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By Kenyon Burch

ONE of the advantages presented by electric drive in many classes of work is the ease with which the electric motor can be controlled automatically. In a large number of cases certain features of the control are automatic-for example, the rate of acceleration may be limited automatically or the equipment may be stopped automatically at the limit of travel-but the equipment is started and ordinarily is stopped by hand. . In other cases the motion of the machinery is utilized to start, control the: speed, and stop the motor automatically, independently of any operator. A considerable proportion of the large mine hoists now in use have certain automatic features, particularly protective devices against over-winding, and, in some classes of electric hoists, devices for preventing excessive acceleration or retardation. The large automatic hoists discussed in this paper, however, are completely automatic, i.e., capable of snaking their trips without the presence of an operator at the control levers. According to circumstances, various advantages may be obtained by automatic control, chief of which are decreased power consumption', increased precision and safety of operation, and decreased, cost of attendance. The first step in the analysis of a prospective automatic mine hoist is to determine whether automatic operation is feasible at all. If men are to be hoisted, or levels changed, the attention of an operator is required for these purposes; but tinder some conditions it may be entirely practicable and advantageous to build the equipment so that, while provision is made for hoisting mien or changing levels, ore can be hoisted automatically from, any one level. If, however, an operator's attention is required every few minutes for changing levels, handling men or drills, or other work requiring hand control, it is obvious that automatic operation between times will not be of any, practical benefit.

Jan 3, 1916

By Nestor Torres-Acuña, Fathi Habashi

Metallic copper of purity equal to commercial electrolytic copper is deposited during the anodic dissolution of technically available white metal, Cu2S, in m acidic solution of' copper(II) sulfate as electrolyte and copper sheets as cathodes. The process may be applied on commercial scale since it has the advantage of by passing the converting and poling steps, decreasing pollution problems due to SO, and recovering the sulfur of the white metal in the elemental form. The anodic dissolution is believed to take place in three steps: The working conditions that lead to 98 pct cathodic current efficiency are: 30 gpl Cu2+ and 100 gpl H2SO4 in electrolyte, current density 1.0 amp per sq dm, and tetnperature of bath 40°C'. DURING the smelting of copper, nickel, lead, and zinc sulfide ores, large amounts of sulfur dioxide are produced. Because the release of this gas in the atmosphere causes pollution problems, many attempts were made in the past for its recovery either in liquified form or processed to sulfuric acid. Although these two forms of sulfur are the usual forms that are consumed by the chemical and metallurgical industries, their storage and transport usually raise economic problems. It was realized, long ago, that a process by which sulfur can be recovered directly in the elemental form would be most attractive. Elemental sulfur is easily stored and transported, and is readily converted to SO2, H2S, or H2SO4 when needed. Processes aimed to recover the metals from their sulfide ores, and at the same time by-product sulfur in the elemental form, were recently reviewed.' As early as 1882, Marchese2 patented a process in which a matte having the composition: Cu 15, Pb 14, Fe 41, and S 25 pct was electrolyzed. According to cohen3 the process was applied on a pilot scale by the Aktiengesellschaft fur Bergbau-, Blei-, und Zinkhiitten-betriebe at Stolberg, Rheinland, Germany. The process was unsuccessful, however, owing to the contamination of the electrolyte during electrolysis. Studies in this field were reported by Bernfeld4 and Egli.5 Borchers et a1.6-8 developed the process further by using white metal (Cu 78.2 pct, S 19.6 pct) instead of the matte, and a pilot plant was operated by the Mansfeldschen Kupferschiefer Co. at Eisleben, German~.~ It appears, however, that the process never went into commercial operation. Further studies in this direction were carried out by Russian workers.10-23 The International Nickel Co. of Canada erected a pilot plant at Port Colborne in 1951 to apply the process to nickel matte which is essentially pure nickel sulfide."'- 26 Full-scale plant went into operation at the Thompson Refinery in Manitoba in 1964.27 In this method nickel sulfide matte is melted and cast into anodes analyzing 76 pct Ni and 20 pct S with small amounts of copper, cobalt, and iron. These anodes are then electrolyzed in an aqueous solution of NiS04 at pH 4. Further work on this method was reported in the literature.28-31 In this paper, experiments on the anodic dissolution of white metal in aqueous copper sulfate solution are reported. EXPERIMENTAL White metal, Table I, obtained from The Anaconda Co., was cast in form of anodes 10 by 7.5 by 1 cm, Fig. 1. The anodes are mechanically strong and do not break easily; when polished they gave a shiny gray metallic appearance. From the chemical composition shown in Table I, it can be seen that the atomic ratio Cu:S corresponds approximately to the formula CU2.06S. The copper in excess to the formula Cu2S is most probably present as a separate phase since metallic copper could be seen under the microscope, Fig. 2. Fig. 3 shows the X-ray diffraction pattern of white metal which matches fairly well with that of reagent-grade Cu2S.

Jan 1, 1969

Two Canadian mining companies, Noranda Mines, Ltd., and Wright-Hargreaves Mines, Ltd., have agreed to buy $500,000 worth of shares each in Anglo-American Exploration Ltd., controllers of thousands of acres of possible oil-rich land in southern Saskatchewan and Manitoba. Samuel Clarence Nickle, Sr., reported as possible president of the newly formed exploration company, said that $20 million in assets have been accumulated by the firm, mainly in the Williston basin in parts of the Dakotas and Montana, aid extending into Southern Manitoba and most of Saskatchewan. The M. A. Hanna Co. reported a record profit for the seventh consecutive year with total 1951 profit reaching $14,081. The company handled a record 16.8 million tons of iron ore in 1951, compared with 14.9 million tons in 1950. The company is also preparing to open four iron ore mines in the Lake Superior district which are expected to produce more than 5 million tons annually by 1954. The company built two new iron ore concentrating plants at Mesabi range mines in 1951,a with a third plant going into, operations soon.

Jan 1, 1952

APPLICATIONS for loan contracts for the exploration, development and mining of strategic and critical metals and minerals are now being accepted by the Department of the Interior. The RFC is authorized and directed by Executive Order 10161 to make such loans but the Secretary of the Interior must pass on the necessity for the loan. Applications should be addressed to James Boyd, acting deputy administrator, Defense Minerals Administration, Department of the Interior, Washington, D.C. rather than to the Field Offices of the Bureau of Mines as was first planned. Application forms are not yet available but it has been learned that data accompanying the application should include the known quantity and grade of reserves, the anticipated rate of production, the equipment, supplies, and man power required for the additional production, etc.

Jan 12, 1950

By E. Ackerman, L. Y. Tu, S. C. Sun

The use of ultrasonics in forming emulsions is not new. As early as 1927 Wood and Loomis' reported preparation of emulsions with ultrasonics. In 1935 Rschevkin and Ostrawskyz described the use of great ultrasonic power in producing fine emulsions of various oils and paraffin in water. Recently Oyama and Tanakahmployed ultra-emulsification to increase the effectiveness of sodium ethyl xanthate in flotation of chalcopyrite and galena. An emulsion is a two-phase system consisting of two incompletely miscible liquids, the one being dispersed as finite droplets in the other. The dispersed liquid is known as the internal or discontinuous phase, and the surrounding liquid is termed the external or continuous phase. There are two types of emulsions; one is oil-in-water (O/W) and the other water-in-oil (W/O). The word oil refers to the liquid other than water. Circumstances exist in which the emulsion type is not clearly defined, and the internal and external phases both contain portions of the opposite phase. This is said to be a dual emulsion. Among the many hypotheses', 6v proposed for the formation of emulsions, the Bancroft's adsorbed film or double interfacial tension theory is widely accepted. Bancroft ""educed that in the process of emulsification the interfacial tension between oil and water is lowered by the formation of an emulsifying film, which contains the adsorbed molecules and/or ions from the emulsifying agent and the two liquids.

Jul 1, 1955

By J. Chipman, G. G. Hatch

T. ROSENQVIST*—It is a pleasure to see the excellent way in which the experimental part of this work has been handled. There seems to be little doubt that the distribution data obtained corresponds most closely to thermodynamic equilibrium under the prevailing reducing conditions, namely equilibrium with graphite and one atmosphere CO pressure. The desulphurization curves in Fig 10 show the same general feature as the curves given by Holbrook and Joseph, but the distribution ratios are from 20 to 40 times greater—undoubtedly due to a closer approach to true equilibrium. In the theoretical discussion, the authors calculate a theoretical distribution (S) ration -jg-. which they find to be about 50 times greater than the experimental. The deviation is so great that the basis for their calculation needs a more thorough examination. The authors base their thermodynamic calculation on free energy expressions where diluted solutions of FeS and CaS are used as standard states. (The activity coefficient in diluted solutions is taken to equal unity.) Such a standard state will change when the nature of the solvent is changed. Taking the free energy of the reaction [FeS] ? (FeS), Eq 2, which is derived from the distribution of sulphur between an iron and a FeO-melt, it is very unlikely that the free energy of this reaction will be the same for a distribution between pig iron and a calcium silicate slag. Therefore a more fundamental basis for the thermodyuamic calculations seems needed, where all thermodynamic equations are referred to unambiguously defined standard states. The most natural standard states for CaO and CaS are the pure solid substances at the same temperature. As standard state for sulphur in iron, pure liquid FeS can be used. This rules out Eq 2 [FeS] ;=s (FeS) because ?F° = 0. The standard equation will then be: FeS, + CaO6 + Cgraph ?Fei + CaS8 + CO. vFo1773 = 25,000 cal It would be more universal and also simpler to refer the escaping tendency of sulphur in liquid iron to the corresponding H2S/H2 ratio which can readily be determined experimentally. As standard state a gas mixture H2S/H2 = 1/1 can be used. (This corresponds at the temperature of liquid iron closely to one atmosphere S2 vapor.) Thus the standard equation for the sulphur reaction can be formulated as follows: H2S0 + CaO3 + Cgraph ?H2o + CaS8 + COg The standard free energy of this reaction has been calculated from the best available data to AF°m3 = —35,000 cal. This gives for the equilibrium constant at 1500°C Now, the solubility of CaS in blast furnace slags has been determined by McCafferey and Oesterle* and corresponds at 1500°C to about 10 pet S (varying somewhat with the composition of the slag.) If the activity of CaS is assumed linear between 0-10 pet as curve 1, (see Fig 11), then acaO = 0.1 (S); (S) being wt. pet sulphur in the slag. For a diluted solution of sulphur in an iron melt saturated with carbon, the ratio H2S/H2 is, according to Kitchener, Bockris and Liberman,f about 0.01 [S], [S] being wt. pet sulphur in iron. Substituting these values in the expression for Kp we find The value 2.103 is only 4 times greater than the experimental coefficient found by Hatch and Chipman, but the value is very sensitive to a small error in AF°. A better agreement with the experimental distribution coefficient can be obtained if one assumes the activity of CaS to run like curve 2 (Fig 11). This (S) will give a lower theoretical W, value, a value which varies with (S) exactly as Hatch and Chipman learned. Such a shape of the activity curve, which corresponds to a positive deviation from Raoult's law, is actually to be expected from the fact that liquid silicate and sulphide phases usually show incomplete miscibility. A closer agreement between experimental and theoretical data can not be expected before we have more complete data for the individual activities of CaS and CaO in the slag. The activities acaS and Ocao referred to the solid phases as standard states, are exact defined quantities contrary to the somewhat undefined expression "free lime," and they are independent of any theory for the constitution of liquid slag. J. CHIPMAN (authors' reply)—The authors wish to thank Mr. Rosenqvist for his very interesting and useful thermodynamic addition. Curve 2 of his figure offers the needed basis for explaining the increase in the ratio (S)/[S] with increasing sulphur content. Attention is called to an error in the printed paper: Fig 2 and 3 are reversed. M. TENENBAUM*—In the figures showing the relationship between excess base and sulphur distribution (Fig 6, 7 and 9) the slope of the curve tapers off in the negative basicity range. Somewhat the same thing is observed with open hearth slags. In that case, the fact that some sulphur distribution between slag and metal is obtained with negative basicity is interpreted as indicating some dissociation of the lime silicate compounds whose existence in oxidizing basic slags has been used to explain various observed phenomena with regard to other slag-metal reactions. In the case of the blast furnace slags, the reduced slope of the sulphur distribution curve with decreasing excess base is attributed to the amphoteric effect of alumina. Has the possibility of other explanations been investigated ?

Jan 1, 1950

By William Glenn

In their account of chromium, Roscoe and Schorlemmer (Treatise on Chemistry, London, 1879) state that "In 1762 Lehmann, in a letter to Buffon, de nova minerœ plumbi specie crystalline rubra, described a new mineral from Siberia, now termed crocoisite." In 1786 Lehmann analyzed it (Nicholson's Jour., Dee., 1798) and found that it contained chiefly lead, and that the " mineralizers " were arsenic and sulphur. It was next examined in 1189 by Macquart and Vauquelin, who stated that it contained an intimate mixture of iron, alumina, and lead peroxide. The account of their work was published over the name of Macquart. Vauquelin (Louis-Nicolas) was a Norman peasant, who had studied in the village school, and at the age of fourteen was a laboratory-boy in a pharmacy at Rouen. Later, he found his way to Paris, and in 1789 was assistant to Fourcroy, a pharmacist and a teacher of note. It was here that he met Macquart, with whom he did the work on Siberian red lead, and at this time his friend Cheradame taught him his Latin.

Jan 1, 1896

By G. S. Hume

Three provinces in Canada—New Brunswick, Ontario and Alberta— produce oil and gas in commercial quantities. In addition a small amount of oil is being produced and refined in the Northwest Territories at Norman on the Mackenzie River. The production at Norman is derived from two wells drilled by Northwest (Imperial Oil) Co. in 1920 and 1923. The refined products of the oil are used locally in connection with mineral developments on Great Bear Lake. The production of petroleum by provinces and the consumption of natural gas are shown in Table 3. In addition a small amount of natural gas is produced in the southwestern part of Manitoba from shallow wells for local use. Tables 1 and 2 give detailed information. The greatest drilling activity in 1933 in Canada centered around the southern end of the Turner Valley field, Alberta. In addition to several wells previously commenced in this area, eleven new wells were begun. There were three completions to the Paleozoic producing zone in 1933 in the southern part of Turner Valley and one well was abandoned as a result of being off the favorable structure. Of two wells completed in

Jan 1, 1934

C. N. FEnner, New York City (communication to the Secretary) : A possible explanation of some of the' phenomena of amalgamation cited by Mr. Bayliss and others has occurred to me. We know that if, to a quantity of mercury, gold and silver are added until a putty-like paste is formed, and if this mass is spread on a flat surface and pressure is applied, a more fluid portion of the mercury will be squeezed out from the rest, carrying gold and silver with it. The proportion of gold to silver will depend, I think, upon various causes and conditions—the relative chemical affinity which gold and silver have for mercury; the amount of pressure used; the presence of other metals:

Jan 1, 1898

Utah Engineering Experiment Station, University of Utah, Salt Lake City, Utah. D. A Lyon, Director. Important work on ore dressing has been carried out at this station Before listing the Technical Papers and Bulletins available, it is well to point out especially that Technical Paper 1, Flotation fundamentals, 4, Flotation fundamentals (pt 2), and 5, Flotation fundamentals, pt 3, are out of print and can only be consulted at libraries or elsewhere. The Technical Papers and Bulletins available are as follows: Technical Paper 6, Recovery of zinc from ferrite compounds in the electrolytic zinc process, 25 cents; 7, Flotation fundamentals (pt 4), 40 cents; 8, The technique of preparing thin sections of rock, 75 cents; 9, Flotation fundamentals (pt. 5) 30 cents; 10, A new development in the preparation of briquetted mineral grains, 15 cents, 12, A method for the determination of cadmium in mill and smelter products, 25 cents; Bulletin 10 (revised 1931), Mine sampling and the commercial value of ores, 35 cents, 14, Report of research investigations (1922-23), with papers on these subjects Hydrometallurgy of zinc, Flotation experiments on Utah sulphur ore, Oil shale investigations, Zinc oxide investigations, 25 cents;

Jan 1, 1933

By Arthur Knapp

OIL-WELL depletion curves, to be of value, should show when a well or lease may no longer be operated at a profit. The difference, at any time, between the total expenditures and the total income of a lease or well may be called the lease status. Plotting this lease status against time will give a curve subject to more accurate and different interpretations than the barrels-time curves. According to the hypothetical barrels-time curves shown in Fig. 1, well A, at the end of 16 mo., is producing twice as much oil as well B and will continue to produce for another year whereas well B will cease producing in about 6 months. DATA FOR LEASE STATUS-TIME OR DOLLARS-TIME CURVE TIME LEASE MONTHS STATUS Lease purchased for $3000 0 -$ 3,000 No expenses chargeable to lease for 3 mo 2 - 3,000 Well A is started; cost of drilling for month is $16,000 3 - 19,000 Well is completed at additional cost of $10,000 4 - 29,000 Well A is brought in and flows 10,000 bbl. first month (see Fig. 1). Necessary to invest in tanks, boilers, pipe lines, etc.: difference between expenditures and receipts gives profit for month of $5,000 5 - 24,000 Investment is small, cost of operating well A is small, so profits are $15,000 6 - 9,000 Well ceases to flow so there is additional investment for pumping equipment and additional operating expense; net earnings from 6,000 bbl. of oil produced is $4,000.... 7 - 5,000 Lease operation now becomes normal and curve becomes smooth 8 - 500 9 2,000 10 4,500 11 6,000 12 7,700 13 8,700 14 9,000 15 9,500 16 10,000

Jan 1, 1921

By PAUL DYER MERICA

PAUL DYER MERICA, who has been awarded the James Douglas Gold Medal for his achievements in non-ferrous metallurgy, is a Hoosier, having been born at Warsaw, Ind., in 1889. His father, a clergyman and educator, was president of the University of Wyoming from 1908 to 1913. After graduating from the University of Wisconsin in 1908, young Merica (not yet twenty years of age) went to China, where he was professor of chemistry in Chekiang Provincial College, Hangchow, until 1911. He then went to Germany to s t u d y and was fortunate enough to receive his Ph.D. from the University of Berlin just a few months before the outbreak of the World War in 1914. Returning to America, his first position was as special investigator at the En¬gineering Experiment Station of the University of Illinois, but before the year was out he joined the staff of the U. S. Bureau of Standards as associate physicist. Since 1918, he has been superintendent of research for the International Nickel Co. His work during those years is excellently summarized in the following quotation from the statement of Zay Jeffries recommending him for the award.

Jan 1, 1929

By Thomas Kesler

THE Cartersville mining district, 35 miles northwest of Atlanta, Ga., has been of varying but continuous importance in the southern mineral industry during the past century. Noted chiefly for its production of brown iron ore, manganese oxide ores, barite, sienna, and magnesian limestone, the district and its environs have produced brick and tile clays, slate, gold, bauxite, and graphitic schist. Minor deposits of serpentine, sericite schist, copper ore, and red iron oxide have been prospected. The obvious deposits of brown iron ore, together with some associated specular hematite, were mined out years ago, although a little ore was left in the workings. Moderately steady production of sienna reached a peak about 1930, then declined rapidly. Manganese mining passed through a relatively active period from the World War to 1931, but has subsided to a small but rather constant output for the Birmingham market. How-ever, the White Manganese Corporation has prepared for possible increased production by constructing a new washer capable of handling about 300 tons of ore per day. Principal activity in the district proper has centered for some years in the production of barite and magne-sian limestone.

Jan 1, 1940

By A. K. Mukherjee, J. E. Dorn, J. D. Mole

Investigations were carried out on the effect of polyslip on the strain hardening of aluminum single crystals. The orientations investigated were those lor which the tensile axis was in the [001], [111], [112], and [012] directions plus another for which the Schmid angles for {111}(110) slip were 1 deg. The experimental data were analyzed on a model based on the intersection of dislocations with particular emphasis on the effect of polyslip on the activation volume for inter-section. It is shown that the rate of strain hardening inreases for those orientations wherein attractive dislocation intersections occur and that those orientations which produce the greater number of such intersections exhibit the greater strain hardening. Good correlation of the data is obtained with the concept that attractive junctions, as proposed by Saada, Play an important role in accounting for the rate of strain hardening. EXISTING concepts on the nature and cause of strain hardening in fcc metals have been deduced principally from experiments on the deformation of single crystals under single slip. The effect of crystal orientation on the shapes of the stress-strain curves for single slip have been summarized by seegerl and more recently by Clarebrough and Hargreaves.2 Tensile specimens whose axes fall near the center of the [001]-[011] line of the standard triangle of the stereographic projection exhibit the longest range of easy glide (Stage I) and the lowest rates of linear hardening (Stage 11) whereas specimens whose axes lie near fie [001]-[111] line of the standard triangle have limited or no easy-glide range and exhibit somewhat higher linear strain-hardening rates. Specimens whose axes lie near the [001] or the [ill] poles do not exhibit easy glide and have the highest rates of linear hardening. Kocks3 has shown that the highest rates of linear hardening Occur under Polyslip when the tensile axis coincides with the [111] or the [ 001] pole. Since the rate of strain hardening is sensitive to specimen orientation and the incidence of polyslip, these relationships might help to discriminate between various dislocation models for strain hardening in fcc metals. Previous attempts to analyze the effect of orientation on strain hardening,1"3 however, did not provide a unique answer to this problem. Consequently the present investigation was undertaken wherein additional data, particularly that for the effect of polyslip on the activation volume for intersection, was also determined in order to provide more complete information on the details of strain hardening. Whereas analyses of these data reveal that several recommended models for strain hardening are at variance with the facts, good correlation of the data is obtained with the concept that attractive junctions4 play an important role in accounting for the rate of strain hardening. I) EXPERIMENTAL APPROACH seegerl demonstrated that slip in fcc crystals at low temperatures is dependent on thermally activated intersection of glide dislocations with forest dislocations. This has been confirmed by tests on single crystals of aluminum by Mitra, Osborne and Dorn5 and on polycrystalline aluminum by Mitra and Darn.' Thus in accord with Seeger's theory, the shear strain rate, ?, below a critical temperature, T, is where .V is the number of points of contact per unit volume between forest dislocations and glide dislocations, A is the area swept out per successful intersection, b is the Burgers vector, v is the frequency of vibration of the segment of the glide dislocation undertaking intersection, U is the activation energy for intersection, k is Boltzmann's constant, and T is the absolute temperature. For aluminum, which has an extremely high staeking-fault energy, the constriction energy is negligibly small and therefore the activation energy decreases practically linearly with the stress according to as will be recomfirmed later, where Uo is jog energy at the absolute zero, G and Go are the shear moduli at the test temperature T and O°K, respectively, L is the spacing of the forest dislocations, t is the applied shear stress for slip, and tGo is the stress field that must be surmounted athermally.

Jan 1, 1965

By Helmer Hedstrom

GRAVITY surveying with the torsion balance or the pendulum for ore prospecting purposes has generally not been considered practical or even possible. It is the intention of this paper to show that a fast and sensi-tive gravimeter can be very useful in ore prospecting, as an auxiliary to the electrical and magnetic instruments. A number of gravimeters have been constructed and put in practical use in the last seven or eight years; for instance, by Ising, Lejay-Holweck, Haalck, Hartley, Thyssen, Noergaard, the Humble Oil and Refining Co. and the Gulf Production Co. Their main application, apart from their use for geodetic surveys, has been for structure mapping in oil prospecting. There is no record that any of them have been used for ore prospecting. About the middle of 1934 the Boliden Mining Co., in Sweden, began experiments in constructing a static gravity meter sensitive enough for ore prospecting. Calculations and considerations that will be discussed later in this paper showed that this would necessitate an accuracy in the measurements of 0.1 milligal-roughly, one ten-millionth part of the total force of gravity. The first successful practical field tests of the instrument were made in January 1936. About the middle of 1937 the Boliden gravimeter was perfected. Ore prospecting with this instru-ment is now regular practice in Sweden, especially for the testing of indications given by geoelectric and magnetic methods.

Jan 1, 1938

By H. H. Kellogg

Available high-fernperatzwe equilibrium measurements and other thermochernical data have been critically reciewed for sulfation reactions of the type: Recommended values for log K and ?Fo as junctions of temperature are given for thirty-six suck reactions involving twenty-six different metals. Methods of calculation and choice between conflict-ing data are discussed. SELECTIVE sulfation now enjoys a considerable renaissance as a metallurgical unit process due, in large part, to the available of the fluid-bed re- actor—a device capable of the close control of temperature and gas composition necessary for a successful sulfation process. An additional need, however, if sulfation chemistry is to be approached in a scientific manner, is a reliable body of data on the equilibrium and kinetics of sulfation reactions in simple and complex systems. This paper offers a critical review and compilation of equilibrium data on pure sulfates (simple systems). The last such review, by K. K. Kelley in 1935:30 has proven itself most useful, but the existence of many new data makes necessary a re-evaluation of the available information. METHODS OF CALCULATION For a simple sulfation reaction such as MS04(c) = MO(c) + SO3 [1] there are two approaches one may take toward establishing the value of ?Fo or K as a function of

Jan 1, 1964

By B. J. Bayles, J. A. Ford, M. J. Salkind

Unidirecltonally sulidijied AL-A13Ni was found to exliibit excellent microstructural stability to 508°C. Above this temperature the transverse micvostructure coarsened in a manner analogous to "Ostwald Ripening", but the A13Ni whiskers did not spheroidize or foreshorlen. The coarsened whiskers reinforced the matrix as effectirely as the finer whiskevs and no reduction in room-temperature tensile strength mas noled after exposure for 90 hr at 96 pel 0-1 the absollite melling temperature of the eulectic. The slability was auribucted to the presence of low-index (and presurrlably lor-energy) cvystallographic interjaces between phases. The driving force for microstructural coursening was presumed to be the reduction of interfacial energy between the phases. Finer micvoslructures were found to coarsen more rapidly than those which weve imitally coarser. FIBER-reinforced metals have been shown to exhibit good short-time tensile properties at elevated temperatures.1-4 However, many elevated-temperature applications require long-time property retention which dictates the necessity for microstructural stability. Two types of instability are common to fiber composities. The first, chemical instability, is due to chemical reaction between the matrix and the relnforcing phase. Petrasek and weeton5 have shown that chemical reaction between tungsten wire and several copper alloy matrices resulted in degradation of the reinforcing phase and reduction in strength of the composite materials. Kreider and Leverant4 have noted similar behavior for boron-reinforced aluminum above 400°C. The second type of instability arises in systems in which the phases are essentially chemically stable with respect to each other and is characterized by spheroidization and/or agglomeration of the reinforcing phase. parratt6 has reported this type of degradation to occur relatively rapidly at moderate temperatures for nickel and cobalt alloys containing whiskers of silicon nitride, aluminum oxide, and silicon carbide and has identified it as "physicochemical" instability. Although both types of instability are the result of the differences in the chemical potential between the fibrous phase and the matrix, they may be differentiated by the fact that the second type, "physicochemi-call' instability, results in little or no net change in the composition or amount of each phase present. It does, however, result in a morphological change which profoundly affects the strengthening mechanism. Chemical interaction. on the other hand, results in a change in the composition and amount of one or more of the phases present, or the appearance of a new phase. In the latter case, the appearance of the mi-crostructure, that of a fibrous phase aligned in a matrix, may remain essentially unchanged, but the chemical degradation of the fiber results in markedly reduced composite strength. This investigation was initiated in an attempt to evaluate the microstructural and related mechanical property changes of a whisker-reinforced eutectic composite after elevated-temperature exposure. The composite system chosen for this study was the uni-directionally solidified A1-A13Ni eutectic which Lemkey. Hertzberg, and Ford7,8 demonstrated to behave as a whisker-reinforced composite. The microstructure of the unidirectionally solidified material consists of aligned needles of A13Ni in a matrix of aluminum. EXPERIMENTAL PROCEDURE Eutectic ingots having a nominal composition of 6.2 wt pct Ni were produced by melting 99.99+ pct A1 and 99.99 pct Ni in recrystallized alumina crucibles in an argon atmosphere. The analyses of the starting materials are listed in Table I. These master heats were cut up? melted by induction heating, and unidirectionally solidified vertically in 1/2 -in.-ID. 6-in.-long graphite crucibles, in a dynamic argon atmosphere. Therma1 gradients in the liquid were determined by measuring the temperature in the melt as a function of apparatus travel distance, as discussed by Kraft and Albright.9 The rate of solidification was assumed to be equal to the uniform rate at which the crucible assembly was withdrawn from the furnace. Ingots representative of nominal growth rates of 2, 5, and 11 cm per hr were produced and the solidification parameters are summarized in Table 11. Ingots used for met allographic analysis were pre-

Jan 1, 1968

By T. Johnston, B. Cox

The results of oxidation and corrosion experiments on niobium in oxygen and steam at temperatures of 350° to 650°C, and in dilute sulphate solutions at 300°C are presented. The oxidation of niobium in oxygen can be explained in terms of a pre-transition period, which obeys an approximately parabolic rate law, and a post-transition period in which a more rapid linear rate is partially stifled by restriction of the gas flow due to the gvowth of the porous outer film. Due to changes in the porosity of the outer layers the restriction presented by the porous outel. film attains a limiting value. Subsequent oxidation obeys a linear rate law and shows an almost linear dependence of the rate on gas pressure. liltimately a second failure of the protective film may take place leading to a further acceleration in the oxidation rate. In water vapor the oxidation of niobium follows a parabolic rate law and does not show a transition to linear kinetics. The higher oxide, Nba05, was usually absent from the NbO/NbO2 film which was formed. The addition of a small partial pressure of oxygen to the water vapo3, resulted in accelerated oxidation according to the normal kinetics for oxidation in oxygen. The oxygen reacted preferentially with the niobium, and the protective oxide film was reformed when all the oxygen had been consumed. This behavior supports the theory that nucleation of Nb205 on the surface of the protective NbO/NbO2 film is the cause of the accelerated oxidation. After oxidation in steam at high-pressure Nb2Os was found in the protective film. The mode of formation of Nb2O5 under these conditions did not produce a change in kinetics, but was thought to explain the comparatively large dependence on pressure of the oxidation rate. The kinetics of oxidation in oxygenated aqueous solutions at 300°C were similar to those for oxidation in oxygen. A penetrating attack on niobium sheet may be related to the second breakaway observed by some investigators of oxidation in oxygen.

Jan 1, 1963

By A. L. Mincher, W. F. Sheely

Mechanical properties of columbium have been studied over the temperature range of -196 to 1093oC. The decreased strengthening influence of cold-work at temperatures below ambient has been interpreted in terms of the Peierls-Nabarro effect. Maxima in the rate of strain hardening observed during tensile testing in the range 250-600°C. have been correlated with interstitial impurities to indicate the temperature ranges at which carbon, oxygen, and nitrogen, respectively, are responsible for strain aging. THE growing need for structural materials for use above the useful service temperatures of the iron-, nickel-, or cobalt-base alloys has caused the refractory metals to be considered as potential engineering materials. These metals, which include columbium, tantalum, molybdenum, and tungsten, are called refractory because the lowest melting point among them,that of columbium, is about 1000°C higher than the average melting temperatures of conventional high-temperature alloys. They are all body-centered cubic transition metals and, as such, their mechanical properties have basic characteristics which distinguish them from the face-centered cubic metals. For example, all show a much steeper rise in strength with decreasing temperature below room temperature than do the face-centered cubic metals, and their mechanical properties are strongly influenced by interstitially dissolved impurities. In order that these new metals may be used efficiently, it is necessary that their characteristics of behavior be fully known. In this paper, the mechanical properties of columbium will be examined over a wide range of temperatures. In particular, the influences of cold-work and individual species of interstitial impurity atoms on mechanical properties will be described, and basic mechanisms which may control the observed characteristics will be explored. EXPERIMENTAL The material used in this investigation was Union Carbide Metals Co. columbium roundels consolidated to four 4-in. diam ingots, three by consumable-electrode arc melting and one ingot by electron beam melting. Impurity contents of the ingots and methods of ingot conversion and treatment are summarized in Table I. The only metallic impurity occurring in any significant quantity was tantalum at about 0.1 pct. Iron, silicon, titanium, and zirconium were each less than 0.015 pct; boron was 1 ppm or less. This should have no appreciable influence on properties. The electron beam melted material, being the purest, will be used as the basis for comparison in the discussions to follow. Tensile tests were conducted from-196 to 1093oC, on both cold-worked and fully recrystallized arc-melted and electron-beam melted columbium using standard 1/4-in. diam, 1-in. long gage length test specimens. A strain-rate of 0.005 in. per in. per min was employed until the 0.2 pct yield strength was achieved and then the strain-rate was increased to 0.05 in. per in. per min for the balance of the test. Samples were protected in an inert atmosphere at tests above 300°C. The tensile properties obtained on the electron-beam melted columbium, E, in both the cold-swaged and recrystallized conditions are given in Fig. 1. The yield strength data of Dyson, et al.,' obtained on recrystallized electron beam melted columbium and the tensile strength data reported by Tottle2 on powder metallurgy columbium are included in Fig. 1. The material used by Tottle had been purified by vacuum sintering. There is excellent agreement between Dyson's data and those obtained in the present investigation. The tensile strengths obtained by Tottle were slightly greater than those obtained in this investigation on electron-beam melted columbium but varied with temperature in a similar manner. Tottle's data showed a maximum in tensile strength near 500°C, as did our data on electron-beam melted material, and also showed a small maximum at 300°C. The significance of these maxima will become evident later in the discussion. The tensile properties of cold-swaged and recrys-tallized arc melted columbium are plotted in Fig. 2. It was found that the properties of the recrystallized arc-melted columbium from all three heats showed very close agreement except at temperatures between about 500" and 800°C. A reason for this range of disagreement will be suggested in the discussion. The generally good agreement, however, attests to the ability of cold-working and subsequent recrystal-lization to erase the effects of the three different primary breakdown procedures and to produce nearly equivalent structures in the samples derived from the three different heats. wesse13 reported tensile data on columbium having interstitial impurity contents between those of the

Jan 1, 1962

By Frank Alfred Fahrenwald

MetallURgical research has discovered many an alloy possessing properties not combined in any single metal, and progress still consists chiefly in the investigation and utilization of alloys. In the case of iron, the demands of automobiles, high-speed machines and high-duty engines have led to the production of special iron alloys which will meet any reasonable specifications in that field. In like manner, the bronzes, brasses and other alloys of copper have been brought to remarkable perfection, and for nearly every industrial purpose some alloy has been , found more suitable than the pure metal. Less complete success has attended the attempt to find substitutes for gold, platinum, and the other precious metals. Indeed, it is not likeiy that a material can be produced which, will possess all the properties of any one of them; yet it is reasonable to hope that, for any given use, the properties required may be found in some less expensive material. Thus, in incandescent electric lamps, the wire passing through the thick glass neck of the bulb was, until recently, almost universally made of platinum, for the single reason that no other known material, suitable as a conductor, had the same coefficient of expansion as glass. But a comparatively recent investigation of the iron-nickel series1 has shown that alloys of those metals maybe produced, the coefficient of expansion of which can be accurately controlled between that of iron or nickel and zero. Thus, in that particular industry, a substitute for platinum has been found. According to statistical reports, not only considerable quantities of gold and iridium, but also more than one-third of the annual supply of platinum, are used (and, in the nature of the case, irrevocably lost) by dentists. Platinum is thus employed in several forms. As a thin foil, it serves various purposes for which its high melting point, pliability, chemical resistance, and other properties—including the ease with which it may be soldered—are invaluable. But it is most extensively used in

Jan 1, 1916