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By John T. Norton

N order to attempt to arrive at a better under-Jl standing of the whole basic problem of sintering, these remarks will serve as an introduction for discussion that is included and will, perhaps, help to isolate specific questions which need to be answered or to suggest some definite avenues of investigation which should be followed. To bring some sort of logical order into the presentation, I will consider the various types of interaction between the metal to be sintered and the atmosphere which surrounds it, depending upon whether the phenomena are essentially chemical or physical in nature. For example, when the only necessary criterion for the satisfactory sintering of a certain powder is the removal of an oxide skin, then the problem of choosing a suitable atmosphere is primarily chemical; however, if a special surface condition as a consequence of the oxide skin removal is necessary for particularly effective sintering, then the problem becomes a physical one. Of course, the two aspects overlap considerably, but it may be possible to make a distinction in principle if not in practice. The chemical characteristics of the phenomena will be emphasized, since these are the better known. Metal-gas reactions involved in sintering are controlled primarily by the thermodynamics of the processes involved. In which direction will a reaction go and how far before it stops? The answer is to be found in the magnitude of the free energy change associated with the reaction. If a constituent is to be removed from the specimen as completely as possible or if a constituent is to be formed in the specimen as completely as possible, then one chooses conditions which are far from equilibrium so that the reaction is driven toward completion. On the other hand, if the composition is to be maintained at a desired value, then conditions are adjusted as closely as possible to the equilibrium point. This aspect of the problem is susceptible to quite precise analysis, provided, of course, that the significant reactions can be recognized and the required thermodynamic data are available. Conversely, if one asks how fast the reaction goes or how far it proceeds in a given time, the answer is frequently much more difficult to answer in quantitative terms. Yet the rate-con trolling factors of the reactions may be of primary importance in the success of a particular operation, especially where competing processes are at work. Both equilibrium and rate factors must be understood if a clear picture is to be obtained. For instance, in a process for carburizing titanium dioxide, is the difficulty of obtaining a stoichiometric Tic due to a true limitation of the equilibrium or simply to a very slow rate of reaction? An example of this appears in the work of Kalish and Mazza.' They showed that the oxygen content of sintered iron compacts was lower when sintered in pure hydrogen than in the case where the hydrogen was diluted with either argon or nitrogen. The equilibrium oxygen content of the iron would be the same in the two cases, since it is determined by the ratio of the partial pressures of water vapor and hydrogen and this pressure ratio is unchanged by dilution. The rate of oxygen removal, however, under the conditions of a constantly replaced furnace atmosphere, depends upon diffusion and thus upon the concentration of hydrogen in the furnace atmosphere. Possibly the clearest way to illustrate the interplay of these two factors is to consider in more detail some of the typical metal-gas reactions. Adsorbed Gases It is common experience that fine metal powders with their very large surface areas often contain large quantities of gas. This gas, which results from exposure to air or perhaps from some step in the

Jan 1, 1957

By E. J. Ripling, M. W. Toaz

Tensile tests were conducted on pure magnesium and on four commercial alloys over a variety of temperatures and strain rates. The high positive slope of the ductility vs testing temperature curves that is found over a short range of testing temperatures for these materaturerials was shown to result from the fact that the microstructure was not stable at these testing temperatures. Pure magnesium did not display a transition temperature, although its sub-room temperature ductility was low. This poor ductility resulted from a grain boundary weakness. The aluminum-bearing commercial magnesium alloys had a higher ductility than the pure magnesium. ness.Thealuminum-bearingcommercialThese alloys did exhibit a transition temperature and grain boundaries that were stronger than the grain material. Both pure magnesium and the commercial alloys began initiating cracks at strains equal to one half of their fracture strain. MAGNESIUM base alloys' enormous potential as structural materials lies in their high strength to weight ratios. At present, the high strength magnesium base alloys such as AZ-80, which will be discussed later, have about as high a tensile strength to specific gravity ratio as the highest strength wrought aluminum alloy, 75s-T6, and, of course, a much higher strength to weight ratio than structural steel. Further, since the magnesium base alloys develop their high strength to weight ratios with moderate strengths and extremely light weights, the ratio of load carrying capacity to the weight of many structures is relatively higher for the magnesium base alloys than their strength to weight ratios would indicate. This results because judicious increases in section size, such as increasing the depth of bending members or adding reinforcing ribs, can frequently increase the weight of a structure linearly while the strength and stiffness increase as the second or third power of the added weight. Strength and rigidity must be designed into lightweight structures by those techniques which establish multiaxial stress states. Consequently, strong, lightweight structures frequently also possess a greater propensity toward brittle failures. In order to insure against these catastrophic failures, an extra premium must be placed on ductility and toughness in light alloys. Current knowledge of the ductility and toughness behaviors—notched behaviors—of magnesium base alloys is limited.* Most of the magnesium base alloys * The state of present knowledge regarding the effect of testing temperature on mechanical properties has recently been summar-ized by Pritchard.' crystallize in the hexagonal system, so that they are expected to exhibit a tough and ductile to brittle transition temperature. Actually, a transition temperature behavior has been reported for commercially pure magnesium in the literature, but the characteristics of this transition temperatureh uggest that it may not be a transition in the usual meaning, but simply the onset of some thermal softening, a performance much like that which face-centered-cubic lead might exhibit slightly below room temperature. If transition temperatures do exist, such important questions as the manner in which they are affected by internal variables such as chemical composition and grain size, or the effect of external variables such as rate of straining or notch severity have never been investigated. The investigation reported upon herein was undertaken in order to define some of the mechanical behaviors of the magnesium base alloys better, to gain a better understanding of the influence of some of the above listed variables, and particularly to understand their effect on ductility and toughness better. Material and Procedure Material-—Pure magnesium and four commercial alloys were used in this investigation. The alloys were selected so that chemically they made up a series with approximately the same minor alloying

Jan 1, 1957

By K. Leutwyler

The key to realistic casing stress analysis in thermal recovery installations is accurate knowledge of the temperatures involved. Much information leading to prediction of heat losses from tubing string to wellbore has been published. This .same information permits calculation of casing temperature under certain conditions. This paper reviews the basis for most of the published work, the line source solution to the diflusivity equation and examines some of its application criteria in the light of unsteady-state conditions. An alternate finite differences method is presented for correlation, and experimental data pertaining to the heat transfer mechanism in the annulus is reported. In the light of the information presented in the paper, it appears that the assumption of a line source for the tubing-wellbore system is valid even for reasonably short periods of heat flow, .such as "steam soak" operations. The empirically modified equation presented earlier matches computer derived results of the finite differences approach lor periods as short as 50 hours. Previously predicted cas ing temperatures and the associated stress levels are thus verified based on these correlative computations and the reported experimental information. Fall out from the computer output resulting in some studies of the influence of insulating cement properties on casing temperature, and experimentally studied effects of nitrogen placed in the annulus at various pressures., are described. INTRODUCTION Generally speaking, predictions of average casing temperatures have been based on an idealized model involving a centralized tubing string at uniform constant temperature radiating energy towards the casing under steady-state conditions.'. ' Heat is transferred away from the casing to the formation by unsteady-state conduction across thermal barriers consisting of cement and the mud sheath. Heat balances written on the casing permit prediction of instantaneous casing temperatures. During early periods of injection, casing temperature varies appreciably as a function of time; however, for long injection times this variation decays as heat flow from the wellbore to the formation stabilizes, and it becomes virtually negligible as conditions surrounding the wellbore become quasi-steady-state (Fig. 1). Carslaw and Jaeger -escribe a solution to the diffusivity equation for a line source (Fig. 2). A constant supply of heat is introduced into the medium from the line placed into the origin of the x-y coordinate system and parallel to the z-axis. Heat spreads outward in the infinite cylindrical solid and the temperature increase on a line going through point (x, y) parallel to the z-axis at a distance r can be predicted by: The following criterion must be considered: the Carslaw and Jaeger equation is obtained on the basis of a large

Jan 1, 1967

By W. G. Davenport, M. Paneni

Experiments in sheets of mercury and water have confirmed that the dynamics of bubble rise are simi-lur in Liquid metal and aqueous systems. RECOGNITION that bubble/metal interactions are important in pyrometallurgical refining processes (e.g., steelmaking, vacuum degassing, deoxidation of copper) has led to a number of investigations into the dynamic behavior of bubbles rising in liquid metals. Terminal velocities of bubbles rising in mercury (20°C)' and silver (1000" to 1050"c)1,2 have been measured. Good agreement between aqueous and liquid metal systems has been obtained. Shapes of air bubbles rising in mercury have been determined experimentally by Davenport, Bradshaw, and Richardsonl who used a system of electric probes to measure maximum horizontal and vertical dimensions, Fig. 5. In the present work the motion and shape of nitrogen bubbles rising in a thin sheet of mercury (i.e., a "two-dimensional" environment) have been studied with the view of confirming dynamic similarity between aqueous and metallic systems. The use of thin sheets of liquid permitted direct visual and photographic comparisons of bubble behavior in clear liquids and in mercury. EXPERIMENTAL METHOD The thin sheets of mercury or water were held in a clear acrylic plastic container, Fig. 1. The sheets of liquid were 80 cm high by 30 cm wide and 0.47 cm thick. Single bubbles were formed by injecting the desired volume of nitrogen into an inverted semicircular cup (stainless steel). The cup was then rotated into the upright position using an external handle thus releasing a single bubble of measured volume. Nitrogen was injected into the cup from a nitrogen cylinder through the external handle and a hollow rotating axle. The volume of a bubble (volume range 0.01 to 10 cu cm) at any instant was obtained by connecting a soap film meter to a small gas space above the liquid. By this technique any change in the volume of a gas bubble in the liquid (i.e., during cup filling or during rise) produces an equivalent displacement from gas space A into the buret B. This displacement is determined by measuring the movement of a horizontal soap film in the buret. Bubble shapes were determined using single-frame photography. Rising velocities were determined by cinephotography with a 1/100-sec stopwatch in the field of view. In both cases dimensions were referenced to a rule attached to the container surface, also in the field of view. Linear dimensions were measured on projections of the single-frame negatives. Rising velocities were calculated from measured heights of rise (10 to 20 cm) and times of rise. The effects of disturbances caused by cup rotation and by bubble release were minimized by photographing bubbles at a point not less than 25 cm above the cup. MATERIALS Mercury: Technical-grade purified: minimum 99 pct Hg; Johnson Matthey and Mallory Limited, Toronto. Nitrogen: Technical-grade purified nitrogen: 99.99 pct Nz, 0.01 pct 02, trace argon; Air Liquide Canada Limitee, Montreal.

Jan 1, 1970

By John Nunes, Frank R. Larson

Temperature-dependent functions of various ten-sile flour stress and fracture parameters were investigated on iron and low composition alloys of Fe-C, Fe-Cr, Fe-Mn, and Fe-Ni. Data were obtained over a range of test temperatures from 200" to -196"C at an initial strain rate of 0.01 min". It was found that the strain-hardening exponent, n, for the Fe-Ni alloys increased significantly at very low testing temperatures with increased alloy addition. Also, the stress and strain at fracture followed a predictable transitional type of behavior. The flour stress-temperature dependence was evaluated employing the relation: M where it is shown that composition can strongly influence the constant M. An empirical formula describing this effect is as follows: M = MI (equivalent at. pct Ni)-'" Some preliminay, tests were run on several commercial steels to test the generality of this relationship. One of the phenomenological explanations of the ductile-to-brittle transition encountered in bcc metals is based upon the difference in the temperature dependence of the flow and fracture stresses.' It states simply that the fracture stress is relatively insensitive to temperature and that the yield or flow stress rises rapidly with decreasing temperature so that, when the flow stress reaches the fracture stress, brittle fracture occurs without appreciable plastic deformation. This behavior is illustrated schematically in Fig. 1 where the ductile-to-brittle transition is shown to occur at two possible temperatures. The lowest temperature, TB, represents essentially completely brittle behavior while the higher temperature, TN, represents "notch" brittle behavior. Support for this theory is obtained when it is observed that fcc metals, which do not commonly have a ductile-to-brittle transition, also do not commonly exhibit any strong temperature de- pendence of the yield stress. This relationship of yield or flow stress behavior with the ductile-to-brittle transition has been generally observed for most metals representative of these two crystallo-graphic structures. One exception to this generalization appears in the case of tantalum where no apparent ductile-to-brittle transition has been observed. However, this may simply be an indication that this type of behavior is not directly related to the flow stress and that some other mechanism such as twinning must also be operative. A comparison of the typical temperature dependence of the yield stress of some representative metals is shown in Fig. 2. In the study of the temperature dependence of the strength of metallic materials, considerable ef-

Jan 1, 1963

By P. Sanchez-Mejorada

GEOLOGISTS who are acquainted with the mines of northeastern Mexico realize that the most important lead-silver replacement deposits of the province are confined to a single formation. But since the formation is several hundred meters thick, the author has determined the relative position of the lead mantos in the belief that this information will prove useful in the search for new mines. This article describes the stratigraphic location of lead-silver replacement deposits known in several mines situated in a region comprising part of the states of Coahuila and Nuevo Leon. The area studied extends for 200 km* (125 miles) from east to west and 70 km (45 miles) north to south. Metallogenic Province: The most important metallic deposits of the region have the following common characteristics: 1) The orebodies occur as manto replacements of calcareous sediments. 2) The horizons that have contributed large tonnages of ore are in similar positions in the corresponding stratigraphic columns (as it will be shown later on). 3) Lead is the most important metal in the ores. Silver is commonly present in small amounts. Occurrence of zinc is dependent on the degree of oxidation of the primary sulfides. 4) A large proportion of the total production has been in the form of oxidized ores. 5) The deposits are located on anticlines. Rocks of Cretaceous age crop out over large areas of the states of Nuevo Leon and Coahuila. forming part of a belt that extends to the south along the eastern Sierra Madre. The sediments are cut by a small number of intrusive stocks ranging in characteristics from rhyolite to diorite. The most prominent structural feature of the region is a series of folds trending northwest-southeast. Faulting is not conspicuous in the region, although a major fault zone is found farther East.' The physiography closely reflects structural features, with mountains formed by anticlines and valleys conforming with intermediate synclines. Narrow valleys have also been developed along the axes of many anticlines, where solution of limy sedi- ments and erosion have proceeded along axial tension fractures. Stratigraphy: Rocks of the Upper Cretaceous are exposed in only a small percentage of the total area. Generally they have been eroded away from the mountains and are covered by recent talus and alluvium in the valleys. Humphrey' has published an excellent paper describing the Cretaceous formations of the Sierra de los Muertos, a short distance west of Monterrey. A brief summary of these formations is given below to convey an overall picture of the stratigraphic sequence that prevails just south of the area under consideration. Upper Cretaceous Indidura: Essentially thin shaly sediments. Cuesta del Cura: Limestone in thin wavy beds

Jan 1, 1959

By L. M. Kaas

Production planning techniques, particularly a production scheduling model are proposed for use in taconite mining in Minnesota. Applications of the scheduling model, on a two-year mine plan, which evaluates the equipment involved, are detailed. Data and tables are included. INTRODUCTION Fifty years ago Walter Swart, a mining engineer investigating the Minnesota taconites for the Jackling interests, made this report: "There is no doubt in my mind that this taconite mining is a game worth playing and that it can be played to a successful finish. It seems now only a question of men, money, methods and details."' The prosperous industry envisioned by Swart and other taconite pioneers is today a reality. Its growth has been spurred by technological advances in mining and beneficiation, depletion of natural ore reserves, and improvement of the economic climate. However, the massive problems that were solved to make this development possible are only a foreshadowing of the questions of "men, money, methods and details" that will be encountered in the future. The increasing demands for higher quality taconite pellets have already forced producers to examine better methods of quality control for their operations. THE NEED FOR PRODUCTION SCHEDULING The maintenance of fairly constant crude ore characteristics is of major importance to mill quality control. Through careful mixing of ore from storage bins, the concentrator staff can partially reduce the deviations of the feed analysis from the analysis desired. However, the limited effectiveness of bin mixing systems has caused some mining companies to utilize large capacity blending piles to reduce grade variations. Although the analysis of material being reclaimed from such a pile is relatively uniform, raw materials still must be scheduled from the mine into the pile in such a manner that the average analysis of all material is close to the feed analysis prescribed by the mill. PRODUCTION SCHEDULING MODEL Minnesota taconite mining companies have used three analyses to estimate how a certain ore will react to concentration. These factors are the crude magnetic iron content of the ore, the iron content of the plant concentrate produced from the ore at a standard grind, and the grindability index of the ore. The actual laboratory tests used to determine these factors have been described by Apuli.2 These data are obtained from analysis of diamond drill cores, and are the established criteria used by mine planning engineers to formulate taconite production schedules. Variations in the grade of mine output should be controlled by any production scheduling system. However, to be truly practical, production scheduling methods must also consider many of the less tangible variables that affect mine operation. These include pit layout, available equipment, and ownership of ore leases. The number and scope of the variables inherent in this type of mine planning suggested that a computer simulation could be used to solve the problem. The preparation of information for use with a computer simulation program was the initial phase of this project. Meaningful data was developed from logs of diamond drill cores. Analyses were related to their respective areas of influence by means of mine maps, Fig. 1. The three assay variables and tonnages for each area were punched on cards. In addition to these values, a location code number was punched in the first eight columns of the cards. This code is explained as follows: Column 1 Bench number Column 2 Quadrant location as determined by mine reference lines Columns 3-5 East-west coordinate Columns 6-8 North-south coordinate The heart of any simulation techniques is a well engineered mathematical model. To develop a model for taconite production scheduling, the relationship between the three assay variables had to be established. Because changes in each analysis factor affect the mill circuits in different manners, a weighting system was used to determine the relative im-

Jan 1, 1967

By F. J. Chernosky

Most previous studies of coal flotation utilized chemically pure reagents. Since such reagents are not available in quantity, a study of various wmmercially available reagents as frothers was undertaken. Flotation procedures similar to those used in a large number of commercial coal flotation plants were employed. The reagents used were compared on yield-selectivity-wst basis. The selectivity was found to be relatively constant with yields above 70% but the reagent cost varied greatly. The types of reagents available were compared. In the past, a number of papers have been written on the use of various reagents as coal flotation frothers. For the most part, these have been an attempt to correlate the intrinsic chemical and physical proper- ties of the reagents or reagent groups to the floata-bility of various fine coals. Because of the type or nature of evaluations made, chemically pure reagents were normally used. Generally, these reagents are unavailable in commercial quantities. Therefore, the results obtained with these reagents were usually limited in usefulness to the plant operator or metallurgist. This paper presents the results of a study in which commercially available forms of various reagents were used as flotation frothers. Flotation procedures which would conform in general to those employed in a large number of commercial coal flotation plants were utilized. The objective of the test was to compare these reagents on yield-selectivity-cost basis, that is, 1) the yields obtained, 2) the ash levels obtained and 3) the reagent cost relating to these results. REAGENTS The reagents employed have been grouped into the following chemical classes: 1) aliphatic alcohols, 2) terpines, 3) glycols (synthetic water-soluble

Jan 1, 1963

By S. C. Sun, A. M. Gaudin

This paper presents the results of a. study of the relationship of the electrokinetic or zeta potential to flotation phenomena. The relationship is established on the experimental evidence that mineral behavior in flotation and in cataphoresis is generally governed by the chemical properties and amount of the reagents adsorbed at mineral surfaces. Cataphoresisl-5 or electrophoresis is the name given to the movement of a charged particle in a liquid medium under the influence of an applied electric field. Mineral behavior in cataphoresis, as indicated by the magnitude and sign of its ionic charge, can be represented by the term zeta potential. In this paper, the zeta potential represents the difference in potential between the immovable liquid layer attached to the surface of a solid particle and the movable liquid layer in the body of the liquid, and is the result of the tendency of ions on the surface of the particle and within the liquid boundary layer to establish a condition of equilibrium. A high positive zeta potential means that the mineral surface is dominated by cations, a high negative zeta potential indicates domination by anions, and a low zeta potential indicates that the surface is influenced almost equally by cations and anions. In terms of observed quantities the zeta potential is given by the relation _ 4µ(300)² Z= kx in which z is the zeta potential expressed in in volts, µ the viscosity of the solution in poises, u the velocity of particles in centimeters per second, x the impressed potential gradient in volts per centimeter, and k the dielectric constant of the solution in c.g.s. units. A convenient source for the derivation of the equation is the book by Thomas. The term zeta coefficient is an expression coined to denote the difference between the magnitude of the zeta potential of a mineral suspended in solution A, and that of the same mineral suspended in solution B, which consists of solution A and an additional chemical agent, but is at the same pH. For example, the difference between the zeta potential of galena particles in distilled water and that in any chemical solution at the same pH is a zeta coefficient. Or, when the zeta potential of a mineral particle is measured first in distilled water, then in a mixture of water and copper sulphate, and finally in a mixture of water, copper sulphate and xan-thate, we can calculate the zeta coefficient

Jan 1, 1947

By A. M. Gaudin, S. C. Sun

This paper presents the results of a. study of the relationship of the electrokinetic or zeta potential to flotation phenomena. The relationship is established on the experimental evidence that mineral behavior in flotation and in cataphoresis is generally governed by the chemical properties and amount of the reagents adsorbed at mineral surfaces. Cataphoresisl-5 or electrophoresis is the name given to the movement of a charged particle in a liquid medium under the influence of an applied electric field. Mineral behavior in cataphoresis, as indicated by the magnitude and sign of its ionic charge, can be represented by the term zeta potential. In this paper, the zeta potential represents the difference in potential between the immovable liquid layer attached to the surface of a solid particle and the movable liquid layer in the body of the liquid, and is the result of the tendency of ions on the surface of the particle and within the liquid boundary layer to establish a condition of equilibrium. A high positive zeta potential means that the mineral surface is dominated by cations, a high negative zeta potential indicates domination by anions, and a low zeta potential indicates that the surface is influenced almost equally by cations and anions. In terms of observed quantities the zeta potential is given by the relation _ 4µ(300)² Z= kx in which z is the zeta potential expressed in in volts, µ the viscosity of the solution in poises, u the velocity of particles in centimeters per second, x the impressed potential gradient in volts per centimeter, and k the dielectric constant of the solution in c.g.s. units. A convenient source for the derivation of the equation is the book by Thomas. The term zeta coefficient is an expression coined to denote the difference between the magnitude of the zeta potential of a mineral suspended in solution A, and that of the same mineral suspended in solution B, which consists of solution A and an additional chemical agent, but is at the same pH. For example, the difference between the zeta potential of galena particles in distilled water and that in any chemical solution at the same pH is a zeta coefficient. Or, when the zeta potential of a mineral particle is measured first in distilled water, then in a mixture of water and copper sulphate, and finally in a mixture of water, copper sulphate and xan-thate, we can calculate the zeta coefficient

Jan 1, 1947

By R. H. Winn

A method for the selection of the most suitable corrosion inhibitor for a particular system is given. The method involves the evaluation of surface passivity by means of copper ion displacement after the metal surface has been subjected to the corrosive atmosphere. The application of the method to the selection of suitable inhibitors for use in producing wells is described. Correlation with recognized laboratory tests has beet1 found to be good within the limitations of the test. The use of the test to evaluate inhibitor persistencc is described. INTRODUCTION Corrosion as it is associated with the industry shows wide variations in its qualitative as well as its quantitative aspects. This complicates the work of the corrosion engineer. In the past few years the efforts of the corrosion engineer have been further taxed by the large numbers of products being marketed as corrosion inhibitors by various manufacturers. These products are submitted to him together with a limited amount of data to support their use as inhibitors. The data are usually authentic and reliable yet all too often when these products are applied to an actual corrosive system the results are disappointing due to the ineffectiveness of the inhibitor and the corrosive system. The corrosion engineer must select a comparatively limited number of inhibitors for field trial from the large number available. The selection is usually made on the basis of a standardized laboratory test such as that adopted by the National Association of Corrosion Engineers or by field experience in an area; however, testing of this type is discouraging on large numbers of compounds, particularly in view of the specificity of environment. It has been an object of this work to devise a method which will allow the corrosion engineer to select the best inhibitor for a specific environment under field conditions. The test would of necessity be rapid and inexpensive. It would preferably eliminate the need for expensive and delicate instruments. STATEMENT OF THEORY The test as developed makes use of the fact that metal ions will be displaced from solution by metals having a more positive electrode potential. Thus, if an active iron surface is exposed to a solution of a copper salt, free copper will plate spontaneously on the iron surface as it is displaced from the salt solution by iron ions. If the iron surface is passified, as by coating with an insulating-type organic corrosion inhibitor, it is no longer capable of displacing the copper ions due to its own limited ionization. The result will be a change in the amount of copper plated upon exposure to a neutral copper salt solution. In practice it has been found possible to measure the magnitude of the alteration of the cell potential by determining the copper deposited on a standard iron surface under controlled conditions. This means that, as the film builds up, the resulting shift in the electrode potential tends to cause the iron surface to act more like a noble metal, resulting in a reduction in the cell potential to a point that copper will no longer plate spontaneously. Obviously, the salts of other metals such as silver, gold or platinum might be used for this operation; however, copper was selected because of the color difference of the plate, the comparatively low cost of copper salts and the ease of evaluation of the plated copper. Furthermore, its high cell potential provides a substantial driving energy. The determination of the copper is readily done colorimetrically by dissolving it in 5 per cent ammonium hydroxide solution containing 2 per cent potassium per-sulfate. The blue color of the copper ammonic complex ion so developed may be compared with standards prepared by dissolving known quantities of copper powder in the same reagent. In routine screening it is seldom desirable to determine the amount of copper plated. It is usually more important to determine the concentration of inhibitor required to prevent the plating of copper.

By J. W. MacDonald

Review of equipment, performance, and shaft design plans including head-frames for sinking and forms for lining are given. Also included are comparative data for shafts of 11 x20 ft and 193/4 x 30 ft with 756 and 666-ft depths, respectively. Advantage from curtain wall installation with "slip forms" which warrant consideration for normal lining are outlined. A preliminary review is also made of "chemical grouting" to stop water inflow leakage with Halliburton equipment and service. Two coal mine shafts recently completed in Franklin County, Ill., afford experience and accomplishment to warrant review. These shafts provide access to a tract with a potential recovery of one hundred million tons. This work provided the initial sinking by other than a contractor's organization since 1918. Four additional shafts required during the interim were sunk under contract arrangement with others. Supervisory contact and inspection afforded experience to govern planning and conduct of the recent work. TEST DRILLING Core test holes were drilled within each of the two shaft locations. Four additional cable tool holes were drilled on a radius of 700 ft from the shaft bottom to determine the coal seam elevations and govern the underground layout plans for each shaft. A graphic log of the hoist shaft test drillhole is shown by Fig. 1. A very soft sandstone was found at a depth of 16 ft. Cored recovery of the sandstone proved much weaker than the overlying compacted sand secured with coring facilities for soil recovery. Gradation from the very soft sandstone to fairly hard material occurred with the next 14 ft, extending to a depth of 30 ft. The weak character within the upper portion entailed need of adequate protection when sinking as described later. A part of the sandstone provided sufficient porosity and permeability to warrant further investigation. Adjacent cable tool drilling for temporary water supply disclosed inflow was limited to 2 gpm with a depth of 40 ft. It was increased to 12 gpm during the next 50 ft of drilling and occasioned subsequent precaution when sinking. General arrangement of facilities for sinking the hoist shaft is shown by Fig. 2. An available steel frame building was used to accommodate the hoist, compressor, shop, and shower or change room. The stiff leg derrick with 90-ft length of boom permitted removal of forms from the wood shop to the storage area or delivery within the shaft. Reinforcing steel and other needs were similarly handled, in addition to headframe erection. The headframe was placed over one end of the shaft to enable passage of forms for lining through the adjacent half next to the stiff leg derrick. The steel headframe as shown by Fig. 3 was fabricated locally. Side anchored cables from the

Jan 1, 1961

By H. J. de Haan, L. Schenk

Scope for Thermal Recovery in Shell's Heavy Oil Fields in Venezuela The main heavy oil reservoirs on the East coast of Lake Maracaibo (Fig. I), known as "Bolivar Coast", initially contained some 20 billion bbl of oil in place with gravities in the range of 10 to 15° API. The current total production rate is about 400,000 B/D. Since the recovery to date is on an average only 12.5 percent of the initial oil in place, these fields offer a vast potential for secondary recovery methods. The reservoirs are characterized by moderate depth (generally 1,000 to 3,000 ft; maximum 5,000 ft), good formation properties such as net oil sand thickness (50 to 300 ft), high porosity (30 to 40 percent) permeability (1 to 3 darcies) and oil saturation (initially about 80 percent) and high oil viscosity (100 to 10,000 cp in situ), all of which are favorable for the application of thermal recovery processes. Since 1957, steam drive, steam "soak" and underground combustion have been tested or are being tested in this area.1-3 This paper deals with a major steam drive test in the Tia Juana field. The test was commenced in Sept., 1961, on the basis of encouraging results of laboratory experiments and pilot field tests, which will be discussed briefly. Early Laboratory Investigation of the Steam Drive Process In 1956 a series of model experiments was carried out in the Koninklijke/Shell Laboratorium, Amster- dam, to investigate the displacement of heavy oil by steam.' The prototype studied was a horizontal, un-consolidated heavy oil reservoir, subjected to a linear steam drive. The model, representing a slab from this reservoir along the main flow direction, consisted of a steel tube filled with oil-saturated sand, provided with layers of rock at the top and bottom to simulate conductive heat losses to cap and base rock. Lateral heat losses, perpendicular to the main flow direction, were minimized by insulating the sides of the model. Heat flow and viscosity and gravity forces were scaled by taking the steam injection rate and sand permeability inversely proportional to the geometric reduction factor of the model, and using materials (oil, steam, cap rock, etc.) identical with those of the prototype. The main feature of the process was a frontal displacement mechanism that was observed within wide ranges of injection pressure and rate, oil viscosity, initial oil saturation and sand permeability. The high stability of this front can be attributed to the high volumetric steam flow rates, combined with the reduction in oil viscosity. High recoveries were obtained due to the low residual oil saturation of about 15 percent in the zone swept by steam. The latter value pertains to the specific test conditions (heavy oil, uncon-solidated sand) and may be lower for light oil, due to the effects of steam distillation. The applicability of this experimental approach is limited, as it does not take into account the fact that

Jan 1, 1970

By S. Ramachandran, N. J. Grant, T. B. King

MANY investigations of the rate of the sulfur transfer reaction between carbon-saturated iron and blast furnace type slags have been made." It is evident that the reaction is complex, the rate being affected by the presence of elements dissolved in the metal that are readily oxidized and therefore capable of existing in the slag phase. Thus Goldman, Derge, and Philbrook- have shown that carbon, silicon, manganese, and aluminum, in order of increasing effectiveness, accelerate sulfur transfer from iron containing these elements to blast furnace type slags. Quantitative information is still, however, not available on the relation between what have been termed side reactions, such as silicon transfer and CO evolution, and the sulfur transfer reaction itself. In other words, the stoichiometry of the reaction has not been investigated. In the present investigation, the transfer of all reacting elements and the evolution of CO have been measured simultaneously in order to establish the mechanism of the reaction which occurs in practice. Information of this nature cannot be deduced from equilibrium studies. It should be pointed out that in kinetic studies of this type quantitative conclusions are applicable only to the system studied. This restriction should be borne in mind when attempts are made to compare results from different investigations. Apparatus The apparatus used enables slag and metal samples to be taken at frequent intervals and also provides a continuous record of the amount of gas evolved. A sketch of the apparatus is given in Fig. 1. It may be considered in three sections: 1) furnace section, 2) blank volume section, and 3) pressure measuring section. The furnace section is shown in detail in Fig. 2. It consists of two graphite crucibles, C and D, super-

Jan 1, 1957

By U. N. Bhrany, N. Arbiter

Over the last one hundred years the problem of assessing the efficiency of energy consumption in producing rock breakage has been studied by many investigators from a variety of viewpoints. Their contributions fall into three main categories: (1) those characterized by a priori assumptions of a relation between the energy required for fracture and the degree of fragmentation produced (e.g. Rittinged(l), Kick(2) Bond(3)); (2) those studying simple systems with controlled energy applications (Gross(4)?(5) ); (3) those treating operating data to develop practical relative measures of efficiency (Coghill(6), Taggart(7)). Closely involved in the efficiency problem is the characterization of size distributions produced by comminution. Unless an experimental size distribution can be approximated by a distribution function and its constants, it becomes difficult if not impossible to develop quantitative energy-particle size relationships. While many such functions have been proposed, none are both completely adequate and convenient. The simpler fonns usually describe only a part of the sizing data, while those which apply to a greater extent are cumbersome(8). The thesis underlying the study here reported can be stated as follows: Size reduction in a tumbling mill subjects ore particles to a relatively constant fracture-producing environment. The intensity of the forces is determined by such factors as the mass of the breaking bodies (rods, balls, rock), and the speed and dimensions of the shell. For a particular ore the extent of size reduction will depend both on the intensity and on the duration of exposure. The latter is the residence time in a batch mill, or is determined by the effective volume and the flow rate in a continuous mill. Size reduction can thus be regarded as a rate process in which the weight of material in size intervals varies as a function of grinding time. Although both the rates of disappearance of coarser sizes and

Jan 1, 1961

By J. W. Mills

In 1956 the discovery of nickel on Jumbo Mountain, Snohomish County, Washington, focused attention on this part of the Cascade Range, far more renowned for its timber than for its mineral resources. Hand specimens assaying as high as 13 pct Ni encouraged Discovery Mines Inc. of Mount Vernon, Wash., to stake 12 claims in Township 31 North, Range 9 East of the Willamette Meridian. The property was leased to Climax Molybdenum Co. in January 1957. Trenching, sampling, and geologic studies were carried out during the late summer of 1957 when most of the snow had disappeared. Although the deposits are only about four miles south of the logging town of Darrington and about two miles. as the crow flies, southeast of the end of a good gravel road from that town, all camp supplies and equipment were air-dropped, owing to the extremely rugged nature of the terrain. GEOLOGY The rocks of Jumbo Mountain comprise a series of folded Tertiary sediments forming a belt one half to three quarters of a mile wide, trending northwest about parallel to the strike of the beds. This belt is sandwiched between two extensive in-trusives—gabbro on the northeast and quartz dio-rite on the southwest—and has been intruded by dikes of fresh and serpentinized dunite. Shear zones follow many of the dunite-sedimentary rock contacts, and in these the nickel mineralization is concentrated. A few transverse faults offset the sediments and ultrabasics. Sedimentary Rocks: Two kinds of quartzite make up the greater part of the sedimentary section. One is dark purplish gray, very fine-grained, and thin-bedded; the other is light gray to white, medium-grained, and well-bedded. Locally the light-colored quart lites contain grit and conglomerate horizons, rich in pebbles of white chert and very fine-grained quartzite. Intercalations of dark argillites near the summit of the mountain give many of the cliffs a striking banded appearance. Dark gray to black, aphanitic, thin-bedded argillites occur throughout the entire sedimentary belt. Beds vary from a few inches to a few tens of feet thick and some, near the summit, contain numerous fossile (willow?) leaves. Only the thicker beds were mapped. The sediments are quite fresh on the northeastern side of the belt and become more metamorphosed (hornfelsed) toward the southwestern side. Brown biotite is present in the metasediments in increasing amounts as the quartz diorite is approached. Near the intrusion, porphyroblasts of plagioclase, up to 1 in. across, testify to the soaking of sedimentary rocks by solutions emanating from the quartz diorite. Most of the sediments mapped lie along the southwestern limb of an anticline, the axis of which follows the crest of the mountain and plunges at a low angle to the northwest.

Jan 1, 1961

By T. K. Perkins, L. R. Kern, R. E. Wyant

Many factors influence the results of hydraulic fracturing to stimulate well productivity. Most of these factors have been studied and their effects discussed in the literature. However, the movement of sand through the crack during fracturing has received little consideration. Exactly where the sand goes in the fracture, how it gets there, and how this might influence results have not been studied, judging from published reports. To get an answer to some of these questions we have studied sand movement through a simulated crack segment in the laboratory. Although the work is preliminary, we have answered some questions about sand movement in a semiquantitative sense. We are reporting our results at this time in the hope of stimulating interest and further study in this important aspect of fracturing. LABORATORY EXPERIMENTS Fig. 1 is a schematic diagram of equipment used in this study. A segment of a vertical crack 0.25-in. wide was formed between two Plexiglas plates, and movement of sand in fluid through the crack was observed under various conditions. Sand and fluid were injected into the crack at constant rates. The top and bottom of the crack were closed so that the fluid flowed horizontally. Because of gravity most of the sand settled to the bottom before moving very far through the crack. If the fluid velocity exceeded a certain critical value, then all the sand injected was washed on through the crack even though it had settled to the bottom. When the fluid velocity was less than this value when sand injection was started, most of the sand which settled in the crack remained in place until enough of the area open to fluid flow was blocked by the settled sand to increase the fluid velocity to the critical value.. At this point all injected sand moved on through the crack even though it settled to the lower portion of the moving fluid section. All sand previously settled remained in place. When fluid velocity was increased at this paint by increasing fluid injection rate (without also increasing sand injection rate), some of the previously settled sand was washed out until enough area was open to flow that the velocity dropped to the critical value. Conversely, when the fluid velocity was decreased by decreasing the fluid injection rate (without changing the rate of sand injection), additional sand would settle until the critical velocity was again attained. In short, the critical velocity is an equilibrium value which the system will automatically seek, if possible. The equilibrium (or critical) velocity was measured under several conditions. The results of these measurements are shown in Pig. 2 where the equilibrium velocity is shown as a function of the amount of sand injected per minute. The points falling in the shaded band shown in Fig. 2 were obtained with water. The higher viscosities were obtained by adding CMC (carboxymethylcellu-lose). Data indicate that the equilibrium velocity is not very sensitive to sand size or transport fluid viscosity, or to sand injection rate (except at very low rates). Points connected by the solid CUrve in Fig. 2 were obtained with water and 20- to 40-mesh steel shot. The equilibrium velocity is apparently fairly sensitive to difference in density between particle and fluid. Only one run was made with a gelled fluid and that was gelled water at zero sand injection rate as shown in Fig. 2. (Measurements of equilibrium velocity at zero sand injection rate were made by filling the crack

By L. B. Davidson

The petroleum literature contains many reports on the relative permeability properties of porous media. However, only recently have studies of relative permeability at elevated temperatures been made.1 -5 Each of these studies presents relative permeability data on water-oil systems in linear sandpacks or sandstone cores under isothermal conditions. The results of these investigations are dissimilar. Edmondsonl found that in Berea sandstone a temperature-dependent effect was present, while Shilobod,2 using the same material, found no temperature dependence after normalizing for initial water saturation. Workers at Texas A&M U.3-5 found that the ratio kw/ko was temperature dependent in an unconsolidated system. The differences in results of these studies are probably a consequence of differences in the material employed, in the experimental procedures followed, and in the properties of the porous systems used. This paper describes an experimental investigation of permeability ratio temperature dependence, conducted to clarify some of the results obtained by previous workers. Each experiment described in this paper involved the isothermal displacement of Chevron No. 15 white oil by either nitrogen, steam, or distilled water and displacement of water by nitrogen. All permeability ratios were calculated using the Welge procedure. Values of the water-oil permeability ratio were obtained over the temperature range 75OF to 540°F. Results indicate the ratio is temperature dependent at low water saturations, probably due to interfacial effects. However, as the saturation is increased, temperature dependence decreases until, above some minimum saturation, the ratio becomes insensitive to temperature. Previously published work indicates that the dependence reappears at very high water saturations, a region of the ratio curve not completely examined in the present study. It appears that water-oil permeability ratios are temperature dependent at the extremes of the ratio curve where changes in interfacial tension with temperature induce variations in residual saturations. Between the extremes, there is a region in which the permeability ratio is insensitive to temperature. The size and location of this region is probably a function of the characteristics of the porous system. Gas-oil permeability ratios calculated from nitrogen-white oil displacement experiments indicate a definite temperature dependence over the range 75OF to 500°F and over the entire gas saturation range studied. Evidence discussed in this report indicates that this dependence is a consequence of molecular slippage in the gas phase. This is an extension of the Klinkenberg effect6 to two-phase systems at high temperatures (the existence of slippage in two-phase systems at room temperature has been demonstrated7). Evidence for a similar source of temperature dependence in superheated steam-white oil experiments

Jan 1, 1970

By Charles E. Wait

It is said by some that the occurrence of a deposit of sulphide of antimony in Southwestern Arkansas has been known for fifteen or twenty years. Whether or not such is the case I am not prepared to say, but I am not able to find any record of such a discovery, or any analysis of antimony ore obtained from that section, published at so early a period. The present discoveries, that seem to be attracting some attention, date back to the winter of 1873-74. At that time a vein of ore was found by Mr. Robert Wolf, in honor of whom the vein was named, and still is called, "the Wolf lode." At the time of the discovery the ore was unknown to the prospector, and its composition was not thoroughly understood in that locality until samples were sent to several analytical chemists, who pronounced it sulphide of antimony—stibnite. Since the discovery of this ore there have been three mines opened, and a number of interesting minerals of the antimonial series have been found. I have had an unusually good opportunity to collect specimens from these mines; and it is owing to the constant inquiry concerning the character of these ores that I have collected for publication the results of quite a number of analyses, sufficient I trust to clearly point out their composition. This is one of the few localities in the United States where antimony ore is found in workable quantities ; I say workable quantities, because two different shipments of ore have been made to English reduction works, and in both cases excellent returns were made. The discovery of these deposits will, it is hoped, give rise to a prosperous and remunerative industry at no distant day, and when fully developed they may yield ore in sufficient quantity to supply the regulus for the home demand, thus adding wealth not only to those interested, but also to the State of Arkansas. The three mines are situated in the northern part of Sevier County, and may be reached by the St. Louis, Iron Mountain and Southern Railway to Fulton, thence by wagon-road to Columbus, Nashville, Centre Point, and to the mines. During most seasons of the year the

Jan 1, 1880

By J. Gurland

The effect of four different second-phase additions on the strength of composite alloys with a common matrix was investigated. The four compositions each consisted of 85 pct by volume of silver with additions of 15 pct of either tungsten, molybdenum, tungsten carbide, or nickel. These particular additives were chosen because of their low mutual solid solubilities with silver at room temperature, the alloys consisting essentially of a dispersion strengthened silver matrix in which the second phase is distributed randomly. Test specimens were prepared by a powder metallurgy procedure consisting of ball milling the mixed powders, compacting, and sintering at 920°C for 1 hr in hydrogen. The constituent powders were of CP quality and of particle size between 2 and 10 ?. The compacts were subsequently hot pressed at 1000 psi and 1400° in an Inconel die, coined at room temperature at 60,000 psi and finally annealed and outgassed in vacuum at 800°F. The microstructures of the alloys are shown in Fig. 1, and the microscopically observed porosity grade was A-2 or better as evaluated by ASTM Recommended Practice B 276-54. The properties of the sintered compacts are listed in Table I, and the load-deformation curves in bending are shown in Fig. 2. The samples, of rectangular cross section, were loaded at the center of 58 in. span, and the reported stress was calculated on the basis of linearly elastic behavior in order to allow the comparison of specimens of slightly different dimensions. It is apparent that the tungsten, molybdenum, and tungsten carbide alloys exhibit very similar deformation curves. The moduli of elasticity were determined from the slopes of the stress-deflection curves at small loads. The measured values agree quite well with those calculated by the strength of materials approximation proposed by Paul1 for the elastic constants of mixtures, the calculated values being 15.0, 15.0, 17.4, and 13.4 million psi, respectively, for the tungsten, molybdenum, tungsten carbide, and nickel combinations with silver. The strength of the Ag-Ni composition is appreciably lower than that of the other three alloys. The discrepancy between the two groups is accounted for by the following characteristics of deformation and failure which were observed microscopically during the tests: A) The deformation of the W, Mo, and WC alloys did not involve the second phase particles to any appreciable extent. Slip and fracture took place in the silver-rich matrix alone, although the fracture path generally skirted the particles by favoring the phase boundaries. The deformation proceeded according to the following sequence: 1) formation of small, discontinuous microcracks in areas of the matrix adjacent to a particle, 2) general slip in the matrix and extension of cracks, 3) failure of specimens by propagation of cracks through matrix. The near coincidence of the 3 load-deflection curves suggests that the nature of the second phase particles does not decisively influence the plastic behavior of composite alloys of this composition as long as the particles do not undergo any considerable deformation themselves. B) A markedly different behavior was exhibited by the Ag-Ni composition where the relatively low flow strength is associated with the low yield strength of the nickel grains. Slip in the nickel grains was first observed at a stress of approximately 10,000 psi, although failure, at a later stage, took place by the propagation of cracks through the matrix. The ductility of this aggregate, in which both components deform plastically, is appreciably greater than that of the elastic-plastic composites. In summary: 1) The measured values of the moduli of elasticity of the composite alloys under discussion are in good agreement with the "strength of materials" approximation proposed by Paul.' 2) The overall plastic behavior of these particle-strengthened alloys is unaffected by the nature of the second phase particles, if the latter remain elastic. This work was supported by the Office of Naval Research. The experimental results are presented

Jan 1, 1962