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By T. A. Dungan

THE thermal processes for the production of metallic magnesium can be divided into two general classifications, the direct reduction of magnesia with carbon and the indirect reduction of compounds of magnesium by reducing agents that are themselves products of carbon reduction. The latter are so chosen as to cause reduction of magnesium compounds wherein only the magnesium is liberated in the vapor phase. Reducing agents used are: calcium carbide, silicon carbide, silicon, aluminum, various silicides or combinations of calcium, aluminum, silicon in iron. All of these are products of highly endothermic reactions and, with the exception of scrap aluminum, can be produced in an open, submerged arc furnace; that is, the arc is covered only by the charge itself. The more investment in energy required to prepare such a reducing agent, the less is the energy required in the subsequent step to reduce the magnesium compound to the metal. It is impossible, however, to avoid the laws of thermodynamics, no matter how much circumambulation is resorted to in the preparation of successively more powerful reducing agents. Since each such step carries forward its own inefficiencies, it appears evident that the ultimate status of such processes is dependent upon the development of by-products. EARLY EXPERIMENTS IN DIRECT REDUCTION The direct reduction of magnesium oxide by carbon has a decided appeal to both the scientist and the industrialist. The successful production of the carbothermic plant at Permanente is a significant fact in the substantiation of this concept. Like most developments, however, the history of carbon reduction of magnesia is not one of triumph after triumph, or immediate heady success to the investigators. It is understood that one of the early investigators conducted an experiment wherein he placed carbon and magnesia in one end of an evacuated tube and managed to heat this end to a temperature high enough that magnesia and carbon deposited at the other end of the tube. The charge, unreduced, appeared to have been completely transported from the hot to the cold end of the tube. This raised doubt for some time as to whether magnesia could be reduced at all with carbon. It was correctly suspected, however, that the magnesia was in fact reduced and the resultant magnesium vapor and carbon monoxide reacted upon one another upon reduction in temperature to reform the starting ingredients. Attempts were then made to dilute the two vapors by passing a considerable stream of hydrogen through an arc furnace charged with magnesia and carbon. Thus by dilution of the products it was expected to obtain metallic magnesium. The results were positive and metallic magnesium was

Jan 1, 1944

By AIME AIME

THOUGH born in England-on Nov. 23, 1372 William Wraith was brought to this country at the age of ten. Eight years later he entered the University of Illinois, transferring to the Michigan College of Mines where he got his E.M. in 1894. For the next three years he was a mine surveyor for the fuel department of the Santa Fe Railroad. Then he got into the copper-mining industry, which has occupied his attention for the last forty years. First he was engineer, at Butte, for the Boston & Montana company, and then helped to build the Washoe smelter at Anaconda, of which he was assistant superintendent from 1906 to 1913. The Anaconda company then sent him to Salt Lake City as manager of its subsidiary.

Jan 1, 1938

By P. W. George

This paper presents geological data regarding deposits of over 7,500,000 tons of fine-grained sulphide ore in barite gangue. A series of pyroclastics and arkoses was intruded by sills of quartz porphyry in connection with batholithic intrusions of granite 3 miles from Buchans. Gentle folding, with fracturing acid shearing of tuff beds and intruded quartz porphyry, accompanied and followed the intrusion of granite and porphyry. The sulphide-barite mineralization is localized primarily in fractured and sheared tuff beds, but also in the sheared quartz porphyry. Two structures have proved particularly favorable for mineralization-one, the center of an anticline; the other, a series of weak, incompetent tuff beds intruded by thin sills of quartz porphyry and located between strong beds of arkose. During the folding the weak tuff with intruded quartz porphyry was intensely sheared and contorted and subse-quently mineralized by sulphides and barite.

Jan 1, 1937

By Elton A. Youngberg

The Holden mine operated by the Chelan Division of the Howe Sound Co. is on the east slope of the Cascade Range in north central Washington on the south slope of Railroad Creek valley at an elevation of 3500 ft. The mine may be reached by a 40 mile boat trip from the town of Chelan which is at the southern tip of Lake Chelan, to Lucerne at the mouth of Railroad Creek and an 11. mile bus ride up Railroad Creek to Holden. A11 freight and concentrate is moved over this route to Chelan Falls on the Columbia River which is on the railroad four miles below the town of Chelan. The mine is now producing 2000 tons of gold, copper, and zinc ore per day which is treated in the Holden mill. Gold-copper and zinc concentrates are made, the first of which is shipped to Tacoma, Wash., and the latter to Kellogg, Idaho, for smelting. Ore is broken by long-hole blasting using the Noranda system which has been modified to meet local conditions. Until recently, blastholes have been drilled by diamond drills. Now a partial substitution of percussion drill holes, drilled with tungsten carbide insert bits, is being made. Geology The ore body occurs as a replacement deposit in a highly metamorphosed series of sedimentary rocks, mainly gneiss and schists, in a shear zone several hundred feet in width and of undetermined length. Commercial ore has been found in mineable widths of 25 to 100 ft for approximately 2500 ft along its strike. The commercial minerals are chalcopyrite, sphalerite, and gold. During the period of mineralization considerable silicifica-tion took place giving the ore an abrasive drilling characteristic. Following the period of mineralization, numerous dikes were introduced into the ore body. The earlier ones were of granite composition having a width of a few inches up to 80 ft. These were followed by much younger, fine grained basic dikes which usually do not exceed 2 ft in width. Development of Percussion Blasthole Drilling Equipment Test work with the 1½-in. tungsten carbide bit was carried on in development headings for several months early in 1947. The short life of the bits, because of gauge loss caused by the abrasive nature of the rock, prevented its adoption for this use. However fast drilling speed and ability to drill a long uniform hole suggested its use for drilling blastholes in competition with diamond drills as diamond costs were steadily increasing and exper-ienced drillers were difficult to obtain. The 1½-in. bit was the largest available at the time initial test work was started with sectional steel. The 1½-in. hole limited the diameter of the steel thread and coupling which could be used. Type F couplings were first used but because of the small thread section excessive breakage of the steel was experienced. Type H couplings were tried next. In order to use this coupling which is 15/8 in. in outside diameter, it was reduced to 1 3/8 in. giving 1/8 in. clearance between the coupling and the hole. Rod breakage at the thread was substantially reduced but some coupling breakage was experienced, however the overall performance was considered satisfactory (see Fig 1 for illustration of coupling and thread). Early test work with the 1½ in. bit indicated machines of piston diameters larger than 255 in. would cause inserts to loosen or break. It was found however that the additional weight of the sectional steel cushioned the blow enough to prevent bit failures when 3-in. Leyners were used. Rods used with the 1½-in. bits were 7/8 in. q. o. for sectional steel and 1 in. q. o. for all chuck pieces. In May 1948, 2-in. tungsten carbide bits became available and test work was immediately started. The 2-in. hole approximated the AX (1 15/16 in.) diamond drill hole which was being used exclusively for blastholes and permitted their substitution for diamond drill holes in a ring without alteration of pattern, burden, or explosives. The 2-in. bit also gave room in the hole for larger couplings and permitted the use of heavier rods and 3½-in. machines, increasing the

Jan 1, 1950

By D. C. Jillson

BRIDGMAN1,2 melted metals in a graphite or hard glass tube and lowered the tube through a furnace to make it cool from one end only. Because of the difficulty of eliminating all vibration of the mold, others have raised the furnace instead. Neither way seems as desirable as a setup with no motion of either the mold or the furnace. A furnace in which both the shape and the slope of the temperature gradient could be controlled and varied over a wide range and in which such a gradient could be moved from one end of the furnace to the other, freezing the specimen from one end to the other, at any desired rate, all by means of isolated external control, seemed to offer definite advantages. In addition to eliminating the possibility of vibration due to moving parts, it might also give better control over the direction and rate of heat flow. Such an apparatus was assembled and is shown schematically in fig. 1. Equipment Furnace: A clay-carborundum tube of 3 1/2 in. ID with a % in. wall thickness was used as the core. This had a main winding of No. 12 B.&S. gauge Nichrome V with some compensation for heat loss at the ends. Taps to this winding were made at points 12 in. from each end. Fig. 2 shows details of this winding and of the two end windings. Each end winding was wound over Micanite over the main winding. No. 15 B.&S. gauge Nichrome V was used for these, and again taps were supplied at two inter-mediat,e points on each. The tube was supported in an 18 in. OD black iron shell with brick insulation. The input to each of the windings was regulated by means of a variable transformer. Temperature Regulation: A chromel-alumel thermocouple located near the furnace wall in the center of the furnace was connected with a Celec-tray controller, type PIC, 300" to 900°C range, which opened and closed a shunt across an external variable resistance in the main winding circuit. An "anticipatory response" device also was incorporated to minimize the cyclic effect of the control mechanism. Eleven survey couples in a common pyrex glass protection tube were located near the furnace wall and spaced 2 in. apart. The couple leads went to a common reference junction box where they were connected to copper leads from a selector switch which, in turn, was connected to a type K potentio-meter. This arrangement permitted rapid temperature surveys. The knob on the controller dial was replaced with a threaded brass spool turned at a controlled rate by a thin iron wire one end of which was attached to a gear train and the other to a small weight heavy enough to prevent slipping of the wire on the spool. The gear train, driven by a 1-rpm Telechron motor, contained a series of different sized interchangeable gears and threaded drums permitting a range of travel speeds from 0.10 in. per hr up to a hypo-

Jan 1, 1951

By Frank H. Macpherson

Few people realize the tremendously important part that Saline and Pulaski Counties in central Arkansas have played in the winning of the war The present favorable war situation might have been very different if we had not had the bauxite produced during the past two years from these two small areas, a total Of about 15 square miles. As a general statement, it can be said that the Arkansas bauxite deposits are, individually, relatively small, irregular in thickness, somewhat scattered and, therefore, compared with coal or iron-ore or open-pit copper deposits, relatively ill adapted to a rapid and drastic expansion in output. A few years ago it would have seemed an impossibility for these two counties to produce over six million long dry tons of bauxite in one year. However, with the cooperation of the operators, that is what happened in 1943, when the state of Arkansas achieved the seemingly impossible with a production of 6,020,684 1 long tons (dried equivalent) of bauxite ore during the calendar year, compared with an average annual production of 323,7252 tons in the period 1931 to 1941. It became apparent early in the year '94' that the united States soon might be drawn into the war, and, therefore, that an immediate study of the domestic metal situation was necessary. Aluminum is by far the most important metal used in the manufacture of aircraft and many other implements of war and it was evident that there would have to be a tremendous increase in the domestic production of bauxite, which is practically the only present source of this metal. AS more than 95 per cent of the known bauxite reserves of the United states was in Arkansas, careful preliminary studies were made in that state by representatives of the united States Bureau of Mines, the United States Geological survey and the War Production Board in the summer of 1941 Reserves in other states also were studied. The result of these studies was a recommendation by the War Production Board that mining in the bauxite.producing areas of Arkansas be geared for maximum production, in order to supply sufficient ore for this country's war requirements and, if necessary, to supply the war needs of Canada as well. The annual goal of eight million long tons (dry weight) set for Arkansas by the war Production Board was exceeded in 1943, when in August the output reached a rate equivalent to more than 8,300,000 long tons, dry basis. Because of the comparatively small tonnage of bauxite reserves, Congress appropriated funds for an extensive drilling program to be carried out by the Bureau of Mines in cooperation with the Geological Survey. Drilling began in May 1942 but owing to delay in delivery of drills, and trucks upon which the drills were mounted the program did not get into peak operation until early in 1943. By the end of July 1944, the Bureau of Mines records indicated an addition to the Arkansas reserves of 10,000,000 long tons (wet basis) in place,

Jan 1, 1946

By E. H. Roberts, L. G. Swenson, F. C. Nix, R. A. Morgen

THE binary system lead-antimony has been the subject of comprehensive investigations in these laboratories by Dean' and his associates. The effect of a third constituent on this system, particularly on the lead-rich alloys in which dispersion hardening was found, has a commercial value as well as an academic interest. This paper covers the effect of the addition of copper, bismuth and tin, all of which are likely to be found in commercial lead-antimony alloys, and is divided into three parts, as follows: I. The System Lead-Antimony-Copper II. The System Lead-Antimony-Bismuth III. The Lead Corner of the System Lead-Antimony-Tin These three systems are of three different types, and hence may be considered as covering three general kinds of additions. Bismuth forms no compounds with either lead or antimony and forms solid solutions with both. Copper forms several compounds with antimony as well as solid solutions but with lead it forms a two liquid layer system and no appreciable solid solution. Tin is soluble in both lead and antimony in the solid state and also forms a compound with antimony. The effect of small amounts of bismuth on the lead-antimony alloys is small, having no appreciable effect on the solubility of antimony. The temperature of the solidus floor is lowered appreciably by the presence of bismuth, cutting down the range of heat treatment. Copper, on the other hand, due to compound formation, increases the apparent solubility of antimony. The excess antimony is tied up with the copper finally and so is not available for dispersion hardening. The net result of addition of small amounts of copper is to shift the dispersion hardening peak of the

Jan 1, 1928

By Guy Bjorge

IN recent years the Homestake mine has been served by three shafts, the B. &. M., the B. & M. No; 2 and the Ellison, supplemented by an inside shaft, the Milliken, extending from the 2000-ft. level to the 3200-ft. level. In 1932, when a new operating shaft was under consideration, the bottom of the mine was at the 3200-ft. level. The B: & M. and the B. & M. No. 2 shafts were down to the 1550-ft. level and the Ellison was being deepened from the 2600 to the 3200-ft. level. All ore was hoisted at the B. & M. and-Ellison shafts. Levels below the 2600 level, which were under development only, were served by the Milliken shaft. Below the 1550-ft. level, the mine was served only by the Ellison shaft from the surface. Within a few years, when ore reserves above the 1550-ft. level would be depleted, operation would be limited to the Ellison shaft and the auxiliary underground shaft. The Ellison shaft alone was not adequate for hoisting the entire output from the deeper levels and also handling all men and supplies. Further-more, assurance of safety and uninterrupted operation required- two fully equipped shafts to the deeper levels. Therefore a new operating shaft was authorized in November, 1932, and was named for A. J. M. Ross, the mine superintendent.

Jan 1, 1935

By Frank J. Tolonen, Nicholas H. Manderfield, Paul Jasberg

EARLY in the study of the low grade iron formations of Michigan, wide variations in their structure and texture became evident. Because of these variations no simple method of concentration is possible, and those portions of the formations that can be exploited profitably under a given stage of metallurgical progress and existing economic conditions must be searched for carefully. Both structure and texture of the formations have an important bearing on their amenability to beneficiation. By structure is meant the banding planes of easy fracture, the porosity, and the degree of leaching. Texture, which includes grain sizes, shapes, and degree of interlocking, determines the amount of grinding necessary to liberate the mineral grains. Structure determines the liberation of portions richer in one mineral. Structure and texture may be termed the gross features of the formation

Jan 11, 1957

By R. E. Zimmerman, Michael Sokaski, E. R. Palowitch, M. R. Geer, H. F. Yancey, W. Deurbrouck, S. C. Sun

PART 1: DENSE MEDIUM SEPARATION by M. SOKASKI, M. R. GEER and H. F. YANCEY INTRODUCTION In the early days of coarse-coal treatment by the dense-medium process in Europe, loess was one of the materials used for medium solids. Newly developed cyclones were used to reclaim and thicken :he loess suspension. On occasion, when the cyclone thickener at the Maurits mine in the Netherlands plugged, the overflow was found to be filled with clean coal free of impurity. From this observation stemmed the concept of the cyclone as a cleaning device. Development took place during World War 11 in the laboratory of the Dutch State Mines under the direction of M. G. Driessen. A 15-ton-per-hour pilot plant was in operation in the laboratory by 1945, when, in September, Driessen made the first public disclosure of the process in a paper presented to the Institute of Fuel in London. In April 1945,2 operation of this pilot plant was observed by one of the authors, who was so impressed with the potential of the cyclone process that, on his return to the United States, a research program on the cyclone was started by the Bureau of Mines immediately. This work led to an AIME paper in 1946 in which the first details of cyclone operation on American coals was made available. Commercial adoption of the cyclone proceeded in Europe, initially in the Netherlands, Germany, and France. In the United States, where coal is less costly and most of the coals are so easy to clean they respond well to simpler cleaning systems, the first cyclone plant was not built until 1961.3 As of the spring of 1967, a total of 31 commercial cy- clone plants had been installed or were under construction in the United States; this does not include eight Dynawhirlpool plants. The capacity of the cyclone plants ranges from 50 to 1300 tons per hour and totals 6600. THEORY Before discussing the theory of a dense medium cyclone, a brief description may be helpful to some readers who are not familiar with its basic operation. In a typical dense-medium cyclone, illustrated in figure 10-1, the mixture of medium and raw coal enters tangentially near the top of the cylindrical section, thus forming a strong vertical flow. The refuse moves along the wall of the cyclone and is discharged through the under- flow orifice. The washed coal moves toward the longitudinal axis of the cyclone and passes through the vortex finder to the overflow chamber.

Jan 1, 1968

By E. I. Organick, B. H. Golding

A simple correlation is presented for the prediction of saturation pressures in condensate-gas and volatile-oil mixtures. Saturation pressure is related directly to the composition of the mixture with the aid of two generalized composition characteristics, B, the molal average boiling point, and W, the modified weight average equivalent molecular weight. The need for hydrocarbon equilibrium constants is entirely eliminated. Only the values of the two conlposition parameters need be obtained, and these are calculated in a simple and reproducible manner from the stream analysis of the mixture and the ASTM distillation for the heavy ends. The correlation is given .in the form of a set of 14 working charts in which saturation pressures, either retrograde dew points or bubble points, are plotted cs temperature, forming partial phase envelopes for mixtures having discrete values of the composition parameters, B and Wul. A locus of critical states on each chart intersects the partial phase envelopes, distinguishing retrograde dew point pressures from bubble pressures. A comparison Between experimental and predicted saturation pressures reveals that: the probable error of the predicted values, when considering the data as a whole (214 experimental points), is five per cent; for high gasjoil ratio condensate fluids (approximately 40.000 or more cu ft/bbl) the probable error is about 8 per cent. In either case, however, the probable error is comparable with the overall uncertainty of the data from which the correlation is derived. INTRODUCTION There is a present need for a simplified, yet reasonably accurate method for predicting upper phase boundaries of reservoir fluids. In the case of high gas/oil ratio fluids, namely the so-called highly volatile oils and the condensate gases, no simple method, accurate within 5 to 10 per cent, is now available by which bubble point and retrograde dew point pressures may be predicted. In order to calculate the upper phase boundary of a volatile reservoir fluid, using correlations now available, it is necessary to find and employ the proper K-values (equilibrium volatility ratios of the hydrocarbons in that fluid). This process of finding the Proper K-values usually involves a double trial and error computation. Since the K-values are in themselves dependent upon the composition of the fluid, their use in the calculation of a saturation pressure actually represents an unnecessary complication. The correlation described in this paper relates saturation pressure directly to the stream composition, entirely eliminating the need for K-values. The only data required to calculate the Stream composition are obtained from the customary low temperature fractional analyses of separator gas and liquidt and from the ASTM distillation of the c,+ fraction of the separator liquid. A considerable simplification in the procedure for predicting saturation pressures is thereby effected without significant loss in accuracy. BASIS FOR A CORRELATION Empirical relationships between the saturation pressure and the composition of the fluid in question have already been partially explored by one of the authors.V n particular, a relationship between the critical pressure for a hydrocarbon mixture and its composition was developed. The critical pressure is in reality a saturation pressure, as it repregents a limiting case either of a dew point or of a buhhle point pressure for any given mixture. It was found that the critical pressure may be correlated as a function of two generalized composition characteristics or variables. One characteristic expressed a molal average prop-erty, the other a weight average property of the mixture. Specifically, the molal average boiling point (MABP, or B as it

Jan 1, 1952

By H. D. Dahl, Roger C. Parsons

In order to improve roof stability, Continental Oil Co.'s research program, initiated in 1969, was directed toward defining the geological parameters that affect the severity of roof conditions in any particular area of the mine. In addition, the program was seeking to define why roof falls in the Humphrey No. 7 mine (and in northern West Virginia-southwestern Pennsylvania coal mining areas) are oriented so that they occur primarily in north-south rooms or entries. Conclusions and recommendations from this study of roof fall orientation are given.

Jan 1, 1973

By A. M. Gaudin, A. F. Taggart

Flotation of ores is a practical utilization of the energy that resides in the surfaces of solids and liquids. The best known manifestation of this energy is called surface tension; an equally important, though less apparent, phenomenon is adsorption. This paper reviews some of the recent investigations of these phenomena, and gives the results of certain experiments performed by the authors. Surface tension is a manifestation of energy having its seat at the bounding surface between the adjacent phases of a multiphase system. Thus, at the interface between a liquid and a gas, or between two immiscible liquids, or between a solid and a gas or a liquid, there are forces capable of doing work, their magnitude depending on the nature of the adjacent phases and the extent of the bounding area. These surface forces are inappreciable when the ratio of surface to volume of the adjacent phases is small, but they become powerful when this ratio becomes large, as it does when one of the phases is highly dispersed. Froth flotation, which consists in buoying solids heavier than water to the surface of water by means of gas bubbles, utilizes the force of surface tension to attach the solid particles to the gas bubbles and again to maintain the floating mass of bubbles as a more or less persistent froth at the surface of a pulp for a sufficiently long time to allow its removal. It follows from the second law of thermodynamics that the potential energy of a system in equilibrium is a minimum. Therefore a multiphase system, tending toward equilibrium, will arrange itself in such a way that the total energy of the interfaces will be the least possible. This end can be accomplished in two ways: by a change in shape that will reduce the interfacial area; by a change in the nature of the surface layer in

Jan 1, 1923

By A. F. Taggart, A. M. Gaudin

Flotation of ores is a practical utilization of the energy that resides in the surfaces of solids and liquids. The best known manifestation of this energy is called surface tension; an equally important, though less apparent, phenomenon is adsorption. This paper reviews some of the recent investigations of these phenomena, and gives the results of certain experiments performed by the authors. Surface tension is a manifestation of energy having its seat at the bounding surface between the adjacent phases of a multiphase system. Thus, at the interface between a liquid and a gas, or between two immiscible liquids, or between a solid and a gas or a liquid, there are forces capable of doing work, their magnitude depending on the nature of the adjacent phases and the extent of the bounding area. These surface forces are inappreciable when the ratio of surface to volume of the adjacent phases is small, but they become powerful when this ratio becomes large, as it does when one of the phases is highly dispersed. Froth flotation, which consists in buoying solids heavier than water to the surface of water by means of gas bubbles, utilizes the force of surface tension to attach the solid particles to the gas bubbles and again to maintain the floating mass of bubbles as a more or less persistent froth at the surface of a pulp for a sufficiently long time to allow its removal. It follows from the second law of thermodynamics that the potential energy of a system in equilibrium is a minimum. Therefore a multiphase system, tending toward equilibrium, will arrange itself in such a way that the total energy of the interfaces will be the least possible. This end can be accomplished in two ways: by a change in shape that will reduce the interfacial area; by a change in the nature of the surface layer in

Jan 1, 1923

NEW MEMBERS. The following list comprises the names of those persons who became members during the months of July and August, 1913: Members. ALDERSON, VICTOR C., Prest. of Colorado School of Mines :.Golden, Colo. ALLEN, JOSEPH W., Secy. & Treas. International S. & R. Co;, 42 Broadway, New York, N. Y. AMMON, ROBERT, Chief Sampler B. & M. Reduction Wks., Anaconda Copper Min.Co., Great Falls, Mont. BARBER, RAYMOND J., Min. Engr 234 Newbury St., Boston, Mass. BARDWELL, EARL S., Genl. Concen rator Foreman Boston & Mont. Reduction Plant, Great Falls; Mont.

Jan 9, 1913

By Oliver Smalley

Except for the work of Guillet, who conducted a systematic investigation on the zinc-replacing value of nickel in brass, and extended his investigation with a view to developing commercial high zinc content nickel brasses, the author does not know of any other systematic research on the subject. The most promising commercial alloys and their physical properties obtained by Guillet are given below: These test results scarcely justify the use of such quantities of so expensive a metal, and could have been obtained from ordinary commercial brass. For purposes of comparison, the physical properties of ordinary brasses, ranging from 70 per cent. to 50.1 per cent. Cu in both the cast and normalized1 conditions are included in 'Table 1. These incidentally furnish a useful standard of the properties of castings and of rolled, extruded and forged brass when correctly annealed. A close study of some of the well-known special brasses containing nickel reveals a series of alloys which bewilder by their complexity, and me can only hazard a guess at the function and commercial value of each of the many elements used.

Jan 1, 1926

By Harrison R. Cooper

The key to concentrator automation is practical means for obtaining continuous assay data from concentrator streams. The technique most successfully used is x-ray fluorescence analysis. The practical reality of on-stream x-ray analysis has been achieved through effort over the past twenty years, marked by an occasional breakthrough, but more typically a step-by-step development to which many individuals and organizations have contributed. The net result of this progress is the present capability to install on-stream x-ray analyzer systems on a turn-key basis. It is now possible to provide all components of an x-ray analysis system as a completely engineered unit which can be put into immediate use, minimizing needs for specialized application knowledge to benefit from continuous assaying in process control. The economic factors which influence the choice of system and limitations of the x-ray fluorescence technique for slurry analysis are reviewed.

Jan 1, 1976

By P. A. C. Wilson

Instantaneous outbursts of carbon dioxide in coal mines have occurred in Germany only in one part of the Waldenburg-Neurode mining district.' This mining region comprises the northeastern fold of the "Innersudetian" coal basin. The basin (Fig. 1) is in the form of a geologic trough approximately 60 km. (37 miles) long and 30 to 35 km. (19 to 22 miles) broad and is enclosed on three sides by ancient truncated mountain ranges—the Riesengebirge, the Bober-Katzbachgebirge and the Eulenge-birge. Only the southeastern part of the trough is not enclosed by mountains of older rock formation. The floor of the basin before the building up of the coal measures was formed on the western, northwestern and northeastern borders by the material from Archean rocks (gneiss and mica schists); in the northern part over this was deposited the Silurian formation. The carboniferous period is represented both by the Lower ("kulm") and Upper Carboniferous, with an unconformity between the stages; that is, the kulm was tilted up and partly eroded before the Upper Carboniferous was deposited. The kulm is a salt-water formation (with marine fauna) but Upper Carboniferous rocks are nonsaline water deposits, with fresh-water flora only. The Lower Silesian coal measures were thus formed in a lime basin fed by the running water coming down from the mountains. As already indicated, the bottom series of the Upper Carboniferous formation, termed "Waldenburg strata" were laid down unconformably on the Lower Carboniferous. Over the Waldenburg strata there are the "Weisstein strata," an intermediate barren stage without coal beds, 400 to 500 m. (1300 to 1600 ft.) thick. Another unconformity followed, which is overlain by the '(Saarbrucken" series, which contain the upper coal measures, and the ('Ottweil" strata. In the last named, it is only on the southwestern fold that beds of coal are developed.

Jan 1, 1931

By M. E. Nicholson

IN order to understand how alloying elements influence hardenability through their effect on the rate of pearlite nucleation, it is advantageous to use a model to describe the mechanism of pearlite nucleation. The model which currently is most widely accepted has been described, among others, by Mehl et a1.1-3 and by Hultgren.4 Pearlite nucleation involves both the nucleation of ferrite and cementite.4,5 Cementite nucleates first, followed rapidly by the formation of ferrite at the cementite-austenite interface. The conclusion that cementite is the first phase to form during the process of pearlite nucleation is based, in part, on the observation that proeutectoid cementite is continuous with pearlitic cementite and that the orientation relationship between proeutectoid ferrite and austenite is not the same as that between pearlitic: ferrite and austenite.6,7 Recently, Smith" has suggested that the dissimilarity in orientation relations, instead of indicating the pearlite nucleation sequence, may be evidence that pearlite is nucleated in a grain adjacent to the one in which it is growing. Also, Modin9 as shown that ferrite in pearlite may be continuous with proeutectoid ferrite, and he has also shown that proeutectoid cementite is not always continuous with pearlitic cementite. Thus, it appears that the conclusion that cementite always initiates the pearlite nucleation process is open to serious question. The author believes that important evidence on the question of how pearlite is nucleated exists in the rates of pearlite nucleation of different steels. The following is a review and analysis of this evidence. If the nucleation of pearlite is considered as requiring the nucleation of both cementite and ferrite, then the time to nucleate pearlite consists of the time to nucleate the first phase to form, plus the time to nucleate the second phase at the advancing interface of the first. In the absence of a visible proeutectoid constituent, the second phase must be nucleated very soon after the first. If cementite is the first phase to form, the time to nucleate pearlite will be approximately equal to the time to nucleate cementite. Since the nucleation rate of a phase precipitating from solid solution increases with the degree of supersaturation, it would be expected that the rate of pearlite nucleation should increase with increasing carbon content. Digges10 has shown that the reverse is true. He determined the quenching velocity necessary to suppress pearlite formation in plain carbon steels as a function of carbon content. His results showed that pearlite formation could be suppressed with lower quenching velocities as the carbon content of the steel increased, at least up to 1.25 pct C, the highest carbon content he studied. Thus, it would appear that in plain carbon steels, in which pearlite is formed at the nose of the C-curve, the hypothesis that cementite nucleates first does not predict the observed change in nucleation rate. The validity of the current model of pearlite nucleation may be tested also by determining whether or not it predicts the relative influence of alloying elements on the nucleation of ferrite and pearlite. This can be done best by a consideration of the changes in a TTT diagram produced by a change in alloy content. Hultgren4 suggests that the general shape of a TTT diagram, as well as what constituents will form from austenite, can be predicted from the relative nucleation rates of ferrite and cementite. This is illustrated in the schematic diagram for a hypoeutectoid low alloy or plain carbon steel shown in Fig. 1. The C-curves for ferrite nucleation and for cementite nucleation are represented by AA' and CC', respectively, and the start of ferrite formation and pearlite formation are represented by AX and BC respectively. Adopting the current theory, Hultgren suggests that between X and C pearlite forms directly from austenite, since cementite nucleates more rapidly than ferrite in this temperature range. Conversely, at temperatures above Tx, ferrite is the first to nucleate and proeutectoid ferrite is formed. As proeutectoid ferrite grows, austenite becomes enriched in carbon, so that the cementite nucleation rate is increased. As a result, pearlite nucleation above temperature Tx is accelerated, beginning along BX and not along C'X. Temperature T, represents the temperature at which the nucleation rate of ferrite equals that of cementite. By extending this type of reasoning, using the principle that the nucleation rates of ferrite and cementite increase with increasing supersaturation of austenite with respect to these phases, it should be possible to predict the influence of carbon content on the shape of the isothermal transformation diagram. For a slightly higher carbon content than that of Fig. 1, the curve A A' representing the beginning of ferrite formation should be moved to the right, whereas the curve CC' representing the beginning of cementite formation should be moved to the left. For hypoeutectoid plain carbon and low alloy steels, this prediction does not agree with existing data. Instead, as the carbon content is increased, the pearlite curve moves to the right along with the ferrite curve and always appears to join it tangen-tially. This behavior is demonstrated by the TTT-curves of a series of manganese steels" shown in Fig. 2. In this figure, TTT-curves for four alloys containing 0.20, 0.40, 0.60, and 1.20 pct C are superimposed. The curves are identified in the figure legend. The letters F, P, and C are used to indicate the start of ferrite, pearlite, and cementite formation, respectively. In these steels, it appears that the nucleation of ferrite and of pearlite are related processes. As a result of the foregoing evidence, it is proposed that the formation of pearlite be considered as follows: Either ferrite or cementite may nucleate from austenite, then grow until the remaining phase is nucleated at the interface between the growing phase and austenite. (The growth of the first phase to form is assumed to be accompanied by a composition change in the adjoining austenite.) According to this model there are two modes of nucleating pearlite: 1—where cementite initiates the succession

Jan 1, 1955

By J. Chipman, H. R. Larson

The data previously reported for the quantity as a function of oxygen pressure at 1550°C have been used to compute the activities of Fe, FeO, Fe2O3, and COO in slags of the ternary system. Activities of the first three have been obtained also for two quasi-ternaries involving fixed CaO:SiO2 ratios. IN a previous paper1' the authors reported the results of an investigation into the effects of oxygen pressure on the composition of various simple slags analogous to some of those which are found in steel-making practice. The ratio of ferric iron to total iron was studied at 1550°C in iron oxide melts to which lime, magnesia, lime-plus-silica, and other oxides were added. The oxygen pressures involved those of air, carbon dioxide, and carbon dioxide plus carbon monoxide in several proportions. Although very low oxygen pressures could not be used, the slag-metal equilibrium studies of Fetters and Chip-man' permitted extending the results to slags in equilibrium with iron. For the ternary system CaO-FeO-Fe,O, the oxygen pressure-composition relationship has been determined from zero percent lime to lime saturation over an oxygen pressure range from air to that represented by equilibrium with liquid iron. Lime and silica were added to iron oxide in the ratios 0.54, 1.306, and 2.235 to form three quasi-ternary systems which were also studied over the entire region of liquid melts at 1550°C. Ternary Gibbs-Duhem Equation Wagner" has developed a method by which the activities of two components of a ternary system can be calculated if' the activity of the third component is known throughout the composition range being considered. The fundamental form of the Gibbs-Duhem equation for ternary systems is N, d In a, + N2 d In a, + N3 d In a3 — 0. Wagner has developed a usable form of this equation by introducing the term y = N3/(N3 + N1) and rearranging the equation to give (? In a1/?N2)x = -y/(1-N2)2 (? In a2/?y) x2 N2/1-N2 (? In a2/?N2) y To apply this equation to the slag system CaO-FeO-Fe,O,, the activity of one of these components must be known. However, the only activity which is known from the experimental data is the activity or pressure of oxygen in the gas phase with which the slag is in equilibrium. The activity of oxygen in the slag can be defined as the square root of the oxygen pressure. In order to use oxygen as one component, the composition of the slags must be converted to the basis Fe-O-CaO. Oxygen, exclu-sive of that contained in CaO, then becomes com-ponent 2 in Eq. 1, Fe is selected as 1 and CaO as 3. Then y = Ncao/(Ncao + NFe). Eq. 1 then becomes (? In a fe/? Nx) y = -y/(1-No)2 (? In ao/?y) xp - No/ 1- No (? In ao/ O No) y. In order to evaluate Eq. 2, the boundary conditions must be known. The obvious choice of a standard state for iron is to assign slags in equilibrium with iron an activity of one. Then In a,., or log aFe, which is substituted for convenience, is determined by integrating along a line of constant y from the slag in equilibrium with iron to the composition at which log a,, is to be determined. Mathematically this can be expressed as log aFe (Nlog y) = log a'Fe + (? log a Fe/? No) dNo where the primes indicate equilibrium with liquid iron and a'Fe = 1. When Eq. 3 is integrated along a line of constant y, the following is obtained: log a Fe (No, y) = - y No ?/ No ? y ( log ao/(1- No)2) No d No - No/1-No d log ao. Lime-Iron Oxide Slags Iron Activity: The oxygen pressure of lime-iron oxide slags is shown in Fig. 1 as a function of j, de-fined as j = Fe+++/(Fe++ + Fe +++) for various constant mol percentages of lime. The j values at 0 to 60 pct lime were then determined for oxygen pressures of 1, 10-1, etc. to 10-" atm. For purposes of calculation, the line for zero percent lime was extrapolated to

Jan 1, 1955