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By G. E. McElroy

Much attention has been directed to mine-air flow in recent years, more especially in Great Britian where there is frequent reference to a theory of fluid flow developed by English engineers. Briefly stated, this theory is that for similar passages of the same relative roughness, in which fluid flow occurs, the conditions of flow are exactly the same for W D V equal values of the product where W = density of the fluid, D = diameter of the passage through which flow occurs, V = mean velocity of flow, and p = absolute viscosity of the fluid flowing. This, the "Reynolds Criterion" of fluid flow, had its origin in the work of Reynolds1 more than 40 years ago. Later, Rayleigh2 amplified the theory which has been conclusively proved for small pipes by the experiments of Stanton and Panne13 over a large flow range, and by Lacey4 over a somewhat more limited range. Concordant results on small pipes have also been obtained by numerous other investigators with single fluids over more or less limited ranges of flow. According to this theory, results in one medium, such as water, are immediately applicable to another, such as air; and experimental results on models are (theoretically, at least) applicable to full-scale designs. This is of great importance in aeronautics and can be of considerable value in mine ventilation research. Hodgson, in a recent paper,6 has outlined the application of this theory to mine-air flow and recent English experiments6 on the resistance of a timbered mine airway have been expressed in this form.

Jan 1, 1927

By W. F. Holbrook, C. E. Wood, E. P. Barrett

The high-frequency laboratory induction furnace with a rotating liquid crucible enables research workers to conduct certain investigations heretofore very difficult or impossible to realize because vessels are not obtainable that are capable of resisting the physical conditions or the chemical actions to which they are subjected. Applications for patents covering commercial uses of centrifugal liquid crucibles were filed in the United States in 1919,' in France in 1925, in the United States and Germany in 1926,2 and in France in 1927.3 In 1928, Schuette and Maier,4 of the Bureau of Mines, reported the construction of a whirling table beneath a high-frequency induction furnace. Shape and Size of Centrifugal Liquid Crucibles When a vessel containing a liquid is rotated, the inner surface of the liquid takes the shape of a paraboloid under the simultaneous action of centrifugal force and gravity. The internal dimensions of the paraboloid rotating liquid crucible are governed by the diameter of the container and its speed of rotation. Melted Wood's metal was poured into cylinders 2 1/2 in. in diameter, which were rotated at 180, 300, and 468 r.p.m. When the metal was solid, a slurry of plaster of Paris was added, and rotation continued until the plaster had set. Fig. 1, a photograph of sections of the cylinders, shows the effect of speed of rotation of the containers upon the shape of the inner surface of the rotating liquid crucibles. Types of Furnaces Three types of high-frequency induction laboratory furnaces using liquid-metal crucibles were designed and constructed by the Blast

Jan 1, 1939

By W. F. Holbrook, C. E. Wood, E. P. Barrett

The high-frequency laboratory induction furnace with a rotating liquid crucible enables research workers to conduct certain investigations heretofore very difficult or impossible to realize because vessels are not obtainable that are capable of resisting the physical conditions or the chemical actions to which they are subjected. Applications for patents covering commercial uses of centrifugal liquid crucibles were filed in the United States in 1919,' in France in 1925, in the United States and Germany in 1926,2 and in France in 1927.3 In 1928, Schuette and Maier,4 of the Bureau of Mines, reported the construction of a whirling table beneath a high-frequency induction furnace. Shape and Size of Centrifugal Liquid Crucibles When a vessel containing a liquid is rotated, the inner surface of the liquid takes the shape of a paraboloid under the simultaneous action of centrifugal force and gravity. The internal dimensions of the paraboloid rotating liquid crucible are governed by the diameter of the container and its speed of rotation. Melted Wood's metal was poured into cylinders 2 1/2 in. in diameter, which were rotated at 180, 300, and 468 r.p.m. When the metal was solid, a slurry of plaster of Paris was added, and rotation continued until the plaster had set. Fig. 1, a photograph of sections of the cylinders, shows the effect of speed of rotation of the containers upon the shape of the inner surface of the rotating liquid crucibles. Types of Furnaces Three types of high-frequency induction laboratory furnaces using liquid-metal crucibles were designed and constructed by the Blast

Jan 1, 1939

By Noel S. Christensen

COBALT is a silvery white metal with a slight bluish cast, strongly resembling nickel in its appearance and properties, notably its resistance to corrosion, although its alloys with other metals differ quite decidedly in their properties from those of nickel. The name cobalt was derived from the German "Kobold" meaning goblin and this came to be applied to the cobalt minerals which, although they resembled ores, did not readily yield metal when smelted by the primitive processes available in the Middle Ages. Cobalt minerals were used as pigments by potters and glass workers before the Christian era. Cobalt blue glass was found in the tombs of the Egyptians and in the ruins of Troy, and many colors used by the ancient Greeks and Romans contained cobalt. The ancients were entirely unaware that the colors they used were caused by cobalt and the metal itself was only isolated about the middle of the eighteenth century by Brandt although the preparation of cobalt compounds had been carried on in a small way ever since the opening of the silver-cobalt deposits at Schneeberg, Germany, in 1470. The metal is fairly hard, with a density when pure of 8.81 in the cast state and 8.92 after working. The commercial grade of cobalt has a density of about 8.75 in the cast state. The atomic weight is 58.97. The Brinell hardness of the pure metal is 124; that of the commercial grade varies from as low as 100 to as high as 138, depend¬ing upon the impurities present. Pure cobalt has a sharp melting point at 1478°C. The tensile strength of the pure metal in the cast condition is said to be higher than that of any other pure metal. Kalmus gives it as 34,400 lb. per sq. in. for cast unannealed metal; the effect of annealing at 850 to 900°C. is to raise the strength slightly. The yield point is close to the ultimate strength and the reduction in area and elongation are both low. Mechanical working raises the tensile strength of pure cobalt rapidly and in the form of wire it will be over 100,000 lb. per sq. in. The presence of small quantities of carbon in the commercial metal raises the tensile strength to as high as 61,000 lb. per sq. in., the reduction in area and elongation being raised at the same time to approximately 20 per cent.

Jan 1, 1933

By L. L. Melton, D. L. Lord, B. W. Hulsey

A mathematical model d1.20p/4L = A(8v)8 derived from the Blasius equation is proposed to be applicable to turbulent flow through straight cylindrical pipe for time-independent fluids which produce a diameter family of straight parallel lines on a log (dp/4L) vs log (8v/d) plot or stress-flow diagram. Such a correlation should permit scale-up with data taken from one pipe diameter for Newtonian, inelastic non-Newtonian and viscoelastic fluids, such as dilute polymer fracturing fluids, which produce considerable frictional pressure reductions. The Newtonian diameter exponent value 1.20 is shown to be empirically valid for turbulent non-Newtonian flow by application of numerical analysis methods. Multiple regression analysis is applied to a logarithmic linearization of the proposed model. An improved data fit results from further linearization achieved by taking linear terms from a generalized Taylor's series expansion about the multiple regression coefficients. Extensive experimental data obtained in five pipe diameters with water, sodium carboxymethyl-celIulose solutions, guar gum solutions, bentonite clay suspensions and calcium carbonate slurries are presented. Except for calcium carbonate slurries, which were investigated rather than time-dependent cement slurries, the fluids studied contain drilling or fracturing fluid additives. The behavior exhibited by these fluids is considered typical of most fluids encountered in drilling, cementing and fracturing operations. INTRODUCTION Considerable difficulties have been encountered in predicting turbulent flow pressure drops produced by non-Newtonian fluids flowing through straight cylindrical pipe. Correlations previously presented require extensive experimental data which represent several pipe diameters and a wide flow rate range to estimate the necessary scale-up parameters.l-7 One must implement either elaborate experimental apparatus or spend considerable time and effort to gather these data. Presented here is a correlation method which should minimize the experimental effort and data analysis normally required by utilizing flow data taken with only one pipe diameter. Turbulent flow data (up-stream and down-stream pressure and volumetric flow rates) were collected for five pipe diameters through operation of a small pipeline system having an electronic data acquisition and digitizing system. A mathematical model derived from the Blasius equation was utilized to describe the functional relationship between pressure drop and the two independent variables, diameter and average flow velocity. A correlation, which should produce a valid single-pipe scale-up, resulted from a computer-implemented statistical and numerical data analysis for several time-independent non-Newtonian fluids.

By Donald R. Rathburn, Jung K. Mok

An historical review and a survey of current practice in the application of fine dry grinding in the iron ore industry are given. Both closed and open-circuit applications are reviewed, and the advantages, disadvantages, and process considerations for these two systems are discussed. The ground ore temperature rise, and the cool-ing of ground ore and mill ventilation are also discussed, along with the agglomerating characteristics of dry ground ore. Screening during the production of high-grade lump ore for blast-furnace burden, particularly from recently developed ore deposits in Australia, South America, and Africa, has resulted in large tonnages of fine iron ore. Certain owners have decided to stockpile these fines until some later date. Others have either sold these fines "as is" for agglomeration at the steel plant or have established their own pelletizing plants to produce a premium quality agglomerate. In almost all cases some grinding is required prior to pelletizing. Most of these ores occur in the weathered state which may result in difficulty in the thickening and/or filtering stages when ground in a wet system. The resulting filter cake would probably require partial drying to provide a product suitable for the subsequent balling operation; however the partial drying and subsequent material-handling steps often produce random agglomeration. Normally, these agglomerates will cause problems in the green ball formation process. Thus dry grinding has developed as a solution to this problem. Most of the dry iron ore grinding installations utilizing the standard-type rod or ball mill are grinding high-grade natural ores that do not require beneficiation. Although power consumed per ton of final product is 120% or greater in dry grinding as compared with wet grinding, the additional power required for dewatering and handling a wet ground product can easily exceed the initial power savings. Dry grinding of raw feed and clinker has been practiced in the cement industry for many decades but its major application to the iron ore industry has taken place only within the past ten years. The successful application of dry grinding to iron ore has required the solution of several unique design and operating problems. The purpose of this paper is to review recent developments in fine dry grinding of iron ore for pelletizing and to discuss the various designs and operating parameters involved.

Jan 1, 1971

By Thomas Leonard Watson

SULPHIDE ore-bodies of more or less lenticular shape occurring in metamorphic crystalline schists, gneisses, and. slates, and conforming closely in strike and usually in dip to the inclosing rock, have been recognized and described along the, Atlantic seaboard from Quebec to Alabama. The ore-bodies do not entirely conform, in all cases, to the structure of the inclosing schists, but they sometimes cut across the foliation in dip, though conforming more closely with the direction of strike. In composition the principal sulphide mineral is usually pyrite or pyrrhotite; or both, accompanied by copper, frequently gold, and almost always some sphalerite and galenite. Other. metallic ores are, so far as these sulphide bodies have been investigated, less common; silver is not uncommon, and in some of the pyrrhotite masses nickel is present in quantity sufficient to be commercially valuable. Cobalt frequently accompanies .the nickel, usually in smaller amount, and the two vary much in relative proportion. Quartz and calcite are probably the most common of the, non-metallic minerals. A number of silicate minerals are frequent representatives in one place or another; garnet, amphibole, biotite, pyroxene, zoisite and others. The sulphide bodies of Virginia, comprising both pyrite and pyrrhotite, are among the most extensive along the Atlantic seaboard. Among the pyrite bodies may be mentioned the well-known and extensively worked mines of Louisa and Prince William, counties, located on' the main pyrite belt (A, Fig. 1) of the middle and northern, eastern Piedmont region in Virginia, and among the pyrrhotite bodies is the famous " Great Gossan Lead "(B, Fig. 1) of the Floyd-Carroll-Graysou coun-

Sep 1, 1907

By Eric Hedburg

This paper was originally prepared as a picture of the situation presented by the mining industry referred to at the end of the year 1899; and some of the descriptions and drawings of special mines, etc., may not completely show their condition a year later. The statements made as to the cost of mining and concentration, however, still hold good. As to other general statements made in the paper, it is believed that the following additional facts cover all that is required to complete them for the additional year. The condition of the mining industry in the Joplin district was better at the close of 1900 than at any time during several preceding years. Values seemed to have adjusted themselves, in considerable degree, to the commercial and technical circumstances, the cost of mining-supplies of all kinds had returned to a normal basis, and the product of ore found a ready sale,

Jan 1, 1902

By James E. Little

(Wilkes-Barre Meeting, June, 1911.) OF the several extensive deposits of brown iron-ore in Cuba, including those of Mayari and Moa, that of Mayari was the first to be systematically explored, and was selected as the scene of the first operations in the development of this class of ore. Construction-work, begun in the spring of 1907, involved the building of 16 miles of standard-gauge railroad and two large double-track inclines, the installation of mining-machinery, a nodulizing-plant, power-plant, shops and shipping-facilities, and the dredging of an extensive basin for deep-draught vessels. Unusual weather-conditions delayed the completion of portions of this work so that the entire plant was not in operation until December, 1909. The ore in its natural state contains a very large percentage of water, which increases to some extent with the depth below the surface. Near the surface it is red in color, with somewhat granular structure. The color gradually changes with depth, finally reaching a bright yellow. The consistency also changes towards, the bottom to a clay-like, sticky mass. The relative proportion of red and yellow ore is quite variable; in some places the yellow reaches close to the surface, while in others the red extends almost to the underlying serpentine. Fig. 1 is a map showing the Mayari division of the Spanish-American Iron Co. The ore lies on an irregular plateau about 15 miles long and 5 miles wide at the widest point, entirely covered with pine trees and brush, which grow directly on the ore. The elevation at the northern extremity, which is approached by the railroad, is about 1,700 ft. above sea-level. At the southern end the general elevation is about 2,000 ft. Ore is removed by means of scraper-bucket excavators and steam-shovels, these machines loading into special standard-guage, side-dump steel cars of 100,000 lb. capacity. A short haul

Aug 1, 1911

By Joseph A. Holmes

I. INTRODUCTORY. THE plans for the investigation of fuels and structural materials now being conducted by the Technologic Branch of the United States Geological Survey were, before being decided upon by the Director of the Survey, submitted for consideration to the National Advisory Board, upon which there are nine representatives from the membership of the American Institute of Mining Engineers, viz.: Messrs. John Hays Hammond, Robert W. Hunt, B. F. Bush, and E. V. d'Invilliers (representing the Institute); Messrs. Julian Kennedy and C. S. Robinson (representing the Iron and Steel Institute); Dr. Charles B. Dudley (representing the American Society for Testing Materials); Mr. F. H. Newell (representing the U. S. Reclamation Service); and Dr. Richard Moldenke (representing the American Foundrymen's Association). It seems fitting, therefore, that a report of these investigations of the past three years should be submitted to the Institute for publication in its Transactions. The above, together with other representatives of the national engineering societies and allied organizations, were invited by President Roosevelt to serve, along with the Chiefs of the several Government Bureaus who have charge of public works and large. fuel purchases, on the National Advisory Board to give advice concerning these investigations. The appointment of this National Board grew out of a wish on the part of the President, the Secretary of the Interior, and the Director of the Geological Survey not only that the appropriations for these investigations be expended in a manner most beneficial to the several branches of the government

Jan 7, 1908

By H. L. Shergold, O. Mellgren

Concentration of fine quartz particles at the iso-octane/water interface has been investigated under different conditions of pH and dodecylamine concentration. The results obtained from the related studies on the effect of amine concentration and pH on the interfacial tension, adsorption density, electrokinetic potential, contact angle, and concentration of the various amine species in the system are presented. A good correlation was obtained between these different variables. It is well-known that very fine mineral particles are difficult to float in conventional flotation machines. Flotation rate studies have revealed that the rate of flotation of fine mineral particles is much smaller than that of coarser size fractions. The theories accounting for this behavior have been discussed by Arbiter and Harris1 and also Meloy.2 Theoretically, a hydrophobic fine particle might never make contact with a bubble because of the presence of an energy barrier in the vicinity of the air/water interface.' This energy barrier will have electrostatic, hydrodynamic, and Van der Waals force components. It was thought that by using an oil phase instead of air the energy barrier would be decreased so that fine particles could be concentrated at the oil/water interface more readily than at the air/water interface. The technique used involves dispersing the fine particles in water, containing the appropriate chemical reagents, and injecting a fine dispersion of iso-octane oil droplets into the pulp. After vigorous conditioning, the pulp is passed into a separating column where the oil droplets coated with a layer of mineral particles rise to the surface to form a separate layer. Air is introduced into the base of the separating column to ensure that heavy agglomerates of oil and particles report with the organic layer. This technique has been described previously4 and adopted by Lai and Fuerstenau5 who studied the alumina-dodecyl sulfonate system. The interfacial phenomena in the system composed of hematite, water, and iso-octane in the presence of sodium dodecyl sulfate have been studied and the results reported" earlier. This paper describes the results obtained from investigations into the interfacial phenomena in the quartz/water/iso-octane system in the presence of dodecylamine. The technique used in measuring the interfacial tension, electrokinetic potential, contact angle, and adsorption density were similar to those described previously? Materials Selected pieces of a high purity natural quartz, from the Isle of Man, were crushed in a laboratory jaw crusher and pulverizer. The — 52+72 mesh size fraction was retained and leached with successive washes of hot concentrated hydrochloric acid to remove iron impurities. When no iron was detected in the solution by ammonium thiocyanate, the quartz was washed thoroughly with distilled water until the conductivity of the wash water assumed that of the distilled water. Samples of 25 g of the —52+72 mesh quartz were ground for 5.25 min in an agate vibratory mill. The ground product was 100% —44 m and 57% —10 am, as determined by the Andreasen pipette. The specific surface area of the sample used for the adsorption and flotation tests was 0.94 sq m g-l. This corresponds to a mean particle diameter of 2.4 am. The —44 am quartz sample was stored under vacuum in the presence of silica gel crystals. For the contact angle determination between the three phases, quartz, iso-octane, and water, a piece of the natural quartz was ground into a block about 15 mm long, 15 mm wide, and 5 mm thick. One surface of the block was then polished by successively finer grades of silicon carbide "paper." The final polishing was conducted with alumina on a "hyprocel" paper. The polished quartz specimen was cleaned using nitric acid and ethyl alcohol followed by a wash with distilled water and then stored under distilled water. This pro-

Jan 1, 1971

By R. Kerby, T. R. lngraham

The rates of cadmiuln cementation from buffered solutions were studied on both the cylindrical and circular faces of a rotating zinc disk. The activation energies are equivalent on both surfaces, but the rate is more rapid on the cylindrical face. At higher temperatures and at pH values above 6.4, the rate of deposition increases because of an increase in the cathodic area of the deposit. The rate may also be increased by decreasing the thickness of the diffusion layer by rapid stirring. The presence of small amounts of copper, cadmium, lead, iron, or aluminum in the zinc does not affect the cementation rate, but when srnall amounts of copper, cobalt, and arsenic were present in the solution cadmium deposition ceased shortly after it started. Small amounts of copper in solution become cemented with the cadmium to form a coarse deposit of Cd3Cu. When zinc ores containing cadmium are processed for electrolysis, the cadmium appears with the zinc in the leach liquors. Because of the discharge potential of the cadmium ion and the hydrogen overvoltage on metallic cadmium, the cadmium ion must be removed prior to zinc electrolysis to prevent its codeposition. Cadmium is usually removed from acidic zinc sulfate solutions by cementation on zinc. When zinc sheets are used with the appropriate conditions of pH and temperature, a finely divided, high-purity cadmium powder is obtained; it floats to the surface with attached hydrogen bubbles and, after careful washing, may be processed directly to a marketable product.' The reaction on zinc sheets is relatively slow because of the limited amount of exposed cathodic area on the sheets. A much more rapid reaction is obtained when zinc powders are stirred into the solution, but this procedure does have a potential disadvantage: some unreacted zinc may be trapped in the cemented cadmium and thus lower its grade.1 The equilibrium constant at 25°C for the displacement of cadmium by zinc is of the order of lo", which indicates that at equilibrium the displacement would be essentially quantitative and no back reaction need be considered. This indication is not entirely true, however, because in the presence of oxygen any loose cadmium which is out of contact with metallic zinc tends to redissolve after cementation.' The overall effect is much the same as that to be expected if the equilibrium constant were much smaller. Previous experimental work on cementation reac- tions3 is in general agreement that the rates of cementation usually follow first-order kinetics. The metal on which cementation occurs is considered to consist of anodic areas from which metal dissolves and cathodic areas onto which the reactive metal is cemented. For the reaction to continue, the cemented deposit must remain open and porous for the removal of ions. Usually, the deposited metal influences the rate of cementation; when it blocks the pores in the deposit, the rate of cementation will be decreased. Alternatively, when the cemented metal grows as den-drites or as coarse powder the cathodic area is correspondingly increased and the rate of cementation increases,3 Thus, it is only during the initial stages of cementation, prior to the development of deposit effects, that the kinetic behavior of the reaction may be studied without ambiguity. In this paper, experiments will be described for cementation of cadmium from dilute solutions onto the surface of a rapidly spinning zinc cylinder. The effects of ionic concentration, disk rotation speed, temperature, and impurities will be described. APPARATUS AND PROCEDURE The apparatus used for the experiments was described in a previous paper.4 It consisted of a 2-liter vessel in which the contents were protected, against oxidation, by a stream of prepurified nitrogen. The vessel was immersed in a water bath which controlled

Jan 1, 1970

By Morris J. Elsing

FOR MANY YEARS lead and zinc have had the so-called protection of a tariff and it is the purpose of the following brief discussion to show what' such protection actually accomplishes with a view to forecasting the possible results of the present copper tariff. In analyzing the subject, tabulations of the United States production, consumption, imports and exports, including ore and concentrates and all of the metallic products, of both lead and zinc have been made for each year since 1900. Of these data, the relationship of the imports and exports and the relative foreign and domestic prices are shown in Table 1. The conclusions drawn from these figures are listed below. 1. The United States is an exporter of zinc. 2. The United States is an importer of lead. 3. The average price of zinc at St. Louis for the last 32 years has been no higher than on the London market even though zinc and zinc ore have "enjoyed" a protective (?) tariff of varying amounts per pound for 22 years of this period. 4. The average price of lead on the New York market for 32 years has been 1.2c. per pound higher than on the London market, the tariff varying from 0.75 to 1.5c. per pound of lead in ore, and 1 to 2c. or more on manufactured lead.

Jan 1, 1932

By J. Chipman, N. J. Grant, H. L. Bishop

In a recent review1 of the iron-oxide activity of simple open-hearth type slags containing lime, magnesia, silica, and iron oxide, it was established that activity values were lacking in the range of slag composition most interesting to open-hearth operators. That is, laboratory experimental results were not available for simple slag compositions having basicity ratios ranging from about 1.5 to 4.0 and iron-oxide concentrations ranging from about 10 to 30 pct. However, in order to estimate iron-oxide activities for the range of slag compositions of interest to open-hearth operators, activity values were calculated using ionic concepts of slags by following the treatment of Flood and Grjotheim.2 A study of these data indicated that the desired slag compositions were probably not obtained due to the limited solubility of the basic constituents lime and magnesia. Thus, it was decided to make additional heats equilibrating molten carbon-free iron with slags containing MnO, P2O5, and A12O3 in percentages commonly found in open-hearth refining slags, and to examine the liquid slag field over a greater composition range than that of the simple slags studied previously. The ranges of the constituents used in the present study are summarized as follows: Metal Pct 0 0.070-0.201 PctMn 0.005-0.142 Slag Pet CaO 24.45-41.90 Pct MgO 3.23- 9.21 Pct MnO 1.13- 9.62 Pct FeO 20.08-48.7 Pet Fe2o3 2.23-10.14 Pct SiO, 3.51-28.50 Pct P2O5 0.23- 3.65 Pct A12O3 0.43- 3.38 The experimental procedure consisted of equilibrating the slag and metal in an induction furnace provided with a carbon-arc slag heater as described previously by Winkler and chipman.3 The data obtained were used to establish both the iron-oxide activity values and the activity coefficients for FeO and MnO in the open-hearth type slags. RESULTS AND DISCUSSION I) Iron-Oxide Activity of Open-Hearth Type Slags—The iron-oxide activities of various iron-oxide contents of the open-hearth type slags, as calculated from the oxygen content of the metal by the method of Taylor and Chipman, 4 are plotted against the molar ratio of bases to acids in Fig. 1. The data represent slag-metal studies carried out in the temperature range 1530" to 1700°C. For the purpose of this study, the constituents CaO, MgO, and MnO are assumed equal on a molar basis in their effect on the iron-oxide activity; and, PO2,5 is calculated as an equivalent to SiO2 and A12O3 on a molar basis. The total iron content of the slag is calculated to FeO and is represented by the symbol (FeO) The points presented in Fig. 1 represent the results of this investigation for iron-oxide slags containing between 1 and 8 mol pct MnO and less than about 2 mol pct each of A12o3 and PO2,5 The curved lines shown in Fig. 1 represent the results of the summary1 of the iron-oxide activities of simple slags of the system (CaO + MgO) - SiOz - (FeO),. The solid portions of the curved lines represent experimental data, and the broken portions represent iron-oxide activities calculated from ionic concepts of slags. The iron-oxide values of the open-hearth type slags of this study are in good agreement with the values of the simple iron-oxide slag system. Only a slight modification is indicated. The results of this study suggest that the line for 20 mol pct (FeO), should be lowered slightly in the basicity range 1.5 to about 3.

Jan 1, 1959

By W. A. Krivsky, R. Schumann

Relaxation calculations were made to find the temperature distribution in the refractory wall surrounding a tuyere pipe. One set of boundary conditions approxiwated those of a standard copper converter while a second set represented a hypothetical,thermally insulated tuyere pipe. The pvonounced cooling effect of the tuyere is related to the problem of tuyere accretions and tuyere bunching. PARTICULARLY severe service conditions are encountered in the tuyere zone of a basic copper converter during the matte blow. High-temperature gradients result from the juxtaposition of the hot charge and the tuyere pipe carrying cold air. Refractory temperatures near the tuyere mouth vary rapidly with time when the blast is turned on or off. One of the most serious problems is the formation of magnetite accretions around the tuyere mouth, which occurs very rapidly under some operating conditions. As a result, continual punching of the tuyeres is necessary to maintain a satisfactory rate of converting. Thus, if some means could be devised for keeping the tuyere pipes fully open without necessity for punching, a considerable saving should result from reduction in labor cost, maintenance of full capacity operation, and reduction in refractory costs. Recent quantitative studies of the FeO-Fe,O,-SiO, system1 have shown that the solubility of magnetite in iron-silicate slags decreases rapidly with de- creasing temperature in the range of copper converting temperatures. Data taken from the previous work are shown in Fig. 1. Thus the formation of "horns" and accretions around the tuyere mouth can result simply from the freezing out of magnetite on the cooler areas of refractory immediately adjacent to the tuyere pipes. One might expect to find a correlation between the severity of magnetite formation and the area of refractory surface which is cooled below the freezing point of the slag (corresponding to magnetite precipitation). Magnetite itself has a very high melting point (1597°C) so that the accretions are for all practical purposes infusible. The accretions might be dissolved by increasing the silica content of the slag and at the same time raising the temperature, but this approach is not feasible because it results in rapid corrosion of the basic refractory lining of the converter as a whole. In order to understand better the problems involved in tuyere design and operation, it seems essential to have at least a semiquantitative idea of the thermal conditions in the tuyere zone. Accordingly, this paper presents results of thermal calculations for an idealized copper converter tuyere. These calculations follow the so-called relaxation

Jan 1, 1960

By R. J. Sherman, M. R. Achter

Creep rates have been measured for nickel at 1200°F in air and in vacuum, and related to the depth of surface cracks in the specimens tested in the two environments. The surface cracks were observed to grow faster in air than in vacuum in both short-time and long-time tests. Crack depths, however, could be correlated with creep rates only in the short-time tests. Although no cracks were observed in a relatively brittle Ni-Cr-A1 alloy creep tested at 1300°F, the appearance of alloy specimens fractured after interruption in creep indicated that there was a decrease of intergranular cohesion resulting from the diffusion of atmospheric gases into grain boundaries. PREVIOUS investigations1-3 have demonstrated that the effect of atmosphere on the high-temperature strength of nickel and nickel-base alloys may be reversed by changes in the stress or temperature of the test. At high stress and low temperature the creep-rupture life is longer in vacuum than in air, while at high temperature and low stress the relative strengths are reversed. A mechanism to explain this behavior was proposed based on two competing processes. Oxidation hardens and strengthens a metal, but adsorption of gas, by lowering surface energy, reduces the work required to propagate an intergranular crack. The controlling process is determined by temperature and stress. Basic to this mechanism is the concept that environment determines the ease of propagation of intergranular cracks and thus affects creep rate and rupture life. To explore the mechanism in greater detail, this investigation was undertaken to determine the effect of atmosphere on crack initiation and propagation rates in nickel1 and a relatively brittle Ni-Cr-A1 alloy.3 EXPERIMENTAL PROCEDURE The materials were the same as used previously. Nickel of 99.8 pct purity had the following impurity content: 0.02 pct Co, 0.03 pct Fe, 0.02 pct Mg, 0.03 pct Si, and 0.008 pct C. Rods were cold swaged from 1/2 in. to 3/8 in. in diam and machined into speci- mens with gage sections 1/4 in. in diam by 1-1/4 in. long. They were annealed in vacuum at 1600" F for 1 hr to achieve a grain size of 0.07 mm. The alloy was composed of 19.1 pct Cr, 3.6 pct Al, 1.7 pct Si, 0.57 pct Fe, 0.10 pct Mg, 0.027 pct C, 0.004 pct S, and the balance Ni. Sheet specimens of 0.500-in. width and 1.25-in. gage length were machined from 0.033-in.-thick strip and annealed in vacuum at 2000° F for 2 hr, resulting in a grain size of 0.036 mm. Large amounts of an intergranular phase were introduced as a result of the anneal. Creep tests on both materials, using equipment previously described by Shahinian; were conducted in air and in a vacuum of 1 x 10-5 mm Hg. They were continued to rupture and interrupted at various stages of the test. Although extensions were measured from dial gage readings of movement of the lever arm, it is considered that valid comparisons of creep rate may be made in this manner.l Two parameters were measured metallograph-ically* on longitudinal sections of nickel specimens interrupted during creep—the mean depth of surface cracks 2, and the density n as the number of cracks per unit length of surface. They were combined into one parameter by the relation p = n-d [1] As used here, p is equal to the total of crack depths per unit length of surface. RESULTS Nickel. It is well known that the incidence of intergranular cracking is increased with increasing rupture life. Indeed, it is evident in Tables I and I1

Jan 1, 1962

By Louis A. Rosales, Kanji Ono

The anomalous behavior of hydrogen in iron is examined and a new model is proposed It is postulated that hydrogen single and di-interstitials are in equilibrium with each other. When the binding enthalpy of the di-interstitial, B, is assumed to be about 10 kcal per mole, the predicted temperature dependence of the solubility agrees reasonably well with the reported data. Effective diffusiuity is calculated assuming the di-interstitials to be immobile. Since the number of mobile single interstitials is greatly reduced at lower temperatures, the effective diffusivity is decreased. A good agreement in the temperature dependence of diffusivity between theory and experiment is provided with B - 10 kcal per mole. The predicted diffusivity is also a function of total concentration of hydrogen and this appears to be Partly responsible for the large scatter in the reported data. HYDROGEN is known to form an interstitial solid solution with iron.''' At elevated temperatures, it has been well-established that hydrogen enters iron in the dissociated form and occupies the interstices, and that diffusion of hydrogen in iron is via the interstitial mechanism. The concentration, c, permeability, P, and diffusivity, D, of hydrogen in iron have been separately determined and are consistent with each other under the steady-state condition for temperatures above approximately 400°C; that is, the relationship P = c-D holds. At lower temperatures, however, anomalous behavior of hydrogen in iron has been observed by many investigators. The results of experimental studies4-'' of the diffusion of hydrogen in iron are summarized in Fig. 1, in which the values of D are plotted against the reciprocal temperature. Although there is an increasing divergence in observed values of D with decreasing temperature, the values of D at temperatures below approximately 200°C are definitely small as compared with the extrapolation from high-temperature data. The lines shown bracket the region containing the most probable data. The observed values of c6," are plotted against the reciprocal temperature in Fig. 2, where the dashed lines represent Geller and sun's'' most probable isobars at 1 and 100 atm. At high external hydrogen pressure and low temperatures, the values of c observed are higher than those expected from high temperature data. It is generally accepted that certain trapping mechanism is responsible for the anomalies, but the nature of the trapping mechanism has not been clarified. Various types of hydrogen traps were suggested in the literature, such as "rifts" in the lattice dislocations, voids, microcracks, and so forth. However, no quantitative account of the observed behavior has been given in terms of these trapping mechanisms. Formation of methane in hydrogen-charged steel was found by ~odgurski." This appears to explain the existence of the so-called "residual" hydrogen,4 but not the observed anomalies of hydrogen in iron. McNabb and Foster' proposed a mathematical analysis in terms of a trapping mechanism. However, the physical significance of the traps was not clarified. The necessity of evaluating five parameters in their theory made comparison with experiment difficult. In the present paper, a model is proposed in which the anomalous behavior of hydrogen is attributed to the formation of hydrogen di-interstitials at lower temperatures. In this model, it is postulated that single and di-interstitials are in equilibrium with each other. (The hydrogen di-interstitial is to be distinguished from a hydrogen molecule which may exist in voids.) It can then be shown that most of the anomalies can be explained by assuming that the di-interstitials are virtually immobile and that the binding enthalpy of the di-interstitial, B, is approximately 10 kcal per mole. Predictions of the theory agree with the available experimental data reasonably well. THEORY The basic postulate of the present analysis is that single and di-interstitials are in equilibrium with each

Jan 1, 1969

By R. S. Rickard, H. D. Peterson, J. D. Miller, M. C. Fuerstenan

Pure chrysocolla is floated with chelating agents that form insoluble complexes with copper at ambient temperature. Complete flotation is obtained with potassium octyl hydroxamate as collector at pH 6. Flotation response is enhanced with increased temperature when low additions of hydroxamate are involved. A natural ore was floated with 0.4 1b per ton octyl hydroxamate at pH 6.5 and 58°C, and a flotation recovery of 76% was obtained with a concentrate grade of 31.6% copper. The flotation characteristics of the oxide copper minerals, malachite, azurite, and cuprite, have not presented the difficulty for concentration as have those of the copper silicate, chrysocolla. The copper carbonates and oxides respond reasonably well to flotation with conventional collectors, whereas chrysocolla will not respond to flotation with fatty acids or xanthates under normal flotation conditions. In this view then, other reagents will have to be devised to function as collectors for chrysocolla. The most obvious general class of reagents for this purpose would seem to be the organic copper chelating compounds. The utility of chelating agents as collectors in flotation systems has already been demonstrated. For example Vivian1 has floated cassiterite using ammonium nitrosophenylhydroxylamine. Holman2 studied the flotation of nickel oxide ores with dimethylglyoxime and also suggested the use of taurine on oxidized lead ores. A rather detailed study on the application of certain chelating agents to some flotation systems was presented by Gutzeit.3 This work indicated that the formation of surface insoluble chelates is probably responsible for flotation in many cases. The role that soluble chelating agents assume was also presented, that is with effective removal of polyvalent cations by complex formation, effective depression of quartz can be obtained. DeWitt and Batchelder4,5 have shown that oximes function well as collectors for chalcocite, malachite, azurite, and cuprite. Ludt and DeWitt6 have presented the possibility of using dyes, such as octyl malachite green, as a collector for chrysocolla. These works presented by DeWitt et al suggest that organic copper chelating compounds offer considerable promise for concentrating chrysocolla, but that the most suitable chelating reagent from the standpoint of cost and flotation response has yet to be determined. The present investigation was undertaken to study the flotation response of chrysocolla to selected copper chelating compounds, that is ethylenediamine, hexamethylenetetramine, potassium octyl hydroxamate, dimethylglyoxime, and benzoin a-oxime. EXPERIMENTAL MATERIALS Chrysocolla: The chrysocolla used in the microflo-tation studies was from New Mexico and analyzed 20.8% copper. X-ray diffraction showed this material to be amorphous in character, but some faint lines of quartz were noted. A natural oxide copper ore from Utah was also used in the investigation. This ore contains malachite principally but also contains chrysocolla and tenorite together with some sulfide copper. The sulfide copper comprises from 15 to 20% of the total copper content of the ore. Water: Conductivity water was used in the microflo-tation experiments, while Golden tap water was used in the experiments with the natural ore. Reagents: Reagent grade n-amyl alcohol was used as frother in the experiments with pure mineral, while MIBC was used in the work with the ore. Ethylenediamine, hexamethylenetetramine, dimethylglyoxime and benzoin a-oxime were reagent grade in quality. Pure potassium octyl hydroxamate was prepared as follows: 1) 1.0 mole of KOH in 140 cc of methanol was combined with 0.6 mole of hydroxyl-amine hydrochloride in 240 cc of methanol at 40°C (KC1 precipitates under these conditions and to effect complete removal of KCl, the system was cooled to 10°C and filtered), 2) a light methanol wash was then given the KC1 cake, 3) the filtrate was agitated at room temperature and 0.33 mole of the methyl ester of the organic acid (i.e. methyl octanoate) was

Jan 1, 1965

By Donald W. Scott, Nathaniel Arbiter, A. C. Richardson

THIS paper describes the application of amine flotation to a specific problem-that of increasing the grade of magnetite concentrates derived from an iron ore requiring extremely fine grinding for mineral liberation. Experiments conducted on an iron ore from Wisconsin had shown that concentrates containing 60 to 62 per cent iron and 12 to 14 per cent silica could be produced by magnetic separation. The residual silica occurred as quartz and hornblende, either entrained or locked with magnetite. Most advantageous utilization of the concentrate, however, necessitated that the silica content be reduced to about 5 per cent, equivalent to an iron content of 67.5 per cent. It had been demonstrated that tabling of the magnetic concentrate removed sufficient quartz and hornblende to yield an acceptable concentrate, but disadvantages inherent in tabling dictated that flotation be investigated as a substitute. The goals set for the flotation investigation were: (I) the production of concentrates of about 68 per cent iron content from the magnetic concentrate; (2) an iron recovery of about 85 per cent of that in the feed to flotation; and (3) minimum reagent cost. Both batch and continuous flotation tests were employed; the former, to establish the procedure and the latter to verify it. Although the data were obtained on a specific ore, and with a commercial application in view, it is believed that they have a bearing on other problems where amine flotation is being used or is anticipated. SAMPLES Two samples, designated "minus 100mesh magnetic concentrate" and "minus 150-mesh magnetic concentrate," were used for the batch experimental work. They differed only in the degree to which the crude ore was ground prior to magnetic separation. They were stored moist in steel drums in quantities sufficient for all the experimental work reported. This procedure had the advantage of allowing all tests to be made on common samples, but had the disadvantage that the individual flotation samples, because of the difference in storage time, were subject to various stages of surface alteration. Previous work had indicated that common samples were desirable for the batch studies, and it was decided that if these data appeared sufficiently promising the effect of surface alteration could be checked best by continuous tests. The size distributions and the assays of the samples are given in Table I. The minus 150-mesh magnetic concentrate, on which most of the flotation tests were made, assayed 60.9 per cent iron, 13.3 per cent silica, and 0.016 per cent phosphorus. The minus 325-mesh portion represented 78.1 per cent of the sample by weight, and assayed 67.9 per cent iron. Thus, the insoluble, mainly silica, was concentrated

Jan 1, 1945

By S. E. Haszko

Fused alumina or silica crucibles were used as the containing vessel. X-ray powder photographs were taken with CrKa radiation and the use of Straumanis type Norelco cameras of 114.6 mm diam. Crystallographic data for these compounds are shown in Table I. These results are in agreement with others of this series reported previousiy by Wernick and Geller.l The abnormally large atomic volume of Eu and Yb metal3 is manifested in EuA12 and YbAl2, when one compares them with the compounds reported in Ref. 1. However, the behavior of Yb in the Ni compound is the same as that observed in Ni5Yb having the Cu5Ca structure.4 Thus, it appears that Yb has a valence closer to 3 only in the Ni compounds; i.e.. the 2s and Id electrons are lost to the conduction band. 1,4 Europium in EuAl2, appears to have a valence closer to 2. In previous work.' X-ray patterns of ingots of NdCo2 indicated a multiphase material with faint indication of the presence of a phase having the MgCu2 structure. It was thought that NdCo2 formed peri-tectically from the melt, resulting in a multiphase system when cooled under nonequilibrium conditions. An X-ray pattern of a sample from a melt cooled more slowly than in past work showed that the major phase was NdCo2. The lattice constant, Table 1, is in excellent agreement with the value one can predict from the data of Ref 1. One of the other phases was identified as Co,Nd. The author wishes to thank J. H. Wernick for his guidance in this work, and D. Dorsi for the preparation of these compounds. 'J. H. Wernick and S. Geller: AIME Trans., in press. 'J. H. Wernick and S. E. Haszko: to be published. 'F. H. Spedding and A. II. Daane: Progress in Nuclear Energy, Series 5, Eds.: H. M. Finniston and J. P. Howe, McGraw-Hill Book Co., 1956. 'S. E. Haszko: to be published. 'J. H. Wernick and S. Geller: unpublished work. 6J. 11. Wernick and S. Geller: Acla Cryst., 1959, vol. 12, p. '162. The Influence of Hydrogen on the Lattice Parameters of Ti-Sn Alloys A. Coucoulas and H. Margolin A reinvestigation of the lattice parameters of Ti-Sn alloys by the present authors has revealed consistently higher c and a values than those obtained by Worrier. The difference is most pronounced in the c-parameters which are, therefore, used as a basis of comparison. This discrepancy was not due to air contamination, since precautions were taken to exclude this possibility. Specimens for Debye-Scherrer photograms were prepared by arc-melting 15-g buttons of Bureau of Mines titanium and 99.99 pct Sn, with compositions of 6, 8, 10, and 12 at. pct Sn. These buttons were forged under an oxygen-acetylene torch to 1/8-in. sq rods to produce relatively fine grained material. Scale and some surface were ground off, and the rods, after wrapping in molybdenum and titanium sheet, were vacuum annealed 15 min at 800 °C to remove hydrogen. Heat treatment of one of the samples at 875°C to produce ß and reveal a at the surface showed no surface contamination. Following the vacuum treatment, the specimens were wrapped in molybdenum and annealed for 1week at 800°C under two atmospheres of argon. After water-quenching, the rods were ground so that the thickness tapered to 0.1 mm at the tips. The ground specimens were then recapsuled as previously and reannealed 1 hr at 800°C to remove cold work. The

Jan 1, 1961