Search Documents

By H. Siebel, N. A. D. Parlee

MIZIKAR, Grace, and parlee' studied rates of absorption of oxygen in stagnant liquid silver in a new type of open-ended gas-liquid metal diffusion cell, where the capillary diameters used were 1.5, 2, and 3 mm. They reported that the rates appeared to be controlled by the rate of diffusion of oxygen atoms in liquid silver and they used their data to arrive at the following equation as a reasonably good representation of the diffusivity (D) of oxygen in liquid silver: D = (14.7)10-4 exp (-7100 ± 3200)/RT cm2/sec Since this type of diffusion cell offers a promising method of measuring diffusivities of gas atoms in liquid metals, the senior author of this note and his students are carrying on a critical examination of the method, and are attempting to improve and extend the technique. The research reported briefly here was designed to examine more carefully the earlier conclusion1 that the absorption rate is diffusion-controlled, and to find out whether the diameter of the cell could be greatly increased and thus extend the method to systems where gas solubilities and diffusion rates are much smaller than in the case of oxygen in silver. For the purpose of these experiments, the open-ended capillary cell used by Mizikar, Grace, and Parlee was replaced by a small cylindrical crucible (1 to 1.7 cm in diam) containing pure silver (to a depth of 1.3 to 3 cm) resting in the bottom of a closed-ended vertical quartz tube, with an evacuated quartz filler tube just above the crucible to reduce dead volume. The method of measuring the rate of absorption was otherwise very similar to that of Mizikar, Grace, and Parlee and all the same precautions were taken. A much smaller and shorter tube furnace was used for heating, but simi- lar precautions about temperature gradients were observed. This technique was nothing more than the application of a Sieverts apparatus to the measurement of rates of absorption in small crucibles of stagnant liquid silver. In each run the volume of gas absorbed (V) was plotted against the square root of time (vt) and apparent diffusivities were calculated from the slope of the line, as described by Mizikar, Grace, and parlee.' Care was taken to use only the data obtained during the early part of the total absorption period while the cell functioned as one of infinite depth. The results at 1000°C are summarized in Table I and Fig. 1. The following conclusions may be drawn: 1) Diffusion cells up to 1.7 cm in diam yield, within experimental error, the same values for the diffusivity of oxygen (D) as the capillary cells of 1.5, 2, and 3 mm in diam employed by Mizikar, Grace, and Parlee. Cell diameters as large as 1.7 cm are probably not desirable for the most precise work. Intermediate sizes, perhaps 0.5 cm, will be most practical. 2) All absorptions measured were consistent with a model where the rate is controlled by the diffusion of gas atoms in the metal. The fact that runs at absorption pressures ranging from 0.1 to 1 atm (at any one temperature) give

Jan 1, 1965

The Gooseberry Mine is located 38 krn (24 miles) by road east of Reno, 13 km (8 miles) south of Interstate 80. The mine was originally discovered in 1906 and remained in the control of the Martin family of Fresno, who worked the-property with Mexican ranch hands for 68 years. Westcoast took over the property in 1976 from Apco Oil Corporation. During the time the Martins operated the mine, a 305 m (1,000 ft) inclined shaft was sunk with drifts developed on eight levels exceeding a total of 3,000 m (9,000 ft) in length. It is interesting to note that for over one -half century all development ore was stockpiled. West- coast, the United States mining subsidiary of Home Oil Company Ltd., Calgary, Alberta, completed sinking another vertical shaft to the 396 m (1,300 ft) level. Development work between 122 m and 305 m (400 ft and 1,000 ft) levels has proved the existence of a fine ore body over 300 m (1,000 ft) long. The silver-gold ore grade is fairly consistent in the vertical section, but copper, lead and zinc may show slight increases with depth. Average width of the ore bearing portion of the vein is 2.5 m (8.3 ft). Stoping is by cut-and-fill method. Average silver values within the ore zone have increased from the 152 m (500 ft) level to the 305 m (1,000 ft) level, although the gold values do show some decrease. It is not possible for the geological staff to predict the depth of the ore. However, several years of ore reserves have been proved in the existing mining areas. Important ore minerals are argentite, native gold, and electrum. Trace amounts of galena, chalcopyrite, and sphalerite are associated with the precious metal mineralization. The vein is mainly composed of calcite and quartz. Mine-run underground ore is dumped from the hoisting skip into a coarse ore bin followed by a jaw crusher, an impact crusher, and a 600 mt (650 st) fine ore bin. The mill has a capacity of 317 mt per day (350 st per day). Two-stage grinding is done by a rod mill followed by cyclones with the underflow sent to a ball mill in closed circuit with the cyclones. Cyclone overflow after conditioning receives a primary float in four 1.7 cu m (30 cu ft) cells and a second stage of conditioning ahead of 24 0.8 cu m (30 cu ft) secondary flotation cells. No cleaning stages are used. Flotation tailings are cycloned for a sand-slime separation with the sands used as underground stope fill and the slime portion to tailing dam storage.

Jan 1, 1981

By E. L. BROKENSHIRE

FLUORSPAR, a little known non-metallic mineral, referred to technically as fluorite, chemically as calcium fluoride, is a compound of calcium and fluorine in the ratio of one molecule of calcium to two of fluorine. By weight it is composed of 51.3 per cent of calcium and 48.7 per cent of fluorine. Its specific gravity is 3.2. It is brittle, has a hardness of four and can be easily scratched with a knife. It weighs about 200 Ib. per cubic foot and has a melting point of 1650" F. The color of fluorspar ranges from pure white and opaque white, according to its purity, to various hues of yellow, green, pink, lavender, blue and brown, to bluish black. Although the lumps have color, when ground the fluorspar becomes pure white. The reason for this is because the mineral usually carries no fixed pigment, the color being produced by the re- fraction of light rays within the crystal structure and small quantities of organic matter which readily oxidizes. It crystallizes in the isometric system with perfect octahedral cleavages.

Jan 1, 1929

By J. C. McDonald

A DDITIONAL experimental data are presented in this note on a phenomenon which has been touched on but lightly in the literature. The common magnesium base rolling alloy (AZ31B) contains about 3 pet A1 and 1 pet Zn. When cold rolled, it hardens until it starts to break up in the rolls at 30 to 50 pet reduction. When it is heated after rolling to full hardness, it softens. However, other magnesium alloys have shown themselves capable of being cold rolled indefinitely, provided the ratio of roll diameter to starting gage is sufficiently high. As measured by the tensile test, these alloys actually soften when the reduction becomes large (60 to 90 pct). A subsequent heating at 300' to 500°F can produce hardening of this metal. Heating at higher temperatures (600' to 800°F) causes recrystalliza-tion and softening. Menzen' has shown that a magnesium base alloy can be cold rolled without intermediate anneals as much as 90 pet. The alloy studied, Mg-1.5 pet Mn, softened considerably between 20 and 90 pet reduction, as measured by tensile properties; a decrease in yield strength of 30 pet, and an increase in elongation from 3.2 to 16.7 pet (longitudinal direction of the sheet). However, Menzen gives no data on the reaction of this metal. to heating. Ansel and Betterton2 and Hurst and Hatch3 report a similar effect in Mg-1.5 pet Mn-0.1 pet Ca. Their data show an initial hardening, followed by softening. The former authors also show that the alloy softened by cold rolling will harden when heated at low temperatures, and that these effects are absent in Mg-3 pet Al-1 pet Zn. In the course of work4, 5 some years ago, the author observed similar effects with alloys containing cerium, thorium, or zirconium; but not with elements like aluminum, silver, or zinc. Table IA contains the results of an experiment which shows these effects rather well. A binary alloy with 0.3 pet total rare earths (Mischmetal* added) was rolled hot to 1/16 in. and then annealed to full softness by heating 30 min at 800°F. Rolling was continued at 1.5 pet per pass to 80 pet total reduction on 8 in. diam rolls. The metal was harder after 20 pet work than initially but, at 80 pet reduction, properties were back to their original values. Heating for 1 hr at 450°F produced about the same hardness whether the reduction was 20 or 80 pet. At intermediate reductions, the metal hardened, but not to as high values. Extensive cold rolling may also be carried out on metal hot rolled at temperatures sufficiently low to produce a semihard temper. Mg-0.6 pet Zr was rolled to 0.1 in. at 700° to 800°F, 30 pet per pass. As shown in Table IB, a further cold reduction of 85 pet, at 1.5 pet per pass, definitely softened the metal.

Jan 1, 1959

By Charles Janin

ONE of the most interesting features of the world's platinum situation has been the steady increase of Russian production, which had dropped to 11,000 oz. in 1920, but increased to 92,000 oz. in 1926, and to probably over 100,000 oz. for 1927. It is ex-pected that Russian production of platinum will, be-fore long, closely equal its pre-war production, or approximately 200,000 oz. annually. The world production before the war was around 250,000 oz.; that for 1925 has been estimated at 160,000 oz., and for 1926 probably 170,000 oz. The consump-tion of platinum has, however, decreased. The esti-mate of the International Selling Agency was a de-mand of 130,000 oz. new platinum against a normal pre-war demand of over 200,000 oz. The high price of platinum during the war gave an added impetus to the search for substitutes for the metal, and sev-eral were developed that are now used extensively in place of platinum. The demand for platinum for high-class jewelry, however, was not greatly affected by the high prices, but "white" gold did replace platinum in the cheaper jewelry. Colombia is the most important producer of plati-num, next to Russia, and the production has increased from around 10,000 oz. pre-war production to 55,000 oz. or more in 1927. In 1924 important discoveries of platinum were made in South Africa. Prior to these discoveries practically all platinum was recovered from alluvial deposits, and the South African opera-tions are first to work an ore profitably for the pri-mary recovery of platinum. A number of companies were formed to develop these deposits, but only a few made any real progress. Total production for 1926 was about 5000 oz. The United States production is unimportant; that in Canada has increased to around 9000 oz., principally as a by-product in nickel-copper ores.

Jan 5, 1928

By Archer E., Wheeler

COPPER operations in the Congo mean the operations of the Union Miniere du Haut Katanga, because there are no other copper industries there. There is a mine at Bwana M'Kubwa, a little way to the South, in Rhodesia, which has been operated on a small scale, and-another farther south, the Falcon mine, but in quite a different section of the country. This Bwana M'Kubwa mine has recently been reorganized financially and the Minerals Separation interests have taken an extensive share in it, so that it may come into operation. The Union Miniere's operations are in Katanga, the most southeastern province of the Belgian Congo, and the company's concession is in the southeastern part of that province. The usual route for going into the country is by way of Cape Town, thence over the South African Railways through Kimberly and Mafe- king to Bulawayo, then by the Beira, Mashonland and Rhodesia Railways to the Rhodesia-Congo border, passing Victoria Falls on the way, and finally by the Belgian road, the Chemin de Fer du Katanga, to Elisa- bethville, the African headquarters of the company. From Cape Town to the border it is about 2150 mi. and from the border to Elisabethville about 158 mi., making a little over 2300 mi. from Cape Town, by rail.

Jan 1, 1924

By Milton H. Fies

EARLY in 1945 the laboratories of the Southern Research Institute will begin active research investigations on behalf of industrial clients. This achievement has come after four years of planning by a group of Alabama businessmen, and is in partialanswer to an urgent need in the South. Those who conceived the Institute have long realized that a marked relationship exists between scientific research and the economic well-being of the several regions of the country. Clearly, technological research, generally absent in the South, is the medium through which are created new finished goods industries, and the increase of technological research is perhaps the most important long-range project in the South.

Jan 1, 1945

By E. W. Davis

DURING late years, the proportion of beileficiated iron ore shipped from the Lake Superior District has increased very rapidly. By benefication is meant washing, screening, drying, sintering or any process by which the grade or structure of the crude ore is improved before shipment. In 1915, only 3,000,- 000 tons, or 9 per cent, of t6e total Minnesota shipment was beneficiated ore, compared with 13,500,000 tons, or 35 per cent, of the total Minnesota shipment in 1925. This increase is, of course, due to the fact that iron and steel can be made more cheaply after beneficiating these ores than they could have been had these ores not been so treated. Fundamentally, however, several causes contribute to the necessity for beneficiating iron ores, such as depletion of the reserves of high-grade ores, the iron ore leasing systems and taxation methods and, at the smelting plants, a better understanding of blast-furnace operations, increased operating costs and increased sulfur content of blast-furnace coke. As economic conditions change, it is by no means certain that the proportion of beneficiated ore shipped each year is going to continue to increase. Undoubtedly some of the beneficiation operations are not economically sound at the present time and what the future has in store for the iron ore industry is problematical. Generally speaking, the cost of fuel for blast-furnace operations will increase as time goes on and in order to continue to produce cheap iron and steel, some of the other costs must be lowered. Freight and labor rates probably can- not be reduced. The cost of producing iron ore cannot be reduced much below the present price. It therefore appears that the best opportunity for maintaining iron and steel prices at their present level in spite of in- creased costs of labor and raw materials is to use. less or cheaper raw materials. This, of course, contemplates an improvement in metallurgical processes all along the line and, as a matter of fact, we can confidently expect these improvements because scientific investigations will undoubtedly be even more productive in the future than they have been in the past.

Jan 1, 1926

By G. W. LAAiIBOURNE

FEW mines possess a history of more fascinating interest than the Ontario at Park City, Utah. The famous Bonanza's production record of over $50,000,000; the great extent of its workings; the remarkable character of its mineralization; the fact that recent discoveries have shattered preconceived theories of the geology of the camp practically assuring the half-century old property a future as active and as prosperous as the past make the Ontario one of the unique mines of the world. A mere accounting of the wealth created by this historic property not only exemplifies the great profits

Jan 1, 1925

By AIME AIME

The 102d meeting of the Institute was held at the Institute headquarters in the Engineering Societies Building, New York, N. Y., on Feb. 19, 20 and 21, 1912. A Bureau of Information, in charge. of Mr. George Buckman, was maintained during the meeting. The proceedings opened with an informal social meeting on Monday evening, Feb. 19, in Assembly-Room No. 1, on the

Mar 1, 1912

By F. R. Milliken

EXPERIMENTS, in what has come to be known as flash roasting began some ten years ago. The principle underlying the operation was not a new one, but the experimental work started at that time was the first that was carried through to a logical conclusion, followed by construction and operation of a pilot plant, and then full-scale production. For a short working definition, flash roasting may he considered the instantaneous and complete oxidation of finely ground sulphide particles, partially suspended in air or gas, the oxidation reaction evolving enough heat to make the reaction self-sustaining, or nearly so.

Jan 1, 1937

By F. William Bloecher, William B. Plank

CURRENTLY 12,892 students are enrolled in the mineral engineering schools of the United States and Canada, marking an all-time record high for these schools. It shows a remarkably rapid recovery from the effects of World War II. Enrollment in all the other engineering branches has also increased but not so rapidly as in the mineral engineering branch. Almost all the data in this report are from the eighth questionnaire study of the mineral engineering schools made, as formerly, under the auspices of the Mineral Industry Education Division of the AIME. Every school is represented in the data, for which the authors thank the deans and professors who supplied the information. For this reason, the data of all the studies are comparable, an achievement not always possible in endeavors of this kind. For comparison with the general engineering enrollment situation, data are included from the January 1947 issue of the Journal of Engineering Education.

Jan 1, 1947

By C. M. White

CITIZENSHIP is a rather abstract subject on which a great deal could be said-a subject on which a great deal is said -and still one which too many of us seldom think about and seldom work at. Too many of us engineers and business men have but a vague idea of citizenship. We think that if we go to the polls on election day and obey the laws scrupulously, with the exception of an occasional traffic violation, we are pretty good citizens and are doing our duty by our city, state, and nation. But when you think it over, that's a very passive observance of the important right of counting oneself a citizen of a country. There is nothing very positive in that attitude. There is nothing that indicates that we have sufficient interest to really go out and do a job for the -welfare of our country, forgetting any personal advantages or inconveniences that might arise. In other words, this type of voting-on-election- day, law-abiding citizenship does not keep us awake a single minute; it does not take any particular thought or require the expenditure of any time or energy.

Jan 1, 1939

By A. Patton, F. N. Speller

The use of roll scale in the Bessemer process dates back, to the best of our knowledge, at least 20 years. It was first used by the Ohio Steel Go., Youngstown, Ohio (now the Ohio Works of the Carnegie Steel Co.) under the direction of Sam McDonald, Superintendent of the Bessemer Department at these works. Two 10-ton vessels and one blowing engine capable of blowing one heat at a time were employed. The object of using the scale was to shorten the length of the blow, or in other words, to increase the production with the same equipment. Various means were tried out for introducing the roll scale into the bath of molten iron: It was shoveled into the vessel before the heat was charged, so that the metal would flow over the scale; it was shoveled into the bath after the vessel was turned up; it was dumped into the empty iron ladle by the wheelbarrow-load, and at times was dumped on top of the molten metal in the iron ladle. But the practice of introducing the scale into the iron ladle had to be abandoned on account of danger from explosions and of skulling the ladles. It was soon learned that the proper place to charge the scale was in the empty vessel, so that when the molten iron was poured into the vessel it flowed over the scale, causing a considerabIe reaction to take place before the heat was turned up. Eventually, cylindrical chutes similar to those now in use were installed. Into these chutes the scale is dumped and carried into the empty vessel. Before this convenient means of introducing the scale was adopted, the Ohio Works had satisfactorily demonstrated that roll scale would increase production, by blowing 107 heats in one 12-hr. turn (1,087 tons) with one blowing engine, blowing one heat at a time; whereas, prior to the use of scale, the best practice at these works was about 80 heats under the same conditions. In using roll scale and other oxides of iron to facilitate and control the refining of pig iron in the converter, the Bessemer plant has borrowed one of the most active agencies used in the open-hearth process with, as would be expected, much the same results. The effect of such additions to the Bessemer charge may be discussed as to the influence of this practice on quality, production and cost.

Jan 1, 1917

By J. W. JESSUH

TO certain people the name of Northern Rhodesia brings only a vague recollection of a distant country somewhere in Africa; to others, it means a big game territory and the opportunity for excellent shooting; to some, a land of sunshine and peace; but to mining men the name signifies the land where the latest discoveries of copper ore are astonishing the mining world and bid fair, in a few years, to make Northern Rhodesia one of the largest copper- producing countries. There is a fascination about this part of the globe that is somewhat similar to southern California, and at the same time there is that feeling of mystery peculiar to a tropical climate. Perhaps it is the isolation, the fear of wild animals, or the influence of an undefinable something which cannot be expressed.

Jan 1, 1931

By W. J. Romanow

RECENT papers by Williams, Sherwood, and Boothby,1 Seybolt et al.2 Heikes; and Roberts4 attest to the increasing importance of the hexagonal ferromagnetic compound MnBi. Since the magnetic properties of MnBi crystals are highly anisotropic, it is useful and necessary to have appropriate aids for determining their orientations—a (00.1) standard stereographic projection and a corresponding table of crystallographic angles for this structure. The tables of crystallographic angles for the hexagonal system available in the literature5 are computed for c/a ratios greater than that of MnBi and cannot satisfactorily be used to find the crystallographic angles of MnBi. A table of angles between the crystallographic planes (HK.L) and (hk.1) was calculated for MnBi from the formula0 F=are cos Hh+Kk+ 1/2(Hk+hK) + 3/4 (a/c)2Ll/v(H2 + K2 + HK + 3/4 (a/c)2L2) (h2+ k2+hk + 3/4 (a/c)2l2) on an IBM Type 650 Magnetic Drum Data Processing machine. The lattice constants used are listed in Table I and are those determined by Willis and Rooksby7 at 20°C. More recently published values obtained by both X-ray and neutron diffraction"' show no difference from these significant to the calculation. From the crystallographic angles between the basal plane (00.1) and the general plane (hk.1) in Table I, an (00.1) standard stereographic projection was made for MnBi which is shown in Fig. 1. Acknowledgments The author wishes to thank R. G. Treuting and J. N. Hobstetter for their technical assistance, and Miss D. P. Booth for programing the IBM machine for the calculations. He appreciates the opportunity to read the paper of B. W. Roberts of General Electric Co. prior to its publication. References 1H. J. Williams, R. C. Sherwood, and 0. L. Boothby: Bulletin Amer. Physical Soc., 1956 vol. 1, p. 132. 2 A. U. Seybolt, H. Hangen, B. W. Roberts, and P. Yurcisin: AIME Trans., 1956, vol. 206, p. 605: Journal oF Metals, May 1956. 3R. R. Heikes: Physical Review, 1955, vol. 99, p. 446. .B. W. Roberts: A Neutron Diffraction Study of the Structures of Manganese B.W.Roberts:ANeutronDiffractionBismuthide, Physical. Review, 1956, vol. 104, p. 607. 5 A. Taylor and S. Leber: AIME Trans., 1954, vol. 200, p. 190; JouRNal of Metals February 1954. « C. S. Barrett: Structure of Metals, 2nd Ed., p. 635. McGraw-Hill Book Co. New York and London, 1952. 7B. T. M. Willis and H. P. Rooksby: Proceedings Physical Soc., London, 1954, vol. 67B, p. 290.

Jan 1, 1958

By Luke L. Y. Chang, Bert Phillips

ThE tendency toward further oxidation of the intermediate oxides and the high volatilization rates of the higher oxides have prevented direct attainment of equilibrium data for the system tungsten-oxygen. As a result, St. Pierre et al.1 have proposed a phase diagram (to 800°C) based on thermody-namic data to 1200°C for the known tungsten oxides (WO2z, W18O49, W20O58, and WO3) and a report on a tungsten suboxide W3O.2 Recent modification of a technique previously described3 5 now permits adequate preservation of compositions of mixtures of metallic tungsten and metal oxides (e.g., of tungsten, cobalt, calcium, samarium, titanium) in order that condensed phase relations may be established to 1700 This method has been applied to study the high-temperature stability of tungsten oxides. In the method used, the desired compositions were sealed in nonreactive containers such that only a small gas volume remained. Each sample then established its own equilibrium atmosphere at temperature. This method has advantages in the study of systems of the W-0 type where knowledge of the condensed phases is desirable but for which composition and pressure of the gas phase are not readily attainable because of oxide volatility. Mixtures of 99.99 pct tungsten metal powder and purified tungsten anhydride (WO3) or in some cases W18O49* were equilibrated in pellet form in sealed

Jan 1, 1964

By James E. York

THE honor so fairly earned and so incompletely and tardily paid to Henry Cort, the inventor of the puddling-furnace and the, rolling-mill, has been fully set forth by Mr. Charles H. Morgan,1 and needs no further emphasis here. In view of the importance of the rolling-mill in the treatment of iron and steel, the paucity of information concerning it is surprising. With the exception of a hook, written about 35 years ago, by Peter Bitter von Tunner, an Honorary Member of this Institute, and of desultory articles on simple sections, which have appeared in technical journals, I know of no pub¬lication attempting to treat this subject, although volumes have been written on the scientific theory and technical manipulations involved in other branches of the iron- and steel-industry. This strange anomaly may be due to the fact that roll-turning cannot be called a scientific business. It does not ordinarily come within the range of an educated engineer; yet it cannot be performed by an ordinary mechanic. It demands some of the qualifications of an engineer, in designing, and those of a mechanic, in execution. The men who have followed this trade have controlled the training of their successors. In many cases the technical knowledge required bas been handed down from father to son, and there has been a motive of private interest to prevent its public dissemination. Moreover, the statement of the various principles involved in the process would require, besides manual experience, a degree of scientific knowledge which roll-turners do not usually possess; and, finally, any book on the subject, in order to possess real, practical value, would have to be so fully illustrated as to make it very costly to publish. Regarding my own experience, I may say that I served a six-

May 1, 1906

By Daniel C. Jackling

WHAT is written here features some of the things that I would say if I were to de- liver a Presidential address during the Annual Meeting to be held this month in New York. I am aware that custom favors written rather than vocal delivery of such a discourse; and, as this accords exactly with my own preference, I assure readers that they will never be called upon to hear these remarks spoken- anyhow, not by me. My year as President is drawing to a close. As I look back I like to classify and analyze the impressions that have been left with me. It has been a delightful and fascinating experience to me personally; I have appreciated the courtesies and aids, and have been deeply gratified at the honors accorded me. Perhaps the source of greatest satisfaction is the opportunity I have had to sense more about the provinces of this Institute and about the useful functions of the profession that it represents. For 38 years I have been a member. I served two terms as Director-one in 1914-'16 and again in 1927-'29. I have been honored by selection as a Saunders Medalist. I thought I was reasonably familiar with the functions, the ideals, and the activities of the Institute. But the things that I have discerned during the past year have dispelled that conceit. I still think that, a year ago, I was as well informed as most members; but since then I have had the rare privilege of executive service and insight. That has given me a perspective that I feel can be obtained in no other way-as I think the illustrious engineers who have preceded me in office will agree. I wish that I had the power to translate to every member somewhat of the feelings of pride in our organization that a year as President cannot help but instill.

Jan 1, 1939

By E. Miller, K. Komarek, W. Johnson

The activity of aluminum in solid Cr-A1 alloys has been measured by an isopiestic technique between Cr-A1890' and 1126" and 13 and 80 at. pct Al. The integral free energy of mixing has a minimum value of —5600 cal per g-atom at 59 at. pct Al. The maximum solid solubility of aluminum in chromium was determined to be 43 at. pct Al, and the composition limits of the compounds CrA14, Cr4A19, and Cr5Al, at 1000"~ were found to be 79 to 80, 66 to 70, and 59 to 63 at. pct Al, respectively. The thermodynamic properties of the Cr-A1 system have been investigated as part of a thermodynamic study of aluminum-transition metal systems.172 Little information is available on the equilibrium properties of the Cr-A1 system. The heats of formation of solid Cr-A1 alloys have been determined by Kubaschewski and Haymer at 600" and low-temperature specific heat data have also been obtained.~ More extensive work has been performed on the phase diagram, and a compilation has been provided by Hansen and Anderko,~ their phase diagram at elevated temperatures being essentially based on the work of Bradley and LU.~ The high-temperature portion of the phase diagram shows an intermediate phase CrA14 decomposing peritectically at 1018°C and existing at 82 at. pct A1 at 1000°C. They also identified the compounds with solubility limits of 72 to 75 at. pct A1 at 1000°C, and Cr5A1,, existing at 61 at. pct A1 at 1000°C. The maximum solid solubility of aluminum in chromium at 1000°C was found to be 46 at. pct Al. These elevated-temperature data were obtained by examination of quenched samples and were considered as less precise than the lower-temperature data. Koester, Wachtel, and Grube7 have revised the phase diagram as a result of their magnetic susceptibility and X-ray study. The results of this work differ appreciably from those of Bradley and Lu at temperatures above 800°C. The CrA1, compound is given as existing between 79 and 81 at. pct A1 at 1000°C, and they do not indicate the presence of a CrA13 phase reported by Bradley and Lu. They also report the compound Cr4Alg as having solubility limits of 66 to 70 at. pct A1 at 1000°C, while Bradley and Lu show this compound stable only up to 870°C. Koester et al. state that the high-temperature modification of the compound Cr5A18 is stable down to 1125"C, and not 980°C as stated by Bradley and Lu, and that the low-temperature modification of Cr5Al, has a range of homogeneity of 58 to 63 at. pct A1 at 1000°C. They also report that the maximum solid solubility of aluminum in chromium is 43 at. pct A1 at 1000°C. APPARATUS AND EXPERIMENTAL PROCEDURE An isopiestic method was employed which has been successfully applied to the determination of aluminum activities in solid ~e-All and Ni-Al alloys. Alloy specimens were held at different positions in a temperature gradient and were equilibrated with aluminum vapor from an aluminum reservoir kept at the temperature minimum of an impressed thermal gradient in a closed alumina system. Diffusion of aluminum into the specimens occurred until equilibrium was reached, at which the partial pressure of aluminum in each of the specimens was given by the vapor pressure of the pure aluminum reservoir. The activity of aluminum referred to liquid aluminum as the standard state in a given equilibrated sample at temperature T could therefore be expressed by: vapor pressure of pure aluminum at _ the temperature of the reservoir Vapor pressure of pure liquid aluminum, at specimen temperature T Since both the temperature of the aluminum reservoir and the specimen temperatures were determined experimentally, and the vapor pressure of pure aluminum is known as a function of temperature,' the activity of aluminum in a given aluminum alloy of known composition could be calculated. Initial runs were made with samples consisting of pure chromium chips placed in alumina crucibles. These runs exhibited large inconsistencies, indicating that equilibrium was not attained. High aluminum content Cr-A1 alloy powders were therefore substituted for the pure chromium specimens. The starting composition of the alloys was adjusted through experimentation until the concentration change necessary to attain equilibrium was small. In this manner, consistent results were obtained in reasonable times. SPECIMEN PREPARATION Alloy specimens were prepared from chromium of 99.997 pct minimum metallic purity: with 0.028 to 0.038 pct H, 0.0002 pct N, and 0.27 to 0.46 pct 0 (Aviquipo, Inc.). The aluminum had a purity of 99.99+ pct and the following impurities: 0.003 pct Cu; 0.002 pct S; 0.002 pct Fe; 0.001 pct Pb; 0.001 pct Ga (Aluminum Corp. of America). Alloy powders were prepared from weighed mixtures of chromium and aluminum by double-arc melt-

Jan 1, 1969