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By Philip Schane

THE subject of steel cleanliness has always been a major one in the steel industry and much study and effort have been expended toward improving the cleanliness of steel and meeting the ever increasing demands of customers for steels that will give better performance in service and permit economies in design and efficiency of the final product. Sometimes wee may feel that-these demands are unnecessarily stringent, and probably this is true in some instances. However, the pressure for higher quality has acted as a stimulus toward improving quality and, therefore, has tended to promote progress. In this paper, the whole subject off cleanliness is covered in a general way. In the discussion' on steelmaking practices, remarks have been limited to basic electric- furnace practice in the making of alloy steels.

Jan 1, 1947

By Ed Van Eeckhout

As part of a U.S. Bureau of Mines-sponsored project on the utilization of "stiff" backfill to minimize potential rock burst hazards, a finite element study was undertaken to predict stresses and displacements around a stope mined up from the 5400 level of the Sunshine mine, Kellogg, Idaho. This stope was to be backfilled using a high-modulus fill. In preparation for that configuration, certain instrumentation was installed near the 5400 level to monitor stress changes. Due to untenable economics, only 2 cuts of the stope were ever made. This paper presents the results of the instrument readings taken during the first cut and compares them with the numerical predictions, as well as presents the modeling results of closure and fill stresses in the stope if it had been mined.

Jan 1, 1984

By Arnulf Muan, Klaus Schwerdtfeger, L. S. Darken

The equilibrium ratios CO/CO, of. a gas pharse coexislitrg with selected oxide phase assemblages of the system "FeO"-MnO-SiO2 and metallic iron have been determined at 1150°C. The data obtained are combined wilh the thermodynamic data on fayalite (Fe2SiOi) and "FeO"-MnO solid solutions to derive the actiuity-coiHpQsiUon relations for the various oxide components of the olivine (Fe2SiO4-,lIn2Si04) and pyroxenoid (standard free energies of formation of ferrosilile (FeSiO,), tephroite , and rhodonite from their oxides have been evaluated. In the Appendicc~s by Darken and Schivcerdtjeger the ideal solution law for solid deri oed. THE quaternary system Fe-Mn-Si-0 is of interest in many important phases of iron- and steelmaking. For instance, reduction in the blast furnace of ores containing Fe-Mn silicates, deoxidation of liquid steel with Mn-Si alloys, formation and subsequent alterations of oxide inclusions in steels, and the oxidation of manganese- and silicon-containing steels during processing are all governed largely by the thermodynamic relations existing in the system Fe-Mn-Si-O. Although the equilibria between liquid iron and Fe-Mn silicates have been studied in detail previously,' experimental data are lacking for equilibria among the solid phases. The present paper provides such data for a selected temperature, 1150°C. I) PREVIOUS WORK The general feature of subsolidus phase relations in the system iron oxide-manganese oxide-silica under strongly reducing conditions is known.' Fig. 1 represents an isothermal section at 1150°C. The phases present, in addition to silica, are three solid-solution series, viz.. the oxide solid-solution series "Fe0"-MnO (manganowiistite), the orthosilicate solid-solution series Fe2SiO4-Mn2SiO4 (olivine), and the metasilicate solid-solution series FeSi03-MnSi03 (pyroxenoid). The "FeO"-MnO solid solution is continuous between the two end members wustite and manganositeV3 as is the orthosilicate series between the two end members Fe2SiO4 and Mn2 SiO4. 4 The metasilicate solid solution, on the other hand, extends only part way from the MnSi0.l end member toward FeSiO because the latter end member is unstable relative to the phase assemblage fayalite + silica. The letters a through m in Fig. 1 identify end members of the individual solid phases dealt with [for instance, c designates fayalite (FeZSiO4) in equilibrium with wustite, e designates fayalite in equilibrium with silica, and so forth]. In addition to the phase relations there are some thermodynamic data available for the end members of the silicate solid solutions and for the "FeO" -MnO solid solution. The free energy of formation of fayalite (Fe2Si04) from its oxide components has been studied by several investigators. Unfortunately, the data obtained show considerable discrepancies. According to recent tabulations by Kelley, the change in standard free energy Affn for the reaction

Jan 1, 1967

By Donald C. Violetta

LIMITATIONS of the sintering process as applied to the agglomeration of fine iron-ore concentrates are related directly to the sizes and aggregating properties of the ore particles. A normal sintering mixture is composed predominantly of material which ranges in size from 5/8 in. to 100 mesh, whereas concentrate is composed of material which ranges in size from 100 mesh to less than 10µ. Unless the concentrate has high aggregating properties, it is quite impervious to a gas stream and, as such, inhibits the capacity and operability of the conventional sintering process. Material has Poor Aggregating Properties Aggregating properties, in this case, may be defined as the ability to form small agglomerated fragments or accreated masses by a normal mixing action, and the ability to maintain these shapes during drying and firing. Coarse-screened ores are a natural aggregate, and fine, slimey ores have good aggregating properties. However, specular-hematite flotation concentrate has a very low tendency to aggregate, due to its particle sizes, shapes, and surface chemistry and, as such, is readily air borne in a gas stream when dry.

Jan 3, 1958

By Frederick Rhines

IT has been shown elsewhere1 that the data on the rates of diffusion in solid metals are fragmentary and in many cases unacceptable. As a result, relatively little is known concerning the factors determining rates of diffusion and the variations in these rates with temperature. The first form of Fick's law (equation 1 below), ? in which the diffusion coefficient D is assumed invariant with composition, has been recognized for many years as only an approximation. The differential equation representing the second form of Fick's law (equation 4 below) has only recently been integrated by Matano,2 and unfortunately only in cases where a full diffusion-penetration curve (concentration-distance curve) has been obtained can the Matano solution be applied. The proper analysis of diffusion data is thus confined to the data of Grube and Jedele and of Jedele.§ These data are essentially for one temperature alone and do not furnish any information on the variation of the activa-tion heat of diffusion, Q, with concentration: no information exists on the variation of Q with concentration within a singles olid solution field. Much of the argument concerning the properties of metals that deter-mine D and Q has been drawn from data in which variations of the quan-tities with concentration are unknown, for these data- have been taken from experiments that could not furnish this information. Speculation concerning the properties of metals that may be effective in determining D and Q on the basis of data in which the chosen D and Q values are averages over wide concentration ranges of values at particular concen-trations, ranges often of 100 per cent, is likely not to be fruitful.

Jan 1, 1938

By C. C. Singleterry, D. L. Katz

The critical phenomena have been studied during the past century but our knowledge of the critical temperatures and pressures of complex hydrocarbon mixtures still is very limited. The critical temperatures and pressures of pure substances have been examined in large numbers120 and in great detail.11.17 No experimental determinations of the critical phenomena have been reported on such complex hydrocarbon systems as a reservoir fluid. The critical temperature is defined by Taylor18 as follows: "there is some temperature for each gas above which the gas cannot be liquefied. This temperature is called the critical temperature." The critical pressure of a pure substance is the vapor pressure at the critical temperature. It should be noted that these definitions refer to a given substance in the pure state and do not mean that the pure substance cannot be liquefied in the presence of a second constituent. The normal procedure for obtaining the critical temperature of a substance is to heat it in a glass tube 1,20 under pressure until the meniscus between the liquid and vapor phase disappears, although other methods, especially for mixtures, have been used.13,14 However, when considering oil and gas reservoirs, it is more enlightening to consider a critical phenomenon that occurs when a mixture of oil and gas are compressed at a reservoir temperature until the meniscus disappears because the two phases become equal in composition. This conception, along with erroneous applications of the definition of the critical phenomena of a pure substance to that pure substance when it is part of a complex mixture, has caused confusion even among persons familiar with the classical theories. The purpose of this paper is to discuss the critical phenomena of pure substances and mixtures and to report experimental data on a mixture of

Jan 1, 1939

By C. C. Singleterry, D. L. Katz

The critical phenomena have been studied during the past century but our knowledge of the critical temperatures and pressures of complex hydrocarbon mixtures still is very limited. The critical temperatures and pressures of pure substances have been examined in large numbers120 and in great detail.11.17 No experimental determinations of the critical phenomena have been reported on such complex hydrocarbon systems as a reservoir fluid. The critical temperature is defined by Taylor18 as follows: "there is some temperature for each gas above which the gas cannot be liquefied. This temperature is called the critical temperature." The critical pressure of a pure substance is the vapor pressure at the critical temperature. It should be noted that these definitions refer to a given substance in the pure state and do not mean that the pure substance cannot be liquefied in the presence of a second constituent. The normal procedure for obtaining the critical temperature of a substance is to heat it in a glass tube 1,20 under pressure until the meniscus between the liquid and vapor phase disappears, although other methods, especially for mixtures, have been used.13,14 However, when considering oil and gas reservoirs, it is more enlightening to consider a critical phenomenon that occurs when a mixture of oil and gas are compressed at a reservoir temperature until the meniscus disappears because the two phases become equal in composition. This conception, along with erroneous applications of the definition of the critical phenomena of a pure substance to that pure substance when it is part of a complex mixture, has caused confusion even among persons familiar with the classical theories. The purpose of this paper is to discuss the critical phenomena of pure substances and mixtures and to report experimental data on a mixture of

Jan 1, 1939

By Ronald L. Longwell

PROPERTY LOCATION Located in the Copper Creek area of the Galiuro Mountains, the Old Reliable is on ground first claimed for mineral value during the Civil War. The deposit was mined sporatically from 1880 to 1919 and again in 1953 and 1954, with a total of about 30,000 tons of ore removed. The ore body is a near vertical breccia pipe containing approximately 4,000,000 tons of 0.80% copper with mineralization occuring as chalcocite, chalcopyrite, malachite, chalcanthite, and chrysocolla. The host rocks are extrusive lavas of cretaceous age which were intruded and mineralized by Copper Creek Granodiorite, which is Laramide in age. The ore zone, which occurs on the toe of a ridge, is about 300 feet by 600 feet in plan, with the bulk of the deposit extending from the surface to a depth of 500 feet.

Jan 1, 1974

By Thomas M. Drown

ZING is, as is well known, very brittle at a temperature of about 210' C. (410' F.), and may then be readily pulverized in a mortar. By sifting it may be obtained of uniform grain. I have been accustomed to prepare products passing through 40, 60, and 80-mesh sieves, and also by bolting through a fine handkerchief. The principal analytical uses to which I have hitherto applied this material are to the reduction of iron directly from the ore by heating it with the pulverized zinc, and the reduction of ferric to ferrous compounds in solution. In the first case the pulverized ore, 0.5 gram or less, is intimately mixed with about ten times its weight of the pulverized zinc (the finer the zinc the better), in a porcelain crucible, and this mixture is covered with about the same amount of zinc. The crncible is then heated at the top of the flame of a Bunsen bhrner, at a dull red heat, for about ten minutes. The crucible should not be covered. When cool, the crucible, with its contents, is placed in a flask treated with hot dilute sulphuric acid, and brought quickly to a boil. The zinc and reduced iron are dissolved in a few minutes and the flask is then tightly corked and allowed to cool. When cool, the iron is directly titrated by potassium permanganate.

Jan 1, 1879

Prof. Mathesius analyzes the running of Howland's furnace No. 19, according to the method described by him in Stahl and Eisen, 1916, Nos. 30 and, 31, and in his work "Die physikalischen und chemischen Grundlagen den Eisenhüttenwesens" (Spamer, Leipzig). By assuming 500 Cal. lost from the hearth by radiation and cooling water per kilogram of pig iron made, a throat-gas temperature of 600° C., and taking the ratio of C02/CO as 0.64, he finds that his diagram would show 0.68 kg. of carbon oxidized per kilogram of pig iron, while Howland gives 0.66 kg. He expresses himself as well satisfied with this test of the accuracy of his theory. Making the further assumption that the heat losses from the shaft are 1,000 Cal. per kilogram of pig iron (twice as

Jan 5, 1917

By Mary Louise Theodore, R. G. Aspden, D. A. Colling

T RACES of sulfur have a marked influence on the physical and mechanical properties of many iron-base alloys. The commonly used combustion method for the determination of sulfur content is not accurate enough at the 50 ppm level by weight and below to be useful in determining the influence of sulfur. Kriege and Wolfe' have described a method for the determination of sulfur in iron alloys in which the sulfur is evolved as hydrogen sulfide followed by reaction with N, N-dimethyl-p-phenylenediamine, and iron (111) to form methylene blue which is measured spectrophoto-metrically. This method of determining sulfur has been used to study the activity of sulfur in Fe-Si-S alloys,' but has not been previously applied to the determination of sulfur in Fe-Ni alloys because of the insolubility of nickel in dilute hydrochloric acid. Dissolution of nickel in dilute hydrochloric acid, however, can be greatly accelerated by the addition of a small amount of platinic chloride.3 By combining these two techniques in a procedure in which 0.005 pct platinic chloride in 1:l hydrochloric acid is used as the dissolving fect on the strength of the material. However, ductility is influenced by the presence of discontinuous precipitation. In Fig. 5, percent elongation data at room temperature and 1400°F is shown for two sets of specimens of Waspalloy which were solution heat treated at 1950°F and either quenched or slow cooled to the aging temperature and then aged for 100 hr at 1292" and 1598ºF, respectively. At room temperature the existence of a discontinuous precipitation cell at grain boundaries (see data point marked by arrow) has no apparent effect on ductility. However, at elevated temperatures a pronounced lowering of ductility occurs when discontinuous precipitation has occurred in the specimen. It would appear that the morphology of discontinuous precipitation "cells" at grain boundaries would be highly conducive to the initiation of cracks which in turn lead to premature "grain boundary" failure.

Jan 1, 1970

By John Johnston

WHEN I was honored by being invited to give the Howe Memorial Lecture, I decided to read Howe's book, "The Metallography of Steel and Cast Iron," published in 1916-that is, about 25 years ago-in search of a text. I found the book written in fine, clear, attractive, yet precise style, as I expected, knowing that his father Dr. Samuel Gridley Howe, his mother Julia Ward Howe, and all of his four brothers and sisters had lived in a New England literary atmosphere and had written books. This leads me to suggest that many authors of metallurgical papers and books could well study Howe's writings with a view to the improvement of their own. I failed to find a specific text, but did find a subject, for in reading his book I was struck by the few instances in which time is considered explicitly as a factor in the phenomena examined, and by the fact that many of the hottest arguments would have been settled had time been taken properly into account. Indeed, Howe hardly mentions time except in a rather incidental way, as in a few references to lag; for instance: The lowering of temperature at which the transformation occurs by rapid cooling . . . is a phenomenon of undercooling or lag. It is in part explained by the fact that the transformation itself is a time-consuming reaction which, setting in during a rapid fall of temperature, is naturally protracted till the temperature has sunk far below that at which it is due. He does discuss, quite fully, the iron-carbon equilibrium diagram, as known at that time, introducing it by stating: As he is a reasonable man who is not deterred from using a hand' truck for moving his trunk by the consideration that he has thus to move a trunk plus a truck, so am I reasonable in putting into your hands this useful, indeed indispensable, tool for mastering the ABC of iron metallurgy. Somewhat later, in introducing a discussion of the phase rule, which "it would be hardly proper to pass ... by without an attempt to outline its meaning," for "a clear exposition of its applicability or jurisdiction is needed to restrain the half¬initiated from misusing it and the uninitiated from being misled by these misuses," he writes-and I quote his statement because we cannot properly discuss the influence of time on a process until we know the state of equilibrium which would ultimately be reached by the system under consideration: It is a most remarkable and valuable generalization, its conceptions help greatly toward getting a broad outlook on metallography, but its misconception has brought out a flood of obscuring writings. It tells us about the constitution towards which alloys tend, that which they reach when equilibrium is complete, when all tendencies have corrected themselves and have been complied with completely. Its application, in absence of true equilibrium, is like determining density with a telescope or even with a tuning fork; it is like the mad tea party at which the butter put into the works of the watch was the best butter. If the reader learns no more than to beware of attempts to decipher the conditions of inequilibrium by a law which touches only the conditions of exact

Jan 1, 1942

By O. A. Cheadle, F. E. Lane

ThE computer program for arbitrary crystal systems reported by Camp and Clum' has been modified to make it more convenient for hexagonal crystals. The program' uses the Miller indexes (hkl) which can be confusing for hexagonal crystals while the modified program uses the Miller-Bravais indexes with four axes; e.g., the angles between the (110) planes, Fig. 1, are 0 and 90 deg but in the (hkil) system the angles between the (1150) planes are 0 and 60 deg. If a Laue photograph is taken of a crystal oriented with the prismatic planes nearly parallel to the film then the spots on the stereo graphic projection will be from high-index planes. The probable positions of the low-index planes, e.g., (0001) plane, can only be obtained from the intersection of zones and this is not accurate to 1 or 2 deg. The number of planes considered by the program (card 1)' has to be limited to the ones of low index or the program time is excessive but a solution will not be obtained if one of the spots has an index that is not being considered. To overcome this problem the program1 was modified so that if no fit was obtained at *1 deg (card 3) of the tabulated angles then ±2 or ±3 deg was tried. If still no solution was obtained either due to one of the angles not being measured correctly to ±3 deg or because one of the spots was from a high-index plane, then the last spot was discounted and a fit tried for the remaining spots at i1 deg, and so forth. The minimum number of spots that the program will try to fit is five. If the limit on any individual index is 4 (card 1) and (h + k + l + 1) is six then twenty-three planes are considered and there are over 1000 interplanar angles. Many pairs of planes have very similar interplanar angles and with the errors previously mentioned the program will often produce several alternative solutions to a group of spots particularly at ±2 or ±3 deg. However without the program the alternative solutions would probably not have been found. If a large number of spots are used the number of possible fits is reduced. In the example shown in Fig. 2, if only spots which are on the film are used (case 1) the program gives six possible solutions, Table I. However if points 7 and 8 are also used (case 2) the program gives only one fit which also agrees with a standard projection of the crystal. In addition to time-saving the program ensures that a correct solution is obtained since it is unlikely that all the alternatives would have been gound manually; the first would probably be assumed to be the correct solution. The program has been used for zirconium crystals but is equally suitable for other hexagonal materials.

Jan 1, 1969

By J. Brett, S. Friedman

A study of the diffusion of nickel into both fibrous and recrystallized 0.065-in.-diam silica-alumina doped tungsten wire at 1200°C has been conducted. The diffusion profiles were determined by chemical dissolulion of successive circumferential layers and spectro-photometric determination of nickel in the etchant. It was shown that the diffusion of nickel into tungsten is markedly structure-sensitive. No significant amount of nickel could be introduced at 1200°C into tungsten which had first been recrystallized at temperatures of 2300°C, leading to an upper limit estimate for the bulk diffusivity of nickel in tungsten of 10-11 sq cm per sec at 1200°C. However, nickel did diffuse into initially fibrous wires, caused re crystallization, and was alsays present at the advancing recrystallization front. The accumulation of nickel in an initially fibrous region ceases when the recrystallization front arrives. The characteristics of the resulting diffusion profiles are explained in terms of the relation between diffusion processes and micro structural changes. WHILE it is well-known that the presence of nickel and certain other metals causes low-temperature recrystallization of the cold-worked fibrous structure of doped tungsten,''' the character of the phenomenon is not well understood. Recently it was shown that the recrystallization reaction can be induced at low temperatures by the presence of solid nickel on the surface of doped wire, but not by exposure to nickel vapors.3 Once recrystallization was initiated, a continued source of nickel was required for propagation of the recrystallization front. The phenomenon appeared to be a complicated solid-state reaction since, in addition to the change in structure of the tungsten from fibrous to equiaxed grains, diffusion of nickel from the surface into the recrystallized and fibrous structures was occurring with possible chemical reaction between nickel and tungsten at the surface and interaction of nickel with the dopants which ordinarily stabilize the fibrous structure within the wire. The objective of the present work was to study the diffusion of nickel into fibrous and recrystallized tungsten structures in order to clarify the relationship of the diffusion process to nickel-induced recrystallization. Studies of interdiffusion in the Ni-W system4"7 have been principally concerned with the mobility of tungsten in nickel. Information on diffusion of nickel in tungsten is meager, and there seem to be no studies of the mobility of nickel in tungsten which elucidate the structural aspects of the phenomenon. The present experiments were designed to determine the diffusivity of nickel at 1200°C in fibrous tungsten, in large-grained tungsten prerecrystallized at high tem- perature, and in tungsten recrystallized at 1200°C due to the presence of nickel. Although the concentration profiles were determined in these experiments, unexpected changes in boundary conditions or complex diffusion paths complicated the analysis of these profiles so that the interpretation could not be readily expressed in terms of simple diffusivities. EXPERIMENTAL PROCEDURE The experiments were conducted on Sylvania 0.065-in.-diam silica-alumina doped commercial tungsten wire, hereafter designated as ordinary doped wire. A special lot of 0.065-in.-diam silica-alumina doped low-nickel wire was also used. Impurity analyses of the wire are given in Table I. The experimental design is shown in Fig. 1. All heat treatments were conducted in vacuum. Two groups of ordinary doped wire were prepared for diffusion with nickel. One group in the as-received (fibrous) condition was elec-tropolished, nickel-plated, and annealed at 1200°C for 20 and 40 hr, or was exposed to nickel vapor at 1200°C for 20 and 40 hr. The second group was recrystallized to an equiaxed grain structure at 2300°C for 3 hr, electropolished, nickel-plated, or exposed to nickel vapor for anneals at 1200°C for 20 and 40 hr.

Jan 1, 1969

J. E. Stead, Middlesborough, England (communication to the author): Prof. Howe's valuable paper on cast-iron brings forward most prominently the correct explanation of the part played by combined carbon in pearlite and cementite, in determining the strength and hardness of cast-iron. On a previous occasion I haveoshown that castings made by melting a white Cleveland iron and glazed iron, one containing 1.5 and the other from 4 to 5 per cent. of silicon, and each about 3 per cent. of carbon, were stronger than those made of ordinary foundry-iron; the difference in the final castings being a differ-

Jan 1, 1902

By E. T. Stephenson

Wert and Marx1 pointed out that a straight-line relationship exists between the activation energy of a relaxation process and the temperature at which the maximum relaxation occurs. The data available at the time indicated that this relationship held for a number of Snoek peaks, several grain boundary peaks, and pair relaxation in a brass. Theoretical justification for the observed relationship was found in the following equation, which Wert and Marx derived from the theory of interstitial atomic diffusion coefficients:' where AH is activation energy, R is the gas constant, T is the internal friction peak temperature, v is the interstitial atomic frequency, f is the frequency of the applied stress, S is entropy of activation. More accurate internal-friction data on interstitial diffusion in bcc metals have become available since Wert and Marx's paper. Table I gives activation energies calculated by several authors from a combination of elastic aftereffect data and the peak temperatures at several frequencies of measurement. (In the case of Fe-C and Fe-N, the referenced authors5'7'8'10 also used high-temperature diffusion data.) However, diffusion experiments at 150°C and above1'-13—rather than anelastic techniques—were used to determine the activation energy of hydrogen diffusion in Fe-H. In order to plot this recent data as a AH vs T graph we calculated the peak temperatures of the systems listed in Table I (with the exception of Fe-C, Fe-N, and Fe-H) by using published values3'' of AH and Do. These calculated peak temperatures varied by only a few degrees from experimentally determined peak temperatures. The calculated values were felt to represent the better average. A number of investigators have found the peak temperatures in Fe-C and Fe-N to be 38 to 40°C and 20° to 24°C, respectively. The values of 39" and 22°C (312° and 295°K in Table I) were determined by carefully executed experiments.6'8 The hydrogen peak temperature has been measured at 1 cps,12 20 cps,14 and 35,000 cps.15 All hydrogen peak temperatures were adjusted to 1 cps for Table I using AH = 3000 cal per mole. As Fig. 1 shows, the data of Table I fit a straight line at least as well as the earlier data used by Wert and Marx. Linear-regression analysis was applied to the data in Table I. The Fe-H data was omitted because the activation energy has not been experimentally determined in the temperature range of the peak. The analysis yields the equation: with a standard error of 860 cal per mole. The agreement of the data in Table I with the Wert-Marx equation is excellent. Strict application of Eq. [I] forces the linear regression analysis through the origin. In this case, the analysis gives a slope of 62.1 cal per mole per deg, and a standard error of *890 cal per mole. With this value, it follows from internal-friction theory that Hence, Do varies by only 30 pct among these bcc-interstitial systems. Thus, a concept suggested originally by Wert and Marx1 is confirmed by recently published data. The

Jan 1, 1965

By J. C. Febles

HISTORY. THE use of iron for the precipitation of copper was known at least as early as the fifteenth century. Both Paracelsus and Basil Valentine refer to it in their writings, as early as 1500 A. D. It was used in Peru, for this purpose prior to 1637, and at Rio Tinto, Spain, as early as the sixteenth century. The statement has been made repeatedly that in the early history of the mining industry at Butte, the practicability of this method of recovering copper from solution was overlooked, and that enormous quantities of copper-bearing water were allowed to go to waste, the copper in which might easily have been recovered at small cost; and that this oversight on the part of the mine operators was due to ignorance of this method of recovering copper. As a matter of fact, very little copper-bearing mineral was encountered in the mines of Butte until a depth of 400 or 500 ft. bad been reached, and in many cases much greater depths were necessary to reach the copper-bearing zone. The water encountered in the upper levels (although in most cases quite highly mineralized) contained little or no copper, and it was only after considerable areas of copper-bearing ore had been uncovered and developed that copper sulphate began to. appear in the mine water in any considerable quantity. In fact, the first water that was observed to contain copper carried it in such small amounts as to be of little or no importance. It was only after years of underground work had opened extensive areas of stopes, drifts, and other underground workings, these being subsequently filled with waste, nearly all of which contained small copper values, which became oxidized by exposure to the air and were acted upon by the slowly percolating mineral water, that the recovery of copper from mine water became commercially important.

Jan 7, 1913

By Frank T. Sisco

The discovery of phosphorous is usually credited to the German alchemist Brand, in 1669, and the element was rediscovered the next year by Boyle in England. IT was more than 100 years later, however, before its presence was detected in high-carbon iron produced in early blast furnaces. In 1781 the German chemist Meyer published the results of his investigation on the ?white earth? that he had found in cast iron made from bog ores. This white earth was metallic in appearance, it was extremely brittle, it was readily fusible, and it was not attracted by magnet. Meyer noted that cast iron containing this white earth was more fusible than other cast iron, and he was sure that he had discovered a new metal ? for which he proposed the name Wassereisen, or the Latin term Hydrosiderum. Two years later the distinguished Swedish Chemist Bergmann made the same discovery, finding a ?white calx? in cast iron, which he also mistakenly considered to be a new metal, and for which he proposed the Siderum.

Jan 1, 1944

By AIME AIME

T HE appointment of Herbert Hoover to the portfolio of Commerce in the President's Cabinet is to engineers the fulfillment of a long deferred hope to have an engineer in high political office and is a matter of congratulation to us for three reasons; because he is a mining engineer who represents the highest type of idealistic engineering effort; because he is a past president of the Institute; and because he has probably a broader grasp of world problems than any other living engineer. Frank A. Vanderlip in the preface to his book "What Happened to Europe" tells of the many interviews he had with the most prominent men in Europe which were made possible for him by his eminence as a banker and by the courtesy of the American ambassadors. He cites by name such well known figures as Austin Chamberlain, Sir Auckland Geddes, Monsieur Delacroix, Monsieur Briand, Mr. Padkrewski, Mr. Venizelos, Colonel House, General Pershing, Mr. Baruch, and many others and says :

Jan 1, 1921

By R. E. Ogilvie, A. R. Kaufmann, S. H. Gelles

The solid-solubility limits of iron in beryllium were determined between 850o and 1200oC by analysis of differential type multiphase diffusion couples, using an X-ray absorption technique. The maximum value of the solubility limit was found to be 0.92 ± 0.02 at. pct (5.46 wt pet) at the eutectic temperature 1225°C. The solubilities of nickel and beryllium were determined between 900°and 1200°C by the same technique and the maximum solubility was found to be 4.93 + 0.01 at. pct (25.2 wt pet) at the eutectoid temperature, 1065°C. A previously unreported high-temperature phase which decomposes eutectoidally at 1065 °C was found to exist in the beryllium-nickel system at a composition of approximately 8 at. pct Ni (36 wt pet) by diffision-couple analysis. The presence of this phase was confirmed by thermal analysis and metallo-graphic analysis of the structure resulting from the eutectoid decomposition. G. V. Raynor1 has treated the solid solubilities of some of the elements in beryllium on the basis of the "Hume-Rothery" rules2 which have been modified to include ionic size and ionic distortion effects. It was predicted that the solubility of iron and nickel in beryllium should be slightly less than that of copper. The lowering of the solubility, according to Raynor, is due to a more unfavorable relative valency effect and an ionic size effect. Kaufmann and corzine3 have compiled data on the solubilities of elements in beryllium and have discussed them in the light of the Raynor paper. These authors feel that, because the elements having the greatest solubility in beryllium systematically fall in the Group VIII and IB Columns of the periodic table, the electronic structure greatly influences the maximum solid solubility of elements in beryllium. The solubility of iron in beryllium was determined by Teitel and cohen4 as part of the study of the beryllium-iron phase diagram. The determination was carried out by X-ray and thermal analysis and according to the phase diagram presented, the maximum solubility of iron in beryllium is 0.41 at. pct (2.5 wt pct) at 1225oC. However, it is estimated that the uncertainty in the position of the a-beryllium primary solid-solution boundary is about 0.5 at. pct (3wtpct). Losana and Goria3 in studying the beryllium-nickel phase diagram, determined the solid solubility of nickel in beryllium by thermal analysis. They found the maximum solubility to be between 1.65 and 2.65 at. pct (10 to 15 wt pct) at 1240°C. This value decreased rapidly with decreasing temperature. In determining approximate ranges of solubilities for different elements in beryllium, Kaufmann, et al,8 reported a value of between 1.3 and 1.7 at. pct (7.9 to 10.1 wt pct) for the solubility of nickel in beryllium. The value was obtained by metallographic examination of quenched alloys and lattice-parameter measurements. However, the authors also noted a single-phase structure for a 1.7 at. pct Ni alloy (10 wt pct) on cooling from the liquid. This would indicate a higher solubility range than was reported. ~isch,' in his X-ray studies of beryllium-copper, beryllium-nickel, and beryllium-iron intermetallic compounds, reports the disappearance of a second phase (Ni,Be2) in the beryllium primary solid solution at approximately 4 at. pct (20 wt pct). THEORY The analysis of concentration gradients in diffusion couples has proven to be a useful tool in determining phase equilibria.8-14 In this particular study the diffusion couples were chosen to straddle the expected composition range of the phase boundary, then heat treated at a given temperature and the concentration gradient evaluated. The composition of the phase boundary for a given temperature appears at a point of discontinuity of the composition gradient. Examples of typical phase diagrams and the concentration gradients which should be found in such systems are shown in Fig. 1. In the present work, gradients of the form of Fig. l(c) were obtained in diffusion couples made of pure beryllium and two-phase alloys of beryllium with either iron or nickel. The composition at the point where the gradient becomes discontinuous, Cs, corresponds to the solubility limit of either iron or nickel in beryllium. The analysis of the concentration gradients was carried out by an X-ra absorption method developed and applied by Ogilvie and later used by Moll13 and Hilliard.l4 It depends on the fact that the absorption of X-rays by matter is determined by the concentration and type of the various atomic species present. The relationship for the intensity, I, of a monochro-

Jan 1, 1960