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By T. J. Bosworth

The effect of hydrogen pretreatment of alumina, magnesia, and zirconia crucibles on reduced oxygen levels in iron charges has been studied. Hydrogen treatment of commercial high-purity magnesia crucibles was observed to produce as high as 70 pct reduction in oxygen content in iron melts. Hydrogen treatment of the commercial high-purity grade zirconia crucibles produced a 25 pct reduction in oxygen levels in iron melts. An average reduction of Knoop hardness of 47 pct was recorded on the iron charges melted in hydrogen-treated crucibles. On the basis of the experiments and the free-energy diagram, it appears that the major source of reducible oxygen to the iron charge is the suboxides and impurity oxides rather than the major oxide of the crucible. Suitable pretreatment of the crucibles to reduce and remove these oxides yields low oxygen levels in iron melted in the crucibles. DURING the last decade, attempts to produce more pure and uniform alloyed metals have brought about the development of many new melting techniques. Notable among these are vacuum-induction melting, inert and consumable-electrode melting, the cold-mold technique, and numerous techniques for removal of impurities by chemical reaction. However great the achievements in this field, metals must still be melted in contact with media of varying reactivity; i.e., gas, ceramic, and slag. Studies have been made to attain an understanding of the reactions that take place during melting, including slag-metal reactions and equilibria, equilibrium of hydrogen and water vapor, and carbon dioxide and carbon monoxide with oxygen in molten iron. These reactions have been treated quite thoroughly. There is one condition, however, that has been widely overlooked, and, to the author's knowledge, only cursive investigation has been made of it. This is the reaction between the ceramic crucible material and the iron charge. In recent years, Hadley and Bianchi' made a series of studies on hydrogen deoxidation of iron in magnesia crucibles. Bianchi2 studied crucible-FeO equilibria in the temperature range 1525°to 1650°C in high vacuum with, however, inconsistent results. Richardson and Jeffes3 in their series of articles on thermodynamic reactions in the making of iron and steel refer to Wentrup and Hieber's4 work on iron and aluminum deoxidation. Their pork included melting iron in alumina crucibles and measuring the aluminum and oxygen content in the iron. Because of the low values obtained, question has arisen of their analytical accuracy.3 Dastur and chipman5 obtained values on hydrogen-oxygen equilibrium in molten iron contained in alumina crucibles similar to those obtained in experiments in the present program. Hochmann6 studied removal of impurities in chromium irons in high vacuum. His results with respect to oxygen level in chromium-iron melted in magnesia crucibles are consistent with results we have obtained.

Jan 1, 1959

By C. D. Hunter, J. B. Browning

During the year 1934, Kentucky oil and gas operators have partly overcome their past depression fears and in the oil industry, with possibly more abandonments of old oil producers than the completion of new oil wells, produced 4,814,904 bbl. of oil in 1934 against 4,501,511 bbl. in 1933. In the gas industry of eastern Kentucky, 115 gas wells were completed during 1934. This production is delivered through two 20-in., one 16-in., one 12-in., one 10-in., and two 8-in. pipe lines to supply both domestic and industrial markets in Cincinnati, Ohio; Louisville, Lexington, Frankfort, Winchester, Ashland, Covington and other Kentucky towns; Washington, D.C., and other eastern cities. The largest percentage of these gas wells and production are from the Devonian black shale area of Floyd, Pike, Knott, Martin and Magoffin counties, Kentucky. In this area the largest percentage of 1889 wells, developing 421,-215 acres, has been completed in the past 10 years, of which 55.3 per cent produce from the 400 to 550 ft. of Carbonaceous Devonian black shales. The successful results obtained from these Devonian shales are due to the physical effects of the 5000 to 6000 lb. of gelatinated nitroglycerin with which the entire 400 to 550 ft. of shale is shot. A very small number of the shale wells are natural producers and do not require shooting. Other than the Devonian shale gas production, the remaining 44.5 per cent of the gas in this field is encountered throughout the entire strati-graphic section above this horizon; namely, salt sands of Pennsylvanian age and Maxon, Big Lime and Weir of Mississippian Age. A very small percentage is encountered in the Corniferous Devonian lime and the Silurian Big 6 below the black shales. In western Kentucky, in the counties of Henderson, Webster, Hopkins, McLean, Christian, Muhlenburg, Ohio, Daviess, Hancock, Brecken-ridge, Hart, Barren and Warren, many gas wells have been completed, but, because of insufficient market, activity has been somewhat desultory. The area is served by the pipe lilies of the Kentucky Natural Gas Corporation, with headquarters at Owensboro. Their market is increasing and the gas is delivered to Owensboro, Henderson, Madisonville, and many

Jan 1, 1935

By C. S. Matthews, H. C. Lefkovits

The performance of depletion-type reservoirs at the stage in which the gas is at such low pressure that gravity is essentially the sole driving force has been investigated both theoretically and by use of scaled models. A simple theory is developed which completely explains the scaled model experiments. It also agrees with some field data. When the range of production rates to be considered is less than 25, the theory predicts that the production rate decline curve for homogeneous reservoirs in which there is a free surface will be of the hyperbolic type with n = 2: The theory gives a physical significance to the parameter y. INTRODUCTION This investigation was undertaken to determine a method for prediction of performance of reservoirs where gravity is the sole driving agent. Depletion-type reservoirs fall into this category after the pressure has fallen to some low value. Some examples of this type are found at Healdton ('Oklahoma), Oklahoma City (Oklahoma), Midway-Sunset (California), and East Coalinga (California). Generally the production rate per unit thickness is quite low in such reservoirs, with the conse- quence that this stage is sometimes called the stripper stage. However, per well production rates may be of the order of 50 B/D because of the considerable sand thickness open in some of the reservoirs. In the past, predictions of behavior of such reservoirs have been based on empirical extrapolation of the rate of production to the economic limit. Difficulties arise when new wells are drilled in the field or when production is artificially curtailed, since in such cases the decline rate of individual wells or leases changes and no clear trend can be detected. It was hoped that the present study would lead to improved methods for evaluation of such reservoirs. The study was initiated by building a scaled model for a particular field and by running a number of experiments on this model. Later a simple theory was developed which explained the laboratory results completely. The theory led, as shown below, to a hyperbolic-type decline equation which had been used previously' in a completely empirical manner. THEORY The General Case The problem to be treated here is the following: We are given a homogeneous cylindrical porous reservoir with exterior radius r, wellbore radius r., and height h,, containing, from the bottom up to a height hit oil, some gas, and interstitial water (see Fig. 1 A). The portion of the reservoir between K, and h, is filled with gas at low pressure, with residual oil, and with interstitial water. If at a time t = 0, the level of the oil in the wellbore is lowered to a height h,, what is the production rate from the reservoir at a time to The configuration within the reservoir at some instant

Jan 1, 1957

By Helmut Thielsch

MeTallographic specimens whose surfaces are to be investigated are too thick to allow either light or electrons to pass through them for microexamination by transmission. This difficulty is overcome with optical microscopes by illuminating the surface through the objective lens. For electron microscopes best results are obtained by preparing thin replicas of the surface of the specimen, placing them in the microscope and passing the electron beam through them. Since electron microscopes represent a rather recent invention, they have found little application as compared with optical microscopes. This is true because, aside from the cost of new equipment and development of new techniques, some of the older replica methods necessitated the destruction of the surface from which a thin transparent replica was obtained. In other processes in which the surface is preserved, either too tedious a procedure is required, unsuited to "mass-production" requirements of industrial laboratories, or replicas of insufficient contrast and sharpness are produced. In general, investigations with the electron microscope involve five steps: (I) polishing the surface of the metal specimen, (2) proper etching of the surface, (3) preparing the suitable replica from the surface, (4) examination and phorography in electron microscope and (5) interpretation. Preparation of Metal Surfaces Usual metallographic polishing is generclly satisfactory. It is important though that the final polish be applied very carefully, since otherwise evidence of a small amount of deformation might show up even on relatively deeply etched surfaces. A high-power microscope should be used to determine the suitability of the polish and etch. This, of course, is not different from optical examinations, but in these, if a deep etch is used, the problem is less serious. It is frequently difficult to detect with optical microscopes poor polishing aside fiom superficial scratches before etching. Figs. I and 2 show micrographs of "well" and "poorly" polished nickel etched by immersing the sample for 20 min. in a solution containing 8 grams cupric sulphate in 40 C.C. of concentrated HCl and 40 C.C. of Hz0 (Marble's reagent). The sample shown in Fig. I was polished in its final stages for 5 min. on a carborundum wheel followed by ro min. on a rouge wheel, whereas the sample shown in Fig. 2 was polished only I min. on the rouge wheel. Generally, this procedure does not guarantee that the surface of the specimen will be either undistorted or deformed. It was applied here merely to show the effects Of good and poor polishing. To the experienced investigator, plastic deformation is

Jan 1, 1946

By Helmut Thielsch

MeTallographic specimens whose surfaces are to be investigated are too thick to allow either light or electrons to pass through them for microexamination by transmission. This difficulty is overcome with optical microscopes by illuminating the surface through the objective lens. For electron microscopes best results are obtained by preparing thin replicas of the surface of the specimen, placing them in the microscope and passing the electron beam through them. Since electron microscopes represent a rather recent invention, they have found little application as compared with optical microscopes. This is true because, aside from the cost of new equipment and development of new techniques, some of the older replica methods necessitated the destruction of the surface from which a thin transparent replica was obtained. In other processes in which the surface is preserved, either too tedious a procedure is required, unsuited to "mass-production" requirements of industrial laboratories, or replicas of insufficient contrast and sharpness are produced. In general, investigations with the electron microscope involve five steps: (I) polishing the surface of the metal specimen, (2) proper etching of the surface, (3) preparing the suitable replica from the surface, (4) examination and phorography in electron microscope and (5) interpretation. Preparation of Metal Surfaces Usual metallographic polishing is generclly satisfactory. It is important though that the final polish be applied very carefully, since otherwise evidence of a small amount of deformation might show up even on relatively deeply etched surfaces. A high-power microscope should be used to determine the suitability of the polish and etch. This, of course, is not different from optical examinations, but in these, if a deep etch is used, the problem is less serious. It is frequently difficult to detect with optical microscopes poor polishing aside fiom superficial scratches before etching. Figs. I and 2 show micrographs of "well" and "poorly" polished nickel etched by immersing the sample for 20 min. in a solution containing 8 grams cupric sulphate in 40 C.C. of concentrated HCl and 40 C.C. of Hz0 (Marble's reagent). The sample shown in Fig. I was polished in its final stages for 5 min. on a carborundum wheel followed by ro min. on a rouge wheel, whereas the sample shown in Fig. 2 was polished only I min. on the rouge wheel. Generally, this procedure does not guarantee that the surface of the specimen will be either undistorted or deformed. It was applied here merely to show the effects Of good and poor polishing. To the experienced investigator, plastic deformation is

Jan 1, 1946

By W. A. Anderson

IN the pressure die-casting of zinc alloys it is customary to force the molten alloy under high pressure into a permanent steel die by means of a plunger moving in a bushing that has a clearance on the diameter of the order of 0.002 in. Successful operation of the plunger type of machine requires the presence in the zinc alloy of certain percentages of aluminum. Without these aluminum additions, the normal reaction of molten zinc on ferrous materials causes sticking of the plunger and a complete shutdown of the equipment. All of the zinc alloys used for pressure die-casting today contain approximately 4 per cent of aluminum, which is more than sufficient to make plunger operation feasible. The clearance between the plunger and its bushing is an important matter. As the space becomes larger, there is a loss in effective metal pressure. Ordinary gray cast iron served fairly well and is still used in some machines. However, the rate at which the plunger clearance increases with this material is considered by many to be far too great. There is, therefore, a serious interest in finding new materials more capable of retaining the desired clearance during long periods of use. Today many die casters are using special materials for plungers and bushings selected by the somewhat expensive and time-consuming test of actual experience. An analysis of the problem reveals two possible end points of plunger operation: (1) the building up of zinc-alloy plunger-material reaction products in sufficient bulk to cause sticking and (2) rapid solution, wear or erosion, all of which will increase the clearance to an undesirable extent. If neither of these takes place, the plunger will operate for a long time, of course. The authors have developed a laboratory apparatus in which the action of a plunger moving in a bushing immersed in molten zinc alloy could be simulated closely. Such a machine made possible a more rapid and less expensive survey of the available construction materials and an analysis of the specific alloying reactions taking place in the clear-ance area.

Jan 1, 1939

By B. M. Larsen, L. S. Darken

SOME years ago we collated all laboratory data then available to us on the distribution at equilibrium of manganese and of sulphur between metal and simple slags, and used the results in setting up an equation, which proved to be in accord with determinations of the distribution ratio of manganese and of sulphur between liquid steel and open-hearth slag, over a wide range of operating conditions. We now present an outline of our calculations and inferences on these two closely related questions, which are of especial importance because of the advisability of conserving manganese wherever possible. In general. our results show that in the open-hearth furnace equilibrium between metal and slag, with respect to both manganese and sulphur, is substantially attained during the finishing period of the heat, or in about a half hour to an hour after any additions were made. This implies that the end result will be identical whether manganese is added as alloy or metal to the liquid steel or as oxide to the slag. The proportion of total manganese retained by the steel is favored: (I) by use of the minimum amount of lime, consistent with other operating limitations, required to give a lime-silica ratio of about 2.4, which usually corresponds to a minimum practical slag volume; (2) by a high concentration in the slag of MnO relative to FeO; (3) by high operating temperature. Absorption of sulphur by the slag from the liquid metal is favored: (I) by large slag volume; (2-by a high concentration of active (or "free") lime and of manganese oxide dis) solved in the slag; (3) by low concentration of silica, iron oxide, and phosphate dissolved in the slag. DISTRIBUTION OF MANGANESE BETWEEN SLAG AND METAL AT EQUILIBRIUM On the basis that the distribution of manganese between liquid steel and slag is controlled by the reaction [FeO + Mn ;7± MnO + Fe [A] slag metal slag metal] the distribution at equilibrium, at a given temperature, is expressed by the equilibrium constant for this reaction, which is defined as [K" aFPI OFeO ? aMn] where a is the activity of the molecular species denoted by the subscript. The activity of each of the several components, although it is not known precisely, is approximately equal to the concentration of each component expressed as its mol fraction; that is, as the ratio of the number of mols of the given component to the total number of mols of all the molecular species present in the metal or slag, as the case may be. Moreover, since the activity, or concentration, of iron in the liquid metal is in fact substantially constant, the term aFe may he combined with K" to give a new constant K'. Making these changes.

Jan 1, 1942

By R. J. Fruehan, F. D. Richardson

Electrochemical measurements have been made of the activity of oxygen in copper and its alloys with silver and tin at 1100" and 1200°C. The galvanic cell used was Pt, Ni + NiO/solid ellectrolyte/[O] in metal, cermet, Pt The results do not support any of the equations so far designed for predicting the activities of dilute solutes in ternary solutions from activities in the corresponding binaries. If, however, a quasichemical equation is used with the coordination number set to unity, agreement between observed and calculated activities shows that this empirical relationship can be useful over a fair range of conditions. SEVERAL solution models have been proposed for predicting the activity coefficients of dilute solutes in ternary alloys from a knowledge of the three binary systems involved. Alcock and Richardson1 have shown that a regular model, and a quasichemical model,' in which the dissolved oxygen is coordinated with eight or so metal atoms, can reasonably predict the behavior of both metal and nonmetal solutes when the heats of solution of the solute in the separate solvent metals are similar. But when this is not so, neither model gives useful predictions unless coordination numbers of one or two are assumed. Wada and Saito3 subsequently adopted a similar model to derive the interaction energies for two dilute solutes in a solvent metal. Belton and Tankins4 Rave proposed both regular and quasichemical type models in which the oxygen is bound into molecular species, such as NiO and CuO in mixtures of Cu + Ni + 0. However, their models have only been tested on systems in which the excess free energies of solution of the solute in the two separate metals differ by a few kilocalories. Ope of the reasons why more advanced models have not been proposed is because few complete sets of data exist for ternary systems in which the solute behaves very differently in the two separate metals. For this reason measurements have been made of the activities of oxygen dissolved in Cu + Ag and Cu + Sn. Measurements on both systems were made by means of the electrochemical cell, Pt, Ni + NiO/solid electrolyte/O(in alloy), cermet,Pt [1] The activity of oxygen was calculated from the electromotive force and the standard free energy of formation of NiO, which is accurately known.5 Before investigating the alloys, studies were made of oxygen in copper to test the reliability of the cell and to check the thermodynamics of the system. Of the previous studies those by Sano and Sakao,6 Tom-linson and Young,7 and Tankins et al.8,7 have been made with gas-metal equilibrium techniques; those by Diaz and Richardson,9 Osterwald,10 wilder," Plusch-kell and Engell,12 Rickert and wagner,13 and Fischer and Ackermann14 have been made by electrochemical methods. EXPERIMENTAL The apparatus employed was the same as described previously,9 apart from slight modification. The molten sample of approximately 40 g was held in a high grade alumina crucible 1.2 in. OD and 1.6 in. long. The solid electrolytes were ZrO2 + 7½ wt pct CaO and ZrO2 + 15 wt pct CaO; the tubes 4 in. OD and 6 in. long were supplied by the Zirconia Corp. of America. They were closed (flat) at one end. In one experiment with Cu + O, both electrolytes were used in the cell at the same time. The reference electrodes inside the electrolyte tubes consisted of a mixture of Ni + NiO. They were made by mixing the powdered materials and pressing them manually into the ends of the tubes, with a platinum lead embedded in them. The tubes were then sintered overnight in the electromotive force apparatus at 1100°C. By sintering the powders inside the tubes (instead of using a presintered pellet9) better contacts were obtained between the electrolyte, the powder, and the platinum lead. Troubles arising from polarization9 were thus much reduced. The electromotive force was measured by a Vibron Electrometer with an input impedence of 1017 ohm; the temperature was measured with a Pt:13 pct Rh + Pt thermocouple protected by an alumina sheath. The couple was calibrated against the melting point of copper. The cermet conducting lead of Cr + 28 pct Al2O3, previously found to be satisfactory9 for use with Cu + 0 was also found satisfactory with Cu + Ag + 0 and Cu + Sn + 0. Superficial oxidation was observed, but it did not interfere with the working of the cell. The reaction tube containing the cell was closed at each end with cooled brass heads and suspended in a platinum resistance furnace. The tube was electrically shielded by a Kanthal A-1 ribbon which was wound round it, and the ribbon was protected by a N2 atmosphere between the furnace and the reaction tube. The cell was protected by a stream of high purity argon which was dried and passed through copper gauze at 450°C and titanium chips at 900°C. All the metals used were of spectrographic standard. Procedure. In studies of the system Cu + 0, be-

Jan 1, 1970

By H. A. Deans

A three-parameter mathematical model for one-dimensional flow in porous media is developed. The objective of the model is to predict accurately the longitudinal dispersion associated with the flow of either gases or liquids over a wide range of Reynolds number. A qualitative analysis of the model parameters is given. Published experimental pulse-response curves are compared with results predicted by the model. Several general types of problems are given for which the model can be used. INTRODUCTION The problem of multicomponent single-phase flow through porous media is encountered in the study of petroleum reservoirs, gas chromatographic and ion-exchange columns, industrial fixed-bed con-tacters and elsewhere. These particular examples span the wide range of flow conditions possible; Reynolds numbers of less than l0-4 are not unusual in oil-production problems, while values in excess of 103 are common in large fixed-bed operations. The study of flow-dependent transport phenomena is complicated both by the changes in the character of the flow over this range, and by the irregularity of the flow boundaries inherent to porous media. Dispersion is one of the important phenomena known to depend fundamentally on flow conditions as well as on fluid and medium properties. As used in this paper, the term "dispersion" refers to the observed mixing of fluid elements of different composition which occurs in flow systems. The actual mechanism may be one or more of a number listed below. Only dispersion in the direction of the mean flow (referred to as axial or longitudinal dispersion, or mixing) is considered here, although lateral dispersion arises as part of certain coupled mechanisms. MECHANISMS FOR LONGITUDINAL DISPERSION A number of distinct mechanisms are known3,5,7,8 to contribute to the phenomenon of longitudinal dispersion. The more important of these are as follows. 1. Molecular diffusion in the flow direction. 2. Turbulent (cell) mixing. 3. Lateral transport processes coupled with velocity and/or residence time distributions, including: (a) "Taylor" diffusion caused by the interaction of velocity profiles in individual voids with lateral molecular diffusion; (b) separation and remixing or interdiffusion of streams having different velocities around particles; and (c) the couplipg of gross velocity profiles, caused by viscous instability or inhomogeneous porosity, with lateral dispersion. 4. Finite mass-transfer rate between a porous matrix and the flowing phase, and finite diffusion rate inside elements of the porous matrix. It is a well documented fact that these mechanisms, whether acting individually or in combinations, produce essentially similar integral effects. The observed dispersion can be described approximately by solutions of the diffusion equation with a properly chosen dispersion coefficient. Necessary conditions for equivalence between dispersion and diffusion are discussed by Klinkenberg and Sjenitzer.7 Apparently these conditions are not satisfied exactly in many real systems. "Best fit" solutions of the diffusion equation often depart appreciably from measured breakthrough curves for the usual pulse- or step-forced experimental systems. In particular, pulse response curves usually show some degree of asymmetry and "tailing" which cannot be reproduced by the one-parameter diffusion model. The three-parameter model proposed herein attempts to produce these effects in a realistic manner. Asymmetry and tailing are predicted for certain sets of parameter values, while for other sets the new model agrees with the diffusion model. VELOCITY DEPENDENCE OF DISPERSION Molecular diffusion apparently controls at sufficiently low Reynolds number in both gas and liquid systems.*l3 At Re > 20, turbulent cell mixing is dominant for gases flowing at low pressure; the data of McHenry and Wilhelm8 show that the mixing cell is approximately 1 particle diameter long in random sphere packs. on the other hand, the data

By Earl Greiner

THE constitution of the iron-silicon alloys containing from 14 to 33.4 weight per cent silicon has been studied by a number of investigators, whose results have been reviewed in a monograph published by the Engineering Foundation1. In these previous researches, the solubility of silicon in iron was determined by thermal, microscopic or magnetic methods and the compound Fe3Si2 was reported to be stable at tempera-tures from 0 to approximately 1030° C. This paper describes the results of an X-ray investigation of the solubility of silicon in iron and gives data which prove that the Fe3Si2 phase is unstable below 825° C. In order to obtain the present results on the solubility of silicon in iron, the authors have utilized the lattice constants of the alpha-phase iron-silicon alloys given in a previous publication2, and also some addi-tional data which will subsequently be described.

Jan 1, 1936

By John Hays Hammond

The following notes are descriptive of a country as yet in its infancy as regards the advancement made in mining operations. Its inaccessibility and other militating circumstances have retarded progress in that direction. With the completion of the railroad, now under construction, having the city of Cali as its objective point, with the concomitant civilizing and developing consequences, it is certain that the slopes of the Cordilleras will prove to be a South American Eldorado. Deposits of coal, copper, and minerals other than those of the precious metals are known to exist in quantities which, under more favorable conditions of accessibility, etc., could be profitably mined. The Government of the United States of Colombia, I think, is disposed to encourage and foster mining enterprises. Articles designed for mining are admitted free of duty; the permanency of the government is, at least, as well assured as that of Mexico (which is not noted for its immutability), and a more sincerely friendly sentitment towards Americans prevails in the United States of Colombia than in Mexico. This paper is confined to a description of the property of the Cauca company's mines, and is intended rather as a preliminary notice than as an exhaustive report. The Cauca mining district is reached by the following route: New York to Aspinwall; to Panama; to Buenaventura, a port on the west coast of the United States of Colombia, distant thirty-six hours from Panama by steamer; to Cali in the State of Cauca. The State of Cauca is bounded on the north by the Atlantic Ocean, on the northwest by the State of Panama, on the northeast by the States of Bolivar and Antioquia, on the east by Brazil and Venzuela, on the south by the Republic of Ecuador, and on the west by the Pacific. Ocean. It has a territory of 41,443 square miles, which is about one-tenth of the entire territory of the United States of Colombia. Its population, including the 50,000 savage Indians of the Caqueta (some of whom are cannibals), is nearly 450,000 souls, or about one-sixth of the population of the Colombian republic. Of these, one-fifth are whites (Spanish' South Amer-

Jan 1, 1885

By D. M. Hausen

This study identifies and describes various crystalline phases of the V205-Na20 system, and relates their properties to metallurgical aspects of vanadium production. Phase equilibria and stability ranges of sodium vanadate phases of varying molar ratios of Na20/V205 were investigated in a variety of plant products, ranging from fused "black cakes" (V20 melts) to "salt roast" calcines. Crystalline compounds, Including vanadium pentoxide, V205; sodium vanadyl vanadate, 6 phase, Na2O.V2O5.5V2O5; sodium vanadyl vanadate, y phase, 5Na20.V204.12V205; sodium metavanadate, Na20 .V 05; sodium pyrovanadate , 2Na20 .V205; and sodium orthovanadate, 4Na20.~2~5, have been characterized with the aid of X-ray diffraction patterns, infrared spectra, and optical properties in addition to chemical analyses, as a guide to mineralogical "troubleshooting" of plant problems and processes in vanadium pyro- and hydrometallurgy.

Jan 1, 1984

By S. E. Bretherton

Mr. AllaW Gibb, of Mount Perry, Queensland, Australia, in an interesting and instructive paper,* describes fully the great difficulties metallurgists encounter in seeking to produce marketable copper by smelting refractory ores containing arsenic, antimony and bismuth. After reading this description, I prepared a paper for the Institute, which was, however, through a misunderstanding on my part, published in the San Francisco Mining and S'cie~ztiJic Press of April 4, 1903, after its acceptance by the Council, and without credit to the Institute. Consequently, it cannot be reprinted for the Transactions of the Institute; and I can only here summarize its contents and conclusions, referring the reader to the article above named for further particulars. In that article I omitted the col~sideration of bismuth, which we do not encounter in our smelting at Val Verde, and added lead and zinc, which Mr. Gibb had not discussed; and I undertook to shorn, by the record of a year's practice of the Val Verde Copper Co., Arizona, that copper-ores containing arsenic, antimony, lead and zinc may be successfully smelted, without preliminary roasting, in an ordinary blast-furnace with hotblast, making a normal slag, such as one would aim to make under ordinary conditions with cold-blast, so as to produce a marketable matte, containing not less than 45 per cent. of copper, free from arsenic and antimony, and below the limit in lead and zinc penalized by the refineries.

Jan 1, 1904

By M. C. Udy, F. W. Boulger

AN incomplete phase diagram for the U-Ti systern was determined earlier 1 and more recently, a tentative diagram was presented for the uranium-rich end of the system.' In the present re-examination of the whole system of U-Ti alloys, high purity materials were used. Melting stock for the alloys was high purity uranium, containing about 0.09 pct C as the only appreciable impurity, and high purity iodide-process titanium purchased from New Jersey Zinc Co. Both metals were cold rolled to about 1/6 in. thickness, sheared to about I/' in. squares, and cleaned by pickling. The alloys were arc melted under a helium atmosphere in a water-cooled copper crucible. A thoriated-tungsten electrode was used. The furnace chamber was evacuated, then flushed with helium, prior to each melting. It was finally filled with stagnant helium at one atmosphere pressure. Each alloy was remelted three times after the original melting, to insure homogeneity. The alloy button was turned bottom side up before each re-melting operation. Some 22 alloys were examined. Their compositions were spaced at appropriate intervals between 100 pct Ti and 100 pct U. Analyses were made on chips taken after fabrication. The major contaminant was carbon, which varied from 0.03 to 0.08 pct. It appeared in the microstructure as titanium carbide. Alloy compositions were calculated to a carbon-free basis for consideration on the diagram. Tungsten and copper, possible contaminants from the melting operation, were generally less than 100 parts per million each. Fabrication All alloys were forged and rolled to bars approximately V8 in. square. They were clad either in SAE 1020 steel or in a 5 pct Cr-3 pct Al-Ti-base alloy, depending on the fabrication temperature. A temperature of 1800°F (980°C) was used for alloys near the compound composition. This necessitated using the titanium-base alloy, since iron reacts with titanium at this temperature, producing a low melting alloy. Other alloys were fabricated at 1450°F (790°C), using steel jackets. No iron-titanium reaction occurred at this temperature. The jackets were welded in place in an argon atmosphere. Those alloys sheathed in steel were declad and then reclad between rolling and forging operations. On the other hand, those clad with the titanium alloy were cut to a roughly rectangular shape prior to clading and were then carried through both the forging and rolling operations without opening. Those alloys near the compound composition were found to be cracked when the clading was removed. The cracked materials had been plastically deformed, however, and at least some of the cracking had OCcurred during cooling. Heat Treatment The rolled bars, after being declad and shaped to remove surface contamination, were all given an homogenizing treatment of 160 hr at 2000°F. (Samples were taken for analysis following the declading and shaping operations.) All were heat treated at the same time in one furnace, but each was sealed in a purified argon atmosphere in an individual Vycor glass tube. Argon pressure was such that it was approximately atmospheric at temperature. One end of each tube contained titanium chips and this end was heated to 1200°F (650°C) for 10 min prior to the heat treatment. This purged the atmosphere of residual reactive gases. The balance of the tube was warmed during the purge to liberate adsorbed moisture and gases, which also reacted with the hot chips. The bars were furnace cooled from the homogenization treatment. Specimens of each alloy were water quenched after 2 hr heating at 1000°, 1200°, 1400°, 1600°, 1800°, and 2000°F (540°, 650°, 760°, 870°, 980°, and 1095°C). In addition, some were treated at intermediate temperatures of 1300°, 1500°, and 1700°F (705", 815", and 925°C) and at 2150°F (1175°C). Specimens, about '/s in. cubes, were cut from the bars, sealed in individual Vycor tubes, and heat treated as described. All specimens heat treated at the same temperature were processed together. Samples were quenched by breaking the Vycor tube rapidly under water. Metallographic Examination Specimens were mounted in bakelite and ground wet on 180 grit paper held on a 1750 rpm disk. They were then ground wet by hand, using 240, 400, and 600 grit papers. The rough grinding was continued long enough to get well below the surface. Specimens were mounted separately because of the variation in the rate of etching between alloys. The specimens were polished with rouge on a 4 in., 1725 rpm wheel covered with Miracloth. Alloys on the titanium side of the compound composition were etched with a solution of 2 pct hydrofluoric acid in water saturated with oxalic acid. A few crystals of ferric nitrate were added as a bright -ener. Specimens were immersed 5 sec, polished to remove the etch, then re-etched. With the higher titanium alloys, it was often necessary to start the etch on the polishing wheel, because of the formation of a passive film. In some instances, a plain 2 pct hydrofluoric etch was satisfactory. For the alloys on the uranium side of the compound, a distinction between the compound and the uranium phase developed after standing a short time in air. This could be hastened by the application of heat, such as obtained by placing the specimen on a radiator. A deep etch was necessary to develop details in the uranium-rich phase, such as the Widmanstaetten pattern sometimes obtained by quenching y uranium. A 2 pct hydrofluoric acid solution was used for this deep etching.

Jan 1, 1955

By Gerald G. Griswold, James O. Greenslade, Cherie Tilley, Richard Reseigh

INTRODUCTION The Harrison Western Corporation, a leading Denver based mine contracting and engineering concern, is presently engaged in sinking two 1,006 m (3,300 ft) shafts for the Phillips Uranium Corporation at their Nose Rock Project, approximately 13 miles northeast of the small community of Crownpoint in McKinley County, New Mexico. The Nose Rock Project is the first attempt by the Phillips Uranium Corporation to tap the deep uranium reserves in what has become known as the Grants Mineral Belt. (See Figure 1) Project Description Phillips Uranium Corporation's plan for the large 2700 metric ton per day (2950 tons/day) mining facility calls for a series of deep access and ventilation shafts ranging from 4.27 m (14 ft) to 5.49 m (18 ft) in diameter to approximate depths of 1,006 m (3,300 ft). The initial pair of shafts consists of one production shaft and one ventilation shaft separated by a distance of 91 m (300 ft). The interbedded layers of sedimentary sandstones and shales to be penetrated by the shafts contain several major water producing aquifers, the deepest being the mineralized zone called the Westwater Canyon Member of the Morrison Formation. A series of temporary and permanent water pumping stations is planned. Generally, the temporary stations are located above major aquifers to facilitate water removal while sinking through the aquifer and the permanent stations constitute what, in the final mode, will be the mine dewatering system. In addition, Phillips Uranium Corporation has In- stalled and is maintaining a system of depressurization wells that temporarily pump the major aquifers and considerably reduce the water inflows during shaft construction. The major aquifers are also chemically grouted prior to sinking. Site work for the project was initiated in the fall of 1976. Full scale shaft sinking commenced in November of 1977 on the 4.88 m (16 ft) diameter ventilation shaft and on the 5.49 m (18 ft) production shaft by another contractor. Harrison Western Corporation began work on the project on November 4, 1979 wlth the production shaft at a depth of 633 m (2,076 ft) and the ventilation shaft at a depth of 474 m (1,554 ft). This paper will address only the portion of shaft sinking completed by Harrison Western. Geology and Hydrology The Nose Rock Project is located on the Chaco Slope in the southern extreme of the San Juan Basin in northwest New Mexico. The southern San Juan Basin is generally bound by the Defiance Uplift to the west, the Zuni Uplift to the south and the Nacimiento Uplift to the east. The Grants Mineral Belt occupies most of the southern portion of the San Juan Basin and this project is located on the northern extreme of the Grants Mineral Belt. The San Juan Basin is comprised of sedimentary rock of continental, marginal-marine and marine origin, that dip northward from the Zuni Uplift and Chaco Slope into the interior of the San Juan Basin. (See Figure 2) Major Formations The major geologic formations to be penetrated range from mudstone and shales to siltstones and sandstones. The sandstones are highly productive aquifers which, under static conditions, would flow artesian. Water temperatures in the aquifers are high and therefore are a force to be dealt with. Temperatures range from 18ºC (65OF) in the upper aquifers to 48ºC (118º'F) in the lower. The mudstones are generally bentonitlc. (See Figure 2) GALLUP SANDSTONE: The Gallup Sandstone is the first major regressive wedge in the San Juan Basin of the Cretaceous era and at this project is about 35 m (115 ft) thick. It is medium grained and prior to depressurization carried a hydrostatic water pressure of over 72.5 kg per cm2 (1,031 psi) which 1s artesian. Compressive strength ranges from 334.7 kg per cm2 (4,760 psi) to 421.8 kg per cm2 (6,000 psi). Water temperature is approximately 30°C (86°F).

Jan 1, 1982

By J. R. Thoenen, M. C. Malamphy, G. K. Dale

The beginning of the war and the events leading up to it precipitated a near crisis in the aluminum industry. Demands for the metal reached proportions far beyond the prewar production capacities and, in addition, the submarine menace seriously curtailed the importation of bauxite from South America, hitherto a chief source of high-grade ore. The situation required an intensive search for domestic ore to augment the reserves and in October 1941 Congress directed the Department of the Interior to investigate the extent, mode of occurrence, and quality of bauxite in the United States. In December of that year the Bureau of Mines and the Geological Survey began the search for bauxite in Arkansas, where more than go per cent of the domestic ore had been produced and where the greatest amount of bauxite was known to occur. The program involves the geophysical and geological investigation of the Arkansas bauxite region and the core drilling of areas considered favorable for the occurrence of bauxite deposits. Cores taken from the bauxite-kaolin zone are sampled and analyzed in the Bureau of Mines laboratory in Little Rock. The information from each of the deposits discovered is then assembled, the bauxite is graded with respect to its possible utility, tonnage estimates are made, and the whole is presented in the form of a war minerals report. Thirty-eight new bauxite deposits had been discovered and investigated at the end of the calendar year 1944, and the presence of several others had been indicated by the drilling. More than 5000 holes had been drilled throughout the bauxite region, and more than 60,000 chemical analyses had been made of samples taken from the bauxite-kaolin zone. A study of the chemical analyses led to certain general conclusions not only with regard to the chemical composition of Arkansas bauxite, but also with regard to its component minerals. Charts and diagrams based on these conclusions have been developed for practical use by the Bureau of Mines: (I) to serve as a check against laboratory analyses, (2) to present tonnage estimates of ore bodies based on mineral composition, (3) to illustrate the relationship of tonnages of bauxite to the alumina, silica, and iron content, and (4) to serve as a control for mining operations by providing a means for quick estimates of the value of the ore from a partial analysis of its chemical constituents. The use of charts and diagrams similar to those discussed in this paper-- is not new. The use of the trilinear diagram for studying the ultimate analyses of coals as of proposed by Ralston in Bureau of Mines Technical Paper 93 (1915) showed that the various ranks of coal fell in different areas on the diagram and that volatile matter, calorific value and other properties could also be plotted by the use of contours. A considerable subsequent literature, largely on classification of coals, has accurnulated since then, showing the utility

Jan 1, 1948

By J. R. Thoenen, M. C. Malamphy, G. K. Dale

The beginning of the war and the events leading up to it precipitated a near crisis in the aluminum industry. Demands for the metal reached proportions far beyond the prewar production capacities and, in addition, the submarine menace seriously curtailed the importation of bauxite from South America, hitherto a chief source of high-grade ore. The situation required an intensive search for domestic ore to augment the reserves and in October 1941 Congress directed the Department of the Interior to investigate the extent, mode of occurrence, and quality of bauxite in the United States. In December of that year the Bureau of Mines and the Geological Survey began the search for bauxite in Arkansas, where more than go per cent of the domestic ore had been produced and where the greatest amount of bauxite was known to occur. The program involves the geophysical and geological investigation of the Arkansas bauxite region and the core drilling of areas considered favorable for the occurrence of bauxite deposits. Cores taken from the bauxite-kaolin zone are sampled and analyzed in the Bureau of Mines laboratory in Little Rock. The information from each of the deposits discovered is then assembled, the bauxite is graded with respect to its possible utility, tonnage estimates are made, and the whole is presented in the form of a war minerals report. Thirty-eight new bauxite deposits had been discovered and investigated at the end of the calendar year 1944, and the presence of several others had been indicated by the drilling. More than 5000 holes had been drilled throughout the bauxite region, and more than 60,000 chemical analyses had been made of samples taken from the bauxite-kaolin zone. A study of the chemical analyses led to certain general conclusions not only with regard to the chemical composition of Arkansas bauxite, but also with regard to its component minerals. Charts and diagrams based on these conclusions have been developed for practical use by the Bureau of Mines: (I) to serve as a check against laboratory analyses, (2) to present tonnage estimates of ore bodies based on mineral composition, (3) to illustrate the relationship of tonnages of bauxite to the alumina, silica, and iron content, and (4) to serve as a control for mining operations by providing a means for quick estimates of the value of the ore from a partial analysis of its chemical constituents. The use of charts and diagrams similar to those discussed in this paper-- is not new. The use of the trilinear diagram for studying the ultimate analyses of coals as of proposed by Ralston in Bureau of Mines Technical Paper 93 (1915) showed that the various ranks of coal fell in different areas on the diagram and that volatile matter, calorific value and other properties could also be plotted by the use of contours. A considerable subsequent literature, largely on classification of coals, has accurnulated since then, showing the utility

Jan 1, 1948

By H. W. Graham

The young metallurgist of today who thinks casually of the technical literature of the steel industry might conclude that little has been published concerning the Bessemer process. This conclusion is true as relating to the last decade or two, but there is a fairly voluminous Bessemer literature in the period of 1860 to 1910. Since that time, however, an entirely new level of metallurgical knowledge of steelmaking has been reached; and the present paper is simply an effort to look broadly from this new level and to bring the recorded history of the process up to date. It is an effort to appraise the acid Bessemer method of steelmaking in the light of today's technical knowledge thereof. In this paper matters of history will be dealt with only insofar as they contribute to an understanding of today's situation. Attention will be directed to the apparent causes of past developments in seeking to perceive the true direction of trends now in existence and effective as bearing upon future developments. The paper will discuss the economics of the Bessemer process, but only to the extent that will bear upon the metallurgist's understanding of his responsibility. The problem of the quality of Bessemer steel will be reviewed and examples will be given of the technical data upon which the reasoning of the paper is based. Matters of engineering design, mechanical maintenance, operation and metallurgical investigation will be surveyed. Comparisons will be made between the Bessemer and open-hearth processes for the sake of clear and ready understanding. Production First of all it is considered logical and informative to show how much Bessemer steel has been and is being produced, and the relation of that production to the tonllage made by the open-hearth process. Table 1 shows the tonnages made by the two processes in representative years. It is to be noted that these figures are in net tons of 2000, lb., whereas previous to 1940 the Institute figures were compiled in gross tons. id open-hearth production and steel going into castings are included, since separated data are not available for the early years of the period covered. The ratio shown in Table I is merely the Bessemer tonnage for a given year divided by the open-hearth tonnage of the same

Jan 1, 1941

By H. W. Graham

The young metallurgist of today who thinks casually of the technical literature of the steel industry might conclude that little has been published concerning the Bessemer process. This conclusion is true as relating to the last decade or two, but there is a fairly voluminous Bessemer literature in the period of 1860 to 1910. Since that time, however, an entirely new level of metallurgical knowledge of steelmaking has been reached; and the present paper is simply an effort to look broadly from this new level and to bring the recorded history of the process up to date. It is an effort to appraise the acid Bessemer method of steelmaking in the light of today's technical knowledge thereof. In this paper matters of history will be dealt with only insofar as they contribute to an understanding of today's situation. Attention will be directed to the apparent causes of past developments in seeking to perceive the true direction of trends now in existence and effective as bearing upon future developments. The paper will discuss the economics of the Bessemer process, but only to the extent that will bear upon the metallurgist's understanding of his responsibility. The problem of the quality of Bessemer steel will be reviewed and examples will be given of the technical data upon which the reasoning of the paper is based. Matters of engineering design, mechanical maintenance, operation and metallurgical investigation will be surveyed. Comparisons will be made between the Bessemer and open-hearth processes for the sake of clear and ready understanding. Production First of all it is considered logical and informative to show how much Bessemer steel has been and is being produced, and the relation of that production to the tonllage made by the open-hearth process. Table 1 shows the tonnages made by the two processes in representative years. It is to be noted that these figures are in net tons of 2000, lb., whereas previous to 1940 the Institute figures were compiled in gross tons. id open-hearth production and steel going into castings are included, since separated data are not available for the early years of the period covered. The ratio shown in Table I is merely the Bessemer tonnage for a given year divided by the open-hearth tonnage of the same

Jan 1, 1941

By E. W. Shaw

Continued discussion of the paper of Roswell H. JOHNSON, presented at the New York meeting, February, 1915, and printed in Bulletin No. 98, February, 1915, pp. 221 to 226. See also Bulletin No. 101, May, 1915, pp. 1157 to 1162. E. W. SHAW, Washington, D. C. (communication to the Secretary+). -With the word petrology-literally the science of rocks-being used primarily for igneous rocks, and with geophysics coming to mean the study of lavas and the rocks into which they solidify, contributions to the knowledge of the physical chemistry of sedimentary rocks, even though only ideas which may be used as working hypotheses, become most welcome. The forces which control the formation and subsequent history of the stratified portions of the earth's crust are so little known that no one has yet been able to settle finally the questions as to whether petroleum is of organic or inorganic origin; whether it originated far from its present position, or nearby. Yet both the chemical and physical problems of the rocks in which oil occurs seem to be more simple than those of the igneous rocks. The oil-bearing rocks of western Pennsylvania, for example, have in all probability never been subjected to a pressure exceeding 3,000 or 4,000 lb. to the square inch, nor to a temperature higher than 100° or 200° C. These pressures are considerably below the crushing strength of rocks, and the temperature far below their melting point. The igneous rocks,, on the other hand, have been affected by enormous pressures and very high temperatures and yet steady progress is being made in reproducing in the laboratory the conditions of their formation and subsequent modification within the earth. The solution of the sedimentary-rock problems would seem to be fully as important as those of igneous rocks, and yet we must content ourselves with reasoning backward and our inferences as to what has happened are oftentimes little more than guesses.1 One of the fundamental problems is the origin of the salt water in oil fields. Is the salt water fossil sea water; has it been formed by the solution o-f salts of various kinds from distinct beds, from disseminated par-ticles, and from the weathering of suitable grains in the rock; or is it of deep-seated origin? Its general resemblance to sea water points to the first, but the principles held by some concerning the free circulation of water throughout the earth's crust, and certain peculiarities of composition indicated by the few analyses available, seem out of harmony with such an explanation.

Jan 7, 1915