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By Ralph Hultgren, Prodyot Roy

Manganese vapor pressures from 1250° to 1500°K were measured by conventional Knudsen and torsion-effusion methods in twelve Fe-Mn alloys with compositions from 9 to 80 at. pct Mn. The Knudsen re-sults agveed approximately with previous measurements found in the literature which indicated the solutions were nearly ideal. However, except for the higher manganese compositions, the initial torsion readings indicated much (up to 50 pct) higher vapor presszcres than the Knudsen method. These high readings decreased steadily with time. The results are interpreted as due to depletion of surface concentration of manganese during evaporation. Thus the initial torsion readings are the most nearly correct and Knudsen methods on alloys are to be regarded with suspicion unless it can be demonstrated that diffusion rates are rapid enough to replenish surface concentrations depleted by evaporation. For the lowest manganese contents and highest temperatures, depletion causes initial torsion readings to be too low. FEW thermodynamic data are available for alloys of the high-melting transition metals due primarily to experimental difficulties at the high temperatures involved. Measurement of vapor pressure is one of the most promising techniques to be applied to this problem. From the vapor pressure of a component of an alloy phase, its activity or its partial molar Gibbs energy can be directly calculated. From measurements over a sufficient range of temperatures and compositions the partial and integral Gibbs energies, enthalpies, and entropies may be determined through Gibbs-Duhem integration. For solid phases of variable composition, which commonly are found in alloys, measured vapor pressures are low because of depletion of the surface concentration of the more volatile component as it is selectively vaporized. Diffusion from the interior tends to restore the depleted concentration. The seriousness of the effect depends on the relative rates of diffusion and vaporization. Although depletion has been recognized as a factor,' direct measurements of its rate are lacking and quantitative estimates of its effect on measurements are uncertain. In the present work the vapor pressures above a series of Fe-Mn alloys have been measured by the torsion-effusion method. This method permits a measurement of the vapor pressure of manganese as soon as the sample comes to temperature and continuously throughout the run. The rate of decline of the apparent vapor pressure measures the rate of depletion and the torsion reading at zero time should be correct. At high manganese concentrations (70 and 80 at. pct Mn), the torsion reading remained nearly constant; surface depletion was negligible. There was a slow drop in measured pressure due to bulk loss of manganese from the sample. However, for lower manganese contents, especially at high temperatures, the depletion effect was considerable and the apparent vapor pressure decreased steadily with time. For these alloys the Knudsen method should give pressures which are too low. The measurement of pressure in the Knudsen method cannot be made until enough manganese has been vaporized to be weighable. The Knudsen result is therefore an integrated average between the initial and final vapor pressures. To verify this, conventional Knudsen measurements were also made with results in approximate agreement with previously published Knudsen measurements for these alloys. As expected, for the lower manganese contents the initial torsion readings of pressure were as much as 50 pct higher than the Knudsen. THE APPARATUS The apparatus, shown in Fig. 1, is capable of operating to temperatures up to 2000°K. A vacuum of 5 x 10"6 mm Hg can be maintained. Temperatures were measured to +3° by a W-Re thermocouple placed in the dummy cell, N. The torsion cell consisted of two alumina crucibles with holes in their covers. They were placed in the molybdenum holder shown suspended from the torsion wire. Rectangular torsion wires (1 by 4 mm) were found to have superior sensitivity and less residual distortion than circular (2-mm-diameter) wires. The precision of angular measurement was found to be *0.025 deg; the variation is no doubt due to temperature fluctuation and vibration. For the Knudsen experiments the alumina cell was set on the support, N. SAMPLE PREPARATION 800-g samples were prepared by melting together electrolytic iron and electrolytic manganese and pouring the melt into a water-cooled copper mold. Melting and pouring were done under a helium at-

Jan 1, 1965

By E. S. Grumell

The correct sampling of coal and coke is becoming important to an ever increasing number of producers and consumers. This, therefore, may be an opportune moment to examine where we stand with regard to existing and proposed methods. In this paper an attempt will be made to review, as briefly as possible, some of the considerable amount of painstaking research which has been done in the last 10 years, and which has unquestionably led to a much better understanding of the subject. In so doing we shall try, on the one hand, to make clear where substantial progress has been made, and on the other hand, to draw attention to points that require further investigation. The paper is divided into sections in order to emphasize the major divisions of the subject; further, in order to retain this emphasis, detailed consideration of some of the points has been relegated to appendixes. No attempt has been made to give a complete survey of the literature, as this has already been done by L. A. Bushell.2 The following abbreviations will be used: A.E., average error; P.E., probable error; S.W.R., size-weight ratio; B.S.I., British Standards Institution. Section 1.—Cost It has often been stated that the cost of sampling should bear some relationship to the value of the product, and since coal is a relatively cheap raw material it would be a major error to specify, for ordinary commercial purposes, elaborate and costly methods of sampling which nobody would adopt. Specifications must be of such a nature that they will be used. We believe that one of the achievements of the last 10 years has been to reduce the cost of sampling. There is, however, another point to be considered; via., that the cost of sampling should bear some relationship to the value of the investigation. Correct sampling is a cog (possibly a small one) in the wheel

Jan 1, 1940

By E. S. Grumell

The correct sampling of coal and coke is becoming important to an ever increasing number of producers and consumers. This, therefore, may be an opportune moment to examine where we stand with regard to existing and proposed methods. In this paper an attempt will be made to review, as briefly as possible, some of the considerable amount of painstaking research which has been done in the last 10 years, and which has unquestionably led to a much better understanding of the subject. In so doing we shall try, on the one hand, to make clear where substantial progress has been made, and on the other hand, to draw attention to points that require further investigation. The paper is divided into sections in order to emphasize the major divisions of the subject; further, in order to retain this emphasis, detailed consideration of some of the points has been relegated to appendixes. No attempt has been made to give a complete survey of the literature, as this has already been done by L. A. Bushell.2 The following abbreviations will be used: A.E., average error; P.E., probable error; S.W.R., size-weight ratio; B.S.I., British Standards Institution. Section 1.—Cost It has often been stated that the cost of sampling should bear some relationship to the value of the product, and since coal is a relatively cheap raw material it would be a major error to specify, for ordinary commercial purposes, elaborate and costly methods of sampling which nobody would adopt. Specifications must be of such a nature that they will be used. We believe that one of the achievements of the last 10 years has been to reduce the cost of sampling. There is, however, another point to be considered; via., that the cost of sampling should bear some relationship to the value of the investigation. Correct sampling is a cog (possibly a small one) in the wheel

Jan 1, 1940

By R. M. Rose, D. P. Ferriss, J. Wulff

The effect of orientation on the stresses, nctivation energies, and activation volumes for yielding and plastic flow of tungsten single crystals was investigated. Tensile tests showed the proportional limit to be a function of orientation: crystals whose tensile axes were near the [I10} direction were roughly three times as strong as [loo] crystals. The [ 1101 crystals showed low strain hardening and displayed yield phenomena, whereas the other orientations yielded smoothly and showed considerable strain hardening. The fracture mode was cleavage, except for crystals near the [1101 , many of which gave "chisel" fractures at 300°and 373°K. The activation energy for yielding was approximately one- half an electron; volt at all orientations, and the volume of activation was (12 to 14)b3, except near the [1101, where it was 7b3. Activation volumes generally increased after yielding. The most common theoretical models for yielding and strain hardening of bcc metals were. found to be insufficient to the intepretation of the observations here in. An explanation is proposed, based on the dislocation reaction dislocation networks and jogs, md jogs formed during plus tic flow. PRECLSE knowledge of the Drocesses involved in the yielding and plastic flow of the refractory metals is essential to the formulation of models for their flow and fracture. Despite this need, the single -crystal investigations, especially of tungsten, have been sparse. Slip occurs at low temperature, according to schadler,i in <111> directions on {110) planes; as the temperature rises to room tempera-

Jan 1, 1962

By J. E. Burke, Y. G. Shiau

SEVERAL attempts have been made to account for the fact that grains in a fully recrystallized metal will coarsen on annealing Two fundamentally different hypotheses have been advanced; with several variations of each. One school considers that the cause of grain growth is the surface energy of the grain boundary The theory of Jeffries1 that grain size and grain size contrast control growth is an example The second school considers the primary cause to be a difference in the lattice energy on either side of the grain boundary The more perfect grains are considered to grow at the expense of their less perfect neighbors, with a decrease in free energy, and a consequent increase in the stability of the system. Burgers2 presents the case for the strain or lattice imperfection theory of grain growth quite completely The latter theory is attractive, since there is no doubt that differences in lattice energy or lattice perfection can cause grain boundary migration A recrystallization nucleus grows for this reason as was beautifully demonstrated by van Arkel and Ploos van Amstel3 Although it is generally stated that grain growth does not precede recrystallization, several workers4,5 have shown that small strains may induce a single crystal in an aggregate to grow, or at least may cause some&apos; grain boundary migration The origin and nature of the imperfections that are considered to be responsible for normal grain growth have never been clearly described, but it is generally agreed that they are a consequence of the difficulty of atomic reorientation in the solid state, and that they do not seriously differ from the type of imperfection that-can be introduced by mechanical deformation An object of the present work was to determine whether the introduction of mechanical deformation would cause grain growth in a specimen which would not otherwise show it under the conditions used It was also planned to determine the effect of such deformation the rate of growth in a specimen which would show - growth in the unstrained condition Recently Maddigan and Blank6 have indicated that slightly strained specimens of alpha brass can undergo considerable growth prior to recrystallization if annealed at low temperatures French7 has reported that at deformations less than 17 pct it is very difficult to detect the beginning of recrystallization in the same material. It was therefore planned to broaden this work to include a complete study of the microscopic behavior of alpha brass under conditions of temperature, time, grain size and deformation such that recrystallization would not occur or would occur to only a small extent EXPERIMENTAL PROCEDURE The brass was prepared by melting cathode copper and commercially pure zinc

Jan 1, 1947

By Arthur C. Green

A group of 13 cities situated in Los Angeles and Orange counties in Southern California is engaged in constructing an aqueduct to carry water from the Colorado River at a point near Parker, Arizona, to a distribution point near Riverside, California. The aqueduct will have a total length of approximately 241 miles, and is designed to deliver 1605 cu. ft. of water per second, or a little more than one billion gallons per day. The aqueduct crosses a barren, desert waste and the project includes approximately 91 miles of 16-ft. tunnel. The large amount of tunnel driving that has been done in this country in the past few years has resulted in some remarkable developments in equipment and methods. The building of the Colorado River Aqueduct,, with its 91 miles of tunnels, has called on the best engineering knowledge in the country. New and better equipment has been designed for all phases of the work, and this equipment has been coordinated and adapted to the various conditions with a high degree of efficiency. The result has been that records for tunnel driving have been set under adverse natural conditions that exceed the estimates for progress under good conditions. All of the tunnels in the main aqueduct, except the Valverde and Bernasconi at the western end, have a finished diameter, inside the concrete lining, of 16 ft. Fig. 4 shows a section of the tunnel with the concrete lining in place. Fig. 5 illustrates the finished tunnel in three typical sections. The standard tunnel grade is 3.432 ft. per mile in the 16-ft. tunnels, but the Valverde and Bernasconi tunnels have a steeper grade and a finished diameter of 15 ft. 3 in. The rough bore of the large main aqueduct tunnels averages 12.95 solid cubic yards of material per foot of advance in timbered sections and 10.76 solid cubic yards per foot in unsupported sections. Tunnel Driving While the Conway mucker has been used on tunnel work for years, a larger and more powerful Conway was designed to meet the require-

Jan 1, 1937

By W. H. Emmons

Although gold is one of the rarer metals, it is widely distributed; it is found on all of the continents and in each of the grand metallogenic provinces of the earth. It is prominent particularly in the shield areas of the earth; these areas have produced a large part of the world&apos;s lode gold and in most of them gold lodes are more important than the lodes of other metals. The Scandinavian shield is the only one that has not produced much gold. Nearly all of the world&apos;s gold has been derived from lodes and from sands and gravels where gold placers formed by the destruction of lodes. The gold derived from magmatic segregations, from pegmatites and from contact metamorphic deposits is quite subordinate to that derived from auriferous lodes. The lodes include all veins and related deposits that are formed by hot waters that move along fissures or other openings and that deposit vein &apos;matter :in the fissures and by replacement of the country rocks along the fissures. All of the shield areas of the earth are characterized by large areas of granitic rocks including granitic gneisses, granodiorites and other acid intrusives which here are included in the general term "granite." The granites are intruded into schists, ancient lavas and other rocks which here are designated as the "invaded" rocks. The granites are parts of what once were great batholiths: that is, they are the remaining portions of great deep-seated bodies that slope outward, have very irregular roofs and so far as known have no floors but extend downward to great though unknown depths. Some of them are scores or hundreds of miles across and contain islands or "roof pendants" of the invaded rocks at places where the roofs of the batholiths were low—that is, where erosion has not yet completely unroofed the batholiths. It is in these islands of older rocks and in the narrow marginal belts and cupolas of the batholiths that practically all of the gold lode deposits of the shields are found. Valuable lodes are lacking generally in the granites themselves except in grahite within a mile or less from .the contacts with rocks of the islands (Fig. 1). It is probable that the great areas of granites and gneisses that surround the islands are not all of the same age, and that at places unmapped granite intrudes gneiss or older

Jan 1, 1932

By David R. Maneval, W. E. Foreman, J. Richard Lucas

INTRODUCTION The objective of this chapter is to inform the industry, as well as the public, of the challenges in dealing with problems associated with air and water contamination by coal preparation plants. The need for an informed industry is most important. It is hoped that some contribution may be given to a more efficient and economical approach to the problems of plant waste contaminants at individual plants. The problem has many facets, and consideration should be given to specific areas before any significant problems develop at a given plant. It is then possible to have a reasoned approach before the pressures of an emergency environment force hasty and incomplete solutions. It will be necessary to anticipate these problems in the design of new preparation plants, and advance consideration should be given to all problems concerned with contaminants.

Jan 1, 1979

By G. B. SOUTHWARD

MECHANIZATION is being developed to some extent in every coal field in the United States and it is rather difficult to say which State or section of the country has made the greatest advancement. Statistics now being compiled for 1928 will show the tonnage mined, the amount of equipment used in each of the coal-producing States, and the comparative tonnages and percentages of total tonnage mined in each of these States, and will reveal which field is making the greatest advancement as far as quantity of production is concerned. However, while the tonnage figures are of great importance there-are other phases of coal-mine mechanization, such as the types of equipment, the mining methods and coal bed conditions, which are of equal interest. The change from hand-mining practices in all of the various operations from the face to the railroad cars is, perhaps, more indicative than any other one thing of the real progress being made.

Jan 1, 1929

By C. H. Stewart, R. A. Fagin

A two-dimensional, three-phasereservoir simulator was programmed for a large memory digital computer. It was designed to provide a practical solution to describing the complex physical relation between the natural forces and the physical properties of a heterogeneous reservoir when subjected to a specific set of conditions. A reservoir study is briefly described to illustrate application of the model. A full volumetric account of three phases (oil, gas and water) is performed simultaneously throughout an integration net representing the reservoir. Absence of one or two of the phases is treated as a special case of the more general situation. Expansion (or contraction) of all phases, including rock expansion, is performed so that the pressure calculation is the general unsteady-state case. To account for the large variations of subsurface elevation encountered in some reseruoirs, and to allow for segregation of the various phases, a gravity head term is included in the basic drive potential. Appropriate fluid and rock properties are used in polynominal surface form (functions of pressure and/or depth) or they can be entered as space variables at each position of the integration net. An unsteady-state water influx calculation, based on the method of van Everdingen and Hurst, l was connected to the boundary of the matrix to simulate aquifers of various sizes. In addition to reservoir calculations, three-phase fluid flow from the producing depth to the wellhead, including provisions for gas lift, was incorporated in the simulator. A workover routine was also built which can automatically switch to a different set of production relations when a gas-oil ratio or water fraction reaches a limit; or it can shut-in the well if prescribed. INTRODUCTION This paper describes a reservoir engineering mathematical simulator used to represent the complex interaction of natural forces and physical properties of a reservoir during natural depletion or with various injection schemes. The simulator, which was programmed for a large memory digital computer, is a two-dimensional calculation which handles three mobile fluid phases simultaneously (oil, gas and water). Basic requisites for the method are individual well production and pressure data, hydrocarbon fluid properties, geological data (producing depth and net sand), capillary pressure data, relative permeability data and permeability and porosity information. Matching the past performance of a combination drive reservoir often has yielded information concerning continuity and the validity of basic data. Detailed predictions of future performance can be made for continuation of current depletion methods (natural depletion) as well as for various types of recovery by gas or water injection. Combination injection cases and pattern studies can also be performed. Workover programs, gas lift and different types of artificial lift programs have been investigated using a technique similar to that described by Kern and Nicholson2 except that conditions of pressure and saturation at the block within which the well is located are used rather than average reservoir conditions. Drilling additional wells to optimize profit was explored, both as to number and location, by placing wells at different spots within the reservoir matrix. Special depletion processes can be examined, such as upstructure drainage and lateral (or strike) waterfloods in thin oil columns. In one case the mathematics of the simulator were modified to calculate the displacement in the vertical plane rather than in the horizontal plane. In this manner specific reservoir problems can be studied, such as coning of gas and/or water around production points, fingering along permeable stringers or, more generally, frontal advances in a heterogeneous section.

Jan 1, 1967

By K. H. Ribe

Water often enters an oil reservoir during completion or workover operations on a well and forms a partial "water block" to oil production. A mathematical study of radial two-phase flow, neglecting capillary effects, has been employed to study the formation of such a water block and subsequent re-moval by production from the well. The effects of reduced oil permeability about the well on the well productivity were studied. The fluid saturation distributions about the well during formation and removal of the water block have also been computed. Several relative permeability relations and viscosity ratios were employed. If water has invaded the formation, its influence through relative permeability effects alone can cause the following. 1. Oil productivity will be depressed for extended periods after production is resumed and will build up only gradually as the water is removed. 2. Oil injected for treatment of water blocking will delay rather than promote restoration of full well productivity by enlarging the region invaded by water. Thus, unless the specific action of chemicals contained in the oil is needed, oil injection appears undesirable. INTRODUCTION During oilwell workover operations, water may enter the oil-bearing formation from the wellbore. When production is resumed, oil must flow through the region invaded by this water. The presence of this region can cause both well productivity and oil production rate to be low and oil to be produced with high water-oil ratio for some time after production is initiated. This situation is sometimes described as a water block. The introduction of water into the formation may result in other actions which also lead to reduction in well productivity and which are also usually included in the connotation of the broad term, water block. Often considered, for example, are the possibilities of clay swelling by contact with fresh water and the formation of emulsions with the formation oil. If it is suspected that such specific actions have taken place, remedial treatments are undertaken which usually involve the injection of chemicals in oil. Since the introduction of water, even in the absence of specific interactions with the formation or oil, will cause a temporary water block (which might be misinterpreted as evidence of a more severe situation), it is of importance to evaluate the magnitude and duration of this blocking which results purely from the reduction in relative permeability to oil in the vicinity of the wellbore. It is also of interest to evaluate the effect of oil injection on the productivity of a well blocked by water in this manner. Inasmuch as this unfavorable condition may persist for some time, it may lead to premature condemnation of a workover or premature abandonment of a potentially productive pay zone. A quantitative evaluation of the influence of water entry on the oil productivity through changes in relative permeability was made by solving a radial form of the Buckley-Leverett equation. The distribution of water saturation around the wellbore during the entry of water was calculated and was followed by a similar calculation of the saturation distribution during the period of resuming production. At any stage in the removal of the invading water, knowledge of the distribution of its saturation permitted calculating the attendant loss in oil productivity. The influence of the shape of the relative permeability relationships was also evaluated by carrying out the calculations for two hypothetical cases. Further, the effect of the oil-water viscosity ratio was examined by repeating the calculations, for several ratios of unity and greater, with the same relative permeabilities. Fi-nally, results are presented to show how the length of time a well must be swabbed to resume production depends on the length of time it has been subjected to invasion by water. STATEMENT OF THEORY Differential Equations Water is assumed to enter a producing formation which is initially at the connate-water saturation and contains no gas. The water and oil are treated as in-

By Charles H. Kline

Industrial minerals are the Cinderella of the mining I industry. Often considered as just dirt by traditional hard-rock miners and oil drillers, these products nonetheless comprise the second largest segment of the industry and the fastest-growing one. With annual sales of $5.7 billion, industrial minerals make up 22% of the dollar value of U.S. mineral consumption. By contrast, metals account for only 11%. Fuels, of course, are dominant, representing 67%. The dollar values of production and consumption for the three segments of the industry in 1968 are shown in Table I. The growth rate of industrial minerals is shown in Table II. From 1953-1968, the current-dollar value of all U.S. mineral production increased at the average annual rate of 3.8% while that of the gross national product increased at 5.9%. Industrial minerals are the only segment of the mining industry that approached the growth of the overall economy in this period, with production values increasing 5.1% a year and apparent-consumption values 5.6% These data, expressed in current dollars, include the effects of inflation. The growth in U.S. industrial minerals production is even more striking when expressed in indexes of physical production. As shown in Table III, production of all U.S. industries increased by 4.1% a year from 1953 to 1968. The growth in production of stone and earth minerals just matched this figure. By contrast, the average annual increase for oil and gas was 2.2%: for metals, 1.6% : and for coal, only 0.6 %.

Jan 1, 1970

By David Cole

DAVID COLE, EL PASO, TEXAS (communication to the Secretary*).-I have read with great interest Dr. Gahl&apos;s painstaking paper giving us the details of development of flotation at Inspiration, and it seems to me that he has covered the ground so completely that there is little to discuss or criticize in connection with his subject. While it was in operation, the test mill in which the campaign was carried on was the Mecca of mill men and metallurgists. There was much to interest students of milling methods in addition to the flotation experiments, and readers of Dr. Gahl&apos;s paper will miss the information they hoped to get when the "pilot" mill results were. finally compiled, and I hope that the following remarks outlining from a distance some of the things that happened there will bring forth the rest of the story of the performances recorded in these important experiments. Prior to the use of flotation methods in concentration it had long been recognized that the "unavoidable" losses of sulphides were in the slime which is inevitably produced in the grinding operations required to free the minerals to be separated. Classifying the feed prior to its final stage of treatment had long been in style in milling. This assisted the sand-handling machines and resulted in lowering the tailings made by them, but at the expense of the slime-handling department; and while little was expected of the latter, the wisdom of complicating the process by hydraulic classification was being seriously questioned. Indeed, at the

Jan 10, 1916

By D. M. Waldorf

Steam permeability measurements have been made in the laboratory on several samples of natural reservoir materials. The steam temperatures and pressures were selected to simulate conditions which might exist in a reservoir during the injection of steam. For each sample tested, the experimental permeability to superheated steam was comparable to that measured with air and no evidence of plugging was detected. Some samples were exposed to water at various temperatures and plugging was found to occur in materials which contained significant quantities of monmorillonite clay. Temperature had little effect on the degree of plug-ning between 75 and 325 F. The measured pemeabilities tended to increase slightly with temperature, but the changes were small compared with the initial loss of per~neability on wetting. Sequential pemzeability measurements were made on two samples using air, water, steam, water and air, in that order. Both samples were water-sensitive and plugged extensively after the initial injection of water. Upon exposure to superheated steatm the samples dehydrated and their permenbilities to superheated steam were comparable to those initially measured with air. The remaining measuretnetzts with water and air confirmed that the water plugging was reversible and that the samples were not seriorrsly damaged during the tests. INTRODUCTION The swelling of water-sensitive clays during water floods has long been recognized as a potential source of reservoir damage. The recent extensive application of steam injection and stimulation has compounded this problem since both hot water and steam (as well as fresh water at reservoir temperatures) are, at sume time, in contact with the producing zone adjacent to the bore of a steam injection well. The purpose of this paper is to present data which compare the sensitivity of some natural sedimentary rock samples to water at various temperatures, and to super-heated steam. Some properties of montmorillonite clay are briefly reviewed, and comparisons are drawn between empirical data and the predicted behavior of the montmorillonite known to be present in the samples. PROPERTIES OF MONTMORILLONIT E CLAY Water initially adsorbs on dry N a -montmorillonite clay in discrete layers in the interlaminar space between clal platelets. The platelet spacing, which is 9.6 A (angstroms) for a dehydrated clay, has been observed to expand in discrete steps to 12.4, 15.5, 18.4 and 21.4 A spacings, indicating the formation of four discrete layers of regularly oriented water molecules.&apos; The first two layers are easily formed by hydrating a dry sample to equilibrium in an atmosphere with carefully controlled humidity. The formation of the higher layers is more difficult. The usual X-ray diffraction patterns of the more highly hydrated samples indicate a gradual increase in the average spacing betwcen 15.5 and 19.2 A, followed by a discontinuous expansion to 31 A when the weight ratio of water to dry clay is between 0.5 and 1.2.&apos; Platelet expansion above 31 A proceeds monotonically as the moisture is increased and no regular arrangement of the platelets ib observed. Water-sensitivity in sedimentary rocks is usually associated with Na-montmorillonite clay when it is in the noncrystal-line state. Mering3 found that the average lattice spacing of sodium montmorillonite hydrated at 68 F and 70 per cent relative humidity was 15.5 A, and that the spacing, at 92 per cent humidity was 16.5 A. The water adsorbed at the higher humidity has the same free energy as liquid water at 65.6 F. Kolaian and Low&apos; used a tensiometer to measure the thermodynamic properties of water in diffuse suspensions of montmorillonite clays relative to pure water. They observed that water in suspensions as dilute as 6 per cent clay became partially oriented when left undisturbed. The bonding associated with this orientation was not extensive because the free energy difference between the water in suspension and pure water was only a few millicalories per mole. They also found that the measured free energy difference decreased rapidly with temperature and became negligible above 100 F. This evidence indicates that montmorillonites contained in sedimentary rocks would dehydrate to a crystalline structure when exposed to superheated steam, and that the rock permeability measured with steam would be equivalent to that measured with air. The effect of elevated temperatures on the swelline of montmorillonite clays in aqueous suspensions has not been investigated. The Gouy-Chapman diffuse-ion-layer theory has been used to predict the swelling pressure of clay suspensions in dilute salt solutions at room temperature with reasonable success. theory also correctly predicts the direction of the thermal response of Na-mont-morillonite swelling pressures in dilute salt suspensions, 9 Over the temperature range of 33 to 68 F, an increase in

Jan 1, 1966

By John D. Sullivan

Leaching of copper ores is a comparatively old art, probably dating back to medieval times. The leaching of mixed oxidized-sulfide ores, however, is modern. The first modern plant leaching mixed ores was at Ajo, Ariz., where commercial operations commenced in 1917. While the ore at Ajo was primarily oxidized there was always some sulfide present. The Inspiration leaching plant, which was put in operation in 1926, may be considered the first plant constructed for the extraction of both sulfide and oxidized copper. The pioneers in leaching mixed ores had a difficult task before them since they had very little fundamental data on the chemical and physical factors of leaching. For the very large amount of painstaking experimental work that was done before building the Ajo and Inspiration leaching plants the reader is referred to the original articles.&apos; For a period of several years the writer worked on problems connected with the chemistry and physics of leaching mixed oxidized-sulfide ores. This paper summarizes the experimental work and discusses various factors involved in leaching ores. It also presents many data heretofore unpublished. Among the new data are those on chrysocolla, pages 518 to 519, inclusive; dioptase, page 519; covellite, page 529; virtually all those on chalcopyrite, pages 531 to 533, inclusive; enargite, page 533; and tetrahedrite and tennantite, pages 534 and 533. The oxidized copper minerals of commercial importance in American ores are azurite, Cu3(OH)2(CO3)2; malachite, Cu2(OH)2CO3; chrysocolla, CuSi03.2H2O; tenorite (or melaconite), CuO; and cuprite, Cu2O. Dioptase, CuSiO3.H2O is less common. Brochantite, CuSO4.3Cu(OH)2, while the chief mineral in the ore at Chuquicamata, is not of major importance in the United States. Metallic copper, while chemically not so, is frequently classed as an oxidized mineral of copper. The most important sulfide minerals are chalcocite, Cu2s; covellite, CuS; bornite, Cu5FeS4; and chalcopyrite, CuFeS2. Less important complex sulfides are enargite,

Jan 1, 1934

By F. F. Craig

Many full-scale waterflooding operations are preceded by pilot floods, one purpose of which is to provide an estimate of recoverable oil. A laboratory model study was made to determine the influence of the producing wells&apos; effective productivity on the oil recovery efficiency of single five-spot pilots, as well as single injection well pilot floods. The effective productivity is indicated by the value of Condition Ratio, defined as the actual well productivity to that of on undamaged and non-stimulated, normal-sized well in the same formation. The effects of initial gas satrcration and mubility ratio on recovery eficiency were also investigated in this model study. Model test results skowed that at favorable mobiliry ratios, a five-spot pilot flood can provide a direct quantitative estimate of the recoverable oil in the pilot area. If the pilot producer&apos;s Candition Ratio is 2.2 or more, upwards of 90 per cent of the recoverable oil in the pilot area is recovered from the inside producer, regqrdless of the mobility ratio or initial gas saturation. This Condition Ratio can be achieved with preyent fracturing techniques. Model studies also showed that over the range of imposed injection pressure differences and regional pressure gradients normally encountered in field operations, there was no effect on the recovery efficiency of a five-spot pilot waterflood. Model studies of single injection well pilot waterfloods showed that with no initial gas saturation, the total oil recovery at the offset producing wells can indicate the oil recovery possible by full-scale waterflooding. It is essential that the Condition Ratios of the offset wells be above 1.4. If an initial gas saturation exists prior to water injection, the recoverable oil cannot be directly evaluated by a single injection well pilot flood. However, the production per formance of such a flood can be used to provide information on volumetric sweep efficiency. INTRODUCTION Oil reservoirs are conlplex structures and cannot always be fully studied in the laboratory. Therefore, many operators consider it prudent to evaluate a waterflood prospect by means of a pilot flood. Pilot waterfloods generally involve one of two well arrangements: a single five-spot pilot waterflood, involving four injectors and an internal pilot producing well; and a single injection well pilot flood (sometimes called an inverted five-spot pilot) having one injector and four sur- rounding pilot producers. Some pilot floods are composed of multiple five-spot pilot patterns. To yield information applicable to field-wide performance, the pilot must be located in a representative portion of the reservoir. Pilot floods generally are conducted for one or more of the following reasons: (1) to determine whether water could be injected at desirably high rates, (2) to determine whether an oil bank or zone of increased oil saturation is formed by water injection, and (3) to estimate the oil recovery by waterflooding. Many of the early pilot water-floods were conducted for only the first two reasons. As soon as a buzz in oil production was obtained in the pilot, water injection was initiated throughout the entire lease or field. A number ot laboratory studies have been directed toward determining conditions under which a pilot flood could yield a quantitative estimate of the oil recovery possible by full-scale pattern flooding. One of the early studies of single five-spot pilot flooding&apos; showed that well damage to the inside pilot producer could reduce the total amount of oil recovered. In a study of the single injection well pilot flood pattern,&apos; the results indicated that if the model boundaries were no closer than a half-well spacing beyond the pilot pattern, the pilot performance in the laboratory is unaffected by these boundaries. In another study,? he effect of initial gas saturation and mobility ratio on the ratio of production to injection rate for various groupings of five-spot patterns was defined by mathematical and analog methods. In a study4 involving both potentiometric and flow model experiments at a mobiliry ratio of unity, four different pilot patterns were studied. These included a single five-spot, a single injection well pilot, a cluster of four single injection well pilots and six inverted five-spots. In this study the ratio of well diameter to the distance between injection and producing wells was held constant at 1:1000. The effect of the 7 ratio-—the ratio of the pressure drawdown at the producing wells to the pressure build-up at the injection wells on the pilot performance-was studied. The values of 7 ratio ranged from 0 to 0.34. Results showed that both the total oil recovery and the total fluid production from the pilot relative to the cumulative injection increased with increasing values of the 7 ratio. The effect of both the ratio of injection to producing rates and mobility ratio on the oil recovery performance of a liquid-saturated single five-spot pilot flood was studied in a series of flow model tests.5 Rate ratios ranged from one to four, and mobility rates ranged from 0.1 to 10. Resulls of these tests showed that at low rate ratios, the pilot producers may recover up to four times the recover-

Jan 1, 1966

By W. L. Penberthy, H. J. Ramey

Experimental work on the combustion oil recovery process has consisted of both laboratory and field studies. Although field experiments are the ultimate test of any oil recovery process, they are costly, time consuming and difficult to analyze quantitatively. Laboratory combustion tube experiments can be opertzted far more rapidly and cheaply, but are subject to scaling and interpretation problems. This paper points out some important design problems, operational criteria and considerations in2portunt to interpretation of results. An analytical hcut model of movement of a burning front axiully along a cylinder with heat loss through an annular insulation was developed. The result was used to identify steady-state temperatrrre distributions both ahead of and behind the burning front, with and without heat loss. Results indicate potential operating limitations on the minimum burning front rielocity (or air flux) which may be used for any given combustion tube. Results also enable estimating the effective thermal diffusivity and over-all heat loss from experimental data and thickness of the brnning zone. Resu lts of operation of a combustion tube constructed recently verify this preliminary theory in the region immediately ahead of and behind the burning front surprisinRly well. INTRODUCTION Many field and laboratory studies of the forward combustion oil recovery process have been conducted since the early publications of Kuhn and Kochl and Grant and Szasz2 in 1953 and 1954. In view of the complex and costly nature of this type of investigation, it is not surprising that no complete theory of the nature of the forward combustion Drocess is yet available. However, gross effects are understood well enough that reasonable design procedures are available for planning field operations. Nelson and McNeil 3,4 have published two comprehensive papers concerning design procedures. One major consideration in planning field operations is the fuel concentration at the burning front. Fuel concentration controls air requirements — an important cost factor in forward combustion. Although fuel concentration can be estimated from field test results by various methods, results are subject to great uncertainty in view of natural limitations on experimental observations. Nelson and hlcNeil4 recommend that fuel concentration be determined from laboratory combustion tube studies. Fuel concentration is only one of many important factors which can be studied by combustion tube experimentation. An obvious goal of imporrance must be development of a comprehensive theory of the forward combustion process. If a theory of this process can be established which matches controlled laboratory experimentation, it should be possible to apply this theory to field operating conditions with some confidence. Laboratory combustion tube studies have already yielded important information concerning the combustion process. However, details concerning the design, construction and operation of combustion tubes are rare. Combustion tubes used by various investigators vary in size, length and mode of operation. Therefore, one purpose of this paper is to present considerations important to design, construction and operation of a combustion tube. In regard to previous combustion tube studies, attention is called to Refs. 1 through 9. These references describe a wide variety of equipment types and present a great deal of pertinent experimental data. In general, combustion tubes usually consist of thin-walled stainless steel tubes containing an oil sand pack mounted within a pressure jacket. Provisions have often been made to heat the tube ex tern a lly by separately controlled heaters to reduce heat losses. This step usually permits operation at low air fluxes (air rate per square foot burning front surface) similar to those encountered in field operations. Burning is usually conducted from the air inlet end of the tube to the outflow end. The tube orientation used has been vertical or horizontal. For vertical tubes, burning has been conducted vertically downwards. As a result of laboratory studies, many of the

Jan 1, 1967

By T. R. Ingraham

The thermal decomposition of Nickel (II) sulfate was examined by determining the total pressure of SO3, SO2, and O2 developed over a sample when it was heated in an evacuated system fitted with a Pyrex-bellows mercury manometer. The equilibrium pressures were combined with previously published data on the oxide and sulfide systems to establish a predominance volume diagranz for the Ni-S-O system over the normal range of roasting temperature and gas composition used in the treatment of nickel minerals. The protective coating of NiSO4 which forms on the oxide during roasting, and which causes the sulfation reaction to almost cease, may be disengaged readily by temperature cycling. When nickel sulfide is roasted in air, either nickel sulfate or nickel oxide may be formed by altering the experimental conditions. Because of the differing stabilities of various metal sulfates and oxides, possibilities exist for separating some of the constituents of mineral mixtures by the technique of selective sulfation and oxidation roasting. The experimental information required to make reasonable predictions of the possibilities of this technique is incomplete and, in some cases, in conflict. As part of a general program of providing some of the required information, a study EXPERIMENTAL Materials, Apparatus, and Procedure. Fisher certified reagent-grade nickel sulfate hexahydrate was used in the source material for both nickel sulfate and nickel oxide. The manufacturer&apos;s analysis indicated: 0.001 pct Fe, 0.005 pct Cu, 0.003 pct Co, 0.001 pct C1, other 0.15 pct. The material was dehydrated, before use, by heating at 420°C for 5 hr. The oxide was prepared by roasting the sulfate in an open tray in a muffle furnace for 10 hr at950°C. Preliminary experiments which were made by thermogravimetric analysis and X-ray diffraction analysis established that only one crystal form of nickel oxide and one of nickel sulfate were involved in the equilibrium shown in Eq. [I]. The apparatus used in the experiments was described previously.1,3 The main feature is a corrosion-resistant, flexible Pyrex bellows which is used to protect the mercury in a u-tube manometer. Before a run was begun, the apparatus was washed thoroughly with hot hydrochloric acid and water and dried by heating under vacuum. The mixed sulfate -oxide sample was contained in a platinum bat rest-

Jan 1, 1967

By James F. Kemp

The iron ores of southeastern Cuba present a subject of exceptional geological interest. Their relations to the inclosing rocks are varied and in some cases unusual. The problem of their geological origin is not a simple one and for this reason has occasioned some divergence of views among previous observers. Profiting, however, by these earlier studies and by more detailed field and laboratory observations as well as by the experience of added years of mining, much more satisfactory descriptions and interpretations can now be prepared. Previous Work In 1884, interest in the southeastern coast of Cuba became active among the consumers of iron ore along the Atlantic seaboard of the United States. Active development was undertaken by the Juragua Iron Co., Ltd., a corporation affiliated with the Bethlehem Steel Co., and the Pennsylvania Steel Co. The property of the Juragua company, which is situated about 15 miles east of Santiago, was studied in June and July, 1884, by Dr. James P. Kimball, at the time Professor of Economic Geology in Lehigh University and one of the best known of American mining geologists. Dr. Kimball published on his return two papers, the first important descriptions which we have of the local geology.1 It is

Jan 1, 1916

By C. S. Giggins, F. S. Pettit

The oxidation of Ni-Cr alloys in 0.1 atm of oxygen has been studied at temperatures between 800" and 1200°C. For alloys with 30 wt pct or more Cr, continuous layers of Cr2O3 are formed during oxidation. In the case of alloys with chromium concentrations between approximately 5 to 30 wt pct, external scales of Cr203 are formed over grain boundaries whereas internal precipitates of Cr2O3 and external layers of NiO are formed at other areas on the alloy surface. When such conditions are present on the alloy surface, chromium diffuses laterally from those areas covered with a continuous layer of Cr2O3 to areas where a Cr2O3 sub scale exists and it is possible for the sub-scale zone to become separated from the alloy by a continuous layer of Cr2O3. Whether such a state will be attained depends upon the initial grain size of the alloy and the oxidation time. When the concentration of chromium in the alloy is less than 5 pct, Cr2O3 is formed internally both at grain boundaries and within the interior of grains and the alloy is covered with an external layer of NiO. MECHANISMS which describe the growth of oxide scales on nickel-base superalloys are complex and the effects produced by the various elements in these alloys on the oxidation behavior of superalloys are not clearly understood. In order to determine the influence of the different elements on the oxidation behavior of superalloys, it is first necessary to examine the oxidation properties of binary nickel-base systems which contain the principal elements present in the superalloys and then progressively more complex systems until compositions typical of the superalloys are attained. Chromium is present in virtually all nickel-base superalloys and the purpose of the present studies was to examine the selective oxidation of chromium in Ni-Cr alloys. The oxidation characteristics of Ni-Cr alloys have been extensively studied1-" to date principally as a result of the high oxidation resistance exhibited by some of these alloys. Ni-20Cr* has long been known *All compositions are given as wcight percent unless specified otherwise. to be oxidation resistant and is commonly used as resistance heating elements for service temperatures up to 1100°C. This alloy cannot be used for extended periods of time at higher temperatures because of the apparent reaction of the external scale with oxygen to form gaseous CrO3. In spite of the considerable work cited above some important aspects of Ni-Cr oxidation still remain unresolved. Virtually all of the previous studies agree that small additions of chromium to nickel, e.g., <10 wt pct Cr, result in increased oxidation rates as compared to that of pure nickel, whereas larger additions, e.g., 20 to 30 wt pct Cr, form alloys with substantially lower oxidation rates. The controversial aspects of the oxidation mechanisms for these alloys that still remain unresolved are as follows: 1) A description of the oxidation mechanism for the low chromium alloys. 2) A description of the oxidation mechanism for the high chromium alloys, particularly with respect to the composition of the external scale which results in the lower oxidation rates. 3) The specific alloy compositions at which the oxidation mechanism changes from that obtained for low chromium contents to that of the high chromium alloys and the reason for this transition. EXPERIMENTAL The Ni-Cr alloys listed in Table I were prepared from high purity metals by nonconsumably arc melting and casting as buttons. These alloys were then given a preliminary annealing treatment in argon at 815°C for 100 hr to promote homogeneity. Each button was cut into 0.250 in. thick sections that were subsequently cold-rolled to 0.050 in. thicknesses and annealed in argon at 815°C for 48 hr to provide a twinned, equi-axed grain structure. The grain size for these alloys was not uniform and the limits, within which the average grain size lies, are given in Table I for the single-phase alloys. All the alloys were single phase with the exception of the Ni4OCr alloy in agreement with the Ni-Cr phase diagram.&apos;&apos; Rectangular specimens were cut from the sheet to provide surface areas of approximately 2.5 sq cm. Exact areas were determined with a micrometer after surface preparation was completed. All of the specimens except the Ni-40Cr alloy and pure chromium were polished through 600-grit Sic abrasive paper, ultrasonically agitated in ethylene trichloride, rinsed with ethyl alcohol, and electro-polished. The specimens were electropolished in a 10 vol pct H2SO4 (conc), 6 vol pct lactic acid, methyl alcohol solution at 70" to 80°C for 2 min at a current density of 0.8 to 1.2 amp per sq cm. This electro-polishing procedure did not produce acceptable surfaces on the Ni-40Cr alloy nor on pure chromium and the oxidation properties of these materials were obtained for specimens polished through 600-grit Sic

Jan 1, 1970