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By R. Van A. Mills

ONE of the most important problems facing the petroleum industry is the profitable recovery of oil that is left underground by the ordinary methods of production. It is true that vast quantities of oil are being recovered from fields previously considered depleted by the pressure restoration method, the most widely applicable -and most successful means of obtaining greater recoveries that has thus far been, developed. But notwithstanding the progress that is being made in the field applica¬tion of this method there is urgent need for a better understanding of the fundamental principles that are involved. To meet this need the Petro¬leum Experiment Station of the U. S. Bureau of Mines at Bartlesville, Okla., during the past two years has conducted a series of intensive laboratory and field investigations. The larger part of the work has been carried on in the laboratory to supply the much needed information upon fundamental principles, information which few if any of the oil companies are in a position to supply for themselves. In all of this work the Bureau is endeavoring to correlate the results of laboratory investigations with those in the field, using the results of one to guide or check the other. This paper is primarily a progress report, briefly outlining the Bureau's methods of study, the laboratory and equipment in use, the preliminary problems that had to be solved in order to attack the major problems at hand, the methods of attacking some of the major problems, and some of the results of the investigations to date.

Jan 1, 1928

Tourism is the second largest industry in the Tasmanian copper mining center of Queenstown, Australia, but it is not the historic mine the tourists come to see. The attraction is rather the devastation the mine has brought to the surrounding countryside which has made Queenstown literally the most colorful mining town in Australian history.

Jan 6, 1972

By Joseph Richards

PLATING iron with copper has received great attention from practical sand scientific men, but, aside from the deposit secured by immersion of iron in copper salts, by electro-plating, or by welding together thin sheets of iron and copper, these efforts have met with no success. Failure of these efforts, in the production of copper plating, has been due to the fact that the conditions normally and necessarily present in the plating operation are antagonistic to the production of copper-plated iron. In most, if not quite all of them, a bath of molten copper has been used. The-temperature of a molten copper bath is so high that the iron becomes oxidized before it can be immersed in the molten copper, and unless protective flux for the molten copper is used, the surface of the copper will become oxidized, and, in any event, the plated iron will oxidize immediately on its being withdrawn from the molten bath. I recently had the pleasure of visiting the works of The Metals Plating Co. at Elizabeth, N. J., where I witnessed the plating of iron sheets with copper by a new process.1 The plating metal is applied to the sheet in the form of a liquid mixture by means of rolls, such as inking rolls. The sheet, after being coated with the mixture, is automatically carried forward and deposited on a link-belt conveyor, which carries it through a furnace maintained at a. temperature well above that of molten copper. The basic principle involved in this method lies in the application of the plating metal to the sheet while the sheet is cold and then melting the metal in place on the sheet under conditions which are favorable to the formation of the plating.

Jan 1, 1919

By C. R. Kuzell

STAFF: Editor, Gerhard Derge Carnegie lnstitute of Technology Schenley Pork Pittsburgh 13, Pa. Editorial Assistant, M. A. Redmerski Production Editor, Otto T. Johnson THE METALLURGICAL SOCIETY: C. C. Long, President; John Chipman, Past-President; J. S. Smart, Jr., Vice-President, T. D. Jones, Treasurer; R. W. Shearman, Secretary. PUBLICATIONS COMMiTTEE OF THE METALLURGICAL SOCIETY: D. J. Carney, Chairman; Robert Maddin, Past-Chairman; J. H. Hollomon, J. H. Jackson, H. H. Kellogg, T. B. King, F. C. Langen-berg, D. L. McBride, W. O. Philbrook, J. S. Smart, Jr., R. L. Smith, J. D. Sullivan, and F. L. Vogel Review and selection of manuscripts is under the supervision of the following Publications Committees: Extractive Metallurgy Division: H. H. Kellogg, Chairman; T. 8. King, Post-Chairmon; R. P. Hermsdorf, W. A. Krivsky, R. E. Lund, C. L. McCobe, Poul Queneou, A. 5. Russell, M. E. Wadsworth, and W. D. Wilkinson. Institute of Metals Division: R. L. Smith, Choirman; P. A. Beck, I. I. Bessen, J. O. Betterton, Jr., R. S. Davis, J. J. Gilmon, R. 8. Gordon, C. D. Graham, Jr., R. W. Guard, J. C. Gurlond, J. J. Heger, M. Hermon, J. N. Hobstetter, H. H. Johnson, Jr., I. R. Krarner, W. C. Leslie, R. A. Meussner, R. R. Nosh, G. E. Pellissier, T. N. Rhodin, A. U. Seybolt, L. L. Seigle, I. S. Servi, P. G. Shewmon, L. Slifkin, J. K. Stanley, C. D. Starr, and J. Washburn. Iron and Steel Division: F. C. Longenberg, Chairmon; H. L. Bishop, C. W. Sherman, J. 8. Wagstaff, and E. Whittenberger. Published bimonthly by the American lnstitute of Mining, Metallurgical, and Petroleum Engineers, Inc., 29 West 39th Street, New York 18, N. Y. Telephone: PEnnsylvania 6-9220. Subscription $20 per year for nan-AIME members in United States and North, South, and Central America; $25, foreign; $5 far AlME members. Single copies, $4.00, single copies foreign, $5.00. The AlME is not responsible for any statement mode or opinion expressed in its publications . . . Copyright 1960 by the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc. . . . Registered cable address, AlME New York ...Indexed in Engineering Index, Industrial Arts Index, and Chemical Abstracts ... Second class postage paid at New York, N. Y., and Ann Arbor, Mich. Volume 218, Number 4

Jan 1, 1961

By R. A. Salathiel, A. D. Kaiser, P. H. Monaghan, B. E. Morgan

The productivities of many hydrocarbon-bearing for-rnntions appear to be reduced during drilling, completing and repairing operations. The reason for these othcarwise unexplainable low productivities may be a drastic reduction of formation permeability immediately surrounding the borehole. A possible cause of the reduced permeability is swelling and dispersion of clays present in porous media when contacted by fresh water or mud filtrates. Hence, the invasion of fresh water or mud filtrate into hydrocarbon-bearing formations that contain clays may cause low productivities as a result of formation damage. Present laboratory investigations have yielded results which supplement existing literature on formation damage. An expanded-type clay, montmorillonite, way found in hydrocarbon-bearing formations not previously analyzed. When sand columns and formation cores containing montmorillonite were contacted by fresh water, their oil permeabilities were reduced. This reduction in oil permeability way restored partially but not completely by a repair procedure, i.e., flooding with kerosene containing organic agents or flooding with water containing electrolytes. Hence, where montmorillonite is present in formations, prevention of formation danzage was indicated to be the only complete solution to the problem. To prevernt formation damage, results suggested use of an approximately 1 per cent solution of calcium chloride or stronger solutions of sodium or potassium chloride. In conventional rotary drilling operations the wall of the hole is exposed to drilling mud for days, weeks, and in some instances for as long as several months. During this time, drilling mud filtrate seeps slowly into formations surrounding the hole. The permeability and stability of many formations, especially those containing clayey materials, are impaired by the mud filtrate. Often interaction between the mud filtrate and the formation causes drilling and production difficulties. Serious reduction in productivity of oil and gas formations during drilling, completing and repairing wells has been noted often in recent years. Cases are known of development wells which produced only small volumes of fluid upon completion. However, after a period had elapsed, they began to produce oil or gas in commercial quantities. In other cases, results of drill-stem tests taken during the drilling of deep wells have indicated good production should be obtained from shallow formations. Later difficulty has been experienced in obtaining production from these shallow formations which had remained in contact with drilling muds for an extended time. In yet other cases wells have failed to attain the productivities expected from previous performance after the use of drilling mud as a circulating fluid during workover operations. It is evident from the field behavior cited that the productivities of certain oil- and gas-bearing formations have been damaged by exposure to drilling muds. This reduction in well productivity, called "formation damage", causes serious consequences. In development wells, expensive remedial operations are incurred. In wildcat wells, good formations may appear to be marginal or even non-productive. The importance of formation damage has been recognized by a number of investigators1-s who have considered the effects of fresh water, saline solutions and aqueous mud filtrates on the permeabilities of formations. A general conclusion from such studies is that interaction between water and formation clays reduces permeability of reservoir rock and that the permeability decreases as salinity of the water decreases. Data in these references, however, concern the permeability change with only a single fluid present. A more pertinent and direct consideration in the production of oil and gas from wells is the permeability change when two fluids, oil and water, are present. Recognizing this, Nowak and Kreuger2 and Bertness1" considered several ways in which mud filtrates and saline solutions caused reductions in the oil permeability of formation cores. Investigations discussed here were designed to supplement information in the literature on changes in oil

By R. F. Nielsen, D. E. Menzie

The object of this study was to determine if crude oil could be produced successfully by a process of crude oil vaporization using carbon dioxide repressuring. This process appears to have application to highly fractured formations where the major oil content of the reservoir is contained in the non-fractured porosity with little associated permeability. Crude oil was introduced into the windowed cell and carbon dioxide was charged to the cell at the desired pressure. A vapor space was formed above the oil, and the crude oil-carbon dioxide mixture was allowed to come to equilibrium. The vapor phase was removed and the vaporized oil collected as condensate. Samples of all produced and unproduced fluids were analyzed. Tests were also performed to evaluate the amount of vaporized oil that can he produced by rocking from a high to a lower pressure. The carbon dioxide repressuring process was applied to a sand-filled cell to investigate the performance in a porous medium. A test was performed to evaluate how the condensate recovery changes as the size of the gas cap in contact with the oil changes. INTRODUCTION This study has been directed toward a relatively new process of vaporization of crude oil designed to increase ultimate production of hydrocarbons through the application of carbon dioxide to an oil reservoir. Suggested advantages of carbon dioxide repressuring of a petroleum reservoir are: (1) reduction in viscosity of liquid hydrocarbons due to the solubility of carbon dioxide in crude oil, (2) swelling of the reservoir oil into a larger liquid-oil volume with a resulting increase in production and decrease in residual oil saturation due to an increase in the relative permeability to oil, (3) displacement of more stock-tank oil from the reservoir since the residual liquid is a swelled crude oil, and (4) gasification of some of the hydrocarbons into a carbon dioxide-hydrocarbon vapor mixture. Balanced against these advantages are several detrimental factors which must be evaluated; i.e., high compression costs and corrosion of well equipment and flow lines. Some of the more outstanding contributions to the study of carbon dioxide injection have been reviewed in order to furnish a basis for a continuation of research pertaining to this method. The literature reviewed1-8 has been limited to that dealing with carbon dioxide repressuring processes or with carbon dioxide-crude oil-natural gas phase behavior. Articles relating to carbonated water injection and literature published on the use of low pressure carbon dioxide gas injection in water flooding have not been included in this study. In 1941 Pirson5 suggested the high pressure injection of carbon dioxide into a partially depleted reservoir for the purpose of causing the reservoir oil to vaporize and thus produce the oil as a vapor along with the carbon dioxide gas. By reducing the pressure on this produced mixture of hydrocarbons and carbon dioxide at the surface, it was proposed to separate the hydrocarbons from the carrier gas. He theorized that essentially all the oil in a reservoir could be produced by simply injecting enough carbon dioxide to vaporize the residual oil. This present investigation deals with the vaporization of a crude oil by carbon dioxide, the molecular weight and gravity of the vaporized oil product and the characteristics of the residual oil after several repressuring cycles with carbon dioxide. An attempt is made to evaluate the merits of a vaporization process for the crude oil rather than a flow process where the oil recovery is determined by relative permeability considerations. Such a vaporization of crude oil by carbon dioxide repressuring appears to have possible use in a highly fractured formation where the major oil content of the reservoir is contained in the non-fractured porosity with little permeability. The carbon dioxide flows into the fractures, contacts the crude oil in the matrix and vaporizes part of the crude oil; this vaporized oil is produced and recovered and the carbon dioxide is reinjected again. The specific problem of this study is to attempt to answer this question; Can crude oil be produced successfully (technically, but without economic considerations) from a petroleum reservoir by a process of vaporization of the crude oil by carbon dioxide repressuring? DEFINITION OF TERMS AS APPLIED IN THIS STUDY Carbon Dioxide Contact: One cycle in which carbon dioxide was injected and bled off. Condensate: The hydrocarbon liquid which was condensed out of the mixture of hydrocarbon-carbon dioxide vapor upon reduction of the pressure of the vapor. Hydrocarbons Produced (HCP): All the hydrocarbon!, which were vaporized by the carbon dioxide repressuring process and were removed from the cell during any specific cycle or carbon dioxide contact. Hydrocarbons Unproduced (HCU): All the hydrocarbons which were not vaporized by the carbon dioxide

By W. G. Pariseau, C. H. Schmuck, Fei Duan

The Homestake Mine is located in steeply dipping Precambrian metasediaents, an environment common to a number of world class ore bodies. Development of a pronounced plane of schistosity raises a question concerning the importance of anisotropy to the design of vertical crater retreat stopes. Little is known about the actual influence of elastic anisotropy in such -circumstances; even less is known about strength anisotropy. A cautious step- by-step approach was therefore taken towards a numerical assessment of the role of anisotropy in the analysis of stress and stability. The sequence of analyses begins with elementary test problems for computer program checks and proceeds to the analysis of a study stope area between the 6950 and 7100 Levels of the Homestake Mine. Anisotropy (orthotropy) is important at the Homestake Yine. No simple guidelines for evaluating in advance the need for plastic and strength anisotropy in design analysis appear to be forthcoming, ;o that some physical properties testing is necessary where the question is in doubt

Jan 1, 1984

By L. B. Slichter

It has been estimated that rock exposures in most mining districts aggregate less than 1 per cent. of the total surface area.1 Conclusions concerning the hidden 99 per cent. necessarily have been based on knowledge of only a small fraction of the surface, and from this limited information the geologist has been obliged to deduce the approximate and general nature of the underlying formations. In the search for ore it is necessary to supplement this general picture with greater detail. Fairly accurate knowledge of relatively small zones is required. This knowledge is carefully sought in many different ways—detailed interpretations of geological history, the tracing of float, the use of test pits, of trenching, of drilling, and of other methods. Practical ingenuity, scientific brilliance, great perseverance and patience, and the expenditure of large sums of money have all been a part of this search. The problem of exploring beneath cover with economy, and of obtaining essential information which this cover hides, is obviously a difficult one. It is also a very important one, for geologist's inform us that already the story of the 1 per cent. exposed outcrops has been largely read.V here remains the nearly virgin field comprised in the hidden 99 per cent.: and the importance of this zone is bound to increase continually. In recent years, the problems connected with the exploration of this "99 per cent. zone" have attracted a constantly enlarging group of investigators and at present greater efforts than ever before are being made to resolve them. This work, in it's various special aspects, has enlisted, beside geologists, the cooperative efforts of chemists, physicists, and mathematicians. The progress made in this development should be kept before those directing explorations in order that due advantage may be taken of a changing situation. My subject concerns certain aspects of one of the older physical methods of exploration, the magnetic method. This method is familiar in principle to most of us, arid because of its age., is especially suitable for

Jan 1, 1929

By Robert Mehl

METALLURGISTS are properly interested in papers dealing with subjects ranging from the theories of the metallic state to very practical details on the use of metals. A review of theoretical metallurgy naturally excludes papers concerned with the usefulness of metals and limits itself to those concerned purely with the science of metals. Even in this more limited field the reviewer is confronted with thousands of papers dealing with facts and theories of metallic behavior, from which he can select only a few hundred. The selection is necessarily highly arbitrary. Certain classes of papers definitely fall within the scope of this review. Thus, papers on the deformation of metals, on the structure of alloys, on recrystallization, to select only a few, are fully represented. Other subjects, which verge on what is generally accepted as the science of metals, such as the magnetic properties of metals, the less familiar electrical properties and theories, adsorption of gases by metal surfaces, and the like, are treated scantily. Particular attention is given to reviews of subjects that fall with in the groups chosen; in a summary such as this, which is largely in the nature of a progress report, capably written reviews are of importance, particularly since the monograph and text book literature is so meager in this field.

Jan 1, 1935

By G. H. Kessler

ALTHOUGH considerable attention has been devoted to reaction mechanisms and equilibria of a number of endothermic reactions through which metals or their refractory compounds can be formed upon heated surfaces, only a comparatively small amount of work has been done to develop rate information for these systems. The interestin and very worthwhile work of Holden and Kopelman, Runnalls and Pidgeon,Dijring and Moliere, and Herrick and ICrieble4 is to be noted; however, their work was done under very specific conditions and the rate information which they have developed is not applicable to many systems which have been studied experimentally. That a more generalized approach is needed is shown by the diversity of these systems and of the experimental conditions which they require. These include the preparation of titanium, zirconium, tungsten, molybdenum, chromium, co-lumbium, aluminum, and silicon by decomposition or disproportionation of their halides, in some instances through hydrogen reduction; the preparation of nickel and iron by decomposition of their car-bonyls; and the preparation of copper by decomposition of the acetylacetonate. They may be carried out at temperatures ranging from 100" to over 2000°C and at pressures of from less than one mm Hg to superatmospheric. The physical mechanism of the overall process can be broken down into several steps, any one of which may be rate-determining; and the rate associated with each of these basic physical processes can be predicted. Consequently, by proper application of the present technology of rate processes, it is possible to arrive at a rate of metal deposition in the system of interest and to reach an understanding of the influence of' each major variable upon the deposition rate. It is the purpose of this paper to illustrate how this can be done and to present experimental results for a specific system for comparison with theory. The overall process of deposition of metal upon a heated surface which is immersed in vapors of a compound of the metal can be broken down into the following steps: 1) Transport of the reactant vapors to the surface. 2) Decomposition of the reactant in the immediate vicinity of the surface to a) establish chemical equilibrium if reaction rates are high; or to b) establish a dynamic equilibrium in accordance with the several reaction rates. 3) Diffusion of reaction products away from the vicinity of the surface, with or without simultaneous recombinations to form still other products. The overall process is said to be diffusion controlled if Step 1, or the equivalent Step 3, is slow; it is reaction-rate controlled if Step 2b is slow. When experimental evidence shows the reaction rate to be controlling, the well-known theories of Eyring' and others can be used as a basis for correlating and extrapolating the experimental data. Although these theories give only approximate estimates of reaction rates, they are of considerably greater value in correlating experimental data. Most deposition systems operate at surface temperatures sufficiently high that reaction rates near the surface are very high. Mass-transport rates then become controlling; and it is this regime of diffusion controlled rates which is most often of concern and Which will be considered here. When the system pressure is very low, i.e., in the micron range, then the transport processes are those of molecular movement, and the results of kinetic theory can be applied to specify a rate of arrival of reactant molecules at the heated surface. If the condensation coefficient can be estimated, then the deposition rate will be given by the product (rate of arrival) x (condensation coefficient), Conversely, experimental data can be used to determine a condensation coefficient, as was done by Holden and Kopelman' for the decomposition of zirconium tetraiodide upon a heated molybdenum surface, who found the coefficient for zirconium on molybdenum to be 1.0 at temperatures of 1382°C and above. In this pressure range, the geometry of the system. and in particular the distance between the source of reactant molecules and the heated surface, can exert a considerable effect upon the deposition rate;

Jan 1, 1961

By Sidney Siegel, J. Gardner Brooks, Irvin R. Kramer

IN 1942 Grossmann1 proposed that the hardenability of a steel may be calculated from its chemical composition by considering the base hardenability associated with its carbon content and grain size and multiplying this base by factors for each element present. Since Grossmann's original publication, several investigators2-5 have reexamined the multiplying factors for the individual elements and in general have found that the multiplying principle is valid. However, some of the individual factor curves developed have been in poor agreement. Inasmuch as the carbon-factor curve obtained by Grossmann was dependent [ ] upon the factors for all the other alloying elements present in the steel, it logically followed that his results were in need of correction in the light of the new data available for manganese, silicon, and the other alloying elements. Furthermore, in order to avoid the possibility that errors in the manganese, silicon, or other curves might influence the carbon-factor curve, investigation of iron-carbon alloys containing little or no manganese and silicon was necessary. That the effect of carbon on hardenability was greater than indicated by Grossmann is shown by a comparison of the diameters of completely hardened rounds of iron-carbon alloys with the ideal critical diameter calculated from Grossmann's factors. These alloys have a greater hardenability in a hite quench than predicted by Grossmann's factors for an infinite quench (Table I). [ ] Among the other important variables that were in need of further investigation were the effect of deoxidation practice on the grain-size correction curves and the effect of stable carbide-forming elements on the depth of hardening. Most of the work by Kramer, Hafner, and Toleman4 was done on silicon-killed steels. It was not known whether Grossmann's grain-size correction curves, deter- mined on aluminum-killed steels, was valid when applied to steels with different deoxidation practice. More data on the

Jan 1, 1946

By H. R. Wuthrich

The Metallgesellschaft AG decided in late 1965 to build an Electrolytic Zinc Plant at Datteln (W. Germany). Lurgi-Chemie was entrusted with the engineering and erection of the entire plant. Ground was broken in February 1967 and the operation was started on August 1st, 1968. The new Electrolytic Zinc Plant was designed to produce a minimum of 100,000 metric tons of special high grade zinc and 200,000 metric tons of sulphuric acid. Concentrates from Meggen (W. Germany) and mainly Timmins (Canada) are roasted in two turbulent layer roasters. The sulfur dioxide containing gases are converted in a "Bayer double catalysis unit" to sulfuric acid. The calcine is leached batch wise, the leach residue separated from the pregnant solution by counter-current thickeners and drum filters. For maintaining the sulfate balance a modified jarosite leach is being used. After a two step purification the neutral solution is mixed with spent electrolyte and cooled in unpacked atmospheric cooling towers. Three electrical circuits are supplying the power to the tankhouse, each rated at 30,000 amperes. With a maximum current density of 750 amperes per square meter and a stripping cycle of 24 hours, an average current efficiency of 90 percent is obtained. Cathodes are melted in one induction furnace and cast into shapes, or alloyed with aluminum and copper for die-cast metal.

Jan 1, 1970

By H. I. Meyer, D. F. Searcy

INTRODUCTION The analysls of our previous paper' on the behavior at two immiscible fluids separated by gravity into two dlstinct saturated zones in the porous medium was shown to be theoretically valid only if one of the two fluids was immobile. The practical problems associated with flow of both phases have so far been impossible of solution by these analytic methods. We, therefore, decided to resort to a simulator study to answer the following pertinent questions: 1. If the lighter fluid is produced from a point above the fluid-fluid interface, how long will it take for the heavier fluid to come up to the point where production of both fluids is taking place? 2. After steady-state two-phase production is established, what is the relative production rate of each phase, on what physical variables does this depend, and what are the boundary conditions at the outflow face? 3. A third question was at least partially answered in the course of this investigation: that of the shape of the interface under flow conditions. These questions are of fundamental importance in the fields of hydrology and the reservoir mechanics of oil and gas production. In order to simplify equipment used and still retain a fair physical representation of these phenomena, it was decided to use a Hele-Shaw type of analogy in which the flow took place between two vertically mounted pieces of plate glass. The advantage of this system is that it eliminates any surface effects between the matrix of the porous medium (e.g. packed sand) and also allows equilibrium conditions to be established more quickly. The principle disadvantage (apart from the obvious one of being one more step removed from the prototype) is that our equipment limited us to two dimensional flow studies. In spite of these limitations answers to the questions were obtained which seem adequate for our purposes. We would like to see more work of this nature done to verify and to improve our conclusions. DESCRIPTION OF EQUIPMENT AND PROCEDURE A drawing of the equipment used in this study is shown in Fig. 1. Fluid flow takes place between the two 36 in. x 12 in. pieces of plate glass held apart at the long edges by two spacers of cellulose acetate sheet (Kodapac IV) which is available in several thicknesses. This sandwich was clamped together by small c-clamps whose stress was distributed by long pieces of 3/8-in. keystock. Accurate spacing was obtained by tightening these clamps as indicated by micrometer measurements on the outside of the glass. At the upstream end of the plates a piece of 6-in. diameter pipe simulated an infinite reservoir, while at the downstream end a 2-in. Lucite cylinder with a small hole near the top of the flow region served to drain the fluid. Sealing was achieved by O-rings, the whole system being tightened by pressure on the Lucite tube provided by set screws (not shown in the drawing). The total head

Jan 1, 1957

By A. U. Seybolt, V. A. Phillips

Binary iron alloys containing 1 pct of Al, Cr, Mn, Mo, Si, Ti, or V, and 0.4 pct C, 1 pct Cr steels with and without 1.2 pct A1 or 2.0 pct Ti additions, were ion-nilrided at 550° to 600° in N-H mixtures. Nitriding increased the inicrohardne ss of all the binary alloys except those containing manganese or molybdenutn, and also hardened the heat-treated steels if aluminum or titanium urns present. Transmission electron microscopy revealed particle formation in all casts where hardening occurred. Electron diffraction gare positive identifications for ALN, CrN, and a, Si3N4 in the binary alloys, and AlN and CrN in the aluminum- cold chromium-bearing steels, respectil&apos;uly. Cubic VN with a, = 4.13A was tentatively identified. Particles, apparently of CrN, also formed in the base steel but did not increase the hardness very much. Chromium and vanadium formed nitride platelets on {001}° matrix planes, while titanium gave clusters <15A diam. Aluminum nitride precipitated at grain and subgrain boundaries, and within the grains. Silicon gave profuse precipitates of several Morphologies at grain boundaries and cubical particles within the grains. No effect of the alloy carbides on nitride precipitation was observed in the heat-treated steels. THE nitriding of steel has been a well-established commercial process for about 40 years, but in spite of this comparatively long period of use there have been few studies aimed at understanding the process. Most studies, like the early but very competent work of Jones and organ&apos; and nones.&apos; were concerned with establishing the pertinent engineering variables of steel composition, gas composition, temperature, and time. As far as the present authors are aware, there have been no studies of the composition, size, shape, or distribution of the nitrides formed in the nitriding of steel. Noren and Kindbom3 did, however, examine a few nitrided steels by surface replica electron microscopy, and were able to show the presence of car-bonitrides and AlN and TiN nitrides. pitsch4,5 and Hrivnak6 examined nitrided pure iron by transmission electron microscopy. Baird7 found manganese nitrides in Fe-1.6 pct Mn when nitrided at 650°C, using the same technique. In the present work, emphasis was placed on transmission electron microscopy because of its inherently better resolution, using principally binary alloys of iron containing 1 pct of alloying element. In addition, a few simple 0.4 pct C steel compositions were examined to investigate possible carbonitride formation. It was not anticipated that all of the added elements would form nitrides under the conditions used, but it was considered desirable to obtain direct experimental evidence on this point. It would be considerably easier to ascertain the presence of alloy nitrides by examining appropriate binary alloys in preference to relatively complex steels. The work reported here could have been done using orthodox ammonia-nitriding procedures, but an operating ion-nitriding equipment was available, and was therefore used for specimen preparation. EXPERIMENTAL DETAILS 1) Materials. Binary alloys were made up from vacuum-melted electrolytic iron with 1 wt pct additions of Cr, Ti, V, Al, Mn, Mo, and Si of about 99.9 pct purity. In addition, three steels were similarly made up—a basis steel with 1 wt pct Cr and 0.4 wt pct C and two steels with further additions of 1.2 wt pct A1 or 2.0 wt pct Ti, respectively. The materials were vacuum-melted and cast as 11-lb heats into tapered square molds of about 2 by 2 in. average cross section. The castings were forged and hot-rolled to 11/4 in. rounds. Discs of 4 in. thickness by about 1 in. diam were machined from the rods. Some of these discs were hot-forged and hot-rolled to about 0.020 in. thick, sand-blasted, and then cold-rolled to about 0.003 in. thick. At this point, the surface was cleaned by light etching with HC1, then washed, dried, and vapor-degreased prior to nitriding. 2) Ion-Nitriding Procedure. The type of ion-nitriding equipment used here is similar to that described by Jones and Martin.8 Briefly, a mixture of nitrogen and hydrogen at 5 mm total pressure is placed in a vacuum chamber with a dc potential of 450 to 500 v applied between the work (cathode) and the grounded metal vacuum enclosure (anode). Nitrogen ions are accelerated to the work where a thin layer of Fe4N forms on the surface and thus sets up a nitrogen concentration gradient. This causes nitrogen atoms to diffuse into the surface layers of the alloy forming a finely divided dispersion of alloy nitrides, causing hardening of the surface. In the work to be reported here. the nitriding was carried out at 550° to 600°C to be consistent with commercial nitriding practice. The temperatures cited are those measured by a thermocouple located under a platform on which the work was sitting. Except where otherwise stated, the mixture used in nitriding the binary alloys contained -2.0 pct N, balance hydrogen. The nitrogen concentration in the nitriding gas mixture used for the binary alloys was purposely kept lower than normally used in nitriding steels. 10 to 20 pct, in order to minimize Fe4N formation. In this way only the alloy nitrides would be present as a second phase. However, in the case of steels which would contain a- carbide phase along with as

Jan 1, 1969

By Russell W. Dayton

THE metallurgical polarization microscope has been utilized in several researches in the last few years, thus attaining a fair degree of prominence, but little has been written in a manner suitable to a metallurgist concerning the theory of this instrument. In this investigation the theory was carefully studied, and the results are presented here in a detailed manner, yet as simply as possible. The theory - is discussed with particular reference to the three chief functions of the instrument: (1) determination of anisotropy; (2) effect of strain; and (3) identification of inclusions. Each of these is investigated experimentally, with especial attention to the mechanism of producing any effect. Where possible, the discussion is supplemented by photomicrographs. The instrument used had numerous defects as a polarization microscope; these and their remedies are discussed. In the microscopic study of transparent mineral sections (chalcography) the use of polarized light has aided tremendously in the identification of a mineral. The determination of strain in transparent substances (photoelasticity) by the use of polarized light has lately become a commercial process, used in testing finished glass articles. The success of the use of polarized light with opaque materials has not been so great. The magnitude of the effects obtained is much less than that of the corresponding effects with transparent materials, and the mechanical difficulties are much greater. Königsberger, (1)‡ in 1909, was the first to apply polarized light to the microscopic study of

Jan 1, 1935

By M. C. Leverett

Knowledge of the theory underlying the behavior of mixtures of fluids in reservoir rocks is essential to the proper solution of certain types of problems in petroleum production, but is as yet incompletely developed. The object of this paper is to show the application of well established thermody-namic and physical principles to these problems, and thus to assist in the development of the basic theory. For convenience the problems to be considered here may be divided into two groups: 1. Static problems, involving only the static balance between capillary forces and those due to the difference in densities of the fluids; i.e., gravitational forces. 2. Dynamic problems, involving analysis of the motion oi mixtures of immiscible fluids in porous media under the influence of forces due to gravity, capillarity, and an impressed external pressure differential. Capillary Equilbrium in Sands Under this heading the static type of problem will be discussed and the results of experimental investigations on the capillary properties of unconsolidated sands will be presented. Although the discussion of this section is, in a sense, prefatory to the treatment of problems of mixture flow, the concepts developed here have considerable intrinsic importance apart from their ap-plication to flow problems. For, it is reason-able to postulate that the reservoir fluids are, owing to their long existence in undis- turbed mutual contact prior to exploitation, in substantial equilibrium. It follows that their distribution in the reservoir at the time of tapping should be entirely predictable from the theory of capillary equi librium, provided certain experimentally measurable properties of the reservoir rock are known. Knowledge of the distribution of the several fluids in the reservoir is, ol course, helpful in the estimation of reserves and in other problems. It is to be emphasized that throughout the discussion of capillary statics it is assumed that the fluids are in equilibrium from the capillary standpoint. Thus, water, where it is referred to as being in a reservoir, will be understood to be interstitial water, present at the time of drilling the reservoir, commonly termed "connate" water. The theory developed here is perfectly general for any porous solid, whether a carefully prepared unconsolidated sand or a natural sandstone from an oil reservoir. At present, however, only problems involving clean, unconsolidated sands can be made to yield numerical solutions, since only such sands have been adequately investigated experimentally. Experimental evaluation of the pertinent properties 01 natural reservoir rocks will permit the extension of the numerical treatment to problems involving these materials. We shall now consider in some detail the static equilibrium of fluid mixtures in porous solids: that is, the manner in which the reservoir fluids are distributed vertically whell the Forces due to capillarity are just balanccd by those due to gravitation.

Jan 1, 1941

By M. C. Leverett

Knowledge of the theory underlying the behavior of mixtures of fluids in reservoir rocks is essential to the proper solution of certain types of problems in petroleum production, but is as yet incompletely developed. The object of this paper is to show the application of well established thermody-namic and physical principles to these problems, and thus to assist in the development of the basic theory. For convenience the problems to be considered here may be divided into two groups: 1. Static problems, involving only the static balance between capillary forces and those due to the difference in densities of the fluids; i.e., gravitational forces. 2. Dynamic problems, involving analysis of the motion oi mixtures of immiscible fluids in porous media under the influence of forces due to gravity, capillarity, and an impressed external pressure differential. Capillary Equilbrium in Sands Under this heading the static type of problem will be discussed and the results of experimental investigations on the capillary properties of unconsolidated sands will be presented. Although the discussion of this section is, in a sense, prefatory to the treatment of problems of mixture flow, the concepts developed here have considerable intrinsic importance apart from their ap-plication to flow problems. For, it is reason-able to postulate that the reservoir fluids are, owing to their long existence in undis- turbed mutual contact prior to exploitation, in substantial equilibrium. It follows that their distribution in the reservoir at the time of tapping should be entirely predictable from the theory of capillary equi librium, provided certain experimentally measurable properties of the reservoir rock are known. Knowledge of the distribution of the several fluids in the reservoir is, ol course, helpful in the estimation of reserves and in other problems. It is to be emphasized that throughout the discussion of capillary statics it is assumed that the fluids are in equilibrium from the capillary standpoint. Thus, water, where it is referred to as being in a reservoir, will be understood to be interstitial water, present at the time of drilling the reservoir, commonly termed "connate" water. The theory developed here is perfectly general for any porous solid, whether a carefully prepared unconsolidated sand or a natural sandstone from an oil reservoir. At present, however, only problems involving clean, unconsolidated sands can be made to yield numerical solutions, since only such sands have been adequately investigated experimentally. Experimental evaluation of the pertinent properties 01 natural reservoir rocks will permit the extension of the numerical treatment to problems involving these materials. We shall now consider in some detail the static equilibrium of fluid mixtures in porous solids: that is, the manner in which the reservoir fluids are distributed vertically whell the Forces due to capillarity are just balanccd by those due to gravitation.

Jan 1, 1941

By C. K. Ferguson, J. A. Klotz

This paper describes experimental investigations conducted at the California Research Corporation&apos;s model oil well. The first part describes filter loss from several drilling muds through bore hole walls during mud circulation and drill string rotation. The effect of mud properties and drill string rotation with mud circulation is described. Filtration from a bore hole full of drilling mud, not circulating, but under pressure for extended time periods, is also discussed. The second part describes filter loss to permeable formations from beneath a drilling bit where filter cuke has no opportunity to develop appreciable thickness. If potential flow theory is applied to predict filtrate invasion from this hole bottom, targe invasions arc calculated. But model well experimentation shows that filtrate invasion from the hole bottom is controlled by mud particles that penetrate the formation ahead of the bit. This experimentation provides data to estimate the effect of mud particle penetration on fluid loss to formation. The third part presents an estimate of mud filtration during drilling of a well. INTRODUCTION As oil wells are drilled by the rotary method, drilling mud circulates up the annulus between drill pine and well wall. Drillers adjust mud density so that the pressure at the bottom of the mud column is several hundred psi greater than the pressure of reservoir fluid. As a result of this pressure difference, the liquid part of the mud filters into the rock around the bore and mud solids deposit as a filter cake on the well wall. For many reasons the petrogleum industry, within the past 20 years, has spent much money and energy to determine the volume of mud filtrate that enters rock around the well bore and dedicated much research effort to reduce this volume. Among the reasons for attempts to determine the volume of mud filtrate and to reduce this volume are the following: 1. If filtrate damages the permeability of oil sand, the resultant damage to oil well productivity will depend on the distance that the filtrate invades the oil sand; reduction of filtrate volume may, therefore, increase well productivity. 2. Filtrate that penetrates shale sections may cause the shale to swell and to slough into the well bore. Uncontrolled sloughing may stick drill pipe. Reduction in filtrate volume may reduce drilling trouble. 3. Electric log resistivity curves are changed by invasion of a mud filtrate; the change depends on the depth to which filtrate invades. Knowledge of this depth is necessary before resistivity logs can be interpreted accurately. For these reasons, specifications the place an upper limit to drilling mud filter loss are now written into almost all drilling programs. These specifications are based on APT Recommended practice 29, Standard Field Procedure for Testing Drilling Fluids,&apos; which describes a static filtration test operated at 100 psi filtration pressure and at ambient temperature. Although this test is adequate for mud control, it cannot be used to compare filtration properties of different muds. Schremp and Johnson&apos; showed, for example, that mud with a low API filter loss does not necessarily have low filter loss at bottom hole temperature and pressure. Also, no information has been available about the effect of bottom hole mechanics (mild circulation, drill string rotation, and bit action) on mud filtration. This paper discusses filtration data measured in the California Research Corporation&apos;s model oil well, which models closely oil well bottom hole geometry and hydrodynamic conditions. The filtration processes that

Jan 1, 1955

By A. S. Richardson

AIR conditioning, or air cooling, for the improvement of ventilation in the Butte mines has come into increasing use during the past 10 years. In part, the methods practiced have been described in previous publications of the Institute, but some improvements on earlier methods have been made and a number of new features have been developed. This paper is presented as a record of progress made, and for the sake of completeness describes all general features of the work. The need for air conditioning in the ventilation of mines in the district arises from the fact that the temperature of the ground and mine water has shown a very great increase with increase in mining depth, and has now reached a maximum of slightly over 130ºF. The most difficult part of the ventilation problem is the maintenance of temperature and humidity of a satisfactory standard in the working places, especially on the lower levels. Although ordinary ventilation is adequate to maintain good conditions in most of the working places it is subject to a number of limitations at great depth. Most important among these limitations is that with increase in depth the air becomes heated before it reaches the working places, both by compression from increase in atmospheric pressure and by heat transferred to it from rock at high temperature, so that its capacity for lowering temperatures is greatly reduced before it reaches the operating zone. Increasing depth of mining also increases the distance traveled by the air in its passage through the mine, and this causes a corresponding increase in resistance to air flow, so that there is greater difficulty in maintaining even the same volume in circulation. Thus, in the face of a demand that the ventilating system have a very much greater capacity to remove heat from the mine, the tendency is for that capacity to diminish. The only evident alternatives were (I) the opening of additional air shafts to increase the volume of air in circulation, (2) an extension of the existing system that would be subject to the same limitations, or (3) the adoption of an entirely different method such as air cooling. Fortunately for an economic solution of the problem, the mean annual temperature of the surface atmosphere at Butte is about 40°F., with very low relative humidity in summer, so that there is unlimited natural cooling power at a temperature range adaptable to air-conditioning methods. METHODS Two similar methods of air conditioning are used, as necessitated by service requirements and dependent upon the equipment available. In one, which is the more important and has the greater cooling capacity, water is circulated in a closed circuit, and, alternately, first absorbs heat from warm mine air and then dissipates it in the surface atmosphere by cooling at a cooling tower. The second

Jan 1, 1941

By J. Szekely, G. P. Martins

A formulation is given and a general analytical solution is presented for the problem of spherical phase growth in multicomponent systems. The results are valid for describing the rate of bubble growth in the absence of translational motion and, therefore, should be relevant to heterogeneous nucleation processes. Typical worked examples are given, which include bubble growth due to the simultaneous diffusion of hydrogen and nitrogen in molten steel, and the growth of CO bubbles in steel, due to the reaction: C + 0 = CO. The calculations predict that the presence of additional components would enhance the growth rate and also increase the absolute rate at which the individual components are transferred into the bubble. These findings should be relevant to degassing processes. THE problem of spherical bubble growth in the absence of translational motion is appropriate to the description of the heterogeneous nucleation and subsequent growth of gas bubbles while attached to a solid surface. Such problems are of considerable practical relevance to various vacuum degassing and steelmaking processes where bubble nucleation and subsequent growth play an important part in the overall reaction mechanism. A definitive formulation of spherical phase growth has been given in the now classical paper by Scriven1 and the analogous problem for solid phase growth has been discussed by Horvay,2 furthermore a thorough review of the relevant literature has also become available.3 All this previous work was concerned with one component or binary systems. The purpose of this paper is to show that the technique developed by Scriven may be generalized to alow the consideration of multicomponent systems. The results of this generalization would be particularly relevant, as gas bubble nucleation in the metallurgical systems previously mentioned frequently involves the simultaneous diffusion of several components. In the following a general formulation is given and typical worked examples are presented. FORMULATION Consider the growth of a spherical gas bubble due to diffusion in a quiescent liquid of infinite extent, as sketched in Fig. 1. The formulation of such problems requires the statement of the following conservation equations relating to the liquid phase: Equation of continuity Equation of motion Conservation of the diffusing species—Diffusion Equation. The following assumptions are made: a) The fluid is incompressible, quiescent, and of infinite extent b) The bubble is stationary, i.e., it undergoes no translational motion c) Spherical symmetry is observed throughout d) The mass diffusivity is constant e) Chemical equilibrium exists at the surface of the bubble, and any reactions occurring there are fast compared to the diffusion process f) Inertia and surface tension effects are neglected. Equations derived on the basis of these assumptions by previous investigators were found to provide a reasonable representation of bubble growth while attached to a surface in organic and aqueous systems4,5 For gas bubble growth in molten metal systems assumptions a) to d) chould hold reasonably well. The exclusion of chemical kinetics as a possible rate limiting step may not be universally valid, but should hold for many systems operating at high temperatures. The effect of hydrodynamic inertia may be neglected for moderate growth rates; finally, the assumption neglecting the effect of interfacial tension on the bubble growth was made for the sake of mathematical convenience; its inclusion would have required the use of quite cumbersome numerical techniques. While surface tension effects could be appreciable on the initial values of the overall growth rate, especially at low absolute pressures and in case of small bubbles, they are not thought to modify the relative effects present in multicomponent systems, the study of which is the objective of this paper. Within the framework of the above assumptions

Jan 1, 1970