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William Metcalf, Pittsburg, Pa. (communication to the Secretary*): I am greatly pleased that some one has at last reached what I have long regarded as the only rational explanation yet given of the reasons why steel hardens. Mr. Field claims originality; and doubtless he is entitled to it, but not to priority, mhich must be granted to Prof. John W. Langley.' The difference between them is that Langley says " Tension, probably molecular," and Field says " Tension, probably atomic "; in either case the vital thing after solution is tension. Mr. Field's argument carries with it the idea of increase of density with hardness; if he mill study the facts farther he will observe that the case is just the reverse; that is, the greater the hardness the less the specific gravity; it was just this fact that led Langley to his conclusion, in mhich I have always concurred. Field agrees with Langley that the first requisite for perfect hardening is complete solution of the carbon, not combination; and all of the facts agree with this conclusion. The fact that increase of hardness causes reduction of density was first brought to my notice some 40 years ago, when Major William Wade was testing Jones & Laughlin's cold-rolled iron, and I mas his assistant. We found the well-known increase of tenacity, compressive strength, torsional resistance, and hardness. Specific-gravity tests showed that the cold-rolled iron was less dense than the hot-rolled bars. Major Wade was so surprised at this result that he gave me a lot of samples to weigh, saying that he was not satisfied with

Jan 1, 1904

By A. L. Mincher, W. F. Sheely

Mechanical properties of columbium have been studied over the temperature range of -196 to 1093oC. The decreased strengthening influence of cold-work at temperatures below ambient has been interpreted in terms of the Peierls-Nabarro effect. Maxima in the rate of strain hardening observed during tensile testing in the range 250-600°C. have been correlated with interstitial impurities to indicate the temperature ranges at which carbon, oxygen, and nitrogen, respectively, are responsible for strain aging. THE growing need for structural materials for use above the useful service temperatures of the iron-, nickel-, or cobalt-base alloys has caused the refractory metals to be considered as potential engineering materials. These metals, which include columbium, tantalum, molybdenum, and tungsten, are called refractory because the lowest melting point among them,that of columbium, is about 1000°C higher than the average melting temperatures of conventional high-temperature alloys. They are all body-centered cubic transition metals and, as such, their mechanical properties have basic characteristics which distinguish them from the face-centered cubic metals. For example, all show a much steeper rise in strength with decreasing temperature below room temperature than do the face-centered cubic metals, and their mechanical properties are strongly influenced by interstitially dissolved impurities. In order that these new metals may be used efficiently, it is necessary that their characteristics of behavior be fully known. In this paper, the mechanical properties of columbium will be examined over a wide range of temperatures. In particular, the influences of cold-work and individual species of interstitial impurity atoms on mechanical properties will be described, and basic mechanisms which may control the observed characteristics will be explored. EXPERIMENTAL The material used in this investigation was Union Carbide Metals Co. columbium roundels consolidated to four 4-in. diam ingots, three by consumable-electrode arc melting and one ingot by electron beam melting. Impurity contents of the ingots and methods of ingot conversion and treatment are summarized in Table I. The only metallic impurity occurring in any significant quantity was tantalum at about 0.1 pct. Iron, silicon, titanium, and zirconium were each less than 0.015 pct; boron was 1 ppm or less. This should have no appreciable influence on properties. The electron beam melted material, being the purest, will be used as the basis for comparison in the discussions to follow. Tensile tests were conducted from-196 to 1093oC, on both cold-worked and fully recrystallized arc-melted and electron-beam melted columbium using standard 1/4-in. diam, 1-in. long gage length test specimens. A strain-rate of 0.005 in. per in. per min was employed until the 0.2 pct yield strength was achieved and then the strain-rate was increased to 0.05 in. per in. per min for the balance of the test. Samples were protected in an inert atmosphere at tests above 300°C. The tensile properties obtained on the electron-beam melted columbium, E, in both the cold-swaged and recrystallized conditions are given in Fig. 1. The yield strength data of Dyson, et al.,' obtained on recrystallized electron beam melted columbium and the tensile strength data reported by Tottle2 on powder metallurgy columbium are included in Fig. 1. The material used by Tottle had been purified by vacuum sintering. There is excellent agreement between Dyson's data and those obtained in the present investigation. The tensile strengths obtained by Tottle were slightly greater than those obtained in this investigation on electron-beam melted columbium but varied with temperature in a similar manner. Tottle's data showed a maximum in tensile strength near 500°C, as did our data on electron-beam melted material, and also showed a small maximum at 300°C. The significance of these maxima will become evident later in the discussion. The tensile properties of cold-swaged and recrys-tallized arc melted columbium are plotted in Fig. 2. It was found that the properties of the recrystallized arc-melted columbium from all three heats showed very close agreement except at temperatures between about 500" and 800°C. A reason for this range of disagreement will be suggested in the discussion. The generally good agreement, however, attests to the ability of cold-working and subsequent recrystal-lization to erase the effects of the three different primary breakdown procedures and to produce nearly equivalent structures in the samples derived from the three different heats. wesse13 reported tensile data on columbium having interstitial impurity contents between those of the

Jan 1, 1962

By Charles H. Shamel

I fear most of the Institute members are already weary of the perennial controversy about the apex law. I feel that way about it myself now, though I have been guilty of considerable contribution- to the discussion in the past. The discussion does not seem to perceptibly influence previously held views and I would not again break into print on the subject but for the urgent invitation of the Chairman of our Law Committee. This energetic and able member has firmly determined to secure a revision of the mining law and among other things to eliminate the so-called apex provision from the U. S. mining statutes. He is, however, fair about it and has invited me to make ((the strongest possible argument in its favor." I am suspicious that he is acting on the psychological principle that it is usually easier to convince an audience against a cause vigorously but unsuccessfully defended than against one wholly mute. Nevertheless, I realize that personally he wishes me no harm, much as he hates the apex law, and so am willing that the Institute have whatever benefit may accrue from my taking up again the unpopular side of the discussion. I say this because the attitude of a large part of our "articulate" membership seems irreconcilably hostile; their minds are made up; favorable consideration is foreclosed; and they become impatient and even sarcastic at any attempt to elucidate a favorable view of the apex law. The exact question for discussion at the present time is not whether on abstract, or any other considerations, the apex law is the best possible rule, but the very different proposition whether, after nearly 50 years of statutory life and much longer as a practically universal miners' custom, it is now just and expedient to repeal the apex law. At this point it seems to me that we may profitably devote a paragraph or two to the subject of the origin of law in general, as we are presumed to be considering the subject from the high viewpoint of the general welfare of the nation. The most comprehensive and accurate definition of law in the legal sense is, that it is the body of rules for the regulation of human conduct which is enforced by the State, that is, by the nation.l Legal

Jan 1, 1915

By G. A. Vissac

In the presentation which follows, wash-ability curves, such as are commonly used in making studies preliminary to the cleaning of any coal or to the concentration of any mineral, have been reduced in each instance to a single straight line; thus all the most important characteristics of the coal or mineral are represented in a form more advantageous than that in which such data usually are shown. To obtain consistent results, float-and-sink data must be based on a single definite narrow size range, which may be designated "a coal unit." It will be shown that such units, each embodying a different size range, can be grouped to form what may be termed "a composite coal." A three-dimensional presentation will emerge, which will closely identify the coal, illustrate its characteristics in a new manner and explain many obscure facts. Float-and-sink Tests For the preliminary study of any cleaning or concentration problem, or in the control of any operation, float-and-sink tests must be made. The results of these tests are grouped in tabular form and then illustrated in various systems of curves; but if such a graphic representation is to have the utmost practical value, it must offer at least the following advantages: (I) It must be easier to read than the tabular results, and (2) it must be easy to plot, check and interpolate. The first requirement will be attained by reducing the number of curves to a minimum, and the second by some system of representation that will use only straight lines. Of the many washing curves now in use, only the "recovery curve," often known as the "composite curve"—a somewhat misleading term—will be considered; Any point on the recovery curve will show what percentage of weight of clean coal can be recovered when the mineral is washed at a certain specific gravity. As an example, the tests listed below Fig. I are illustrated in the drawing by a curve obtained by plotting (I) as abscissas the ash content of the coal recovered and (2) as ordinates the corresponding percentage of refuse discarded; but, in general practice, instead of writing down that weight, it is customary to set down its complement, which is the corresponding weight of coal recovered. From this curve can be deduced the information necessary for the solution of most practical problems. New Form of Graphic Presentation The resemblance of the recovery curve ill Fig. 1, or, for that matter, the recovery curve obtained in common practice! to a Power curve is apparent. The general equation of such a curve is Y = axn, where n is negative. Taking logarithms: log y = a + n log x. Using a logarithmic scale, the equation of the recovery curve will be Y = A + bX. On this logarithmic basis! the recovery graph will be a straight line, using the same variables as in Fig. I; namely, the ash con-

Jan 1, 1942

By W. A. Bruce

This paper presents the essentials of a mathematical method of studying the pressure behavior of an oil reservoir as the fluids are withdrawn. Methods are shown Whereby the behavior of a reservoir can be used to predict the future relationship between withdrawals and pressure. The oil reservoir is considered as a small part of a large porous continuum, which contains for the most part water. The expansion of this water resulting from a decrease of pressure in the oil zone causes a movement of water that is an important factor in the relationship between fluid withdrawals and reservoir pressure. Examples are given to illustrate the methods of pressure prediction for a circular reservoir containing undersaturated crude, the pressure distribution over a field that has a uniform production rate, the effect of a fault line near a field, the mutual interference of near-by fields, and the perturbing influence of a gas cap. Applications of the analysis to well-spacing problems are shown. Introduction The pressure-prediction methods to be described here are based upon the conception of an oil pool as a small part of a large porous continuum, containing for the most part water. The formation containing this water may be thought of as extending over an area of many square miles and having one or more small bodies of oil or gas trapped in high spots or reservoirs. It will be treated as having the genera1 aspect of a thin, flat sheet with an over-all tilt to the horizontal and with numerous small high spots, tight zones, and irregularities This porous continuum will be treated as being much more extensive than the oil or gas zones, but will be recognized as terminating at such large boundaries as a general fault, outcrop, unconformity, or pinch-out. Throughout the greater part of this limited porous continuum it is likely that there is a hydraulic connection. If this is true, the removal of fluid in one place will cause a disturbance that eventually will travel to all parts of the continuum. This picture has led to the recognition of water as the major fluid in the porous continuum and in many cases the expansive nature of this water as the main driving force producing the oil. The next step is the solution of the general problem of compressible liquid behavior in porous media. The works of Hurst I and Muskat2 introduced the idea of using heat-flow mathematics to consider the problem of compressible liquid flow in a porous medium. Before their reports, it had been thought sufficient to use the incompressible fluid-flow work of S1ichter.3 Law Muskat4 pointed out in detail how far the incompressible-fluirl assumption, deviated from fact even for water, of which the compressibility is about 3 X 10-6 volumes per unit volume per pound per square inch. He showed that this deviation increased with increases of distance. For example, the incompressible-fluid formula might show good agreement with the

Jan 1, 1943

By W. A. Bruce

This paper presents the essentials of a mathematical method of studying the pressure behavior of an oil reservoir as the fluids are withdrawn. Methods are shown Whereby the behavior of a reservoir can be used to predict the future relationship between withdrawals and pressure. The oil reservoir is considered as a small part of a large porous continuum, which contains for the most part water. The expansion of this water resulting from a decrease of pressure in the oil zone causes a movement of water that is an important factor in the relationship between fluid withdrawals and reservoir pressure. Examples are given to illustrate the methods of pressure prediction for a circular reservoir containing undersaturated crude, the pressure distribution over a field that has a uniform production rate, the effect of a fault line near a field, the mutual interference of near-by fields, and the perturbing influence of a gas cap. Applications of the analysis to well-spacing problems are shown. Introduction The pressure-prediction methods to be described here are based upon the conception of an oil pool as a small part of a large porous continuum, containing for the most part water. The formation containing this water may be thought of as extending over an area of many square miles and having one or more small bodies of oil or gas trapped in high spots or reservoirs. It will be treated as having the genera1 aspect of a thin, flat sheet with an over-all tilt to the horizontal and with numerous small high spots, tight zones, and irregularities This porous continuum will be treated as being much more extensive than the oil or gas zones, but will be recognized as terminating at such large boundaries as a general fault, outcrop, unconformity, or pinch-out. Throughout the greater part of this limited porous continuum it is likely that there is a hydraulic connection. If this is true, the removal of fluid in one place will cause a disturbance that eventually will travel to all parts of the continuum. This picture has led to the recognition of water as the major fluid in the porous continuum and in many cases the expansive nature of this water as the main driving force producing the oil. The next step is the solution of the general problem of compressible liquid behavior in porous media. The works of Hurst I and Muskat2 introduced the idea of using heat-flow mathematics to consider the problem of compressible liquid flow in a porous medium. Before their reports, it had been thought sufficient to use the incompressible fluid-flow work of S1ichter.3 Law Muskat4 pointed out in detail how far the incompressible-fluirl assumption, deviated from fact even for water, of which the compressibility is about 3 X 10-6 volumes per unit volume per pound per square inch. He showed that this deviation increased with increases of distance. For example, the incompressible-fluid formula might show good agreement with the

Jan 1, 1943

By G. A. Vissac

In the presentation which follows, wash-ability curves, such as are commonly used in making studies preliminary to the cleaning of any coal or to the concentration of any mineral, have been reduced in each instance to a single straight line; thus all the most important characteristics of the coal or mineral are represented in a form more advantageous than that in which such data usually are shown. To obtain consistent results, float-and-sink data must be based on a single definite narrow size range, which may be designated "a coal unit." It will be shown that such units, each embodying a different size range, can be grouped to form what may be termed "a composite coal." A three-dimensional presentation will emerge, which will closely identify the coal, illustrate its characteristics in a new manner and explain many obscure facts. Float-and-sink Tests For the preliminary study of any cleaning or concentration problem, or in the control of any operation, float-and-sink tests must be made. The results of these tests are grouped in tabular form and then illustrated in various systems of curves; but if such a graphic representation is to have the utmost practical value, it must offer at least the following advantages: (I) It must be easier to read than the tabular results, and (2) it must be easy to plot, check and interpolate. The first requirement will be attained by reducing the number of curves to a minimum, and the second by some system of representation that will use only straight lines. Of the many washing curves now in use, only the "recovery curve," often known as the "composite curve"—a somewhat misleading term—will be considered; Any point on the recovery curve will show what percentage of weight of clean coal can be recovered when the mineral is washed at a certain specific gravity. As an example, the tests listed below Fig. I are illustrated in the drawing by a curve obtained by plotting (I) as abscissas the ash content of the coal recovered and (2) as ordinates the corresponding percentage of refuse discarded; but, in general practice, instead of writing down that weight, it is customary to set down its complement, which is the corresponding weight of coal recovered. From this curve can be deduced the information necessary for the solution of most practical problems. New Form of Graphic Presentation The resemblance of the recovery curve ill Fig. 1, or, for that matter, the recovery curve obtained in common practice! to a Power curve is apparent. The general equation of such a curve is Y = axn, where n is negative. Taking logarithms: log y = a + n log x. Using a logarithmic scale, the equation of the recovery curve will be Y = A + bX. On this logarithmic basis! the recovery graph will be a straight line, using the same variables as in Fig. I; namely, the ash con-

Jan 1, 1942

INTRODUCTION The preceding chapters have brought us to a point in the mineral appraisal process where the composited sample values can now be used to estimate the grade and tonnage of the total mineral deposit. There are many techniques whereby drill hole composites and/or other sample data are used to assign grade and estimates to the surrounding rock. Matheron and his students have properly called such techniques extension functions. Before embarking upon a detailed discussion of extension functions, it is necessary that we take time to consider the concept of geostatistics as advocated by George Matheron who developed the "Theory of Regionalized Variables," which he published in 1962 (Matheron, 1971). The concept of regionalized variables has important application in the techniques of mineral appraisal. The position or location of a mineral sample within a deposit can be almost as important as its value. Geostatistics, when defined as "the application of the theory of regionalized variables* to the study of mineralized volumes of rock," takes into consideration the position as well as the magnitude of the value of the sample. The principles of geostatistics, as outlined by Matheron, represent a major step forward in the mineral evaluation process, because they provide a sound theoretical and practical basis for quantifying the geological concepts of (1) area of influence of a sample, (2) the continuity or lack of continuity of mineralization within the ore body, and (3) the lateral changes in mineralization according to the trend direction of an ore body and its orthogonal components; or in other words, a measure of the anisotropy of the deposit. Royle (1971) has defined the objects of geostatistic as being: "1. To estimate the most likely value of blocks of ore, or the values of the whole deposit; and 2. to estimate the errors of such estimates. This latter is important as, in addition to providing a check on unwarranted optimism, it shows where more valuation work may be needed." Because of the great importance of these concepts in mineral evaluation, an introduction into the theory of regionalized variables, and the study of a practical approach to its application is outlined here. REGIONALIZED VARIABLES VS. RANDOM VARIABLES Classical statistics, as discussed in earlier chapters, grew out of the study and application of probability theory. Probability is concerned with the outcome of random events and therefore classical statistics is built upon the theory of random variables, i.e., the probability of independent events. The validity of most statistical inferences depends upon sample randomness being assured for unbiased results. Where independent events cannot be assumed the results of statistical inference becomes suspect. On the other hand, geostatistics is concerned with variables that have position in space as well as magnitude, hence the term regionalized variables. Mineral deposits are not the only field to which the theory of regionalized variables is applicable. Many natural phenomena that demonstrate a relationship between change in magnitude and position in space are amenable to application of geostatistical techniques. Mineral deposits vary greatly in their geosta-

Jan 1, 1980

By H. G. Doll

As a continuation of the earlier paper on the general subject of the SP log, a more complete analysis of certain features of the SP log in shaly sands is given. The pseudo-static SP in front of shaly sands is compared, on a theoretical basis, to the static SP in front of clean sands, as a function of the respective amount of shale and sand in the formation, and of the relative resistivities of the shale, of the uncontaminated part of the sand. and of the invaded zone of the sand. As a conclusion, the advantage of using reasonably conduc. tive mud in this case is shown. The discussion is illustrated by field examples. INTRODUCTION The discussion reported in the present paper is based on a theoretical analysis, and not on experiment. The field examples, joined to the text. are shown only as qualitative illustrations of the essential results of this analysis. Although the hypotheses made in the theoretical developments may perhaps be somewhat improved, it seems, nevertheless, that the results obtained account reasonably well for the actual phenomena, and give a fair approximation of their order of magnitude. The paper contains a mathematical analysis of a tri-dimen-sional distribution of potentials and current lines. due to spontaneous electromotive forces arising at the contact of shales and free electrolytes. as a function of the geometry and of the respective resistivities of the different media involved. It is assumed, although this hypothesis is not proven, that the emf's remain the same even if the shale occurs in very thin layers or in dispersed particles. It has already been pointed out 1,2,3 that, all other conditions being the same, the deflection of the SP log in front of a shaly sand is smaller than opposite a clean sand. When the thickness and the conductivity of a clean sand are large enough. the deflection of the SP log reaches a limiting value which is equal to the "static SP" of the clean sand. It is generally convenient to take the static SP of shale as the reference value or "base line." As a consequence, and for the sake of abbreviation, the expression. "static SP of a clean sand," is often used to designate the difference between the static SP of that sand and that of the shales, which difference is a measure of the total electromotive forces involved in the chain mud sand-shale. A similar limiting value is; also observed for the SP deflec-lion opposite a thick shaly sand, but it is smaller. just as if the total electromotive force involved were smaller in that case. This limiting value has been called the "Pseudo-Static SP" of the shaly sand. The static SP of a clean sand depends on the salinity of its connate water with respect to that of the mud, and, to a certain extent. on the differential pressure which controls the electro-filtration potentials, but it does not depend on the resistivity of the sand. On the contrary. the pseudo-static SP of a shaly sand depends not only on the salinity of its connate water and on the differential pressure, but also on the percentage of shale and on the resistivities of the shale, of the uncontaminated part of the sand, and of the zone invaded by the mud filtrate. If the three resistivities above were equal, the pseudo-static SP would be proportional to the percentage of sand in the shaly sand, and its departure from the static SP of a clean sand having the same connate water would simply be proportional to the percentage of shale. In that case, the pseudo-static SP of a shaly sand containing 10 per cent of shale would he 10 per cent less than the static SP of a clean sand. When. however. the sand is. on the average. substantially more resistive than the shale. the percentage of departure of the pseudo-static SP from the static SP of a clean sand is much larger than the percentage of shale. For that reason, the peaks of the SP log opposite shaly sands are systematically of smaller amplitude when the sands are oil-bearing than when they are water-bearing, all other conditions being the same. This feature is observed even when the sand beds are thick. and even when they do not contain a large percentage of shale. All this has already been described in all earlier publication", but mostly in a qualitative way. The present paper will analyze in more detail the action of the local SP currents which are generated inside of the shaly sands, and which are responsible for the abnormally low value of the pseudo-static SP. The quantitative computations have been extended to the general case of thin interbedded layers of sand and shale, where the resistivities of the shale and sand streaks do not have the same value: they are summarized in charts giving values of the pseudo-static SP of a shaly sand as a function of the different parameters involved. DEFINITIONS The static SP of a clean sand has been defined as the potential that would exist in the mud opposite that sand, were the SP current prevented from flowing. Such an ideal condition is represented on Fig. I-A. By analogy, the pseudo-static SP of a shaly sand can be defined as the potential that would exist in the hole, if the circuit shaly sand — surrounding shales — mud column were interrupted by the insulating plugs placed at the boundaries

Jan 1, 1950

By R. D. Pehlke, J. V. Gluck

A study was made of' the effects of up to five additional solutes on the thermodynamic activity of zinc in dilute solution with molten bismuth in the range 450" to 650°C. The experimental measurements were made in a multielectrode galvanic cell apparatus employing fused LiCl-KCl as the electrolyte. The solute additions included indium, lead, tin, cadmium, copper, silver, antimony, or gold. A range of positice and negative interactiotls with zinc was covered. The experinzer~tal observations were cowlpared with the activity coefficients calculated usitlg either Wagner's first-order Taylor series rnodel or a proposed second-order solution itrteraction model. hi general, the truncated first-order Taylor series proposed by Wagner gaue good results for "dilute" solutions (XBi > 0.90) contaitzing up to six solutes. The second-order model, which includes a second-order cross-interaction term, produced a slight improvement in predictions for solutions with XZn = 0.015 and a significant improvement for solutions with XZn = 0.050 hear the limit of Henry's law region). Seveval of the quaternary solutions studied contained a total solute content of 0.215 mole fraction, and fairly good success was achieved in predicting the activity coefficient 01- zinc. ThE study of thermodynamic interactions between dilute solutes in liquid metallic solutions has occasioned much recent interest. It is useful to recall in this respect that Wagner's well-known expression for the activity coefficient' is a practical application of the problem of representing a given function, i .e., In ?, by means of a sequence of polynomials. No specific physical model of a solution is involved in its use. As suggested by Wagner, a Taylor Series is used to expand In ? about a point of infinite dilution with respect to all solutes. The partial differential coefficients of the series have been termed "interaction parameters". Various authors'-6 have proposed formalisms for parameters, the definitions being designed to meet some specific experimental or physical condition. A usual assumption is that terms above first-order in the Taylor Series may be neglected. In that case, the logarithm of the activity coefficient is expressed as a linear function of solute concentrations. The resulting expression is presumed valid for any number of additional solutes as long as the solution can be regarded as "dilute". This assumption can be termed "the hypothesis of additivity". However, experimental tests of that hypothesis for quaternary or higher-order solutions have been extremely limited. Primarily such tests have been confined to studies of effects of added metallic elements on either the activity of carbon or the solubility of gases in liquid iron.7-13 The only known previous study of an all-metal system is the limited work of Okajima and pehlke14 on the effects of multiple solute additions on the activity of cadmium in liquid lead. The present investigation is a portion of the work to determine the effects of various solute additions on the activity of zinc in dilute solution with molten bismuth in the range 450" to 650C It was shown for such ternary solutions that second-order Taylor Series terms could be evaluated at the same time as first-order terms, with no additional experimentation required. A second-order solution model was described which, under certain conditions, is a rigorous representation of solute activity in a ternary solution. (In the sense employed in this paper, the term "model", as distinguished from "equation", is taken to mean an empirical correlation or formalism, but not a hypothetical physical system per se.) Presumably such a model could be extended to produce a better representation of In ? in solutions of even higher order. The feasibility of a generalized Taylor Series approach to solution interactions and inclusion of second-order terms also has been discussed recently by Lupis and Elliott in independent work concurrent with the present investigation. In addition, they discussed empirical means of estimating certain second -order coefficients.17 The utility of such solution models rests on the ability of a truncated series to represent adequately the experimental facts in multicomponent solutions. Questions that arise include: Do the second-order terms really make a significant contribution? How far away from "dilute" solution may such models be applied? Are the types and varieties of the additional solutes important? among others. In order to provide some answers to these questions, an experimental study was made of the effects of two or more additional solutes on the activity of zinc in dilute solution with molten bismuth. Comparisons were then made with calculated activity coefficients obtained using the previously determined ternary interaction parameters. INTERACTION MODELS As an example of the approach to defining activities in multicomponent solutions, consider the Taylor Series expansion for a quaternary system, i.e., three dilute solutes. Writing terms through second order, the result is:''

Jan 1, 1968

By John R. Don

This paper, under the title of "The Genesis of Auriferous Lodes from a Chemical Point of View, Illustrated by Analyses of Samples Taken from the Chief Auriferous Area of New Zealand, Victoria and Queensland, by John R. Don, D.Sc., M.A., Lecturer on Geology in the University of Otago, N. Z.," was submitted by the author with the frank confession that its length, covering several hundred printed pages of the Transactions of the Institute, would preclude its acceptance for publication in full. But the great value of the original work which it records rendered its rejection on that ground highly undesirable ; and, after correspondence with Dr. Don, it was agreed that the Secretary should condense the paper, subject to the author's approval, omitting what was not essentially connected with the original work reported. In the discharge of this laborious and difficult duty, the Secretary's chief trouble has been his regret to cut out the acute criticisms and admirable theoretical and historical summaries of Dr. Don on the general subject of the science of ore-deposits. It should be added, that the original paper has been returned to the author, with full permission to publish it through any other medium (due mention being made of the first publication by the Institute of portions thereof), and a cordial expression of the hope that the treatise, as a whole, may be thus published, to the advantage of science. The Secretary begs to add, that many of the portions necessarily omitted from this condensed version would constitute, in his judgment, interesting and valuable separate contributions. In attempting to condense this paper, it was necessary at the outset to cut out the tint three chapters, of which the following brief outline is therefore given. Chapter I., introductory in character, indicates the importance of chemical analysis in the investigation of the genesis of ore-deposits, emphasizing the value of Prof. Posepny's Institute paper, and especially of the discussion which it aroused, and stating in general terms the theories of "lateral secretion" and "ascension." Chapter 11. describes the scope of the investigation undertaken by the author, the chief purpose of which was to determine which of the above-named theories was favored by the evidence obtained. This evidence consists chiefly (though not wholly) of analyses of the country-rock taken at various distances from the auriferous "reefs," (a) on deep mine-levels; (b) in the surface or "vadose" region : and also (c) of underlying, neighboring or connected crystallines (granite, gneiss, etc.). In addition to these investigations, there is a separate inquiry into the question of the deposition of gold in marine basins, suggested by the fact that most of the gold in the lodes of Australasia occurs in stratified deposits. Chapter 111. discusses the principles and methods followed by the author in the examination of country-rock for the purpose described. After giving his reasons for believing that careful tests of carefully-chosen samples of country-rock taken at varying distances from the ore-deposit might throw light upon the question

Jan 1, 1898

By R. J. Blackwell, J. R. Rayne, J. R. Henderson, W. M. Terry, D. C. Lindley

This paper presents the results of a laboratory investigation of the efficiency of water-solvent mixtures in recovery of oil. These mixtures may have the high displacement efficiencies characteristic of solvent floods and the high sweep efficiencies characteristic of water floods. Thus, the water-solvent process may increase the number of reservoirs in which a miscible-type displacement can be used profitably. The experiments on the use of water-solvent mixtures for recovery of oil were conducted to find the general applicability of the process. These studies demonstrated that, in flowing through sands, water and solvent segregated into a solvent layer on the top and a water layer on the bottom rather than flowing through the sands as a uniform mixture. Calculations based on the simultaneous flow of the water and solvent in layers were used to predict the effective mobility of the mixtures and the optimum operation of the process in steeply dipping, homogeneous reservoirs. As most reservoirs are not suited for the operation of the process under ideal conditions, experimental studies were conducted with sand-packed models scaled to represent more realistic reservoirs. These studies included the effects on recovery of oil of rate of injection, viscosity of oil, variations of permeablity within a formation and variations in water-solvent ratio. For the range of con-ditions studied, higher recoveries of oil were obtained with water-solvent mixtures than with water or practical volumes of solvent alone. INTRODUCTION A group of intriguing—because of their great possibilities—new oil recovery methods at the disposal of the petroleum engineer are the miscible displacement processes. These processes (high-pressure gas drive, en-riched-gas drive and LPG bank driven by methane) displace all of the oil from the portions of the reservoir swept by the injection fluid. The key question confronting the engineer applying one of these techniques to a particular reservoir is, "What fraction of the reservoir can be swept by injection of a practical volume of solvent?"." Intensive laboratory studies have been made during the past several years in seeking answers to the question of the sweep efficiencies which can be expected in solvent floods.' - These studies provided the answer that low-viscosity, low-density solvents channel and by-pass oil in sands with no dip. In horizontal sands, solvent flooding becomes less efficient as the viscosity of the oil increases, the recovery of oil at solvent breakthrough decreases and larger volumes of solvent are required to achieve a given recovery. More efficient displacement of oil by solvent is observed under certain conditions in sands with dip.".' If the permeability and dip of the sand are sufficiently high, gravity segregation of low-density solvent injected updip can prevent channeling. At rates of depletion below a critical rate,"." no channeling occurs. Unfortunately, in many reservoirs, the critical rate is so low that production of oil at rates below this rate is not economically attractive. And at rates over four times the critical rate, channeling is almost as severe in sands with dip as in horizontal sands. These findings pointed out that, for solvent floods to be generally applicable in recovering oil from all types of reservoirs, new methods of improving their sweep efficiencies are needed. Simultaneous injection of water with the miscible fluid was suggested by Caudle and Dyes7 as a method for improving sweep efficiencies. They theorize that water flowing with the solvent would decrease the effective mobility of the solvent and cause it to contact more oil sand. If, indeed, the water and solvent flowed as a uniform mixture, the process should have the advantages of the high displacement efficiencies characteristic of miscible floods and the high sweep efficiencies of water floods. Thus, the method (at least in theory) would greatly increase the number of reservoirs in which miscible-type displacements would be feasible. A research program was conducted to probe the technical feasibility of the water-solvent process. It

By R. Floyd Farris

Al thorough knowledge of the behavior of cement slurries under elevated temperatures and pressures is necessary in order to solve properly the many problems presented in deep-well cementing operations. In the earlier days of the petroleum industry the depths of wells were shallow as compared to those of today, and the subsurface temperatures and pressures were not of sufficient magnitude to affect seriously the problem of proper control of cement-slurry properties. Today, however, the search for new reserves has extended drilling to such depths that bottom-hole temperatures of more than 200°F. and bottom-hole pressures of 3000 to 5000 lb. are not uncommon. Moreover, there is every indication that within the next few years wells will be drilled to even greater depths and bottom-hole temperatures and pressures will be correspondingly higher than those with which we are concerned today. It has been realized for some time that the behavior of cement slurries at high temperatures and pressures might be very different from that at atmospheric tempera-ture-pressure conditions, but while the temperature effects have been investigated with a reasonable degree of thoroughness, the pressure effects have received little public attention. While the trend toward deeper drilling may make changes in cementing technique and the choice of cements imperative, it was the purpose of this investigation to consider factors having a bearing on the latter, only secondary consideration being ,given, for the present, to details of tech-nique and equipment for oil-field use. More specfically, the purpose of this work was to consider the effect of temperature and pressure upon the behavior of cement slurries. Although it has long been recognized that cements thicken and set rapidly with increasing temperatures, practical methods for the quantitative determination of these effects are comparatively recent developments. In 1935 Silcox and Rule1 presented such a method, describing apparatus designed to measure the consistency-time relationship of cement slurries at relatively high temperatures. The practical importance of this apparatus in furnishing useful data for the evaluation of cement slurries for cementing operations has been emphasized in various technical publications by such writers as E. L. Davis,~ I. F. Bing-ham,3 and J. E. Weiler.4 A paper describing the numerous tests now used to evaluate cements for oil wells was presented in 1939 by W. W. Robinson.= Robinson describes the Consistometer and the Thickening-Time Tester, showing similarity of data from the two devices, and points out that the purpose of each apparatus is to determine the allowable time that a cement may be pumped at a given temperature. At the present time, however, it is believed that results from the Thickening-Time Tester and the Consistometer have not given a

Jan 1, 1941

By A. William Johnson

It was pointed out in an earlier paper1 that our understanding of the atomic mechanism by which diffusion occurs in metallic alloys is scarcely in an advanced state. This unsatisfactory condition is the result not of any lack of interest, but of the difficulty of designing experiments that .will yield suitable data. The diffusion coefficient of an alloy, measured in the usual way, is simply a number specifying the rate of homogenization of a nonhomo-geneous metal; this number, of itself, can furnish neither the rate at which the individual atoms move nor information as to the mechanism by which they move. It does not necessarily follow, however, that such information cannot be obtained, even if the path to be followed is still not clear. Much success has been attained in the study of diffusion in ionic crystals. A number of experiments, for which there are few counterparts in connection with metals, yield information often indicating a detailed mechanism by which diffusion probably occurs. From such work, quite acceptable theories of lattice imperfections have been developed by Wagner, Schottky, Frenkel, Jost and others.2 It is postulated that real crystals of stoichiometric composition contain, in equilibrium, certain imperfections of which the most importarlt types are: (I) vacant cation sites, with an equal number of interstitial ions; (2) vacant anion sites, with an equal number of interstitial ions; (3) equal numbers of anions and cations in interstitial positions; (4) equal numbers of vacant anion and cation sites. The classification of a particular crystal according to this scheme then follows from studies of the variation of electrical conductivity with pressure of the electronegative component surrounding the crystal, with ion size, and with temperature; other physical phenomena, such as the Hall effect, have aided in establishing the classification. The relative mobility of the anion and cation may be determined by chemical analysis of the salt at the electrodes following electrolysis. With such information, and knowing that one ion never occupies the lattice site normally belonging to an ion of opposite sign, it is usually possible to ascertain the diffusion mechanism. It is clear that the same experiments are not applicable to metal crystals, and substitute experiments that yield as much information have not yet been devised. Much can be learned, however, about the mobilities of the two* kinds of atoms in alloys by the use of radioactive metals as indicators. Only one such experiment has been performed in the past. In 1933, Seith and Keil,3 in an effort to explain the great difference between the rate of diffusion of gold in lead and of lead in lead, measured the rate of diffusion of radioactive lead in 3 gold-lead

Jan 1, 1942

By R. C. Buehl, J. P. Riott, E. P. Shoub

PILOT-PLANT tests have demonstrated that it is possible to produce low-sulphur sponge iron (0.03 to 0.05 per cent sulphur) as a continuous process in an internally fired rotary kiln from iron ore or mill scale; a solid carbonaceous reducing agent; and dolomite to control the sulphur content. The proportion of dolomite employed is small, so that it does not add materially to the cost of the sponge iron. The entire operation is carried out at temperatures well below the melting point of iron, so that the product is discharged in granular form. Compared with other methods for the production of sponge iron, the rotary-kiln method has the advantage of simplicity and low cost of equipment and; in addition, requires little labor for the operation of the process. The pilot-plant equipment used for this work was sufficiently large to demonstrate that the production of low-sulphur sponge iron in rotary kilns is feasible and that the costs are not excessive for applications in which sponge iron has distinct advantages over competing materials. This report constitutes a part of a program by the Bureau of Mines under a special Congressional appropriation for studying gaseous and solid fuel reduction of iron ores. Numerous articles on various phases of these investigations have appeared in Bureau of Mines publications or technical journals. Other articles are being prepared and will be published in the near future. The present program, which is under the supervision of Dr. R. S. Dean, Assistant Director of the Bureau of Mines, was initiated in .1942. However, a considerable portion of the work was a continuation of previous research performed by the Bureau. Previous investigators1-4 utilizing the rotary kiln for the production of sponge iron did not develop a suitable method for controlling the sulphur content. A review of the literature shows that the sulphur content in the product usually exceeded 0.2 -per cent unless reducing agents with very low sulphur contents were employed. This high sulphur value made the product generally undesirable for use as melting stock in electric or open-hearth furnaces. The production of sponge iron in an internally fired rotary kiln has been described in detail in Bureau of Mines Bulletin 2702; consequently, this article will be confined mostly to new features of the process-that is, means for controlling the sulphur content of the sponge iron. Suitable raw materials include iron ores or mill scale; coal or coke for reducing them, and sized dolomite (-20+100-mesh) as the sulphur-controlling agent. A mixture of the raw materials in granular form is fed into the elevated end of the kiln, which is fired axially from the lower or discharge end. In the reducing zone, which is approximately one third the length of the kiln measured from the dis-

Jan 1, 1946

By R. Floyd Farris

Al thorough knowledge of the behavior of cement slurries under elevated temperatures and pressures is necessary in order to solve properly the many problems presented in deep-well cementing operations. In the earlier days of the petroleum industry the depths of wells were shallow as compared to those of today, and the subsurface temperatures and pressures were not of sufficient magnitude to affect seriously the problem of proper control of cement-slurry properties. Today, however, the search for new reserves has extended drilling to such depths that bottom-hole temperatures of more than 200°F. and bottom-hole pressures of 3000 to 5000 lb. are not uncommon. Moreover, there is every indication that within the next few years wells will be drilled to even greater depths and bottom-hole temperatures and pressures will be correspondingly higher than those with which we are concerned today. It has been realized for some time that the behavior of cement slurries at high temperatures and pressures might be very different from that at atmospheric tempera-ture-pressure conditions, but while the temperature effects have been investigated with a reasonable degree of thoroughness, the pressure effects have received little public attention. While the trend toward deeper drilling may make changes in cementing technique and the choice of cements imperative, it was the purpose of this investigation to consider factors having a bearing on the latter, only secondary consideration being ,given, for the present, to details of tech-nique and equipment for oil-field use. More specfically, the purpose of this work was to consider the effect of temperature and pressure upon the behavior of cement slurries. Although it has long been recognized that cements thicken and set rapidly with increasing temperatures, practical methods for the quantitative determination of these effects are comparatively recent developments. In 1935 Silcox and Rule1 presented such a method, describing apparatus designed to measure the consistency-time relationship of cement slurries at relatively high temperatures. The practical importance of this apparatus in furnishing useful data for the evaluation of cement slurries for cementing operations has been emphasized in various technical publications by such writers as E. L. Davis,~ I. F. Bing-ham,3 and J. E. Weiler.4 A paper describing the numerous tests now used to evaluate cements for oil wells was presented in 1939 by W. W. Robinson.= Robinson describes the Consistometer and the Thickening-Time Tester, showing similarity of data from the two devices, and points out that the purpose of each apparatus is to determine the allowable time that a cement may be pumped at a given temperature. At the present time, however, it is believed that results from the Thickening-Time Tester and the Consistometer have not given a

Jan 1, 1941

By John I. Yellott

Since the days of Newcomen and Watt, when men first sought to turn the energy of fuels to useful purposes, coal-generated steam has supplied most of the power needed for both stationary and mobile applications. The low efficiency and large water requirements of the nineteenth century steam-power plant caused many engineers to turn their thoughts toward more direct means of converting heat into power. As far back as 1791, John Barber secured an English patent on a combination' which he might well have called a "gas turbine." He proposed to generate producer gas from coal or charcoal, to burn it under pressure in air obtained from a reciprocating compressor, and to drive a turbine wheel with the resultant hot combustion products. With the optimism characteristic of the inventor, he hoped that the turbine would not only operate his compressor but also perform useful work. There is no record that Barber ever built his machine, but if he had done so he would have learned that useful power can result from such a combination only when both turbine and compressor are highly efficient and when the temperature of the gas entering the turbine is not far below 1000°F. Hot-air prime movers continued to attract attention, and both Stirling in England and Ericsson in America2 built reciprocating engines that operated with some success upon coal-heated air. The internal-combustion engine, burning liquid fuels, supplanted the hot-air type, and, for the first time, challenged the supremacy of both the steam cycle and its familiar fuel, coal. Liquid Fuels Compete with Coal As the increasing use of the automobile multiplied the demand for gasoline, the supply of residual fuel increased rapidly, and heavy oil declined in price to the point where it became competitive with coal. First in the marine field and later in stationary plants in areas adjacent to refineries, oil began to be widely used. Oil's greater convenience and higher heating value per pound of weight or per cubic foot of bunker space have caused it to take over much of the marine field. The introduction of the highly efficient diesel engine, capable of burning a fuel that is cheaper than gasoline, again threatened the position of coal, for the operating costs of the diesel became directly competitive with those of coal-burning equipment. In isolated power plants and smaller marine installations, the diesel provided the medium by which oil again successfully invaded fields formerly dominated by coal. The diesel engine, provided with an electrical transmission, found an excellent application in railroad service. The high availability of diesel-electric locomotives, resulting in part from freedom from water

Jan 1, 1947

By John I. Yellott

Since the days of Newcomen and Watt, when men first sought to turn the energy of fuels to useful purposes, coal-generated steam has supplied most of the power needed for both stationary and mobile applications. The low efficiency and large water requirements of the nineteenth century steam-power plant caused many engineers to turn their thoughts toward more direct means of converting heat into power. As far back as 1791, John Barber secured an English patent on a combination' which he might well have called a "gas turbine." He proposed to generate producer gas from coal or charcoal, to burn it under pressure in air obtained from a reciprocating compressor, and to drive a turbine wheel with the resultant hot combustion products. With the optimism characteristic of the inventor, he hoped that the turbine would not only operate his compressor but also perform useful work. There is no record that Barber ever built his machine, but if he had done so he would have learned that useful power can result from such a combination only when both turbine and compressor are highly efficient and when the temperature of the gas entering the turbine is not far below 1000°F. Hot-air prime movers continued to attract attention, and both Stirling in England and Ericsson in America2 built reciprocating engines that operated with some success upon coal-heated air. The internal-combustion engine, burning liquid fuels, supplanted the hot-air type, and, for the first time, challenged the supremacy of both the steam cycle and its familiar fuel, coal. Liquid Fuels Compete with Coal As the increasing use of the automobile multiplied the demand for gasoline, the supply of residual fuel increased rapidly, and heavy oil declined in price to the point where it became competitive with coal. First in the marine field and later in stationary plants in areas adjacent to refineries, oil began to be widely used. Oil's greater convenience and higher heating value per pound of weight or per cubic foot of bunker space have caused it to take over much of the marine field. The introduction of the highly efficient diesel engine, capable of burning a fuel that is cheaper than gasoline, again threatened the position of coal, for the operating costs of the diesel became directly competitive with those of coal-burning equipment. In isolated power plants and smaller marine installations, the diesel provided the medium by which oil again successfully invaded fields formerly dominated by coal. The diesel engine, provided with an electrical transmission, found an excellent application in railroad service. The high availability of diesel-electric locomotives, resulting in part from freedom from water

Jan 1, 1947

By A. William Johnson

It was pointed out in an earlier paper1 that our understanding of the atomic mechanism by which diffusion occurs in metallic alloys is scarcely in an advanced state. This unsatisfactory condition is the result not of any lack of interest, but of the difficulty of designing experiments that .will yield suitable data. The diffusion coefficient of an alloy, measured in the usual way, is simply a number specifying the rate of homogenization of a nonhomo-geneous metal; this number, of itself, can furnish neither the rate at which the individual atoms move nor information as to the mechanism by which they move. It does not necessarily follow, however, that such information cannot be obtained, even if the path to be followed is still not clear. Much success has been attained in the study of diffusion in ionic crystals. A number of experiments, for which there are few counterparts in connection with metals, yield information often indicating a detailed mechanism by which diffusion probably occurs. From such work, quite acceptable theories of lattice imperfections have been developed by Wagner, Schottky, Frenkel, Jost and others.2 It is postulated that real crystals of stoichiometric composition contain, in equilibrium, certain imperfections of which the most importarlt types are: (I) vacant cation sites, with an equal number of interstitial ions; (2) vacant anion sites, with an equal number of interstitial ions; (3) equal numbers of anions and cations in interstitial positions; (4) equal numbers of vacant anion and cation sites. The classification of a particular crystal according to this scheme then follows from studies of the variation of electrical conductivity with pressure of the electronegative component surrounding the crystal, with ion size, and with temperature; other physical phenomena, such as the Hall effect, have aided in establishing the classification. The relative mobility of the anion and cation may be determined by chemical analysis of the salt at the electrodes following electrolysis. With such information, and knowing that one ion never occupies the lattice site normally belonging to an ion of opposite sign, it is usually possible to ascertain the diffusion mechanism. It is clear that the same experiments are not applicable to metal crystals, and substitute experiments that yield as much information have not yet been devised. Much can be learned, however, about the mobilities of the two* kinds of atoms in alloys by the use of radioactive metals as indicators. Only one such experiment has been performed in the past. In 1933, Seith and Keil,3 in an effort to explain the great difference between the rate of diffusion of gold in lead and of lead in lead, measured the rate of diffusion of radioactive lead in 3 gold-lead

Jan 1, 1942

By J. E. Hilliard

It is proposed that shape anisotropy in the internal structure of materials be defined by distribution functions which specify what fraction of the total line length or boundary area lies in a given direction. Methods are descriibed for determinirg these distribution functions from measurements on sections through an opaque material. New derivations, that have certain advanifages over those given previously, are Provided for well-known expressions used in estinzating the total density of lineal or areal features. INCREASING attention is being given to the quantitative description of imicrostructures in metals and other materials. This interest stems from the recognition that the structure often provides a convenient half-way point between the properties on the one hand and the processing variables on the other. Such cross correlations become increasingly desirable as materials become more complex and the demands on them more stringent. One of the principal aims in structure analysis is therefore to find parameters that are readily measurable and specific enough to be correlated with other properties of the material. Certain properties, such as magnetic and mechani cal behavior, are strongly influenced by structural anisotropies; in order to relate such properties to the structure it is obviously necessary to have means of specifying and measuring the type and degree of anisotropy. For the determination of preferred orientations in crystal structure, X-ray diffraction methods are available and are widely used, but scant attention has been given to the estimation of anisotropy in the shape of grains and particles. It is the latter problem that will be considered in this paper. It is evident that shape anisotropy can be describe in terms of preferred orientations of lineal and area elements of the structure. It will be shown that these preferred orientations can, in turn, be specified by distribution functions that define what fraction of the total line length or boundary area lies in a given direction. Methods will be given for determining the distribution functions from measurements on sections through the structure. Even when the orientation distributions are of no interest per se, they still have an important bearing on the measurement of the total line length or boundary area by means of an intercept analysis. The treatment in terms of orientation distribution functions leads to new derivations, that have certain advantages of those given previously, for the well-known expressions used in estimating the total density of lineal or areal features. The treatment is divided into two main sections. The first deals with the orientation distribution of a two-dimensional array of lineal features such as occurs in the projected image of dislocations in electron transmission microscopy. The other section treats the estimation of the distribution of lineal and areal features dispersed in three dimensions.

Jan 1, 1962