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By Herman Garlichs

The development of the extensive Southeast Missouri deposits greatly preceded that of the Iowa and Wisconsin deposits. It began about 1720 at Mine La Motte and other localities, and has continued uninterruptedly to the present time. It is estimated that this district produced about 184,000 tons of lead in the year 1916, having a value of approximately $25,000,000. This is a new high record. The Southwest Missouri orebodies were hardly known before 1845 and were not extensively developed until 1870. Lead production in Southwest Missouri for 1916 was 38,788 tons. Oklahoma produced 14,399 tons and Kansas 2,345 tons, making a total for Southwest Missouri, and the adjoining districts in Oklahoma and Kansas, of 55,532 tons of lead. The first metallurgists in Missouri were the Indian and the hunter. The early settler learned to procure his bullets either by melting ore in his camp fire or by throwing pieces of galena on an old stump and depending on the usual roasting and reaction method to obtain the metal. A little more refined method was to arrange two flat stones in the form of a, V. Wood and galena were placed in the furnace and ignited.. As heat developed, some of the metal was extracted and molded into bullets. The next step in utilizing the lead ores was the log hearth. All lead in Missouri was smelted in this crude affair before 1820. It was built on sloping ground, and consisted of a hearth of stone, surrounded on the front and two sides by a stone wall. The wall was 7 it. high in front. The top and rear end were left open and in front an arch or opening was made, forming the eye of the furnace. In front of this a pit was dug in the ground, to receive the molten metal. Large logs were rolled in at the back and made to rest upon ledges formed inside, to raise them from the hearth and to give a draft. These logs filled the entire width of the furnace. Small split logs were then set up around the two sides and the front, and the ore was piled on until the furnace was full. Finally, the mass was covered with logs and fuel until the ore was completely surrounded. A gentle heat was started, which was raised very gradually. After 12 hr. the heat was increased and continued for 12 hr. more, 24 hr. being required for each smelting. The furnace treated about 5,000 lb. per 24 hr. and the ore yielded about 50 per cent. of its metallic lead. A considerable quantity of the ore was not desulphurized, and fell between

Jan 1, 1918

By Howard Clarke, Cyril Stanley Smith, Clarence Zener

The importance of cold-working in the fabrication of metals is in marked contrast with our ignorance as to the nature of the accompanying internal changes. The failure of the usual methods of testing to provide a consistent picture of these internal changes has given the incentive for the present program of investigating the effect of cold-working upon the internal friction of metals measured at small strain amplitudes. It has previously been shown1,2,3, that the internal friction introduced by cold-work is removed by annealing at comparatively low temperatures. In the present paper the following additional factors are investigated: (I) frequency of measurement, (2) amount of cold-work, (3) temperature of measurement. Special care was taken to minimize the internal friction due to causes other than cold-work. The present paper is purely experimental, the authors believing that any conclusions drawn from this work as to the nature of the internal changes accompanying cold-work would be premature.'l PrEpaRations oF Specimens In this study of cold-work it was desirable to eliminate as far as possible all other sources of internal friction. One disturbing source is the lack of temperature equilibrium between adjacent crystallites of a vibrating specimen.4 Temperature equilibrium is aided by small grain size and by the use of low-frequency vibrations. Unless unduly long specimens are used, low frequencies can be obtained only in transverse vibrations. But in transverse vibrations a second source of internal friction is present, that arising from transverse thermal currents.5 The effect of these may be reduced by increasing the transverse dimensions. The grain size and transverse dimensions of the specimens were thus so chosen as to render the vibrations simultaneously nearly isothermal with respect to intercrystalline thermal currents, and nearly adiabatic with respect to transverse thermal currents. The material for this investigation was a 70-30 brass, part of the same lot of material that was used for some earlier studies on the effect of strain on proportional limit.10 It had the following composition: copper, 70.59 per cent; zinc, 29.39; lead, 0.01; iron, 0.01. This material was received from the brass mill in the form of 3/4-in. rod, cold-drawn to final size by a 65 per cent reduction of area from material that had been annealed to give a grain size of 0.060 mm, Rods of appropriate length were annealed for 2 hr. at 400°C. and cooled in air. The annealed rods (grain size, 0.012 mm.) were then stretched in a tension-testing machine, using special grips1' to ensure axial application of the load. The rate

Jan 1, 1942

By R. K. McGeary, B. Lustman

Orientation relationships and rates of annealing of 97 pct cold rolled zirconium have been studied by X-ray techniques, metallography, and by hardness measurements. The process of annealing occurring by the formation of domains, and their subsequent growth without recrystallization, is demonstrated. NUMEROUS investigators1-' have revealed sub-grain formation after annealing cold worked metal single crystals and have generally described the results in terms of a dislocation mechanism of polygonization.5,6 in heavily cold rolled polycrystal-line aluminum the first stages of heating cause an apparently spontaneous subdivision of regions of the deformed matrix into a great number of slightly disoriented domains followed or accompanied by rapid growth of certain domains to form a recrystallization texture.7,8 In the present investigation the isothermal rate of annealing of cold worked polycrystalline zirconium has been studied by X-ray techniques, metallography, and by hardness measurement. It will be shown that, rather than by the usual nucleation and growth mechanism,"12 the process of annealing can best be explained by the formation of domains early in the annealing treatment and the subsequent growth of these domains without recrystallization. Experimental Procedure All the experimental work was performed on an arc-melted ingot of high purity zirconium crystal bar made by Westinghouse in a production scale deBoer unit. The weight percentage of impurities in the zirconium were as follows: C, 0.04; Fe, 0.05; Hf, 0.014; W, 0.01; Ti, Ni, and Al, 0.003; Si and N, 0.002; Cr and Cu, 0.001. Metallographically the zirconium showed only a single phase. The 4 in. diarn ingot was forged at 760°C to a 1 1/2x3 in. plate and was then rolled at 760°C to 0.150 in. thickness and annealed at this temperature for 20 min to produce an equiaxed grain structure of about 0.1 mm average grain diameter. The hot rolled plate was roller-leveled, surface ground to 0.135 in., cold rolled 83 pct reduction in thickness on a two-high mill, and then to a total reduction of 97 pct on a Sendzimir mill. The 0.004 in. strip material so produced received no subsequent mechanical treatment. Specimens % in. square were sheared from the rolled strip and isothermally annealed at 104 mm Hg in an all glass vacuum system equipped with a Vycor furnace tube. The temperature data presented are the average temperatures during the runs and did not vary more than about k3"C. X-ray Diffraction Methods: When zirconium is drastically cold rolled, a high degree of preferred orientation results in which prism poles, {1010}, are perpendicular to the rolling direction. After fully annealing this material an entirely new texture develops which corresponds to a 20" or 40" rotation of the deformation texture about hexagonal axes of

Jan 1, 1954

By M. R. Hatfield, F. J. Vosburgh

IN a recent article,† it was shown that in the blast furnaces in Germany that are lined with carbon blocks no cooling plates are used, and that shower cooling is employed on the hearth and bosh sections. While one of the authors was in Germany he was told that one furnace was being operated without even the shower cooling on the bosh section, though the hearth section was shower-cooled. In discussion of this interesting situation with a number of blast-furnace operators in this country, it was made clearly and promptly evident that shower cooling was very unpopular, probably because of its messiness and its ineffectiveness. Both of the causes for the dislike of shower coolings are reasonable ones. Shower cooling can be and frequently is messy, but the present cooling of blast furnaces leaves much to be desired on that score. Shower cooling is ineffective as compared with plate cooling, so far as its usefulness in keeping the bricks cool enough not to melt or fall to pieces is concerned. However, the introduction of carbon linings changes the situation. No one is concerned with keeping a carbon lining cool, for no temperature in the blast furnace has any effect on carbon, which is just as stable at 3000°F. as it is at 70°F. The only concern is for the shell-to keep it cool enough for safety and comfort and for that shower cooling is sufficient. Of course, with only the shell to cool, instead of the shell plus all the refractory material, much less water would be required, and the necessity for constant attention to the flow would be lessened, as the hundreds of inlets and outlets would be eliminated. Probably half of the water used in cooling a blast furnace is used for cooling the shaft and tuyeres and the remainder for the bosh and hearth sections. However, in view of the dislike of shower cooling in the United States, and particularly because at least one German blast furnace is operated with no cooling of the bosh section, thought was given to the possibility that a carbon-lined blast furnace might be operated without any cooling of the entire carbon-lined portion. For that reason a series of experiments was performed to determine what might be the temperature of the shell of a blast furnace protected by a carbon lining and operated under varying conditions up to a maximum inside temperature of 3000°F. EXPERIMENTAL PROCEDURE A schematic diagram of the experimental setup is shown in Fig. I and a photograph of the entire assembly in Fig. 2. The heating element was a carbon tube nominally 2 5/8 in. o.d. by 2 in. i.d. by 30 in., used as a resistor. Power was furnished by a 15-kva. transformer operating

Jan 1, 1941

By N. Tiner

In an article on magnesium and its alloys, Gann and Winston! stated that manganese has a limited solubility in the liquid state. W. Schmidt2 showed a diagram according to Joseph Ruhrmann indicating that the solubility of manganese in liquid magnesium falls from about 2.65 per cent at 790°C. to about 0.5 per cent at 675°C. The curve was extrapolated to show zero solubility at the melting point of pure magnesium (Fig. I). This work suggested that at the lowest manganese contents it was not possible to detect either a eutectic or the formation of a solid solution, so that manganese was stated to be present in the structure as large individual crystals. Two years after the presentation of, these results, Gann3 brought evidence to show that some manganese is capable of dissolving to form a solid solution, any excess of manganese present then assuming chiefly the form of small blue-gray particles scattered throughout the primary magnesium crystals, occasionally in clusters but seldom at the boundaries. He presented micrographs of cast alloys containing 0.1, 0.4 and 1.0 per cent manganese that show a small amount of coring around the individual particles due to solid solution, and indicate that the location of the manganese particles is closely associated with the original dendritic structure of the primary crystallization. He also pointed out that the amount of manganese that can be dissolved in magnesium depends on the amount of other alloying elements present, the effect of the second alloying element being to decrease the amount of manganese retained in the alloy. E. Schmid and G. Siebe14 have determined the solid solubility of manganese and its variation with temperature by means of precision X-ray diffraction measurements. They found that the solubility is 3.4 per cent at 645°C. and decreases to practically zero at 200°C. It is apparent that the X-ray diffraction measurements of Schmid and Siebel are not in agreement with the results of Ruhrmann as presented by Schmidt. This disagreement, and also the lack of data on magnesium-aluminum-manganese and magnesium-zinc-manganese systems, led the author to the present investigation, to determine accurately the liquid solubility of manganese and its variation with temperature. Experimental Method The experimental method for making solubility determinations consists of saturating the molten magnesium or the alloys with manganese at various temperatures and analyzing the dip samples taken from these melts. Melting is carried out in a cylindrical steel pot heated by an electric resistance furnace. The pot had a metallic outside coating to protect the steel against oxidation, and a graphite inside lining to prevent the contamination of the melt by prolonged contact with iron. The inside diameter of the pot was 4 in. and the depth 12 inches.

Jan 1, 1945

By John Wulff, J. H. Hollomon

THE opinion has been widely held that the corrosion of alpha brass occurs by the selective solution of zinc. As late as 1939, Fink1 and Evans2 suggested that in the initial stage of the corrosion the selective solution of zinc produces copper-rich areas, which subsequently act as cathodes that facilitate the deposition of copper. Previously Abrams3 had shown that most of the copper found on corroded brass was redeposited and not residual, although he did not consider the nature of the initiation of the corrosion process. Enough data exist to indicate that any metal surface is sufliciently heterogeneous to provide the anodes and cathodes necessary for the initiation of corrosion .4,5 Thus, for alpha brass we need postulate not an initial selective solution of zinc, but only the existence of local differences in electrochemical potential. The heterogeneity responsible for potential differences may arise from oxide and other films as well as from alloy concentration gradients. Even though selective corrosion may be possible in some alloy systems, previous data on alpha brass as well as the experimental work reported in this paper do not require this supposition. Bengough and May,6 in a discussion of Abrams' paper, first suggested the addition of small amounts of arsenic (0.03 per cent) to alpha brass to prevent the redeposition of copper (dezincification). This suggestion was later substantiated by Nixon.7 In their studies of the inhibiting influence of arsenic, Evans and Fink were led to the selective-solution hypothesis in order to explain the initial corrosion of such alloys. "I hey believed that an arsenic film covered anode areas and prevented the formation of copper-rich spots capable of acting as cathodes for the deposition of copper. They (lid not consider, however, the mechanism by which the arsenical film was formed. Bengough and May,8 in another publication, suggested that the commonly found gray or black arsenical film may act to: (1) carry oxygen to the brass surface, (2) increase the discharge potential of copper on brass, (3) precipitate cuprous chloride from colloidal suspension in chloride solutions. Masing9 assumed that the film found upon arsenical brass was metallic arsenic. His measurements of hydrogen overvoltage of bulk arsenic led hint to believe that the inhibition of dezincification occurs because the overvoltage of a brass surface is lowered by the arsenic film. He reasoned that this film would permit the more rapid reduction of hydrogen at the cathode, which would prevent the redeposition of copper. In a recent paper,10 we have pointed out that the film formed (luring the corrosion of arsenical brass and copper in stagnant solutions is essentially arsenious oxide (AS208)

Jan 1, 1942

By Harold Vagtborg

Equilibrium vaporization ratios were obtained for light hydrocarbons, nitrogen, carbon dioxide, and hydrogen sulfide in a reservoir fluid containing 35 mole per cent hydrogen sulfide. The data cover the range from 700 to 2500 psia at 154°F. The results of this study are compared with results obtained by other investigators on systems containing less hydrogen sulfide. When large amounts of hydrogen sulfide are present, the equilibrium vaporization ratios for ethane and heavier hydrocarbons are greater than the ratios for systems containing little or no hydrogen sulfide. Large amounts of hydrogen sulfide have the reverse effect on the ratios for methane. Routine PVT studies were performed on the reservoir fluid including flash and differential liberations of the dissolved gas. The pressure-volume relationships of the saturated fluid were also determined. It is shown that the use of published correlations on physical properties of reservoir .fluids can lead to gross errors when applied to systems containing large amounts of hydrogen sulfide. INTRODUCTION Equilibrium vaporization ratios for various components in naturally occurring crude oil and condensate systems have been reported in the literature.1,2,3,4 Recently, several papers have been published with emphasis on non-hydrocarbon components such as nitro- gen, carbon dioxide and hydrogen sulfide.5,6,7,8,9 The increased discovery of reservoir fluids having high concentrations of these non-hydrocarbon components, particularly hydrogen sulfide, has created a need for a further study of their phase behavior. Equilibrium vaporization ratios are known to vary with pressure, temperature, and overall composition of the system.'" It was anticipated that ratios for systems containing large amounts of hydrogen sulfide would differ from the ratios for systems containing small amounts of hydrogen sulfide. Therefore, the present work was undertaken in order to obtain reliable equilibrium vaporization ratios for the reservoir-fluid in question. PROCEDURE The procedure followed was evolved after considerable experimentation on methods of handling the very sour crude. It was found that drying agents (e.g. CaCl2 and CaSO4) absorbed an appreciable amount of hydrogen sulfide from the gas used to prepare the recombined samples. The concentration of hydrogen sulfide dropped as much as 10 mole per cent in a single pass through a 3-ft drying tube. It was also found that when undried gas was agitated with mercury in the PVT cell, a black scum, believed to be mercuric sulfide, was formed and the hydrogen sulfide content of the gas dropped several mole per cent. Because composition changes during a run could not be tolerated, separation of the mercury and sour fluid was necessary. In order to effect this separation, a stainless steel piston, equipped with Teflon O-rings, was placed in the PVT cell between the mercury and the sour fluid. This piston had to be constructed in three parts because

Jan 1, 1955

By G. W. Nabor, M. Mortada

The effects of anisotropic or directional permeability on the areal sweep efficiency and the flow capacity are examined. The paper points out the importance of taking directional permeability into consideration in planning a flood. It analyzes the two-dimensional flow pattern associated with the skewed line drive for a unit mobility ratio. The direct and staggered line drives are treated as special cases of the skewed line drive. Analytical expressions are developed for the areal sweep efficiency at breakthrough and the flow capacity. They are related to the spacing between like wells, the distance between a row of injectors and the nearest row of producers, and the degree of skewness of the line drive. The latter quantity is defined such that it is equal to zero for the direct line drive and equals one-half for the staggered line drive. The areal sweep efficiency and the flow capacity depend also on the orientation of the flood pattern with respect to the principal axis of anisotropy. The paper provides a simple method for determining the areal sweep efficiency and the flow capacity for a formation in which the permeability in the bedding plane is anisotropic. INTRODUCTION Directional or anisotropic permeability is manifested by the ability of the formation to conduct fluids more readily along certain preferred directions. This situation occurs in many producing formationsl-4 and is usually attributed to depositional features in which the sand grains are oriented in a preferred direction. In some cases it results from the formation of a major and a minor fracture system. 4 Directional permeability should be taken into account in many phases of the production and exploration activities. Recognizing its existence in the formation of interest and planning accordingly can lead to increased recovery and substantial savings. For instance, the areal sweep efficiency in a water flood depends to a great extent on the orientation of the flood pattern with respect to the principal axis of permeability. Anisotropic5 permeability is specified by the directions of its three principal axes and the permeability along each axis. The principal axes of permeability are mutually perpendicular. This paper deals with the areal sweep efficiency at breakthrough and the flow capacity for formations with aniscltropic permeability. The flood pattern considered consists of alternate rows of injecting and producing wells. The rows of wells are parallel and form a developed, skewed line drive which is illustrated in Fig. 1. The staggered and direct line drives are treated as special cases of the skewed line drive. PRELLMINARY CONSIDERATIONS The formations considered in this paper are assumed to be of uniform thickness and porosity. The permeability is uniformly anisotropic, with each principal axis of permeability maintaining

By R. W. Gurry

IN the course of a series of measurements of the rate of diffusion of carbon in austenite at about 960°C. (1760°F.) and 1110°C. (2030°F.), it became necessary to determine carbon concentration when austenite is saturated with graphite, because of indications that the hitherto accepted value of the solubility of graphite in this temperature range is too low. Specimens of carbonyl iron were saturated at temperature in a hydrogen-toluene atmosphere which was in equilibrium with graphite. The carbon content of the steel was measured either by combustion or by the loss of weight after substantially complete decarburization in an atmosphere of hydrogen saturated at room temperature with water vapor. The absence of carbide or graphite as a phase at temperature was demonstrated by microscopic examination of saturated specimens that had been drastically quenched. The mean result of concordant measurements is that gamma iron saturated with respect to graphite contains 1.39 per cent carbon at 957°C. (1755°F.) and 1.89 per cent at 1110°C. (2030°°F.). These two values, plotted along with what appears from the literature to be the best value (0.69 per cent) at the iron-graphite eutectoid temperature (738°C. or 1360°F.), yield a curve that is almost linear, and which, continued upward through a short interval, leads to a limiting solubility of 1.98 per cent at the iron-graphite eutectic temperature1135°C. (2095°F.) instead of the commonly accepted value of about 1.7 per cent. EXPERIMENTAL PROCEDURE The samples of carbonyl iron, with the exception of those for microscopic examination, were cylinders 3.8 cm. long, 0.475 cm. in diameter. They were placed in a graphite holder and suspended in a vertical furnace, the temperature of which was controlled precisely by means of the resistance of the platinum winding.1 In the empty furnace the range of temperature over a distance of 4 cm, at the heat center was 9°C. (16°F.) but at a given location the temperature remained within ±0.5°C. (0.9°F.); it was measured by inserting a platinum-rhodium couple calibrated at the melting point of palladium, 1555°C. Since the presence of the sample probably improved the uniformity of temperature, it was decided to consider the average temperature of the sample to be 3°C. lower than the maximum measured in the empty furnace with the same setting of the controller. Data were obtained in the vicinity of two temperatures, 960°C. (1760°F.) and 1110°C. (2030°F.). The samples for microscopic examination, 2.2 cm. long, 0.475 cm. in diameter, were suspended individually on pure iron wire; for these no temperature correction was applied. The carburizing gas passed into the furnace was dry, oxygen-free hydrogen saturated at room temperature with

Jan 1, 1942

By E. J. Duggan

The mine and mill of the Climax Molybdenum Co. are at Climax, Colorado. Climax is on Fremont pass directly on the Continental Divide, at an elevation of 11,400 feet. Description of Ore The Climax ore-bearing rock is essentially an altered and highly silicified granite, fully half of the gangue being quartz. Molybdenite is the only mineral of economic consequence and most of it is intimately associated with quartz in the form of fine veinlets and stringers. Other minerals are molybdite, pyrite, and chal-copyrite. While the molybdite may be readily extracted by hydrometallurgical methods, its content is too low to make such operations profitable. The pyrite content ranges from 2 to 5 per cent and that of the chalcopyrite from 0.03 to 0.05 per cent. There is not enough copper to make its recovery attractive and one of the metallurgical problems is the elimination of it and the pyrite from the product. On account of the close association of the molybdenite with the quartz and the necessity of eliminating the pyrite and chalcopyrite from the final product, fine grinding followed by flotation is the only feasible method of concentration. History Construction of the first milling unit was started in 1917 and it was operated during parts of 1918 and 1919. In the postwar years, there was almost no demand for the product and production was at a standstill until 1924. The Company's research campaign to develop the use of the metal began to show results in that year. From r926 to 1932 production ranged from 500 to 1200 tons per day. In 1931 an additional mill section was built and production was gradually increased until in 1934 and 1935 about 3000 to 4000 tons was milled per day. This tonnage overtaxed the milling facilities, and as the demand for inolybdenum was growing constantly, additional milling equipment was needed. In 1936 and 1937 another crushing plant, six additional mill sections and the necessary auxiliary plants were constructed and brought into operation. This plant was designed to mill I0,000 tons per day, but it was not long before 12.500 tons was being treated during periods of peak demands. During the summer of 1941, to meet defense needs, the mill has been required to treat 15,500 tons per day. This has been accomplished with little plant expansion and at no loss in recovery, as will be described later. TO increase capacity still further, one more primary section is now being built. This will bring capacity to 18,000 tons per day, which can be stretched to 20,000 tons at a small sacrifice in recovery. Crushing There are two crushing plants: No. I, of 5000 tons capacity (flowsheet in Fig. I) and No. 2, of 15,000 tons capacity (Fig. a).

Jan 1, 1943

By Grover J. Holt

In order to provide a clear picture of the development of the sink-and-float process of concentration as applied to the iron ores of Minnesota, a few pertinent facts should be brought out concerning the ores and the products of concentration. Iron ore is primarily a cheap commodity handled in immense quantities. The price of iron ore at present, based on a natural iron content of 51.5 per cent, varies from $2.55 to $2.70 per gross ton f.0.b. cars at the mine or washing plant in Minnesota. Last year 92,000,000 gross tons were shipped from the Lake Superior district (Minnesota, Michigan, and Wisconsin) to the furnaces. Concentrated iron ores have no greater value per unit of iron content than ores that can be mined and shipped direct from the shafts or open pits. For years only the higher grades of concentrating ores could be treated and sold in competition with the immense reserves of direct shipping ore available. These higher-grade "straight wash" ores required only the simplest treatment; namely, the washing out of fine sand from coarse ore particles. As the exhaustion of the " straight wash " ore is reached, rock is found replacing part of this sand, and the ore no longer responds to the former sizing treatment. Substantial tonnages of this marginal (jig ore) remained to be treated. Because of the limitations placed on concentrates by the furnaces—namely, low price of product and minimum amount of fines—iron-ore concentration oil has been and must continue to be a one-pass process. Only an increase in price or a change in structure of concentrates allowed by the ore consumer will encourage departure from this practice. Faced with the necessity of handling large tonnages, with the limitations mentioned, iron-ore research men have found their search for new and more efficient methods of treatment seriously handicapped and removed from the field of fine crushing. Sink-and-float treatment appeared to offer the best field in coarse concentration and has been proved by several plants to be well adapted to our problem. The use of ferrosilicon as a medium solid was decided upon. In our present practice, the ferrosilicon metal, carrying about 83 per cent iron, 15 per cent silicon and 2 per cent carbon and nonmagnetics, is crushed to pass 65 mesh and used without further sizing. When mixed with water the specific gravity of the medium may be controlled to within 0.02 per cent above or below the required gravity. Table I shows examples of a change in solid content of the medium for varying gravities. the I is based on clean ferrosilicon, whereas some contamination is always present in the mill circuit, tending to

Jan 1, 1947

By Grover J. Holt

In order to provide a clear picture of the development of the sink-and-float process of concentration as applied to the iron ores of Minnesota, a few pertinent facts should be brought out concerning the ores and the products of concentration. Iron ore is primarily a cheap commodity handled in immense quantities. The price of iron ore at present, based on a natural iron content of 51.5 per cent, varies from $2.55 to $2.70 per gross ton f.0.b. cars at the mine or washing plant in Minnesota. Last year 92,000,000 gross tons were shipped from the Lake Superior district (Minnesota, Michigan, and Wisconsin) to the furnaces. Concentrated iron ores have no greater value per unit of iron content than ores that can be mined and shipped direct from the shafts or open pits. For years only the higher grades of concentrating ores could be treated and sold in competition with the immense reserves of direct shipping ore available. These higher-grade "straight wash" ores required only the simplest treatment; namely, the washing out of fine sand from coarse ore particles. As the exhaustion of the " straight wash " ore is reached, rock is found replacing part of this sand, and the ore no longer responds to the former sizing treatment. Substantial tonnages of this marginal (jig ore) remained to be treated. Because of the limitations placed on concentrates by the furnaces—namely, low price of product and minimum amount of fines—iron-ore concentration oil has been and must continue to be a one-pass process. Only an increase in price or a change in structure of concentrates allowed by the ore consumer will encourage departure from this practice. Faced with the necessity of handling large tonnages, with the limitations mentioned, iron-ore research men have found their search for new and more efficient methods of treatment seriously handicapped and removed from the field of fine crushing. Sink-and-float treatment appeared to offer the best field in coarse concentration and has been proved by several plants to be well adapted to our problem. The use of ferrosilicon as a medium solid was decided upon. In our present practice, the ferrosilicon metal, carrying about 83 per cent iron, 15 per cent silicon and 2 per cent carbon and nonmagnetics, is crushed to pass 65 mesh and used without further sizing. When mixed with water the specific gravity of the medium may be controlled to within 0.02 per cent above or below the required gravity. Table I shows examples of a change in solid content of the medium for varying gravities. the I is based on clean ferrosilicon, whereas some contamination is always present in the mill circuit, tending to

Jan 1, 1947

By E. F. Ketterer, D. B. Collyer, A. B. Wilder

AISI constructional alloy steels are a series of steels in which a numbering system signifies the chemical composition limits. SAE (Society of Automotive Engineers) and AISI (American Iron and Steel Institute) use basically the same numbering system. The steels contain, in part, alloy additions of chromium, molybdenum, nickel, and vanadium. They are used widely in the automotive industry but have not been adopted for high temperature service. The purpose of this investigation was to study changes in microstructure observed in typical AISI constructional alloy steels in the welded and un-welded conditions after exposure for 34,000 hr at 900" and 1050" and, in several instances, 1200°F. The tensile and creep rupture properties after exposure for 10,000 hr were also evaluated. The investigation is a continuation of the work previously discussed. Little was known concerning the existence of graphite in medium or low carbon steels before 1943. It is important to note that continued exposure at elevated temperature is required in order to develop graphite in steels. Interest in the presence of graphite in steel, and also in changes in the properties of steels after long service at elevated temperatures, developed after 1943 when a failure of a welded joint of high temperature piping was associated with the graphitization of a relatively low carbon content steel with 0.50 pct Mo,8,0 Numerous investigations have beeen made in recent years studying the relationship of this type of failure to changes in properties. Attempts have been made to evaluate the performance of a number of steels, particularly in the heat-affected zone of welds. It was the unfortunate failure of a weld-heated zone in high temperature piping in the steam-power industry which focused attention upon possible failures, and upon the need for improved steels for high temperature piping service. Investigation by the National Tube Div., U. S. Steel Corp., Lorain Works, has included a wide variety of steels in an attempt to learn the effects of numerous factors and elements upon the long time performance of steels, although many of the compositions studied will never be used at elevated temperatures.1,4-7 Included were the well established AISI steel series, which offered opportunity to test moderately high carbon content steels as well as observe the effect of nickel, chromium, molybdenum, etc., upon the properties of these well known steels. The properties of the AISI steels were also studied for comparison with the previously reported properties of the Cr-Mo steels, now used by the steam-power industry.5,7 Materials and Testing Procedure The AISI alloy steels in Table I were exposed for 10,000 and 34,000 hr at 900°, 1050°, and 1200°F.

Jan 1, 1958

By E. A. Gulbransen, J. W. Hickman

THE physical and chemical structure of the oxide films formed on metals and alloys is of interest in our understanding of their protective properties. According to Pilling and Bedworth,1 if the specific volume of the oxide is equal to or greater than that of the metal, a compact or continuous structure results; if the volume of the oxide is less, a cellular or porous structure forms. With the cellular type of coating the surface layer of oxide offers no impedance to oxidation; at a given temperature the rate of oxidation is quite constant. On the other hand, the compact type of coating acts as an effective barrier to oxygen and the rate of oxidation will follow a parabolic law. The recent work of Gulbransen2 and of Leontis and Rhines3 on the oxidation of magnesium indicates that it is not necessary for the volume of the oxide to be greater than that of the metal in order that the oxidation may follow a parabolic rate law. One exception to the rule of Pilling and Bedworth' is noted by Scheil;4 namely, tungsten. At 500° and 700°C long-time oxidations indicate a linear rate law with time. However, Dunn's5 oxidation measurements from 700° to 1000°C indicate that a parabolic rate law is followed. The oxide is mainly yellow W03 with a thin layer of the blue oxide. Preliminary results on the oxidation of tungsten6 in the temperature range 400° to 500°C indicate that the oxidation does proceed according to a parabolic rate law. Irrespective of the actual rate law that tungsten may obey, it is of interest to compare the results obtained on the oxidation of tungsten in the thin film region with those found when the metal is scaling. A time-temperature study of the oxides formed on both molybdenum and tungsten may indicate whether there exist any peculiarities in the oxide structures of the thin film region compared with those of the scaling region of oxidation. In a recent paper the authors' presented an investigation of the structures of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper. The results of these studies are presented in graphical form as existence diagrams of the oxides on a time-temperature scale. The existence diagrams of the oxides occurring on some of the metals are simple and show few chemical transitions, but there are many cases in which the physical state of the oxide surface changes as a function of time and temperature, as evidenced by the appearance or disappearance of orientation effects and sharpness of patterns. In general an increase in temperature results in an increase in

Jan 1, 1947

By Y. Dardel

Since the first determination of Dumas1 in 1880, many authors have tried to measure the solubility of hydrogen in solid aluminum, or at least the amount of dissolved gas in it. However, the interpretation of the results which have been obtained is still difficult. Sieverts? then Baukloh and Oesterlen,a during their gassing experiments could not determine any solubility of hydrogen in solid aluminum. On the other hand, Portevin, Chaudron and Moreq4 leaving the determination of the hydrogen solubility beyond the scope of their experiments, measured only the amount of gas that they could extract by high voltage positive ion bombardment and found up to 151 cm3 of gas per I00 g of metal. Winterhager,6 by repeated vacuum extraction during severe cold rolling, extracted up to 161 cm3 per 100 g. In both series of experiments, the extracted gas contained chiefly hydrogen with a small amount of nitrogen, carbon monoxide, carbon dioxide and methan. Later, Schmidt and von Schweinitze as well as Chaudron and Moreau7 showed the importance of the adsorbed layer of hydrogen, the extracted quantities being proportional to the surface and not to the weight of the sample, when its cleaning was not perfect. In earlier experiments, Steinhausers extracted from more massive samples nothing but a little amount (< 0. 5 cm3 per I00 g) of hydrogen, carbon monoxide and methane. Thus, according to these experiments the quantity of dissolved gas is probably very small and the effect of the surface could falsify the results of the extraction. However, owing to the care taken by Chaudron and his coworkers, it was clear that all the hydrogen extracted could not come from the superficial layer, or that the links which bound hydrogen to the surface were so strong that the usual method of cleaning could not destroy them. After the main parts of the experiments reported here had already been carried out, Eborall and Ransley9 published the results which they obtained with an analysor having an accuracy of 0.03 cm3 per I00 g, while that of the usual apparatus was only about 0.2 cm3 per I00 g. During all their experiments the adsorbed layer would have been a difficulty, for the value of the adsorbed hydrogen was approximately equal to that of the dissolved amount. Table i—Amount of Adsorbed and Dissolved Hydrogen (After Eborall and Ransley) Extraction Hz Adsorbed „ h2 dissolved Temperature Calculated Extraction OCcma 500 0.057 0.050 600 0.062 o.096 Since always keeping the same adsorbed layer is very difficult, an error in the correction for the adsorption can be made when using the apparatus of. Eborall and Ransley, as well as the earlier apparatus.

Jan 1, 1949

By Robert E. Cuthbertson

IT is the purpose of this paper to describe in detail the laboratory development and mill application of an unusual combination of flotation reagents employed in the concentrator of the Climax Molybdenum Co., on the Continental Divide, near Leadville, Lake County, Colorado. This development originated in an ore-dressing research laboratory maintained by Climax at the experimental plant of the Colorado School of Mines, which is staffed by men directly employed by the Climax Molybdenum Co. Mill-scale testing of laboratory developments was supervised by a representative from the testing laboratory, working in close cooperation with the operating staff at the mill. General milling practice at Climax is ably described in a paper by E. J. Duggan,1 mill superintendent. Other aspects of the Climax project have been described in papers by W. J. Coulter,2 by Butler, Vanderwilt and Henderson3 by Allen Kissock,4 and by Leo H. Glanville.5 Consequently, this paper will be confined to the metallurgical aspects of recent reagent developments, avoiding, as much as possible, repetition of material covered in these earlier publications. BRIEF HISTORY OF REAGENT PRACTICE AT CLIMAX Prior to the year 1937, the only reagents employed at Climax for froth production and collecting action in the flotation of molybdenite were steam-distilled or destructively distilled pine oils. The only exceptions to this practice were brief periods of mill testing, when reagents of various types were tried on an experimental basis. None of these experimental runs was sufficiently encouraging to justify its continuation as regular practice. Sodium, cyanide has been employed since the very early days of milling at Climax as an inhibiting agent for control of pyrite and chalcopyrite. Alkaline reagents such as lime or soda ash have been used in recent years to minimize the detrimental effect of iron salts on flotation of molybdenite. The presence of these harmful salts is attributed to the decomposition of fine metallics abraded from liners and balls in the first stage of regrinding rougher concentrate. Flint pebbles are used in subsequent regrinding, since alkaline reagents are not entirely adequate to offset the inhibiting effect of iron salts as the grind becomes progressively finer and the grade of concentrate progressively higher. Climax metallurgists were familiar at an early date with the use of petroleum products such as kerosene and gas oil as promoters of flotation of molybdenite. Charles C. Oliver6 discussed the use of pine oil and kerosene as early as 1920, in connection with the milling practice at Dominion Molybdenite Co., Quebec. Never theless, the early attempts to apply this knowledge in the Climax concentrator were complete failures. In the light of recent experience, it may seem strange that the early mill tests with petroleum

Jan 1, 1944

By E. J. Duggan

The mine and mill of the Climax Molybdenum Co. are at Climax, Colorado. Climax is on Fremont pass directly on the Continental Divide, at an elevation of 11,400 feet. Description of Ore The Climax ore-bearing rock is essentially an altered and highly silicified granite, fully half of the gangue being quartz. Molybdenite is the only mineral of economic consequence and most of it is intimately associated with quartz in the form of fine veinlets and stringers. Other minerals are molybdite, pyrite, and chal-copyrite. While the molybdite may be readily extracted by hydrometallurgical methods, its content is too low to make such operations profitable. The pyrite content ranges from 2 to 5 per cent and that of the chalcopyrite from 0.03 to 0.05 per cent. There is not enough copper to make its recovery attractive and one of the metallurgical problems is the elimination of it and the pyrite from the product. On account of the close association of the molybdenite with the quartz and the necessity of eliminating the pyrite and chalcopyrite from the final product, fine grinding followed by flotation is the only feasible method of concentration. History Construction of the first milling unit was started in 1917 and it was operated during parts of 1918 and 1919. In the postwar years, there was almost no demand for the product and production was at a standstill until 1924. The Company&apos;s research campaign to develop the use of the metal began to show results in that year. From r926 to 1932 production ranged from 500 to 1200 tons per day. In 1931 an additional mill section was built and production was gradually increased until in 1934 and 1935 about 3000 to 4000 tons was milled per day. This tonnage overtaxed the milling facilities, and as the demand for inolybdenum was growing constantly, additional milling equipment was needed. In 1936 and 1937 another crushing plant, six additional mill sections and the necessary auxiliary plants were constructed and brought into operation. This plant was designed to mill I0,000 tons per day, but it was not long before 12.500 tons was being treated during periods of peak demands. During the summer of 1941, to meet defense needs, the mill has been required to treat 15,500 tons per day. This has been accomplished with little plant expansion and at no loss in recovery, as will be described later. TO increase capacity still further, one more primary section is now being built. This will bring capacity to 18,000 tons per day, which can be stretched to 20,000 tons at a small sacrifice in recovery. Crushing There are two crushing plants: No. I, of 5000 tons capacity (flowsheet in Fig. I) and No. 2, of 15,000 tons capacity (Fig. a).

Jan 1, 1943

By W. H. Brandt

ThEre has been much progress in the last two decades in understanding the hardenability of steel. Roughly, the progress has been along two lines, which may be designated as empirical and fundamental. This empirical work has progressed to the point where steels may be manufactured to the desired characteristics quite closely and heat-treatment and application problems can be approached with considerable confidcnce. Particularly noteworthy among the empirical work is that of Grossmann,12. who has given formulas for calculating hardenability as a function of composition, and the establishment of the isothermal transformation curve by Davenport and Bain.13 The latter does not fall entirely in the class of an empirical study, for while it provides a means of presenting a tremendous amount of empirical data in the form of a single curve, it also outlines clearly the problems that face the fundamental investigator. The isothermal transformation curve shows clearly that the phenomena occurring in the neighborhood of the knee of the curve are those that limit the hardenability of steel. Above the knee of the curve, the product of decomposition of austenite is lamellar pearlite and fundamental progress has consisted chiefly of a detailed study of structure and formation of pearlite, largely at the hands of Mehl and his collaborators.&apos;-5 They have shown that formation of pearlite proceeds by a process of nuclea-tion and growth and they measured both the nucleation and growth rate. However, there is still a wide gap between our empirical knowledge and fundamental knowledge, owing largely to the fact that there is no satisfactory theory of nucleation rate or of growth rate. This paper is being written in an attempt to Hl in a small part of the gap. A method was prcsented recently1&apos; for calculating the velocity of edgewise growth of pearlite using an expression for the carbon concentration that satisfies the diffusion equation. The edgewise velocity of pearlite growth in a plain carbon eu-tectoid steel was calculated, using linear extrapolations of the ferrite and comentite solubilities. While the results are in fairly good agreement with the experimental facts, the calculated velocity of edgewise growth is smaller at 600°C. than G, the radial growth velocity of pearlite nodules, whereas one would expect it to be larger. In this paper the calculation will be repeated using a new extrapolation for the ferrite solubility, which gives better agreement between G and T&apos;, the calculated velocity of edgewise growth. A calculation will also be made of the effect of carbon content on velocity of edgewise growth, and the problems of calculating the effects of other alloying elements on growth rates will be discussed. It will be assumed that the mechanism of pearlite growth, established by Mehl and

Jan 1, 1947

By A. V. Deforest, A. R. Anderson, C. W. MacGregor

ONE of the important problems in the design of structures and machine parts subjected to rapidly applied loads is the determination of the strength and ductility of the material itself under such conditions. Realizing the need for such information, many investigations have been carried out in the past. Most of these experiments have been made using notched bars in bending either with the Charpy or Izod impact machine. While yielding valuable data on the effect of notches in the energy absorption of the material and on the condition of heat-treatment, this form of test does not lend itself readily to a determination of fundamental stress-strain relations. For this and other reasons, more attention has been paid recently to the tension impact test. An extensive literature already exists on the subject and only those investigations somewhat closely related to the present paper will be mentioned. For a more comprehensive list, the reader is referred to the Symposium on Impact Testing of the A.S.T.M., 1938. The work of Mann,1 Clark and Dätwyler,2 Nádai and Manjoine,3 Winlock and Leiter,4 Deutler,5 and Brinkmann,6 however, deserve especial mention. In most of the previous investigations on the subject, when stress-strain relations were obtained under high rates of loading, it was the common procedure to determine stresses based on the original area and strains based on the original length. Stress-strain curves were then constructed by [P OL, plotting So = Ao as a function of eo = Lo] where A o and Lo refer to the original area and gauge length, respectively. At present there exists a paucity of true stress-strain data in the impact problem. The advantages of constructing so-called true stress-strain curves in order to reveal the fundamental physical properties of the material for the tension test were discussed recently by one of the authors&apos; It was shown that the true physical behavior of the material in the tension test could best be represented [by plotting the average true stress, S = P as a function of e = q&apos; = log o = log Log] where P, A, L, S, e, and q&apos; refer to the load, the cross-sectioned area while the load P is applied, the actual gauge length, the average true stress, the true strain and true reduction in area, respectively. Besides giving a better physical representation, the method has certain additional advantages in that the stress-strain curve so plotted becomes a straight line from the maximum load point to fracture. The construction of such- curves, however, while comparatively simple for the slow rates of loading customarily used in the tension test, presents certain difficulties for tensile impact in that both loads and diameters are required throughout the test. The continuous measurement of test-piece

Jan 1, 1941

By W. H. Brandt

ThEre has been much progress in the last two decades in understanding the hardenability of steel. Roughly, the progress has been along two lines, which may be designated as empirical and fundamental. This empirical work has progressed to the point where steels may be manufactured to the desired characteristics quite closely and heat-treatment and application problems can be approached with considerable confidcnce. Particularly noteworthy among the empirical work is that of Grossmann,12. who has given formulas for calculating hardenability as a function of composition, and the establishment of the isothermal transformation curve by Davenport and Bain.13 The latter does not fall entirely in the class of an empirical study, for while it provides a means of presenting a tremendous amount of empirical data in the form of a single curve, it also outlines clearly the problems that face the fundamental investigator. The isothermal transformation curve shows clearly that the phenomena occurring in the neighborhood of the knee of the curve are those that limit the hardenability of steel. Above the knee of the curve, the product of decomposition of austenite is lamellar pearlite and fundamental progress has consisted chiefly of a detailed study of structure and formation of pearlite, largely at the hands of Mehl and his collaborators.&apos;-5 They have shown that formation of pearlite proceeds by a process of nuclea-tion and growth and they measured both the nucleation and growth rate. However, there is still a wide gap between our empirical knowledge and fundamental knowledge, owing largely to the fact that there is no satisfactory theory of nucleation rate or of growth rate. This paper is being written in an attempt to Hl in a small part of the gap. A method was prcsented recently1&apos; for calculating the velocity of edgewise growth of pearlite using an expression for the carbon concentration that satisfies the diffusion equation. The edgewise velocity of pearlite growth in a plain carbon eu-tectoid steel was calculated, using linear extrapolations of the ferrite and comentite solubilities. While the results are in fairly good agreement with the experimental facts, the calculated velocity of edgewise growth is smaller at 600°C. than G, the radial growth velocity of pearlite nodules, whereas one would expect it to be larger. In this paper the calculation will be repeated using a new extrapolation for the ferrite solubility, which gives better agreement between G and T&apos;, the calculated velocity of edgewise growth. A calculation will also be made of the effect of carbon content on velocity of edgewise growth, and the problems of calculating the effects of other alloying elements on growth rates will be discussed. It will be assumed that the mechanism of pearlite growth, established by Mehl and

Jan 1, 1947