the electrode holders and are released by air pressure working against a spring in the clamp control cylinder. The movement of the electrode arms is either automatic or manual. The automatic control is used during melting and is regulated by three Westing-

Jan 1, 1954

By E. T. Turkdogan, P. Grieveson

Experimental results are given for the rate of oxidation of ferrous iron to ferric iron in pure molten iron oxide by carbon dioxide + carbon moloxide mixtures at 1550°C. It is shown that the rate-controlling process is the interdiffusion of iron and oxygen atoms within the melt. The inter-diffusivity of iron and oxygen in the melt is obtained from the results and the value of (5.0 * 1.0) x 10-5sq cm per sec is recommended for the temperature of 1550°C. Similarly, it is also found that the rate of reduction of molten iron oxide is con -trolled by diffusion in the melt; however, apparent interdiffusivity values from these experiments are 10 to 20 pct higher than those obtained in the oxidation experiments, by virtue of convection arising from density difference. The results of the oxidation experintents are used to calculate an estimated self-diffusivity of iron in molten iron oxide of (1.5 * 0.5) x sq cm per sec. BECAUSE of the industrial importance of iron oxides, the study of the kinetics of both the reduction and oxidation of the solid oxides has received a great deal of attention. However, knowledge of the kinetics of similar reactions in the liquid state is very meager. Dancy 1 studied the kinetics of reduction of molten iron oxide by carbon in pig iron and found that the reaction is very fast. It was concluded from the results that the reduction of molten ferrous oxide is a first-order reaction up to 80 pct reduction, while

Jan 1, 1964

By P. K. Koh, H. A. Lewis, H. F. Graff

New data on the distribution of silicon between slag and carbon-saturated iron at 1600Oand 1700OC are presented which, in combination with previously published data, permit the determination of silica activities over a broad range of compositions in the CaO-Al2O3-SiO2 system. The distribution of silicon between graphite-saturated Fe-Si-C alloys and blast furnace-type slags in equilibrium with CO has been described in previous publications.1"3 In this past work the silica-silicon relation was established at temperatures of 1425" to 1'700°C for slags containing up to 20 pct A12O3. This paper presents the results of additional studies at 1600" and 1700° C which extend the silicon distribution data at these temperatures for CaO-A12O3-SiO, slags over a range from zero pct Al2O3 to saturation with Al2O3, or CaO.2Al2O3. The upper limit of SiO2 is set by the occurrence of Sic as a stable phase when the metal contains 23.0 or 23.7 pct Si at 1600" or 1700°C, respectively. The activity of silica over the expanded range is determined directly from the distribution data.3 Recently4-7 other investigators have studied the activities of SiO, and CaO, principally in the binary system, using different methods and obtaining somewhat different results. EXPERIMENTAL STUDY The experimental apparatus and procedure have been fully described in previous publications.1, 3 Six new series of experimental heats have been made, four at 1600° and two at 1700°C. Master slags of several fixed CaO/Al203 ratios were pre-melted in graphite crucibles, and these were used with additions of silica to prepare the initial slag for each experiment. Slag and metal were stirred at 100 rpm and CO was passed through the furnace at 150 cc per min. The initial sample was taken 1 hr after addition of slag at 1600°C or 1/2 hr after addition at 1700°C. The run was normally continued for 8 hr at 1600°C or 7 hr at 1700°C, and the final sample was taken at the end of this period. Changes in Si and SiO2 content indicate the direction of approach to equilibrium, and in a series of runs where the approach is from both sides this permits approximate location of the equilibrium line. Fig. 1 shows the results of such a series of 15 runs at 1600°C for slags of CaO/Al,O3 = 1.50 by weight. Figs. 2 and 3 record other series at 1600°C and Fig. 5 a series at 1700°C with fixed CaO/Al0 ratios. The results of the experiments at 162003°C have been reported in part in a preliminary note.3 In the experiments recorded in Figs. 4 and 6, the slags were saturated with A12O3 (or with CaO.2A12O3 within its field of stability) by suspending a pure alumina tube in the melt during the course of the run. The final slag analyses were used to establish the liquidus boundaries8 in the stability fields of CaO.2Al2O3 and of Al20,. ACTIVITY OF SILICA The free-energy change in the reaction has been calculated by Fulton and chipman2 from recent and trustworthy data including heats of formation, entropies, and heat capacities. The more recent determination by Olette of the high-temperature enthalpy of liquid silicon is in satisfactory agreement with the values used and therefore requires no revision of the result which is expressed in the equation: SiO2 (crist) + 2C (graph) = Si + 2CO(g.) [1] &F° = + 161,500 - 87.4T The standard state for silica is taken as pure cristobalite and that of Si as the pure liquid metal. Since the melts were made under 1 atm of CO and were graphite-saturated, the equilibrium constant for Eq. [I] reduces to K1 = asi /asio2. The value of this constant is 1.77 at 1600°C and 16.2 at 1700°C. Through K1, the activity of silica in the slag is directly related to the activity of silicon in the equilibrium metal.

Jan 1, 1960