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By C. Richard Honeycutt, Frederick C. Langenberg, Guenter Pestel

Otto Schaaber (Institut für Harterei-Technik, Bremen-Schönebeck, Germany)— Langenberg, Pestel, and Honeycutt gave an interesting example of the grain refining effect nonstationary magnetic fields may execute on a solidifying metal. Probably some additional comments, based on more than a decade of experience with this method of influencing crystallization, may be useful. They refer to an attempt to explain the mechanism of grain refinement by such fields, and to recent European developments which have not been mentioned in the paper. I. During studies of the temperature distribution in a metal body near the phase boundary solid/liquid, an anomaly was observed under certain special conditions: a) direction of heat transfer as horizontal as possible, b) steady state (equilibrium, i.e,, solidification resp. melting rate exactly zero). In the liquid phase, immediately adjacent to the phase boundary, the temperature was found to be constant over an appreciable distance in spite of a high value of heat transfer (40.000 to 70.000 keal/ m2h).3 Convection, which might explain this phenomenon, could not be observed. Therefore another explanation had to be sought. The assumption that a metallic melt, especially at temperatures near the point of solidification, contains some sort of atomic arrangement with a higher degree of order than the surrounding liquid, now is generally accepted. Considering the differences in energy between such an arrangement and its environs, a transport of heat even in absence of any temperature gradient is conceivable by continued formation and redissolution of regions with a higher degree of order, i.e., with lower energy level.3 At this stage, it was not necessary to postulate any special condition as to the form or size of these regions or the distance between arrangements to be newly formed and those to be redissolved. However, a simple consideration shows that an energy transfer from one region to another will only be possible without loss of energy, if the distance between will be equal to the lattice parameters, and if, secondly, crystallographic axis or planes will be parallel.4 By the way, this assumption might give a reasonable explanation of the well known orientation effect of the heat flow during solidification. Any measures to prevent columnar crystallization should act upon this ordering mechanism: a) the regions with a lower energy (higher order) should not be allowed to arrange themselves parallel to the direction of heat flow, and their growth should be disturbed; b) all conditions leading to an appreciable heat flow of uniform direction should be avoided or removed. Condition a) may be satisfied by a physical force preferably under 90 deg to the main axis of the columnar crystals (i.e., parallel to the solidification front) acting on the ordered regions; condition b) by equalizing any differences in

Jan 1, 1962

By M. R. Pickus, I. W. Pickus

Ordinarily age-hardening is thought of as being associated with a limited solubility of one metal in another. Much less has been written about the type of age-hardening that attends the formation of superstructures. Solid solutions generally have a disordered or random arrangement of atoms; that is to say, in a unit cell, such as that of the face-centered cubic lattice, there is no distinction between atomic sites. Atoms of a given metal may occupy cube corners or face centers. Under certain conditions, however, some alloys develop what is known as an ordered structure. In this case, cube corners would be occupied by only one type of atom and face centers by another type. Associated with this ordering process are many interesting changes in physical and electrical properties. Moreover, in many instances the alloys become susceptible to age-hardening. From the evidence now to be described, it appears that age-hardening in 14-carat gold alloys is due to the formation of both a superstructure and a precipitate. Alloys of the metals gold, silver and copper were known in antiquity. The available knowledge regarding their constitution has been ably summarized and extended by Sterner-Rainer,' Jänecke,2 Carter,3 Wise,4 and Coleman.5 Despite the long familiarity with these alloys and the numerous investigations of their properties that have been made, there is still much that remains unexplained. It has been known for a long time that the hardness of these alloys is closely related to the rate of cooling. Similar changes have been observed in the binary gold-copper systemI6 one alloy of which corresponding to the formula CU³AU, has been the subject of a careful and competent report by the English investigators, Sykes and Evans.7 They have established the fact that the shift of atoms from the ordered to the disordered condition takes place in some critical temperature range. At temperatures above the critical range the structure is random, and at temperatures below it the structure is ordered. No difference between these two structures is revealed by the microscope. Both have a face-centered cubic lattice and complete solubility, so that there is no evidence to suggest that the changes in properties are associated with a phase change. The more slowly the alloy is cooled, the higher is the degree to which the ordering process proceeds and the more marked is the increase in hardness. As experimental data were accumulated on I4-carat gold alloys, several contradictions arose. Certain observations tended to confirm the existence of a superstructure, while other observations seemed to be inconsistent with such a transformation. Present Investigation As a focal point about which to develop this subject, it is expedient to consider first

Jan 1, 1943

By M. R. Pickus, I. W. Pickus

Ordinarily age-hardening is thought of as being associated with a limited solubility of one metal in another. Much less has been written about the type of age-hardening that attends the formation of superstructures. Solid solutions generally have a disordered or random arrangement of atoms; that is to say, in a unit cell, such as that of the face-centered cubic lattice, there is no distinction between atomic sites. Atoms of a given metal may occupy cube corners or face centers. Under certain conditions, however, some alloys develop what is known as an ordered structure. In this case, cube corners would be occupied by only one type of atom and face centers by another type. Associated with this ordering process are many interesting changes in physical and electrical properties. Moreover, in many instances the alloys become susceptible to age-hardening. From the evidence now to be described, it appears that age-hardening in 14-carat gold alloys is due to the formation of both a superstructure and a precipitate. Alloys of the metals gold, silver and copper were known in antiquity. The available knowledge regarding their constitution has been ably summarized and extended by Sterner-Rainer,' Jänecke,2 Carter,3 Wise,4 and Coleman.5 Despite the long familiarity with these alloys and the numerous investigations of their properties that have been made, there is still much that remains unexplained. It has been known for a long time that the hardness of these alloys is closely related to the rate of cooling. Similar changes have been observed in the binary gold-copper systemI6 one alloy of which corresponding to the formula CU³AU, has been the subject of a careful and competent report by the English investigators, Sykes and Evans.7 They have established the fact that the shift of atoms from the ordered to the disordered condition takes place in some critical temperature range. At temperatures above the critical range the structure is random, and at temperatures below it the structure is ordered. No difference between these two structures is revealed by the microscope. Both have a face-centered cubic lattice and complete solubility, so that there is no evidence to suggest that the changes in properties are associated with a phase change. The more slowly the alloy is cooled, the higher is the degree to which the ordering process proceeds and the more marked is the increase in hardness. As experimental data were accumulated on I4-carat gold alloys, several contradictions arose. Certain observations tended to confirm the existence of a superstructure, while other observations seemed to be inconsistent with such a transformation. Present Investigation As a focal point about which to develop this subject, it is expedient to consider first

Jan 1, 1943

By C. H. Mahoney, A. L. Tarr, P. E. Le Grand

Magnesium, it is now generally realized, differs in some important aspects from most other structural metals, not excepting even its close neighbors, the aluminum-base alloys. This is particularly true with respect to the effects of elevated temperatures on the two light metals when in the molten state. Aluminum, 0' the one hand, should not be raised above its melting point any higher than is absolutely necessary if one is to avoid danger of gas absorption and a tendency toward grain growth in the resultant casting.' Magnesium alloys, in sharp contrast, actually benefit by being heated to temperatures considerably above their melting point, It is a commonly accepted practice to establish the desired fine grain in the industrial magnesium alloys of the aluminum-hearing group by raising the temperature of the melt after the refining treatment to some 250°C (482°F.) above the melting range. To recall briefly the typical practice for magnesium alloys, the molten metal is refined by fluxing at about 730°C. (I350°F.), and after the melt has been covered with a suitable flux, the temperature is raised to between 870°C. (I600°F.) and 930°C. (1700°F.). It is then cooled as quickly as possible to the casting temperature. This superheating, as it is called, results in a fine-grained cast metal structure which has superior mechanical properties, enhanced amenability to 'solution heat-treatment, and better machinability than cast metal that has not been superheated. The minimum temperature of superheating varies to some extent with the composition of the alloys to be treated and usually increases with the percentage of magnesium in alloys containing the same constituent metals.' It should be noted that the grain-refining effect of superheating is markedly apparent only in connection with the alloys containing aluminum as an alloying Constituent—the binary alloy containing 1.5 per cent manganese, for example, is not refined in grain to any noticeable extent by a superheating effort. While the phenomenon of superheating is well known in the magnesium industry, the mechanism of the process has remained a mystery During the superheating cycle something occurs that forces a fine grain upon the solidifying metal. The process has been controlled in an empirical manner, and occasionally, especially on large-scale melts, and for no apparent cause, no grain refinement is obtained from a superheating treatment. Only a few papers of importance have been published on the subject. Of these, one of the most helpful is the paper by Achenbach, Nipper and Piwowarski,3 which gives considerable data concerning the effect of superheating on various properties such as fluidity, shrinkage and hot crack

Jan 1, 1945

By C. A. Pierce

STUDIES of roof and floor movement are of interest to those actively engaged in mining. This is especially true in the case of an entirely new area where there is no precedent for guidance. The potash deposit being mined is in the southeast corner of New Mexico, about 20 miles east of Carlsbad. The deposit was formed by the land-locked, shallow, Permian Sea that extended through parts of western Texas, Oklahoma, Kansas, southeastern Colorado, and eastern New Mexico. The saline deposits vary from 500 to 4000 ft. thick. Neither of the companies operating in this area has delimited its com-mercial ore bodies. As all production so far has been from Federal and State leases, the Department of the Interior and the State of New Mexico have a direct interest in the development and extraction of these ore horizons. The ore is composed of an intimate mechanical mixture of sylvite (potassium chloride) and halite (sodium chloride). It lies generally in a horizontal bed varying from 5 to 12 ft. in thickness, and has a cover of approximately 1000 ft., consisting of about 500 ft. of salt beds and 500 ft, of sediments. The immediate mine roof for several feet is principally salt with some potash and clayey material. The next 500 ft. above, from the standpoint of structure, may be considered rock salt with a few inter-bedded potash members. The upper 500 ft. is of sedimentary (Permian and Triassic) origin and contains several water-bearing formations with flows varying from 10 to 500 gal. per minute. This water intensifies the interest in convergence problems as the ore and surrounding for-mations are water soluble. Potash salt (sylvite) and rock salt (halite) are plastic minerals. Plasticity is defined as a "property of solids by virtue of which they hold their shape permanently under the action of small shearing stresses but are readily deformed, worked, or molded under larger stresses."1

Jan 1, 1938

By Robert I. Jaffee, Bruce W. Gonser, Eugene M. Smith

There has been little investigation of the gold-germanium binary alloys. Haughtonl does not mention any work on the system. In a review article commemorating the fiftieth anniversary of the discovery of germanium, E. Einecke2 mentioned a gold-germanium eutectic at 24 atomic per cent Ge (10.4 weight per cent) melting at 359°C., but did not give the source of his information. From measurements of electrical conductivity, J. 0. Linde3 estimated that at least 0.6 weight per cent germanium is soluble in gold. The recent availability of germanium in this country in commercial quantities has led to interest in its properties and its alloys. This study is part of a program of investigation on germanium alloys; work on ternary alloys involving germanium and gold will be reported later. In this investigation, the composition and melting point of the Au-Ge eutectic reported by Einecke has been found to be substantially correct. Eutectic composition has been placed at I2.0 per cent germanium, however. An alloy of 10.4 per cent Ge, Einecke's value, was found to have a few gold dendrites in it. The cutectic temperature has been determined as 356.0 6 ± 0.5°C., slightly less than the temperature of 359°C. reported by Einecke. The liquidus curves and the solid solubility of ger- manium in gold have been determined, and are shown in Fig. I. Materials and Alloying The germanium used in this investigation was prepared by the Eagle-Picher Lead Co. from pure germanium oxide, by reduction in clay crucibles with sodium cyanide. The regulus is quite pure, assaying over 99.9 per cent Ge. High-purity gold obtained from Handy and Harmon was used. Alloying was carried out in graphite crucibles in an atmosphere of purified hydrogen. The temperature was brought up to 1050" to iioo°C., and the metal was allowed to freeze in the crucible. Prepared in this way, the gold dendrites in hypoeutectic alloys were somewhat segregated at the bottom and sides of the ingot, and on the hyper-eutectic side the lighter primary germanium tended to gather at the top. Most of the alloys were made from virgin metal. Low-germanium heats were made by alloying pure gold with the eutectic. Melting losses were consistently a few milligrams or less, and the composition could safely be taken from the intended analysis. The 30 per cent and 50 per cent germanium heats for thermal analysis were made in part from remelted higher germanium heats, and they may be OR composition as much as one per cent. Because of the high cost of materials, the weight of heats for thermal analysis were 15 to 20 grams and heats for metallo-graphic, X-ray, and hardness specimens were 2 to 4 grams.

Jan 1, 1945

The American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc, shall be composed of constituent parts as follows Section 1 Societies-The Institute shall be divided into three or more Societies as follows a The Metallurgical Society of AIME Society of Mining Engineers of AIME Society of Petroleum Engineers of AIME Other Societies may be formed within the framework of AIME or granted member¬ship in AIME as approved by the Board of Directors Section 2 Divisions and Subdivisions-The several Societies of the Institute shall consist of Divisions as follows a The Metallurgical Society of AIME 1 Institute of Metals Division 2 Iron and Steel Division 3 Extractive Metallurgy Division Any Divisions or Subdivisions which may be formed in the future with the approval of the Board of Directors Society of Mining Engineers of AIME I Coal Division 2 Industrial Minerals Division 3 Minerals Beneficiation Division 4 Mining and Exploration Division

Jan 1, 1960

By John D. Wiebmer

First, a definition of a small scale miner is in order. The US Bureau of Mines classifies him as one who produces 360 t/d (400 stpd) of ore or less. In Canada, he would be refered to as a "junior company." Mexico identifies the small scale miner as one whose gross income from operations is less than $880,000 per year. A small surface mine in India employs less than 400 people, and a small underground mine employs less than 150. Peru considers a small scale miner one who produces less than 54 000 t/y (60,000 stpy) of ore. Obviously, the term is relative. What may be a small mine in one country is a medium or large mine in another. This lack of agreement is understandable since small scale mining does not often cross national boundaries. Rather, its effects are felt at the regional and local levels within each nation. Its importance doesn't lie with any huge contribution to the GNP or balance of trade. Instead, its value is as a local employer and as a frontrunner in geologic exploration.

Jan 2, 1979

By W. R. Hibbard

IN ref. 1, on the basis of tension and torsion experiments with single crystals of a brass, the values given in Table I were obtained for elastic coefficients. It was pointed out by Zener that the values for the 71.2 pct Cu were not satisfactory, since they resulted in a negative value for the bulk modulus, namely —4.17X1012 sq cm per dyne. In reevaluating the data of this investigation, it was determined that the reason for this negative bulk modulus lay in the extrapolation of the reciprocal Young's modulus to the zero value of the orientation function shown in Fig. 5 of ref. 1. This extrapolation was reevaluated by the method of least squares (50 pct probability) and a new value of the coefficient S,, was determined as 18.9220.42X 10M sq cm per dyne in lieu of the value originally reported of 18.82x10 sq cm per dyne. This new value of S, leads to a new value of S, of — 9.43 X101" sq cm per dyne. The values of the other coefficients are unchanged. results. This value compares with the value of 12.3X10 sq cm per dyne reported by Schmid and Boas? The new results are summarized in Table 11. These results follow similar qualitative trends, previously published,' relative to the effect of zinc content. However, the derived values of C11, C,, C,, and K are so sensitive to the uncertainty in the first decimal place of the S, values that they are probably not useful. This uncertainty must also apply to the previous results of Masima and Sachs," who obtained S, values from a similar extrapolation drawn wholly above their data points. Acknowledgments Advice and assistance on the statistical methods were obtained from R. W. Guard. The calculations were carried out by Miss E. Saacke.

Jan 1, 1958

By E. V. Kleber, V. F. Novy, R. C. Vickery

The constitutional diagram has been determined in part for the sgstem Gd-Fe. Seven intermetallic compounds have been found at compositions corresponding to the following Gd-Fe ratios; 2:3, 1.2, 1:3, 2:7, 1:4, 1:5, and 2:17. The GdFe, com-pound has a congruent melting point above 18000C, whereas all of the remaining compounds melt incongruently, A eutectic exists at 13 wt pct Fe at a temperature of 860°C. ALTHOUGH an increasing amount of information is becoming available on the metallurgy of pure rare earth metals, relatively few studies have been made on alloy systems of the rare earths with the transition metals; iron, nickel, and cobalt. Even less data are extant on gadolinium alloys although it could be expected that such alloys might possess interesting structural and magnetic properties. In this paper, we report investigation of the gadolinium-iron alloy system. Studies on systems containing nickel and cobalt will be presented in subsequent papers. Previous data on gadolinium-iron compounds have been reported by Endter and Klemm1 and Jep-son and Duwez.2 Both reports agree on the existence of the GdFe2 phase, which crystallizes with the C-15type structure (face-centered cubic). This is in accord with results of the present work. EXPERIMENTAL The gadolinium metal used was prepared by met-allothermic reduction of high purity gadolinium fluoride. A typical analysis of the metal thus produced indicated the principal impurities to be oxygen, 0.24 pct, and tantalum, 0.2 pct. The iron metal used for alloying was a reagent grade material. Alloys were prepared by arc melting mixtures of the respective metals. Appropriate quantities of the two component metals were carefully weighed, blended and compacted. The compacts were then melted in an arc furnace consisting of a water-cooled copper hearth plate and a water-cooled tungsten-tipped counter electrode contained in a brass vacuum chamber. The furnace was evacuated to an absolute pressure of less than 1 with the leak rate established as being less than 20 per min. The furnace was then back-filled to a pressure of 25 mm of Hg, with a 75 pct He-25 pct Ar mixture. Arc melting at 25 v and 300 amp was maintained for about 30 to 60 sec until the entire visible area of the sample became molten, by which time surface tension had drawn the molten metal pool into a large bead. After allowing the furnace to cool, the alloy button was inverted and the melting process repeated. A series of melts was made covering entire composition ranges from 100 pct Gd to 100 pct Fe. All samples were examined metallographically in the as-melted condition. As the phase diagram became rationalized, and differential thermal analysis had given indications of temperature arrests, annealing was carried out in vacuo or in argon. Generally, compositions containing more than about 60 pct Gd were heat treated at 750°C and alloys containing less than this quantity of gadolinium were annealed at 1000°C. Prolonged annealing times were of the order of 100 to 200 hr. Metallographic examination was repeated on the annealed materials. Although little material loss was noted during alloy preparation, chemical analyses were made on all specimens prepared. The following standard, analytical techniques were used. Samples were dissolved in hydrochloric acid; insoluble material was filtered off, ignited and fused with potassium pyro-sulfate. The cold melt was leached with dilute acid and the solution thus obtained added to the main sample solution. Gadolinium was always determined gravimetri-callv as oxide from oxalate ignition. Iron was removed from an aliquot sample by electrolysis on a mercury cathode at approximately six volts. Gadolinium in the iron-free electrolyte was then precipitated as oxalate which was subsequently ignited to oxide. Iron was determined volumetrically in an aliquot solution by reduction with stannous chloride fol-

Jan 1, 1962

By S. R. Balajee, I. Iwasaki

The interaction between British gum 9084 and dode-cylammonium chloride (DAC) at quartz and hematite surfaces was established from coadsorption studies and streaming potential measurements. The cationic DAC interacts with the somewhat anionic British gum 9084, leading to the formation and adsorption of a binary complex of DAC-British Gum 9084 at the interface. The parallel ability to depress quartz along with hematite as a result of the interaction between DAC and British gum appears to be the main reason for the ineffective depressant action of starches and starch derivatives in the cationic flotation of iron ores. Amines are not particularly selective collectors for the flotation' of siliceous gangue from iron ores and, therefore, a suitable iron oxide depressant is needed for a satisfactory separation. Various starches and their derivatives have been extensively tested with oxidized iron ores,'-3 and it has been empirically established that British gums and dextrins are preferable. However, for the flotation upgrading of magnetite-taconite concentrates from 8 or 8.5% Si O2 to about 5% Si 02, British gums, which have been used so successfully on oxidized iron ores, have been found to have no effect and oftentimes are actually deleterious.4 In previous articles,5-7, starches were shown by adsorption measurements, flotation tests, and floccula-tion tests to interact with calcium ions in solution, and it was thought that a study on the interaction between starches and dodecylammonium ions would be able to shed some light on the anomalous flotation behavior described above. In fact, starches are known to interact markedly with paraffin-chain-type surface active agents and, thereby, to precipitate the starch or inhibit the iodine-starch reaction.8 From X-ray diffraction studies and viscosity measurements, the formation of a helical complex between mylose and a surface active agent has been postulated.9 The interaction with other types of hydrophilic colloids, such as synthetic polymers and proteins, has also been investigated and is usually explained in terms of van der Waals' force interaction and/or ion-ion interaction. In the present investigation, the interaction of British gum and dode cylammonium chloride on quartz and hematite was studied by adsorption and streaming potential measurements in an attempt to establish the mutual adsorption behavior of British gum and dode-cylammonium chloride on mineral surfaces and to clarify the anomalous depressant activity of British gum in the cationic flotation of iron ores. All the measurements were carried out at a natural pH of near 7 because dodecylammonium chloride gives maximum selectivity of flotation separation at this pH2 and to avoid any third parameter in the system. EXPERIMENTAL MATERIALS AND METHODS Minerals: The quartz and hematite samples used for the adsorption tests were prepared as described in a previous paper,"J except that the specific surfaces of the samples were increased to 5,860 and 16,000 Sq cm per gm, respectively. For the streaming potential measurements, the 48165-mesh fractions screened out of the original samples were etched with hydrochloric acid, washed repeatedly with water, and stored under water in Pyrex bottles. Reagents:DodecyIammonium chloride (DAC) was prepared1 1 by bubbling dry hydrogen chloride gas through a benzene solution of high-purity dodecylamine supplied by Armour and Co. British gum 9084, received from Corn Products Co., was solubilized by first dispersing it in water to produce a 0.05% solution and then homogenizing it in a blender for 5 min. Distilled water was used in the preparation of the samples and the solutions and for all test work. Adsorption Measurements: The procedure for the adsorption density determinations was also the same as that described in the previous paper.1° The residual concentrations of the British gum and the DAC in the supernatant solution were analyzed colorimetrically by the phenol-sulf uric-acid and amine-picrate methods, respectively. The validity of the mine-picrate method for the colorimetric analysis of DAC in the presence of British gum and the analysis of British gum in presence of DAC were checked by establishing calibration curves between optical density and concentration. Streaming Potential Measurements: The cell assembly for the streaming potential measurements was similar to that described by Fuerstenau.' The streaming potential

Jan 1, 1970

By H. E. Stauss

THE time-to-fracture test has been applied to pure platinum and to two alloys of platinum under the special conditions of small cross-sectional area of the specimens and of a test temperature above the annealing temperature. While the results are similar in character to those secured with large specimens of steel at temperatures below the annealing temperatures, two differences are noted: (I) an upward inflection in the curves for log stress vs. log time for the alloys, and (2) a sharp break in the curve for log stress vs. log time for pure platinum when single crystals filled the wire. The experiments showed that: (I) platinum and 10 per cent rhodium-platinum maintained their strengths at 1100°C. better than did 10 per cent iridium- platinum, and (2) the rhodium-platinum after a time exceeded the iridium-platinum in strength at 1100°C. Platinum alloys in their service at high temperatures encounter conditions some- what similar to those that exist in the usual form of the time-to-fracture "l test with steel. This paper is intended primarily to present results obtained by a "time-to- fracture" test under conditions approximating actual service for platinum (at the temperature 1100°C. under oxidizing conditions) with three materials, pure platinum (99.99 per cent), a platinum alloy with lo per cent iridium, and a platinum alloy with 10 per cent rhodium. The experimental procedure differed from that previously used in this type of measurement in that the samples were of small diameter (0.010 in.), were fully annealed, and were tested at a temperature definitely above their annealing points (600°C., 1000°C. and 1050°C., respectively, for 60 per cent cold reduction and 15 min. heating time2,3). The experimental arrangement was similar to that previously described,4 using as heating unit a small, horizontal, platinum- wound furnace, ½ by 12 in., maintained at constant temperature by an automatic controller. The samples were 0.010-in. wires, which had been annealed at 1200°C. by drawing them slowly through the furnace. The time-to-fracture was measured electrically. Elongation was not determined because of the difficulties inherent in the experimental arrangement. Life-that is, the time-to-fracture-was considered the important property in these first tests. No attempt was made to measure the reduction in area, but the types of fracture were noted qualitatively; in the text they are referred to as (I) the normal, plastic, or necked fracture, (2) the knife-edge fracture, and (3) the brittle or intercrystalline fracture with small reduction of area. Results for different constant applied stresses are plotted in Fig. I. In all cases at least two trials were made for each stress, although they cannot always be indicated separately on the curves. The breaking stresses drop very rapidly to a small frac-

Jan 1, 1943

By G. L. Chierici

Starting from Muskat's theory of water and gas coning, maximum permissible oil production rates without water and/or free-gas production have been determined, in a broad range of reservoir and well parameters, using the potentiometric model technique. The main assumptions made are as follows: (1) the reservoir rock is homogeneeous (either isotropic or anisotropic); (2) the volume of the aquifer underlying the oil zone is very small, so that it does not contribute to reservoir energy; and (3) the gas cap expands at a very low rate, so that it can be assumed to be in quasi-static conditions. The results obtained are presented in the form of diagrams which can be used for solving two types of problems: (1) given the reservoir and fluids characteristics, as well as the position and length of the perforated interval, determine the maximum oil production rate without water and/or free-gas production; and (2) given the reservoir and fluids characteristics only, determine the position and length of the perforated interval which optimize the maximum permissible oil production rate, without water and/or free-gas production. INTRODUCTION In oil reservoirs where the oil-bearing formation is underlain by an aquifer which does not participate in the production mechanism, water-coning is a limiting factor to the flow rates of producing wells. Production rates are usually kept to a value that will prevent the water from entering the wells. The entry of water into a well lowers its productivity by increasing the weigbt of the fluid column; moreover, the separation of water from the effluent, at the surface, may constitute a very difficult problem in cases of heavy viscous oils. A similar situation is encountered in oil reservoirs with a gas cap overlying the oil-saturated zone; here a downward gas cone is induced by the flow of oil towards the producing wells. Production rates must be low enough to prevent the gas from being produced; producing gas from the gas cap would be a waste of energy. Of course, water-coning and gas-coning phenomena can occur at the same time in the same reservoir if the oil-producing formation is both overlain by a gas zone and underlain by a water zone. Due to its relevant practical importance, the mechanism of coning was studied by many people.2,3,5-8 Defining the conditions for getting the maximum water-free and/or gas-free oil production rate is a difficult problem, often encountered under one of the following aspects: 1. Predict the maximum flow rate that can be assigned to a completed well without the simultaneous production of water and/or free-gas. 2. Define the optimum length and position of the interval to be perforated in a well, in order to obtain the maximum water and gas-free production rate. A systematic study of these problems was made by means of the electrical analog technique. The results of this study are presented here, under the form of a set of curves providing solutions for the above stated problems. These curves are valid only for homogeneous forrnations, either isotropic or anisotropic. Should the formation be non-homogeneous (by horizontal or vertical variation of permeability, shale diaphragms, fractures, etc.), a specific potentiometric study would be required for each specific case. Especially when shale diaphragms of some radial extension are present, the critical rates observed are much larger than would be expected from the diagrams. STATEMENT OF THE PROBLEM In the present study the aquifer is supposed to be of such limited volume that it does not contribute to the energy of the reservoir. Moreover, the gas cap is supposed to expand at such a low rate that the potential gradient in the gas cap is negligible. Under static conditions water-oil and gas-oil interfaces (T1 and T2) are both horizontal. When the reservoir production starts, below each well these interfaces take a cone-like shape (Fig. 1) having as an axis the axis of the well. This shape results from the equilibrium between potential gradients in the oil zone and gravitational forces due to density differences between oil and water and between oil and gas. Assuming the oil-bearing formation to be homogeneous and the oil to be incompressible, the analysis of the problem (see Appendix) shows that the oil-water and gas-oil interfaces are stable only if the oil production rate of the well is not higher than the following values.

Jan 1, 1965

By H. R. MacMichael

THE rate, at which zinc ore can be sintered varies widely, depending on the characteristics- of the ore. A coarse table concentrate already roasted to a very, low sulfur content may sinter at the rate of-8.6 tons per hour per 100 sq.ft., of wind-box area. At the other extreme is a finely ground flotation, concentrate, with considerable sulfur remaining in the ore as delivered to the sinter plant, for which corresponding rate may be only 3.8 tons per hour, or 44 per cent of the first rate. A usual, size-of sinter machine in zinc plants is one with wind-box 3.5 by 33 ft., making 115.5 sq. ft. of area, and using a 100-hp. fan. Such a machine with the coarse concentrate described would produce 10 tons of sinter per hour; and with the fine, flotation concentrate would produce only 4.4 tons per hour. Ore of the latter class is -sintered at the plant of the Mexican Zinc Co. (subsidiary of the American Smelting & Refining Co.) at Rosita, Mexico. ; Consequently, an unusually large sintering capacity per ton of ore to be treated is required, and provision was made for treatment of 9000 tons concentrates per month, preroasted to. 5 to 9 per. cent sulfur. For this duty three of the usual 33-ft., 100-hp. sintering machines would have been needed.. Considering the auxiliary equipment. necessary for proportioning, handling, and mixing charge, as well as means for disposition of the sinter, a three-unit plant becomes-very complicated, especially if the capacity should be doubled later. After much study it was decided to build a single sintering unit of ample capacity for the work, the plant thus being much simpler and cheaper in construction as well as in operation (Figs. 1 and 2). The sintering machine was built with a wind-box 5.25 by 60 ft. (315 sq. ft.) and provided with a 300-hp. fan.

Jan 1, 1932

By M. G. Benz, J. F. Elliott

Otto Schaaber (Institut für Harterei-Technik, Bremen -Schönebeck, Germany)— Langenberg, Pestel, and Honeycutt gave an interesting example of the grain refining effect nonstationary magnetic fields may execute on a solidifying metal. Probably some additional comments, based on more than a decade of experience with this method of influencing crystallization, may be useful. They refer to an attempt to explain the mechanism of grain refinement by such fields, and to recent European developments which have not been mentioned in the paper. I. During studies of the temperature distribution in a metal body near the phase boundary solid/liquid, an anomaly was observed under certain special conditions: a) direction of heat transfer as horizontal as possible, b) steady state (equilibrium, i.e,, solidification resp. melting rate exactly zero). In the liquid phase, immediately adjacent to the phase boundary, the temperature was found to be constant over an appreciable distance in spite of a high value of heat transfer (40.000 to 70.000 keal/ m2h).3 Convection, which might explain this phenomenon, could not be observed. Therefore another explanation had to be sought. The assumption that a metallic melt, especially at temperatures near the point of solidification, contains some sort of atomic arrangement with a higher degree of order than the surrounding liquid, now is generally accepted. Considering the differences in energy between such an arrangement and its environs, a transport of heat even in absence of any temperature gradient is conceivable by continued formation and redissolution of regions with a higher degree of order, i.e., with lower energy level.3 At this stage, it was not necessary to postulate any special condition as to the form or size of these regions or the distance between arrangements to be newly formed and those to be redissolved. However, a simple consideration shows that an energy transfer from one region to another will only be possible without loss of energy, if the distance between will be equal to the lattice parameters, and if, secondly, crystallographic axis or planes will be parallel.4 By the way, this assumption might give a reasonable explanation of the well known orientation effect of the heat flow during solidification. Any measures to prevent columnar crystallization should act upon this ordering mechanism: a) the regions with a lower energy (higher order) should not be allowed to arrange themselves parallel to the direction of heat flow, and their growth should be disturbed; b) all conditions leading to an appreciable heat flow of uniform direction should be avoided or removed. Condition a) may be satisfied by a physical force preferably under 90 deg to the main axis of the columnar crystals (i.e., parallel to the solidification front) acting on the ordered regions; condition b) by equalizing any differences in

Jan 1, 1962

By J. F. Kemp

PARE Introductory Note. ........... 147 General Topography. ..... ....... 148 General Distribution of the Mines. .149 General Geology.............151 The Non-Titaniferons Ore-Bodies. .1. 54 The Lee Mine. ..........154 The Cheever Mine...........15.5 The Pilfershire and Pease Pits.........1.56 The Mineville and Barton Hill Groups........1.56 Introductory. ........... 156 The Mineville Group..........157 The Miller Pit..........158 Old Bed or Mine 23 .........166 Relations of Old Bed to Miller Pit. ..168 The "21 "-Bonanza-Joker Ore-Body,......168 Summary. .......... 170 O'Neill Shaft and Cook Shaft, .......171 The Barton Hill Group..........172 The Mines on Barton Hill........172 Fisher Hill and Burt Lot........173 The Chemical Composition of the Ores. .. 173 The Geological Relations of the Ores. .176 The "21 "Gneiss..........176 The Orchard Gneiss. . . . . . . . .178 The Barton Gneiss..........178 The Gabbro and Gabbro-Gneiss. . . . . . .180 Minor Rocks...........182 Mineralogical Relations of the Gneisses. ..183 Stratigraphical Relations of the Gneisses. . . . 183 The Origin of the Ores. ..190 Review of Hypotheses . . . . . . 191 Interpretation of the Ore-Bodies as Contact-Deposits on Gabbro,. 193 The Mineralogy of the Mines. . . .......195 Bibliography.............201

Jan 1, 1898

By D. C. Hilty

It has long been known that in melting high-chromium steels, some of the carbon might be oxidized out of the melt without excessive simultaneous oxidation of chromium, and that higher temperatures favor retention of chromium. The advent of oxygen injection as a tool for rapid decarburization of a steel bath permits significantly higher bath temperatures, and it was quickly recognized that the use of oxygen injection facilitated the oxidation of carbon to low levels in the presence of relatively high residual chromium contents. Up to the present time, however, specific data pertaining to the chro-mium-carbon-temperature relations in chromium steel refining have not been available. Individual steelmakers have evolved practices more or less empirically, but there has been very little real basis for predicting how effective any given practice can be in permitting maximum oxidation of carbon with minimum loss of chromium. The current investigation, therefore, was undertaken in an effort to establish the fundamental carbon-chromium relationship in molten iron under oxidizing conditions. As reported below, the equilibrium constant and the influence of temperature on that constant have been derived for the iron-chromium-carbon-oxygen reaction in the range of chromium steel compositions with what appears to be a fair degree of precision. The practical application of the result will be obvious. Experimental Procedure The laboratory investigation was carried out on chromium steel heats melted in a magnesia crucible in a 100-lb capacity induction furnace at the Union Carbide and Carbon Re- search Laboratories. The charges for the heats consisted of Armco iron, low-carbon chromium metal, and high-carbon chromium metal, the relative proportions of which were calculated so that the various heats would contain from approximately 0.06 pct carbon and 8 pct chromium to 0.40 pct carbon and 30 pct chromium at melt-down. When the charges were melted, the bath temperatures were raised to the desired level, and the heats were then decarburized by successive injections of oxygen at the slag-metal interface through a ½-in. diam silica tube at a pressure of 30 psi. The duration of the oxygen injections was from 30 sec to 2 min. at intervals of approximately 5 to 30 min. It did not appear that length or frequency of the injection periods had any significant effect on the results; cansequently, no effort was made to hold them constant and they were controlled only as was expedient to the general working of the heats. Between successive injections, the heats were sampled by means of a copper suction-tube sampler that yields a sound, rapidly-solidified sample representative of the composition of the molten metal at the temperature of sampling. This sampling device is a modification of the one described by Taylor and Chipman.1 An attempt was made to vary bath temperatures between samples, but it quickly became evident that, unless the variations were small or unless the new temperature was maintained for a minimum of 15 min. during which an injection of oxygen was made in order to accelerate the reactions, a very wide departure from equilibrium resulted. For most of the runs, therefore, temperature was maintained relatively constant at approximately 1750 or 1820°C. A few reliable observations at other temperatures, however, were obtained. Temperature Measurement The high temperatures involved in this investigation were measured by the radiation method, utilizing a Ray-O-Tube focused on the closed end of a refractory tube immersed in the metal bath. The immersion tubes employed were high-purity alumina tubes specially prepared by the Tona-wanda Laboratory of The Linde Air Products Co. These tubes were quite sturdy under reasonable mechanical stress at high temperature. They were unusually resistant to thermal shock, and chemical attack on them by the melts was slow. With care, it was found possible to keep these tubes continuously immersed in a heat for as long as 5 hr at temperatures up to 1850°C, before failure by fluxing occurred. The Ray-O-Tube—alumina tube assemblage was similar to those supplied commercially for lower temperature applications. In operation, the alumina tube was slowly immersed in the molten metal to a depth of approximately 5 in., and the device was then clamped solidly to a supporting jig where it remained for the duration of the run. A photograph of the equipment, in operation with Ray-O-Tube in place and oxygen injection in progress, is shown in Fig 1. When in position in a heat, the instrument was calibrated by means of an immersion thermocouple and an optical pyrometer. For calibration through the range of temperatures from 1500 to 1650°C, a platinum -platinum + 10 pct rhodium thermocouple in a silica tube was immersed alongside the alumina tube. Output of the Ray-O-Tube in millivolts and the

Jan 1, 1950

By William E. Ford, Edward Salisbury Dana

The important BARITE GROUP is the only one among the anhydrous sulphates and chromates. Mascagnite. Ammonium sulphate, (NH4)2S0,. Orthorhomhic. Usrially in crusts and stalactitic forms. p = 1.523. Occurs about volcanoes, as at Etna, Vesuvlus, etc. Taylorite. 5K2SOa.(N&)ySOd. 111 small compact lumps or concretions. From the guano of the Chincha Islands. Thenardite. Anhydrous sodium sulphate, Na2S04. In orthorhombic crystals, pyrarnidal, short prismatic or tabnhr; also as twins (Fig. 384, p. 160). White, to brpwnish. 0 tically +. p = 1.477. Soluble in water. Often observed in connection with salt lates, as on the shores of Lake Balkhash, Central Asia; similarly elsewhere; also in South America in Tarapaca, Chilc. In the United States, forms extensive deposits on the Rio Verde, Aria. In Cal., at Borax Lake, San Bernardino Co. Aphthitaiite. Arranite. Glmerite. (Ii,Na)&O1. Rhombohedral; also massive, in crusts. Color white. From Vesuvius, upon lava; at DouglashaU near Weateregeln, Ger- many, in hloditc; Stassfurt, Germany; Rocalmuto, Sicily.

Jan 1, 1922

By Donald J. Drinkwater, M. C. Fuerstenau

Many important contributions to the more fundamental aspects of mineral processing have been made this past year. Mular1 researched the flotation characteristics of pure zinc oxide and also samples that had been doped with Al+++ and Cu++. Correlation of the response of pure zinc oxide to oleate flotation with a calculated zpc (from solution equilibrium) suggests that adsorption of oleate ion is coulombic in nature. Doping the sample with Al+++ (which will make the ZnO more n-type) had a marked effect on the maximum value of pH at which 50% recovery was obtained at constant collector addition. That is, when 0.5 mole percent Al+++ was added, the pH for 50% recovery was reduced by about four units. Treatment with Cu++ was found to have little effect on the flotation response of zinc oxide, even for additions of one mole percent. Since the zero points of charge of the Al+++ doped powders were not measured, it was not possible to correlate flotation data of these samples directly with charge phenomena.

Jan 2, 1966

By W. H. Herrnstein, F. H. Beck, M. G. Fontana

Sulfur solubility in a iron was measured in the 750 to 890°C temperature range and was found to be insensitive to ferrite purity within a limited composition range. The permeability of sulfur in ferrite was determined from the internal sulfidation of Fe-Mn alloys. From the solubility and permeability results, the diffusivity of sulfur in ferrite could be calculated. These results are summarized as follows: Dissolved sulfur decreased the lattice parameter of ferrite. The effect of dissolved sulfur on the tensile properties of ferrite at low temperatures was also determined. SINCE sulfur is an important residual impurity in commercial irons and steels, effects associated with the presence of sulfur as a solute in iron are of considerable practical interest. Unfortunately, certain basic information relative to the Fe-S system appears to be lacking in the literature, e.g., the effect of dissolved sulfur on the lattice parameter and mechanical properties of ferrite. In addition, discrepancies exist in previously reported results for the solubility of sulfur in ferrite. These discrepancies raise questions regarding the sensitivity of sulfur solubility to the purity and microstructure of iron. This study was undertaken primarily in an effort to obtain reliable data on the solubility of sulfur in ferrite. Additional objectives included determination of the permeability and diffusivity of sulfur in ferrite by the internal sulfidation method and determination of the effect of dissolved sulfur on the lattice parameter and tensile properties of ferrite. EXPERIMENTAL METHOD Three grades of iron, encompassing a range of impurity levels, were employed in the study. The grades were designated VME (vacuum-melted electrolytic), SPZR (single-pass zone-refined), and MPZR (multipass zone-refined). The composition of each grade is given in Table I. Poly crystalline and single-crystal strip specimens were employed in the solubility experiments. Uniform grain size strip (ASTM 3 to 5) of 0.005 to 0.020 in. thickness was obtained by alternate cold reductions of 60 thickness 60 to 80 pct and recrystallization at 650°C for i hr in pure, dry argon. Single-crystal specimens were produced in 0.010-in.-thick SPZR iron strip by the strain-gradient anneal technique. Recrystallized strip 0.25 in. wide was strained until a Luders band or bands had propagated over the length of the strip; the strip was then annealed by drawing it through a 150°C per in. gradient (890°C peak temperature) at 1 in. per hr in an atmosphere of pure, dry argon. Laue photographs of the crystals produced exhibited no discernible asterism. Specimens were equilibrated with H-H, atmospheres at temperatures between 750" and 890" by one of two methods, each of which makes use of the reaction: The encapsulation sulfurization method was employed in the majority of the solubility experiments. A strip

Jan 1, 1969