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By S. E. Maddigan, A. I. Blank

Many experimental and theoretical investigations have been made on the processes involved in annealing and recrystallization of metals. Most of these, however, have treated the time element as constant and heat-treatments used have been for relatively short times. Aside from the early work by Carpenter and Elam,' the few that have investigated the effect of time on the processes have usually done so for fairly short time periods. During recent years the growing interest in long-time creep properties of metals and alloys under stress has made increasingly important a better knowledge of the recrystallization during prolonged heating. The recrystallization temperature of 70-30 brass given by Clark and White" in 1932 was somewhat above 400°F. (204°C.) but under 500" (260°C.), whereas in our laboratory recrystallization has been observed in creep specimens at 204°C., the lowest temperature of Clark and White's range. Since the creep properties are quite different above and below the recrystallization temperature, erroneous conclusions can readily be drawn by the application of short-time recrystallization data to creep problems. It was thus considered of both practical and theoretical value to make long-time annealing studies near the minimum recrystallization temperature. In this way useful additions could be made to data on recrystallization temperatures and, since the reactions in this range are relatively slow, additional insight could be obtained into the factors involved in annealing. Several comprehensive reviews of recrystallization processes have been written,3-6 therefore only a brief review of the generally accepted facts will be given here. Though the effects of heat-treatment usually are expressed as related to observations with varying temperatures, it is logical to assume that the same order of occurrence will exist with time as a variable. Thus, we may postulate that with increasing time we mill observe the following

Jan 1, 1940

By G. H. Kessler

ALTHOUGH considerable attention has been devoted to reaction mechanisms and equilibria of a number of endothermic reactions through which metals or their refractory compounds can be formed upon heated surfaces, only a comparatively small amount of work has been done to develop rate information for these systems. The interestin and very worthwhile work of Holden and Kopelman, Runnalls and Pidgeon,Dijring and Moliere, and Herrick and ICrieble4 is to be noted; however, their work was done under very specific conditions and the rate information which they have developed is not applicable to many systems which have been studied experimentally. That a more generalized approach is needed is shown by the diversity of these systems and of the experimental conditions which they require. These include the preparation of titanium, zirconium, tungsten, molybdenum, chromium, co-lumbium, aluminum, and silicon by decomposition or disproportionation of their halides, in some instances through hydrogen reduction; the preparation of nickel and iron by decomposition of their car-bonyls; and the preparation of copper by decomposition of the acetylacetonate. They may be carried out at temperatures ranging from 100" to over 2000°C and at pressures of from less than one mm Hg to superatmospheric. The physical mechanism of the overall process can be broken down into several steps, any one of which may be rate-determining; and the rate associated with each of these basic physical processes can be predicted. Consequently, by proper application of the present technology of rate processes, it is possible to arrive at a rate of metal deposition in the system of interest and to reach an understanding of the influence of' each major variable upon the deposition rate. It is the purpose of this paper to illustrate how this can be done and to present experimental results for a specific system for comparison with theory. The overall process of deposition of metal upon a heated surface which is immersed in vapors of a compound of the metal can be broken down into the following steps: 1) Transport of the reactant vapors to the surface. 2) Decomposition of the reactant in the immediate vicinity of the surface to a) establish chemical equilibrium if reaction rates are high; or to b) establish a dynamic equilibrium in accordance with the several reaction rates. 3) Diffusion of reaction products away from the vicinity of the surface, with or without simultaneous recombinations to form still other products. The overall process is said to be diffusion controlled if Step 1, or the equivalent Step 3, is slow; it is reaction-rate controlled if Step 2b is slow. When experimental evidence shows the reaction rate to be controlling, the well-known theories of Eyring' and others can be used as a basis for correlating and extrapolating the experimental data. Although these theories give only approximate estimates of reaction rates, they are of considerably greater value in correlating experimental data. Most deposition systems operate at surface temperatures sufficiently high that reaction rates near the surface are very high. Mass-transport rates then become controlling; and it is this regime of diffusion controlled rates which is most often of concern and Which will be considered here. When the system pressure is very low, i.e., in the micron range, then the transport processes are those of molecular movement, and the results of kinetic theory can be applied to specify a rate of arrival of reactant molecules at the heated surface. If the condensation coefficient can be estimated, then the deposition rate will be given by the product (rate of arrival) x (condensation coefficient), Conversely, experimental data can be used to determine a condensation coefficient, as was done by Holden and Kopelman' for the decomposition of zirconium tetraiodide upon a heated molybdenum surface, who found the coefficient for zirconium on molybdenum to be 1.0 at temperatures of 1382°C and above. In this pressure range, the geometry of the system. and in particular the distance between the source of reactant molecules and the heated surface, can exert a considerable effect upon the deposition rate;

Jan 1, 1961

By D. P. Harris

This paper examines recent developments and work in progress on the application of quantitative methods and computers to the appraisal of the mineral resource potential of discrete areas by employing reconnaissance geological information and general economic relationships. The perspective of this paper might be that of a firm planning a regional exploration program or of a legislative body seeking to choose between several alternative actions on the basis of their impact upon the regional resources. In addition to this general survey and commentary, an example is presented of the use of geostatistical analysis and computer simulation to evaluate the economic mineral resources of the Seward Peninsula of Alaska.

Jan 1, 1969

By C. L. Dake

Discussion of the paper of. C. L. DAKE, presented at the San Francisco meeting, September, 1915, and printed in Bulletin No. 103, July, 1915, pp. 1429 to 1436. A. C. LAWSON, Berkeley, Cal.-It appears that our bog-iron ores are due in a large measure to the activity of certain iron bacteria, and a paper dealing with this subject that makes no reference to that particular agency strikes me as rather curious. C. L. DANE, Rolla, Mo.-Mr. Lawson's criticism that this paper makes no reference to the activity, of iron bacteria is scarcely true. On p. 1430 I stated: "Certain bacteria precipitate iron by building the hydrated oxide into their body cells," and again, "There are many other means by which, under special conditions, iron may be precipitated in nature. Oxidation, evaporation of CO2, and iron bacteria have been held to be the most important." Thus the activity of bacteria receives as extended mention as the action of any other agency in precipitation of iron. The paper makes no pretense of covering exhaustively the origin of bog ores, but, as its original title suggested, refers to Some Principles Controlling the Formation and Distribution of Bog Iron Ores. Mr. Lawson seems to have entirely missed the main thesis of the paper, which attempts to establish some relation between glaciation and abundance of bog ores now forming. Unfortunately, I have no immediate access to the literature of the subject, but my best recollection is that the data regarding iron bacteria throw no light whatever on the cause of bog ores being so much in ore abundant within the limits of the glaciated regions, and being reported much less frequently from the tropics. This lack of data is suggested in the following (p. 1434): "It has already been shown that bacteria aid in the precipitation of iron. Whether tropical conditions increase or decrease the activity of such bacteria is unknown."

Jan 12, 1915

By B. A. Rogers

ACCORDING to petrographic investigations, 1-4 cooled steel furnace slags contain a number of substances that have been shown to be ferro-magnetic5,6 and hence capable of undergoing appreciable changes of susceptibility with temperature. Since any alteration of the suscepti-bility of a constituent affects the average susceptibility of the sample, information concerning the nature of the substance should be deducible from its magnetic behavior. The possibility of obtaining information concerning slags in this way led to the construction of the apparatus to be described. FUNDAMENTAL PRINCIPLES OF APPARATUS The most convenient method of observing changes in mass suscepti-bility? with temperature is the one employed by Curie7 in his original investigation of the changes in magnetic properties of substances at elevated temperatures. As the method has been described frequently in the literature and in textbooks, only a brief review of the fundamental principles need be given here, but the particular arrangements used in the present work require a more detailed description.

Jan 1, 1939

By Martin Rubenstein

CdS crystals have been grown from a number of metallic solvents such as bismuth, tin, lead, and cadmium. Etching studies have shown that plastic deformation occurs if the crystals are not removed from the solvent prior to the solidification of the solvent, on cooling. The deformed crystals show a umique exciton fluorescence as a function of edge dislocation density. If one grows the CdS in the eutectic alloy of the above four metals (commonly called Wood's metal) the crystals can be removed from the solvent with hot water and no plastic deformation occurs. In this paper, the liquidus solubility measurements of CdS, as a function of temperature, are presented. The data were obtained using a high -temperature filtration technique. CADMIUM-SULFIDE crystals have been grown from a number of metallic solvents1 such as cadmium, bismuth, tin, and lead. Liquidus solubilities of CdS in cadmium,2 bismuth,3 and tin4 have already been measured. Crystals of CdS, in all four metals, have been grown by solution growth: 1) by cooling a saturated solution and 2) by a solution transport method.1'"1 CdS crystals grown in these four solvents have a few characteristics in common: 1) 1.8°K photolumines-cent emission consisted mainly of the radiative recombination of the bound exciton commonly known as I,, 2) slip lines which could easily be seen by the naked eye, and 3) edge dislocation densities in the order of l05 per cu cm.1 It was decided that these slip lines and the high edge dislocation densities were caused by a plastic deformation of the CdS crystals. It was felt that this plastic deformation did not occur during the growth of the crystals nor during the cooling of the solution, but did occur when the solvent which was in contact with the crystals froze. If these assumptions were valid, the slip lines and the high number of dislocations could be reduced or eliminated by removing the crystals from the solvent before the solvent froze. Since crystals of CdS had already been grown separately in such solvents as bismuth, lead, tin, and cadmium, it was felt that crystals could be grown in a eutectic mixture of these four metals. In this work a eutectic (or near eutectic) mixture of bismuth, lead, tin and cadmium in the proportion 50, 26.5, 13.5, and 10 wt pct, respectively, was used to grow CdS crystals. Such a mixture has a melting point of about 70°C and is close in composition to the alloy commonly known as Wood's metals. If the crystals could be grown from this mixture of solvents, and if hot water (>75°C) could be used to separate the crystals of CdS from the metallic solvent, it was hoped that CdS crystals could be grown with little or no plastic deformation which had been ob- served when crystals were grown from these solvents uncombined. CdS crystals were grown from this low melting eutectic mixture of bismuth, lead, tin, and cadmium using the solvent transport method. CdS powder and the appropriate amount of metals were sealed in a quartz tube under a pressure of about 5 X 10-6 torr. This ampule was then placed in a vertical position in a furnace. The temperature was raised to about 900°C. The furnace was designed so that the top of the liquid column within the ampule was between 10° to 40°C higher than the bottom of the liquid column. These temperatures were measured on the outside of the quartz ampule. The ampule was maintained at temperature for 7 to 14 days (depending on the temperature at which transport was taking place) and then the furnace temperature was lowered until the temperature was about 125°C. The ampule was then removed from the furnace, placed in water maintained at about 90°C, and opened in this 90°C environment. The crystals could then be removed from this two-phase liquid (Wood's metal and water) by mechanically picking them out. Alternatively, the crystals could be quantitatively removed by adding an excess of mercury to the mixture of metals, crystals, and hot water. The hot solution of metals and the hot water could be evacuated using a small diameter tube connected to a vacuum. Small amounts of mercury and water could be removed by heating the crystals in vacuum. Crystals prepared using this technique showed no evidence of slip. However, some of these crystals did show edge dislocation densities as high as l04 per cu cm. Some few selected crystals showed no dislocations. Single crystals of CdS were grown as large as 5 by 5 by 0.5 mm. The ampules for the growth of these crystals were 13 mm O.D., 11 mm I.D., 150 mm! LIQUIDUS SOLUBILITY MEASUREMENTS The CdS starting materials was G.E. 118-8-2 powder which was fired in H2S at 1000°C, and then a vapor transport technique5 was applied to produce a "sound" mass of CdS. The Wood's metal was prepared by weighing out bismuth, lead, tin, and cadmium in the proportions of 50, 26.5, 13.5, and 10 wt pct, respectively. The bismuth, cadmium, and lead were from the American Smelting and Refining Co. (ASARCO) and all had purities of 99.999+ pct. The tin was 99.9999 pct spectroscopic grade from the Vulcan Materials Co. The appropriate mixture was placed in a quartz tube, evacuated to a pressure of 5 X 10-6 torr, melted to a liquid, cooled to room temperature under this same vacuum. This ingot was then placed in another quartz tube, evacuated to 5 x l0-6 torr, and sealed off under vacuum. The ampule was then horizontally placed in a furnace. The temperature was raised to 600°C, and over a period of several hours the ampule was vigorously shaken several times. The ampule was then removed from the furnace, and the metallic liquid was

Jan 1, 1970

By R. Janes, F. Everard

Pilot plant studies have been conducted on a variety of iron ores of differing composition and grain size to test their amenability to dry autogeneous grinding and dry magnetic concentration. A general description of the pilot plant and its equipment is given with particular reference to the Aerofall mill and the dry magnetic separators developed by the Ontario Research Foundation. Test results are reviewed in detail with emphasis on power consumption, mill speed, the use of ball charges, types of ores, moisture content, separator speeds, and design. In 1957 the Ontario Research Foundation installed a pilot plant (Fig. 1) for the study of dry autogenous grinding and dry magnetic concentration of iron ores. A 61/2-ft Aerofall mill was installed as the dry autogenous crushing and grinding medium. The Cavanagh fast drum and the Double Helix, two dry magnetic separators developed at Ontario Research Foundation, were also installed. Iron ore samples of 10 to 150 tons have been investigated. These ores varied widely in mineralogy and grain size. Taconite (-325 mesh), fine-grained magnetite (200 to 325 mesh), and medium-grained magnetites (65 to 150 mesh) have been treated with varying degrees of success. Lately, considerable research has also been conducted on the metamorphosed magnetite-hematite complexes of the Labrador Trough. Operational and metallurgical data have been compiled from these tests. The effects of ore type, air flow, mill speed, and ball charge on mill operation are discussed. Metallurgical data are also presented to illustrate the operation of the dry magnetic separators. PILOT PLANT DESCRIPTION Fig. 2 depicts the normal flowsheet used. Minus 6-in. ore from a vibrating feeder is fed to the 6%-ft Aerofall mill powered by a 50-hp 550-v induction motor. The main blower, a 25-hp 550-v fan rated at 7000 cfm, draws air through the mill. Finely ground ore is conveyed by the air stream to a horizontal classifier, where expansion and a change in direction cause the +I50 mesh fraction to fall onto a vibrating

Jan 1, 1962

By E. D. Hummer, J. A. Younkins. J. P. Proctor

Comparatively little has been published relating practical experience with the control of the solid content of washery water systems that must be "closed." A "closed" system is one that for some reason may not be cleaned by the emission Of any effluent Of high ''lid 'content to be rep1aced by 'lean water in Order to hold the solid content of the waste water within reasonable bounds for efficient washing. It is the Purpose of this Paper to describe practical experience with such a water system and to present data that it is hoped may be of some use to those who are faced with a similar problem. The washery clarification system described comprises three thickeners and three filters, and although it is admitted that each of the fields of water settling and thickening and filtration offers a wide scope for investigation, the authors are not attempting to present the answers to these problems but to set down the results of some experience along these lines, making no claims as to the ultimate solution of the problems in hand. The subject of water clarification has vast ramifications; for example, the science of flocculation as applied to water settlillg and filtering opens up fields of wide possibilities of which as yet little is known. A comparatively recent entry into the field of water treatment, which may offer possibilities of practical application, is the use of "wetting" agents such as "Aerosol." General Arrangement of Water System So that the reader may obtain a comprehensive picture of the factors concerned in the control of a closed water system, it is necessary to give a brief description of the washing plant that is serviced by the water system to be described in the following pages. As we are not primarily concerned with the washing plant in detail, only a brief description of the flow of coal as it relates to the water system will be given here. For a more detailed account of this type of washer, the reader is referred to earlier papers,1,2 The washer, which handles o to 4-in, raw coal (750 tons per hour) is an American Rheolaveur plant of two complements; the coarse coal or sealed discharge plant and the fine coal or free discharge plant. The sealed discharge plant (Fig. I) consists of twin 48.in. primary launders, each having two washing boxes, supplemented by one 32-in. rewash launder, which also has two washing boxes. "Push" water for washing and conveying coal in these launders is supplied from a constant-head tank under pressure head of 10½ ft. at the point of introduction at the feed end of the launder. This tank also supplies water for upward or vertical currents used in the Rheolaveur or washing boxes. Each box discharges into a sealed boot elevator (Fig. I).

Jan 1, 1942

By J. A. Younkins. J. P. Proctor, E. D. Hummer

Comparatively little has been published relating practical experience with the control of the solid content of washery water systems that must be "closed." A "closed" system is one that for some reason may not be cleaned by the emission Of any effluent Of high ''lid 'content to be rep1aced by 'lean water in Order to hold the solid content of the waste water within reasonable bounds for efficient washing. It is the Purpose of this Paper to describe practical experience with such a water system and to present data that it is hoped may be of some use to those who are faced with a similar problem. The washery clarification system described comprises three thickeners and three filters, and although it is admitted that each of the fields of water settling and thickening and filtration offers a wide scope for investigation, the authors are not attempting to present the answers to these problems but to set down the results of some experience along these lines, making no claims as to the ultimate solution of the problems in hand. The subject of water clarification has vast ramifications; for example, the science of flocculation as applied to water settlillg and filtering opens up fields of wide possibilities of which as yet little is known. A comparatively recent entry into the field of water treatment, which may offer possibilities of practical application, is the use of "wetting" agents such as "Aerosol." General Arrangement of Water System So that the reader may obtain a comprehensive picture of the factors concerned in the control of a closed water system, it is necessary to give a brief description of the washing plant that is serviced by the water system to be described in the following pages. As we are not primarily concerned with the washing plant in detail, only a brief description of the flow of coal as it relates to the water system will be given here. For a more detailed account of this type of washer, the reader is referred to earlier papers,1,2 The washer, which handles o to 4-in, raw coal (750 tons per hour) is an American Rheolaveur plant of two complements; the coarse coal or sealed discharge plant and the fine coal or free discharge plant. The sealed discharge plant (Fig. I) consists of twin 48.in. primary launders, each having two washing boxes, supplemented by one 32-in. rewash launder, which also has two washing boxes. "Push" water for washing and conveying coal in these launders is supplied from a constant-head tank under pressure head of 10½ ft. at the point of introduction at the feed end of the launder. This tank also supplies water for upward or vertical currents used in the Rheolaveur or washing boxes. Each box discharges into a sealed boot elevator (Fig. I).

Jan 1, 1942

By John McDonald

THE amount of published literature in the field of mechanical proper-ties of magnesium alloys is not great; particularly with respect to rolled alloys. Haughton and Prytherch1 have summarized most of the articles to 1937, including their own work on sheet. Although many papers can be found dealing' with the technology of magnesium and the alloys now in commercial use, there does not seem to be any work dealing exclusively with the variation in properties of rolled alloys as caused by changes in alloy composition. Comparison of published data reveals considerable discrepancies in, properties of alloys of the same composition, probably due to differences in the details of working and heat-treating followed by different workers. The purpose of this paper is to study the proper-ties of alloys in conditions where the effect of such differences have been eliminated. It is well known that the strength and ductility of metals are functions of the working and heat-treating they have received, as well as of their chemical composition. In comparing alloys with respect to these proper-ties, therefore, all possible combinations of the variables of the fabrication procedure ought to be carried out on each alloy. One or more of these treatments will produce the highest ductility, or strength, or both. These highest properties would then be selected as characteristic of each alloy, and alloys would be compared on the basis of those properties. Thus a separation of the effect of composition and that of working and heat-treating would be achieved. In this paper, however, a compromise with completeness has been made by carrying out a restricted number of treat-ments. As a consequence, the properties obtained are not necessarily the best that the alloy is capable of exhibiting; but since all alloys have been treated by the same method, the results ought to be comparable. The elements selected for the study comprise a class that will alloy easily with magnesium, and that are relatively cheap. Each was added in different amounts, up to a limit that varied with the element.

Jan 1, 1939

W. P. PUTNAM,. Detroit, Mich.-There is one company that is heating these tubes in an upright position by passing electrical energy directly through the tube itself. The lower connection is attached to an indicator, which shows the point at which the steel passes through the critical range At that point the clamps are released and the tube is dropped into a well of oil. This method simplifies the heat treatment of tubes in long lengths. H. J. FRENCH.-I am not entirely familiar with. the method outlined, but it appears to have one serious disadvantage; that is, the length of tubing that is directly connected with the electrical contacts is wasted and must be cut off due to either heavy oxidation or burning. That is a serious difficulty, if true in all cases, and cannot be overcome, inas-much as it is very difficult to draw long tubes of thin wall. Having once obtained a lot of tubes, to cut, say 14 ft. in length, there is often little excess metal available to discard. Am I correct concerning the burning or heavy oxidation of the metal where it comes in contact with the tube.

Jan 12, 1919

By Robert A. Cook

In the increasing struggle to cheapen the cost of our iron and steel products a great deal of attention lias been given to economies in the manufacture of coke; and while but little lias been accomplished in this direction in the United States, the narrow margin between cost and market-price, which has obtained here for the past few years of continuing manufactur ing depression, has brought the coke-maker face to face with the problem, how to save, and benefit by it, the hitherto waste products of distillation. I These may be summed up under three heads, generally rank ing, in value, in the following order: 1. Ammonia salts.. 2. Oil- or tar-products. 3. Gas. There are cases in which the last may assume the position of greatest importance. The greatest obstacle encountered by the American coke maker, on investigating the subject, has been the apparent necessity of discarding his existing plant of bee-hive ovens, and erecting an entirely new and very expensive system of retort ovens, against the product of which Be has probably been prejudiced from his earliest knowledge of the subject. The object of this paper is to bring prominently before our coke-experts a brief history of the development at Sheffield, England, of a most successful system of the utilization of by products in connection with all already existing plant of bee hive ovens. This system has now been in satisfactory operation for about five years, and is applied to a series of blocks of ovens, comprising-about 140- in all At this plant, belonging to the well-known firm of Newton,

Jan 1, 1897

By R. A. Vandermeer, P. Gordon

The study of recrystallization in cold-worked metals is complicated by the impossibility of making direct three-dimensional optical measurements. Metallo-graphically, theinternal three-dimensional features of samples must be inferred from their intersections with the two-dimensional plane of polish. The inherent difficulties involved in this procedure have led— particularly during the last few years—to some instances of rather doubtful interpretations of experimental data in terms of nucleation and growth rates in recrystallization. In the present paper an analysis ; is given of the recrystallization characteristics in a polycrystalline alloy containing 0.008 wt pct copper in ZONE-refined aluminum *and an effort is madf to reemphasize the necessity in such studies for attention to the proper statistical relationships between one- two- and three-dimensional features of opaque samples. It is shown that, in common with several recently described cases for other types of transformations,1-5 recrystallization in this alloy can best be rationalized on the basis that all nucleation took place essentially at time zero—i.e., there is no significant time-dependent nucleation during annealing—and that the kinetics are controlled exclusively by the growth-rate parameters. This is true despite the fact that the number of

Jan 1, 1960

By E. Buehler, J. E. Kunzler

High-pu.1-ity molybdenum has been heat treated, melted, and zone refined and the physical and chemical changes that are produced by these processes have been studied by making resistance ratio measurements. Pronounced effects are observed that are associated with recrystalliza-tion at about 1200°C and with melting. Melting alone is found to result in a substantial purification by the evaporation of impurities such as iron. Zone refining is found to be reasonably effective with four passes producing a three-fold decrease in resistance ratio and a minimum ratio of 0.0003. With the aid of low temperature measurenzents, it has been shown that the build-up of a deposit of the material being zone refined on the radio frequency coil used for heating can lead to contamination of the sample. CONSIDERABLE interest in high-purity refractory metals for the study of mechanical properties has developed during recent years. Also the need for highly pure metals in certain fundamental studies, such as electronic band structure, has become quite widely appreciated. Molybdenum can now be produced with sufficiently high purity to make it attractive for such investigations. The most suitable measure of chemical purity of metals used for many of these studies is its resistance ratio, R,.,o,/Ro, During the purification of molybdenum by zone refining and its subsequent evaluation by this technique, a number of informative observations were made. These observations concern the effectiveness of zone refining, the volatilization of impurities at the melting point, and the recrystallization of molybdenum and appear to be pertinent to other refractory metals. Also, the usefulness of low-temperature resistance measurements as an analytical tool for evaluating the presence of chemical impurities and physical defects in metals is again illustrated. Samples of high-purity molybdenum of known mechanical history were heated to various temperatures between 800°c and their melting point. Resistance ratios of the samples were measured after they had been given a specified treatment. The data were used, along with mass spectrographic analysis, as an aid in interpreting the nature of the processes that occurred in conjunction with each treatment. Changes in the concentrations of chemical impurities and physical defects are typical of things that effect the low-temperature resistivity. SAMPLES The starting material was obtained from Westing-house Corp., Bloomfield, N.J. It was in the form of molybdenum rods, usually 1/8 or 3/16 in. in diameter. These had been previously processed from bars, 5/8 in, in diameter, originally reduced from 4 in. diam arc-cast ingots, by hot swaging at about 1300°c. In the final step, the temperature was lowered to about l lOO°C which resulted in the production of elongated grains. Typical grains were about 0.03 mm thick and 0.6 mm long. The molybdenum was quite pure as is indicated by the results of mass spectro-scopic analysis1 given in Column 2 of Table I. Other nongaseous elements not listed in the table were not detected. ZONE REFINING AND THERMAL TREATMENT OF SAMPLES Several sample rods, 8 to 10 in. long, were zone refined or were heat treated at several temperatures. Both types of operations were performed using 3 me-

Jan 1, 1962

By G. R. Smithson, John E. Hanway

This paper, the first of two papers covering the development of a metallurgical process for the treatment of a complex ore, describes the bench-scale experimental Program undertaken as a basis for initial process design. The results of using various potentially applicable process steps are detailed and the basis for selecting certain of these steps for Pilot-plant development is outlined. A process consisting of the steps of sulfate roasting, leaching, copper recovery, solution purification, zinc electrolysis, and brine leaching for lead recovery was recommended for further study. THIS paper describes the bench-scale development of a sulfate roasting process designed to recover copper, lead, and zinc from a complex ore. The extrapolation of the bench-scale results to pilot-plant design and the results of pilot-plant operation will be described by Lund, et al.' in a subsequent paper. Several years ago, the research divisions of the St. Joseph Lead Co. became responsible for the development of a metallurgical procedure to treat a complex sulfide ore containing copper, zinc, and lead sulfides. The primary objective was to devise a procedure which would permit economic recovery of the nonferrous values. As could logically be expected, the study of conventional flotation procedures was undertaken; in addition, however, because the physical nature of the mineral association in the complex ore indicated that physical methods of ore beneficiation might not prove to be entirely satisfactory, a program also was established to investigate alternative methods of direct metallurgical treatment for recovery of the metal values. Exploratory test work by the St. Joseph Lead staff led to the conclusion that a sulfate roasting technique represented the most attractive approach for a direct metallurgical process. Sulfate roasting would provide for the selective conversion of the nonferrous values to forms soluble in conventiona1.1 leaching agents and would permit their efficient separation from the insoluble iron and other gangue materials. It should allow efficient utilization of the thermal energy available from oxidation of the sulfide raw material, and might provide an opportunity for recovering byproducts such as iron and sulfur. The decision to evaluate a selective sulfation procedure as a basic processing step also was influenced by the excellent results obtained by the St. Joseph Lead Co. in using this procedure for the recovery of cadmium from zinc sulfide concentrates. The choice of selective sulfation as a major processing step served as a basis for an extended experimental investigation of the process with bench- and pilot-scale equipment to prove its feasibility. St Joseph Lead Co., aware that Battelle Memorial 1nstitute had participated in the development of several fluidized-bed sulfate roasting procedures, asked Battelle to undertake the bench-scale development of a suitable sulfation process. This paper describes the procedure used and the results obtained at Battelle in the treatment of the complex sulfide ore. EXPERIMENTAL WORK Nature of the Raw Material. The sulfide ore deposits of interest are essentially a massive sulfide, with the indivudual ore minerals being extremely fine grained and intimately intergrown with each other and with the associated gangue. The zinc in the ore is present mainly as sphalerite (ZnS), the lead as galena (PbS), and the iron either as pyrite (Fes2) or as pyrrhotite (FeS). Table I shows the chemical analysis of various individual samples of the ore. These analyses illustrate the variability of the ore body and impose a rather severe requirement on any type of metallurgical process—that of being able to tolerate probable wide variations in the assay of the head ore. The tentative flowsheet designed to serve as a guide for the initial experimental investigation of

Jan 1, 1962

By R. F. Frantz, T. P. McNulty

The upper-level mineralization of the din Buttes, Arizona copper orebody consists primarily of dilute copper silicate impregnation in fault clay and throughout the altered limestone hostrock. Cuprite and native copper are minor with true chrysocolla rare. Owing to the high calcium carbonate and to the hydrogen ion exchange capacity of the clays, acid leaching would be economical only with cheap acid available. Leaching of the silicate copper with reagents other than sulfuric acid is slow and incomplete unless the ore is first heated to disorder the mineralized grains and to reduce partially the contained copper. Following heat treatment, 70 to 90 percent of the nonsulfide copper can be dissolved in aqueous anrmonium carbonate. Recovery of a pregnant solution by counter-current decantation is effective provided ammonium carbonate solution is added to the washing stages in order to oppose adsorption of dissolved copper by clays in the residue. Thermal stripping of the pregnant solution permits recovery of ammonia and carbon dioxide while precipitating copper either as oxide or carbonate. The research program was carried from batch tests through continuous miniplant operation to a five-month campaign in a 20 TPD continuous pilot plant. Pilot plant results, the relationships among key varibles, and a detailed flowsheet are given.

Jan 1, 1973

By O. Mellgren, A. M. Gaudin, P. L. De Bruyn

The adsorption density of ethyl xanthate on pyrite was determined as a function of xanthate concentration. Surface preparation of the mineral appears to have asafunctionsome effect on the subsequent adsorption process, A monolayer of xanthate on the surface is exceeded only in presence of oxygen. The effect of OH- , HS- (and x and CN- S=)and on the amount of xanthate adsorbed was investigated. Competition between OH- and X- (xanthate) ions for specific adsorption sites is indicated over a wide pH range. IN the flotation of sulfide ores, xanthates are most commonly used to prepare the surface of the mineral to be floated so that attachment to air takes place. The quantity of agent required to make the mineral hydrophobic is usually very small, of the order of 0.1 to 0.25 lb per ton of mineral. Details of the mechanism of pyrite collection are for the most part unsettled. Adsorption of collector has long been believed to involve an ion exchange mechanism as demonstrated for galena' and for chalcocite.2 In the work on chal-cocite it was also demonstrated that a film of xanthate radicals unleachable in solvents that dissolve alkali xanthates, copper xanthate, or dixanthogen was formed at the surface of the mineral. The unleachable product increased with increasing addition of xanthate up to a maximum corresponding to an oriented monolayer of xanthate radicals. Pyrite is extremely floatable with xanthate if its surface is fresh.9 ut the floatability decreases rapidly as oxide coatings increase in abundance. Pyrite shows zero contact angle when in contact with ethyl xanthate solution at pH higher than about 10.5;4 at neutrality, a contact angle of 60" is obtained at a reagent concentration of 25 mg per liter. Alkali sulfides and cyanides are pyrite depressants. In this study of pyrite collection the writers have sought to relate measured xanthate adsorption to the method used in preparing pyrite, to the presence or absence of oxygen, to concentration of hydroxyl, hydrosulfide, sulfide, and cyanide ions. The principal experimental tool has been radioanalysis," " using xanthatcx marked with sulfur 35. Experimental Materials Pyrite: Unlike most sulfides, pyrite is a poly-sulfide. The structure given by Bragg7 resembles that of sodium chloride, the iron atoms corresponding to the position of sodium and pairs of sulfur atoms corresponding to the position of chlorine. The edge of the unit cell in pyrite is 5.40 A and in halite 5.63 A. The S-S distance in pyrite is 2.10 A; the Fe-S distance, 3.50 A: and the Fe-Fe distance, 3.82 A. Natural pyrite from Park City, Utah, was used in this investigation. Pyrite 1 was obtained by hand picking pure crystals. Pyrite 2 and Pyrite 3 were obtained from finer textured crystalline material containing inclusions of silicates. The same cleaning technique was utilized for the preparation of Pyrite 2 and Pyrite 3, whereas a different cleaning technique was used for Pyrite 1. Pyrite 1 was prepared as follows: The crystals were ground in a porcelain ball mill and the 200/400 mesh fraction was separated by wet screening with distilled water, followed by washing for 1 hr with deoxygenated distilled water acidified with sulfuric acid to pH 1.5. The acid was removed by rinsing with deoxygenated distilled water on a filter until a pH of 6.0 was reached in the effluent. This filtration was carried out under nitrogen. The sample was then dried in a desiccator under nitrogen. The period of time for which this pyrite sample was in contact with water containing oxygen was about 4 hr. The specific surface as determined by the BET gas adsorption method was 582 cm2 per g. Final material assayed 53.12 pct sulfur and 46.5 pct iron (theoretical, for FeS,: S, 53.45 pct; Fe, 46.55 pct). After crushing, Pyrite 2 and Pyrite 3 were washed with 1 M HCl. rinsed, and fed to a laboratory shakinq table to remove the small amount of silicates. The concentrate obtained was ground in a laboratory steel ball mill. The 200/400 mesh fraction was separated by classification in a Richards hindered settling tube. This fraction was then given a final wash with 0.1 M HCl and deoxygenated water was filtered through the sample. The final effluent showed a conductivity equivalent to that of a solution having a salt concentration of 0.3 ppm. Aqueous hydrogen sulfide solution was then added to the sampln (about 100 ml saturated H,S solution to about 1000 g pyrite under a few hundred milliliters of water) which was stored wet under nitrogen. The sample stored in this manner showed no indication of formation of iron oxides, whereas iron oxides appeared

Jan 1, 1957

By D. J. Coolidge, H. L. Sheakley

THIS paper does not deal with all sands used in the glass industry in Missouri; it covers only that used in the plate-glass factory at Crystal City. However, it is probably safe to say that other sands, produced throughout the state for this purpose, are of identical nature. The glass sand used in Missouri is commonly called the St. Peter deposit, which is ascribed to the Ordovician Rock series in the form of sandstone. This St. Peter deposit, aside from a few small outliers, covers a large area of eastern Missouri. It forms, through a broad curve, the northeast margin of the typical Ozark region between Cape Girardeau on the southeast and Mineola, Montgomery County, on the northwest. The belt is extremely irregular, varying from one to ten miles in width; its length is 150 miles in a straight line. The outcrop near the entrance to the Crystal City mine appears in the form of a sandstone bluff approximately 30 ft. high, running along Plattin Creek (Fig. 1). Above the sand rock an overburden of Joachim limestone appears, which thickens to nearly 300 ft. and forms the hill commonly called Buck Knob. Test holes where drilled at various points and the drillers' log indicate that the St. Peter deposit ranges in thickness from 63 to 71 feet. PROPERTIES OF THE ST. PETER SAND From an analysis of the glass sands of the St. Peter formation in Missouri, the follow-

Jan 1, 1942

By Thomas R. Mager

An in.t!estigation has been made of the equilibrium conditions at 1200°C in the reaction between hydrogen sulfide gas and sulfur dissolved in Fe-Si alloys From this the equilibrium constant, activity coefficient, and activity of sulfur in solution were calculated. A number of studies of the equilibrium of sulfur with iron and iron alloys have given closely agreeing results from which the activity and free energy of the dissolved sulfur may be found. Sherman, El-vander, and chipman1 discussed the significant researches of dilute solutions of sulfur in liquid iron prior to 1950, and the results of this study indicated that the relationship between the ratio of PH2S/PH2 in the environment and the percentage of sulfur in solution is not a linear one. Morris and williams2 studied the equilibrium conditions in the reaction between hydrogen sulfide gas and sulfur dissolved in liquid iron and Fe-Si alloys, and reported that silicon dissolved in iron has a pronounced effect on the equilibrium conditions. They found that the activity of sulfur in iron is increased by the addition of silicon. At a silicon content of 4 pet the activity coefficient of sulfur was about twice that for sulfur dissolved in pure iron. Sherman and chipman3 investigated the chemical behavior of sulfur in liquid iron at 1600°C through the study of the equilibrium: H2 + S = H2S; K = PH2S/PH2 . 1/as [1] From the known equilibrium constant of the reaction between H2, H2S, and S and the experimental data, the activity of sulfur in the melt was determined. They found that the activity coefficient of sulfur defined as fs = as/%s is increased by silicon and decreased by manganese. Morris4 and Turkdogan5 also reported that manganese decreases the activity coefficient of sulfur in liquid iron and iron-base alloys. A recent technique of sulfur analysis developed by Kriege and wolfe6 of the Westinghouse Research Laboratories permits an accurate sulfur analysis of 0.5 * 0.2 ppm in the range of 0.1 to 3 ppm, whereas in the range of 3 to 50 ppm the accuracy is ±1 ppm. This technique of sulfur analysis was utilized in this experiment. Previous unpublished data reported that sulfur analysis by the combustion technique was not accurate below 20 ppm. EXPERIMENTAL PROCEDURE Five 5-lb ingots of high-purity Fe-Si were prepared. Three of these ingots were prepared without the addition of manganese but with a variation of silicon contents from 2 to 4 pet. The remaining two ingots contained 3 pet Si with the addition of manganese. Ingots were made at each of three silicon levels: 2, 3, and 4 pet. No alloys were made with less than 2 pet Si since below approximately 1.8 pet Si the binary alloy exhibits a to ? transformation. The two additional ingots of 3 pet Si-Fe were made at each of two manganese levels: 0.20 and 0.50 pet. To minimize the effects, if any, of impurities on the activity of sulfur on Si-Fe, the best metals available were used for melting. All ingots were vacuum-melted in magnesium oxide crucibles. After obtaining samples for chemical analyses, the ingots were processed. This consisted of hot rolling and subsequently cold rolling the alloys. Each ingot was hot-rolled at 1000°C, reheating between every pass to minimize grain growth. All heating was done in a protective argon atmosphere. The slabs were hot-rolled to strips 50 mils thick. After hot rolling, all the material was pickled to remove the scale formed on the surface of the strip during hot rolling. The material was then cold-rolled to 12-mil strips. Single strips of the material used in this experiment were hydrogen-annealed at 1200°C for 16 hr in an alumina tube. Chemical analyses of strips M-1, M-3, M-4, M-7, and M-8 are given in Table I. Sulfur, silicon, and manganese analyses were made from the millings from the cold-rolled 12-mil strips. The oxygen analyses were made from slugs of the as-cast material. The hydrogen sulfide used in these experiments was supplied from cylinders containing a mixture of argon and 1 pet hydrogen sulfide. The parts per million of hydrogen sulfide were determined from the analysis of the exit gas of the annealing furnace during each anneal. The flow rate of hydrogen was approximately 1 liter per min in all anneals. The

Jan 1, 1964

By Dwight L. Sawyer

IF it had not been for the testimony of former Secretary of the Interior, Harold L. Ickes, before the Senatorial investigating committee the public would have heard little about the Federal Government's suit against California for the ownership of the tidelands. The Ickes-Pauley dispute brought to public attention that the California tideland oil deposits are the last remaining large Federal oil reserves. Ickes contends that these tideland oil deposits belong to the nation for the benefit of all the people of all the states and not solely to the State of California. Ickes also accused California oil man Ed Pauley of offering to give $330; 000 to the Democratic party fund if Ickes would drop the Federal Government's suit against the State of California for the ownership of said tidelands. The tidelands may be considered as the land bordering the coast line between mean high tide and outward under the ocean for a distance of a marine league, or about three statute miles. This strip of land along the coast of southern California contains large oil deposits which have a present and future prospective value of several billion dollars.

Jan 1, 1947