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By Dr. O’Neil Thomas J., Donald W. Gentry

The greatest of all gifts is the power to estimate things at their true worth. LaRockefoucauld INTRODUCTION The primary reason for performing a feasibility study on a proposed mining venture is to investigate all phases of the proposal in as much detail as necessary to justify either dropping the project or continuing expenditures through the next stage. The economic evaluation component of the feasibility study, therefore, must ultimately be based on information which provides an answer to the question, "What is it going to cost?" Unfortunately engineers preparing feasibility studies never have all the engineering or economic information they would like or need. Consequently, the economic portion of the analysis can only be performed if estimates of the various costs associated with the project are made. Project cost estimates, in turn, require estimates of all the physical factors affecting cost components, including anticipated performance of plant and equipment as well as all pertinent geologic, mineralogic, and metallurgical variables. Before useful cost estimating procedures can be applied considerable data must be collected, compiled, and organized. Preparatory work typically includes organization of cost data available for estimating purposes, development of techniques for updating historical costs, and establishing methods of forecasting prices and costs over the duration of the project. Cost estimates for mining and mineral processing projects involve so many features and variables that it is absolutely essential to have some means by which the vast amount of detail can be organized. It is very important to identify, in as much detail as possible, all the cost data available (historical and developed) to the estimator. These costs, after being properly identified in detail, should be com- piled, stored, updated regularly, and made readily available for use in developing new cost estimates Accessing files of current cost information requires a standardized numerical system of classifying cost data. When uniform definitions and procedures are used, every project record contributes to the common store of estimating data.

Jan 1, 1984

By B. Chalmers, L. Bäckerud

The growth temperature of dendrite tips has been measured in a binary alloy system, Al-Cu, as a function of rate of formation of solid phase. Metallographic examination has rerealed the dendritic structure dereloped during different stages of the freezing process and factors influencing the undercooling, such as solute buildup, surface tension, and kinetic effects, have been estimated. Practical implications of the results are discussed. THE development of a dendritic growth pattern during the solidification of metals and alloys has an influence at least equal to that of grain size on the properties of the casting or ingot being produced. and consequently much interest has been devoted to the study of this phenomenon. A review of the knowledge gathered up to 1964 has been given by Chalmers.' Among recent publications in the area the works of Jackson et al 2 and Flemings and his coworkers3,4 are of special interest. This work is an experimental study of the factors which influence the development of a dendritic pattern during the solidification of a typical binary alloy system, A1-Cu, when there is no heat source in the liquid. This means that the temperature and the temperature gradient are controlled by the heat extraction from and latent heat evolved by the growing crystals. EXPERIMENTAL PROCEDURE Samples were prepared from a master alloy made up of aluminum, 99.995 pct, and copper. 99.99 pct, of the concentrations given below and of sufficient size to fill cylindrical graphite molds of 35 mm ID and 35 mm height. Bottom. wall. and lid of the graphite molds were all of 6 mm thickness, Fig. 1. Thin ceramic thermocouple shields could be introduced at different positions in the sample through holes in the lid. The assembly was heated in a small vertical resistance furnace to a suitable temperature. 700° to 720°C. which is well above the melting point of the sample. It was thereafter taken out of the furnace and chilled at selected rates, and the temperature changes in the sample were recorded. For high sensitivity in the temperature recordings, a reference thermocouple was held in a solidifying pure aluminum melt. which was very well insulated and therefore was at a constant temperature. 660°C, for nearly half an hour. The thermocouples were connected so that the difference voltage was fed into the recorder of which the most sensitive range was 1 mV. Temperature variations could be read to within 0.l°C. The thermocouples used were of the Chromel-Alumel type (28- or 38-gage wires) and the recorder a two-pen Moseley strip chart recorder. The different rates of chilling were obtained in the following way. a) The graphite crucible was wrapped in one or two layers of an insulating. feltlike material (Fiberfrax paper from the Carborundum Co.). The drop in temperature per unit time after complete solidification could thereby be varied from 8" to 18°C per min. This corresponds to a rate of heat extraction in the given samples from 0.08 to 0.17 cal cm-' sec-I. 6) The bare graphite mold was placed free on a piece of firebrick. The measured temperature drop was around 50°C per min (-0.5 cal cm-" ' sec- I). c) By blowing compressed air through a tube with many holes surrounding the mold in a ring shape. the rate of heat transfer could be raised to 150' to 200°C per min (-1.7 cal cm-3 sec- I). d) Cooling rates around 1000 C per mill (-9.4 cal cm-3 sec-l) were obtained by substituting the air in the device used in c by water. The range of cooling rates used in these experiments correspond to technical casting processes from slow solidification as obtained in sand molds to very rapid freezing which occurs in some continuous casting and welding processes. EXPERIMENTAL RESULTS The A1-Cu system was chosen for the experiments: the relevant part of the phase diagram is reproduced in Fig. 2. Observation of the Center Temperature. When a thermocouple is inserted in the center of the melt. the type of cooling curves obtained at slow solidification rates differs little from numerous published curves from similar systems. and the solidification pattern

Jan 1, 1970

By Ernest Burchard

A RECONAISSANCE of the chrome and manganese'1ore deposits of Culm was made in the spring of 191s by Albert Burch representative of the U. S. Bureau of Mines and the writer representing the U. S. Geological Survey. The object of the study was to obtain authentic information for use of the: United States Government as to the location, character, size, and availability of the Cuban deposits of the ores of these important steel-alloy metals. The Cuban Government courteously detailed Sr. E. I. Montoulieu, a mining engineer connected with the Treasury Department, to act as escort and associate throughout the work on the Island. Mr. George A. Wright, of Baracoa, Cuba, a mining engineer especially familiar with the chromite deposits of Oriente Province, was a member of the party from Feb. 25 to Mar. 20. It was possible to visit most of, the chrome-ore deposits that seemed to be of promise, but there was not sufficient time to visit all that were brought to our attention, some of which may have merit. Furthermore, no attempt was made to examine the extensive chromiferous iron-ore deposits of the Mayari, Moa, and Cubitas districts, as these deposits cannot be regarded as sources of chromium except indirectly. At the close of the field work the essential data concerning the quantity and quality of ore probably available for shipment during 1918 and 1919, in the event of the continuation of the European war, and of the tonnage of ore in reserve, were furnished to such Government bureaus as were interested, including the Shipping Board and the War Industries Board, and as soon as chemical analyses of the chrome ores could .be obtained, a press bulletin on the subject was published by the Geological Survey. In the present paper the engineering data, and tonnage estimates contained in the unpublished notes of Mr. Burch have been freely used, and their helpfulness is hereby gratefully acknowledged. Many thanks are due Senor Montoulieu and Mr. Wright for their valuable work in the field; to the officials of the Spanish American Iron Co. and of the various other companies; and to individuals holding chromite claims, for courteously facilitating the work of the party. In the study of material for the present paper, chemical analyses have been made by R. C. Wells and petrographic determinations and descriptions were furnished by Miss E. F. Bliss, both of the U. S. Geological Survey.

Jan 9, 1919

By Samuel L. Hoyt

THIS paper gives a short account of plastic deformation as observed in single crystals of zinc, zinc having been selected for the experiments described herein because the phenomena are comparatively so simple and can be studied throughout such a wide range. It is hoped that the paper will serve to show the type of information which studies of single crystals afford and will contribute toward the solution of the general problem of metallic behavior. PRODUCTION OF ZINC SINGLE CRYSTALS The method of Czochralski,1 as modified by von Gomperz,2 was used to produce the crystals studied. The equipment is shown in Fig. 1. Molten zinc is held in a crucible at a temperature which is not far above its melting point, as measured by a pyrometer. A lava disk floats on ,the melt, and is provided with a central hole about 1 mm. in diameter. A glass tube, drawn into a capillary at the lower end, is suspended from a string which is wound up by an electric drive at the speed desired. At the start, the glass capillary is let down into the melt and the hoist is started.. The capillary brings up a small quantity of molten metal with it to a point just above the lava disk. At this point, a jet of hydrogen cools it and causes it to crystallize, with the result that a small crystal forms. As the hoisting is continued, more molten metal is drawn up, in turn to be solidified by the jet of hydrogen. This additional metal continues the growth of the crystal already formed, and a long, cylindrical crystal results. The speed of hoisting used was generally between 0.1 and 0.5 mm. per sec., and the crystals were from 4 to 6 in. long and about 1 mm. in diameter. By varying the conditions, crystals of quite different orientations were obtained and were used in the study of the phenomena to be described.

Jan 1, 1927

By A. B. Bowman

The 1963 Jackling Award lecturer describes the founding of Banner Mining Co. and its trials and tribulations before becoming an established firm. Such aspects as geological description of Banner mining areas, history of exploration and production, areas of present interest to the company and research work conducted by the company are included. Several years ago a wealthy Chinese business friend of mine purchased an interest in a proposed oil well to be drilled a great distance from his home. A few months later it came in as a producer and proved to be a huge success and materially added to his resources. I asked him why a man of his wealth should be so lucky in a venture outside his sphere of knowledge when most people of modest means never seemed to get ahead. His answer was, "Fat Hoy takes a chance." Even though this was his answer, I knew from my association with him that there were other tempering considerations which Mr. Hoy applied before making up his mind to enter any transaction. First, he was a cautious individual. He was also a great believer in details and insisted on knowing everything possible about a situation, and finally, he was what we call a very solid individual with good basic instincts and judgment. This philosophy of Mr. Hoy may be applied to most any business but especially to those engaged in a search for natural resources such as mining where great risks are involved. This article concerns events in the history and growth of Banner Mining Co., with which I have been associated for 27 years in capacities from mine surveyor to vice president. Mr. Hoy's philosophy has played a significant role in the exploration projects of this company over the years, but what is more important, the officers, directors, and controlling interests in Banner have been aggressive in their search for ore reserves. THE BIRTH OF BANNER Banner Mining Company was incorporated in September 1935 by a group of Oklahoma and Texas oil men for the purpose of exploring and developing the Bonney-Manilla mines at Lordsburg, N.M. These properties had a history of intermittent production since the first ore discoveries as far back as 1870. Most of the production from the district has come from four mines, namely, the Eighty-Five, the Atwood, the Bonney-Manilla, and the Misers Chest. The last two are now owned by Banner Mining. The Eighty-Five mine operated between 1885 and 1931, and production totalled 1,494,287 tons averaging 0.11 oz of gold per ton, 1.23 oz of silver per ton, and 2.80% copper. The vein extended for a distance of about 3000 ft northeast and was mined to a depth of 1650 ft. The Atwood mine, adjoining the Eighty-Five mine, to date has been of lesser importance as a producer, but it has been operating for several years producing high silica flux ores for a smelter. Production totalled 352,828 tons up to January 1, 1962 From the Bonney-Manilla and Misers Chest mines, owned by Banner, production through 1961 totalled 2,006,343 tons with an average grade as mined of 0.0192 oz of gold per ton, 0.760 oz of silver per ton and 2.63% copper. Banner built a 150-tpd flotation mill in 1936 after almost a year of development on the 600 level of the Bonney mine. After less than one year's operation, it became apparent that the 150-tpd rate was not sufficient to make a reasonable profit due to the marginal grade ores. The low tenor of the ore, mainly chalco-pyrite in a highly siliceous gangue, made mandatory the close control of costs in order to make ends meet. A 300-tpd unit was added to the mill in 1937, and it is still the operating unit today. The clean sulfides presented no problems in milling. A metallurgist doing research on it at the time stated that the copper minerals seemed to have a built-in desire to float. Mill recovery of copper throughout the 27 years of operation has averaged 96.23%. A PERIOD OF FORCED GROWTH World War II brought many hardships to Banner. Labor and supply shortages caused drastic curtailment in development work. Rapidly rising costs far outdistanced any relief from pegged prices which we received from Government agencies. Finally, a branch of the Government asked us to stop all devel-

Jan 1, 1963

By Arne Bergholm

Australian rutile was chlorinated in the presence of CO or carbon. The chlorination velocity in CO was found to be strongly influenced by temperature and proportional to the CO concentration, but independent of the Cl, concentration. In the presence of carbon, the reaction velocity is much higher. The reactivity of the carbon and the distance between the carbon and the rutile surfaces are important variables. The reaction velocity is approximately proportional to the Cl, concentration and independent of the CO concentration of the surrounding atmosphere. Experiments with fluidized-bed chlorination of carbon-rutile mixtures indicate that the motion of the bed has little influence on the reaction velocity. At low temperatures, the chlorination velocity of dense tablets is much greater than that of TiO, coke mixtures suitable for fluidization. The reaction mechanism is discussed. In the industrial production of TiCl, rutile is chlorinated in the presence of carbon. Disregarding intermediate steps, the reaction may be expressed by the following equations: The ultimate object of this study was to find out whether the reaction velocity was higher in fluidized bed operation compared with chlorination of pelle-tized carbon-rutile mixtures. From a literature survey and preliminary experiments it was learned that some basic knowledge about the reaction mechanism was needed for a good experimental design. Therefore the following sets of experiments were carried out: 1) Studies on the reaction velocity in the chlorination of rutile with CO as the only reducing agent. 2) Chlorination of separate rutile-carbon tablets. 3) Chlorination of rutile-carbon tablets at different temperatures with various kinds of carbon, various grain sizes, and various tablet-making techniques. This series of experiments was carried out not only with pure chlorine but also with mixtures of chlorine with argon, CO and CO,. 4) Chlorination of rutile-carbon tablets made in a strictly standardized manner. 5) Chlorination of static-bed rutile-carbon mixtures. 6) Fluidized-bed chlorination of the same mixture. The experiments 4 to 6 formed the final and direct test of the main question: Static bed vs fluidized bedo. Although there are many patents and papers dealing with the general aspects of chlorination, only few experiments from which detailed information can be obtained have been reported in the literature. Pamfilov and coworkersl3 have studied chlorination of TiO, with CO or carbon as the reducing agent. They found that the weight decrease per hour at 600o to 800°C amounted to 11 to 14 pct with CO and 45 to 51 pct with carbon. They suggest that phosgene might be an intermediate in the chlorination of TiO,. Takimoto and Hattori have chlorinated reduced titanium oxide (TiO) and found a very high rate of TiC1, -production. They proved that the composition of the gas from the chlorination of rutile-carbon mixtures contained mainly CO. They reported for instance 74.7 pct CO, and 5.6 pct CO at 800°C at which temperature the Boudouard equilibrium composition is 12 pct CO and 88 pct CO. Seligman and Segerchano6 have studied the chlorination of TiO. They proved that Ti0 and chlorine react rather rapidly at temperatures as low as 300°C. Above 400°C, the reaction was complete. At 500°C the velocity of this reaction was much higher than was chlorination of TiO, + C. McTaggart,7 Nishimura, et al. and Wilskam have chlorinated mixtures of carbon and various kinds of rutile or beneficated ilmenite. Nishimura, et al. also report the results from reduction of TiO, with H2, CO, or carbon. At 900°C only 1 pct Ti O is formed in 2 hrs. At 1100°C 23.1 pct Ti, 0, was formed if elementary carbon was present. No carbide formation occurred below 1400°C. McIntosh and Cofferll have observed that the CO, content of the exit gases from chlorination of rutile and calcined petroleum coke is appreciably higher than found in the Boudouard equilibrium. At 900°C the ratio (CO, /CO + CO) is about 80 pct, whereas the equilibrium value is about 2 pct. W. E. Dunn12 has studied the chlorination rates of several TiO,-bearing minerals with CO + Cl, or COCl . Chlorinations were carried out either in a fluidized reactor or a fixed-bed reactor, both having a 30-mm diameter. The results obtained in both reactors were comparable. It was proved that benefi-ciated ilmenite (i.e., ilmenite from which the iron oxide had been removed by chlorination) was chlorinated 10 times faster thanrutile. Sore1 slag showed an intermediate rate. When phosgene is used, the

Jan 1, 1962

By Charles S. Barrett

The experiments reported in this paper have been fruitful in disclosing the mechanism of the deformation of iron in compression. They have established the nature of "deformation bands," "etch bands," or "X-bands," that have been a recognized but little understood feature in the structure of cold-worked metals since the early days of metallography, and have shown the role of the bands in the development of preferred orientations by cold-working. The work has also shown the relation of the orientation of individual grains to the preferred orientation of the aggregate. Some of the methods previously used in the determination of the indices of slip planes and slip directions are shown to be untrustworthy in the presence of deformation bands. The conclusion is reached that many slip planes and slip directions must operate during each stage in the compression of a single crystal, and that theories failing to take account of this require revision. In conducting the experiments a method of compression has been used by which extreme reductions can easily be reached, even to the limit set by the metal's capacity to deform without fracture. The work is a portion of a research program on the plastic properties of iron and steel. It is being used as a foundation for studies of orientntions resulting from recrystallization and is being extended to other metals and other types of deformation. Previous Work The previous experiments are few and have given confusing results Onol compressed a polycrystalline alpha-iron specimen between two flan plates of a testing machine and found that severe deformation oriented the crystals into a duplex preferred orientation, one set of crystallites having a cube diagonal of the body-centered cubic lattice parallel to the compression axis, and another set having a cube axis parallel to the compression axis. We shall speak of this structure as a double fiber texture of the type [111] + [100]. Wever2 also made an X-ray determination of the texture

Jan 1, 1939

By Charles S. Barrett

The experiments reported in this paper have been fruitful in disclosing the mechanism of the deformation of iron in compression. They have established the nature of "deformation bands," "etch bands," or "X-bands," that have been a recognized but little understood feature in the structure of cold-worked metals since the early days of metallography, and have shown the role of the bands in the development of preferred orientations by cold-working. The work has also shown the relation of the orientation of individual grains to the preferred orientation of the aggregate. Some of the methods previously used in the determination of the indices of slip planes and slip directions are shown to be untrustworthy in the presence of deformation bands. The conclusion is reached that many slip planes and slip directions must operate during each stage in the compression of a single crystal, and that theories failing to take account of this require revision. In conducting the experiments a method of compression has been used by which extreme reductions can easily be reached, even to the limit set by the metal's capacity to deform without fracture. The work is a portion of a research program on the plastic properties of iron and steel. It is being used as a foundation for studies of orientntions resulting from recrystallization and is being extended to other metals and other types of deformation. Previous Work The previous experiments are few and have given confusing results Onol compressed a polycrystalline alpha-iron specimen between two flan plates of a testing machine and found that severe deformation oriented the crystals into a duplex preferred orientation, one set of crystallites having a cube diagonal of the body-centered cubic lattice parallel to the compression axis, and another set having a cube axis parallel to the compression axis. We shall speak of this structure as a double fiber texture of the type [111] + [100]. Wever2 also made an X-ray determination of the texture

Jan 1, 1939

By Ellis Clark

THE mining town of Pribram is situated in Central Bohemia, on the western slope of the Heiliger Berg, 30 miles southwest from Prague. Birkenberg, the village in which most of the shafts and ore-dressing establishments are situated, is built on a mountain of the same name. It is about a mile from Pribram, is 1700 feet above the sea, and is surrounded by graywacke rocks of Silurian origin, which are intersected by greenstone dikes, and in the southerly, southeasterly, and southwesterly direction are bounded by granite. The graywacke formations consist on one side of graywacke sandstone and quartzite, and on the other of graywacke slates. These last are separated from the first in the immediate vicinity of the mines by a graywacke seam converted into clay. For many years this so-cal led clay seam (lettenkkluft) was considered as a boundary of the ore deposits in both zones of graywacke. The graywacke formation is divided according to its hardness, structure, texture, and color, into fine, coarse, compact, slaty, whitish-gray, reddish-gray, and black graywacke. The, miner divides the formation into four divisions. The first or lowest division, which is in contact with the granite, consists of a fine-grained dirty gray slate; the -second is a very fine to a very coarse schist, white to reddish-gray in color, and rich in quartz, but containing little mica; the third consists of a slate with a contused cleavage, which has a dirty gray, dark gray, and very often black color and is often graphitic in its composition ; the fourth consists of a fine to coarse-grained graywacke schist, of a grayish-white or reddish-gray color, and rich in quartz. The cleavage in all four divisions strikes from northeast to southwest, and the dip is sometimes northwesterly, sometimes southerly, and often vertical. All four zones are cut through by a great number of diorite and greenstone dikes and chimneys. The thickness of these dikes, which are of

Jan 1, 1881

Jan 1, 1957

By Klaus Schwerdtfeger

In order to test the performance of ZrO, (CaO) and Tho,(Yz03) electrolytes in the electrochemical determination of oxygen activities in liquid metals at steel-rrzakitng temperatures , electromotive force measurements have been made with the following cells: The oxygen-- activities are calculated from the electmrnotive forces for the investigated systems. The standard free energy of- formation of MnO and the activity of manganese in Fe-Mn melts are derived. Indications are that the Zr 0z(Ca0) electrolyte exhibits little electronic conductivity at oxygen pressures as low as 10'a atnz at 1600°C; however, the partial electronic conductivity may become noticeable at lower oxygen activities. The Tho,(Yz03) electrolyte is found to be an ionic conductor at the oxygen pressure as low as that for the Mn + MnO equilibrium, but exhibits partial electronic conductivity at oxygen pressures higher than 10"1 atm (1500°C). fi. better control of oxidation and deoxidation reactions in steelmaking may be facilitated if the oxygen activity in the steel is known during various stages of the process. In the present work oxygen activities have been measured in liquid iron, manganese, and iron alloys with galvanic cells using ZrOz(CaO) and s solid electrolytes with the object of establishing the range of oxygen pressure in which these materials can be used as electrolytes at steelmaking temperatures. Calcia-stabilized zirconia and Tho2-Y203 solid solutions are oxygen ion conductors. Such electrolytes were first used by Kiukkola and Wagner1 and Peters and ~ann' in galvanic cells for the determination of thermodynamicquantities of oxide systems in the temperature range 700" to 1200°C. At these moderate temperatures calcia-stabilized zirconia has been found to exhibit predominantly ionic conductivity at oxygen pressures as low as those for the Cr + Crz03 equilibrium,394 but at lower oxygen pressures elec- tronic contribution to conductivity becomes significants4 The Th02-Y203 solid solutions are ionic conductors at oxygen pressures lower than those applicable to zirconia base electrolytes.5'6 At high oxygen pressures Thoz base electrolytes exhibit significant p-type semiconduction. At the time the present experiments were carried out several papers1'-* were published on the electrochemical determination of oxygen activities in liquid iron using the ZrOz(CaO) electrolyte. The results of different authors do not agree well. For instance, according to Fischer and ~ckermann" stabilized zirconia can be used to measure oxygen contents in liquid iron larger than 0.02 wt pct, but according to Baker and west1' ZrOz(CaO) cannot be used for the determination of oxygen content in liquid iron because of high electronic contribution to the conductivity. Fig. 1 is a schematic diagram of the apparatus used. About 500 g of liquid metal is contained in a crucible into which a stabilized zirconia or Th02(Y203) tube is immersed. A platinum contact wire is pressed (with a spring mechanism) against the inside bottom wall of the electrolyte tube. The tube is flushed continuously with a stream of air, CO-CO, (or Hz-C02) (at 0.96 atm and at a rate of about 300 cu cm per min), via an alumina tube inserted inside the electrolyte tube. This alumina tube also contains the Pt-Pt/10 pct Rh thermocouple. A capillary alumina tube shielding the other contact wire is immersed in the melt. The molybdenum contact wires were used mostly; in some cases platinum wire was employed. Molybdenum has the advantage that it dissolves more slowly in the melt than platinum. The whole cell was contained in the alumina reaction tube of a resistance furnace with molybdenum winding. The reaction tube was closed gas tight at both ends and flushed continuously with argon. Because of the poor thermal shock resistance of the electrolyte tubes the cell had to be assembled in the cold furnace. The electrolyte tube and alumina sheath

Jan 1, 1968

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

Lime and dicalcium-silicate crucibles were equilibrated with molten iron and liquid slags containing iron oxide and small amounts of sulfur. The oxygen content of metal, iron oxide activities, and desulfurization values of the slags were determined in the temperature range 1530 to 1700°C. The influence of magnesia in the slag and the temperature dependence of the solubility of lime in liquid iron oxide and the ferric oxide content were established. The temperature contour of the liquidus surface of iron-silicate slags saturated with lime and dicalcium silicate was also established at 1600°C. THE importance of the role that slag composition plays in the refining of steel has been known for many years. Numerous studies have been made using actual plant data in order to establish the relationship between the composition of the slag and metal during the refining of a heat of liquid steel. These results rarely represent equilibrium conditions since completion of the various chemical reactions involved in steelmaking is seldom realized. In order to establish quantitatively the equilibrium conditions existing between the slag and metal, several laboratory studies have been conducted in the past 20 years to determine the reactions important in slag control. These investigations have included studies of simple liquid basic and acid slags as well as more complex slag systems which approach those commonly found during the refining of a heat of steel. Since most of the previous studies of simple basic iron-oxide slags equilibriated with molten iron were made in magnesia crucibles, it was not possible to establish the distribution of sulfur and oxygen between molten iron and slags consisting only of the three essential components, lime, silica, and iron oxide. This investigation was undertaken to establish the equilibrium conditions for simple lime-iron oxide and lime-silica-iron oxide slags. Accordingly, it was expedient to prepare crucibles both of lime and dicalcium silicate to establish the equilibrium conditions between molten iron and iron-oxide slags saturated with the refractory materials and free from other components. The only other studies of the equilibrium between molten iron and lime-saturated slags are those of Fischer and vom Ende, 1, 2 in which the solubility of oxygen was determined in an air atmosphere. The

Jan 1, 1959

By M. S. Seltzer

High temperature steady-state creep rates have been determined jor lead sulfide single crystals whose defect concentrations were fixed by equilibration under controlled sulfur pressure. The activation energy of creep, Qc , for undoped lead sulfide, is a function 01 composilion, decreasing from 2.9 to 2.2 ev as the carrier concentration increases from 9 x 1016 to 8 1018 electrons cm-3 for lead excess crystals, and increasing from 1.7 to 2.3 ev as the concentration of holes increases from 4 x 1017 to 1 x 1018 cm-3 in sulfur excess material. For five different composilions, Qc for undoped and bismuth-doped crystals has been found to be equal to Qpb + Qs, the self-diffusion activation energies for lead and sulfur in PbS. It is well-established1 that high-temperature steady-state creep of pure metals is a diffusion-controlled process, where the activation energy of creep is equal, within experimental error, to the activation energy of self-diffusion. The relationship between the activation energy for steady-state creep and those for self-diffusion in binary compounds is more complicated, however, because two different diffusing species must be considered, and becayse the activation energies may be influenced by compositional variations and by foreign atom additions.2-4 In some cases experimentally determined creep activation energies are correlated with those for self-diffusion of the slower-moving species, but such agreement is by no means universal. Interpretation of experimental results is difficult because few investigations include measurements of creep rates and self-diffusion coefficients of both diffusing species on single crystals of similar composition and foreign atom concentration. The objective of this investigation, therefore, is to determine the influence of stoichiometric defects and foreign atoms on steady-state creep and self-diffusion for a well-characterized binary compound. Lead sulfide, a compound semiconductor which crystallizes in the NaC1-type structure, and whose homogeneity range includes compositions on either side of the 1:l atom ratio, was chosen for study in this investigation. The pressure-temperature-composition relations for PbS are available,5,3 and deviations from stoichiometry may be monitored by electrical measurements.7 Single-crystal specimens are available to allow observation of effects due to bulk phenomena without interference from grain-boundary effects. These crystals have been employed to determine steady-state creep rates under compressive stress for "pure" and bismuth-doped PbS as a function of sulfur pressure and temperature as well as crystal orientation and applied stress in order to establish the relationships between defect concentrations and creep rates. EXPERIMENTAL PROCEDURES Crystal Growth. Lead sulfide crystals, prepared by the Bridgman method, are grown in evacuated quartz crucibles, filled with almost equal atomic proportions of high-purity (99.999 pct) lead and sulfur, and heated to a temperature above the melting point of PbS (about 1127°C) so that the lead and sulfur react to form molten PbS. The crucible and melt are dropped through the hot zone of the crystal-growing furnace at the rate of 1 cm per hr. The maximum melting point of PbS is slightly on the lead-rich side of the 50:50 composition; hence crystals grown from a near stoichiometric melt are usually n-type semiconductors containing excess lead atoms. Typically the lead excess concentration in solid solution with the PbS is 3 x 1018 atoms cm-3. Crystals containing either 1/20 or 1/2 mole pct Bi2S3 were prepared by addition of the foreign atoms prior to crystal synthesis. Preparation of Specimens of Controlled Stoichiom-etry. Since it is difficult to grow crystals of desired composition, the process of crystal growth and control of stoichiometry are separated into two distinct operations. Equilibration of as-grown PbS to a desired composition is most easily accomplished by first annealing the n-type crystals under high sulfur pressure (about 1 atm) at temperatures above 700°C. This process serves to put excess lead precipitates into solution, yielding 0 -type crystals upon quenching to room temperature. Inter diffusion occurs readily in crystals so treated, and the methods described by Bloem may then be employed to obtain crystals of controlled stoi-chiometry. For the creep measurements made in this study, this involves heating crystals in mixtures of H2 and H2S The equilibrium constant for H2S is given by: Thus the sulfur partial pressure is obtained from knowledge of the H2/H2S ratio and Kh2S for the temperature in question. Fig. 1 shows the p-T-x diagram for PbS. It can be seen that, within the stability limits for single-phase lead sulfide, desired compositions may be obtained by equilibrating under a specified sulfur pressure and temperature. Characterization of Crystals. The principal methods for evaluating PbS crystals include measurement of electrical properties and mass-spectrographic analysis. The measured electrical parameters include Hall coefficient, conductivity type, and electrical resistivity Bloem7 has shown that there is a 1:l relation between the defect concentration and carrier concentration obtained. Hence, if the contribution to the carrier con-

Jan 1, 1968

By R. K. Datta

Eluropium -activated yttrium vanadate, excited by short- and long-wavelength ultraviolet radiations, shows enzission lines near 6100A, the principal ones correspondirzg to transitions of EU+3 ions from 5Do to the F2 energy level. The ~neclmlallistns of absorption and etnissiorz of this phosphor have been empirically studied. The absorption is caused by two separate processes in the matrix. The phosphor YVO4:Eu and tlie matrix YVO, haue essentially the same resectance spectra in the region 2500 to 4000if. There are two broat ah~o?~ption bands: natnely, around 2600 and 3600A regions. Whet? compared with the reflectance spectra of the constituent oxides, namely, Y2O3, V205, Eu2 03, the absorption bands of the tnatvix and the phosphor in the short- and long-wavelength ultraviolet regions can be interpreted as due to charge-transfer processes involving i) Y-O and ii) 17-0, respecti~~ely. The excitation spectrum' of the phosphor has two broad bands with peaks at about 2600 and 3600A regions. U can be postulated that enevgy absorbed under short- crud long-wavelength ultraziolet excitatzon, respectzcely, by Y-0 and V-O parts of the niatrix is transferred by radcatio~zless process to EU+3 ions. Thzs postulate can empirically be proved on the basis of the spectra of the systems (YVO4,-YPO4,):Eu. PO? ~ons do not have' any appreciable absorption in the short or long uv regions. When P0't3 ions are substitlited for v0i3 ions in YVO,:Eu phosphors, the absorption and excitation in the lo~zg uv region are gradually reduced. Ailoreover, the £«+3 emission under 3650A excitation is decreased zuitlz increase in PO^ content, lt~lzereas the emission under 253711 excitation remains esserztially constant with as IILUCIL as 60 mole pct of YPO, in YVO,:En. EUROPIUM-activated yttrium vanadate (YV04:Eu) is a well-known phosptor.'-3 When excited by cathode rays, 2537, or 3650A radiations, YV04:Eu emits typical narrow-band spectrum of EU'3 fluorescence in the region of 5900 to 7100A, a very strong maximum occurring at about 6190A. This emission is considered to be due to 5Do — 7F2 transition of excite: EU*3 in 4f state. Moreover, the emission under 3650A excitation increases with temperature markedly. Because of these properties, YV04:Eu phosphor finds wide application in industries, namely, in color television tube, laser, and high-pressure mercury-vapor lamps. It is the purpose of this paper 1) to present the empirical study of the mechanism of absorption and excitation of YV04:Eu phosphor by ultraviolet radiation, and 2) to offer an explanation for the process of emission. It should be mentioned that a theoretical discussion on the mechanism of absorption in terms of the crystal or ligand field theory is beyond the scope of this paper. Empirical studies presented here are based primarily on spectroscopic and crystal-chemical investigations. EXPERIMENTAL i) Preparation of Materials. The synthesis of vanadate phosphorinvolves preparation of (Yi-.tEuj^Oj, blending the mixed oxide with an oxidic compound of vanadium, such as V205 or NH4V03, and firing the mixture at about 1000°C for several hours when YVO4:Eu forms as a primary phase. (Y1-xEux)203 compositions are prepared by coprecipitation of oxalates, and igniting them at about 1000°C. The vanadium compound is added in excess of the stoichiometric proportion for fluxing purposes. The charge is cooled, ground, and the excess of vanadium is removed by a hot wash (-80°C) of alkali or ammonia. Y(VP)04:Eu samples are prepared by mixing (Yi-xEux)203 with stoichio-metric proportions of (NH4)2HP04 and the vanadium compound. The mixtures are prefired at 700" to 800°C for 1 or 2 hr, then ground and refired at 1150°C. The firings of the phosphors are done in silica crucibles, and the homogeneity of the final products checked by X-ray diffraction analysis. ii) Spectroscopic Measurements. Diffuse reflectance sqectra of the samples within the range 2500 to 7000A are obtained by using CaF2 as standard in Cary Recording Spectrophotometer, Model No. 14. The emission spectra from phosphor plaques, excited under different ultraviolet sources, are obtained by a direct-recording spectroradiometer4 adapted with a grating monochromator with nearly constant dispersion. Maximym sensitivity in the spectral region from 2500 to 7000A is obtained with a quartz-windowed, S-20 response p$otomultiplier. The total' band pass is kept about 30A. The spectra are calibrated against the light from a standard tungsten filament lamp reflected from a magnesium-oxide plaque. Brightness data given throughout this report $re measured from the height of the main peak (6190A) of the emission spectra. The excitation spectra are measured using sodium salicy-late as standard. RESULTS AND DISCUSSION The diffuse reflectance spectra of both pure and activated YV04, along with their constituent components, are shown in Fig. 1. YVO4 shows two broad absorption bands, namely, around 2500 and 3600A, respectively. Since there is little difference between the reflectance spectraoof YVO4 and YVO,:Eu in the uv region (2500 to 4000A), it can be postulated that excitation of the phosphor is mainly due to absorption by the matrix, i.e., YVO4. The question, now, is whether the matrix (Yv04) is excited as a whole, or different components are responsible for the two absorption bands. The characteristic absorption spectra of molecular ions involving transition metal ions, both in aqueous solutions and in crystals, are due to electronic transi-

Jan 1, 1968

By Louis E. Reber

Jan 1, 1922

By F.B. Foley, S.P. Howell

Not infrequently, in the case of the failure of a metal structure, such as a bridge, tank, airplane, gun carriage, etc., a doubt arises whether the failure was due, among other causes, to the effect of an overburden or of an explosive maliciously or accidentally exploded in contact with it. As few means of discriminating between the effects of these causes have been known and these means were of a rough qualitative character, it was surprising to find in the record of an inquiry into the failure of a structure, the statement that, by observations on the Neumann bands in the structure, it was possible to determine the speed of breakage in the metal and to distinguish between a fracture caused by an explosion and one caused by an ordinary mechanical strain. Such a criterion, if well proved, was of value to the explosives experts of the Bureau of Minea, the Ordnance Department of the United States Army and the Bureau of Ordnance of the United States Navy, but search showed no record of it in the literature nor did any of the metallurgists and metallographers consulted know of any data on which such a criterion could be based having been assembled and critically studied. However, it was universally held that there was promise in the idea and that there exkted unique facilities at the Bureau of Mines Experiment Station at Pittsburgh for the preparation, under definitely known conditions, of material for study by metallographers, and that material of value might also be obtained from the proving grounds of the Army and Navy. Therefore, with the approval of the Director of the Bureau of Minea and the Chiefs of Ordnance of the War and Navy Departments, the Chairman of the Division of Engineering of the National Research Council, on April 12, 1919, appointed a Committee on the Investigation of Neumann Bands, which has since been engaged in this study and which, after some slight change in its personnel, consists now of the following: Dr. William Campbell, Advisory Metallurgist, Bureau of Ordnance, Navy Department. P. B. Foley, Metallurgist, Bureau of Mines. S. P. Howell, Explosives Engineer, Bureau of Mines. Comdr. 0. M. Hustvedt, U. S. N., Bureau of Ordnance, Navy Department. Dr. Charles E. Munroe, Chief Explosives Chemist, Bureau of Mines.

Jan 1, 1923

By S. P. Howell, F. B. Foley

Not infrequently, in the case of the failure of a metal structure, such as a bridge, tank, airplane, gun carriage, etc., a doubt arises whether the failure was due, among other causes, to the effect of an overburden or of an explosive maliciously or accidentally exploded in contact with it. As few means of discriminating between the effects of these causes have been known and these means were of a rough qualitative character, it was surprising to find in the record of an inquiry into the failure of a structure, the statement that, by observations on the Neumann bands in the structure, it was possible to determine the speed of breakage in the metal and to distinguish between a fracture caused by an explosion and one caused by an ordinary mechanical strain. Such a criterion, if well proved, was of value to the explosives experts of the Bureau of Minea, the Ordnance Department of the United States Army and the Bureau of Ordnance of the United States Navy, but search showed no record of it in the literature nor did any of the metallurgists and metallographers consulted know of any data on which such a criterion could be based having been assembled and critically studied. However, it was universally held that there was promise in the idea and that there exkted unique facilities at the Bureau of Mines Experiment Station at Pittsburgh for the preparation, under definitely known conditions, of material for study by metallographers, and that material of value might also be obtained from the proving grounds of the Army and Navy. Therefore, with the approval of the Director of the Bureau of Minea and the Chiefs of Ordnance of the War and Navy Departments, the Chairman of the Division of Engineering of the National Research Council, on April 12, 1919, appointed a Committee on the Investigation of Neumann Bands, which has since been engaged in this study and which, after some slight change in its personnel, consists now of the following: Dr. William Campbell, Advisory Metallurgist, Bureau of Ordnance, Navy Department. P. B. Foley, Metallurgist, Bureau of Mines. S. P. Howell, Explosives Engineer, Bureau of Mines. Comdr. 0. M. Hustvedt, U. S. N., Bureau of Ordnance, Navy Department. Dr. Charles E. Munroe, Chief Explosives Chemist, Bureau of Mines.

Jan 1, 1923

By W. L. Crentz, E. E. Donath, D. Doherty

Maurice Rey—The influence of cyclone diameter upon the fineness of separation is an important point which, however, cannot be discussed adequately if the injection pressure or the rate of flow are not specified. Perhaps some light can be thrown on the matter by using the formulas derived by Dahlstrom. Let us consider several geometrically similar cyclones where the apertures e and b are equal and proportional to the diameter D and which are operated with the same pressure drop. Eq 8 of Dahlstrom's paper can be written: Q Q = K D'. " or. if F is constant: Q = K D18 K is a constant of proportionality. Introducing this value of Q in eq 13 gives elimination efficiency = K D0' " Elimination efficiency, in the terminology of Dahlstrom, means the diameter of particles, in microns, which divide equally between the underflow and the overflow. This denomination is regrettable and it would be preferable to call it diameter of separation or characteristic size or any other name connoting a size rather than an efficiency. Whatever the name used, the above equation shows a slow increase in the fineness of separation when the diameter of the cyclone decreases. For example, if a 14-in. cyclone gives a 400-mesh separation (37 microns), geometrically similar cyclones, having the same pressure drop will give separations at the sizes shown below.

Jan 1, 1951

By B. C. Allen

Liquid surface tensions of copper and 18 Group IV-A to VIII transition metals (Ti, Zr, Hf, V, Cb, Ta, Mo, W, Re, Ru, Rh, Pd, Os, Ir, Pt, Fe, Ni. Co) have been measured by the static pendant-drop and dynamic drop-weight methods on the same rod sample. The drops were formed by electron-bombardment heating in high vacuum. Application of necessary corrections enabled determination of surface tensions to k2 pct and agreement between methods to * 1 to 4 pct for all the metals studied. Evidence is presented that the liquid surface was well screened by metal vapor, suggesting negligible adsorption of gaseous impurities and that the surface tensions measured are characteristic of the metals involved. Correlations between liquid surface tension and melting point, molar volume, heat of vaporization, and atomic number are presented and discussed. Temperature coefficients of surface tension were calculated using Eötvös' law. SURFACE tension and interface energies of metals are the result of incomplete atomic coordination resulting in a force perpendicular to the boundary, tending to minimize its area. These energies are important in many phases of metallurgy, including microstructure, sintering, joining, electronic emission, and lubrication, which in turn affect many physical and mechanical properties of metals. Liquid surface tension refers to the interface between the liquid and its own vapor or nonreactive atmosphere, and is considered a physical property of the liquid. Since equilibrium shapes can be readily obtained with liquids, the units of surface tension (force per length) and interface energy (energy per area) are interchangeable. Thermo-dynamically, the surface tension ?LV is given by the change in free energy F with surface area A at constant pressure P, temperature T, and composition N: for commercially important refractory metals, vanadium, columbium, tantalum,13,14 molybdenum,14 and tungsten,l5 and none for the rare platinum-group metals and rhenium. Measuring the surface tensions of transition metals is difficult because of their high reactivity and melting points. Of the many techniques available,16-18 the pendant-drop 19-21 and drop-weight methods17,22 are considered superior because they can be modified to eliminate persistent sources of contamination such as supports and capillaries necessary in the popular sessile drop, capillary rise, and maximum-bubble-pressure techniques. The necessary modification is to melt a drop on the tip of a vertical rod, which provides support through a solid of the same composition.13,15 The object of the work was to study the surface-tension behavior of copper and transition metals, having reasonably low vapor pressures. Liquid surface tension of each pure metal was systematically determined by using a combination of the static pendant-drop and dynamic drop-weight methods on the same rod. Liquid drops were formed by electron-bombardment heating in high vacuum. EXPERIMENTAL WORK As indicated in Table I, the metals studied were high purity and generally were obtained in rod form. The exceptions were titanium and zirconium, which were machined from crystal bars, and molybdenum (tot 11, osmium, and ruthenium, which were sintered and arc cast into rods. All the metals were ground or swaged to desired sizes between 1- and 7-mm diam, and centerless ground round and smooth to a finish better than 50 µ in., rms. Each rod was thoroughly cleaned with steel wool, degreased, acid etched, and dried. In a typical run, the rod was vertically clamped in a modified floating-zone electron-bombardment furnace designed after Calverley23 and Carlson.24 The specimen was outgassed and maintained positive at several kilovolts in a dynamic vacuum of 10-5 to 10-7 mm. The bottom end was enclosed by a tantalum pillbox and heated by electrons emitted from a hot concentric tungsten filament mounted on a movable bracket. The bombardment power was slowly raised until melting was observed. Power requirements ranged from 30 w for copper to 1300 w for 4-mm tungsten. The stabilized and out-gassed drop of near-maximum size was photographed at 4. 1X on panchromatic film at desired time inter-

Jan 1, 1963

By C. D. Thompson, D. C. Violetta, C. A. Czako

The mechanics of the continuous sintering process are briefly reviewed and the application of this process for the beneficiation of principal minerals used in making cement is shown. Pilot plant tests using pyrobeneficiation techniques were conducted with mixtures of limestone and shale in various ratios. Results are illustrated and show the percentage removal of carbon, carbonates, sulfur, alkalies, and volatiles as a function of the limestone-shale ratio. Tests with varying quantities of solid fwls, added to mixtures containing limestone and shale in a 4 to 1 ratio, were made to attain optimum elimination of the volatile constituents. Experimental results show that 90 pct of these constituents were removed during the calcination sintem'ng process. The advantages of using the beneficiated material for making cement are discussed with regard to prepam'ng, handling, and clinkering operations. A sintering process for treating raw materials or kiln waste products which contain high amounts of alkaline materials is described. Tests were performed with a high alkaline waste dust mixed in a 1 to 1 ratio with raw cement meal. The data from these tests and others using different halides for aiding alkali removal are evaluated by the alkali content of the cement clinker. Test results showed that the Dwight-Lloyd process could be applied with facility in beneficiating raw materials for cement making. Substantial quantities of deleterious volutile constituents were removed by calcining and sintering techniques. The continuous sintering process has been applied for a number of years as a means of beneficiating minerals for subsequent conversion to merchantable products. The process was developed and first used for nonferrous metallurgical applicatfons. However, it has risen to prominence for ferrous metallurgical applications where last year in the U.S. and Canada nearly 40 million tons of iron ore were treated by grate firing processes. Through the years of process development many investigators have realized the versatility of the sintering process and have directed experiments toward the use of it for applications with nonmetallic minerals. These have included calcining limestone, carbonizing coal, expanding shale, and burning cement raw meal. Today commercial sintering plants produce cement clinker from mixtures of limestone and shale, lightweight aggregate from shale or clay, and calcined products from phosphate shale. The mechanics of the downdraft sintering process have been presented by many authors. In general practice the materials to be agglomated are mixed as moistened fines with a solid fuel and this mixture is spread uniformly on the grates of the sintering machine. The charge is then momentarily directed under an ignition furnace. After ignition a continuous downdraft of air promotes combustion of the fuel and through heat transfer particles become partially fused into a coherent mass. This is cooled from continued draft induced after combustion. Many investigators have shown that distinct zones are formed during the process of sintering iron ores. At the midway point of the sintering process these are prominent and are, respectively, from the top of the bed to the bottom, comprised of a cooling zone of sintered material, a combustion zone of sinter formation, a calcination zone, a drying zone, and a zone of unreacted materials. Completion of sintering occurs near the discharge end of the machine where the firing zone approaches either the grates or grate dressing material called hearth layer. Here the peak draft temperature usually can be noted in the windboxes. The zonal pattern has been illustrated with the use of graphs which show thermal gradients as they progress through the bed of materials during sintering. Fig. 1 shows, in simplified form, thermal gradients existing when clinkering cement on a sintering machine. The thermal gradients illustrated are for periods of initiation, midway and completion of the clinkering process. The occurrence of these zones has importance for the beneficiation of cement raw materials. A research program was performed at the Dwight-

Jan 1, 1961