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By Maynard H. Jameson

Earlier investigations of the potential-drop-ratio method of electrical prospecting have indicated that under suitable conditions this method is well adapted to the location of formation boundaries in stratified ground. A description of this development was given several years ago by H. Lundberg and Th. Zuschlag.l The curves published by these authors for the potential-drop-ratio variation above a horizontal contact indicated a definite relation of the position of the curve peak to the depth of the interface. The theory underlying this relation was subsequently studied by Z. Mitera in greater detail,' and the theoretical deductions were compared with the results of tank experiments. The investigations available at this writing were confined to studies of horizontal formation boundaries. It is the purpose of this paper to extend the scope of the previous work to the problem of dipping layers. Theory Consider the case of three media of different resistivities, whose interfaces are not parallel. If a point-source is located in one of these interfaces, its images do not lie in a straight line, but on the circumference of a circle whose center is at the hypothetical junction of the interfaces. R. F. Aldredgea determined the relation that exists between the degrees of dip of the two interfaces and the distances between the various images and the point for which the potential is to be found. As seen in Fig. I, three media of resistivities PO, p1, and p2 are involved, and the source I is located at the interface of the media Coo) and (p1). The perpendicular depth of the lower interface is h, 0 is the dip, R is the distance between source I and potential point P, and r is the distance between the images and that point. To distinguish between images lying above the ground interface and those below, the notation "odd" and "even" images will be employed; images below the ground interface will be termed "odd" and those above "even." The following relations govern the distances between either kind of images and the potential point: EvEn Odd Ta — R r1 - [rl] - [RS + 4h(h + R sin 01½ r, = [r] =. [R1 + 4h cos 0)2(h + -R sin 0)1½ ri - [r3] ={r3} [R* + 4h(4 cos2 0 - i)1 (h + R sin 0)l½ r4 = [r4] = [R2 + 4h(4 cos $ cos 30)1 (h + R sin 0)]½ r, — [r4] - [R2 + 4h(4 cos9 R cos 20 + cos 48)2 (h + R sin 01½ I RI + 4h[2 cos 30(4 cos2 0 - I)12 (h + R sin 8)1 ½ rn - [r4] - [R2 + 4hlf(cOs 0)18(h + R sin R)l½ As previously pointed out, the images of the source are on the circumference of a circle. If the angle of dip is 0, the angle measured from the horizontal to the first image is 28; to the second image it is 48, and so on. Since the limit of the reflecting interface is at its outcrop, the last possible

Jan 1, 1946

By Maynard H. Jameson

Earlier investigations of the potential-drop-ratio method of electrical prospecting have indicated that under suitable conditions this method is well adapted to the location of formation boundaries in stratified ground. A description of this development was given several years ago by H. Lundberg and Th. Zuschlag.l The curves published by these authors for the potential-drop-ratio variation above a horizontal contact indicated a definite relation of the position of the curve peak to the depth of the interface. The theory underlying this relation was subsequently studied by Z. Mitera in greater detail,' and the theoretical deductions were compared with the results of tank experiments. The investigations available at this writing were confined to studies of horizontal formation boundaries. It is the purpose of this paper to extend the scope of the previous work to the problem of dipping layers. Theory Consider the case of three media of different resistivities, whose interfaces are not parallel. If a point-source is located in one of these interfaces, its images do not lie in a straight line, but on the circumference of a circle whose center is at the hypothetical junction of the interfaces. R. F. Aldredgea determined the relation that exists between the degrees of dip of the two interfaces and the distances between the various images and the point for which the potential is to be found. As seen in Fig. I, three media of resistivities PO, p1, and p2 are involved, and the source I is located at the interface of the media Coo) and (p1). The perpendicular depth of the lower interface is h, 0 is the dip, R is the distance between source I and potential point P, and r is the distance between the images and that point. To distinguish between images lying above the ground interface and those below, the notation "odd" and "even" images will be employed; images below the ground interface will be termed "odd" and those above "even." The following relations govern the distances between either kind of images and the potential point: EvEn Odd Ta — R r1 - [rl] - [RS + 4h(h + R sin 01½ r, = [r] =. [R1 + 4h cos 0)2(h + -R sin 0)1½ ri - [r3] ={r3} [R* + 4h(4 cos2 0 - i)1 (h + R sin 0)l½ r4 = [r4] = [R2 + 4h(4 cos $ cos 30)1 (h + R sin 0)]½ r, — [r4] - [R2 + 4h(4 cos9 R cos 20 + cos 48)2 (h + R sin 01½ I RI + 4h[2 cos 30(4 cos2 0 - I)12 (h + R sin 8)1 ½ rn - [r4] - [R2 + 4hlf(cOs 0)18(h + R sin R)l½ As previously pointed out, the images of the source are on the circumference of a circle. If the angle of dip is 0, the angle measured from the horizontal to the first image is 28; to the second image it is 48, and so on. Since the limit of the reflecting interface is at its outcrop, the last possible

Jan 1, 1946

By D. G. Russell

Two techniques have been developed with which the applicability of pressure build-up analyses can be extended to include pressure data which previously have been considered virtually unusable. One of the interpretation methods makes possible the analysis of pressure build-up performance during the wellbore fill-up or after production period which occurs soon after a well is closed in. The other technique is an extension of a method for analyzing pressure build-up performance during the late-time portion of the pressure build-up which occurs after boundary eflects first begin to alter the shape of a conventional pressure build-up curve. With both of these methods it is possible to obtain estitnates of the kh product, the skin factor and the reservoir pressure. In addition, with the late-time analysis technique it is possible to obtain an estimate of the contributory drainage volume of the well being tested. This means that in some cases a check on reservoir limit test and (or) material-balance calculations can now be obtained from pressure build-ups. Both methods are slightly more time-consuming than conventional pressure build-up analysis methods because trial-and-error plots of pressure data must be made. The late-time method for analysis of pressure build-ups is in principle applicable to the late-time portion of a two-rate flow test or a pressure drawdown test. The interpretation formulas and procedures for these types of tests are also outlined. In these cases, as with pressure build-ups, it is significant that an estimate of the contributory pore volume is also obtained. On the basis of limited experience with the new techniques, it appears that satisfactory estimates of the kh product, skin factor, reservoir pressure and, for late-time analysis, contributory drainage volume can be obtained. INTRODUCTION The analysis of bottom-hole pressure build-up behavior in closed-in wells has been a a subject of interest in petroleum engineering circles for many years. In fact, few other subjects have received as much attention as pressure buildup analysis methods have. The cause for this interest is essentially twofold in nature. First, the pressure behavior of a well can normally be measured with a reasonably high degree of accuracy so that good data for analysis can be obtained. Secondly, over a fairly wide range of operating conditions, valuable information as to the quality of the reservoir rock and completion efficiency of the well can be obtained at a nominal cost. In recent years, numerous papers have been prepared on the effects of various operating conditions and reservoir heterogeneities on pressure buildup behavior. Very little work has been done, however, on extension of pressure build-up analysis methods to those pressure data which are not amenable to analysis by the present methods. The theory upon which the analysis of shut-in bottom-hole pressure build-up data is based is derived from the solution of the radial flow equation for a slightly compressible fluid for constant-rate conditions. It requires that the well be closed in for a sufficient period of time to obtain a clearly defined linear portion on the plot of observed bottom-hole pressure vs log (t + ?t)/ ?t (where At is shut-in time, and t is producing time to the instant of shut-in). From the slope of the plot and other normally obtainable data, the formation permeability, the well damage or skin factor, and the reservoir pressure at infinite shut-in time (if the reservoir were infinite) can be estimated. The successful application of this procedure depends on being able to recognize the straight-line section on the basic pressure build-up plot. The presently used pressure build-up interpretation theory also assumes that a well is closed in at the sand face and that no production into the well occurs after shut-in. In practice, of course, the well is closed in at the surface, and inflow into the well continues until the well fills sufficiently to transmit the effect of closing-in to the formation. This adjustment period is commonly referred to as the "afterproduction" or "fill-up" portion of the pressure build-up. During the period that the well fill-up effect is most pronounced, the basic pressure build-up plot is nonlinear. At later shut-in times after the effects of a drainage boundary have been felt at the well, deviation from the straight-line behavior of the pressure build-up plot also results. In many cases either of these effects or a combination of both can make the straight-line portion on the pressure build-up plot difficult to recognize. Obviously, an extension of pressure build-up analysis methods to include the afterproduction period and the period in which boundary effects are being felt would be desirable and might render valuable pressure data which for years have been considered virtually unusable. The principal reference of note concerning pressure buildup analysis during the afterproduction period is a paper by Gladfelter, Tracy and Wilsey.1 In the approach of these authors it is necessary to measure the rate of influx into the well during the afterproduction period. This is done through sonic measurements or through measurement of tubing-head and casing-head pressures simultaneously with

Jan 1, 1967

By J. P. Zannaras

If we assume that testing of the model started at time t1, that time t2 was the instant at which the elastic limit of the material was passed at the points of the maximum stress, and that at time t3 the failure of the model was completed as shown in the typical photograph (Fig. I), then actually the photograph shows the final results of what took place between time t2 and t3. By the principle of similitude all conclusions drawn from the behavior of the model were applicable and valid for actual mine roofs up to the time t2 after time t2 motions and friction came into play during the destruction of the model. The events between t2 and t3 and the photograph itself are not representative of the events expected in an actual mine roof unless corrections imposed by the principle of similitude are made. It can therefore be stated that all conclusions and observations of the author from the photographs are applicable only to his small-scale experiments and not to actual mine roofs. Without investigation of the true stresses or the combined maximum stress induced in the beds it has been assumed by the author that failure occurred solely due to bending stress caused by loading of the beds. (The author states that D was taken to be the theoretical strain given by elementary beam theory.) Fig. 1 shows that the beds were clamped together. This clamping was necessary to prevent slipping of the beds due to the horizontal shear. However, this clamping caused an uncontrolled and undertermined com-pressive stress S at the end of the beds, and this com-pressive stress caused a true tensile stress ?S (? PoiS-son ratio). This true tensile stress combined with the tensile stress produced at the end of the beds due to loading (fixed beam uniformly loaded), and the horizontal shear which is maximum at the end appears to be the most probable maximum stress produced in the beds. It is therefore evident that the author in performing this experiment has introduced stresses in the model not existing or dissimilar to actual mine roofs, and therefore his conclusions may be applicable to his small-scale experiments but inapplicable to actual mine roofs. Louis A. Panek (author's reply)—The discusser's difficulty is related to mechanics of materials rather than similitude. The effect of time did not enter into the tests in any way, being simply excluded from consideration in this study, because all quantitative results entering into the design equations are based on measured (between time t1 and time t2) bending strains that are well below the breaking strain (i.e., in the elastic range) for the model material. Time does not become a significant factor until the rock stress reaches 80 to 90 pct of the breaking stress." The objective of this investigation was not to predict that bolted roof will fail after time t, but was instead to develop a safe roof, that is, roof in which the bending strain is much less than (say less than 50 pct of) the breaking strain. The models tested to failure had no direct bearing on the design equations. Although for some rocks time may influence the magnitude of stress or strain at which fracture occurs, breaking stress or breaking strain values were not employed for any purpose in this investigation. Tests to failure were made only to obtain additional evidence regarding the behavior of the bolted laminae' as evinced by the locations of the cracks. As stated in the last paragraph of the paper, if one wishes to predict the time or stress conditions for which the roof will fail, additional information is required. The reason for clamping the laminae is to make them behave liked clamped beams, which closely approximate the clamped-plate condition of the actual mine roof beds (Ref. 5, p. 1; Ref. 6). The writer has previously demonstrated that the bending stresses induced by centrifugal loading in a clamped model beam are in agreement with those predicted by theory;' hence clamping has no significant effect on the bending ,trains measured during a test. Moreover, actual ,in, roof beds are likewise subject to a clamping effect due to weight of superincumbent strata carried by the pillars or ribs on each side of the opening. It is emphasized that this study was restricted to evaluating only the reinforcing effect produced by the bolts. Procedures employed in the experiments and in the data analysis were such as to deliberately exclude the effects of other factors. The objections offered are therefore invalid,

Jan 1, 1957

By Robert B Sosman

The relative temperature distribution within a coke oven and among the ovens in a battery can be obtained automatically for the operator's guidance by sighting a total-radiation pyrometer on the face of the coke as it is pushed out, and recording the surface temperature. Keeping the instrument clean and keeping its view of the coke unobstructed by smoke and dust are the principal problems. Typical records from three plants are presented in this paper, showing that the temperature patterns are reproducible. Development OF Method The method of coke pyrometry described in this paper was introduced in 1936 by E. A. Lee, then Assistant Superintendent, now Superintendent, of the Coke Plant at Lorain Works, National Tube Co., Lorain, Ohio. At the request of the Coke Committee of the United States Steel Corporation, the Research Laboratory of the Corporation undertook to adapt the method to the somewhat different conditions met with at the Gary Works of the Carnegie-Illinois Steel Corporation, Gary, Ind., and at the Clairton Works of the same Corporation at Clairton, Pa. This work was done in cooperation with the Leeds and Northrup Co. of Philadelphia and later with the Brown Instrument Co. Division of Minneapolis-Honeywell Regulator Co., Philadelphia. We of the Research Laboratory wish to express our appreci- ation of the courtesies extended by Mr. Lee, by A. N. Cole, Superintendent of the Gary coke plant, and by D. P. Finney, Assistant General Superintendent in charge of coke-plant operations at Clairton. We are also indebted to the instrument companies for the loan of a part of the equipment. At Gary and Clairton the instruments were installed and various experiments were made by J. W. Bain, of the Research Laboratory of the United States Steel Corporation. Pyrometry of Coke The coke inside a by-product oven is almost completely inaccessible to pyro-metric instruments. The temperature in the walls can conceivably be measured with thermocouples, but the atmosphere is usually strongly reducing, a condition well known to be destructive to the accuracy of the customary high-temperature couples. In some plants, periodic readings are taken with an optical pyrometer sighted into the top of the combustion flues. This is a useful measure for safety and general control, as it tends to prevent the damage that would result from overheating of the ovens. It does not, however, tell much about the temperature of the coke itself, because of the continually changing gradient in the wall between the coke and the combustion chamber. The best indication of the temperature of the coke itself must therefore be obtained by observation of the product as it is pushed out of the oven. The human eye is very sensitive to variations in brightness of a surface, and particularly to differences in brightness over a continuous hot surface.

Jan 1, 1943

By Robert B. Sosman

The relative temperature distribution within a coke oven and among the ovens in a battery can be obtained automatically for the operator's guidance by sighting a total-radiation pyrometer on the face of the coke as it is pushed out, and recording the surface temperature. Keeping the instrument clean and keeping its view of the coke unobstructed by smoke and dust are the principal problems. Typical records from three plants are presented in this paper, showing that the temperature patterns are reproducible. Development OF Method The method of coke pyrometry described in this paper was introduced in 1936 by E. A. Lee, then Assistant Superintendent, now Superintendent, of the Coke Plant at Lorain Works, National Tube Co., Lorain, Ohio. At the request of the Coke Committee of the United States Steel Corporation, the Research Laboratory of the Corporation undertook to adapt the method to the somewhat different conditions met with at the Gary Works of the Carnegie-Illinois Steel Corporation, Gary, Ind., and at the Clairton Works of the same Corporation at Clairton, Pa. This work was done in cooperation with the Leeds and Northrup Co. of Philadelphia and later with the Brown Instrument Co. Division of Minneapolis-Honeywell Regulator Co., Philadelphia. We of the Research Laboratory wish to express our appreci- ation of the courtesies extended by Mr. Lee, by A. N. Cole, Superintendent of the Gary coke plant, and by D. P. Finney, Assistant General Superintendent in charge of coke-plant operations at Clairton. We are also indebted to the instrument companies for the loan of a part of the equipment. At Gary and Clairton the instruments were installed and various experiments were made by J. W. Bain, of the Research Laboratory of the United States Steel Corporation. Pyrometry of Coke The coke inside a by-product oven is almost completely inaccessible to pyro-metric instruments. The temperature in the walls can conceivably be measured with thermocouples, but the atmosphere is usually strongly reducing, a condition well known to be destructive to the accuracy of the customary high-temperature couples. In some plants, periodic readings are taken with an optical pyrometer sighted into the top of the combustion flues. This is a useful measure for safety and general control, as it tends to prevent the damage that would result from overheating of the ovens. It does not, however, tell much about the temperature of the coke itself, because of the continually changing gradient in the wall between the coke and the combustion chamber. The best indication of the temperature of the coke itself must therefore be obtained by observation of the product as it is pushed out of the oven. The human eye is very sensitive to variations in brightness of a surface, and particularly to differences in brightness over a continuous hot surface.

Jan 1, 1943

By S. Weinig, J. Winter

The grain boundary adsorption of solutes as a function of bulk concentration and solution temperature was studied using internal-frictimz techniques. From the variation of the cor-responding energy of activation for the Phenomenon, the inter-actior2 energy between a solute atom and a high-angle boundary was calculated. Interaction energies in the range of 0.3 ev were obtained, and were used to obtain the actual concentration of solute at the grain boundary. In corroboralory creel, studies the direct grain boundary contribution to the total creep strain was measured. It was found that the interface creep varied with the type and magnitude of the solute adsorbed. Subscribing to the theory of their being energetically favorable sites at the grain boundary for solutes of both Positive and negative size deviations, ternaries were investigated in Which solutes of both types were present. A marked increase in the resistance to grain boundary creep was manifested. THE major difficulty which has been encountered in investigations of the grain boundary segregation of solutes has been the lack of a sufficiently sensitive method of measuring the amount of adsorbed solute at the boundary. For the general case of a high-angle boundary, no direct method of measuring the adsorption at the boundary has been found to date. Internal friction has been used in several studies of grain boundary adsorption1-3 and although it is somewhat indirect, it was demonstrated to have the necessary sensitivity. In this investigation the authors have used internal-friction techniques in conjunction with a study of the grain boundary contribution to the total creep strain. As both parts of the investigation were performed on the same specimens it was possible to combine a highly sensitive technique with a somewhat more direct method in order to obtain information about the adsorption phenomenon. From internal-friction studies the rate of increase of the activation energy was observed to be a function of the difference in size between the solute and solvent atoms. It was proposed that if Gibbs' adsorption isotherm is considered, i.e., where r is the excess solute at the boundary, c is the bulk concentration, and ay/ac is the change in grain boundary energy with bulk concentration, then AH b/ac must vary in the same way as ay/ac and therefore In this way a relative measure of the grain boundary adsorption of solutes is directly obtainable from in-ternal-friction studies. If the previous work in the field of grain boundary adsorption of solutes is examined, certain apparent information is desirable if the phenomenon is to be understood. The most important questions that must be asked are as follows: 1) Is the adsorption of solutes at the grain boundary an equilibrium process? 2) Can the Mott model of the grain boundary be used as a basis of setting up an elastic interaction between the grain boundary and solute atoms? 3) Is it possible to obtain an exact measure of the excess solute at the grain boundary as a function of temperature and bulk concentration rather than merely a relative measure of the adsorption 4) Are the conclusions obtained from an indirect method such as internal-friction studies meaningful in considering gross grain boundary effects such as creep? EXPERIMENTAL PROCEDURE The material used in this investigation was Bureau of Mines "superpurity" titanium (79 Bhn—1500 kg

Jan 1, 1960

By George Burrell

INTRODUCTION THE senior author of this paper, while in Colorado on other official business, made a trip to the Cripple Creek gold-mining district to get more data than are at present available regarding the composition of the gas that issues from the rock into the mines of the district. This was done at the suggestion of George S. Rice, Chief Mining Engineer of the Bureau of Mines. There are many questions of interest and importance in connection with the ventilation of the mines in the Cripple Creek district, such as the menace to life and mining of a suffocating gas entering the mines from the rock, the danger due to powder smoke (from blasting operations), and danger of continued inhalation of rock dust by the miners. This report confines itself to the first problem, the gas from the rock, and principally to one phase of this question, the composition of the gas and its effects on men and lights. A more thorough study of this and other ventilation problems is planned. That the, rock gas is a real menace is shown by the fact that miners (variously estimated from 25 to 50 by different persons interviewed) have been killed by it in the 25 years that mining has been vigorously carried on at Cripple Creek. Many men have had narrow escapes from death, some of them having been incapacitated for days. In addition, much loss of time results because at certain periods of the year or on certain days it is impossible to enter some workings. At a few mines fans force air into the workings, thus supplementing the natural ventila-

Jan 5, 1916

By H. N. Treaftis, J. W. Cahn

THE previous determinations of the solvus of tin in solid lead disagree with one another by as much as 40°C or almost 10 at. pct. Even determinations that appear to be careful differ considerably in both the solubility and its temperature coefficient. Recent kinetic workl -3 on the rate of precipitation of tin from lead-tin alloys and thermodynamic work4 on the heat of solution of tin in lead have given some insight into the time necessary to reach equilibrium in this system. As this time is longer than that used in almost all previous determinations of the solvus, these determinations are questionable. Since the interpretation of recent kinetic results requires accurate values of the equilibrium solubility the present work was undertaken. DISCUSSION OF PREVIOUS RESULTS The methods used in previous studies may be placed into three classes: 1) Several alloys covering a range of compositions are allowed to reach "equilibrium" at a certain temperature.5-7 Some property, such as the X-ray lattice parameter of the lead-rich phase or the re- sistivity of the alloy, is then measured as a function of composition. The solubility limit for that temperature is taken to be that composition at which a discontinuity in the property occurs. However, the recent kinetic work has shown that tin precipitates in two stages. The first stage is rapid but leaves the lead still supersaturated. The second stage is very slow, and it seems from the equilibration times quoted by the investigators of the solvus that the end of the first stage of precipitation was usually mistaken for equilibrium. This is especially true at temperatures below 100°C where the first reaction is still quite rapid (from minutes to months), but where the second stage is so slow that very long holding times are required to reach equilibrium. Alternatively micrographic work8 on several alloys of different compositions seems to have given good results if done carefully. 2) The beginning of precipitation in a homogenized alloy is measured as it cools slowly8-10. Since reactions in solids undercool easily, such determinations will always give too low a temperature for the solvus. 3) Some property of an alloy is measured as a function of temperature while the alloy is above the solvus.5,9,11 The range of temperature can usually be extended slightly into the two phase region. Then the alloy is precipitated at a much lower temperature and slowly reheated. The solvus is taken to be the lowest temperature where the property of the reheated alloy is equal to that previously determined for the homogeneous alloy. Usually one also expects a discontinuity at the solvus in the temperature variation of the property for the reheated alloy. The difficulty in this method is the sluggishness of the dissolution process, and this method may give too high a solvus temperature. EXPERIMENTAL The phase boundary or solvus temperature was determined by a modification of method 3 for a series of chemically analyzed high-purity alloys, ranging from 5.1 to 26.4 at. pct Sn. The resistance, as a function of temperature, of a sample of homogenized alloy (which could easily be undercooled) was compared with the equilibrium resistance which that alloy sample attained after precipitation at room temperature followed by long isothermal anneals at various temperatures. Before each anneal the sample was rehomogenized and reprecipitated. The solvus temperature could be located to within 1°C as the intersection of the resistance vs temperature curves for the homogenized and equilibrium alloys. No attempt was made to locate the phase boundary more accurately since the limiting factor was the precision with which the alloys could be analyzed. This precision was ±0.1 wt pct Sn and corresponds to an error of 1 deg in temperature. This use of isothermal anneals differs from some of the previous investigations in which method 3 was used with baths of slowly rising temperatures. It was found early in the investigation that solvus temperatures tended to be high if the latter method was used even at extremely slow heating rates. For example a

Jan 1, 1961

By William G. Pariseau

Advances in numerical methods of analysis and computer technology during the past decade have brought many formerly intractable ground control problems within easy reach of present day graduate mining engineers. However, the new technology brings with it new problems. The identity of these problems are largely those arising from a lack of familiarity with the capabilities and limitations of the new technology. In this regard, the central problem in ground control planning is the calculation of ground motion associated with mining. The fundamentals of this problem leading to a form suitable for computer programming are therefore reviewed. Solution procedures in the broad sense including the gathering of input data and the interpretation of output are described. Computer program capabilities necessary for ground control analysis are discussed and the steps necessary to implement an analysis are outlined.

Jan 1, 1983

Aamot, Olav Crone, Chem. Engr., Norsk Elektrokemisk, Kongensgt. 18, Oslo, Norway. '29 Abbott, Clarence E., V.P., Charge of Raw Materials, Tennessee Coal, Iron & R. R. Co., 1242 Brown-Marx Bldg., Birmingham, Ala. '04 Abel, Raymond L., Prof., Dept. of Pet. Refin., Univ. of Pittsburgh ..Pittsburgh, Pa. '28 Abel, Walter D., Cons. Engr 364 S. Cloverdale Ave., Los Angeles, Calif. '32 Abele, Louis T R.F.D. 1, Adamsville, Ohio. '31 Abell, Leo M., Ore Dressing Investigator, School of Mines Adelaide, S. Australia. '31 Abenius, Hakan V., Mine Supt., Bolidens Gruvaktiebolag Boliden, Sweden. '37 Aborn, Robert H., Asst. Met., Research Lab., U. S. Steel Corp., Lincoln Highway, Kearny, N. J. '19 Abraham, W. E. V., East India United Service Club, 16 St. James' Sq., London, S.W. 1,, England. '28

Jan 1, 1937

By R. Schuhmann

Available thermodynamic data applicable to copper smelting systems are collected and tabulated, and the important gaps are pointed out. A few examples are given of estimations which can be made from the available data. An experimental research program is proposed to supply the thermodynamic data that appear most essential to better quantitative understanding of the chemistry of copper smelting. The proposed program is designed also to shed specific light on the practical problems of slag losses and magnetite behavior. OPPER smelting, from flotation concentrates to V-/ blister copper, is conspicuous among the large scale chemical processes which are conducted with only relatively incomplete knowledge of the physical chemistry involved. For example, no common metallurgy text explains adequately why copper enters the matte phase while iron enters only to the extent that sulphur is left over after satisfying the copper. Explaining this important phenomenon as a manifestation of the greater affinity of sulphur for copper than for iron is unsound because the affinities of copper and iron for sulphur are about the same at smelting temperatures. As will be shown, other affinities are really decisive in the relatively clear-cut separation of copper in the matte. In contrast, thermodynamic studies have contributed much to our understanding of copper refining, zinc oxide reduction, magnesium production, steelmaking, etc. For each of these processes, the important reactions are clearly recognized, and fair to good quantitative values of the free-energy changes and equilibrium constants are available. Such data have proved to be of constantly increasing practical value in process development and improvement. Work in other fields has furnished much thermodynamic data applicable to copper smelting systems. In fact, several promising starts have been made in applying such data to specific smelting problems. Kelleyl made an appraisal of the possibilities of recovering elementary sulphur from low grade matte. His calculations and compilations of thermodynamic data have represented the starting point for much of the work in this field, including the present survey. Huang and Hayward2 nd Aksoy3 used thermodynamic methods in the study of copper losses in reverberatory slags. Peretti4 used thermodynamic data in explaining the chemistry of converting. The recent publications of Darken and Gurry"." and of Darken,' dealing with the iron-oxygen and iron-silicon-oxygen systems, respectively, present equilibrium data that are applicable to copper smelting systems. Also additional data were reported recently on the affinity of sulphur for copper, manganese, and iron8 and on the sulphur pressures of iron-sulphur melts." The survey presented in this paper was made as the basis for planning an experimental program on the thermodynamics of copper smelting. Few researches on the chemistry of copper smelting have been reported in recent years, so that a reappraisal and coordination of old and new data are essential if further work is to take the directions of maximum value. The experimental program is now in progress, and the plan of attack is outlined at the end of this paper. Progressive Oxidation and Desulphurization of Copper-bearing Liquid Phases: The chemical activities of sulphur and oxygen are two of the most important thermodynamic yardsticks to be applied to copper smelting processes. Virtually the entire smelting and refining sequence involves a series of systems characterized by decreasing sulphur activity and increasing oxygen activity. In this section, therefore, an attempt is made to define and explain these activities in terms of equilibrium partial pressures of SO2, s2, and O,. Also, estimates of these quantities are presented, the estimates being based largely on calculations presented in a later section of this paper. The sequence of steps from raw flotation concentrate to fully oxidized copper ready for poling involves progressive and controlled oxidation. Iron is oxidized and enters the slag. Sulphur is oxidized and leaves in the gas. Table I summarizes several important features of this oxidation and desulphurization sequence, starting at the beginning of the matte blow in the converter. The top line gives in order the principal smelting and refining stages up to fully oxidized copper, plus the additional step, not used commercially, of oxidizing all the way to Cu,O. In the second line are shown the principal copper-bearing liquid phases which characterize the process. Through most of the sequence the copper

Jan 1, 1951

By Laurence Pellier

Electron microscopical studies were made of the effect of sensitization at 1200oF on a Type-.104 stainless steel with high carbon and low nitrogen and oxygen contents, after solution annealing and after cold working. The loci of the carbide precipitates in the early stages of sensitization were followed in dry stripped plastic replicas. Some observations were made by direct electron transmission on thinned films. Intragranular dislocations showed a high degree of stability through the annealing necessary to produce sensitization. I HE present work was undertaken to determine the effect of sensitization, at 1200°F, for 1/2 hr, on the electron microstructure of a Type-304 stainless steel with high carbon, and low nitrogen and oxygen contents, after solution annealing and after cold working. Many electron microscopical studies of sensitization of 18-8 stainless steels have already been made. Most of them utilized extraction replicas, from which the morphology and composition of the precipitated carbides could be established.'-" ry stripped replicas were seldom used for such studies, although it was demonstrated that they are applicable, in general, to EurveYs of the general microstructure of many alloys' and, in particular, to the observation of precipitated carbides in austenitic stainless steels.3

Jan 1, 1963

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Jan 1, 1938

By M. H. Waxman, M. Gondouin, H. J. Hill

Streaming-potential experiments were conducted within the Muddy- and Dakota-sandstone interval of a Denver basin well. Analysis of the data shows that, for this case, streaming potentials opposite sands were higher than those opposite shales when the mud was fresh. Streaming potentials opposite shales, however, were of sufficient magniiIlde to be important in SP interpretation. They were linearly dependent upon pressure differential, and they increased with mud filtrate resistivity. The magnitude of streaming potentials opposite sands was influenced by the characteristics of the original mud cake formed at the time of drilling. Use of mud samples taken at the time of logging may not always be satisfactory for determining streaming-potential corrections. Both the streaming and electrochemical potentials were found to be affected by the previous history of the borehole system. Following a change in mud characteristics, several days were required for SP stabilization. This was, in part, due to the mud cake acting as an imperfect shale membrane. INTRODUCTION Laboratory investigations by Wyllie,1 Salisch,2 Moore," Sen Gupta and Bannerjee,0 and Hill and Anderson' have shown that streaming potentials developed across mud cakes deposited on permeable filter beds are of sufficient magnitude to be critically important in SP interpretation. Streaming potentials across shales have been reported by Schenck,' Gondouin and Scala; and Hill and Anderson." The magnitude of the shale streaming potentials obtained by Schenck and by Gondouin et a1 led these authors to conclude that in many cases the shale streaming potential would approximately equal the mud-cake streaming potential. Hill and Anderson, however, obtained somewhat lower magnitudes of shale streaming potential. The field experiment described in the present paper was a cooperative project carried out by the respective operations and research departments of Schlumberger Well Surveying Corp., Shell Development Co. and Shell Oil Co. The primary objective of the experiment was to determine in the borehole the streaming-potential behavior of both shales and mud cakes under conditions approaching, as nearly as possible, those normally encountered in logging practice. METHODS AND EQUIPMENT WELL A Muddy- and Dakota-sandstone vie11 in the Denver basin was chosen for the experiment. Both sandstones were water-bearing and, since reservoir pressures in these sandstones are abnormally low (gradient of approximately 0.25 psi/ft), it was expected that studies of streaming potential could be conducted from low-pressure differentials (approximately 200 psi) to about 27000 psi by bailing mud from the hole, filling up and then applying wellhead pressure. The selected well encountered the Muddy sand-

By E. C. Burke, W. R. Hibbard

Plastic deformation in magnesium single crystals was studied by tensile tests at room temperature utilizing an improved preparation and testing technique. Consistent critical resolved shear stress values for basal slip were obtained. The advent of pyramidal slip at room temperature was rationalized upon the basis of grip constraints. A bend-twinning hypothesis was advanced as an explanation of mechanical twinning which occurs as a complex stress-relief mechanism. INVESTIGATIONS of the plastic deformation of magnesium have been limited to the determination of the fundamental kinetics which may be summarized as follows: 1—Twinning on the {102).l 2— Slip on the (001) plane in the [loo] direction at room temperature.' 3—Slip on the {101) or {102) plane in the [loo] direction above 225°C." 4—Critical resolved shear stresses for basal slip in tension at room temperature of 83 g per sq mm with a variation from 57 to 127 g per sq mm." Bakarian' studied the compression of thin wafers of magnesium single crystals and classified the components of the deformation mechanisms as follows: 1—The Basal field: (001) at an angle of less than 20" to the compression surface. Fracture along {101} or slip on (001) followed by {101} fracture. 2—The prism field: (001) at an angle greater than 60" to the compression surface. Twinning on the {102) generally occurring during the early stages of loading, basal slip in the areas of original orientation and (001) slip within twins. 3—The central field: (001) at angles greater than 20" but less than 60" to the compression surface. Slip on the (001). 4—The critical resolved shearing stress for {101} slip above 225°C was 400 g per sq mm. Observations of mechanical twins in hexagonal close-packed metals have been summarized by numerous investigatorsb-' emphasizing a lateral or rotational atomic adjustment, in addition to the pure twinning shear, and the importance of reorienting the basal plane to a position more favorable for continued slip, rather than the resulting small dimensional changes. Criterion for the operative twinning planes has not been clearly established. Schmid and Boas hurmised that an energy condition related to the atom movements is the determining factor. MillerQ bserved that twinning stresses in zinc crystals decreased as the amount of prior deformation increased. Preparation of Specimens Magnesium single crystals % in. in diam x 8 in. long were grown from the melt under an argon atmosphere in a gradient furnace similar to that described by Jillson." Magnesium containing 0.018

Jan 1, 1953

By M. S. Burton, B. W. Christ, G. V. Smith

Evidence of the effects which high-angle grain boundaries and veining subgrain boundaries have on the yield phenomenon of zone-refined iron is reported. Room-temperature tensile tests on 50-mil wive at several gram sizes produced upon recrystallization at diffevent temperatures below 910C (a-y phase-transfornzatzon temperature) show that upper and lower yield stress decrease with increasing grain size. The upper yield point effectively disappears at grain sizes of 81 and 102 u in samples of this diameter. However, samples of 129 p grain size. produced during recrys-tallization at 950°C, exhibit a pronounced upper yield point and an increased lower yield stress. Possible causes of the reversal in the grain-size dependence of yielding are discussed. Veining substructure, detected with picval-HC1 etchant, but not with 2 pct nital, is formed during the a-y transformation, and is believed to account for the observed effecls. The strengthening associated with high-angle boundaries in zone-refined tron is discussed in terms of: 1) the stress dependence of slzp multiplicity, and 2) the stress dependence of dislocation emission from grain boundaries. WIDE use of transmission electron microscopy and dislocation etch-pitting techniques has led to a growing awareness of the presence of dislocation substructures in annealed pure metals. Whereas much speculation'-4 has developed about the influence which subgrain structures have on the mechanical behavior of metals, particularly the yield strength, only limited experimental evidence correlating subgrain structures with lower yield strength has been presented. 2,3,5-7 It is the purpose of this note to present experimental evidence of the effects which grain boundaries and subgrain boundaries have on both the upper and lower yield strength of zone-refined iron. Effects due to high-angle boundaries formed upon recrystallization below the a-y phase transformation are compared with effects due to veining subgrain boundaries formed upon "recrystallization" above the a-y phase-transformation temperature. These effects are further compared with the reported influence 2,3,5-7 which low-angle boundaries have on the lower yield strength of bcc transition metals. EXPERIMENTAL PROCEDURE The starting material for these experiments was a 1-in.-diam zone-refined ingot prepared at Battelle Memorial Institute. Initial purification of electrolytic iron by vacuum-induction melting was improved by a floating zone-melting treatment in ultrapure hydrogen.' Chemical analysis of this zone-refined iron appears in Table I. Tensile samples of 50-mil wire were prepared by rolling and drawing portions of the ingot. An intermediate recrystallization anneal at 625°C after rolling to a reduction in area of 85 pct was carried out in an evacuated Vycor capsule (10-=5 mm Hg). Further reduction in area of 91 pct was followed by recrystallization in evacuated Vycor capsules at temperatures between 600" and 950°C, see Table 111. All samples

Jan 1, 1967

By J. N. Sicking, F. H. Brinkman

A new method for obtaining equilibrium vaporization ratios (K-values) for reservoir fluids has been developed and tested. By application of the method, complex experimental measurements of liquid and vapor phase compositions are eliminated. This simplified technique reduces the cost of experimental equilibrium-ratio data for reservoir studies of condensates and volatile crude-oil systems. The method is designed for systems of constant composition and, therefore, is best suited for depletion studies where compositional changes at high pressures are minor. The basic data required, in addition to the composition of the initial reservoir fluid, are the relative vapor-liquid volumes and densities at reservoir temperature and variom reservoir pressures. Tests demonstrated that the method predicts equilibrium ratios accurately for condensates. A single test on a crude oil was not conclusive; further testing will be necessary before the accuracy of the method can be determined for crude-oil systems. In addition to determining equilibrium ratios, the calculation method provides information on the physical properties of the "plus" component in the vapor and liquid phases. The "plus" component is that mixture of components heavier than the least volatile fraction analyzed. This information is useful in studies of both natural depletion and cycling operations for condensate reservoirs where the heptanes-plus component in the gas phase is produced from the reservoir. INTRODUCTION As more volatile oil and condensate reservoirs are found, the use of phase behavior techniques to predict their performance is increasing in importance. These techniques have long been used for condensate fields and have more recently been applied to crude-oil fields containing oils of medium-to-high volatility. In these phase behavior methods, equilibrium ratios (K-values) are used to predict compositional changes in the reservoir fluids—thereby accounting for the recoverable oil that exists in the gas phase. The reliability of the predictions depends to a large extent on the equilibrium ratios used. These values must be obtained for each component for the entire pressure range being investigated. Unfortunately, because of the complex nature of hydrocarbon mixtures, accurate K-values are hard to obtain. The equilibrium ratios for a particular component will vary not only with the temperature and pressure, but also with over-all composition of the system. The importance of composition is quite critical at elevated pressures, but becomes negligible at pressures below about 300 psia. Therefore, because most phase behavior problems involve the high-pressure region, each fluid system becomes a special case. Experimental programs to determine characteristic K-values are quite difficult and time-consuming. Thus, it is often necessary to resort to approximations of the K-value data. Charts giving K-values for various mixtures and classes of mixtures are available in the literature. However, there are two major difficulties in using them: (1) the K-values of the "plus" component (that mixture of components heavier than the last one analyzed) must be obtained by extrapolation from the K-values of the other components; and (2) the K-values obtained must finally be adjusted by trial and error to agree with observed volumetric data. To eliminate these difficulties, a new method of determining equilibrium ratios was developed. Briefly, after the composition of the system as a whole has been analyzed, the method uses empirical correlations and the gross fluid properties of the system (relative vapor-liquid volumes and densities) to calculate K-values. Because the calculative procedure is long, it is best solved on a digital computer. About one hour of machine time on an IBM 650 computer is required to develop a K-chart for the fluid being examined. DEVELOPMENT OF THE METHOD OF OBTAINING K-VALUES Equilibrium ratios are defined as the ratio of the mole fraction of a component in the vapor phase to its mole fraction in the liquid phase. This statement is expressed in Eq. 1. A typical plot of equilibrium ratios for a particular system is shown in Fig. 1. It should be noted that, at pressures near the saturation pressure, the K-values appear to converge to a common point. This apparent convergence point is called the convergence pressure and is a characteristic of the system involved. Various empirical correlations of K-values have been noted. It has been observed that an isothermal plot of

By Stanley Reichert

The manganese deposits of the Embree Iron Co., Embreeville, Tenn., are thought to be fairly typical and representative of the East Tennessee type of deposit, and so to warrent rather detailed description. The methods used by the Embree Iron Co. for prospecting and mining, and to a lesser extent for milling; should therefore be applicable to other East Tennessee manganese deposits, as yet' undeveloped. Early History and Discovery of Manganese Brown iron ore (limonite) was mined by the Embree Iron Co. at various times from 1890 to 1910. The early method was simply pick-and-shovel mining in open pits. Later hydraulic giants were used and sluice lines carried the ore down the mountain slopes to log washers.. During this phase of mining, manganese ore was discovered under the iron ore in some of the pits. In other areas oxidized zinc ore was found under the iron. It thus happened that the valuable zinc deposits were discovered in 1914. During the World War period, from 1914 to 1918, there was sporadic prospecting for manganese ore among the abandoned iron workings, but the main activity then centered around the recently discovered lead and zinc deposits. It was not until 1934 that manganese mining began in earnest, under the supervision of R. D. Pritchett, Mine Superintendent. Geology of the Manganese Deposits United States Geological Survey Folios 151 (Roan Mountain) and 118 (Greeneville show that Bumpass Cove is a synclinal structure thrust faulted along the southeast flank, but with normal sequence of strata along the northwest flank. Fig, l. shows the areal geology of Bumpass Cove as taken from the folios superposed on the U.S.G.S. -T.V.A. 1/24,000 topographic maps of the Erwin and Telford 7 ½ minute sheets. The manganese mines occur near the contact of the unfaulted Shady dolomite and the Erwin quartzite. This contact zone is deeply weathered, with overburden averaging 40 to 60 ft. thick. The material overlying' the bedrock along this normal contact is a very tough, plastic clay, termed "buckfat" or "ocher" by the miners. It is not a true ocher, however, in the sense of having commercial value. The manganese deposits occur along this "ocher" band. Fig. 1 also shows how the manganese deposits occur along the broad topographic terrace between the 2100 and 2200-ft. contour lines. This terrace lies at the foot the Erwin quartz ridge. Apparently it is the topographic is expression of the deeply weathered zone along the Shady-Erwin contact.

Jan 1, 1941

By C. R. Kyle, R. L. Perrine

A transparent model of a reservoir has been used to study some characteristics of instability in miscible displacement. The linear model dimensions are 1/4 in. x 91/2 in. x 10 ft. The model is packed with spherical glass beads. Thee groups of experiments have been performed. The objectives were to measure, respectively, the rate of growth of the transition zone, flow velocity variations in the transition zone, and the effect of a graded viscosity zone on stability. All experiments were compared, where possible, with theory. The transition zone grew almost linearly with distance traveled, regardless of flow rate, where adverse viscosity ratios were used. At very adverse viscosity ratios and large distances traveled, some reduction below linear growth was noted. This could be attributed to the effects of mixing. General similarity in flow pattern was commonly shown in different tests, although exceptions occurred at the higher viscosity ratios. Injection of tracer spots permitted direct experimental measurement of velocity variations. Statistical methods were used to compare observed velocity variations with recently published theories. Surprisingly good agreement with some theoretical predictions was obtained. In the experiments using an initially graded viscosity zone, macroscopic stability was reached before predicted by theory. Under conditions theoretically considered to be slightly unstable, any fingering tendency was too slight to become observable within a 10-ft long system. The general correlation of all experiments with published theory was good, and suggests that theoretical predictions can be extended to reservoir problems. INTRODUCTION Early laboratory studies of miscible displacement demonstrated the high recovery efficiency possible with this method. Linear laboratory models showed that, under some circumstances, all in-place hydrocarbons could be recovered using as little solvent as 5 per cent of the pore volume. These results led to a series of pilot field projects. Under realistic conditions, however, other laboratory studies showed that a small solvent bank may not recover much more oil than a conventional gas drive. The cause of this lack of efficiency is unstable viscous fingering. The size of the solvent bank required to give optimum recovery is, therefore, a question of great economic significance. The object of the experiments described in this paper was the quantitative measurement of unstable flow parameters, the verification of present theories on the miscible displacement process, and correlation of these theories with ex peri mental observation. Of the theories which have been advanced, those by Dougherty, Koval and Perrine show promise of predicting reservoir performance with reasonable accuracy.l-7 The present experiments were correlated, where possible, with the theories of Koval and Perrine. Dougherty's theory was not used because of the additional computational difficulty it presented and the belief that no further information would result. EXPERIMENTAL EQUIPMENT A transparent reservoir model, consisting of a vertical reinforced plexiglass column, was used for the experiments. The column was packed with glass beads, which served as the porous medium. To induce a known velocity disturbance in the flow, a double cosine wave restriction in the transverse cross-section was placed at the top of the column. To mark the flow field and provide a means of measuring the local fluid velocity, a dye-spot injection system was provided. The column was 10 ft high by 1/2 in. wide by 1/4 in. deep. The cosine restriction was placed 16 in. from the top of the column. The glass beads were smooth and spherical and had a mean diameter of 0.0102 cm. Liquids entered the top of the column through a manifold allowing three points of entry (left, center, and right, or any combination of these). A positive-displacement pump with variable-speed drive was used to control liquid flow rates. The pump transferred viscous oil from a reservoir to an accumulator, which displaced the test liquid into

Jan 1, 1966