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Jan 1, 1938

NEW MEMBERS The following list comprises the names of those persons who became members during the period Jan. 10 to Feb. 10, 1915: Members AGASSIZ, RUDOLPH Louis, Vice-Pres.,Calumet & Hecla Mining Co., Boston, Mass. AMIDON, RICHARD G., Min. Engr 3659 Girard Ave. N., Minneapolis, Minn. ANDERSON, HECTOR G. S., Min. Engr 323 N. 13th St., Muskogee, Okla. ANDERSON, JOHN CARTER, Petroleum Engr 2307 S. 33d St., Omaha, Neb. CLARKE, ALEXANDER FIELDER, Works Mgr., Firth-Sterling Steel Co., McKeesport, Pa. CROSS, CARLOS GARCIA, Min. Engr Calle Valparaiso 194, Vina del Mar, Chile. DAWSON, THOMAS WILLIAM, Min. Engr., Asst. Chief Engr., H. C. Frick Coke Co., Scottdale, Pa.

Jan 3, 1915

By R. S. Wagner, W. C. Ellis

A new mechanism of crystal growth involving oapor, liquid, crnd solid phases explains many observations of the effect of implurities in crystal growth from the vapor. The role of the impuuitq is to form a liquid Solution with the crystalline tnalerial to be grown from the vapor. Since the solution is n prefevred site for deposition firorti the uapor, the liquid becorrles supersaturated. Crystal growth occurs by precipitatzon from the supersaturated liquid crt tlie solid-liquid zntevfnce. A crystalline defect, such as a screw dislocation, is not essetztial for VLS (vapor -liquid-solid) growth. The concept of the VLS mechanism is discussed in detail with reference to tire controlled growth of silicon crystals using gold, platinum, palladium, nickel, silver, or copper as an implurity agent. RECENTLY a short communication' described a new concept of crystal growth from the vapor, the VLS mechanism. In this paper we present a detailed description of the process and its application to the growth of silicon crystals and we discuss its relevance to existing concepts of .'whisker" crystal growth. Crystal growth from the vapor is usually explained by a theory proposed by Frank2 and developed in detail by Burton, Cabrera, and Frank.3 In this theory a screw dislocation terminating at the growth surface provides a self-perpetuating step. Accommodation of atoms at the step is energetically favorable, and is possible of much lower supersatu-ration than required for two-dimensional nucleation. Crystals of a unique form resulting from aniso-tropic growth from the vapor are "whisker" or filamentary ones. Such crystals have a lengthwise dimension orders of magnitude larger than those of the cross section. For most filamentary crystals both the fast-growth direction and directions of lateral growth have small Miller indices. The special growth form for a whisker crystal implies that the tip surface of the crystal must be a preferred growth site. sears4 proposed that, according to the Frank theory. a whisker contains a screw dislocation emergent at the growing tip. Such an axial defect provides a preferred growth site and accounts for unidirectional growth. The hypothesis was extended by Price. Vermilyea. and Webb," still implying the presence of a dislocation at the whisker tip. They postulated that impurities arriving at the fast-growing tip face become buried while those arriving on the surface of slow-growing lateral faces accumulate and thereby hinder growth. These considerations led to a whisker morphology. There is increasing evidence that most whisker crystals grown from the vapor are dislocation-free. Webb and his coworkers6 searched for an Eshelby twist7 in zinc? cadmium, iron. copper, silver, and palladium whisker crystals. They found unequivocal evidence for an axial screw dislocation in only one element, palladium. However, not every palladium crystal examined contained a dislocation. Observations with the electron microscope have failed to show dislocations in whisker crystals of zinc, silicon.9 and one morphology of AlN.10 Since many whiskers are completely free of dislocations, an axial dislocation does not appear to be required for whisker growth of many substances. A significant advance in understanding whisker growth has been a recognition of the need for impurities. This requirement has been clearly demonstrated for copper,11 iron,13 and silicon9-1 whiskers. For silicon, detailed studies proved conclusively that certain impurities, for example, nickel or gold, are essential. Another pertinent phenomenon which has received little attention is the presence of a liquid layer or droplets on the surface of some crystals growing from the vapor. Crystals in which this has been observed include p-toluidine,14 MoO3,15 ferrites,16 and silicon carbide.'" The liquid layers or globules were considered to be metastable phases, molecular complexes, or intermediate polymers originating from condensation of the vapor phase. The possibility has been suggested that the halide being reduced is condensed at the tip18 or adsorbed on the surface11 of a growing metal whisker, for example copper. The literature on whiskers discloses illustrations of rounded terminations at the tips. These appear. for example, on crystals of A12O3,19,20 sic,21 and BeO.22 For BeO, Edwards and Happel suggested that during growth of the whisker the rounded termination consisted of molten beryllium enclosed in a solid shell of BeO. A recent paper9 on the growth of silicon whiskers contains many observations pertinent to an understanding of the mechanisnl of whisker growth. These observations are summarized as follows. 1) Silicon whiskers are dislocation-free. 2) Certain impurities are essential for whisker growth. Without such impurities the silicon deposit is in the form of a film or consists of discrete polyhedral crystals.

Jan 1, 1965

By N. J. Grant, B. C. Giessen, M. Morris

The slvuclures of alloys in the system In-Bi have been investigated after (levy vapid queuching from the mell (splat cooling) to -190°C. Tuo-phase fields could be suppressed over most of the tota1 concentvalion range; five melastable phases a1, a2, ?, ?1. and ß exisl, of which four have simple elementtike structures. For example, ß has the A5 struclure of white till. Crystal-tographic data and coordination numbers for these phases aye given, as well as addilional information on the equilibrium diagram, where a new phase In5Bi3 teas found. THE phase diagrams of binary combinations of B elements from the groups B2, B3, B4, and B5 are usually of a simple type and show considerably fewer intermediate phases than combinations of these elements with A metals, transition metals, or the B1 noble metals. Aside from phases such as the typical B3-B5 compounds with the ZnS-B3 structure type, few stoichiometric phases are known; among them are In2Bi and 1nBi.l Nonstoichiometric phases include ß (In-Sn), a1, (In-Pb), and the tin-rich ? phases in the In-Sn, Cd-Sn, and Hg-Sn systems.' The first two phases have a close relationship to indium, while the latter group are known to be structurally related to a Sn. Thus, there are generally no immediate experimental data for the correlation of the crystal structures of B metals and B metal combinations with certain monotonously varying parameters, such as the valence electron concentration (VEC), or the average atomic size. Such parameters have been recognized as structure determining, e.g., for the transition 4 Sn — y phase,2,3 where nonintegral valence electron concentrations are encountered. It should be possible to extend such correlations to other binary systems, if nonequilibrium single-phase alloys could be produced over broad valence electron concentration ranges, and if their crystal structures could be regarded as being imposed by their electronic states. It has been shown in the case of the tin-rich 7 phases3 that alloy phases with typical crystal structures can be produced in B metal alloys rapidly quenched from the liquid to -190°C by the splat cooling technique due to Duwez,3-8 and reviewed in Refs. 5 and 6. The In-Bi system was selected because it extends over a valence electron concentration range in which several metastable, nonstoichiometrir phases could be expected to occur. Further, the low melting points of the known intermediate phases, In2Bi and InBi, Fig. 1(a), indicated low binding energies and thus possibly low driving forces for the formation Of the equilibrium structures. EXPERIMENTAL TECHNIQUES AND RESULTS The preparation of the quenched foils followed the practice described in Ref. 3. Master alloys were produced by melting of indium (99.97+) and bismuth (99.99+) in evacuated Vycor capsules or in an inert gas arc furnace; quantities of 20 mg were splat-cooled onto copper and silver substrates held at - 190°C; and crystal structures and lattice parameters were determined on a GE XRD-5 diffractometer using Cu Ka, radiation at -190°C and at room temperature. The duplication of each run with both substrates permitted the elimination of overlap of the substrate diffraction pattern and that of the investigated substance. The XRD patterns were usually taken from sin2 " = 0.03 to 0.35; the substrate was used as a means of internal calibration. The fractional accuracy of the lattice parameters of metastable phases is approximately 10-3 In the following, all percentages are in atomic percent. The stable and metastable phases found after rapid quenching to -190°C are listed in Table I, together with estimated concentration ranges and crystallographic data. The investigated alloys and phases present in them are given in Table 11. Except for the region between indium with 33 and 50 pct Bi, where a revision of the equilibrium phase diagram became necessary to include a new stoichiometric phase In5Bi3, the diffraction patterns taken after heating to room temperature agreed with those expected from the phase diagram, Fig. l(a). This suggests that the new nonstoichiometric phases are not stable at room temperature, thus following the observations made for the y phases based on tin.3 Results concerning the equilibrium phases In2Bi and In5Bi3 and the revision of the equilibrium phase diagram which is made necessary by the inclusion of In5Bi3 will be treated first. The Crystal Structure of In2Bi. Makarov7 had identified In2Bi as belonging to the AlB2-C32 type ; however, in a later paper the structure was revised.8 In2Bio was found to be of the Ni21n-B8ß type,21 with a = 5.496A, c = 6.57.9A, and N = 6 atoms per unit cell.9 This crystal structure was confirmed in the present work; definite evidence for the doubling of the c axis, as compared to the A1B2-C32 type, and for the proposed order structure, was found in the powder pattern. The observed lattice parameters agree well with those of Ref. 8; those measured at -190°C are given- in Table I. The Crystal Structure of In5Bi3. A new, equilibrium, intermediate phase was identified in slow-cooled, as-cast alloys; it was identified as In5Bi3. The structure has been worked out by Giessen and Grant;" lattice parameters at -190°C are given in Table I. This phase is probably identical with "In3Bi2", produced by vapor deposition techniques, but not recognized as an equilibrium phase by Palatnik et a1.11 After completion of the present work, the existence of In5Bi3 has also been demonstrated by superconductivity measurements on In-Bi alloys.20

Jan 1, 1968

By Leonard D. Jaffe

IN recent years, the advantages of tempered martensite as a microstructure for steel parts have been well established. For parts that must not fracture brittlely when loaded at high rates, at low temperatures, or under conditions of combined stress, tempered martensite is especially desirable. One of the factors that determine whether a steel part will have a martensitic structure after heat treatment is the hardenability of the steel. Despite the large amount of recent research, there are still many unsettled basic questions concerning hardenability and its relation to chemical composition, and, indeed, considerable disagreement among investigators in the field. Much of the uncertainty that beclouds the existing knowledge of hardenability arises from the fact that hardenability is still a wholly empirical concept, and has not been quantitatively related to the more fundamental knowledge of isothermal decomposition of austenite. Hardenability is, essentially, a measure of the time required for small percentages of austenite to decompose, during continuous cooling, to pearlite, bainite, proeutectoid ferrite, or proeutectoid carbide. In the practical heat-treatment of steel, also, the decomposition of austenite is usually not isothermal but rather during cooling, or, in general, is not at a single constant temperature. Thus, both hardenability and practical heat treatment involve anisothermal decomposition of austenite. In a previous publication1 the author and his collaborators outlined the principles that govern the relations between isothermal and anisothermal decomposition of austenite, and reviewed the experimental information available in 1945. To avoid repetition, familiarity with that article (Paper 1) will be assumed, and attention given primarily to work carried out or published since 1945. The method generally employed was explained in Paper 1: anisothermal transformation is studied through investigation of the effect of holding austenite at one temperature upon its subsequent decomposition at another temperature. Both temperatures are below the stability range of the austenite. This paper is confined to studies in which only a small amount of transformation occurred at the first temperature. This is the only case of importance in practical heat treatment when an essentially martensitic structure is sought. MATERIALS AND PROCEDURE It was necessary to use different steels for the studies involving proeutectoid ferrite and for those involving proeutectoid carbide, because the two constituents have not been found to form in the same steel. Several steels were tried and rejected

Jan 1, 1947

By R. J. Schilthuis, T. V. Moore

In a previous paper,' the results of some experimental work on the measurement of slippage in the flow of oil and gas mixtures through vertical pipes were presented. The data obtained were correlated and equations were deduced from which the performance of the experimental gas-lift could be predicted with reasonable accuracy. However, attempts to apply the equations to the calculation of pressure drops in actual flowing wells yielded erroneous results. At the time the results of the experimental work were published, no satisfactory explanation could be offered for the failure of the empirical equations to express properly the performance of wells. However, recent work has led to the development of a new hypothesis which presupposes certain conditions affecting the flow of oil and gas in wells. When the proposed equations are corrected to allow for these conditions, an agreement between the observed and calculated performance of the actual wells is obtained which in most cases is quite satisfactory, although it is subject to certain limitations. In this paper, the method of calculating the pressure drop in actual wells is considered, and the application of the method to the design of tubing is discussed. (For nomenclature used in this discussion, see Table 1.) Factors Affecting Slippage and Efficiency At the outset, a few of the principle factors affecting slippage and efficiency in the gas-lift discussed in the previous paper will be reviewed. In the flow of the mixture of oil and gas in a vertical pipe, slippage is the phenomenon of gas moving upward with a. linear velocity greater than that of the oil. Under steady conditions, if given quantities of oil and gas enter the tubing per unit of time, the same quantities of oil and gas per unit time must, on the average, pass every section of the tubing; otherwise, there would be accumulation or depletion of the oil or gas at some sections, and the flow would be unsteady. Therefore, if the gas is to flow at a greater linear velocity than that of the liquid,

Jan 1, 1933

By Thomas E. Garnar

Zirconium and hafnium are curious elements because they are almost always found together in nature. Zirconium was discovered by Klaproth in 1789 and isolated 35 years later by Berzelius. Because hafnium's chemical properties are so close to those of zirconium, it was not discovered until 1923 when Coster and Von-Heresey detected it using x-ray spectrographic analysis. These elements occur most commonly in nature as the mineral zircon (ZrSiO4) and less commonly as the oxide baddeleyite (ZrO2). They also are found as a variety of other silicates. Zircon was identified as a component in alluvial and beach sands in 1895, but it was not produced in any quantity until 20 years later. Zircon is always a coproduct from TiO2 mining and processing. During World War I it was produced as a coproduct of beach sand mining for titanium minerals just south of Jacksonville Beach, FL, and was patented as a refractory. It was not until the 1930s when Zircon Rutile, Ltd. began mining at Byron Bay on the east coast of Australia that zircon was first used as a foundry sand. Later in the 1940s, NL Industries, Humphreys Gold Corp., and E. I. du Pont de Nemours & Co., Inc. began production of zircon sands from fossil beaches in northeast and northcentral Florida. Baddeleyite first became available as a commercial product in 1916, but never in the quantity of zircon. Zircon holds a unique position as an industrial mineral because it is used for both its physical and chemical properties as well as an ore of zirconium and hafnium metals. Australia is the major zircon producer followed by South Africa and the US. Zircon is also produced in India, Sierra Leone, Sri Lanka, Malaysia, China, Thailand, and Brazil. Undeveloped heavy mineral beach sand reserves containing zircon are known to occur in Egypt, Malawi, Senegal, and Tanzania. Locations are shown in Fig. 1. Mineralogy Zirconium and hafnium are always present together in naturally occurring compounds. Most commonly they form as the silicate sometimes containing iron, calcium, sodium, manganese, and other elements. Less commonly they are found as oxides in combination with titanium, thorium, calcium, and iron. Zircon is the most common form. It is extremely resistant to weathering, therefore, often it is present in ancient beach sands and placer deposits. Although resistant to alteration from external sources, it is vulnerable to internal alteration as the result of thorium and uranium substituting for zirconium either in the zircon lattice or in solid solution. Alteration to the metamict state takes place as radioactive emanations from these elements disorder the crystal lattice, accompanied by hydration, reduction in specific gravity, and changes in color. The mineralogy of zircon and baddeleyite and variation of physical and chemical properties are shown in Table 1. The effects of zircon's internal alteration and darkened color can be corrected by heating to 1000°C for 30 min or so. A certain time-temperature relationship makes it possible for decolorization and reordering of the crystal lattice to take place when heating at higher temperatures for shorter periods or at lower temperatures for longer periods. After heating, x-ray diffraction patterns are sharper, the grains may be harder, and except for particles of malacon, the grains will be white or colorless in the absence of grain surface coatings. The color change is only temporary and the particles slowly darken with time. Zircon fluoresces light yellow in shortwave ultraviolet light. If exposed to ultraviolet light for extended periods of time, white (calcined) zircon turns purple. With time the induced color begins to fade and eventually disappears (e.g., calcined Florida zircon exposed to ultraviolet light for 24 hr still retains faint, but discernible, purple color after six months).

Jan 1, 1983

By J. Brian Eby

As is generally understood, the word geophysics means literally ?the physics of the Earth? and the science of geophysics is therefore that which treats of the study and measurements of the various physical properties of the Earth. The broad and general study of the elastic, the gravimetric. or the magnetic properties of the Earth as a whole belongs to the general science of geophysics. The detailed application of this science to rocks of shallow depth and in small areas for the purposes of ascertaining data on their character and structural attitude gave rise to the present well-known science of ?applied geophysics.? Since the discovery of enormous new quantities of oil, gas, and sulphur has been by far and wide the principal benefaction of geo-physics in the United States, this paper will refer only to geophysical methods employed in the search for these particular minerals. The application of methods and appliances originally used for geophysical research to the solution of the practical problems of finding new oil-fields, plus the counterflow or new and highly refined techniques and Instruments from the company and consulting geophysical research laboratories and into non-economic geophysical research, has provided another case of that gen-eral cycle of events which is familiar to all scientists. That this closed-circuit flow or scientific current has been tremendously important to the whole science of geophysics is probably well known to all members of this audience, but the gen-eral status of the exploratory geophysical arts as now used In the search for new oil-fields, the scales on which different methods are being used, the magnitude of the costs involved, and the far greater magnitude of the practical results achieved may not necessarily have come so directly to your attention. It is, I understand, for this reason that this paper has been sug-gested, and I shall seek to provide the information requested by using as case-illustrations those changes in the oil-reserve picture for the United States as a whole, and for the Gulf Coast, California, and Illinois Basin regions in particular, which have occurred in the period of the past 17 years, during which time oil-field discoveries have proceeded at a rate which served to build up known and readily-available (or proven) oil supplies to a reasonable figure, and have dispelled the fears of a serious oil shortage during any period for which valid fore-casts can be made. Not that geophysical-prospecting methods have alone been responsible for this transformation, but they have an indispensable and leading part in the picture of exploration and production-to which geophysics, geology, engineering, and general technical progress have jointly made contribution. So far as the United States as a whole is concerned, its total proven, probable, and possible oil reserves (discoverable and recoverable by then-known methods) were estimated at about nine billion barrels in 1920, whereas proven reserves alone are now com-puted at about 16 billion. In 1920 the driller in ?wild-cat? territory was faced with the knowledge that for every new oil-field opened by a successful well, from 20 to 100 unsuccessful wells would have to be drilled and, in some territories, that the chances for a discovery were really less than one in 100 for new drilling, in contrast to which may be cited the record for the past year in parts of Louisiana where the 67 wells drilled opened 16 new oil-fields, that is to say, where the score of hits to misses was increased to approximately one out of four.

Jan 1, 1940

By J. L. Gillson

In a brief summary of the many occurrences of fluorspar in our western states, it is not possible to go into detail in regard to the geology, mining and milling methods, and reserves about individual deposits. Rather a broad review is made of the occurrences and an analysis of how the western deposits may fit into our future domestic economy is presented. General Statement on Fluorspar Situation Fluorspar has been used for years as a flux in the manufacture of basic open-hearth steel, in foundry cupolas for melting pig iron, in the manufacture of opalescent glass and in the preparation of hydrofluoric acid. In 1880 the annual production of fluorspar in the United States was around 4000 tons per year. By 1900 it was up to 21,656 tons and between 1902 and 1908 it averaged about 40,000 tons annually. Prices were then so low, by present standards, that it seems impossible to believe now that mining could have been performed profitably at the price levels then prevailing. In 1890 fluorspar sold at the mines for $6.70 per ton, in 1901 for $5.81, in 1916 for 85.92. When the United States entered World War I, flyorspar production and price skyrocketed; the production reached 263,817 tons in 1918, with prices above $20.00 per ton, and prices were even higher in 1919 and 1920. After 1920, the domestic production fell from the 1918 level to about 125,000 tons annually and the average price dropped back to about $18.00 per ton. By 1935 the average price had fallen to $15.00, but in 1940 with a rising demand the average price of all grades had gone back up to $20.31. Today it is 75 per cent higher than in 1940 and presumably the price of acid grade at .least would be even higher if it were not for price ceilings. The first subsequent year that the domestic production exceeded that of 1918 was 1941, and the 1944 production is expected to exceed 400,000 tons, or over one and a half times that of 1918. In five-year periods, average production and imports were as are shown in Table I. Many people concerned with the consumption of fluorspar believe that the postwar period ahead will show a repetition of price trends of the last such period. They believe that imports will be again an important factor in the available supply and the price will fall back gradually toward the prewar level. The following basic factors are pertinent in analyzing this conclusion:

Jan 1, 1948

By H. D. Hoskold

This paper is presented in fulfillment of the promise made in my paper, " Remarks upon Surveying-Instruments,"" etc., and much of the material which would constitute an appropriate introductioil here is omitted, because it has been already published by the Institute, in connection with my own contributions- or those of Mr. Scott and others, in vols. xxviii. to xxxi. of the Transactions, and in the special Institute volume on Mine-Surveying Instruments. In these preceding publications will be found, for instance, descriptions of the writer's " miner's transit-theodolite" of 1863,† and his later " angleometer,"‡ both of which were steps of the progress in engineering instruments and methods which originated in the work of Bourns, before 1842, on the " BoxTunnel " of the Great Western railway in England, in which he had to make connections by direct telescopic sights down the shafts. About 1870 the writer devised a practical and much superior plan, and made detailed drawings for an instrument to meet all the conditions he had proposed prior to that year. The detailed plans were communicated to a celebrated optical firm in London; but, owing to their loss (in Paris or Germany, it is believed) and to other reasons, the matter was, for the time, allowed to lapse. Following upon Bourns's idea, my friend, the late Mr. Beansland, introduced, in 1856, a new system and a portable astronomical instrument.§ Such instruments, however, were neither common nor convenient, and did not come into general use among engineers.

Jan 1, 1902

By J. L. Gillson

In a brief summary of the many occurrences of fluorspar in our western states, it is not possible to go into detail in regard to the geology, mining and milling methods, and reserves about individual deposits. Rather a broad review is made of the occurrences and an analysis of how the western deposits may fit into our future domestic economy is presented. General Statement on Fluorspar Situation Fluorspar has been used for years as a flux in the manufacture of basic open-hearth steel, in foundry cupolas for melting pig iron, in the manufacture of opalescent glass and in the preparation of hydrofluoric acid. In 1880 the annual production of fluorspar in the United States was around 4000 tons per year. By 1900 it was up to 21,656 tons and between 1902 and 1908 it averaged about 40,000 tons annually. Prices were then so low, by present standards, that it seems impossible to believe now that mining could have been performed profitably at the price levels then prevailing. In 1890 fluorspar sold at the mines for $6.70 per ton, in 1901 for $5.81, in 1916 for 85.92. When the United States entered World War I, flyorspar production and price skyrocketed; the production reached 263,817 tons in 1918, with prices above $20.00 per ton, and prices were even higher in 1919 and 1920. After 1920, the domestic production fell from the 1918 level to about 125,000 tons annually and the average price dropped back to about $18.00 per ton. By 1935 the average price had fallen to $15.00, but in 1940 with a rising demand the average price of all grades had gone back up to $20.31. Today it is 75 per cent higher than in 1940 and presumably the price of acid grade at .least would be even higher if it were not for price ceilings. The first subsequent year that the domestic production exceeded that of 1918 was 1941, and the 1944 production is expected to exceed 400,000 tons, or over one and a half times that of 1918. In five-year periods, average production and imports were as are shown in Table I. Many people concerned with the consumption of fluorspar believe that the postwar period ahead will show a repetition of price trends of the last such period. They believe that imports will be again an important factor in the available supply and the price will fall back gradually toward the prewar level. The following basic factors are pertinent in analyzing this conclusion:

Jan 1, 1948

By A. Hellawell

Specitlrens of the Al-Ge eutectic alloy have been frozen unidivectionally at rates between 2.5 x 10-6 and 2.5 x 10-4 cm per sec and the structure examined by optical and X-ray methods. There is no epitaxial relationship between phases, the aluminum having random orientation and the germanium a preferred (011) fiber textuve. Lamellar colonies which are BINARY eutectic alloys occur between either silicon or germanium with the metals aluminum or silver. common in this alloy are constructed from axial and nonaxial (111) plates of germanium which are related by a variety of twin configurations. Irregular or globular regions of the microstructure are composed of continuous single crystals of each phase, the germanium being heavily twinned. There is limited solid solubility in these systems, and the eutectic phases all involve diamond cubic with fcc crystal structures. In the microstructures of these eutectic mixtures the silicon and germanium crystals exhibit an almost infinite variety of shapes which are notably sensitive to

Jan 1, 1968

By G. Sachs, E. P. Klier, W. Beck

HYDROGEN embrittlement of steels has recently attracted much attention because it is asso- ciated with a variety of failures, especially those of aircraft structural components.' For instance, one of the undesirable properties of the ultra-high strength steels used for landing gears is their pronounced susceptibility to hydrogen embrittlement during plating. The presence of hydrogen in these steels becomes particularly apparent through delayed or sustained load failures of parts which have been subjected to low loads for an extended time. A number of variables are involved in causing a reduction of strength and ductility through hydrogen

Jan 1, 1957

By C. W. Lawr

THE ores mined by the Santa Gertrudis Co. at Pachuca, Mexico, are mainly silver-bearing; they also yield some gold and carry a little copper. Strong cyanide solutions are used to dissolve the silver and gold, and the mechanical loss of cyanide at the tailings filter has been considerable. Prior to the year 1923, the pulp, after agitation, was given a 35 to 37-min. wash with barren solution in a Butters-type leaf filter; the discharged slime cake was repulped and pumped into eight Merrill self-sluicing slime presses in which the slime was given a further wash with barren solution for 25 to 35 min., followed by a 10-min. water wash. At that time the barren solution titrated around 0.350 per cent. free KCN and 0.500 per cent. total KCN. (Aero brand cyanide is used.) It can readily be seen that a 10-min. water wash would leave considerable cyanide in the filter cake, which of course was a total loss. This averaged 0.522 kg. (1.15 lb.) KCN per ton of solution. As the daily discharge to. the dam was 1600 tons1 of slime of a 2: 1 ratio of liquid to solid, the value of this mechanical loss of cyanide was an important item and its recovery held alluring possibilities.

Jan 1, 1929

By John F. Elliott, Robert D. Pehlke

The rate of reaction of nitrogen with liquid iron and with binary alloys of iron and Al, Cb, Cr, Ni, O, S, Si, and W were measured. The surface active elements, oxygen and sulfur, decrease the rate markedly. The other alloying elements have very little effect on the rate except when they function as deoxidizers, The rates of absorption and de-sorption were found to be equal. Several possible reaction mechanisms which may control the rate are considered. In order to describe completely the behavior of nitrogen in steelmaking processes, the mechanisms of mass transfer between the gaseous and liquid phases, nitrogen and iron, respectively, must be understood. A kinetic study to determine the nature of these mass transfer processes was undertaken, and the results of that investigation are presented in this paper. Specifically, the study was directed toward determining the influence of alloying elements on the rates at which pure nitrogen gas at constant pressure is absorbed and desorbed by liquid iron solutions: A previous paper1 reported measurements of the equilibrium solubility of nitrogen in liquid binary iron alloys. The experimental data are presented and discussed first and then several possible rate limiting mechanisms are considered. PREVIOUS RESEARCH The results of several investigations on the rate of absorption of nitrogen by liquid iron and iron alloys have been reported.2-14 There is little agreement on the rate coefficients among these studies because of the influence of geometry on the experimental system and of the purity of the liquid iron. The rate was found to be influenced by alloying content for the binary liquid iron systems: Fe-Al,2 Fe-C,4,6 Fe-Cr,4,5,8 Fe-Mn,5 Fe-Ni,5,8 Fe-O,9,10 Fe-O,9,10 and Fe-Si.2,6,7,11 Several investigators12"15 have reported that the rate of nitrogen absorption is increased in a reducing gas mixture and decreased in an oxidizing atmosphere. A mechanism for the retardation by oxygen of the absorption of nitrogen has been described by Naeser18 as the formation of an iron oxide film at the gas-metal interface. The film slows the absorption rate until it disolves in the metal, thus permitting nitrogen to enter the liquid iron. Karwat17 discussed the influence of oxygen in terms of the formation of gaseous molecules of nitrous oxide which represent a higher energy form than the nitrogen and oxygen or the oxidizing gas and consequently constitute an energy barrier for the process. Fischer and Hoffmann10 showed that the oxygen markedly reduces the rate of absorption of nitrogen, the rate constant being one order of magnitude smaller in liquid iron containing 0.15 to 0.24 pct 0 as compared to that in melts containing 0.001 to 0.02 pct 0. Although Chipman and Murphy2 reported that the rate of absorption of nitrogen in liquid iron was essentially independent of temperature, Eklund3 found that the rate increases strongly with increasing temperature as did Kootz4 and Saito.5,6 Karnaukhov and Morozov7 also reported a large temperature coefficient, but related it to increased stirring at higher power inputs in an inductively heated system. All of the authors above have treated their results assuming that the reaction is diffusion controlled, that the surface reaction is in equilibrium with nitrogen gas, and that a "first order" reaction takes place. Karnaukhov and Morozov7 and Humbert; who studied the rate of absorption in a closed system by observing pressure changes in the system as a function of time, concluded that their results best fit a diffusion-type analysis. This was further verified by von Bogdandy, Dick, and stranski18 and Fischer and Hoffmann10 who found the initial rate of

Jan 1, 1963

By R. T. DeHoff, F. N. Rhines

The problem of determining the number of particles of a phase distributed randomly in unit volume c an opaque matrix from measurements made on random plane sections is closely investigated. A formalized derivation for the general case is presented. Applications of this formal result are made to specific types of aggregates dispersed in a matrix; circles, particles with flat circular ends, cylinders, and constant shape aggregates of ellipsoids of revolution. Quantitative measurements of the average geometric properties of these aggregates are developed. In 1953 R L. ullman' developed a technique for determining, from measurements made on random plane sections, the number per unit volume, Nv, of particles imbedded in an opaque matrix. Using meas urements previously developed for volume fraction, vV,' and surface area per unit volume, .SV,= he was able to determine average volume, average surface area, and average dimensions of particles, independent of size distribution, for spheres and circular disks,' as well as for uniformly sized cylinders of any axial ratio.4 The technique is mathematically rigorous for the cases studied. Recent studies of this problem have yielded rigorous solutions for the general case of cylinders, permitting evaluation of NV independent of size distribution and with all axial ratios intermixed. Generalization to shapes having flat, circular ends has been deduced. A solution has also been obtained for the ellipsoid of revolution, independent of size distribution, but requiring a constant axial ratio in the generating ellipses. In the following derivations, as in Fullman's work, it is assumed that the problem is purely a combination of geometry and probability theory,that is,eithe the particles to be measured are imbedded randomly in the matrix, or a sufficient number of random plane sections are taken to make the sample representative. A relationship exists between the number of par- ticles of a given size and shape that may be situated in unit volume (Ny) and the number of intersections a random plane can be expected to make with these particles (Na). It is the purpose of the following section to derive this relationship. The probability of Intersecting Convex Bodies. Consider a convex, closed surface, that is, one for which no two surface normals point in the same direction, situated at some arbitrary position and orientation in a cube of material that is one unit long at each edge. It is not necessary to assume that this surface is symmetrical. Let planes be constructed in the cube parallel to the top face and at random distances from it. Those planes which lie between the two planes which are just tangent to the top and bottom of the surface will intersect it. The probability that a plane will intersect the body may be defined as the limit of the fraction of planes that lie between the two tangent planes as the total number of planes constructed becomes infinite. This fraction, in the limit, is equal to the distance between the two tangent planes, DV, divided by the total length over which planes are constructed, which has been taken as unity. If the body is now rotated to a new orientation, applying the same argument, the probability of intersection is again numerically equal to the distance between tangent planes. Let DV ($, 0) be defined as the distance between tangent planes of a convex body as a function of orientation, Fig. 1. The probability, Pr, of intersecting the body with a randomly oriented and randomly positioned plane, is then equal to the average value of DV (0, $) over all possible orientations. It may be easily shown that for a system of spherical coordinates the probability of finding an orientation between Q and Q + de, $ and $ + d$ is (1/4n) sin $ dB d$, so that This relationship may be applied to each body in an aggregate of convex bodies. In particular, if the bodies in an aggregate are classified according to size and shape, and the ithsuch class is considered, Eq. 111 may be applied to this entire class, the probability of intersecting any body in this class being

Jan 1, 1962

By Sidney A. Swensrud

This paper reviews the subject of gasoline margins, discusses some of the more current marketing problems, and gives some consideration to the main urges to marketing expansion, or overexpansion, in the oil industry. Margins In an earlier paper1, some comparisons were shown for the years 1929, 1930 and 1931, of the margin between the refinery cost of gasoline in Oklahoma, the market price in Oklahoma, and the average retail price in 50 representative cities of the United States. These figures indicated a small margin for the refiner in 1929 between his gasoline cost and the wholesale price, which, however, had turned into a loss by 1931. The margin between either refinery costs or wholesale prices and the retail price in the 50 cities showed a continuous decline during the three years. We have now worked out these figures on a similar basis for a longer period—from 1928 through 1936. The figures for refinery gasoline cost are slightly different from those in the earlier study, owing to the use of

Jan 1, 1937

By B. C. Allen

Grain-boundary gvoocing was studied irz chronziu?n. molybdenum, tungsten, and the solid-solution alloys, Cr-35Re. Mo-33Re, and W-25Re at 0.6 to 0.9 of the absolute liquidus temperature under an inevt atmosphere , foveign nzetal zlapor, and liquid metal. The controlling mechanism of matter transport was deduced frolr groove size and shape. kinetics of growth, and cotnparisoz with theoretical relatiotzships derived by Mullins. Grooves in chowzizon formed prittzarily by volume diffusion tkrongk kelium or argon at 1 atm pressure and by e1)apovation-condensatiotz in a static vacuum. Groozles in the other nzetals and alloys forrned priniarily by sirface diffusion, the coefficients of which were calculated. Carbon was found to decrease the acti7:ation energy for surface diffusion on molybdenun. Sitrface diffusizities weve sinzilav for iWo-0.0ZC and Mo-33Re. The presence of about 1 -?nm pressure of silver or tin vapor did not affect the neckanis)n of grooz;e formation. In liquid titz or silz:er, pain bolindary gvooves formed by zolume diffusion in the liquid. BASED on theories of ullins," the mechanisms of grain-boundary grooving have been determined for low-melting metals such as copper in an inert atmospheres or in liquid lead.4 The purpose of this investigation was to study grain-boundary grooving in the refractory Group VI-A metals, chromium, molybdenum, and tungsten, and the bcc solid-solution alloys, r-35e, 0-33e,= and -25e,' at 0.6 to 0.9 of included to see whether Mullins' theories were applicable to them as well. EXPERIMENTAL WORK The materials chromium, molybdenum, tungsten, Cr-35Re, Mo-33Re, and W-25Re were in the form of 0.050-cm-thick sheet assaying 99.98 pct or better. The nominal carbon level was generally 30 ppm. The oxygen + nitrogen + hydrogen content was -50 ppm. Mo-33Re and W-25Re were prepared by powder-metallurgy methods and supplied by Chase Brass and Copper Co. The remaining materials were arc-cast. Chromium and Cr-35Re were prepared at Battelle by arc melting, extruding, swaging, and rolling. Mo-0.003C was supplied by Climax Molybdenum Co., and Mo-0.02C and tungsten by Universal Cyclops Corp. As a source of liquid metals, tin and silver granules assaying 99.98 pct were used. Spectrographic analyses indicated the presence of -100 ppm each of iron and silicon. Vacuum melting reduced the combined gas content to c5 ppm (2.60,, 0.9N2, 0.4H2 in tin and l.602, 0.7N2, and c0.04H2 in silver). Specimens were prepared for grain-boundary grooving. Coupons 0.5 by 1.5 cm with a small hole in one end, or substrates 1.5 by 1.5 cm, were cut from sheet. The specimens were annealed in containers of the same material to provide a vapor-solid equilibrium as well as to protect them from gaseous impurities. Outgassing was done at 2 x 10"5 mm for 15 to 30 min at 1150°C for chromium and Cr-35Re, 1750°C for molybdenum and Mo-33Re, and 2600°C for tungsten and W-25Re. Then recrystallization to a stable grain size of about 0.5 mm was accomplished by annealing at least 1 hr at 1600°C for chromium, 1800°C for Cr-35Re, 2350°C for molybdenum, and 2300°C for Mo-33Re in a rhenium-element resistance furnace under 1 atm of static argon or helium. The atmosphere was gettered by tantalum radiation shielding. Tungsten and

Jan 1, 1967

By John L. Lamont, Walter Crafts

STUDIES of the effect of composition of steel on hardenability by Grossmann,1 and as-quenched hardness by Field2 and by the authors,3 have made it possible to predict the results of quenching when the composition and cooling rate are known. In order to extend the application of the hardenability calculation to the quenched and tempered condition in which steel is finally used, a survey has been made of the hardness changes caused by tempering. From this study a method has been developed for the prediction of hardness and tensile strength of steel in the tempered condition. The method of calculation was developed from Rockwell C hardness tests on quenched and tempered Jominy specimens and is expressed in Rockwell C hardness units. It is of an additive type in which the degree of softening from as-quenched hardness is estimated. Tempered properties may be calculated within about plus or minus 5 Rockwell C hardness or plus or minus 15,000 lb. per sq. in. tensile strength. This degree of accuracy is less than that necessary for the control of heat-treatment, but is adequate for the comparative evaluation and selection of alloy steels. The formula indicates that tempered hardness is primarily dependent on as- quenched hardness and, as in the hardening reaction, the progress of tempering is controlled mainly by the carbon content- Alloys tend to retard softening by a secondary hardening mechanism in which the alloy appears to migrate from ferrite to the carbide phase. The factors for the effects of alloys in tempering vary so much from the effects of alloys in hardening that different steels of equivalent hardenability may, after lie heat-treatment, differ considerably in tensile strength. PROCEDURE In developing the method for calculating tempered Rockwell C hardness, simple and complex steels were tested over a range from 0.08-to 0.65 per cent carbon and up to 2.68 per cent manganese, 2.18 silicon, 3.50 chromium, 4.94 nickel, and 1.06 molybdenum. The steels were made as small induction-furnace heats at the Union Carbide and Carbon Research Laboratories, Inc. The accuracy of the method was finally checked on a variety of carbon, low-alloy and high- alloy types of heat-treating steels produced under commercial conditions. The method was based on a study of tempered Jominy bars, and its validity was tested by correlation with the center hardness and tensile strength of oil-quenched and tempered bars from ¼ to 4 in. in diameter. The method of calculation was derived from the differences in Rockwell C hardness between as-quenched and quenched and tempered Jominy specimens. Prenormalized Jominy hardenability specimens quenched from a normal temperature for austenitization were used to obtain a range of as-quenched Rockwell C

Jan 1, 1946

By N. Plint, E. T. Pinkney

Copper segregation developments within the Anglo American Group are described with particular reference to the work of the TORCO Project Team. Some radical differences have been adopted in the mechan-ical approach as compared with methods used by previous workers. Most important among these are the following: (1) The heating unit is a fluidized-bed roaster. (2) A moving bed segregation chamber is used in which a packed bed of heated ore, to which reagents have been added, moves slowly downwards under gravity and is discharged at a controlled rate by means of a suitable valve mechanism. (3) The quantities of reagents used (sodium chloride and some form of carbon) are only a small fraction of those recommended by other investigators. (4) Retention times of only 2 min have been satisfactory for the complete segregation of many types of ore. Project TORCO is the code name given by Anglo American Corp. of South Africa, Ltd., to the investigation undertaken in Zambia to develop a plant capable of treating large tonnages of refractory copper-bearing ores by the segregation process. The process has now been under investigation for six years (1960-66) and during that period work has progressed from bench-scale laboratory tests through small-scale pilot-plant work to a 500-tpd commercial pilot unit. Test work has been carried out mainly on the ores of the Zambian Copperbelt and results have been encouraging. Recoveries on the order of 90% have been obtained on all Copperbelt ores tested with high concentrate grades. PRELIMINARY INVESTIGATION Laboratory scale segregation test work on Nchanga banded sandstone ore and oxidized ore from Kansan-shi was originally conducted by Professor Maurice Rey. SociCtC Miniere et Mktallurgique de Pefiarroya, in 1957. Both ores responded favorably to the process. In November, 1960, the consulting engineers of Anglo American Corp. of South Africa, Ltd., initiated preliminary investigations on the application of the segregation process to Copperbelt ores. In early laboratory work, samples were heated in a closed, externally heated tube furnace for one hour at temperatures ranging from 800 to 830°C. The free moisture content of the ore feed was 4% and reagent additions were 0.5% salt and 1.0% coal. Both salt and coal were pre-crushed to -48 mesh Tyler.* All samples except an ore from the Bancroft mine responded well to the process and recoveries of over 90% were obtained. The presence of dolomite was responsible for the relatively poor recoveries from the Bancroft ore, as tests on one of the other ores with additions of calcite or dolomite confirmed. Recoveries dropped from 94 to 45% Grades of all the rougher flotation concentrates produced were low at 10-15% copper. The laboratory investigation was then followed up on a pilot-plant scale. An attempt was made to carry out the segregation process in a coal-fired 5-ft-diam fluidized-bed roaster. The feed consisted of a banded sandstone from Nchanga to which 0.5% sodium chloride had been added. Reducing conditions were maintained in the roaster by the addition of coal in excess of that required for heating the feed. The excess coal and added salt constituted the segregation reagents and the temperature of the bed was held at approximately 750°C. Recoveries of copper and grades of concentrates were low. The reasons for lack of success were: (1) The reaction is a gaseous one and a fluidized-bed roaster is therefore unsuitable as a segregation unit. (2) Coal in excess of that required for heating was introduced into the fluidized bed and under these conditions some of the copper would be reduced in situ. The term "reduced in situ" is used here to describe any copper mineral reduced to the metallic state in its original site within the ore particles. If this copper is to be recovered by subsequent froth flotation it must first be liberated from the gangue by grinding or some other method which, in practice, is usually not feasible on ores of this type.

Jan 1, 1969