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By Brahm Prakash, R. Schuhmann

Chemical conditions for flotation and nonflotation of cassiterite and fluorite with oleic acid as collector and with alizarin dyes as modifying agents were studied by means of small-scale, vacuum-flotation tests. Artificial cassiterite was prepared for these tests by high-temperature methods, especially by crystallization from borax melts.

Jan 1, 1950

By Archer E. Wheeler, Milo W. Krejci

The Boston & Montana Reduction Works at Great Falls, Mont., was formerly the reduction works of the Boston & Montana Consolidated Copper & Silver Mining Co., and continued as the reduction plant for the independent company until June 1, 1910, when the consolidation of a large number of the operating companies of Butte was effected. It then became merged in the Anaconda Copper Mining Co. as the Boston & Montana Reduction Department of the Anaconda Copper Mining Co. The history of copper converting at this plant, while not covering the entire period of the commercial use of the process in this country, does cover by far the larger part of it, and as the operation of and appliances for the process have undergone many changes during the time, it may, perhaps, be of some interest to put the record of these changes into permanent form. The plan followed in the preparation of this paper has been to give first a brief chronological record of the principal events and changes and then, even at the risk of some repetitions, to give more detaild accounts of some of these changes under separate headings. The headings for the complete paper are as follows: 1. General. Chronological Review. 10. Development of Different Classes 2. Mechanical Manipulation. of Converters After Class I. 3. Casting of Finished Copper. 11. Basic Lining. 4. Tamping of Linings. 12. Number and Size of Tuyeres. 5. Early Acid Linings. 13. Cast Copper Tuyeres. 6. Acid Linings With the Use of Ore. 14. Efficiency of Air. 7. Introduction of Flux Through the 15. Size of Converter Mouth. Tuyeres. 16. Height of Converter. 8. Bottom Blast. 17. Summary. 9. Disposal of Converter Slag, General Chronological Review. Ground was broken for the general concentrating and smelting plant in the spring of 1,891. The first departments to start operations were the concentrator in March, 1892, and the Brückner roasting and reverbera-tory smelting departments in April, 1892. The converter department

Jan 1, 1914

By OTTO HERRES

TITANIUM is estimated to be the ninth most plentiful element, ranking after iron, aluminum, and magnesium, and ahead of copper, lead, and zinc. Vast quantities of titanium are widespread throughout the world in ore deposits and beach sands. Before the war, processing plants were operated in England, France, Italy, Czechoslovakia, Norway, Russia, Australia, United States, and Japan. In spite of its widespread occurrence, however, the U. S. Department of Justice has held the titanium industry to be a world monopoly and action was taken in the Federal court during the summer of 1945 to enjoin international patent and marketing agreements and to restore free competition. Possibly the rather surprising lack of public familiarity with this industry of international importance arises from its astonishingly rapid development and growth in the strong hands of some of the greatest chemical companies in the world, including the important foreign companies, Imperial Chemical Industries (British), Montecatini (Italian), I. G. Farben (German), and Titan Kogko Kabushiki Kaisha (Japanese). The rapid growth of the titanium industry in the United States is indicated by a tenfold increase of ore imports in the 1930 to 1940 decade before the war began to affect shipments from overseas. The fact that the industry formerly derived practically all ore for chemical processing in American plants from foreign sources probably also accounts for lack of general public knowledge of titanium. In 1939, to meet the requirements of increasing demand for the white pigment. titanium dioxide, more than 250,000 tons of titanium concentrates moved to this country, principally from the Travancore coast of India where the ilmenite concentrate from the beach sand runs as high as 60 per cent in titanium dioxide. Global warfare put a stop to shipping and thus gave rise to the development of titanium mining on a substantial scale in the United States during 1941.

Jan 1, 1946

Teamwork: The famous first sentence of an essay en- titled Aphorisms, by Hippocrates, is as follows: "Life is short, the Art long, opportunity fleeting, experience treacherous, judgment difficult." The future of science does not depend so much on the number of scientists or the number of colleges, but rather on the individual qualities and the degree of perfection of a limited group of leading scientists and colleges. These are individual factors which require inherent talent which in turn is a condition evolved after generations of culture. Thus, very elaborate higher education for indiscriminate masses of humanity or students may not necessarily show the expected results. In other words, it is possible that higher specialized education should be given only to the few talented individuals, and their capacity and worth should be judged by as highly qualified and talented teachers. Quality is the greatest of all competitive aids. An essential qualification that must be possessed by a quality mineral industries college is a high caliber teaching staff, for the mineral sciences will advance in the coming years only if the leading minds of today are made avail- able as the mental springboards for our scientists of tomorrow. Mineral industries schools are finding it increasingly difficult to maintain a high caliber staff of instructors and administrators in competition with private business and governmental demands for similar

Jan 1, 1950

By H. M. Ziesemer

PRIOR to 1909 that mountain of porphyry, known as. Sacramento Hill, had remained hardly touched but had always aroused suspicions as to the presence of ore within.. During that year, exploratory work was started by underground methods; drifting and raising continued until 1913. It was proved that a mineralized zone existed, the limits of which had not been determined; so, because of the lower costs of exploratory work and the greater desirability of vertical sections, it was decided to prove the extent of the ore zone by churn drills. Drilling continued until the year 1917, when it seemed almost certain that the horizontal limits of the orebodies had been determined. Ore continued in depth in one direction beyond a point where it was economical to explore by churn drilling; this extension is still being developed by underground methods. The irregularities of the boundaries of the ore zones, together with the variable grades of ore encountered, made it necessary to drill on the corners of 100-ft. squares. Two ore zones were proved, known as the East and West Orebodies. The Sacramento Hill porphyry stock intruded into the Dividend fault. The fault ran roughly east and west with a dip to the south, having pre-Cambrian schists on the north against Paleozoic limestone on, the south. This intrusion was accompanied by a silica breccia on the south periphery, along the limestone contact side. The ore lay in the silica breccia and in the porphyry, some distance from the breccia. No ore was found in the heart of the porphyry mass on the north side, along the schist contact. The West Orebody is elliptic in shape, having a major axis of 1200 ft. (366 m.) and a minor axis of 800 ft. (244 m.); these diminish with depth until, at 300. ft., the axes are 500 ft. and 300 ft., respectively. The ore consists of chalcocite, some bornite, chalcopyrite, and considerable pyrite in a silicious gangue. About 30 per cent. of the copper is caused by

Jan 2, 1922

By R. P. Smith

In 1937 the employees of the Hollinger Consolidated Gold Mines Ltd.. at Timmins. Ont., Canada, approached organized medicine for a plan to provide themselves and their families with a complete medical service including hospitalization. This approach was made because of two conditions: (1) the necessity for some organization whereby contributions could be made in instalments to offset the sudden and large expense connected with illness for which the average employee is not prepared, and (2) the need for a more cohesive quality of service to replace a contract practice then in vogue, which did not take care of the employee's family or dependents. In different parts of the United States and Canada similar plans were in force, not only for employed groups but for numbers of people in circumscribed areas. In Europe different countries had adopted various forms of health insurance plans. It then was no surprise that these employees as a group should ask for some similar plan. With the cooperation of the management, a plan was instituted. The plan has one object only—the provision of medical services, including the accessory services such as hospitaliza-tion, X-rays, nursing, and necessary drugs and medicines. It is not concerned with cash benefits, sickness and accident payments, or any form of monetary return as the result of illness, but is simply an organization to provide medical services and pay for them from a central fund. It is a nonprofit organization and the only shareholders are the employees and their families who contribute and who in turn receive services. The Hollinger plan is limited to the employees of the Hollinger mine, who live in Timmins and the immediate vicinity. At first, the membership was voluntary. In the third year, it was made a condition of employment, with the proviso that at the end of any Association financial year an employee may withdraw if he wishes to do so. After withdrawal, he cannot again become a member until the end of the next Association year, and then only by the payment of the back dues. This step was taken to ensure continuity, and to prevent employees from withdrawing when well and reentering when faced with impending illness or operations. The employee himself is subject to medical examination on application for employment, and if accepted is subject to further examination by a specialist in chest diseases under the Workmen's Compensation Board of Ontario. Thus it is possible to exclude those who have heart disease, tuberculosis, or other disabling conditions when first employed. Wives and families of employees are not subject to medical examination but other dependents of an employee—mother, father, or other relative—who are declared by the employee to be wholly dependent upon him must be examined. The employee

Jan 1, 1946

By J. A. Norden

MUCH has been written concerning the hoisting equipment of various mines -throughout the country, but most of the literature on the subject, if not all, describes equipment of extraordinary capacity and the small and medium-sized outfits have been neglected. The hoisting equipment here described is capable 'of handling about 1200 tons per day. It has not been worked, to capacity, but 600 to 700 tons, together with men and materials, have been handled in two shifts without any great effort. Only one shaft extends from the surface to the lowest levels of the mine; see Fig. 1. It is composed of three compartments, two of which are used for hoisting and the third for water, air, and electrical lines, and for sinking purposes. In 1909, this shaft was raised from the 1000-ft. (304-m.) level to the 700-ft. There a station was cut and an air hoist installed. At this time all mining operations were confined to the upper levels of the mine; that is; above the 700-ft. The. ore was-dropped to this level through chutes from the 300-, 400-, 500-, and 600-ft. levels and then lowered in cars on cages to the 1000-ft., which is the main haulage adit, the mill and railroad bins being about 3000 ft. from the shaft. Orebodies were, in due time, developed on the 1000-ft. level and below. Therefore, in 1913, the shaft was sunk to the 1150-ft. level and thereafter sinking was continued at regular intervals until the 1500-ft. level was reached. But, hoisting from the 1300-ft. level was a difficult, and slow process with the antiquated air hoist, so, in 1916, it was derided to raise the shaft to the surface and install a modern, electrically operated hoist. This was completed early in 1917 and the hoist was in operation in March of that year.

Jan 8, 1920

By M. B. Hopkins

FOR years the expression "except rubber, tin, and manganese" has appeared in practically every discussion of the natural resources of the United States. Knowledge that natural rubber is not produced in the United States has now spread from the relatively few who have reason to be interested in the country's basic raw material supplies to all those who ride in automobiles, which means everybody. This "everybody" reads in the daily papers that we have a stock pile of natural rubber and that plenty of synthetic rubber is just around the corner. Statistics as to the United States' rubber requirements and sources of supply are of interest to him only to arrive at an answer to the question : "After taking care of rubber requirements for military purposes, will there be rubber for my automobile and the many other rubber articles I want?" More than 30,000 different rubber articles are manufactured in addition to the tires and tubes which use up about 70 per cent of the rubber supply.

Jan 1, 1942

By Charles E. Locke

DEPRESSION in all lines of the mineral industry except gold, which began in 1930 and continued, even worse, through 1931, had its effect on ore concentration. Construction was limited to the completion of plants already begun. Every possible economy was adopted. Changes and improvements involving expense were postponed. Research was largely abandoned. Operations became highly efficient and costs were cut down, although this did not necessarily mean a lower cost per ton because of the greatly reduced capacity at which mills were run. Lower metal prices caused the operators to seek the optimum ratio of concentration and grade of concentrates looking toward maximum economic recovery; that is, net profit. In the crushing field no marked changes occurred. The Symons cone crusher for intermediate work is in use almost everywhere. Its manufacturers claim that 900 machines have been installed in 21 countries, replacing two previous steps of crushing and yielding a product sufficiently fine to form a satisfactory feed for rod mills and ball mills. A new Telsmith crusher has appeared which has curved jaws something like the Symons cone and consequently the same advantage as the latter.

Jan 1, 1932

By W. L. Saunders

(New Haven Meeting, February, 1909.) This paper deals specifically with heading-driving as distinguished from the broader term tunnel-driving. A heading is a pilot or path-finder for the main tunnel. Some headings are complete tunnels in themselves; that is, conditions at times warrant driving a heading the full diameter of the proposed tunnel. A tunnel 10 ft. in diameter might be driven to advantage through a single heading, provided the nature of the material admits, but it usually pays to drive rock tunnels of large diameter through the heading-and-bench system. Much de-pends upon the material, as in soft ground tunnels of much larger diameter are driven in a single heading. In mines, the tunnels, drifts, cross-cuts, adits, etc., are usually of small diameter, hence the driving of headings applies to completed tunnels in minim-work, except, of course, in cases like drainage-tunnels and main entries leading into coal-mines, where conditions call for tunnels of large diameter, approximating those driven for railway-service. In building aqueducts the tunnels are driven from 6 to 8 ft. in diameter up to 15 or 20 ft., while in railway-service the dimensions vary from 18 to 30 ft. in diameter. There is no department of rock-excavation so difficult as that of heading-driving. This work. also belongs to the most expensive class in rock-excavation. A heading is driven .directly in the solid. There are no lines of lesser resistance towards which to direct the energy of the blast, but. the material must be blown out by main force. The completion of the heading simplifies all the rest of the work of excavation. It is easy, for instance, to enlarge a heading either from above, below or oil the sides, by breaking towards the open face through holes approximately at right angles to the axis of the heading; or the enlargement sometimes takes place by holes driven outside

Apr 1, 1909

(The following -list, contains the navies of those members of the Institute of whose connection with military service we have only recently become acquainted; it also includes the names of a few who have recently been promoted or transferred. A com-plete list was published in the Year Book, issued as a supplement of the Bulletin for March, 1918.) ADDICKS, LAWRENCE, Naval Consulting Board. ALINE, P. A., Camp Lewis. BARCUS, WALTER .J. E., Captain, Ordnance Department. BAUSH, JOHN R., Private, 1st Army Headquarters Regiment, Co. M. BENNETT, A. F., Lieutenant. BILLINGSLEY, PAUL, Engineer Officer, Aviation Section, Signal Officers' Reserve Corps. BOOTH, L. E., Ordnance Department. BROWN, JAMES F., 2d, 1st Lieutenant, Ordnance Reserve Corps, A. E. F.

Jan 4, 1918

By Augustus Locke

In 1900, when. the public first heard of "secondary enrichment," the Butte chalcocite seemed clearly supergene. Mining, through successive regions of leached capping, bonanza sulfide, and sulfide less rich, had paused at lean bottom levels which, though chalcocite-bearing, suggested the waning of copper. The deepest chalcocite, at 1500 ft., was yet too shallow to disturb the supergene hypothesis. But, with deeper mining, lean levels yielded to fat ones. Here and there they showed, within the same vein, an inverted distribution, chalcopyrite above and chalcocite below. To the miners' astonishment, they carried chal-cocite, unaffected by cross faults, on an independent course to the depth of 2500 ft. The pattern of ore distribution, hitherto revealed only in fragments, was now appearing in perspective, and, in the depth of the chalcocite, was beginning to make Butte differ from all districts where the chalcocite is indubitably supergene. The idea of hypogene origin at length came into favor; by 1913, when Sales' advocated this origin, the argument had become a powerful one. This argument rested on field evidence; but, already, there was beginning to emerge microscopic evidence not included in this argument. Especially pertinent was the proof that (1) the deep chalcocite lies in-mixed with bornite, often microscopic; (2) the deep chalcocite often replaces bornite; and (3) replacement of bornite by chalcocite is accomplished more easily than that of pyrite, enargite, or chalcopyrite. The microscopic evidence has been accumulating for ten years and it demands

Jan 1, 1924

By B. C. Craft

Development and exploratory work in Mississippi during 1934 was rather active, resulting in the expansion of the proven area and the drilling of a number of important wildcat wells. Mississippi showed a decrease in drilling operations during 1934. There were 36 completions from 18 counties during this period compared with 58 completions from 22 counties during 1933. There was a considerable decrease in activity in the Jackson gas field in Hinds and Rankin counties with only 9 completions, resulting in 8 gas wells and 1 dry hole compared with 17 gas wells, 2 oil wells and 7 dry holes during 1933. Leasing and geophysical work was reported from several sections of Mississippi last year. Extensive exploration and drilling were carried on in Lamar, Hancock, Pearl River, Greene and Stone counties and on the flanks of the Jackson anticline. Exploration will be continued in these areas during 1935. Four important wildcats were completed during 1934, all of which were reported as being structurally high, but without having important shows of oil or gas. These tests were: Hix and Germany's, J. J. Newman Lumber Co. No. 1, sec. 21-4N.-15W., Lamar County, abandoned at 3520 it. in the Wilcox; United Gas Public Service Company's Davis No. 1, sec. 30-1N.-5W., Greene County, abandoned at 7439 ft.; Gulf Refining Company's May L. Williams No. 1, sec. 33-5S.-17W., Pearl River County, abandoned at 4800 ft.; and Clarke County Oil Company's S. B. Kirkland No. 1, sec. 10-2 N.-16E., abandoned at 4002 ft. in the Eutaw. Another interesting wildcat was Gulf Refining Company's Dantzler Lumber Co. No. 6, sec. 22-4S.-llW., Stone County, abandoned at 7700 ft. (according to reports below the Selma chalk). A total of 114 of the 132 gas wells completed in the Jackson gas field are still producing and have a combined open-flow capacity of 4,145,-696,000 cu. ft. Four of the abandoned gas producers were never connected to the lines. The open-flow capacity of three wells in the Amory field is approximately 1,000,000 cu. ft. Producing against a line pressure of 50 lb., the demand during December greatly exceeded the capacity.

Jan 1, 1935

By R. C. Dalzell, A. E. Wells

In 1866, Thomas Graham1 called attention to the volume of gases, three times the volume of the sample, evolved from a meteoric iron heated in an evacuated porcelain tube. From that time to this the occurrence and significance of gases in metals have been the subject of investigation by many workers, among whom Sieverts,2 Iwasé3 and 0. W. Ellis4 stand preeminent. Sieverts and Iwasé concerned themselves with the solubility of a number of gases in metals in the liquid and solid states. They determined the absorption coefficients of these gases, and in all cases found a sharp change in solubility at the melting point of the metals. Ellis analyzed the gases evolved by solidifying copper and those occluded by the solidified metal. Lobley and Jepson5 endeavored to determine the effects of hydrogen, carbon monoxide and nitrogen on the porosity of copper that was allowed to solidify in the presence of each gas after 30 min. exposure to it in the

Jan 1, 1930

By C. Stansfield Hitchen

THE introduction of the logarithmic sector method of quantitative spectrography by Scheibe and Neuhäusser in 1928, and the subsequent .modification and improvement of the method by Twyman and Simeon, would seem to have marked yet a further advance in quantitative spec-trum analysis and its industrial application, inasmuch as it offers a simple means of eliminating some of the uncertainties inherent in the older methods based upon mere visual comparison of line intensities. In their recent admirable review of the position and capabilities of industrial spectroscopy, Brownsdon and van Someren1 say: Ways and means of facilitating the comparison of line-intensities so as to give them numerical values are helpful, and of these a logarithmic sector rotating in front of the slit appears to he one of the most promising; . . . the success recently experienced by the author in using this method for the examination of steels and solutions of metallic salts prompted him ,to investigate its possible use in estimating the impurities commonly present in crude and refined tin. The results of this investigation are submitted in the present paper. Details of a number of spectrographic analyses of tin for various impurities have already been published. Thus, Schweitzer2 describes the spectrographic examination of tin for lead, bismuth and cadmium, and was able to distinguish between such atomic percentages as 0.01, 0.05, 0.10, 0.30, 0.60, 1.20, 3.00 and 10.00. Negresco3 investigated the bismuth content of tin over a range of from 0.0005 to 35 per cent. Meggers, Kiess and Stimson4 compare spectrographic and chemical analyses of tin metal for copper, lead, iron, zinc, silver, nickel and bismuth. They stress also the value of spectrum analysis in the examination of tin used for boiler plugs, where the requirements that only minute quantities of impurities shall be present render the chemical analysis both tedious and difficult.

Jan 1, 1933

By A. E. Wheeler, H. Y. Eagle

The copper industry in the Province of Katanga, in the Belgian Congo, which is now controlled and operated by the Union Minére du Haut Katanga, had its inception many years ago in the vision of a Scotsman, Robert Williams, now Sir Robert Williams, Baronet. He it was who personally negotiated the mineral concession with King Leopold of Belgium, sent in the prospecting parties who located most of the present mines of the company, later arranged for the Belgian participation from which the present company was formed, and has been its active mentor ever since. The idea back of his efforts was the establishment of an industry on the Congo-Zambezi divide, of sufficient importance to draw up to it the head of the Cape to Cairo Railroad, the dream of Sir Cecil Rhodes, and the consummation of which he had left as a legacy to Mr. Williams, his successor. The reports of the prospecting expeditions showed that copper in profitable quantity was there, but many difficulties lay in the way of the establishment of the infant industry. The isolated location of the mines, various tribal wars, the Boer War, and many other factors contributed to making progress very slow. However, in spite of these difficulties the railroad was finally built and a blast-furnace plant erected at Lubumbashi, near Elisabethville, the capital of the Province. Operations of this plant were started in 1911, treating high-grade oxidized ores and producing pig copper by a reducing smelting. Production has been continuous since that time and the company has grown so that at present it ranks as the largest individual copper producer in the industry. It is a fitting monument to the foresight, optimism and driving force of its founder, and the progressive policies of his Belgian colleagues. In January, 1914, the Union Miniere du Haut Katanga engaged as its consulting engineer, Archer E. Wheeler, metallurgical engineer, at that time general superintendent of the Great Falls plant of the Anaconda Copper Mining Co. Mr. Wheeler was commissioned by the Board of Directors to proceed into Katanga, and make all necessary investigations to enable him to report on a comprehensive development program, and to recommend a scheme of treatment particularly for their low grade

Jan 1, 1934

By Gerald Edmunds

In a paper1 before this Institute in 1940, the writer reported that the surface orientation texture of zinc and cadmium differed from the texture existing within the casting, in that basal planes were parallel to the surface. He was unable to rationalize the , origin of this surface texture. It is conceivable that the surface orientation texture is influenced by the atomic force fields, which are different at the surface and within the body of metal. It was considered that a radical changc in the surface against which the metal is cast might alter the surface texture. In trial of this, zinc has been cast against a surface of molten lead, but the same result has been obtained—i.e., (001) parallel, ± 2oo, to the surface—as was obtained when it was cast against air, Transite or iron.' Into the bottom of an open cast-iron tray, 7 by 14 in. by 2 in. deep, preheated to about 275°C., about 1/4 in. of lead, then 1/2 in. of zinc was poured, and the whole was covered with an electric heater to enforce freezing from the bottom upward. After a lapse of time sufficient for the zinc but not the lead to solidify, the zinc slab was raised free of the molten lead. The bottom surface of the zinc casting was coated with a thin layer of lead. A specimen of the slab 136 in. square was metallographically polished to flatten it and remove the slight film of lead, and the orientation was determined by the method used before,' with the result stated above. Some determinations have also been made on other metals, as follows: Surface orientation determinations were made on the 3/8-in. diameter grip section of two 1/4-in. diameter aluminum-alloy die-cast tensile bars and on a 1/8 by 1/2-in. flat aluminum-alloy die-cast tensile bar. None of these three aluminum die castings exhibited any preferred orientation at the surface. A brass die casting (nominal composition: 60 Cu, 37.75 Zn, 1.00 Sn, 1.00 Pb, 0.10 Al, 0.15 Si) furnished by C. S. Smith was also examined. The surface showed a random orientation of alpha and beta. Summary A zinc casting solidified against a molten lead surface was found to have the same surface orientation texture, (001) parallel to the surface, as other zinc and cadmium castings. Aluminum and alpha-beta brass die castings were found to have random grain orientation textures at the surface. Acknowledgment The X-ray determinations were conducted by M. L. Fuller.

Jan 1, 1945

By G. R. Speich

The age-hardening of Fe-18 to 21 pct Ni marten-sites containing small amounts of titanium, aluminum, copper, or molybdenum has been studied by hardness measurements, transmission electron microscopy, extraction replicas, and X-ray and electron diffraction. Electyon-probe microanaly-sis of the extracted precipitates was also performed. The effects of temperature and composition on the aging kinetics have been studied in detail for Fe-20 pctNi-Ti martensites. All the martensites hardened on aging at 400" to 500 "C with a single aging peak. In the Fe-20 pct Ni-Ti martensites hardening was associated with the formation of a fine dispersion of NisTi. No precipitation was observed in an Fe-21 pct Ni-2.6 pct A1 alloy, although the hardness increased from 327 to 545 Dph during aging at 500°C. Copper was precgitated from an Fe-20 pct Ni-10.7pct Cu alloy, at least during the later stages of age-hardening. Hardening in an Fe-18 pctNi-5pct Mo alloy was associated with the precipitation of an intemzetallic compound tentatively identified as NisMo. The formation of austenite and the recovery of the defect structure of the martensite occur simultaneously with the normal precipitation processes &ring aging of these alloys. THE age-hardening of substitutional iron-base martensites is an important subject for study since age-hardening is one of the principal means of strengthening the substitutional iron-base martensites in precipitation-hardening stainless steels1 and maraging steels.a~4 In contrast to Fe-C martensites, these martensites are relatively soft and ductile in the as-quenched condition, due to the low solid-solution hardening effect of the substitutional elements as compared to carbon. Also, these martensites are hardened by aging at low temperatures in contrast to Fe-C martensites which generally soften on tempering. Titanium and aluminum, singly or in combination, as well as copper and molybdenum, have been the principal alloying additions to stainless steels to obtain an age-hardening reaction.' Ti-A1 or Co-Mo-Ti combinations have been used in the case of maraging steels.3"4 The present work has been confined to a study of the age-hardening characteristics of an Fe-18 to 21 pct Ni martensite to which small amounts of titanium, aluminum, copper, and molybdenum were added in order to study the effects of each alloying element separately. The age-hardening characteristics of these alloys were studied by hardness measurements, transmission electron microscopy, extraction replicas, and X-ray and electron diffraction. Electron-probe micro-analysis of the extracted precipitates was also performed. The types and dispersion of precipitates, the formation of austenite, and the recovery of the defect structure of the martensite all were studied. EXPERIMENTAL PROCEDURE Alloys. The compositions of the alloys studied are listed in Table I. The level of 18 to 21 pct Ni was chosen to assure complete transformation to martensite on quenching and is the same nickel level used in maraging steels. The concentrations of titanium, aluminum, copper, and molybdenum were chosen after a study of the and Fe-Ni-MO' ternary diagrams indicated how much of each alloying element could be dissolved in austenite. Alloys with 2 and 4 pct Cu were also studied, but these did not show precipitation hardening at the nickel levels studied and will not be discussed further. The alloys were prepared from electrolytic iron and high-purity* nickel, titanium, aluminum, copper, and molybdenum by vacuum melting of 20-lb heats. These were vacuum-cast into two 8-lb ingots. The ingots were hot-rolled at 1100°C to 1/2-in. plate and subsequently cut into 3/8-in. cubes. The cubes were sealed in evacuated quartz capsules and solution-treated for 16 hr at 1100°C, except for the Fe-20 pct Ni-10.7 pct Cu alloy and Fe-21 pct Ni-2.6 pct A1 alloys which were solution-treated for 16 hr at 1300" and at 1250"C, respectively. Metallographic examina-

Jan 1, 1963

By Carl F. Floe, Hung Liang, Michael B. Bever

DATA on the solubility of hydrogen in iron-silicon alloys are of practical interest, as hydrogen causes gas unsoundness and embrittlement in iron and steel and is also a factor in the metallurgy of cast iron. Zapffe and Sims1 have recently demonstrated that in deoxidized iron and steel castings gassiness and bleeding are primarily functions of the hydrogen content of the liquid metal. These authors also suggested convincingly that ordinary melting and casting practice provides several sources of hydrogen for absorption by the metal. Norbury and Morgan,2 and Boyles3 have shown that dissolved hydrogen affects the graphitization of cast iron. Schneble and Chipman4 included in a study of the effects of superheating on the properties of cast iron an investigation of the part played by hydrogen. Schwartz, Guiler and Barnett6 investigated the significance of hydrogen in the metallurgy of malleable cast iron. A complete interpretation of investigations of this kind calls for equilibrium values of the solubility of hydrogen in the liquid and solid phases. From the theoretical standpoint, the solubility of gases, especially hydrogen, may reveal some aspects of the nature of liquid metallic solutions. This was implied in the early work of Sieverts6 on the effect of alloying additions on the solubility of hydrogen in copper. Recent work by Bever and Floe7 has shown that in liquid copper-tin alloys the solubility of hydrogen changes abruptly at the composition of the intermetallic compound Cu3Sn. It is of considerable interest to determine whether liquid alloys of iron also have compositions at which the solubility of hydrogen exhibits a discontinuous or otherwise unique behavior. Among the various alloys of iron the iron-silicon system is important because of the presence of silicon in various structural alloy steels, transformer sheets, cast irons and special acid-resisting castings. The various grades of ferrosilicon, finally, cover almost the entire remainder of the composition range. Published information on the solubility of hydrogen in iron-silicon alloys is meager. The first values for pure liquid - iron were reported in 1910-1911 by Sieverts and Krumbhaar8 and by Sieverts.9 They found that 100 grams of iron absorbs 28 C.C. of hydrogen at 1550°C. and one atmosphere pressure, and 31 C.C. at 1650°C. In 1938 Sieverts, Zapf and Moritz10 published a value of 26.3 c.c. at 1550°C. Data on the solubility of hydrogen in liquid iron-silicon alloys and in liquid silicon

Jan 1, 1946

By Wayne L. Worrell

Thermodynamic data for the stable carbides and oxides of chromium, molybdenum, and tungsten have been critically eualuuted and are used to determine the stable condensed phases at 1 atm total pressure in each metal-carbon-oxygen system. Pourbaix-Ellingham diagrams have been constructed and are used to estimate the minimum temperatures neces.see)*y to oblain these metals by corbolhermic redlrction under reduced pressures. USING recently reported data for the carbides and oxides of chromium, molybdenum, and tungsten, the stable phases in the Group VI metal-carbon-oxygen systems at specific temperatures and pressures can be determined. The thermodynamically stable regions in each metal-carbon-oxygen system can be completely pictured using a Pourbaix-Ellingham diagram in which the two coordinates are oxygen potential (-RT In Po2) and temperature. Worrell and chipman' have described and constructed such diagrams for the metal-carbon-oxygen systems of vanadium, columbium, and tantalum. Downing2 has used similar diagrams to provide a description of the reactions in submerged arc furnaces. One of the examples which he cited was the Cr-C-O system; however, an improved diagram is presented in this paper using recently obtained data for the carbides of chromium. Although some of the oxides and carbides of the Group VI metals exist over slight ranges of composition,3 all solid phases are represented as stoi-chiometric compounds in the subsequent diagrams. Any error introduced into the calculated equilibria by neglecting the compositional variation of these phases is less than the uncertainty in the thermodynamic data. In a Pourbaix-Ellingham diagram for a three-component system, the phase rule requires that at equilibrium four condensed phases specify a point, three condensed phases determine a line, and two condensed phases define an area. To obtain a well-defined area at high oxygen potentials and teniperatures, the initial carbon to oxygen mole ratio is specified to be more than sufficient to reduce the oxide but not enough to convert all the metal to carbide. Thus, the lowest regions in the subse- quent Pourbaix-Ellingham diagrams represent areas in which the metal and its carbide are the stable condensed phases. Cr-C-O SYSTEM A) Thermodynamic Data. To simplify the subsequent calculations, all thermodynamic data are presented in the form of linear Gibbs-energy-of-formation* equations which were derived for the temperature range 505° to 2000°K and are reasonably accurate over the entire temperature ranges of the diagrams. The thermodynamic data for the compounds occurring in the Cr-C-O system are summarized in Table I. Several volatile chromium oxides have been reported,4 but their influence is negligible in the Cr-C-O system. Thermodynamic data for CO and CO2 were taken from the compilation of Coughlin.5 The only solid chromium oxide sufficiently stable to exist below 1800°K in the Cr-C-O system is Cr2Os.11 The Gibbs-energy-of-formation equation for Cr2O3 was obtained by revising the data tabulated in Coughlin,5 using the heat of formation of ah' and the high-temperature thermal data for chromium.7 In 1953 Richardson8 re-evaluated the original work of Kelley and coworkers,9 who measured the thermodynamic properties of the chromium carbides. However, the high-temperature equilibrium results of Boericke9 yield values for ?G°f of Cr2O3 which are 2 kcal more positive than the accepted data. His results for the chromium carbides are based on the same questionable equilibria. Gleiser10 recently determined the Gibbs energy of formation of Cr3C2 and the equation in Table I was calculated from her data and the thermal data of Kelley and coworkers.9 Thermodynamic data for the Cr7C3 and Cr23C6 carbides were obtained by combining the Cr3C2 data

Jan 1, 1965