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By Arthur O. Gates

RittingeR's law of the energy expended in crushing is, as roughly stated by Profcssor Richards,' that the work of crushing is proportional to the reduction in diameter; or, as I have more fully expressed it: "The work done in crushing is proportional to the surface exposed by the operation; or, better expressed for this purpose, the work done on a given mass of rock is proportional to the reciprocal of the diameter of the final product—assuming that all the mass has been reduced to one exact sine, which is only theoretically possible."² Kick's law is stated by H. Stadler as follows :3 "The energy required for producing analogous changes of configuration of geometrically similar bodies of equal technological state varies as the volumes or weights of these bodies." In other words, the energy expended is proportional to the volume reduction, instead of the diameter reduction. That these two laws would give widely different results may be shown by a simple imaginary case. A ton of 16-in. cubes is broken to 1-in. cubes at the first operation, and these are broken to 1/16. cubes at a second operation. Since the first operation produces only one-sixteenth as much new surface as the second, the ratio of energy expended in the two operations would be by Rittinger's law as 1 to 16. By Kick's law, since the volume-reduction ratio is the same in both cases, the ratio of energy would be 1 to 1. This discrepancy is great enough to challenge a test by actual experiment, of which there has been, hitherto, but little compared with the amount of argument. The present paper is the record

Jan 1, 1916

By Hsun Hu

Direct observations were made on the recrystalli-zntion of a cold-rolled (110) [001] crystal of 3 pct Si-Fe by annealing thin sections of the specimen inside the electron microscope during examination. Subgrain formation, presumably by polygonization, occurs rapidly, followed by a slow increase in the subgrain size before recrystallization can be detected. No migration of the subgrain boundaries was observed, and the formation of recrystallization nuclei by coalescence of subgrains is suggested. Re-c~ystallization characteristics of various texture components were individually examined. AS reported in a previous paper: orientations of the various deformation texture components in a 70 pct cold-rolled (110) [0011 crystal of 3 pct Si-Fe were completely confirmed by transmission electron diffraction patterns taken at various areas of the specimen. These orientations can be summarized as follows: Over most areas of the deformed crystal (111) planes are parallel to the surface. These areas correspond to either $- the two main defor: mation textures, the (111) [112] or the (111) [112].2-5 Within a few areas, (100) planes parallel to the surface are frequently found. These areas represent the minor deformation texture component, the (100) [Oll] type, which is derived from rotated Neumann bands.2'4'5 Only in very rare instances are (110) planes found parallel to the surface. This orientation corresponds to the very weak texture component of the (110) [001] type. In a pole figure, this (110) [0011 orientation is located within the orientation spread between the two main (111) [1121 type textures. Usually the electron diffraction patterns taken at various areas of the specimen are very simple ones, i.e., for any one area the pattern consists only of sharply defined spots of a single orientation. In some areas, however, more or less continuous rings of weaker intensities are superimposed on a simple pattern, indicating the presence of a wide range of additional orientations. In order to understand in detail the recrystallization of this cold-worked crystal, the recrywtallization characteristics of each of the various deformation texture components must be examined. This can best be done by using a high-temperature stage and transmission electron microscopy techniques, whereby small areas corresponding to the various texture components can be selected individually for examination. The present paper presents results obtained by this method. MATERIAL AND METHOD Specimens were prepared from a previously studied1 single crystal of a commercial grade 3 pct Si-Fe alloy with an initial orientation (110) [00l], cold-rolled 70 pct from 0.014 in. to 0.004 in. in thickness. Thin foils were prepared by electrolytic polishing as described in the earlier paper.' Specimens of this thin foil were then mounted in a high temperature stage similar to the one designed by Whelan.6 A direct current was used as the heating source. The temperature of the heating grid was calibrated by means of a Pt vs Pt-10 pct Rh thermocouple in a vacuum chamber (0.01 to 0.02µHg). Maximum variation within the temperature range of 250o to 000°C was about ± 25°C. After the desired areas were selected for examination, the specimen was heated to a low temperature for some time while the selected area was constantly watched. When no further change in structure and orientation could be observed, a higher temperature was applied. Photomicrographs and diffraction patterns were taken from time to time during examination, with the heater temporarily turned off* while the photographs were

Jan 1, 1962

By W. Francis

Before attempting to describe the application of recently acquired knowledge to the classification of coal it will be as well to consider the objects at which a scientific classification should aim. Here one can not do better than to follow the example of Clarence Seyler,l by quoting from Huxley's "Classification of Animals:" "By the classification of any series of objects is meant the actual or ideal arrangement together of those which are like and the separation of those which are unlike, the purpose of the arrangement being to facilitate the operation of the mind in clearly conceiving and retaining in the memory the characters of the object in question. Thus there are as many classifications of any series of natural or other bodies as they have properties or relations to one another or to other things. But the statement of the characters of the class ... is something more than an arbitrary definition ... it expresses firstly, a generalization based on and constantly verified by very with experience; and, secondly, a belief arising out of that generalization—in other worda. the definition of the class is a statement of a law of correlation or coexistence . . . from which the most important conclusions are deducible." In that same sense writes John Stuart Mill, in the chapter on classification in his "Logic:" "The ends of scientific classification are best answered when the objects are formed into groups concerning which a greater number of general propositions can be made, and these properties more important, than could be made respectiug any other groups into which the same things could be distributed. The properties, therefore, according to which objects arc classified should, if possible, be those which are causes of many other properties, or, at any rate, which are sure marks of them." Now in the case of coal, the properties which have been used from time to time for classification purposes are the ultimate analysis, volatile matter, caking power, calorific power, burning properties, etc. Seyler has shown that there is a general law of correlation or coexistence between the ultimate composition and the other properties. The ultimate composition, therefore, of the natural series of bodies known as coal is the

Jan 1, 1930

By W. F. Laverty

Two recent papers in this journal1,2 contain experimental evidence for an anomaly in the concentration gradient for tracer diffusion. In both papers, the authors suggest that this anomaly is due to a Gibbs' absorption effect. Their hypothesis is that surface active tracer elements tend to remain in or near the surface adsorption layer, thereby altering the diffusion flux and concentration gradient. It is not clear how the anomaly can be explained in terms of an adsorption effect. Surface tension forces act parallel rather than perpendicular to a surface and therefore should affect only the rate of spreading of surface active agents tangentially across a surface. Frenkel3 has given a short treatment of surface tension as a driving force for surface diffusion. While the equilibrium concentration of a surface active agent at the surface of a solution is known to be higher than in the bulk, its chemical potential is necessarily the same. It is difficult to see how adsorption can result in an anomaly in the chemical potential gradient, which is the driving force for diffusion. A more detailed explanation by the authors of the adsorption mechanism is in order. A similar anomaly does not seem to arise where

Jan 1, 1970

By Å. Sterten, R. Tunold, J. Brun, K. Dalatun

The subjects of this study are two corrosion phenomena familiar to operators of aluminum plants employing Soderberg anodes of the vertical type, namely the sul-fide scale formation observed at the steel contact spikes and the corrosion wear observed at the lower edge of the gas collecting skirts. The causes of these corrosion phenomena are discussed on the basis of observations from practice and measurements on commercial cells as well as on laboratory experiments. It is concluded that the anode spike corrosion is mainly due to the attack by sulfur compounds contained in the anodically evolved gases and that this attack is greatly promoted by cracks and pores in the anode carbon embedding the lower spike ends. The corrosion of the gas collecting skirt is mainly attributed to anodic dissolution of the iron during occasional contacts with the melt. ANODE SPIKE CORROSION The visible result of this corrosion is the formation of a brittle loosely adherent scale on the lower ends of the mild steel spikes maintaining the electric contact to the carbon anode, Fig. 1. The thickness of the scale usually varies from 0.5 to 3 mm, but in some cases scale of about 10 mm thickness has been observed by the writers. During the spike pulling, usually repeated every 3 weeks, part of the scale often loosens and remains in the anode carbon, resulting in contamination of the aluminum with iron. This corrosion has been attributed to reaction of the iron with gaseous sulfur compounds originating from the anode paste materials.'-4 This paste usually consists of 70 pct precalcined petroleum coke with 1.2 to 1.4 pct S and 30 pct coal tar pitch containing 0.5 to 0.7 pct S. During operation the gasification of the anode materials takes place in two ways: First, gases are evolved by the gradual baking of the anode paste added on top of the anode. Due to the sealing effected by the upper semifluid zone of the paste, these gases, containing sulfur compounds from the pitch, are forced downward through pores and cracks in the rigid anode carbon. At the temperatures of the zone of the lower ends of the spikes, 700" to 900°C, the original components of the baking gas must undergo decomposition, similar to that taking place with the production of coal gas, resulting in a gas mixture consisting mainly of H2 and CH4 with small percentages of H2S as the main sulfur compound.5 Second, the anodic reaction results in a mixture of C02 and CO, the total quantity of which is about 15 times that of the baking gas. These anode gases must carry the entire sulfur content of the carbon gasified by the anodic reaction. Henry and Holliday6 have shown that COS is the main sulfurous component of the anode gases from Soderberg cells. Soderberg anodes usually exhibit a network of vertical cracks, frequently traversing from one spike to the next one and to the outside of the block and widening downward to the working face of the anode. In addition the anode carbon, particularly that below the spike ends, is rather porous, as indicated in Fig. 1. It therefore seems probable that the anode gases also may partly penetrate to the spike ends. As the anode is partly immersed in the melt, the static pressure of this must forward this penetration. I) SPIKE SCALE COMPOSITION A great number of freshly extracted spikes from industrial plants were inspected and samples of the scale collected for examination. Before analyzing the samples a thin iron oxide layer, formed by air oxidation of the outside of the red hot scale immediately after spike pulling, was removed. On the average the Fe/S ratio found by these analyses corresponded to I the composition FeSl. oo7. X-ray powder patterns showed no oxide and otherwise agreed with those found by Haraldsen7 for iron sulfide with 50.00 at. Pct

Jan 1, 1970

By M. E. Wadsworth, R. L. Pearson

THE dissolution of UO, in carbonate solutions can occur only il the tetravalent uranium is oxidized to the hexavalent state. The carbonate system is of particular interest because it provides a means whereby the oxidized uranium may be dissolved by forming the complex ion UO,(CO3)3-1. In the presence of oxygen the over-all reaction may be written UO+1/2O,4CO3T+2HCO2UO,(CO4)11+H2O [1] UO, was used in this study because it could be obtained in high purity and also because it is representative of the most refractory of the primary uranium minerals. The mineral ulrichite is the natural counterpart of the synthetic UO, used. The kinetics of the leaching of UO, should be similar for any of the uraninite type minerals. A pressurized system was used not with the hope it could be extended to commercial systems as a primary purpose but simply to provide the means whereby important temperature and pressure parameters could be varied for the evaluation of the kinetic processes. The importance of such pres-

Jan 1, 1959

By J. E. Dutrizac, R. J. C. MacDonald, T. R. lngraham

When sintered disks of synthetic chalcopyrite (CuFeS2) were leached in acidified aqueous solutions of ferric sulfate, the following reaction stoichiometry was obtained: CuFeS2 + 2Fe2(SO4)3 = CuSO4 + 5FeSO4 + 2S Over the temperature range from 50º to 94ºC, the reaction displayed parabolic kinetics. The parabolic rate constant for the dissolution of copper is given by the equation: log.k(mg2/cm4-hr)= 11.850 - 3780/T The activation energy for the dissolution process is 17 ± 3 kcal per mole. The parabolic kinetics have been attributed to the progressive thickening of a sulfur film on the surface of the chalcopyrite. When the leaching solutions contain less than 0.01 molar Fe+3 , the Fe concentration influences the rate of leaching, probably through a mechanism involving the diffusion of ferric sulfate through the sulfur layer. At higher Fe+3 concentrations, the rate control in the leaching. reaction has been attributed to the diffusion of ferrous sulfate through the sulfur. The rate of reaction is insensitive to changes in acid concentration and in disk rotation speed. ThE reaction of acidic ferric sulfate solutions with various sulfide minerals is of practical interest for both bacterial and heap leaching. This leaching medium is generally used with low-grade ores that cannot be treated profitably by conventional means. In both bacterial leaching1-3 and heap leaching, the active agent for sulfide dissolution is ferric sulfate. Although the reactions of ferric sulfate with chalcocite, covellite, and bornite have been investigated,4*7 the kinetics of leaching chalcopyrite with ferric sulfate have not been thoroughly studied. This paper reports a study of that reaction. EXPERIMENTAL Reagent-grade sulfur was purified by the method of Bacon and FanelliB and then it was vacuum-distilled to remove any soluble magnesium salts that had been introduced during the purification procedure.9 From stoichiometric quantities of the purified sulfur and hydrogen-reduced electrolytic copper sheet (99.90 pct Cu), CuS was synthesized at 450°C in a vacuum-sealed, pyrex vessel. About 24 hr was required for the completion of the reaction. A similar procedure involving hydrogen-reduced iron wire (99.90 pct Fe) was used to synthesize FeS1.002. A 2-furnace arrangement was required. The iron was heated to 800°C while the sulfur was maintained at about 400°C. Although the reaction to consume the sulfur was rapid, the material required additional heating (1 week) in a sealed silica ampoule at 800°C before it was homogenized. X-ray powder diffraction analysis confirmed that the copper sulfide was covellite and that the iron sulfide was troilite. The composition of the iron mineral was confirmed by wet chemical analysis. The two sulfides were ground to minus 100 mesh, weighed in equimolar amounts, mixed thoroughly, and pressed into pellets at 80,000 psi. The pellets were vacuum-sealed in pyrex ampoules and then sintered for 3 days at 550°C after an initial heating at 450°C for a few hours. The pellets were then cooled, polished with 3/0 emery paper, rinsed in acetone, and stored. The material had the characteristic brassy color of chalcopyrite and was shown by X-ray diffraction to be CuFeS2. Microscopic examination of the polished surfaces revealed small inclusions of pyrite (approximately 0.5 vol pct) as the only impurity. The presence of small amounts of a second iron compound will not alter the amount of dissolved copper but might increase the amount of ferrous ion slightly. It was calculated that dissolution of all of the pyrite and 100 mg of Cu (a typical value) would change the expected ferrous concentration by only 4 pct. Microscopic examination of a pellet after leaching revealed that the pyrite was not preferentially solubilized; only those pyrite grains at the surface were attacked. Hence, the pyrite is unlikely to alter the rate of copper dissolution. The chalcopyrite disks were about 1.7 mm thick and 27 mm in diam. They were about 80 pct of theoretical density, and for this reason their true reaction area was somewhat larger than the 5.8 sq cm area presented by the polished face. The disks were cemented to lucite cylinders in such a way that only the polished face was exposed. The disks were then leached by methods previously described.6,7 RESULTS AND DISCUSSION Stoichiometry and Kinetics. The initial experiments were directed to the problem of resolving the stoichiometry of the leaching reaction. Disks of CuFeS2 were leached at 80°C for various periods of time in acidified ferric sulfate solutions that were protected from oxidation by a cover of flowing nitrogen. When the disks had been partly leached, they were removed, their soluble salts were washed out, and then they were treated with CS2 in a Soxhlet extraction apparatus. The ratio of elemental sulfur to dissolved copper thus obtained was approximately 2 to 1. After the extraction of elemental sulfur from the pellet, the residue consisted of unreacted chalcopyrite only. For runs in which an appreciable amount of copper was dissolved, the ratio of ferrous ion to cupric ion in the solution was

Jan 1, 1970

By Frank H. Macpherson

When it became apparent early in 1941 that the United States might be drawn into the war, studies were made of the bauxite situation in Arkansas, principally because 9.5 pct of the known bauxite reserves of the country were located in that State. Bauxite mining was then geared for maximum production to supply ore to meet this country's war requirements and, if necessary, to supply the needs of Canada as well. In view of the comparatively small bauxite reserves, Congress appropriated funds for an extensive exploratory drilling program to be carried out by the Bureau of Mines in cooperation with the Geological Survey. An alumina plant was erected near Bauxite and an aluminum plant near Hot Springs, Ark., by the Defence Plant Corp. The Metals Reserve Co. established a schedule of prices, arranged for stockpile sites and a buying agency. Operators cooperated to step up production and new ones came into the field. Production Record Prior to 1941, the greatest annual production in Arkansas was 562,892 long tons, dry basis in 1918. During the single month of August 1943, 693,596 long tons were mined—130,704 tons more than for the entire year of 1918. In general the Arkansas bauxite deposits are relatively small, irregular in thickness, somewhat scattered and, compared to coal, iron or open-pit copper deposits, are ill-adapted to an expansion in output. Commercial deposits range in horizontal extent from less than an acre to about 40 acres and are usually very irregular in outline. The average thickness of all known workable deposits is between 12 and 15 ft. with a maximum of about 60 ft. The ore bodies are usually somewhat undulating and nearly horizontal although locally some deposits dip as much as IS°. Types of Bauxite Three physical types of bauxite may be recognized: pisolitic, granitic and amorphous. Pisolitic ore is the most common type. It consists of small pebble-like nodules, ranging from the size of a pin head up to several inches in diameter, all set in a fine grained matrix. Transported bauxite is usually- pisolitic. Most residual bauxite is granitic. It is believed not to have moved appreciably from the location where it originally was formed. This is indicated by the fact that it appears to grade into unaltered nephelite syenite, which it overlies. Amorphous ore is the least abundant. It is nonpisolitic and resembles clay, has no characteristic texture, and can be identified definitely only by chemical analysis. Uses of Bauxite Bauxite is chiefly used for, and at the present time is substantially the only

Jan 1, 1948

By Frank H. Macpherson

When it became apparent early in 1941 that the United States might be drawn into the war, studies were made of the bauxite situation in Arkansas, principally because 9.5 pct of the known bauxite reserves of the country were located in that State. Bauxite mining was then geared for maximum production to supply ore to meet this country's war requirements and, if necessary, to supply the needs of Canada as well. In view of the comparatively small bauxite reserves, Congress appropriated funds for an extensive exploratory drilling program to be carried out by the Bureau of Mines in cooperation with the Geological Survey. An alumina plant was erected near Bauxite and an aluminum plant near Hot Springs, Ark., by the Defence Plant Corp. The Metals Reserve Co. established a schedule of prices, arranged for stockpile sites and a buying agency. Operators cooperated to step up production and new ones came into the field. Production Record Prior to 1941, the greatest annual production in Arkansas was 562,892 long tons, dry basis in 1918. During the single month of August 1943, 693,596 long tons were mined—130,704 tons more than for the entire year of 1918. In general the Arkansas bauxite deposits are relatively small, irregular in thickness, somewhat scattered and, compared to coal, iron or open-pit copper deposits, are ill-adapted to an expansion in output. Commercial deposits range in horizontal extent from less than an acre to about 40 acres and are usually very irregular in outline. The average thickness of all known workable deposits is between 12 and 15 ft. with a maximum of about 60 ft. The ore bodies are usually somewhat undulating and nearly horizontal although locally some deposits dip as much as IS°. Types of Bauxite Three physical types of bauxite may be recognized: pisolitic, granitic and amorphous. Pisolitic ore is the most common type. It consists of small pebble-like nodules, ranging from the size of a pin head up to several inches in diameter, all set in a fine grained matrix. Transported bauxite is usually- pisolitic. Most residual bauxite is granitic. It is believed not to have moved appreciably from the location where it originally was formed. This is indicated by the fact that it appears to grade into unaltered nephelite syenite, which it overlies. Amorphous ore is the least abundant. It is nonpisolitic and resembles clay, has no characteristic texture, and can be identified definitely only by chemical analysis. Uses of Bauxite Bauxite is chiefly used for, and at the present time is substantially the only

Jan 1, 1948

By J. L. Taylor, P. Duwez

PARTIAL phase diagrams of titanium with iron, cobalt, and nickel have been established by previous investigators.1-3 These diagrams seem to be reliable, at least for concentrations of titanium ranging from 0 to about 50 at. pct. More recently, Long and his collaborators have presented a tentative titanium-nickel diagram covering the titanium-rich side.' These various studies indicate that in each system three intermediate phases exist and correspond to the compositions Tia, TiX, and TiX2 (or TiX3). The purpose of this paper is to review the available information on the crystal structure of these phases and to give the results of additional X-ray diffraction studies. Previous Work A summary of the work of Wallbaum and his collaborators"-' is presented in table I. The first intermediate phase on the titanium-rich side of the three systems, with iron, cobalt, and nickel, is of the Ti2X type and has a face-centered cubic structure. Although it is stated that the unit cell contains 96 atoms: no lattice parameters are given. The second phase is centered around the compositions TiX for the three systems. The crystal structure of this phase is mentioned in a short note" as being body-centered cubic (CsCl type), but no parameters are given. The analogy between the three systems, which is perfect as far as the two phases of the type Ti2X and TiX are concerned, disappears at the titanium-poor end of the diagrams. In the system titanium- iron, TiFe2 has an hexagonal (MgZn2 type) struc-ture with the parameters given in table I. The existence of TiFe3 has also been reported8 (table I) but was questioned by other investigators2 and is also refuted by the present study. In the system titanium-cobalt, a phase corre-sponding to the composition TiCo2 has been investi-gated by Wallbaum and Witte6 who claim that the structure is cubic (MgCu2 type) for alloys slightly deficient in cobalt and hexagonal (MgNi2 type) for alloys slightly deficient in titanium. The parameters of the two phases are given in table I. In the system titanium-nickel, the nickel-rich phase corresponds to the composition TiNi3 and has been described as hexagonal7 with the parameters given in table I. The present investigation was initiated for the purpose of filling in the gaps in the knowledge con-cerning the structure of the various phases sum-marized in table I. Since the titanium used by Wallbaum and his collaborators was only 95 pct pure,' it was found desirable to redetermine the lattice parameters of the alloys prepared with a

Jan 1, 1951

By William Braden

IT is obvious that the choice of the method to be employed in the handling of blast-furnace slags and mattes depends upon local facilities and conditions which may indicate as advisable some particular plan. As a result of the variety of such conditions hardly any two smelters use identically the same method, though they be located only a few hundred feet apart. For instance, of the several plants in Leadville, Colorado, each has a more or less distinctive system. The same is true of Salt Lake City and vicinity. In view of this it is evident that the existing diversity of practice cannot be accepted, prima facia, as evidence

Jan 1, 1897

By M. T. Simnad, G. Derge, Ling Yang

A method is described for using radioactive tracer for the direct determination of ionic mobility in a molten electrolyte. The ionic mobility of Fe" in silica-saturated iron silicate is found to be 0.0009 (*0.0002) cm2 sec ' volt L at 1250°C. eLECTROCHEMICAL studies', ' of molten iron eE oxide and iron silicates have shown some ionic conductivity at all compositions. The current efficiency in electrolysis increases with the concentration of silica to a maximum of 90 pct at about 34 pet SiO,. In the silica-saturated melts the transport number of ferrous ions is near unity, indicating that

Jan 1, 1957

By J. K. Abraham

In recent years there has been interest displayed in the precipitation phenomena occurring in austenitic alloys based on the binary Fe-Ni system.1'2 Previous communications have been extended covering the kinetics of clustering in the Fe-Ni-Ti system and the effect of cluster size on subsequent mechanical properties.3'4 To a great extent the question of coherency, which has a dominant role in determining the mechanical properties, is dictated by the degree of misfit between the precipitate and matrix. Thus, the change in lattice parameter of the matrix with composition is an important variable that should be examined. The lattice parameter, ao, of austenite was determined for Fe-29.75 Ni-1 to 6 Ti and Fe-27 Ni-1 to 10 Ti alloys in this study. The alloys used in this investigation were melted in a vacuum induction furnace from a starting stock of plast iron (99.95), electrolytic nickel (99.9), and ti- tanium sheet (99.5) in a MgO crucible. The alloy compositions in atomic percent are given in Table I and their relative position in the Fe-Ni-Ti ternary is indicated in Fig. 1. The chemical analyses were taken from the homogenized bulk materials treated in a manner related earlier.3 A diamond file was used to obtain powder from the bulk. To remove the stresses induced by filing, the powders were austenitized at 1875°F for

Jan 1, 1969

By P. E. Chapman, J. E. Worthington, I. T. Kiff

Increases in the price of gold starting about six years ago, and rapid fluctuations since then, have created a substantial popular interest in the noble metal. Gold prospecting had been at a low ebb since the end of World War II in most of the United States, except for a flurry of activity in Nevada after the Carlin and Cortez discoveries. The last few years, however, have seen a great awakening of interest in gold exploration as well as an opportunity for education for many explorationists in the geology and other vagaries of gold deposits. The writers have participated over the last few years in a search for gold deposits throughout the United States. This search was greatly influenced by the geologic studies of Dr. William Spence at the Haile gold mine in South Carolina, as reported in a companion paper. Spence's studies resulted in definition of a geologic model that has proven useful in a number of other geologic environments in the United States. These programs were all carried out under the auspices of Cyprus Mines Corp. and permission by Cyprus to present these results is gratefully acknowledged. The writers, however, reserve for themselves all responsibility for the results and conclusions. The exploration program to be described began in the southeastern United States. Spence's studies provided a reasonable basis for interpreting and understanding the geology of the Haile deposit, and also provided a means for predicting additional occurrences. This concept was then expanded to other gold occurrences in the Piedmont, and became an effective tool for evaluating other prospects. Finally, it became evident that the concept could be applied in some western gold districts. The following discussion will then include descriptions of other Piedmont examples and a few western districts that also appear to fit the pattern.

Jan 1, 1981

By J. H. Swisher

The solubility of graphite in CaO-S2O2-Al,O3 slags was measured by equilibrating slag samples with graphite crucibles and CO gas. Carbon contents as high as 2 ut pct were obtained in CaO-saturated, CaO-A1,O3 slags, and 1.3 wt pct in slags of the composition CaO.Si0,. Although the observed conditions for Sic formation were in agreement with those predicted from thermodynamic data, CaC, was found to form at a lower temperature than predicted frotn thermodynamic data. From measurements of the equilibrium carbon content as a function of CO Partial pressure, it was found that carbide ions dissolve in CaO-A12O3 melts with a valence of minus two. The carbon content increased with CaO concentration in Ca0-Al,O3 melts and increased with SiO, content along the CaO'AlO3-CaOSi0 join in the ternary system. When solid CaC2 was added to CaO-A12O3 and CaO-SiO2-A12O3 slags, it was found that one of the oxides in the slag was reduced by the carbide (Al2O3 in the forrner and SiOz in the latter). In electric furnace steelmaking, a double-slag practice is frequently used to meet alloy specifications. Initially a flush slag, which is oxidizing in nature, is used to remove phosphorus and carbon from the steel bath. Later in the refining period, the flush slag is replaced by a highly reducing carbidic slag. When calcium carbide is formed in or added to a finishing slag, the slag is effective as a desulfurizing agent and also permits alloying elements such as chromium, vanadium, and tungsten to be added to the slag in the form of oxides. The oxides are readily reduced by calcium carbide, thereby minimizing the use of expensive ferroalloys. More work has been done on the thermodynamics of silicon carbide in slags than on calcium carbide. Baird and alor' and Kay and alor' determined the free energy of formation of Sic by measuring the partial pressure of CO in equilibrium with solid silica, silicon carbide, and graphite. Using a similar technique, they determined SiOz activities in CaO-SiOz and Ca0-Si0,-A1203 slags. Rein and chipman3 also determined the free energy of formation of Sic using slag-metal equilibrium measurements. A literature survey has uncovered only one experimental study of the behavior of CaC, in slag systems. Shanahan and cooke4 report the results of some preliminary experiments on the solubility and stability of CaC, in a CaO-A1,03 and a Ca0-Si0-A1,03 slag at a temperature of about 1500". The carbon solubility as CaC, in a slag containing 50 pct CaO and 50 pct A1203 was reported to be 0.6 pct. They also review earlier work on the binary CaO-CaC, system. A eutectic exists in this system, but various investigators disagree on the eutectic temperature and composition. eal has given an explanation for carbide furnace erruptions in terms of the thermodynamic properties of CaC,; his analysis is not based on experimental data, but on compiled data for the free energies of formation of CaC, and CO.' , These data for steel-making temperatures are all extrapolated from the results of low-temperature measurements. In the experiments described in this paper, slag samples were equilibrated with graphite crucibles and with mixtures of CO and argon or with CO gas at 1 atm total pressure for measurement of the carbon solubility. Most of the work was done on Ca0-A1203 binary slags, although in some experiments CaO-SiO, and Ca0-Si0,-A1,03 slags were used. EXPERIMENTAL Slag samples of the desired composition for the solubility measurements were obtained by blending pre-fused master slags. The master slags were prepared by fusing mixtures of reagent-grade CaC03 with either A1,03 or Si0, in a graphite crucible. The master slags were crushed, then decarburized in air in a muffle furnace at 1200O C. A schematic diagram of the apparatus is shown in Fig. 1. The source of carbon for the solubility meas-

Jan 1, 1969

By T. P. Papazoglou, N. A. D. Parlee, W. C. Phelps

HE high vapor pressures of metals such as lead, calcium, lithium, bismuth, and magnesium at steel-making temperatures present experimental problems which have thus far rendered it almost impossible to obtain really reliable data for their solubilities in liquid iron. Many investigators have attempted to equilibrate liquid iron in the same crucible with the undissolved liquid phase of such volatile metals. The published results,l-6 although useful, are often questionable on the grounds of not being obtained under true equilibrium conditions. Such information is not always of practical value in any case since the equilibrium vapor pressure is often several atmospheres and steel is not currently made at these pressures. Solubility measurements at lower partial pressures (< 1 atm) appeared to be more practical and easier to make. These data could be used to calculate solubilities at other pressures where Henry&apos;s Law is obeyed, and to estimate solubilities under other conditions of temperature and pressure with useful accuracy. This note outlines the development of a general technique for the measurement of solubilities in systems of this kind. The method involves equilibration of the high-boiling metal at known temperatures with the vapors of a low-boiling metal at known partial pressures. Analyses of quenched samples provide vapor pressure-solubility data and make calculations of alloy thermodynamics possible. The principle involved is similar to the closed-system diffusion-transport method which is difficult to apply with most high-melting liquid metals like iron, due to closure problems. A two-zone horizontal (molybdenum wire element) tube furnace, Fig. 1, provides two constant-temperature zones in a reaction tuve (3/4 in. ID by 1 in. OD by 36 in.). A high-boiling metal sample, 9, introduced in the higher-temperature zone, is maintained at temperature T1, and a volatile metal sample, 7, in the lower-temperature zone, is held at T2. A stream of argon with 10 pct hydrogen is passed via flowmeters, 1, and mixing-drying towers, 2 and 3. through the reaction tube at a favorable flowrate and acts as a carrier gas which entrains vapor from the volatile liquid metal at a specific constant partial pressure. The gas mixture passes through a system of constrictions, 6 and 8, to the higher-temperature zone, establishes intimate contact with the high-boiling liquid sample, 9, and exits through a small condenser tube. The entire system is at (nearly) atmospheric pressure and the volume of carrier gas passed is measured with a wet gas meter. When the high-boiling sample attains equilibrium with the vapor phase, both samples are removed and quenched. Analysis of the high-boiling sample for solute content reveals its solubility for the low-boiling metal at a vapor pressure calculated from carrier-gas volume and either a) weight loss of volatile metal or 6) weight gain of high-boiling sample plus condenser (which collects the undissolved vapors). To test the capabilities of the method, liquid silver at 1403&apos;C was equilibrated with lead vapor at various partial pressures. The relatively simple Pb-Ag system was particularly suitable for uncovering experimental problems and providing the first step toward investigations with more volatile metals and more difficult combinations.

Jan 1, 1965

By Sage B. H., Lacey W. N., G. W. Billman

The composition of the coexisting phases in the methane-ethane-n-pentane system was determined at 100°F. This was accomplished by withdrawing samples of the coexisting phases under isobaric-isothermal conditions. The relative amount of each of the components present in the liquid and gas phases was determined by conventional analytical fractionation methods. The phase behavior of this system approximates that estimated from generalized correlations which take into account the influence of the nature and amount of each of the components present upon the equilibrium. It was found that for particular pressures and temperatures the equilibrium constant of each of the components was influenced significantly by the composition of the system and this effect was more pronounced at the lower pressures for methane than for the components of greater molecular weight. However, at the higher pressures approaching the maximum two-phase pressure for the system at this temperature the composition markedly influences the equilibrium constants of all the components at a particular pressure and temperature. The results of this study are presented in graphical and tabular form. Introduction The phase behavior of many of the binary systems containing parafin hydrocarbon components from methane through n-pentane has been investigated during recent years. In addition the compositions of the coexisting phases in mixtures of crude oil and natural gas have been studied.&apos; However, these results do not establish the influence of the nature and amount of the other substances making up a multi-component system upon the gas-liquid equilibrium constant of any one component. A preliminary correlation on the basis of values for binary systems was made2 utilizing such experimental information as was available. However, there is need for much additional information regarding behavior in systems containing more than two components. Study of the phase behavior of ternary systems offers a feasible attack upon the determination of the influence of composition as well as of pressure and temperature upon the several equilibrium constants concerned. An investigation of the phase behavior of the methane-propane-n-pentane system at 100°, 160°, and 220°F was reported.".&apos; This work served to illustrate the marked influence of concentration of the other components upon the equilibrium constants. Variations of as much as 50 pct in the equilibrium constants for methane for fixed temperature and pressure were observed in regions remote from the critical state. Likewise there was a marked variation in the equilibrium constants of propane and n-pentane as a result of changes in the composition. These results indicated the desirability of investigating additional ternary systems. The present paper deals with a study of the methane-ethane-n- pen-tane system at 100°F, which is similar in many respects to the work upon the meth-ane-propane-n-pentane system cited above.

Jan 1, 1948

By Sage B. H., G. W. Billman, Lacey W. N.

The composition of the coexisting phases in the methane-ethane-n-pentane system was determined at 100°F. This was accomplished by withdrawing samples of the coexisting phases under isobaric-isothermal conditions. The relative amount of each of the components present in the liquid and gas phases was determined by conventional analytical fractionation methods. The phase behavior of this system approximates that estimated from generalized correlations which take into account the influence of the nature and amount of each of the components present upon the equilibrium. It was found that for particular pressures and temperatures the equilibrium constant of each of the components was influenced significantly by the composition of the system and this effect was more pronounced at the lower pressures for methane than for the components of greater molecular weight. However, at the higher pressures approaching the maximum two-phase pressure for the system at this temperature the composition markedly influences the equilibrium constants of all the components at a particular pressure and temperature. The results of this study are presented in graphical and tabular form. Introduction The phase behavior of many of the binary systems containing parafin hydrocarbon components from methane through n-pentane has been investigated during recent years. In addition the compositions of the coexisting phases in mixtures of crude oil and natural gas have been studied.&apos; However, these results do not establish the influence of the nature and amount of the other substances making up a multi-component system upon the gas-liquid equilibrium constant of any one component. A preliminary correlation on the basis of values for binary systems was made2 utilizing such experimental information as was available. However, there is need for much additional information regarding behavior in systems containing more than two components. Study of the phase behavior of ternary systems offers a feasible attack upon the determination of the influence of composition as well as of pressure and temperature upon the several equilibrium constants concerned. An investigation of the phase behavior of the methane-propane-n-pentane system at 100°, 160°, and 220°F was reported.".&apos; This work served to illustrate the marked influence of concentration of the other components upon the equilibrium constants. Variations of as much as 50 pct in the equilibrium constants for methane for fixed temperature and pressure were observed in regions remote from the critical state. Likewise there was a marked variation in the equilibrium constants of propane and n-pentane as a result of changes in the composition. These results indicated the desirability of investigating additional ternary systems. The present paper deals with a study of the methane-ethane-n- pen-tane system at 100°F, which is similar in many respects to the work upon the meth-ane-propane-n-pentane system cited above.

Jan 1, 1948

By O. D. Gaither

This paper is an analytical study of the flow of fluids through small vertical conduits. Small conduits are defined as 11/4-in. nominal diameter tubing size and smaller, and approximately twice this area for annular conduits (i.e., 1- X 21/2-in. annulus and smaller). Experimental data are presented for the 1-X2-in. and 11/4- X 2%-in. annuli, and the I-in. and 11/4-in. tubing, since these represent the small conduit sizes and configurations generally encountered in oilfield applications. Data have been gathered for these conduits for single-phase water, single-phase gas and two-phase water-gas mixtures, with particular emphasis on high gas-liquid ratios. Water rates in excess of 2,000 BID and gas rates in excess of 2.5 MMcf/D, and two-phase flow ratios in between these two, represent the scope of the data gathered. Existing equations have been applied to predict flowing pressures and compared with experimental data. New correlations have been developed. INTRODUCTION The increased economic pressure on the domestic oil industry in the United States has constantly required the use of new techniques and equipment designed to reduce the cost of finding and producing oil and gas. Since tangible items are most readily apparent in economic analysis, the advent of lower-cost well completions was inevitable. One of the methods used to reduce costs which has received widespread attention is the slim-hole completion technique where tubing is used as the well casing and in which small conduits are used for tubing if necessary. Small conduits, defined by Kirkpatrick1 as "11/4-in. diameter nominal tubing and smaller for tubing flow and less than twice the 11/4-in. diameter nominal tubing internal flow area for annulus flow", have also found widespread usage as siphon strings for de-watering gas wells and as "kill" strings in deep high-pressure oil and gas wells. The growing use of small-diameter tubing has resulted in an increased need for development of improved methods to measure or predict flowing bottom-hole pressures since the physical dimensions generally preclude the use of subsurface-recording pressure gauges. Even in the cases where small bombs are available, the relatively high velocities encountered at nominal flow rates make it necessary to use excessive weight bars or special hold-down devices. Attempts to use recognized correlations to accurately predict flowing or gas-lift performance in wells equipped with small conduits have been generally unsuccessful. Insufficient field data were available to allow the development of a correlation on this basis, and an experimental approach was applied in an attempt to obtain a workable relation. The experimental approach used to obtain the data presented in this paper was actually a compromise between a field installation and a laboratory study. A test well 1,000 ft in length was used to obtain flow data on single-phase liquid, single-phase gas and two-phase water-gas flowing mixtures. Liquid rates up to 2,200 B/D and gas rates up to 3 MMcf/D were used in the single-phase flow studies. Two-phase flow rates from 100 to 600 B/D with gas-liquid ratios from 500 to 8,000 cu ft/bbl were recorded. Experimental data were obtained for single- and two-phase flow through 1-in and 11/4-in. nominal tubing, and through the annuli between 1- and 2-in. and 11/4- and 2%-in. nominal tubing strings. Experimental results for the two-phase flow are compared to the Poettmann-Carpenter correlation2 which is widely used as a comparative standard for development of multiphase flow predictions in flowing and gas-lift wells. Correlations developed by Tek,3 Baxendell and Thomas" were also investigated. The experimental data recorded herein fell in between the two flow regimes as defined by Ros," and this correlation also failed to yield satisfactory results. The fact that existing correlations failed to confirm the experimental data led to the need for development of a new correlation. Although a two-phase flow study was the primary objective of this investigation, data were also recorded for single-phase flow of water and gas, and constants were developed relating to pipe roughness and equivalent diameters for annular flow. These single-phase studies assisted materially in the development of certain of the two-phase flow results. Considerable previous work has been published which presented relationship of surface measurements to bottom-hole condition. The works of Buthod and Whiteley,6 Jones,&apos; Poettmannb and the Texas Railroad Commission" are classic examples of the successful use of mathematical relationships which allow acceptable predictions of subsurface pressures, when gas is the flowing fluid. Darcy and others have derived relationships which may be used with minor modifications to predict subsurface flowing conditions in injection and water-supply wells. As previously stated, the application of the single-phase flow relationships

By E. T. Turkdogan, L. J. Martonik, R. J. Fruehan

Electrochemical measuretnents of the solid oxide electrolyte galvanic cells CY-Cr2O3 I ZrO2 (CaO) 1 O (in Fe alloy) CY-Cr2O3 I Tho2 (Y2O3)I O en Fe alloy) have been made at 1600°C (2912°F) in order to test the Performance of such cells at liquid steel temperatures. The oxygen pvobe (cell) consists of a disk of ZrO2 (CaO) or Tho2 (Y2O3) electrolyte fused at one end of a silica tube filled with a mixture of Cr-Cr2O3 which is the reference electrode. Upon immersion in liquid steel, the electromotive force readings achieve a steady value within a few seconds, and remain steady for 30 win or more. The perforwzance of the probes has been tested using Fe-O, Fe-Si-O, Fe-Cr-O, Fe-V-O, and Fe-Al-O alloys; the oxygen contents of liquid steel derived from the measured electromotive forces are in satisfactory agreement with those determined by arulysis. Use of the probe in the deoxi-datiorz of steel, in laboratory experiments, is discussed. The results indicate that there is insignificant electronic conductivity in ZrO2(CuO) at oxygen activities down to those corresponding to 10 ppm in steel. At lower oxygen activities, probes tipped with ThOn (Y2O3) disks perform satisfactorily at oxygen activities down to 1 ppm O or less. THE key to the control of deoxidation of steel is a sensing device to measure rapidly the concentration of oxygen in liquid steel in the furnace, ladle or tun-dish at any desired stage of deoxidation. The analysis of the cast steel by the neutron-activation or vacuum-fusion method gives total oxygen as oxide and silicate inclusions. This analysis is important for guidance to steel cleanliness; however, such a postmortem is of little value in the control of deoxidation of liquid steel. At the General Meeting of the American Iron and Steel Institute in New York, 1968, Turkdogan and Fruehan&apos; presented a paper on the preliminary results of the work done in this laboratory on rapid determination of oxygen in steel by an oxygen probe. Details of the work done in this laboratory leading to the development of a galvanic cell for the determination of oxygen in liquid steel, and the results of the tests made are given in this paper. It was through Wagner&apos;s contributions, since the early Thirties, to the physical chemistry of semiconductors in general that it ultimately became possible to construct galvanic cells for application at high temperatures. In 1957, Kiukkola and wagner2 successfully demonstrated the use of several solid electrolytes in measuring the free energies of several chemical reactions, in particular, the use of lime-stabilized zir-conia in high-temperature oxidation reactions. Starting 7 years later, a number of papers appeared in the technical literature3-&apos; demonstrating possible applicability of galvanic cells for the determination of oxygen in liquid steel. In the earliest work, Japanese investigators3j4 experimented with various types of reference electrodes, e.g., graphite-saturated liquid iron at 1 atm CO or Ni-NiO mixtures; the results obtained, though promising, were not of sufficient accuracy. Except for the work of Baker and West,6 all other investigators5,7,8 showed that ZrO2(CaO) electrolyte could be used for this purpose. The main part of the galvanic cell used by Fischer and ~ckermann&apos; and by schwerdtfeger7 (the latter work was done in this laboratory), consisted of a ZrO2(CaO) tube, -1 cm ID, closed at one end, with a platinum contact wire fixed mechanically inside the closed end. The tube was flushed with a gas of known oxygen partial pressure, e.g., air, CO-CO2 or H2-CO2 mixtures; gas along with the platinum lead wire served as the reference electrode. The oxygen contents derived from measured electromotive forces agreed reasonably well with the oxygen contents determined by vacuum-fusion analysis. It is evident from recent investigations that the electromotive force technique using a solid oxide electrolyte is fundamentally well suited for the determination of oxygen in liquid steel. However, it is equally clear that the cell arrangement of the type as commonly used is in need of considerable improvement, as it exhibits several shortcomings for industrial and even laboratory use. 1) Because of its size, the zirconia tube, though stabilized, has a poor resistance to thermal shock. 2) Fine pores and microcracks, which are invariably present in zirconia tubes, are detrimental to the satisfactory operation of the cell, particularly when gas reference electrodes are used. 3) Air or carbon dioxide reference electrodes give rise to high electromotive force readings; as a result, the determination of oxygen in steel becomes less accurate. For higher accuracy, the oxygen partial pressure of the reference electrode should be in the range similar to that of oxygen in steel. 4) Even in laboratory experiments, difficulties are experienced when flushing the tube with gases and maintaining the proper gas flow rate. Fischer and Ackermann,&apos; who used air as the reference electrode, reported that when the flow rate was too low, furnace gases would leak into the electrolyte tube, therefore lowering the oxygen potential and measured electromotive force. The required flow rate in order to avoid leakage depended on the tightness of the electrolyte tube which varied with different tubes, thus making it difficult to predict in advance the required flow rate. However, if the flow rate is too high the inside wall of the electrolyte tube would be cooler than the wall

Jan 1, 1970