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Freeport's Floating Mine Begins Sulphur Operation Eight years of research were culminated when Freeport Sulphur Co.'s floating mine plant went into operation on Bay Ste. Elaine in the remote Louisiana bayou country 60 miles southwest of New Orleans.

Jan 1, 1953

By C. F. Jenkins, G. V. Smith

Serrated plastic flow in stable austenitic alloys based on Fe/Ni has been shown to be related to the presence of carbon and/or chromium in the systems. Strength peaks and plateaus in the serrated-flow temperature region for a commercial alloy correlate with an increased dislocation content, arising, presumably, from enhanced multiplication as a result of a strong interaction between dislocations and solute atoms. The data generally support a mechanism controlled by migration of vacancies, with the energy for vacancy motion being modified by the presence of chromium. Chromium atom -dislocation interaction is responsible for effects above 500°C, whereas the defect interacting with dislocations between 200" and 500°C is suggested to be a carbon-vacancy Pair. ThE phenomenon of jerky flow, serrated flow, or the Portevin-le Chatelier (P-C) effect in austenitic stainless steels is usually attributed to substitutional at1,2 mospheres1,2 or to precipitates&apos;-4 which form at dislocations during plastic deformation. On the other hand, evidence exists which supports a direct inter-stitial-dislocation interaction mechanism for serrated flow in fcc Ni-C,5,6 Ni-H7-9 and in nickel-austenites containing carbon." The present work consists in a study of serrated plastic flow in stable austenitic al-loys. The effects of carbon and of chromium were investigated separately, and a commercial stainless steel with different levels of interstitial impurity concentration was studied in an attempt to delineate the combined effects of the alloying elements. EXPERIMENTAL TECHNIQUES a) Materials and Fabrication. A commercial AISI 330 stainless steel and several specially prepared aus-tenitic alloys have been studied. The experimental alloys were prepared by arc melting the constituents under purified argon. Analyses of the materials are given in Table I. The commercial alloy was obtained as 5/8 in. bar stock and rolled to 0.092 in. sq, with several intermediate anneals. At this stage some of the material was annealed in Pd-purified hydrogen at 1100°C to establish different levels of interstitial content. All other heat treatments were in vacuum (10-5 torr). The "pure" alloy ingots were swaged to 0.120-in. rod and annealed in Pd-purified hydrogen at 1100°C. The analyses for these conditions are also contained in Table I. Following the above treatment, the final wire sizes Table I. Chemical Analyses of Test Materials Hrin Hydrogen at Cr, Ni, Alloy 1lOO°C wt pct wt pct C, ppm* N, ppm* Type 330 As-received 14.78 33.25 430 300 Type 330 64 14.78 33.25 40 50 Type 330 200 14.78 33.25 27 21 Fe/35 Ni 72 - 35.10 <10 62 Fe/35 Ni 200 35.10 <I0 44 Fe/35 Nil15 Cr 72 14.95 34.94 <I0 61 Fe/35 Ni/15Cr 200 14.95 34.94 <10 45 Fe/35 Ni/C $ 35.OM 380 *Sensitivity: N t 5 ppm Ct10ppm. f Nominal Ni content. % A master NiC alloy was used in preparation of this material; courtesy of D.E. Sonon. were obtained by either swaging or cold drawing. The test results did not vary with these techniques. b) Specimen Preparation. Two sizes of specimen and two gripping systems were used. i) 0.070-in. wire with a chemically milled gage section: 0.75 in. long, 0.060 in. in diam. These were fastened into grips containing tapped grooves. ii) 0.050 in. wire, gage length 1.5 in. Ball bearings were welded to the ends of the wires and the gage length was taken to include all material between the welds. Socket-type grips were used with these specimens. With specimens of type ii), joining was performed in a specially constructed brass jig, under argon, and automatic timing was utilized in the procedure. No adverse effects of welding were noted. Specimens were encapsulated and solution treated for 1 hr at temperatures selected to produce the same average grain size, -50 µ. Annealing twin boundaries as well as normal crystal boundaries were counted. The temperatures used are listed in Table 11. Table 11. Specimen Size. Temperature of Heat Treatment and Resulting Grain Diameters for Test Materials Recrystallization Resulting Material Condition Temperature Grain Sue AISI 330 Not H purified 0.070 120O°C 45 to 55µ in, wire AlSl 330 H , pure, 0.070 in. 1150°C 45to55µ wire Fc/35Nil15Cr Pure, 0.070 in. wire 1000°C 45tossp Fe/Ni Pure. 0.070 in. wire 775°C 45 to 55µ Fe/Ni/C Pure, 0.050 in. wire 850°C 10 to 20p AlSl 330 Not purified, 0.050 1150CC 45to55p in. wire AlSl 330 ti, pure, 0.050 in. 1150°C 45to55p wire

Jan 1, 1970

By George S. Rice

GROUND movement and subsidence is an important matter from several points of view and it is regrettable that more papers have not been written on this subject in the past year. Damage may be done to surface buildings or to the higher workings of a mine, and a study of the subject gives valuable in- formation on hanging-wall or roof control. The latter objective is strikingly shown in a recent paper presented by Jack Spaulding on Oct. 21, 1937, before the Institution of Mining and Metallurgy, of Great Britain, entitled "Theory and Practice of Ground Control in the Kolar Gold Field, India." All may not agree with some of his theories that were deduced from studies of the many violent rock bursts at depths of 5000 to 7000 ft., but the data obtained are of great value. His theories of symmetrical ring stresses and symmetrical domes which are pictured as perfect are rather hard to understand as such uniformity is un- likely in view of the irregularities in the formation due to folds and fractures of various kinds. All will agree in principle with this idea of domal effects, which have been observed in many countries, but they are generally irregular.

Jan 1, 1938

By T. B. Counselman

AFTER several years study, the Universal Atlas Cement Co. decided to rebuild its plant at Leeds, Alabama. The entire old plant, which was to operate during the new construction, was then to be scrapped with the exception of two kilns. The quarry was to be mechanized, new and larger kilns installed, with the most modern type of equipment all through the plant. Raw grinding operations at all of the Universal Atlas plants were dry. However, the dust hazard of this operation and the growing emphasis on occupational diseases made wet grinding attractive. Coal at Leeds is cheap, so that a slightly higher coal practice was unimportant. Power was cheap, so that waste-heat boilers were not desirable. Since new kilns were to be installed, these could be made long enough to make filters unnecessary. Wet raw grinding could be either the old practice of open-circuit compartment mills or closed-circuit grinding in accordance with metal-lurgical practice. The latter saved power and steel wear and saved initial investment. This had been demonstrated in cement plants. Also, the elimination of tramp oversize was a most important advantage. Ease of chemical control was another factor. Blending in the thickener, with elimination of slurry mixers had been found practicable. Therefore, if wet raw grinding were used at all, the advantages were clearly in favor of closed-circuit grinding. Detailed layouts of the most modern possible closed-circuit dry-grinding plant and of a closed-circuit wet-grinding plant were prepared, and careful estimates were made of initial invest-ment and operating costs. Full consideration of all the factors involved resulted in a decision to install wet closed-circuit grinding.

Jan 1, 1939

By T. B. Counselman

AFTER several years study, the Universal Atlas Cement Co. decided to rebuild its plant at Leeds, Alabama. The entire old plant, which was to operate during the new construction, was then to be scrapped with the exception of two kilns. The quarry was to be mechanized, new and larger kilns installed, with the most modern type of equipment all through the plant. Raw grinding operations at all of the Universal Atlas plants were dry. However, the dust hazard of this operation and the growing emphasis on occupational diseases made wet grinding attractive. Coal at Leeds is cheap, so that a slightly higher coal practice was unimportant. Power was cheap, so that waste-heat boilers were not desirable. Since new kilns were to be installed, these could be made long enough to make filters unnecessary. Wet raw grinding could be either the old practice of open-circuit compartment mills or closed-circuit grinding in accordance with metal-lurgical practice. The latter saved power and steel wear and saved initial investment. This had been demonstrated in cement plants. Also, the elimination of tramp oversize was a most important advantage. Ease of chemical control was another factor. Blending in the thickener, with elimination of slurry mixers had been found practicable. Therefore, if wet raw grinding were used at all, the advantages were clearly in favor of closed-circuit grinding. Detailed layouts of the most modern possible closed-circuit dry-grinding plant and of a closed-circuit wet-grinding plant were prepared, and careful estimates were made of initial invest-ment and operating costs. Full consideration of all the factors involved resulted in a decision to install wet closed-circuit grinding.

Jan 1, 1939

By Frank T. Sisco

DURING the past year the iron and steel industry of the world as a whole operated on a satisfactory basis. No discoveries nor new processes of outstanding importance were announced either here or abroad, although rumors of such were persistent. In general, the efforts of operating and research men in the iron and steel industry seemed to be confined to improving quality and reducing cost, not a new aim, for the same efforts have been noted in nearly all of the annual reviews of the industry for at least fifty years. Most published papers on blast furnace or steel-making practice were of minor importance, at least when judged by the criterion of radical change in process or product. If the number of reports in the technical journals, or articles in the trade press, is used as a basis for comparison, continuous-mill sheet is still the most important single product of the industry; papers were published detailing the results of the investigation of various phases of the

Jan 1, 1938

Coal Transport Via Pipe Line Claimed Feasible Moving coal via pipe line is a project proposed by the U. S. Bureau of Mines. A pipe line 100 miles long capable of transporting 5000 tons of coal a day with water could be built for about $10 million. The cost of moving the coal 100 miles would be between $1.28 and $2.01 a ton.

Jan 9, 1951

Jan 2, 1950

APPROXIMATELY 3500 people thronged the Hotel Statler from February 18 to 24 for the 173rd general meeting of AIME. It was a technical extravaganza in that 82 technical sessions were held, at which 500 authors presented some 350 papers. Fortunately, Jerry Peirce, outgoing President, didn&apos;t have, to preside at all the events although after his year&apos;s stint as President, he has more than a nodding acquaintance with some of the latest problems in the mining, metals, and petroleum industries. Although the Welcoming Luncheon on Monday noon was the official opening of the meeting, Local Section Delegates and the Board of Directors convened on Saturday and Sunday, respectively. The large attendance and business like demeanor of these two groups was in accord with the energetic and competent service they have rendered the Institute through the year. To the applause of engineers and their wives who thronged the grand ballroom of the Statler for the Welcoming Luncheon, President Peirce introduced Oliver B. Hopkins, president of the Canadian Institute of Mining and Metallurgy and C. Gerow, secretary of CIM. Dr. Hopkins brought greetings from the CIM and expressed his satisfaction in the splendid spirit of cooperation that exists between the two Institutes. Dr. Hopkins is president, Interprovincial Pipe Line Co., Toronto, and counts as a close personal friend M. L. Haider, who is the 1952 President of AIME and lately of Toronto where he was a director and general manager of Imperial Oil Ltd. Mr. Haider will be known shortly as Mike to thousands of AIME members as he makes his Local Sections presidential tour. There was a pause in luncheon proceedings when Judge Harold R. Medina arrived amid the applause of the audience and somewhat breathless from his trip via motorcade from an antitrust trial against investment bankers at the courthouse downtown. With the Judge at his elbow, President Peirce took the opportunity in his introduction to good humoredly chide the Judge for the vixenish habits of public servants in their treatment of astute businessmen. The successful inventor who patents his inventions is a monopoly; the copper manufacturer who buys his competitors a drink is in collusion; but the business failure need only look to the government for a subsidy, Mr. Peirce pointed out. Judge Medina, quickly captured the admiration of his listeners. He spoke about justice, deploring partisan deals on nominations for judge-

Jan 1, 1952

By K. Huessener

This paper attempts a survey of the principles involved in the combustion of blast-furnace gas in boilers and stoves. I do not expect to be able to give much information which is actually new, since the laws and methods of calculation pertaining to this problem are contained in a number of handbooks; but, so far as I am aware, they have nowhere been treated exclusively with reference to this one problem of gas economy. The road which I follow is less that of strictly scientific research than that of the practical engineer, faced by operation problems which require a quick solution by easily accessible means without a prolonged search in scientific handbooks. For this purpose I give a number of tables and diagrams, as well as the results of many years1 practical working experience as combustion engineer, which I trust will prove useful to my readers. HlSTORICAL Considering the tremendous efforts made during the last 15 years to increase the efficiency of all kinds of power plants, it is highly surprising that until a comparatively very recent period, progress in the economical combustion of blast-furnace gas has been so slow, The explanation generally put forth, that fuel has been so cheap that it was hardly worth while to bother about this economy, will not hold good, for the greatest trouble was taken to improve the combustion of coal and to reduce the consumption of steam, The most plausible explanation appears to be the general impression, held as an accepted fact, that gas, especially hot, uncleaned, blast-furnace gas, was not a good boiler fuel. Many managers of high repute had tried unsuccessfully to improve the conditions of its use, and the dictum went forth that efficiencies of over 60 per cent., particularly with high loads, were impossible. This was the situation not only in the United States, with very cheap fuel, but also in Europe, where fuel prices are twice and three times as high.

Jan 1, 1916

By Augustus Locke

I WISH to urge on this Committee the task of evaluating mining geology. -My motive is as follows: It, is a. duty of the Institute from time to5 time, to establish the social perspective of the professions grouped within it, not simply to promote their use, but to determine with engineering definiteness their true powers and functions. This becomes the delegated duty, therefore, of this committee in respect to geology. Be- cause my own subject is mining, I shall confine my remarks to mining geology. But I believe that the evaluation should be made to include all of that geology termed economic. The perspective for such evaluation is shown in the nature of the public support given to geology. The federal Geological Survey, the leading organization on the economic side, is actuated by the zeal of a small group of devoted professionals who consider its work valuable, &apos; It proceeds, however, on a starvation ration of appropriations, and that implies that neither the corporations, the voters nor the vote getters consider it important. Altogether, in&apos; the public consciousness, geology is negligible. That, at the same moment, .the profession should act with full confidence, while everyone else should act&apos; with opposite motives, is not fitting. For us, as a committee, to remain incurious regarding such a disparity of beliefs is quite impossible.

Jan 1, 1931

By AIME AIME

READERS of a technical paper, or the audience if the paper is presented orally, judge the paper on several counts. The September 1940 issue of MINING AND METALLURGY contained an excellent short article by S. Marion Tucker en- titled "Are You Going to Present a Paper," which considered the general subject of presentation. In it Dr. Tucker referred to the large number of poorly prepared and badly delivered papers that are presented annually before the large number of technical and other societies that meet regularly, and he stressed the point that good delivery, length of paper, content, and composition are of great importance. All of Dr. Tucker&apos;s points were well taken; however, good illustrations are equally important in explaining certain phases of some papers.

Jan 1, 1941

By Frank Woolley, John F. Elliott

The high-temperatzrre solulion calorimeter has been modified and an extension dynamic analysis of i/s transient behavior has provided an improved basis for interpretation of the experimental data. The partial molar heats of mixing, Him, of aluminum, copper, and silicon in the corresponding binary liquid-iron alloys haz,e been measured directly at 1600°C. The resulls in kcal per g-alom are: THE high-temperature1,2 solution calorimeter was planned and designed to obtain directly the partial molar heat of solution of solute elements in a variety of liquid metals that might serve as solvents. Results obtained in the temperature range of 1000° to 1200°C were described in the two earlier publications. However, a long-term goal in the program has been to obtain measurements at 1600°C of the heats of solution of elements in liquid iron. Hence, subsequent to the work last reported,2 and based on the experience of the first two studies, the calorimeter system has been modified and operated at 1600°C to obtain measurements on the Fe-Si, Fe-A1, and Fe-Cu systems. This paper reports the results of the work. THE MODIFIED SYSTEM It was clear from the earlier results that the most precise measurements can be obtained with the high-temperature solution calorimeter when the solution time is less than approximately 30 sec. This can be achieved only when the bath temperature, Tb, is above the melting (liquidus) temperature of the solute material being dropped. A second point of importance is that the refractories used earlier liberated considerable water so that, although the oxygen potential of the atmosphere in the system was satisfactory for work with nickel and copper, it was too high for work with iron, silicon, and so forth. Third, for work at 1550" to 1650°C, an improved temperature-sensing unit is needed. The modified calorimeter in its latest form is shown schematically in Fig. 1. The refractory brick and the Kanthal-Super heating elements which formed the furnace for heating the solute addition have been replaced by a smaller resistance-heated tube furnace which is insulated with bubble-grain alumina. A more elaborate gas purification system was installed to maintain a satisfactorily low oxygen potential in the atmosphere of the calorinieter chamber and of the solute addition furnace. As was the case in the earlier work, at the beginning of a run the calorimeter chamber is evacuated and then filled with purified argon so that a total pressure slightly in excess of 1 atm is maintained during the run. When either of the furnaces within the enclosure attains a red heat, 6 pct H2 is added to the atmosphere. Throughout the run, gas from the calorimeter is circulated through a de-oxidation system at the rate of approximately 5 standard liters per min; the changeover time for the gas within the calorimeter enclosure is approximately 1 hr. The essential stages of the deoxidation system are: a copper furnace at 600°C, a drying tube of anhydrite, and a titanium furnace at 800°C. The oxygen potential of the gas stream in the purification system can be monitored at several points by a stabilized zirconia oxygen cell. This cell is invaluable in detecting the development of leaks in the container vessel and the gas circulating system. The installation of the solute-addition furnace allowed either of two types of temperature-sensing units to be mounted on a water-cooled probe. The first was a small optical device using a silicon diode that was

Jan 1, 1968

By K. L. Sutherland, J. Rogers

The relationships between collector and mineral, activator and mineral, and activator, collector and mineral will be considered herein. We propose to criticize current theories of flotation but we will not repeat the many pertinent arguments presented by Wark and Cox28 in 1937 in which the "chemical" or more strictly the "solubility" theory proposed by Taggart and co-workers22 is shown to be untenable. Recently Taggart, Arbiter and Kellogg24 have studied the long-chain aliphatic amines as collectors and have attempted to resuscitate the solubility theory for these particular collectors. Dean and Ambrose3 have felt that "we stumble over words" when we distinguish different mechanisms of adsorption. Our view is that nothing is more stultifying to the development of a science than attempts to force widely different phenomena into one classification. This oversimplification leads immediately to difficulties in the interpretation of results. Experimental Procedure The response of minerals to activator and collector was determined by "captive-bubble" tests. The methods of preparation of specimens26 and of testingin have been previously described. Results from captive-bubble tests were confirmed by flotation tests in glass-stoppered cylinders.26 The full lines shown in the figures relating solution composition to contact (flotation) distinguish solutions in which contact (flotation) is possible from those in which it is not. The curve is derived by successive approximation and the accuracy is ±o.2 pH units and ±5 mg. per liter of collector or depressant. Solution compositions for which it was shown experimentally that contact or flotation is possible are marked by a circle, those for which it is not possible by a cross and those for which it is doubtful by a cross within a circle. It is assumed that at all other solution compositions within (without) the curve, contact or flotation is possible (not possible). After testing in the collector solution, the mineral was removed, washed, and tested by the captive-bubble method in water, or floated in a cylinder with frother only. In this way the composition of solutions in which a mineral was conditioned but in which properties of the collector solution prevented contact or flotation can be defined. The composition of solutions in which conditioning was possible lie between the full and broken curve, the experimental results being indicated on the figures by a square. The curves show the limits of composition of solution in which flotation in a cell would be possible. Many factors other than those considered in these tests determine recovery or grade of a given mineral in practice.

Jan 1, 1947

By J. Rogers, K. L. Sutherland

The relationships between collector and mineral, activator and mineral, and activator, collector and mineral will be considered herein. We propose to criticize current theories of flotation but we will not repeat the many pertinent arguments presented by Wark and Cox28 in 1937 in which the "chemical" or more strictly the "solubility" theory proposed by Taggart and co-workers22 is shown to be untenable. Recently Taggart, Arbiter and Kellogg24 have studied the long-chain aliphatic amines as collectors and have attempted to resuscitate the solubility theory for these particular collectors. Dean and Ambrose3 have felt that "we stumble over words" when we distinguish different mechanisms of adsorption. Our view is that nothing is more stultifying to the development of a science than attempts to force widely different phenomena into one classification. This oversimplification leads immediately to difficulties in the interpretation of results. Experimental Procedure The response of minerals to activator and collector was determined by "captive-bubble" tests. The methods of preparation of specimens26 and of testingin have been previously described. Results from captive-bubble tests were confirmed by flotation tests in glass-stoppered cylinders.26 The full lines shown in the figures relating solution composition to contact (flotation) distinguish solutions in which contact (flotation) is possible from those in which it is not. The curve is derived by successive approximation and the accuracy is ±o.2 pH units and ±5 mg. per liter of collector or depressant. Solution compositions for which it was shown experimentally that contact or flotation is possible are marked by a circle, those for which it is not possible by a cross and those for which it is doubtful by a cross within a circle. It is assumed that at all other solution compositions within (without) the curve, contact or flotation is possible (not possible). After testing in the collector solution, the mineral was removed, washed, and tested by the captive-bubble method in water, or floated in a cylinder with frother only. In this way the composition of solutions in which a mineral was conditioned but in which properties of the collector solution prevented contact or flotation can be defined. The composition of solutions in which conditioning was possible lie between the full and broken curve, the experimental results being indicated on the figures by a square. The curves show the limits of composition of solution in which flotation in a cell would be possible. Many factors other than those considered in these tests determine recovery or grade of a given mineral in practice.

Jan 1, 1947

By F. E. Gregory

MINING methods and customs in many districts of England are to this day strangely bound about by the records and traditions of the past. In some mining fields this is more apparent than in others, yet it is everywhere in evidence, for Cornwall with her mines under the sea, Wales with her famous quartzites, and Derbyshire with her remarkable cavern deposits, are all tinctured with quaint customs that have come out of the almost forgotten past. Here, modernism has never replaced tradition, and many of the laws are woven of the woof and warp of ancient custom. Indeed, these things exist because they have come to be part and parcel of the civil laws. And these laws are observed with meticulous care and accorded all the reverence due their venerable age. All activities pertaining to the mining of metals are hedged around by curious and ofttimes clumsy laws, each minute and trivial detail being covered by the civil code, and each petty law enforced by an ofttimes pompous official.

Jan 1, 1933

By William Gilman

IN the past five years, and without much fanfare, Turkey has emerged as a significant figure in the world mining picture. This has been accomplished by a five-year plan now in its last year. A second five-year plan is already under way, ahead of schedule. It will concentrate even more than the first in developing Turkish mines in order to increase present exports of coal, chrome ore, and copper, and to develop new mineral exports as well. To be fully understand the republicic?s mining program should be considered as something more than merely tapping rich resources in the East along the Aegean Sea, in the North among the mountains descending to the Black Sea, and in the West at the foot of the Taurus Mountains. It should also be viewed in the light of a strong nationalist policy with many aspects of state socialism. Turkey declares frankly that all mineral re- sources belong to the nation and all exploitation should be by the state for the twin purpose of modernizing the state and securing foreign exchange for the state by exports. Accordingly, the principal mines are state-operated and a few lesser enterprises, although not state-owned, have at least been put in the hands of Turkish capital.

Jan 1, 1938

By A. G. H. Anderson, A. W. Kingsbury

Silicon bronzes containing ken are used to a considerable extent in industry, under the trade name of P.M.G. alloys. Various classes of wrought alloys fall in the composition range 1.5 to 3.5 per cent silicon, and 0.5 to 2.5 per cent iron. Castings may contain as much as 6 per cent silicon and 3 per cent iron at present. The constitutional diagrams of these alloys are thus of considerable practical importance. Copper-silicon-binary alloys have been thoroughly investigated by a number of workers, the latest reports being those of C. S. Smith1 and of A. G. H. Andersen.2 Although much work has been done on iron-copper alloys,3 recorded investigations on the copper-rich copper-iron binary constitutional diagram are not numerous. Tammann and Oelsen4 etermined the solubility limits of iron in copper by means of magnetic measurements, and found that the solubility of iron in copper amounts to a fraction of one per cent at 400°C., increasing slowly to one per cent at 800°C. From 800°C., the solubility increases rapidly and attains 4 per cent at iioo°C. Hanson and Ford,5 using electrical resistivity measurements and the microscope, determined a somewhat different solubility limit. of earlier X-ray works on the copper-iron system, very little has been published. The work by Bradley and Goldschmidt6 on copper-iron-aluminum alloys includes some information on the copper-iron binary. These investigators conclude that substitution of iron in the copper lattice decreases the spacings, which is contrary to the evidence of the present work. Hanson and West? have investigated the ternary alloys of copper with iron and silicon. Although their diagrams are valuable contributions to the understanding of these alloys, they did not recognize the kappa phase,l,2,7,8 and their diagrams do not everywhere conform to the phase rule. The present work contains a check by means of X-rays of the solid solubility limit of iron in copper, and an X-ray investigation of the ternary-phase diagram, which, owing to present conditions, it became necessary to curtail considerably. Preparation of Samples Castings weighing about 75 grams were melted under vacuum. The charges were made up of ingot iron, copper cathodes from Laurel Hill, and refined silicon supplied by the Electrometallurgical Co. Alundum crucibles were generally used. The exceptions were alloys 77 and 78, which were melted in graphite crucibles. The ingots were annealed at 800°C. for one week, then samples were cut for chemical analysis. Longitudinal sections of the binary alloy ingots were hammered into plates 1/8 in. thick. Wherever possible, these plates were homogenized at temperatures ensuring

Jan 1, 1943

By A. G. H. Anderson, A. W. Kingsbury

Silicon bronzes containing ken are used to a considerable extent in industry, under the trade name of P.M.G. alloys. Various classes of wrought alloys fall in the composition range 1.5 to 3.5 per cent silicon, and 0.5 to 2.5 per cent iron. Castings may contain as much as 6 per cent silicon and 3 per cent iron at present. The constitutional diagrams of these alloys are thus of considerable practical importance. Copper-silicon-binary alloys have been thoroughly investigated by a number of workers, the latest reports being those of C. S. Smith1 and of A. G. H. Andersen.2 Although much work has been done on iron-copper alloys,3 recorded investigations on the copper-rich copper-iron binary constitutional diagram are not numerous. Tammann and Oelsen4 etermined the solubility limits of iron in copper by means of magnetic measurements, and found that the solubility of iron in copper amounts to a fraction of one per cent at 400°C., increasing slowly to one per cent at 800°C. From 800°C., the solubility increases rapidly and attains 4 per cent at iioo°C. Hanson and Ford,5 using electrical resistivity measurements and the microscope, determined a somewhat different solubility limit. of earlier X-ray works on the copper-iron system, very little has been published. The work by Bradley and Goldschmidt6 on copper-iron-aluminum alloys includes some information on the copper-iron binary. These investigators conclude that substitution of iron in the copper lattice decreases the spacings, which is contrary to the evidence of the present work. Hanson and West? have investigated the ternary alloys of copper with iron and silicon. Although their diagrams are valuable contributions to the understanding of these alloys, they did not recognize the kappa phase,l,2,7,8 and their diagrams do not everywhere conform to the phase rule. The present work contains a check by means of X-rays of the solid solubility limit of iron in copper, and an X-ray investigation of the ternary-phase diagram, which, owing to present conditions, it became necessary to curtail considerably. Preparation of Samples Castings weighing about 75 grams were melted under vacuum. The charges were made up of ingot iron, copper cathodes from Laurel Hill, and refined silicon supplied by the Electrometallurgical Co. Alundum crucibles were generally used. The exceptions were alloys 77 and 78, which were melted in graphite crucibles. The ingots were annealed at 800°C. for one week, then samples were cut for chemical analysis. Longitudinal sections of the binary alloy ingots were hammered into plates 1/8 in. thick. Wherever possible, these plates were homogenized at temperatures ensuring

Jan 1, 1943

By Robert A. Rapp, Ronald L. Pastorek

Solid-state electrochemical measurements by three alternative experimental procedures were made with the cell FeO, Fe3O4 |Zro.85Cao.15O1.85 |Cu| Zr0.85CaO.15O1.85 | FeO, Fe304 to establish the solubility and diffusivity of oxygen in solid copper in the temperature range 800" to 1030°C. The solubility of oxygen in solid copper and the diflusivity of oxygen in solid copper Dgu = 1.7 X 10-2 exp(-16,000/RT) Cm2/sec were determined and confirmed in alternative experiments. The enthalpy of solution of oxygen in solid copper equals —10,000 cal per mole; the partial excess entropy of the oxygen atoms in the Cu-O dilute solution is approximately the same as that found for interstitial atoms in other metals. The diffusivity of oxygen in solid copper is consistent with that expected for an interstitial atom. RELIABLE values for the saturation solubility N(s) and diffusivity DO of oxygen in solid copper have not been unambiguously established in the literature. Following three early determinations by others,1"3 Rhines and Mathewson4 reported that the solubility of oxygen in solid copper increased from 0.007 at. pct 0 at 600°C to about 0.015 pct at 1050°C. Phillips and skinner,, using essentiially the same analytical procedure, reported that the solid solubility increases from 0.0018 at. pct 0 at 550°C to about 0.0075 pct at 1050OC. The only previous value for the diffusivity of oxygen in solid copper was reported by Ransley.6 Ransley deoxidized Cu-Cu2O alloys in an atmosphere of carbon monoxide gas to yield a solubility-diffusivity product. He used the solubility data of Rhines and Mathewson to calculate the diffusivity values. Another method for obtaining the solubility-diffusivity product (N(s) DO) is by measuring the widths of internal-oxidation zones in copper alloys as reported by Verfurth and Rapp.7 However, the calculated N(S)Do products depend upon the alloy content of the specimen, so that the internal oxidation of copper alloys does not follow ideal internal oxidation kinetics. As a result, unequivocal values for the N(s) DO product were not obtained by this procedure. A solid-state coulometric titration technique similar to that employed in this work was introduced by C. Wagner8 to study the dependence on silver activity of the Ag/S ratio in silver sulfide in the temperature range of 160" to 300°C. Similar experiments have been carried out by C. Wagner and co-workers9-11 to study the stoichiometry range of silver and copper tellurides, cuprous sulfide, and cuprous selenide. Numerous authors have carried out electrochemical measurements with a solid oxygen-ion-conducting electrolyte to determine the solubility and/or diffusivity of dissolved oxygen in several liquid metals.12-l6 Rickert and Steiner17,18 have used solid-state electrochemical measurements to determine the diffusivity of oxygen in solid silver from 760" to 900°C. Two different cell geometries were used. In the cell of linear geometry Fe, FeO | ZrO2 + (CaO) | Ag + [0 (dissolved)] [1] oxygen diffused from the interior of the silver electrode to the silver/electrolyte interface where the oxygen activity had been lowered from a fixed initial value to practically zero by the application of voltage to the cell. The diffusivity of oxygen in solid silver was determined from the solution of the diffusion equation and the time dependence of the cell current. However, this determination of the diffusion coefficient depended upon a knowledge of the solubility of oxygen in solid silver. A cylindrical geometry was used for the cell Pt, O2(Po2 = 0.21 atm) | ZrO2 + (CaO) | Ag + [0 (dissolved)] [II] which also allowed the diffusivity of oxygen in solid silver to be determined. These values were in agreement with other available data.l9 Recently, Raleigh20,21 used a method involving the measurement of diffusion-limited currents in a cell involving the AgBr solid electrolyte to determine the diffusion coefficient of silver in Ag-Au alloys at 400°C. Diffusivity values on the order of l0-14 sq cm per sec were measured in the alloy composition range 10 to 60 at. pct Ag in a single experiment. From numerous electrical conductivity and galvanic cell measurements,9&apos;22"26 the solid solution Zr0.85 Ca0.15 O1.85 has been established as an electrolyte with predominant oxygen ion conduction over a wide range of intermediate and high oxygen activities. For interrelating the thermodynamics and the kinetics of the dissolution of oxygen in solid copper in this investigation, a galvanic cell was constructed with FeO-Fe3O4 as the reversible reference electrode, the Zr0.85Ca0.15 O1.85 electrolyte, and a pure copper specimen under-saturated in oxygen as the other electrode. THEORETICAL ANALYSIS Three variations of a high-temperature electrochemical technique were used in this study to provide two determinations each of the solubility and diffusivity

Jan 1, 1970