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By John N. Dew, William L. Martin, `

This paper describes the results of a laboratory investigation conducted to obtain data for an evaluation of the in situ combustion process as a method of producing crude oil from reservoirs. Air and fuel requirements, rates of advance, com-bustion temperatures, and coke and fluid distributions are presented. The mechanism of oil recovery by in stiu combustion is discussed. Five crude oils ranging in gravity from 10.9 to 34.2"' API were prodrrced from a semiadiabatic, uncon-.solidnted sand pack by in situ combustion. Experimental conditions were varied over a wide range in order to determine the inter-relation-.ships of process variables. The mini-mum air flux requirement for self-sustained combustion was found to he less than 10 scf/hr-ft'l. The rate of advance of a self-sustained combustion zone was found to be nearly proportional to the air flux at the combustion front. The effects of presrure and injected air flux were studied in a series of experiments using a 21.2" API crude. A minimum air require-ment was observed at an air .flux of 20 scf/hr-ft'. The oil saturation con-sumed as fuel averaged 5.5 per cent of pore volume. The effect of air pressure was, found to be .small for experiments having high combustion eficiencies. This study should promote a better understanding of the problems and mechanisms involved in labora-tory investigations and field applications of the in situ combustion pro-cess. The data presented will be use- ful in the interpretation of results of field tests. When tempered with volu-metric sweep efficiencies, the data can be used in making preliminary economic appraisals of the process as applied to reservoirs containing high porosity unconsolidated media. INTRODUCTION The purpose of this work was to obtain laboratory data for an evaluation of the in situ combustion process as a method of producing crude oil from reservoirs. In situ combustion basically consists of (1) injecting air into a reservoir through selected input wells to create an air sweep through the reservoir, (2) igniting the crude at the injection well, and (3) propagating the combustion front through the reservoir by continued air injection. By this means, oil is swept toward producing wells in the area. The fuel for combustion is supplied by heavy residual material (coke) which has been deposited on the sand grains during distillation and cracking of the crude oil ahead of the combustion front. Recovery of petroleum by a combustion or heat wave process is not a new idea. F. A. Howard was granted a patent in 1923 on a process in which air and a combustible gas were pumped into an injection well and ignited.' Russian engineers reported on field experiments with a crude oil gasification process in 1935'. Other known early field tests include those conducted near Bar-tlesville and Ardmore, Okla., in 1942." More recently completed field tests include an inverted seven-spot by Sinclair Oil Co. in the Delaware-Childers field, Nowata County, Okla.'; a three-well and an inverted five-spot test by Magnolia Petroleum Co. in Jefferson County, Okla."."; and a test by California Research Corp. in the Irvine-Furnace field in Kentucky. The Worthington Corp. has completed a test in cooperation with the Forest Oil Corp. in Clark County, 111.l Several field tests are now in progress. Sinclair has acquired a 600-acre lease in the Humboldt-Chanute field, Allen County, Kans., and is under way with a large-scale operation. Three field tests are under way in California. The General Petroleum Corp. is conducting an inverted five-spot pattern test in the South Bel-ridge field in Kern County under a cooperative agreement with 11 other companies, including Continental Oil Co. California Research Corp. is conducting a four-well pattern test in Midway-Sunset field near Maricopa, and Richfield Oil Corp. is under way with a test in the Ojai field in Ventura County. Although the published information is valuable concerning results of field tests, little laboratory data other than that reported by Kuhn and Koch5 are available to aid in appraising the tests from a technical or economic standpoint. Engineering data needed to evaluate the process include the amount of air required per barrel of oil recovered, minimum injection rates which will support combustion, rates of advance, air required per unit volume of reservoir cleaned, amount of oil recovered, and amount of oil consumed as fuel. The present laboratory investigation was undertaken to provide these data for that portion of the reservoir swept by the combustion zone. The first phase of this investigation was exploratory in nature and was conducted at injection pressures less than 100 psig. Data were ob-

EUROPE continued to be unsettled, financially, commercially and socially. October opened with Germany in a state of turmoil following the Government's cessation of passive resistance to the French and Belgians. In many places there were riots with much bloodshed. In Bavaria a military dictator-ship was set up in order to keep peace. In the meanwhile France continued in an uncom-promising position.. Great Britain, having been diplo-matically discredited, disappeared from any prominence in the international picture. Under the constraint of circumstances the policy of deflation in Great. Britain was temporarily abandoned. Perhaps no other course was open, for with declining trade and heavily reduced revenue, and no chance for cutting expenses propor-tionately, a check to deflation comes of its own accord. The effects of this should become manifest in the course of a few months and should appear in the form of an improved margin between the prices for commodities and the wage costs in producing them. About Oct. 20 an effort was made to set up the Rheinland as a separate republic. On Oct. 26 were published communications from Lord Curzon to Secre-tary Hughes and the latter's reply. In these Lord Curzon drew attention to the gravity of the situation in Europe and expressed the hope that France might listen to renewed suggestions for a general inquiry. Secretary Hughes promised American cooperation, in this, with the reservation that the question of inter-national debts should not enter into the situation. In the latter part of October there were military mutinies and disorders in Greece, which resulted in the reestablishment of martial law by order of Col. Plas-tiras, who is virtually the dictator of Greece. The incipient revolt was promptly crushed.

Jan 10, 1923

By Harold F. Unger, Byron S. Snowden, William H. Engelmann

The effects of using surfactant solutions while diamond drilling in amygdaloidal basalt of the Upper Michigan copper mining district were investigated. Nonionic, anionic, and cationic surfactant solutions, all biodegradable, were tested with size AX surface-set bits mounted on a drill instrumented for continuous recording of thrust, rotational speed, and torque levels. Water flow and penetrations rates were also recorded. A drilling study was carried out, testing two rotational speed levels, two diamond bit grade levels, and four flushing agents (including water as a control). Comparison of all low-speed/high-thrust groups of tests shows that the non-ionic surfactant produced a 35% overall average increase in penetration rate over water, the anionic a 29% increase, and the cationic a 28% increase. These increases in, penetration rates resulted in a 22 to 26% reduction in cost over flushing with water alone. With the high-speed/low-thrust combination, the surfactants produced less benefits in penetration rate increases over water (14% increase for nonionic, 14% decrease for anionic, and 2% decrease for cationic type). Particle size analyses were run on drill cuttings produced by the three surfactant solutions and by water. All surfactant solutions showed a 20 to 50% increase in solids content over that of water alone. Since flushing rates were constant, these increases in solids content agree well with the penetration rate changes. The diamonds were recovered from each bit by matrix dissolution, and bit wear was measured in terms of total loss of weight. Flushing with surfactant solutions showed a savings in bit wear in most cases. The drill team noted also that surfactant flushing improved recovery of drill core by allowing easier removal of the core from the barrel.

Jan 1, 1976

By Thomas T., Read

DESIRABLE as it is to summarize what has been set forth in preceding chapters, the task can only be approached with great hesitation. What follows represents the personal views of the author at the moment of writing, reserving the privilege to change them on more mature reflection or in the light of further evidence. With that reservation they may be stated somewhat as follows. Education for the mineral industries falls into two categories; general education and technical vocational, using the word vocational not in its usual sense but to signify preparation for specific activities, in which sense a law school is a vocational school. Even at the beginning, as indicated in the first chapter, mineral industry education was partly general and, partly technical and that relationship still persists, because technical education requires a firm basis of general education. Our general American system is to provide free public' general education through the twelfth grade, or completion of high-school work, though there are already many technical vocational high schools, and even in a community where nearly all the young people are preparing for entrance to college there will be some who wish to qualify for employment at the end of the high-school course, or even on completing junior high. Our educational system, therefore, has not only to provide education for those who intend to proceed beyond the twelfth grade but also for those who, for a variety of reasons, may wish or be forced to cease full-time education at any level between the first and twelfth grades. This study has been chiefly concerned with the problem of what kind and how much technical education to provide for those who have completed the twelfth grade and who wish to make their living in the mineral industries. The obvious fact that the mineral industries employ all sorts of trained persons,

Jan 1, 1941

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Jan 1, 1938

By Williams, J. A.

THE Alaska Juneau mine has been developed through an adit driven at the elevation of the top of the mill and all mining is done above this main haulage level. As a result of wholesa1e"mining operations about 11,000 tons rock containing one dollar' per ton in gold is, hauled to the. concentrator during every 24 hr. Due to the method of mining, whereby a system of oreways delivers-the.ore direct from the stope to the bottom level of the mine, no tramming of ore is done on any of the upper levels. However, ;in doing exploratory drifting and crosscutting on the upper levels, the broken material is trammed by hand in 1-ton 18-in. gage cars to a nearby raise connecting with one of the several oreways. This constitutes the only tramming operation except that on the main level.

Jan 1, 1931

By A. L. Holley

THIS process is performed in the Pernot puddling furnace; it removes from 75 to 80 per cent. of the phosphorus, most of the sulphur, and practically all the silicon, from crude iron, in from five to eight minutes. It has been in regular use since March, 1877, and has prod uced over seventeen thousand tons of washed metal for the open-hearth furnace. During two years, nearly all, and lately, all the open-hearth steel produced in these works has been made from about 5 tons of washed pig and 2 tons of scrap per open-hearth furnace heat. There are 12 open-hearth furnaces, of which 4 to 9 are running, according to the state of orders. A large amount of highly phosphoric iron from France and Belgium has been also washed and then puddled for parties who have taken, or are expected to take, licenses. The washing of pig for puddling, however, is not a practice at Krupp's works, because pure pigs are nearly as cheap as impure ones. The author and his assistant, Mr. Laureau, spent, during the last month, three days at Krupp's works, examining this process. They copied out of the office books characteristic analyses and physical tests, some of which are given herewith. They also brought hone many samples of pig, cleaned metal, puddle bar, and steel, which they saw treated. Analyses of some of these samples appear in Table IV. As there are no blast furnaces at Essen, the iron is melted in two Bessemer cupolas with fore-hearths; they melt 12g pounds of iron with 1 pound of coke. The metal is run by a spout from the fore-hearth into an opening at the side of the main door of the washing-furnace. The Washing furnace.-This is a regenerative gas furnace. It has a Pernot revolving-hearth of 12 feet external diameter and 3 feet depth. (See Plate.) The four regenerator chambers have 780 cubic feet capacity, which is about the same as the average regenerator capacity of open-hearth steel furnaces of equal tonnage. The lining is 13 inches thick on the sides and 9 inches on the bottom, thus giving a hearth 9 feet 10 inches by 2 feet 3 inches deep. The lining is composed of lumps of highly refractory ores

Jan 1, 1880

By L. W. McKeehan

THE occurrence of twins in large ferrite crystals, made by a new process, was reported in a recent note. This paper describes a typical case of such twinning and suggests, on the basis of the observed facts, why smooth slip-planes are rarely observed in this metal. METHOD OF PREPARATION The material In which the crystals here dealt with were grown was made from 1/8 -in. Armco iron welding rod containing C, 0.04; S, 0.037; P, 0.003; Si, 0.008, and Mn, 0.02 per cent. This rod was cold drawn into wire about 1 mm. dia. A piece of this wire was supported vertically and was locally heated in hydrogen at atmospheric pressure to about 1400° C. by an alternating current (60 cycles per sec.) of about 35 amp., passed through it between a pair of travelling contacts about 8 cm. apart. The rate of travel for the case in hand was 12 cm. per hr. After some 30 cm. of the length of the wire had been heated and cooled in this manner the whole wire was immersed for a few seconds in dilute nitric acid, not restrained by alcohol. Etching was continued until, as nearly as could be judged by eye, the original smooth cylindrical surface of the wire was no longer capable of specular reflection.

Jan 1, 1927

By A. L. Holley

This process is performed in the Pernot puddling furnace; it removes from 75 to 80 pel. cent. of the phosphorus, most of the sulphur, and practically all the silicon, from crude iron, in from five to eight minutes. It has been in regular use since March, 1877, and has produced over seventeen thousand tons of mashed metal for the openhearth furnace. During two years, nearly all, and lately, all the open-hearth steel produced in these works has been made from about 5 tons of washed pig and 2 tons of scrap per open-hearth furnace heat. There arc 12 open-hearth furnaces, of which 4 to 9 are running, according to the state of orders. A large amount of highly phosphoric iron from France and Belgium has been also washed and then puddled for parties who have taken, or are expected to take, licenses. The mashing of pig for puddling, however, is not a practice at Krupp's works, because pore pigs are nearly as cheap as impure ones. The author and his assistant, Mr. Laureau, spent, during the last month, three days at Krupp's works, examining this process. They copied out of the office books characteristic analyses and physical tests, some of which are given berewith. They also brought home many samples of pig, cleaned metal, puddle bar, and steel, which they saw treated. Analyses of some of these samples appear in Table IV. As there are no blast furnaces at Essen, the iron is melted in two Bessemer cupolas with fore-hearths; they melt 124 pounds of iron with 1 pound of coke. The metal is run by a spout from the forehearth into an opening at the side of the main door of the washingfurnace. The The washing-furnace.—This is a regenerative gas furnace. It has a Pernot revolving-hearth of 12 feet external diameter and 3 feet depth. (See Plate.) The four regenerator chambers hare 780 cubic feet capacity, which is about the same as the average regenerator capacity of open-hearth steel furnaces of equal tonnage. The lining is 13 inches thick on the sides and 9 inches on the bottom, thus giving a hearth 9 feet 10 inches by 2 feet 3 inches deep. The lining is composed of lumps of highly refractory ores

Jan 1, 1880

By Jack C. Haptonstall

This paper describes the analytical characteristics of Western subbituminous coal and the manner in which these characteristics apply to their use in a utility-sized steam generator. It compares these characteristics with those of typical Midwestern coal and Eastern bituminous coal. The paper also reviews in detail the design considerations that must receive attention when various blends of these three coals, or any combinations thereof, are planned to be used. This research paper describes variations in analytical and utilization characteristics when coals from different origins are blended in order to achieve a predetermined sulfur content for the purpose of predicting sulfur oxides emissions as they affect environmental regulations and the resulting alterations in utilization characteristics such blending would cause, and how such blends of coal would affect a utility-sized steam generator.

Jan 1, 1979

By AIME AIME

ON Thursday a most interesting symposium on "Gases in Metals" was held, with both morning and afternoon sessions. The morning was devoted principally to the considerations of the steel maker, the nonferrous field being taken up in the afternoon period. Dr. John Johnston, as chairman, introduced the subject with "A Short Analysis of the Gas-metal Problem and Its Practical Importance." He then introduced P. H. Brace who explained in considerable detail the various vacuum fusion and other methods in use at present, both here and abroad, in the study of "gases" in metals. He was fol¬lowed immediately by H. W. Graham on "The Effect of Oxygen in Steel." The papers elicited considerable discussion, the point being particularly noted by both Dr. Rawdon and Dr. Sauveur that a knowledge of "total oxygen" alone is not sufficient information for the metallurgist, distribution of oxygen being probably the more important. Dr. Johnston, in commenting on the lack of agreement among many of the methods now in use, such as the Ledebur and vacuum fusion, spoke of the contemplated plan of the Iron and Steel Division to have a number of standard samples analyzed by many laboratories by the various methods, the Bureau of Standards acting as a clearing house, so that more definite information may be obtained on the comparative accuracy of the method.

Jan 1, 1933

"With a total value to date of well over $200,000,000.00 for its ore production, the Tintic mining district, which is about 100 miles southwest of Salt Lake City, ranks as one of the three main ore producing areas of Utah. In it are located the biggest silver mines of the country, silver having been the chief metal produced in the camp since its start. Tintic's silver production to date has a total value of over $ 100,000,000, approximately half of the value of the camp's ore production, the balance being roughly divided among lead, gold and copper.Discovery of the camp was made in the late sixties. Lack of transportation and ore reduction facilities delayed extensive development of the area for nearly a decade.In recent years Tintic's ore production has ranged from 350,000 to 400,000 tons annually. In 1 924 the camp produced one-eighth of the silver produced in the nation with an output of 7,729,700 ounces. Its lead production was 77,765,000 pounds and its gold production 26,285 ounces.The known mineralized area of the district is found in a broad syncline striking north and south. The west limb plunges sharply and extends for a distance on its dip of approximately one and a half miles to the trough. The east limb raises gently through a distance of about two miles to the east limit of known mineralization. This general structure is broken by local faulting throughout the district, the local structural conditions playing an important part in the ore deposition. The north end of the fold is obscured by a rhyolite flow and the south end stops against a monzonite stock."

Jan 1, 1925

Jan 1, 1885

By Ira B. Joralernon

THREATS of a coming metal famine in the United States have filled many columns in magazines and newspapers in the past three years. This asserted menace has diverted attention from the actual results of recent exploration. Because no one had bothered to look into the facts, the statistical experts assumed that little ore was being found. They often subtracted the staggering tonnage of metals produced during the war from earlier published reserves, and assumed that the difference was all we had left. Naturally, they shuddered, with all possible publicity. For their figures showed an imminent lack of nearly all the metals needed for an industrial civilization, as well as for mechanized war. They concluded that only wholesale imports and development and production of metals by Federal agencies could avert the famine.

Jan 1, 1948

By WILLIAM COUPER

THE completion of the excavation of the tunnels through Bergen Hill for the extension of the Pennsylvania Railroad into New York City, together with the fact that the excavation for the rest of the tunnel-line has been practically completed for some time past, arouses sufficient interest to justify a description of the engineering- and contracting-work, and the organization by which it has been accomplished. The finishing of the excavation is a long step towards the completion of the entire tunnel-project. It will be interesting to the members of the Institute, who last spring were taken through a great part of this work, to know that by the excavation now completed it is possible to walk by tunnel from a, point near Sunnyside yard, Long Island, east of the 34th Street ferry, to the central passenger station site in the City of New York, and thence by tunnel to the Hackensack meadows, and by an embankment constructed across these meadows to Newark, N. J. This New York tunnel extension is being constructed as a part of the Pennsylvania Railroad system by the Pennsylvania Tunnel & Terminal R. R. Co., a corporation of the States of New Jersey and New York. It extends from a point near Newark, N. J., to the Sunnyside yard, Long Island, as indicated on the accompanying plan.

Jan 7, 1908

By A. Weiss, W. A. Coster

The search for ore is characterized by a great variety of uncertainties, each of which can be resolved by obtaining information at a cost. Three exploration stages may be distinguished in which information can be obtained, based on inherently different cost structure: 1) the reconnaissance or scanning stage, 2) the examination or screening stage and 3) the project stage. This exploration sequence would roughly coincide with replies to questions as to: where, how, why and how much. As complete information in each stage is too costly to acquire, we must assess the probability that adequate information will be furnished by a limited amount of effort and attempt to maximize the expected value of ore to be found for a given exploration expenditure. Several problems are discussed relative to the mathematical formulation and possible computer procedures for determining the optimum allocation of a total exploration effort. Based on the available literature possible solutions to this problem are indicated. When scanning through published literature on mineral exploration, it seems at first that there is little room for substantial and systematic improvements in the efficiency with which the problem of discovery of new ore deposits is presently being handled by large organizations active in exploration. It appears equally difficult to offer something relevantly new which could generate a break-through in exploration thinking and cause a marked improvement in the ratio of successful undertakings to the total exploration projects started. On the other hand, a number of experts in recent years have urged that the problems in prospecting be analyzed in a more skillful and sophisticated manner than in the past. Their thesis is based mainly on the premise that the cost of finding mineral deposits will increase with increasing technical difficulties. In present large-scale exploration ventures, especially in those regions where outcrops and immediately visible geologic evidence are scarce, older methods of prospecting are increasingly being replaced by more indirect and systematic geophysical and geochemical methods with more emphasis on correct statistical design of exploration patterns. It is perhaps the oil industry which has made the greatest strides in developing statistically, well justified patterns in its search for oil; possibly because oil seepages, as indicators of the presence of oil, left off at an earlier point in time than did outcrops as indicators of base metals. Among the pioneers in the field of statistics and operations research, as applied to mineral exploration, the excellent works of Allais, Slichter, Koop-man, Mickey, de Guhnin, Krumbein, Griffith, Sichel, Krige, de Wijs, and Matheron may be mentioned. It should, however, be pointed out that three subjects of basic importance to the allocation of exploration efforts have so far received only scant attention in published literature, even by the aforementioned authors. In the first place, a more precise definition of the object of the search, i.e., a minimum-size orebody, seems to be outstanding. Secondly, a decision model is not a widely-discussed subject. Thirdly, no concentrated attempt so far seems to have been made to establish probabilities of the occurrence of economic deposits on a regional scale and to arrive at a slightly more accurate knowledge of the probability laws governing the deposition of ore. It is not the purpose of this paper to create new order in the complexity of uncertainties in which our decision processes in exploration necessarily have to be conducted. Rather, we intend to highlight some of the outstanding, hitherto unmapped territory, where diligent compilation and a utilization of present and historic data may statistically improve our chances of success. We hope that the contribution of this paper will lie in bringing allocation problems into better focus and in increasing the mineral industry's realization of the magnitude of the factors involved. THE MINIMUM-SIZE OREBODY The concept of target specifications for what constitute a minimum-size orebody in exploration is a rather variable one and depends to some extent on

Jan 1, 1963

By A. B. Hersberger, R. S. Dean

Although it is obvious that in any flotation process we must have a froth, in recent years the development of collecting reagents has caused the possibilities of better frothing agents to be overlooked. Some investigators have even gone so far as to say that the number of satisfactory frothing agents was sufficient. A little consideration will show, however, that the reagents available in the past were far from ideal frothers. The properties of an ideal frother for flotation work may be set down as follows: 1. It must form in low concentrations a copious but not too persistent froth. 2. It must be insensitive to hydrogen-ion concentration of the pulp; that is, it must froth equally well in an acid or alkaline medium. 3. It must be insensitive to salts, even in high concentration. 4. It must be absolutely noncollecting to both sulfides and nonsulfides. 5. Its frothing properties must not be affected by collecting reagents, including soap, the most generally used nonsulfide collector. 6. It must readily emulsify and disperse any insoluble collecting agent that is likely to be used. Clearly the existing frothers do not qualify. Pine oil, for example, is an acceptable frother for many purposes but if used in soap flotation a delicate balance between pine oil and soap must be struck because, as pointed out by Coghill1, these two reagents are incompatible in certain concentrations. The objections to soap itself as a frother are obvious, and the cresols and their substitution products all have some collecting power and very little emulsifying power. The mechanism of frothing in flotation was early explained on the basis of the Harkins-Langmuir theory of oriented molecules.2 These investigators showed that if an organic compound having an unsym-metrical molecule (in which one end of the molecule contained water-

Jan 1, 1939

By R. S. Dean, A. B. Hersberger

Although it is obvious that in any flotation process we must have a froth, in recent years the development of collecting reagents has caused the possibilities of better frothing agents to be overlooked. Some investigators have even gone so far as to say that the number of satisfactory frothing agents was sufficient. A little consideration will show, however, that the reagents available in the past were far from ideal frothers. The properties of an ideal frother for flotation work may be set down as follows: 1. It must form in low concentrations a copious but not too persistent froth. 2. It must be insensitive to hydrogen-ion concentration of the pulp; that is, it must froth equally well in an acid or alkaline medium. 3. It must be insensitive to salts, even in high concentration. 4. It must be absolutely noncollecting to both sulfides and nonsulfides. 5. Its frothing properties must not be affected by collecting reagents, including soap, the most generally used nonsulfide collector. 6. It must readily emulsify and disperse any insoluble collecting agent that is likely to be used. Clearly the existing frothers do not qualify. Pine oil, for example, is an acceptable frother for many purposes but if used in soap flotation a delicate balance between pine oil and soap must be struck because, as pointed out by Coghill1, these two reagents are incompatible in certain concentrations. The objections to soap itself as a frother are obvious, and the cresols and their substitution products all have some collecting power and very little emulsifying power. The mechanism of frothing in flotation was early explained on the basis of the Harkins-Langmuir theory of oriented molecules.2 These investigators showed that if an organic compound having an unsym-metrical molecule (in which one end of the molecule contained water-

Jan 1, 1939

By E. A. Gulbransen, K. F. Andrew

THIS paper. will present the results of our studies on the kinetics of the gas phase reactions of co-lumbium and tantalum with O2, N2 and H2. Studies on zirconium and titanium have been previously reported.9,11 Due to their high melting points and their many excellent physical and chemical properties, colurn-bium and tantalum have been finding their places as useful metals in science and industry. Chemically the metals are very inert to gas and liquid phase corrosion at room temperature. However, at moderate temperatures of 250°C and higher the metals react readily with oxygen and hydrogen. It is of interest to study the gas phase reactions of these metals for the following reasons: (1) to compare the rates of the several reactions with those of other metals and to correlate the rate data with theory and structure predictions, (2) to add basic information on the practical difficulties of the reduction, refining and working of columbium and tantalum, (3) to anticipate new uses for the metals and (4) to understand the role that the metals play as components in high temperature alloys. Literature Survey A number of papers exist in the literature on the gas phase reactions of columbium and tantalum with O2, N2 and H2; however, only fragmentary data have been reported on the kinetics of these reactions. Although the free energy of formation of the oxide Ta2O520at 25°C has been determined and some thermodynamic work has been reported on columbium and its oxides, the data are not sufficient to make equilibria calculations at elevated temperatures. Oxidation: 1. Kinetics: The rate of oxidation of columbium and tantalum has been studied by McAdam and Geil23 using the interference color method. Tantalum is reported to oxidize more slowly than columbium, zirconium and iron. The amounts of oxidation of columbium after 20 hr in air for several temperatures are reported by the Fansteel Metallurgical Corporation.36 Columbium starts to oxidize in air at about 200°C. The oxide is said to be adherent and prevents further oxidation until the temperature is raised. Columbium is reported not to become brittle on heating in air for short periods like tantalum because the oxide film prevents further reaction. The columbium oxides dissolve into the metal when heated in a vacuum at temperatures between red heat and 1200°C. Above 1200°C the oxides are reported to evaporate. Columbium, in the oxide free state, is an active getter in vacuum tubes. 2. Preparation and Structure: G. Grube, O. Kuba-schewski and K. Zwiauer15 have studied the decomposition of Cb2O5 in argon. They find that CbO2 is formed slowly at 1150° and rapidly at 1300°C. Cb2O5 can be reduced to CbO2 by moist H2. The reduction of this dioxide to the lower oxides is rapid. By varying conditions CbO2, Cb2O3, CbO and Cb2O can be formed. CbO2, CbO and Cb2O have independent lattices while Cb2O3 is a stoichiometric mixture of CbO and CbO2. In a later paper O. Kuba-schewski" has shown that CbO is cubic and that CbO2 has a rutile type of lattice. The most exhaustive work on the oxides of columbium is that of G. Brauer.8 The number and constitution of the solid phases in the binary system Cb-O were investigated by the preparative, analytical and X ray methods. He indicates that only the oxides Cb2O5, CbO2 and CbO exist with limited regions of homogeneity. The solid oxide Cb,O, exists

Jan 1, 1951

By H. I. Aaronson, H. A. Domian, G. M. Pound

Zener's two-parameter theory of the y a reaction in Fe-X alloys is extended to encornpass austenite-stabilizing as well as fewite-stabilizing elements, and is then cottzbitzed with statistical thermodynamic theories of Fe-C alloys to permit development of a ther-modynamic description of the proeutectoid fewite reaction in Fe-C-X alloys. Equilibrium tielines are calculated for tile a + y rep'on from experimental data and frort extrapolations of the y/y +a equilibrium surface. Sectzovs of the y/y + 0 surface are calculaled for the tzetastable sstuation LYL u-kich alloyrtg eleitzents do not partition betzseen azrstenite andfer-rite. The finding that the metastable y/a + y curves Lie close to their equilibriuwz counterparts when X = Si, .Vo, Co, Al, and Cu but well below them when X = A/ln or Ari pr-elides a thermodunamic explanation for the expcri1?7e?ztally obserted absence of partition during the proeutec toid ferrite reartlon in the fortner alloys and for the occurrence of partition at hzgher ternperatures in the latter alloys. Cotarison ofno- patitzoa free-energy changes and y/y i a curr,es in Fe-C-X alloys with the equilibrium 11al1es of these quantities in Fe-C alloys furnishes additional qualitative insight into the irqluence of allojling elements upon the kinetics of the proeutectoicl ferrite reaction. THE introduction of a substitutional alloying element, X, appreciably complicates calculation of the thermodynamics of the formation of proeutectoid ferrite from austenite. As noted in the preceding paper,' the positional entropy of the interstitial species is the principal component of the free energy of an interstitial solid solution with which theory has so far been able to deal. One would expect, however, that other components of the free energy of this type of solid solution may be significantly altered by the addition of a substitutional alloying element. Even if the assumptions are made, by analogy to the case of Fe-C alloys,' that changes in the positional entropy of carbon represent a significant part of the thermodynamic effects of an alloying element, and that the remaining effects can be taken into account by fitting the equations developed on this basis to experimental data on Fe-C-X phase diagrams or on the activities of carbon in alloyed austenite and ferrite, the experimental information available on either of these quantities is not yet sufficiently accurate or extensive, respectively, to make such an approach useful. An attempt made by Zener on the former basis to explain the effects of alloying elements on the thermodynamics of Fe-C alloys in terms of a temperature-independent "free-energy change" (actually enthalpy hane') required to transfer 1 mole of an alloying element from austenite to ferrite, in which the "free-energy change" was determined by fitting the theoretical relationships developed to Fe-C-X phase diagrams, thus proved inadequate in part because of deficiencies in the available ternary-phase-diagram data.= Other difficulties of a more fundamental nature, however, also indicated the desirability of a different approach to the problem.3y4y6 zener6 subsequently proposed that the free-energy change associated with y — a transformation in pure iron can be decomposed into magnetic and nonmagnetic components. Alloying elements were assumed to affect those components separately. One parameter was used to describe the quantitative effect exerted on each component. These parameters were evaluated from Ms (martensite-start) temperature data and from other experimental information usually either readily available or measurable with acceptable accuracy. Zener applied this treatment only to the calculation of Fe-X phase diagrams in which X is a ferrite-stabilizing element. In the present study, this treatment is extended to include austenite-stabilizing elements, and then combined with treatments previously considered for Fe-C alloys1 to permit calculation of the thermodynamic quantities of interest in the austenite - proeutectoid ferrite transformation in Fe-C-X alloys, where a number of representative, and commonly used alloying elements are chosen for X, including Si, Mn, Co, Mo, Al, Cr, and Cu. The results are used to explain important features of the partition of alloying elements between austenite and proeutectoid ferrite, as reported in a companion paper7 on the basis of electron-probe analysis, and to provide some additional understanding of the influence of alloying elements upon the kinetics of nucleation and growth of proeutectoid ferrite. Portions of this treatment6 have been clarified in the course of a review by Kaufman and Cohen.3 The consolidated summary of these developments with which this section is begun provides a basis for further clarification of the treatment, from which extension to include austenite- as well as ferrite-stabilizing elements is a natural consequence. The division of the free-energy change associated with the 7 - a transformation in pure iron, into two independent components is formally stated as:

Jan 1, 1967