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By D. J. McAdam, G. W. Geil, R. W. Mebs

As shown in previous papers by the authorsg-17t the resistance of a metal to fracture, like its resistance to plastic deformation, is a function of all three principal stresses. A technical cohesion limit is the technically determined resistance to fracture under a specific stress system. The technical cohesive strength thus comprises an infinite number of technical cohesion limits corresponding to the infinite number Of possible com-binations of the principal stresses. The technical cohesive strength, therefore, may be represented by a surface in a diagram with the three principal stresses as coordinates. As shown in previous papers,'-'' the technical cohesive strength increases with plastic deformation, with decrease in temperature, and with increase in the strain rate. The technical cohesion limit, therefore, is affected by the same factors that affect the flow stress,$ namely, the stress system, plastic deformation, temperature, and the strain rate. More- over, the influence of each of these factors on the technical cohesion limit has been shown to be qualitatively similar to the three of the same factor on the flow stress.9-18 Advance of knowledge about the conditions determining fracture of metals has been retarded by the reluctance of some investigators to abandon preconceived ideas about how metals ''should,, behave. The incorrect idea is still prevalent that the conditions determining resistance to fracture are very different from those determining the flow stress. Attempts are still being made to express resistance to fracture in terms of a single parameter, such as a limiting value of the greatest principal stress, the maximum shearing stress, or the volume stress (one-third the algebraic sum of the three principal stresses). In these attempts, a sharp distinction is sometimes made between a ductile or ,plasticdeformation, fracture,, and a "brittle frat-ture.H In making this distinction, however, the meaning attached to the term "brittle fracture" sometimes is not made clear. The term could mean fracture after very little plastic deformation or it could be used to designate the type of fracture. An ordinary fracture of a ductile metal at room temperature starts as a cleavage, generally transverse to the direction of the greatest principal stress, but eventually changes to a shearing fracture' In some conditions, however, the metal fractures entirely by cleavage, with no evidence of plastic deformation during the fracture; the surface of such a fracture may have a

Jan 1, 1948

By R. W. Mebs, G. W. Geil, D. J. McAdam

As shown in previous papers by the authorsg-17t the resistance of a metal to fracture, like its resistance to plastic deformation, is a function of all three principal stresses. A technical cohesion limit is the technically determined resistance to fracture under a specific stress system. The technical cohesive strength thus comprises an infinite number of technical cohesion limits corresponding to the infinite number Of possible com-binations of the principal stresses. The technical cohesive strength, therefore, may be represented by a surface in a diagram with the three principal stresses as coordinates. As shown in previous papers,'-'' the technical cohesive strength increases with plastic deformation, with decrease in temperature, and with increase in the strain rate. The technical cohesion limit, therefore, is affected by the same factors that affect the flow stress,$ namely, the stress system, plastic deformation, temperature, and the strain rate. More- over, the influence of each of these factors on the technical cohesion limit has been shown to be qualitatively similar to the three of the same factor on the flow stress.9-18 Advance of knowledge about the conditions determining fracture of metals has been retarded by the reluctance of some investigators to abandon preconceived ideas about how metals ''should,, behave. The incorrect idea is still prevalent that the conditions determining resistance to fracture are very different from those determining the flow stress. Attempts are still being made to express resistance to fracture in terms of a single parameter, such as a limiting value of the greatest principal stress, the maximum shearing stress, or the volume stress (one-third the algebraic sum of the three principal stresses). In these attempts, a sharp distinction is sometimes made between a ductile or ,plasticdeformation, fracture,, and a "brittle frat-ture.H In making this distinction, however, the meaning attached to the term "brittle fracture" sometimes is not made clear. The term could mean fracture after very little plastic deformation or it could be used to designate the type of fracture. An ordinary fracture of a ductile metal at room temperature starts as a cleavage, generally transverse to the direction of the greatest principal stress, but eventually changes to a shearing fracture' In some conditions, however, the metal fractures entirely by cleavage, with no evidence of plastic deformation during the fracture; the surface of such a fracture may have a

Jan 1, 1948

By Frank V. Hicks

THE following paper-in no sense a technical paper-is a summary of a safety campaign instituted by a coal-mining company to improve an unfortunate safety record. The experience should be suggestive equally to coal and metal-mining companies. With few precedents to follow in the beginning, the course was charted by trial and error. The endeavor, often disheartening, finally resulted in the capture of the most coveted safety trophy in the mining industry, "The Sentinels of Safety," awarded by the Hercules Powder Co. of Wilmington, Del., through the U. S. Bureau of Mines. The period described covers the 10-year interval, 1924 to 1933, the year 1933 being that for which the award was made. The coal company considered has produced annually for a number of years an average of 2,750,000 tons of coal, employing at various times from 1.800 to 3000 men. Prior to 1924, the

Jan 1, 1935

In the Texas Panhandle 277 oil wells and 60 gas wells were completed during 1942, as compared with 647 oil and 52 gas wells completed in 1941. Fourteen dry holes were drilled in the Texas Panhandle in 1942, of which five were wildcats, resulting in four failures and one gas-field discovery in Sherman County; the latter being Hazy-Herrington-Marsh No. I Bivins completed for 5,600,000 cu. it. ol gas from 2989 to 3226 feet. During the year 1942 the Texas Panhandle produced, by counties, the following quantities of oil:

Jan 1, 1943

In the Texas Panhandle 277 oil wells and 60 gas wells were completed during 1942, as compared with 647 oil and 52 gas wells completed in 1941. Fourteen dry holes were drilled in the Texas Panhandle in 1942, of which five were wildcats, resulting in four failures and one gas-field discovery in Sherman County; the latter being Hazy-Herrington-Marsh No. I Bivins completed for 5,600,000 cu. it. ol gas from 2989 to 3226 feet. During the year 1942 the Texas Panhandle produced, by counties, the following quantities of oil:

Jan 1, 1943

By Heinrich Ries

In another place,* the writer has called attention to the modern methods of the laboratory investigation of clay, and it is desired here simply to discuss one branch of the subject, which, though of considerable importance, has heretofore received little attention in this country, viz., the rational analysis of clay. In order, however, the better to point out the bearings and advantages of this procedure, it is necessary to refer briefly to the ultimate analysis as well. The remarks in this paper refer only to the use of clay for the manufacture of clay-products. Pure clay or kaolin-f is extremely refractory, possesses little plasticity, and usually shrinks aud warps considerably in burning. Even the smallest proportion of impurities changes these properties, so that the kaolin exhibits variations in shrinkage, plasticity, tensile strength, fusibility, and often color when burned. The majority of nearly pure kaolins consist of kaolinite (A1,O2 2SiO,, 2H20), undecomposed feldspar, and quartz. The kaolinite generally forms the finest particles of the clay and is known as the clay-substance, while the rest of the clay-particles are collectively spoken of as sand. In the ordinary or ultimate analysis, the substances generally determined are silica, alumina, ferric oxide, lime, magnesia, alkalies and water. An analysis of this type simply regards the clay as a mixture of elements or oxides, but gives no clue as to the actual condition in which these substances exist, i.e., whether as silicates, oxides or carbonates, etc., a point which it is of the highest importance to know; for the individual components of the clay influence its properties not only according

Jan 1, 1899

By H. C. George

Since 1911, when J. L. Dunn first used compressed air for repressuring depleted oil sands in southeast Ohio, the rejuvenation of many depleted oil fields has been directly due to repressuring by means of air or gas. Developments in repressuring in recent years have resulted in its successful use in the early life of some deep, high-pressure oil fields, conserving the natural gas dissolved in and associated with the oil by returning it to the producing oil sand after it has been compressed above the existing rock pressure of the reservoir. One of the most successful operations of this type is that of the Humble Oil & Refining Co., on the DeWalt salt dome at Sugarland, Texas. I quote from a personal communication with reference to this field: "Structurally, the field is dome-shaped, having a closure of approximately 350 ft. Production comes from a sandy shale interbedded with a clean sand and lying over a cap rock which is about 3400 ft. deep on top of the structure." A feature of the operation of this field is the production of the required amount of oil with the minimum of gas production. Wells on top of the dome have high gas-oil ratios, while those down structure have lower ratios, depending upon the distance of the well from the peak. To date, it has been possible to produce the oil needed from the wells circling the dome above the water zone and below the gas zone, and in this manner the average gas-oil ratio has been kept low. The gas from all separators is turned into a gas system which serves the entire field. From this system, all drilling rigs and utilities requiring gas for a fuel draw their requirements, and the remainder of the gas (about two-thirds of the production) is delivered to a compressor plant which boosts the pressure until it can be returned to the sand at the top of the dome where the rock pressure is 1400 lb, per square inch. "The Sugarland wells produce through 2-in. tubing with a 3/8-in. choke in one wing of the well-head manifold. The pressure builds up as high as 1300 lb, per square inch on the casing while on the tubing it varies from 0 to 900 lb. per square inch, depending upon the amount of gas produced with the oil."

Jan 1, 1931

By E. A. Peretti

BEFORE embarking on a detailed investigation of the system indium-antimony-bismuth, experiments were carried out to determine the existence of quasi-binary sections. The bordering binary systems are known1 and show the occurrence of three intermetallic binary species corresponding closely to InSb, InBi and In2Bi. Attention was focused on the low-indium end of the ternary diagram where the possible quasi-binary sections, excluding ternary compound formation, would involve the pairs: InSb-Bi, InBi-Sb and InSb-InBi. The latter pair revealed itself as a true quasi-binary, so it was investigated fully by thermal analysis, x-ray and microscopic examinations. All compositions were made by proper combination of three elements involved. The indium had a guaranteed purity of 99.97 pet; the antimony contained 99.99 pet Sb, and the bismuth had a purity of 99.99 pet. Alloys were made by melting together antimony, bismuth and indium in evacuated, sealed pyrex-glass tubes at a temperature of 600°C with vigorous agitation. The melts, weighing about 80 grams, were allowed to freeze in the sealed tubes and finally were transferred to glass tubes for the taking of cooling and heating curves. A protective atmosphere of helium was used, and the melts were stirred mechanically while cooling at rates of from 0.5 to 3°C per min. Temperatures were measured with a calibrated chromel-alumel thermocouple and were recorded graphically on a Minneapolis-Honeywell extended-range recorder working in conjunction with a Leeds and Northrup type K-2 potentiometer. Conventional polishing techniques gave satisfactory results in preparing specimens for microscopic examination. Etching was carried out with Vilella's reagent or aqueous mixtures of chromic oxide with either nitric acid or sulfuric acid plus dichromate. Conclusions deduced from the thermal analysis and microscopic examinations were confirmed by X-ray photograms using Co-K alpha radiation. The phase diagram is shown in Fig. 1. The liqui-dus consists of an uninterrupted line running from the freezing point of InSb (525°C) to a eutectic point experimentally indistinguishable from the freezing point of InBi (110°C). X-ray patterns of the InSb show a slight expansion of the lattice with the addition of InBi, and microscopic work indicated the solid solubility of InBi in InSb to be less than 0.5 pet at room temperature. Acknowledgment We wish to thank the Indium Corporation of America for the loan of the indium used in this investigation. References 1 E. A. Peretti and S. C. Carapella, Jr.: Trans. ASM., 1949, vol. 41, P. 947. T. S. Liu and E. A. Peretti: Trans. ASM, 1952, vol. 44, p. 539. Metals Reference Book, vol. 1, 2nd ed., AIME, p. 345.

Jan 1, 1959

Jan 1, 1970

By D. A. Lyon

Discussion of the paper of DORSEY A. LYON and ROBERT M. KEENEY, presented at the San Francisco meeting, September, 1915, and printed in Bulletin No. 104, August, 1915, pp. 1707 to 1730. LAWRENCE ADDICKS, Douglas, Ariz.-I think papers of this character, while general in, nature, are of particular value and interest, because when we figure on competing with the East in electrometallurgical industries, on account of the cheap power on the Pacific Coast, we have to take two or three things into account. In the first place, power very rarely amounts to more than 20 per cent. of the total cost of an operation, even .though it be electrometallurgical, and I think it is the common opinion among those who are not familiar with those particular industries, that it amounts to more than 50 or 60 per cent. Take copper refining; we may say that it is 15 per cent. of the total cost. In the second place, around New York City, with 100 per cent. load factor and a reasonably large load, say 10,000 kw., we can generate from a certain class of coal 1 kw.-hr. for about 0.3c. I might say, however, that 0.3c. does not include overhead charges, interest on the investment, etc. The third factor we have to consider out here is that any product to be salable, must command a retail market. It would be useless to produce wire bars here on the Pacific Coast because there is no place to roll them. If we were going to establish a copper refinery, that part of its output which goes into wire bars would have to be taken care of by building a rolling mill alongside of it to turn it into wire and finally make a product that is salable. I do not think, however, that Mr. Lyon need have excluded copper refining from his industries. There are perhaps 50,000,000 lb. of copper a month refined in this country on a custom basis. I think the smelting companies would be very glad to build refineries here if conditions warranted it. The recent extensions of the Great Falls refinery and of the Tacoma refinery in the last few months give evidence of that.

Jan 12, 1915

By Heath B. Fowler

The surface mining operations of the Simplot Fertilizer Co. are on the Fort Hall Indian Reservation approximately 16 miles east of Fort Hall, Idaho (Fig 1). The Phosphoria formation outcrops in sec. 2, 3, 11, 14, 15, 22 and 27, T 4 S, R 37 E, Boise Meridian. The ownership of these phosphate-bearing lands is divided between individual Indians and the Bannock-Shoshone Tribe, and the royalties are paid to the respective owners on a tonnage basis, as the rock is mined. The geology and mineral resources of the Fort Hall Reservation were studied by the U. S. Geological Survey in 1913 and reported on in 1920. † However, it was not until the winter of 1945 that exploratory work was undertaken by private enterprise. Diamond drilling was begun by the Simplot Fertilizer Co. in April 1946, and stripping operations were started in June. A camp was established near

Jan 1, 1950

By A. W. Gauger

It is with some trepidation that I approach my subject, for I know that I shall at once incur the suspicion of the mechanical engineer, with his concern for boiler tests and efficiencies; of the mining engineer, with his mechanization problems; and of the chemical engineer with his unit processes. Nevertheless, it must be recognized that the technology of fuels, the systematic body of knowledge relating to the production, processing and utilization of mineral fuels, has grown to such proportions and involves so many widely diverse applications of fundamental science and engineering that it behooves us to stop and consider just what its status is in relation to other technologies, as well as in relation to the present and future needs of the social order. The time has come when technologists, applied scientists and engineers must consider the possible effects that their achievements may have on Society. The development of a machine to - -replace -several hundred men is a fine achievement when considered solely from the point of view of creative endeavor. But what of the men who are displaced by the machine! Does not the responsibility for the development of this machine embrace as well the consequences of obsolescence and technological unemployment resulting from such development? I believe that it does and that we must recognize this fact in our practice of engineering and tech- nology as well as in the training of future engineers and technologists. Magnitude of the Fuels Industry Fuel technology is the body of knowledge that relates to the mineral fuels. The fuels industry is by far the most important of all Our mineral industries. The chart in Fig. I, reprinted from U. S. Bureau of Mines Information Circular No. 6643, indicates the compartive values of metals, fuels and other nonmetallic minerals for the year 1929. Of the grand total of 13¼ billions of dollars in value of minerals at the mines, the mineral fuels contributed 48 per cent. Coal, with 34.4 Per cent, exceeded the value of any other single mineral. In fact, the value of the production of the Pennsylvania anthracite mines alone anand exceeds the value of the gold production of the entire world. Petroleum and natural gas in 1929 contributed 14.3 per cent and 3.3 per cent, respectively, of the total value of world mineral production. So much for the world picture; let us now look at the situation in the United States. Over the 60-year period 1880 to '939, $46,409,727,000 of metal1ic products, $80,788,852,000 of fuels (coal, petroleum, natural gas, natural gasoline) and $27,871,-ooo,ooo of nonmetallic minerals other than fuels were produced. The mineral fuels have contributed 52.7 per cent of the entire mineral wealth produced over this period that has seen such tremendous industrial development in our Our As a matter of fact, our present industrial civilization has been made possible through the use of the

Jan 1, 1942

By A. W. Gauger

It is with some trepidation that I approach my subject, for I know that I shall at once incur the suspicion of the mechanical engineer, with his concern for boiler tests and efficiencies; of the mining engineer, with his mechanization problems; and of the chemical engineer with his unit processes. Nevertheless, it must be recognized that the technology of fuels, the systematic body of knowledge relating to the production, processing and utilization of mineral fuels, has grown to such proportions and involves so many widely diverse applications of fundamental science and engineering that it behooves us to stop and consider just what its status is in relation to other technologies, as well as in relation to the present and future needs of the social order. The time has come when technologists, applied scientists and engineers must consider the possible effects that their achievements may have on Society. The development of a machine to - -replace -several hundred men is a fine achievement when considered solely from the point of view of creative endeavor. But what of the men who are displaced by the machine! Does not the responsibility for the development of this machine embrace as well the consequences of obsolescence and technological unemployment resulting from such development? I believe that it does and that we must recognize this fact in our practice of engineering and tech- nology as well as in the training of future engineers and technologists. Magnitude of the Fuels Industry Fuel technology is the body of knowledge that relates to the mineral fuels. The fuels industry is by far the most important of all Our mineral industries. The chart in Fig. I, reprinted from U. S. Bureau of Mines Information Circular No. 6643, indicates the compartive values of metals, fuels and other nonmetallic minerals for the year 1929. Of the grand total of 13¼ billions of dollars in value of minerals at the mines, the mineral fuels contributed 48 per cent. Coal, with 34.4 Per cent, exceeded the value of any other single mineral. In fact, the value of the production of the Pennsylvania anthracite mines alone anand exceeds the value of the gold production of the entire world. Petroleum and natural gas in 1929 contributed 14.3 per cent and 3.3 per cent, respectively, of the total value of world mineral production. So much for the world picture; let us now look at the situation in the United States. Over the 60-year period 1880 to '939, $46,409,727,000 of metal1ic products, $80,788,852,000 of fuels (coal, petroleum, natural gas, natural gasoline) and $27,871,-ooo,ooo of nonmetallic minerals other than fuels were produced. The mineral fuels have contributed 52.7 per cent of the entire mineral wealth produced over this period that has seen such tremendous industrial development in our Our As a matter of fact, our present industrial civilization has been made possible through the use of the

Jan 1, 1942

The Manufacturer's Viewpoint A prominent manufacturer of mining 'machinery not long ago expressed himself as being confident that he was securing the best kind of publicity for his product through the advertising pages of the monthly Bulletin of the American Institute of Mining Engineers. Such an expression coming from such a man is highly gratifying; yet it is justifiable when the high quality of reader and subscriber is taken into consideration. In fact, the majority of those using our advertising pages feel the same. It is to be regretted, of course, that others catering to our field do not realize the means at their disposal for presenting the points of interest of their product to the mining man. The question has been asked, " Do your members read their Bulletin?" They not only read the editorial pages, but they "admit being up-to-date enough to peruse the advertising section to "see what is new." The next question the prospective advertiser asks is, " Will the Bulletin bring inquiries?" The answer to this question holds good for any publication having as subscribers those who have purchasing or recommending power-yes, if the article advertised is not a stock one, that has been before the public for any length of time. To secure inquiries on, say, a standard centrifugal pump or any other standard product, the features of which are well known, is a most difficult proposition. Yet, of course, some inquiries are secured, but mostly from those having use for the catalogue or trade literature for reference purposes. It is safe to say that the traceable returns from advertising in trade publications hardly, if at all, pay for the advertising. The real returns are intangible, and result from the constant publicity, and keeping ?everlastingly at it." Who can say what subconscious effect is taking place when an advertisement is "glanced at," to say nothing of the effect produced when the copy is attractive and interests the reader. Time after time it has been proved that sales have been secured as a result of an advertisement, yet no inquiry had been made directly traceable to advertising.

Jan 8, 1915

By F. N. Speller

Interest in the corrosion problem seems to continue without abatement and is bringing practical results. At least four important conferences on this subject have been held during the last 5 months. Those interested in steel-frame structures are taking steps to study vulnerable points on account of the failure of some minor parts in certain buildings after 35 years of service. The steam power-plant group, including the railroads, realize the importance of a better knowledge of corrosion, especially under modern high-temperature boiler operations. The chemical and refrigerating industries have already conducted a systematic study of depreciation of metals by corrosion, for which they have spent considerable money and time during the last 2 years with encouraging results. More has probably been done to control corrosion in the atmosphere and in closed water systems, because the work on these phases of the problem started over 15 years ago and the important factors are now fairly well understood. As a result of all this work, there is now little excuse for corrosion in water conduits, recirculating condensers and cooling systems, since economical means of prevention have been worked out to meet nearly all situations where such corrosion occurs. The entire Baltimore water supply was treated with lime at a cost of only 35 c. per million gallons and the rate of attack on the pipes has been reduced to not over 20 per cent. of what it was before the treatment. Yearly damage to water mains in Baltimore is estimated at $300,000, and in New York City at $5,000,000, not including damage to water conduits in buildings. In some cities corrosion is now recognized by water works' engineers as a major problem. In the oil industry, there are evidently three general classes of corrosion, relating to: (I) Production, (2) transportation, and (3) refining. (1) Production.—Some fields, those of California for example, have little corrosion trouble in the wells. In others this is a major problem and should be a strong incentive to the development of more resistant metals at a reasonable cost. E. G. Woodruff,' consulting geologist, has pointed out that more of the oil of the future will probably come from the

Jan 1, 1927

By Phil Hulse

The Atlanta mine is located in east-central Nevada, approximately 360 km (225 miles) from Las Vegas. It lies in Lincoln County, 116 km (72 miles) south of Ely and 80 km (50 miles) northeast of Pioche. The property is currently operated by the Standard Slag Co. under a joint venture agreement with Bobcat Properties Inc, of Fort Lauderdale, Fla. Operations began in May 1975, and the mill is currently processing 109 000 to 122 500 t/y (120,000 to 135,000 stpy) of gold- and silver-bearing ore. Open-pit mining takes place in a breccia zone that occurs between Ordovician limestones and dolomites on the footwall and Tertiary rhyolites on the hanging wall. The quartz breccia ore is among the most abrasive in the world-shovel teeth must be replaced every week, 19-mm-thick (3/4-in.) steel chutes last about a month.

Jan 9, 1978

By James Terry Duce

The gross production on the Island of Sahreirl during 1944 was approximately 6,700,000 U. S. bbl. No additional wells were drilled in the field during the year, but a number that were plugged off during the critical days of the war were brought back on production. This work is continuing. The construction of the extension of the refining plant was continued during the year and the new crude still was started in November. In Arabia, the production for the year 1940 was 5,074,838 U. S. bbl. Four wells were completed in Dammam field and all were commercial producers. Production for 1941 was 4,310,110 U. S. bbl. Seven more commercial producing wells were completed in Dammam field, and Well No. I at Abqaiq was complcted at 6180 ft. and was also a commercial producer. In 1942 production was 4,530,492 U. S. bbl. Abqaiq No. 2 was drilled to 5785 ft. but was left standing because of mechanical difficulty. The 1943 production was 4,868,- 184 with one well drilled, Abqaiq No. 3 completed at 6488 ft. and a commercial producer. Total production in Arabia for the year 1944 was around 7,800,000 U. S. bbl. and at the close of the year was running at approximately 40,000 bbl. per day. The small refinery, built in 1939, at Ras Tanura was in operation in the fall and a new refinery is being constructed. Only three wells were completed during the year—the El Jauf well in Northern Arabia (completed at 10,974 ft.) which did not bring in commercial production and Wells No. 4 (completed at 6270 ft.) and No. 5 at Abqaiq (completed at 6751 ft.), which were brought in as substantial commercial producers. Production for the year was entirely from the Dammam field. In this field, some of the wells that had been plugged off early in the war were brought back in production and this work is continuing. At the close of the year, one well was drilling in the Abqaiq field and an additional well was drilling at Qatif, the latter being a wildcat. Neither of the wells in question had reached producing horizons on the first of January.

Jan 1, 1945

By FOSTER HEWElT

THE scope of this paper is the description of two districts in Peru in which deposits of vanadium have been found, and the consideration of much laboratory-work that I and others have done to determine the nature of these deposits. It is with regret that I present some of the data in a state of evident incompletion, particularly the analyses of a few of the minerals, which leaves some doubt as to whether the true nature of the minerals is understood. I make no apology, however, since in this case, as in many others referring to ore-deposits, conclusive opinions cannot be stated until a great amount of work has been done, and the deposit has been thoroughly exploited. I believe that the data and the tentative conclusions here presented indicate a unique and interesting condition which may assist others in work along similar lines; and further, what is of more practical importance, stimulate a search for a metal which, though long considered rare, is probably so merely because proper care has not been taken to recognize it. An excellent bibliography on the occurrence of vanadium in nature is given by F. W. Clarke in his paper, Data of Geo-chemistry;1 and in the preparation of this paper I have consulted many of the references contained in the Bibliography of the Chemistry of Vanadium, by M. Moissan.2 A brief review of the subject having special reference to the metallurgy of vanadium is contained in the small book by P.. Nicolardot.3 One of these vanadium-deposits has already been briefly

Mar 1, 1909

By P. Chiotti, R. J. Hecht

Vapov pressure data of solid and liquid alloys along with phase diagram data WERE employed in calculating the thermodynamic properties for the Ca-Zn system. The relative excess partial molal free energy for zinc in the liquid alloys was fitted to the relation wnvre i is we tvmpvrutiirc in ucgrees neivtu ana in is the tr~ole fvaction. Relations for the standard free energy of fortnation for the eight cornpounds were developed. ThE phase diagram for the Ca-Zn system as determined by Messing et a1.' is reproduced in Fig. 1. Earlier work on the phase diagram has been summarized by Hansen and Anderko2 and the very limited thermodynamic information for this system has been reviewed by Hultgren et a1.3 The heat of fusion for the compound CaZn2 has recently been determined to be 9260 cal per mole.4 Solubility data for calcium in zinc for the temperature range of 650" to 725°C were fitted by the relation and reported by Johnson and Dilloon5 In the present investigation zinc vapor pressure data were obtained by both the dewpoint and Knudsen methods in order to calculate the thermodynamic properties for liquid and solid alloys. The dewpoint method as employed in this work requires that only one of the components be significantly volatile, in this case zinc, and that the vapor pressure of pure zinc be known. For calculation purposes the vapor pressure data for pure zinc3 were fitted to the relations; for temperatures below 692.7K, the melting point of zinc. The corresponding free-energy relations for vaporization and sublimation of pure zinc are respectively. Some of the calculations also required knowledge of the free energy of fusion of zinc and calcium and the free energy for the 721°K allotropic transformation of calcium. The free energy of fusion of zinc was taken to be the difference between Eqs. [4] and [5], or The free energy of fusion and transition for calcium were based on the enthalpy values of 2040 and 222 cal per g-atom, respectively, as reported by Chiotti et al. 4 and the heat capacity data given by Hultgren et a1.3 and are represented by the relations, In the latter expression the difference in heat capacity between the a and 0 forms of calcium was neglected. MATERIALS AND EXPERIMENTAL PROCEDURES The metals used in preparing the alloys were Bunker Hill slab zinc, 99.99 pct pure, and Ames Laboratory calcium. The average impurities in the calcium in parts per million by weight, ppm, were N-17, H—77, Ba—216, Mg-15, Si—7, C—157, and Fe—9. The zinc was cleaned in dilute nitric acid and the calcium was used as received. The calcium was stored and handled in an argon-filled glove box and when removed from the dry box it was kept in an argon-filled desiccator. Tantalum was found to be a suitable alloy container. The alloy components were contained in a 1-in.-diam cylindri-

Jan 1, 1968