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By W. Rostoker, R. P. Elliott, B. W. Levincer

Phase equilibria in the Ti-Cr-Mo system have been investigated for alloys containing 100 to 40 pct Ti in the temperature range 550° to 1300°C. Five experimental isothermal sections and a surface of incipient melting are presented in addition to a summary projection of the space. Seven vertical sections have been constructed from the isothermal sections. A STUDY of the system Ti-Cr-Mo was undertaken as part of a program sponsored by Watertown Arsenal toward the development of titanium-base phase equilibrium diagrams of potential technical importance to alloy development. The scope of the investigation included the composition range contained by the titanium corner and the line of 64 pct Ti (all compositions are by weight) and the temperature range 550" to 1100°C. A surface of incipient melting was constructed from measurements on a large number of alloys. The system Ti-Cr has been established.&apos;-? The phase diagram is characterized by a wide miscibility field of the solid solution at elevated temperatures and a eutectoid reaction of the type: (15 pct Cr) + TiCr, (685C). The a solid solution has a very limited capacity for solution of chromium (< 0.5 pct Cr). The intermediate phase TiCr2 has at best a very narrow composition range. It has been shown that two allotropic modifications of this phase exist. However, this behavior does not appear to be perceptibly reflected in the form of phase boundaries of the type + TiCr,. In the system Ti-Mo,9-10 the phase is stabilized to successively lower temperatures with increasing molybdenum content. There are no known intermediate phases. The a solid solution is limited to less than 0.5 pct Mo. Because of the very extensive range of the phase, the ternary system was ideally suited to the determination of the phase boundaries by the parametric method of Andersen and Jette." A parametric surface was constructed to provide the necessary basis for the application of this method. Preparation and Treatment of Alloys More than 60 alloy compositions were prepared for the study of this system. Alloy buttons of 10 grams were arc-melted in a nonconsumable electrode furnace using inert atmosphere protection and a water-cooled copper crucible. The construction and operation of this type of melting unit have been adequately described elsewhere.&apos;&apos; To insure complete solution of alloy additions, the buttons were remelted alternately on top or bottom as many as five times. This was accomplished by a suitable mechanism for "flipping" over the ingots. Iodide titanium (99.97 pct Ti) was used as the alloy base. An especially high quality chromium (99.9 pct Cr) was obtained from the National Research Corp. Molybdenum sheet (0.005 in.) of 99.9 pct purity was used.

Jan 1, 1954

By Robert A. Rapp, Ronald L. Pastorek

Solid-state electrochemical measurements by three alternative experimental procedures were made with the cell FeO, Fe3O4 |Zro.85Cao.15O1.85 |Cu| Zr0.85CaO.15O1.85 | FeO, Fe304 to establish the solubility and diffusivity of oxygen in solid copper in the temperature range 800" to 1030°C. The solubility of oxygen in solid copper and the diflusivity of oxygen in solid copper Dgu = 1.7 X 10-2 exp(-16,000/RT) Cm2/sec were determined and confirmed in alternative experiments. The enthalpy of solution of oxygen in solid copper equals —10,000 cal per mole; the partial excess entropy of the oxygen atoms in the Cu-O dilute solution is approximately the same as that found for interstitial atoms in other metals. The diffusivity of oxygen in solid copper is consistent with that expected for an interstitial atom. RELIABLE values for the saturation solubility N(s) and diffusivity DO of oxygen in solid copper have not been unambiguously established in the literature. Following three early determinations by others,1"3 Rhines and Mathewson4 reported that the solubility of oxygen in solid copper increased from 0.007 at. pct 0 at 600°C to about 0.015 pct at 1050°C. Phillips and skinner,, using essentiially the same analytical procedure, reported that the solid solubility increases from 0.0018 at. pct 0 at 550°C to about 0.0075 pct at 1050OC. The only previous value for the diffusivity of oxygen in solid copper was reported by Ransley.6 Ransley deoxidized Cu-Cu2O alloys in an atmosphere of carbon monoxide gas to yield a solubility-diffusivity product. He used the solubility data of Rhines and Mathewson to calculate the diffusivity values. Another method for obtaining the solubility-diffusivity product (N(s) DO) is by measuring the widths of internal-oxidation zones in copper alloys as reported by Verfurth and Rapp.7 However, the calculated N(S)Do products depend upon the alloy content of the specimen, so that the internal oxidation of copper alloys does not follow ideal internal oxidation kinetics. As a result, unequivocal values for the N(s) DO product were not obtained by this procedure. A solid-state coulometric titration technique similar to that employed in this work was introduced by C. Wagner8 to study the dependence on silver activity of the Ag/S ratio in silver sulfide in the temperature range of 160" to 300°C. Similar experiments have been carried out by C. Wagner and co-workers9-11 to study the stoichiometry range of silver and copper tellurides, cuprous sulfide, and cuprous selenide. Numerous authors have carried out electrochemical measurements with a solid oxygen-ion-conducting electrolyte to determine the solubility and/or diffusivity of dissolved oxygen in several liquid metals.12-l6 Rickert and Steiner17,18 have used solid-state electrochemical measurements to determine the diffusivity of oxygen in solid silver from 760" to 900°C. Two different cell geometries were used. In the cell of linear geometry Fe, FeO | ZrO2 + (CaO) | Ag + [0 (dissolved)] [1] oxygen diffused from the interior of the silver electrode to the silver/electrolyte interface where the oxygen activity had been lowered from a fixed initial value to practically zero by the application of voltage to the cell. The diffusivity of oxygen in solid silver was determined from the solution of the diffusion equation and the time dependence of the cell current. However, this determination of the diffusion coefficient depended upon a knowledge of the solubility of oxygen in solid silver. A cylindrical geometry was used for the cell Pt, O2(Po2 = 0.21 atm) | ZrO2 + (CaO) | Ag + [0 (dissolved)] [II] which also allowed the diffusivity of oxygen in solid silver to be determined. These values were in agreement with other available data.l9 Recently, Raleigh20,21 used a method involving the measurement of diffusion-limited currents in a cell involving the AgBr solid electrolyte to determine the diffusion coefficient of silver in Ag-Au alloys at 400°C. Diffusivity values on the order of l0-14 sq cm per sec were measured in the alloy composition range 10 to 60 at. pct Ag in a single experiment. From numerous electrical conductivity and galvanic cell measurements,9&apos;22"26 the solid solution Zr0.85 Ca0.15 O1.85 has been established as an electrolyte with predominant oxygen ion conduction over a wide range of intermediate and high oxygen activities. For interrelating the thermodynamics and the kinetics of the dissolution of oxygen in solid copper in this investigation, a galvanic cell was constructed with FeO-Fe3O4 as the reversible reference electrode, the Zr0.85Ca0.15 O1.85 electrolyte, and a pure copper specimen under-saturated in oxygen as the other electrode. THEORETICAL ANALYSIS Three variations of a high-temperature electrochemical technique were used in this study to provide two determinations each of the solubility and diffusivity

Jan 1, 1970

By C. Ernest Birchenall, Robert F. Mehl

APPLICATION of diffusion laws in the customary form to experimental studies in binary metallic solid solutions has shown the diffusion coefficient to vary with concentration for all systems investigated. The factors determining this variation have not been ascertained. However, the question of whether the diffusion coefficient would become a constant, independent of concentration throughout a single phase if the concentration gradient in the diffusion equation were replaced by an activity gradient has been an attractive subject for speculation. Wagner1 derived an expression for the force acting on a diffusing particle in terms of the chemical potential. This was also the approach chosen by Jost2 in his monograph. From a somewhat different point of view, Eyring3 and his co-workers have used activity gradients when dealing with diffusion in concentrated nonideal solutions. The only actual test with experimental data is that given by Darken,4 though this is more qualitative than quantitative. Many others opposed the application in any way of thermodynamic concepts to kinetic phenomena, including diffusion processes. A rigorous examination of this principle requires good data expressing the relationship between activity and concentration for solid solutions for which reliable diffusion work has been done. The literature provides such information only for the interstitial solution of carbon in gamma iron (austenite) and for the substitutional copper-zinc solutions (alpha brass). Activity data for carbon in austenite at 800°C and 1000°C are available from the recent work of Smiths on the equilibrium of hydrogen-methane and carbon monoxide-carbon dioxide mixtures with gamma iron. Combining these with the diffusion studies of Wells and Mehl6 makes possible a quantitative test for this interstitial solid solution. The vapor-pressure determinations for zinc over brass by Hargreaves7 allowed the calculation of activities in this system over a wide range of temperatures and concentrations. Extensive investigation of diffusion in this substitutional solid solution has been carried out by Rhines and Mehl.8 ACTIVITIES IN BRASS9 If the vapor phase of zinc is assumed to behave as an ideal gas, any solid or liquid solutions that are in equilibrium with the same partial pressure of zinc at the same temperature have the same thermodynamic activity of zinc. In order to assign a numerical value to the activity azn, it is necessary to choose some standard reference state to which an activity value of unity is arbitrarily assigned. It is customary to choose the liquid or solid state of the pure material. Then azn is defined numerically by azn = Pza/Pzn° [I]

Jan 1, 1947

Albin, B. R Billings, Mont. &apos;28 Amster, Nathan L . , 25 Broad St, New York, N. Y. &apos;28 Bache, Jules S 42 Broadway, New York, N. Y. &apos;28 Barrett, C. P 5338 Harper Ave, Chicago, Ill. &apos;28 Baum, Frank G Hobart Bldg., San Francisco, Cal. &apos;28 Bayless, Ron. William S Russ Bldg , San Francisco, Cal. &apos; 28 Bean, Louts H., V.P., Dwight P. Robinson & Co, Inc 125 E. 46th St, New York, N Y. &apos;23 Beatty, Ross J 1105 First National Bank Bldg., Chicago, Ill. &apos;28 Benwell, Oswald F 205 Colorado National Bank, Denver, Colo. &apos;28 Beymer, Albert S., V.P., Keystone National Bank Pittsburgh, Pa. &apos;28 Bingham, Charles W 1542 Hanna Bldg, Cleveland, Ohio. &apos;28 Blumenthal, Hugo 44 Pine St, New York, N. Y. &apos;28 Boettcher, Charles Ideal Cement Bldg., Denver, Colo. &apos;28 Bowlus, Thomas H Iola, Kans. &apos;28 Bragg, E. B Carmel, Cal. &apos;28 Brown, Colvin B Chamber of Commerce, Washington, D. C. &apos;28 Burt, Maxwell Struthers Southern Pines, N. C. &apos;28

Jan 1, 1923

By Jack A. Simon, M. E. Hopkins

Coal is defined as a combustible rock that originated in the accumulation and physical and chemical alteration of vegetation. Coal can be ignited and burned like the wood that was man&apos;s earliest fuel, but coal gives more heat than the same amount of wood and has many industrial uses. Unlike wood, coal is not generally found on the surface of the ground but is mined from the solid rock of the earth. Before taking up the occurrence, formation, and the unique character of coal in the rock sequence, let us briefly consider the general character of all rocks in the crust of the earth. Relatively little is known about the very earliest history of the earth, although a number of logical theories have been developed. Manned exploration of the moon and the rocks returned to earth continue to provide some answers to questions concerning the earth&apos;s origin and history. The period of earth history with which we concern ourselves here begins after great areas of water had evolved on earth and substantial land areas of once molten (igneous) rock existed. Weathering and other processes that attacked the surface of the rocks reduced them to small particles. Water provided by rainfall transported this material, ultimately, to large bodies of water where it was deposited. Thus was initiated the geologic sequence of sedimentary rocks that lie above the once molten igneous rocks. The crust and upper mantle of the earth are made up of several large plates along which differential movement (primarily horizontal) takes place. Such movements, although small, are occurring today. These horizontal movements are accompanied by vertical movements causing important changes in the relative position of the continents and oceans. Low-lying coastal swamps with favorable climates are ideal locations for coal accumulation and burial by river-borne sediments, and large areas

Jan 1, 1981

By E. L. Tucker

IN THE metallurgy of precious metals, it has been standard practice for years to use cyanogen compounds, so it was but natural that early investigators in the field of flotation should consider these compounds as possible flotation reagents. In Australian Patent 9508, of 1913, alkali cyanides were described as suitable reagents for the separation of heavy sulfide minerals, the reagents being employed either in an alka-line or neutral circuit. In U. S. Patent 1236501, of 1917, to John M. Tibbet, the use of cyanide in conjunction with soda ash or lime is described. One of the claims of this patent reads, "An improvement in the cyanide process for the treatment of ores comprising, mixing the ore with cyanide solution and oil and alkali: emulsifying the oil in the presence of the ore, the alkali and the cyanide solution, floating a portion of the values in the pulp by producing gas bubbles in the mixture-and removing the values floated." More recently, Sheridan and Griswold, in U. S. Patents 1421585 and 1427235, describe a somewhat similar process and have, successfully introduced it in. the mill of the Timber Butte Milling Co. U. S. Patent 1429544, of 1922, to Stevens, describes the use of double cyanides of copper, zinc, and lead. The success of cyanide as a reagent in the differential flotation of lead and zinc sulfides in highly complex ores is proof that these patents have a solid foundation.. Although the technique of their application to particular ores has been worked out in many cases, no one, so far as is known, has attempted to describe the nature of the action of the cyanide or to determine the ideal conditions for its, application. It was the purpose of the present investigation to gather information on these points. Naturally this would have been an exceedingly ambitious.

Jan 8, 1925

By F. S. Norcross

DEVELOPMENT of the manganese deposits of Cuba is a matter of importance not only to those involved in this industry on the Island but to the United States steel industry and to our Nation as a whole. For years our domestic resources of manganese have been wholly inadequate, but the recent Cuban development points the way toward solution of this strategic mineral problem.

Jan 1, 1939

By G. B. Walker

THE sink-float methods designated by heavy-media separation processes were pioneered by C. Erb Weunsch for the treatment of base metal ores as an improvement over jigs. The work of Weunsch was further developed by Victor Rakowsky and The American Zinc, Lead and Smelting Co. Early in the development of the processes, the inherent unsuitability of galena as the solid constituent of the medium was recognized and ferrous media amenable to magnetic recovery and control were developed. The high efficiency and low cost of magnetic recovery and cleaning of ferrous media regardless of particle size, slime contamination, or surfacial oxidation had led to the adoption of ferrous media by all of the sink-float plants operating under the heavy-media separation processes patents controlled by American Zinc, Lead and Smelting Co. Approximately 2,000,000 tons of base metal and nonmetallic minerals are treated each month by these methods.

Jan 1, 1949

By James M. Stapleton

It has long been recognized by blastfurnace men that correct top distribution of materials is very important in efficient and economical furnace operation. Thousands of experiments on top design, filling, sizing, and other operations have been carried out to improving furnace performance by securing uniform distribution. Many of these experiments have worked out satisfactorily and have been passed along to the industry. Many of them have been discarded and forgotten. It has been the custom to judge the results of such experimentation by the results shown in improved or lowered furnace efficiency. While the effect on furnace practice will have to continue to be the final criterion of experimental changes, it has always been a desire of blast-furnace men to ascertain the reason for failure or success. Efficiency in the blast furnace approaching the maximum can be measured in several ways: (1) by actual operating results as revealed in the coke rate and tonnage figures, and (2), in the degree to which the top gas approaches the limiting ratio of CO/CO2 for the reduction of iron oxide by CO gas. This ratio is shown in the equilibrium curve in Fig. I for the system Fe-O-C and CO2-CO-C. The closer the top gases approach this limiting ratio (set at 1.08 by Martin1 because of the effect of limestone calcination) the more efficiently we may expect a furnace to operate. The fact that low CO/CO2 ratios parallel eficient operating performance caused us to investigate the cause of good or poor distribution and the effect of filling and other changes on furnace operation. Heretofore it has been possible to take a sample of furnace gas (usually from the dust catcher) and from it determine how closely the reducing gases were to the ideal or limiting value as set by the equilibrium diagram. However, to find just where in the top area the distribution was distorted and the top-gas CO/CO2 ratios were distant from equilibrium values has been a difficult and expensive investigational procedure. In an effort to overcome this difficulty, apparatus was designed to take gas samples and temperatures across the top radius of the furnace. It was hoped that with the aid of this apparatus traverse sampling of the ascending gases could be simplified, and the cost of sampling substantially lowered. Routine experimenting could then be maintained and results checked with furnace operation. It must be emphasized that a traverse sampling is necessary for a true picture, as single samples at any one point are unreliable. This statement can be verified by an examination of Tables 3 to 6, showing results obtained at our furnaces in a large number of tests. Apparatus The design of the equipment for taking the samples was governed by the need for providing a simple, routine test that could be performed fairly quickly without adversely affecting normal furnace operation.

Jan 1, 1943

By James M. Stapleton

It has long been recognized by blastfurnace men that correct top distribution of materials is very important in efficient and economical furnace operation. Thousands of experiments on top design, filling, sizing, and other operations have been carried out to improving furnace performance by securing uniform distribution. Many of these experiments have worked out satisfactorily and have been passed along to the industry. Many of them have been discarded and forgotten. It has been the custom to judge the results of such experimentation by the results shown in improved or lowered furnace efficiency. While the effect on furnace practice will have to continue to be the final criterion of experimental changes, it has always been a desire of blast-furnace men to ascertain the reason for failure or success. Efficiency in the blast furnace approaching the maximum can be measured in several ways: (1) by actual operating results as revealed in the coke rate and tonnage figures, and (2), in the degree to which the top gas approaches the limiting ratio of CO/CO2 for the reduction of iron oxide by CO gas. This ratio is shown in the equilibrium curve in Fig. I for the system Fe-O-C and CO2-CO-C. The closer the top gases approach this limiting ratio (set at 1.08 by Martin1 because of the effect of limestone calcination) the more efficiently we may expect a furnace to operate. The fact that low CO/CO2 ratios parallel eficient operating performance caused us to investigate the cause of good or poor distribution and the effect of filling and other changes on furnace operation. Heretofore it has been possible to take a sample of furnace gas (usually from the dust catcher) and from it determine how closely the reducing gases were to the ideal or limiting value as set by the equilibrium diagram. However, to find just where in the top area the distribution was distorted and the top-gas CO/CO2 ratios were distant from equilibrium values has been a difficult and expensive investigational procedure. In an effort to overcome this difficulty, apparatus was designed to take gas samples and temperatures across the top radius of the furnace. It was hoped that with the aid of this apparatus traverse sampling of the ascending gases could be simplified, and the cost of sampling substantially lowered. Routine experimenting could then be maintained and results checked with furnace operation. It must be emphasized that a traverse sampling is necessary for a true picture, as single samples at any one point are unreliable. This statement can be verified by an examination of Tables 3 to 6, showing results obtained at our furnaces in a large number of tests. Apparatus The design of the equipment for taking the samples was governed by the need for providing a simple, routine test that could be performed fairly quickly without adversely affecting normal furnace operation.

Jan 1, 1943

By Tony B. Szwilski, K. Unrug

INTRODUCTION Since the introduction of longwall coal mining systems, reliable predictions of roof support requirements at the face and the roof caveability in the gob area have been major contributors to the success of the longwall face by means of safety and face productivity. That is, the successful operation of a longwall is well-served by good regular caving of the gob. In recent times, with the advent of increased coal face mechanization and capital investment, the evaluation of the feasibility of longwall mining has become essential. In the United States, where a face unit for a face length of about 150 metres may cost around $6 million, a quantitative system that would assist in selecting the best equipment for the coal would prove extremely beneficial. There have been many such varied investigations in the past few years. A vast -amount of work has been invested principally by West Germany [3, 7, 8, 91 , Poland [I, 101 , United Kingdom [4, 5, lo], France [4], and South Africa [4]. It is the object of this paper to review this previous research work and give an outline that may be used as guidelines for long- wall evaluation. Essentially, for the initial design phase for a longwall system, account must be taken of the geometry of the coal panel, its position relative to the surface (depth), direction of the coal cleat system, faults and in-situ stresses and other neighboring workings in the same coal seam and other seams both above and below. The advance of the coal panel disturbs the stress field and in doing so creates an abutment zone around the face. At this stage the condition of homogeneity of the surrounding rock mass does not apply. The magnitude of the rock strata pressure may exceed the ultimate strength of the rocks and create zones of clastic, plastic and elastic material, the limits of which are difficult to determine. The collapse of the gob and resulting expansion of the displaced waste roof rock, create a statically undefined support complicating an already unclear rock structure. For example, it is often a point of debate whether, indeed, the vertical strata pressure develops to regain the original magnitude of virgin stress. Under these post-failure circumstances an analytical approach based on simplified and idealized assumptions can only be considered a very general approximation. Theoretical concepts, however, may be adequately supplemented by empirical methods that are based on numerous underground observations and surveys [3, 4, 7, 8]. These methods employ the use of rock indices that very handily correspond to the competence of the roof rock mass. Scale model work [3, 41 , using equivalent materials representing the surrounding rock mass within the coal seam zone, have given valuable qualitative and sometimes quantitative data in addressing the behaviour of the rock mass around longwall panels. To characterize the state of art of caveability predictioqthe principal concepts will be reviewed with special emphasis placed on practicality for the planning of longwall operation. It has been the general observation of the authors that many of the literature surveys published in English often neglect reference to other international mining literature. It is with this point in mind that an overall review has been written including mining concepts identified with the principal coal mining countries. THEORETICAL CONCEPTS Arching Theory For the development of this theory, assumption has been made that an extracted height, h, in a coal seam results in an extracted panel of width, w . Also, the coal seam is horizontal and the rock strata of both the roof and floor are homogeneous. The primary (virgin) stress distribution will change in the roof as well as the floor. As a result of lack of support caused by the excavation (in the gob area) an additional load is developed due to the redistribution of the load around the sides of the panel, referred to as the abutment, R, where: [ ]

Jan 1, 1982

By D. L. Katz, M. J. Rzasa

The derivations of three methods of computing the static pressure gradients in natural gas wells have been presented to show the assumptions made. Charts were developed from which the pressure gradients may be read when the well-head pressure, the well fluid gravity, depth, and the average well temperature are given. A chart for estimating the well fluid gravity from the condensate content and separator gas gravity is included. The effect of the increased average well temperature after flow on the calculation of the static pressure gradient is discussed. Introduction Reservoir pressures have been calculated from well-head pressures for gas wells for many years. As the pressure measurements become more accurate, the need for a reliable calculation of the static pressure gradient often arises. This paper will develop the several methods for computing the pressure gradient in gas wells and make a comparison between them. The method of calculating static pressure gradients in common use is Eq. I (ref. I) or its counterpart which includes a factor for the deviation of the gas from the ideal gas law. P2 - P1 = P1(e0.0000347GX _ I) Eq. [I] in which P1 = pressure at well head, lb. per sq. in. abs. PP = pressure at bottom of well, Ib. per sq. in. abs. G = gas gravity X = depth of well, ft. An alternate method is to compute the average density of the gas in the well and multiply by the well depth in a manner similar to that used for liquid gradients. Derivation of Formulas A static pressure gradient is a special case of the general fluid-flow equation. Consider a pound of fluid flowing in a vertical column from point I to point 2, Fig. I. By an energy balance for fluid flowing from I to 2: U1 + P1V1 + u12/2g + X1 + q = U2 + P2V2+ u22/2g+X2 +W [2] in which U = internal energy, ft-lb. per lb. P = pressure, lb. per sq. ft. V = volume, cu. ft. per lb. u = average linear velocity, ft. per sec. X = height above datum, fl. q = heat absorbed by fluid, ft-Ib. pcr lb. W = work done by system, ft-lb. per lb. An energy balance on the fluid itself gives: U = ?TdS - ?PdV + etc. [3] in which T = temperature, deg- R- S = entropy, ft-lb. per deg. R. per lb.

Jan 1, 1945

By H. G. Kok

The continuous increase in energy costs has made it necessary to consider a broader use of belt conveyors for the transportation of material from the mine pit to the processing plant. Hard rock has to be crushed before it can be moved by belt conveyors. Systems are in the planning stage for mining hard rock, such as copper and iron ore, by using high-capacity, mobile, or semi-portable crushers. The mobile crusher is located in the pit, and the crushed material is transported by energy-efficient, shiftable belt conveyors out of the pit.

Jan 1, 1983

By C. W. Parmelee

THE ideal fuel for burning ceramic wares is the one that, among other characteristics, has little or no sulfur. For that reason wood was long considered the most desirable fuel but its high cost has practically eliminated its used except in regions where it is very abundant or other circumstances warrant its choice. The fuels commonly employed are natural and producer gas, oil, and coal. The last named is undoubtedly the most important, not only in this country but abroad. Occasionally anthracite is used but the larger part is bituminous. The quality of the coal used depends on the kind and the value of the products being manufactured. For some materials, such as common brick, hollow block, etc., the quality of the coal is of less importance than in the manufacture of polychrome terra cotta, pottery, porcelain, etc. It is obvious that in burning clays that contain notable amounts of pyrite, marcasite or gypsum, as is the case with many common clays, the sulfur content of the fuel is of much less importance. The permissible amount of sulfur in the coal used will depend on the kind of product being manufactured. "A good sample&apos; of coal commonly used in pottery ovens has something like this quantity of sulfur." PER CENT. Total sulfur 1.20 Sulfur in the ash 0.11 Volatile sulfur a 1.09

Jan 9, 1919

By H. J. Ramey

Conventional calculation of total system isothermal compressibility for a system containing a free gas phase involves, among other things, evaluation of the change of oil and gas formation volume factors and the gas in solution with pressure. Preferably, this information should be obtained from laboratory measurements made with particular oils and gases. Often, experimental measurements are not available. In this case, it is necessary to obtain pressure-volume-temperature relationships from general correlations such as those of Standing&apos; for California oils. In order to speed estimates of compressibility, generalized plots have been prepared of the change of both oil formation volume factors and gas in solution, with pressure from Standing&apos;s correlations. A generalized plot for estimating the change in the two-phase (oil and gas) formation volume factor with pressure is also presented. Usually, the effect of gas dissolved in reservoir water upon the total system compressibility is neglected for gas saturated systems, due to the low solubility of gas in water. Results of this study indicate that the increase in total system compressibility caused by solution of gas in water is often as large as the compressibility of wafer, and can be magnitudes larger for low pressure systems. Generalized results for estimating the change of gas in solution in water with pressure are presented in tabular and graphical form. INTRODUCTION During the past decade, pressure build-up and drawdown techniques have gained an important place in reservoir engineering. Build-up and drawdown analyses are only two special applications of the broad field of transient fluid-flow theory. All solutions of transient fluid-flow problems contain a parameter called the total system isothermal compressibility. This property of fluids and porous rock is a measure of the change in volume of the fluid content of porous rock with a change in pressure, and it may vary considerably with pressure. Evaluation of total system isothermal compressibility is not difficult, but it is tedious and time-consuming. Often compressibilities are estimated roughly, or transient flow methods are neglected completely. The benefits of using accurate system compressibility in properly-executed build-up or drawdown analyses are: 1. Better planning of pressure build-ups may be achieved to avoid unnecessary loss of revenue due to excessively long shut-in periods, or to shut-in periods too short to yield useable data. 2. Better and more reliable estimates of static formation pressures for reserves estimates and rate performance estimates. 3. Reliable information for evaluation of well completion effectiveness, and planning and interpretation of well stimulation efforts. The purpose of this paper is to clarify the nature of the total system isothermal compressibility, and to present useful methods for estimation of compressibility, particularly for systems containing a gas phase. DEVELOPMENT Numerous publications have presented solutions to transient single-phase flow of slightly compressible fluids, stressing pressure build-up applications. In transient flow, a compressibility* term arises to permit volume content of fluids in porous rock to change as pressure changes. The basic nature of the compressibility term is usually taken for granted. Problems arise in practical applications of transient fluid theory because most published works consider only one flowing fluid—in an ideal porous system containing only one fluid. In 1956, Perrine2 presented an intuitive extension of single-phase flow pressure build-up methods to multiphase flow conditions. Later, Martin- established conditions under which Perrine&apos;s multiphase build-up method had a theoretical foundation. Perrine has shown that improper use of single-phase build-up analysis in certain multiphase flow situations can lead to gross errors in estimated static formation pressure, permeability and well condition. It is likely that, much pressure build-up data for oil wells should be analyzed on the basis of multiphase flow. For both single-phase and multiphase build-up analysis, the isothermal compressibility term in dimensionless time groups often should be interpreted as the total system compressibility. All real reservoirs contain one or more compressible fluid phases. In addition, rock compressibility can contribute in an important way to the total system compressibility. The proper total system compressibility expression may contain terms for compressibility of oil, gas, water, reservoir rock and terms for the change of solubility of gas in liquid phases.

Jan 1, 1965

By FREDERICW K. BRADLE

I HAVE been puzzled by two lines of thought&apos;; one emanating from Washington, D. C., to the effect that we must all cheer up, that in a very short time, measured in terms of months, prices would begin to recover, business would become normal, and prosperity would continue on its way just as before the interruption of a year ago; and a second, coming from certain industrialists and economists, expressing fears that all commodity prices were in for a long downward trend, which would cause much unemployment, eventually drag down wages and so restrict purchasing power as to further aggravate the situation. One basis for the fear of a downward trend in commodity prices&apos; is that ifter great wars a depression could last for something like 40 years-the downward trend to such a depression after our recent World War having been postponed for some reason or other; and the basis for another fear was that the production of gold was becoming less. I had &apos;also been trying for some time past to refresh my recollection as to how my ow11 particular lead interest climbed out of the depression of 1893; and as all the metals have had, and still have. relative values and prices, I can best express what I have in mind by talking principally about lead.

Jan 1, 1930

By Dilip K. Das, Douglas T. Pitman

ONE of the major uses of barium in metallic form is as a getter material in vacuum tubes. Because of the high chemical reactivity of the metal, Ba-Al alloys are extensively used. Numerous methods for the preparation of Ba-Al alloys have been published, a few of which1-4 are cited here. Most of these methods were found to be quite elaborate, involving the reduction of BaO, and not too well adapted for the close control of the final composition of small amounts of alloys prepared for laboratory use. A simple laboratory method for the preparation of Ba-A1 alloys in small batches starting from pure metals was devised, so that it was possible to control the desired compositions to within 1 pct. The pertinent features of the alloy system Ba-Al5 are 1) an intermediate compound BaAl, with the melting point of 1050°C, and 2) a eutectic between aluminum and BaAl4 at 98 pct Al. The accompanying sketch shows the experimental arrangement for the preparation of the alloys. Weighed amounts of aluminum and barium were placed in an alumina and a stainless steel crucible, respectively. According to the supplier&apos;s specification, the purity of the metals used in the alloys is as follows: a) aluminum rods—99.9 pct Al, and b) barium rods—99.5 pct Ba. The stainless steel crucible, tapered at the bottom and having a 1/16 in. diam hole, rested on top of the alumina crucible. The assembly was placed inside a graphite sleeve which rested on a refractory platform. The platform moved the assembly up and down through the field of a radio frequency coil. A glass bell jar was placed between the crucible assembly and the radio frequency coil to maintain a steady flow of helium around the melt. A small window was cut out on the wall of the alumina crucible to observe the progress of the re- action and to record the temperature with an optical pyrometer. The platform was first raised high enough to move the barium out of the radio frequency coil field in order to allow only the aluminum to melt. The assembly was then lowered so that the barium began to melt and flow out through the small orifice into the molten aluminum. In order to keep the violence of the exothermic reaction under control, the rate of flow of barium was carefully regulated by raising or lowering the crucible assembly. All the samples prepared by this technique were examined by a Norelco X-ray diffractometer using CuKa radiation, The diffraction specimens were prepared by placing the finely powdered samples in flat specimen holders. The Ba-Al alloys prepared with a high barium content were found to consist mainly of BaAl4. The structure of BaAl4 has previously been reported by Alberti and Andress.8 They found that BaAl4 was body-centered-tetragonal with an a0 = b0 = 4.530Å and c0 = 11.14Å. An alloy whose composition was found by chemical analysis to be almost 100 pct BaA1, was used to determine the relative intensities. The d-spacings were obtained from the same alloy to which a small amount of tungsten had been added as a calibrating material. Accurate values for a, and c, were calculated according to the method proposed by Taylor and Floyd.&apos; The calculated values are: a, = b, = 4.566Å and c0 = 11.250Å. The measured d-values for BaAl4 are shown in Table I along with relative peak intensities above background and hkl indices. Acknowledgment The authors are grateful to L. J. Cronin, the head of the Techniques Dept., for suggesting the problem and for his constant interest. References 1Froges and Camargue: German Patent No. 809107, 1951. French Patent No. 935324, 1949. 2E. Bonnier: Annales de physique, 1953, vol. 8, pp. 259-312. 3M. Orman and E. Zemhela: Prac Institute of Metals; 1952, vol. 4, pp. 437-445. 4E. Fujita and H. Yokomizo: Reports Gov. Chemical Industrial Research Institute, Tokyo, 1952, vol. 47, pp. 291-297. 5E. Alberti: Ztsch. fur Metallkunde, 1934, vol. 26, p. 6. 6E Alberti and K. R. Andress: Ztsch. fur Metallkunde, 1935, vol. 27, p. 126. 7 A. Tnslor and R. W. Floyd: Acta Crystallographica, 1950, vol. 3, p. 285.

Jan 1, 1958

By M. W. BERNEWITZ

ALL live producers and manufacturers of metals and alloys are investigating new uses for their products. The tin and tin-plate industry is no exception. One-third of all the new tin mined and refined is consumed in making tin plate. Several billions of cans are each year made from tin plate for the preservation of nearly 200 kinds of food. There are more than 500 tin-plate mills or individual stacks in the United States, which country makes more tin plate than all other countries combined and exports large quantities. As much as 1,800,000 tons of till plate has been made in a year in this country, and 28.000 tons of tin has been used in this period for this purpose. In sonic years a third of the till is so consumed; in 1933 it was half of the supply.

Jan 1, 1935

By Yuri D. Tretyakov, Robert A. Rapp

The stoichiometry ranges ofNiOl+y and LiFe,O,-d were established by high-temperatwe electrochemical meas7rements in a stabilized-zirconia electrolyte cell. The results were consistent with doubly ionized cation vacancies in NiO,+y and interstitial lithium or iron ions in . The defect structure of the ternary ferrite was derived from the consideration of equilibration with respect to oxygen between the solid and the gas phase. The absolute magnitudes of defect concentrations were calculated. Pavtial molar enthalpies of oxygen in the compounds were calculated and interpreted in terms of the enthalpy of defect formation in these crystals. NICKEL oxide (NiO,,?) is a metal-deficient, p-type, extrinsic semiconductor whose properties are consistent with a structural model based on the presence of cation vacancies as the predominant ionic defect at sufficiently high temperatures and oxygen activities. A survey of previously reported conductivity studies and the presentation of some more recent conductivity measurements will be given in a later paper.&apos; The absolute magnitude of the equilibrium vacancy concentration in NiO has been reported from combined conductivity and thermogravimetric data of &apos; However, disagreement exists concerning the state of ionization of the nickel vacancies in NiO. Some authors3-&apos; have proposed that the predominant defects in NiO are singly ionized nickel vacancies and positive holes (h&apos;) formed by the reaction where, accorhng to the notation of Kroger and Vink,6&apos;7 Oq represents an oxygen ion on its normal lattice site. Other authors"27E have proposed that doubly ionized nickel vacancies (V{i ) and positive holes are predominant and are formed by the reaction One purpose of the present investigation was to establish the nature of the predominant defect in NiO,+? as well as its equilibrium concentration and thermo-dynamic properties at elevated temperatures and known oxygen activities. To accomplish this purpose, the coulometric titration of oxygen into and out of NiO was accomplished using a galvanic cell involving the calcia-stabilized zirconia electrolyte. The ternary oxide, lithium ferrite (LiFe50,-6) is ferromagnetic and has the inverse spinel structure LiFe,O,-d Thus, in the ideal stoichiometric XY204 lattice, Fe3 ions occupy one-eighth of the tetrahedral (A) sites, and i&apos; and Fe3&apos; ions share at random one-half of the octahedral (B) sites within the fcc sublattice of oxygen ions.g The structure and thermodynamics of the spinel structures have been comprehensively decribed.&apos;-&apos; A recent compilation of literature for lithium ferrite is also available. 15 Oxygen-excess LiFe50sis not expected to exist because both i&apos; and 17e3& ions are in their highest normal valency states (positive hole formation is not favorable). As will be discussed, equilibration of the ferrite crystal with oxygen of a surrounding gaseous phase will result in the introduction of equilibrium concentrations of ionic and electronic defects. In the Results and Discussion section a defect model for LiFe50,-d is proposed. This defect model is tested by high-temperature coulometric titration experiments. EXPERIMENT The oxygen activities in nonstoichiometric NiOl+, (and also LiFe,O,-d) were measured by means of coulometric titration with the high-temperature galvanic cell The critical characteristic of a suitable experimental cell is the complete isolation of the phase to be investigated in a minimum sized chamber which is free from extraneous sources and sinks for oxygen (leakage). Then oxygen is only admitted to the chamber or removed from it in known amounts by coulometric titration, which involves the passage of oxygen ions through the solid electrolyte with electrochemical oxidation and reduction reactions at the platinum contacts to the electrolyte. The experimental cell is shown in Fig. 1. The cap of the cell was the tip from a closed-end alumina tube, which was found to be leak-free from a helium leak-detector test. This alumina cap was about 1.2 cm OD and about 1.5 cm high. A Zircoa calcia-stabilized zirconia tablet (crucible lid) of 1.5 cm diam and 0.3 cm thickness served as the solid electrolyte. A Pyrex ring of about 0.1 cm thickness was placed between the electrolyte and the cap. The electrolyte tablet was painted with platinum paste on the entire outer face and on that part of the inner face which would be within the enclosure; these electrodes were further prepared by heating in air at 1000°C for 2 hr. Nickel oxide powder, listed as 99.999 pct pure, was purchased from Leico Industries, Inc. Pills of the NiO were cold-pressed and sintered at 1050°C for 3 hr in a platinum crucible. This poorly sintered NiO was crushed, and chunks were wrapped in 52-mesh Pt gauze (to catalyze the solid-gas exchange) for place-

Jan 1, 1970

By T. L. Joseph, G. Bitsianes

The gaseous reduction of dense iron ore is a topochemical process in which reduction takes place at distinct interfaces between solid phases or layers. Under normal conditions, these interfaces remain parallel to the exterior surface of the ore body as they move inward. Certain conditions, such as cracking, high porosity, impurities, entrapped residual oxides, may cause departures from normal topochemical behavior. THE gaseous reduction of dense iron ore proceeds at interfaces between several solid phases or layers.&apos;,&apos; Under normal conditions, these interfaces progress inward and remain parallel to the exterior surface of the ore body. This topochemical behavior is clearly illustrated in Fig. 1 which shows partially reduced specimens of natural and synthetic hematite. Using a coordinated sequence of macro, micro, and X-ray examinations, the authors1-&apos;2 found that the number of interfaces and participating phases was in agreement with the Fe-0 system. Above 570°C, reduction of the ore involved a maximum of three common boundaries between four solid phases: iron, wiistite (Fe,O), magnetite (Fe,O,), and hematite (Fe,O,). Below 570°C, reduction proceeded through two interfaces between three phases: iron, magnetite (Fe,O,), and hematite (Fe,O,). The decrease in the number of phases below 570°C was due to the instability of wiistite below this temperature. The sequence of phases was also consistent with the equilibrium requirements. For example, the layers of iron oxides that were formed in topochemical fashion were always orientated in the order of increasing oxygen content. Thus, in Fig. 1 an outer layer of metallic iron is followed in turn by a thick intermediate band of black wiistite, by a thin layer of light magnetite, and finally by a relatively large core of hematite. This arrangement of the oxide layers was due to restrictions in reducing conditions which were imposed by the physical structure of the solid. The highly reducing gas on the outside of the particle gradually lost its reducing power as it penetrated into the specimen. On a macro scale, the layers of the various oxides appeared to be sharply defined and uniform in composition. Microexamination of the sections, however, revealed that the interfaces did possess measurable widths which varied with the porosity and chemical activity of the oxide phase undergoing reduction. For example, Fig. 2 shows three interfaces in a dense hematitic ore which was partially reduced at 850°C. At the iron-wiistite interface where the greatest porosity developed, the reaction proceeded over a zone 25 to 30 microns in width. Toward the interior, the interfaces became progressively narrower until at the magnetite-hematite boundary the reaction zone was about 1 micron wide. In this region the structure was exceedingly dense; the hematite possessing a porosity on the order of 3 pct. A careful micro study across polished layers of the various oxides revealed generally homogenous and single-phase structures. As reported in a previous paper,&apos; the wiistite layer was characterized by an increase in oxygen content with depth of penetration. The topochemical behavior of reduction was studied in six types of ore of different origin, composition, and physical structure. In most cases, reduction proceeded at the boundaries of well defined layers or phases, and this behavior may be regarded as normal for most dense fine grained ores. Deviations from Ideal Topochemical Behavior A number of deviations from the normal topochemical behavior were noted. In these cases, the continuity of the reduction interfaces was disrupted in one of four ways: 1—Cracking of the specimen interrupted the geometric configuration, and the interfacial advance was no longer parallel to the exterior surface. 2—As a result of high porosity, the interfaces were spread over an appreciable distance and all but obliterated. 3—Impurities in the ore promoted a variety of deviations, including cracking. 4—A residual oxide phase was entrapped in the reaction product and left behind the advancing macro interface. Results from Cracking: A crack leading into the interior of an ore specimen presents a path of least resistance for the counter-flow of reducing gases and gaseous reduction products. Higher reducing conditions can be maintained along such cracks and reduction accordingly will propagate well ahead of the normally advancing reduction interfaces. Cracking was caused by a number of factors, one of which was the thermal spalling of impurities in the massive form. A more general type of cracking was due to reduction and was found in all dense varieties of natural and synthetic hematite, particularly in the temperature range of 500" to 700°C. The effect is shown clearly in Fig. 3. In this case, a dense sphere of pure hematite was partially reduced at 650°C for 100 min. The macrosection shows that one large reduction crack had penetrated the specimen and disrupted the normal topochemical advance of the interfaces. The outer layer of iron was only slightly affected but the thin dark layer of wiistite, adjacent to the ferrite, had widened perceptibly as it progressed along the crack. Farther inward, the magnetite layer was greatly disrupted and had penetrated irregularly to form islands of unaltered white hematite. A great deal of internal cracking is evident in the magnetite phase. From a practical point of view, the cracking of dense ores in the blast furnace could lead to desirable as well as undesirable effects. The general result

Jan 1, 1956