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By C. B. Smith, A. G. Guy

The power and convenience of tensor analysis are employed in deriving the equations that describe three-dimensional diffusion in an n-component system plus vacancies. A "Kirkendall coordinate system, '' defined in principle by Kirkendall markers, is used in defining the intrinsic diffusion coefficients that are of primary interest. The defining equations are then transformed to local cartesian coordinates and to fixed cartesian coordinates, the latter being convenient for experimental measurements. Finally, it is shown how the intrinsic diffusion coefficients can be calculated from the experimentally determined quantities. It is generally recognized that any treatment of the essential diffusion phenomena in metallic systems—the jumping of atoms from one lattice position to another—must be based on movement of the atoms past Kirkendall interfaces.' A logical extension of this idea is the proposal that, fundamentally, diffusion must be described mathematically in terms of "Kirkendall coordinates." The basic equations thus obtained may then be transformed into other coordinate systems, when such transformation leads to simplification of either the experimental or mathematical treatment of diffusion data. Tensor analysis is clearly the appropriate mathematical tool for this purpose, since it provides methods both for determining general equations that are valid for all coordinate systems and for conveniently transforming the equations from one coordinate system to another system related to the first in some known fashion. For the present purpose three coordinate systems are used, and it is convenient to begin with a description of the relations among these three systems. FICK LAW FOR KIRKENDALL COORDINATES The reference coordinate system, and the one that is useful for most experimental measurements, is a cartesian coordinate system, xi (i = 1, 2, 3), fixed with respect to some point in the specimen, such as an end of the alloy bar undergoing diffusion. A second set of coordinates, the Kirkendall coordinate system, is one that in principle can be described by the location of inert markers (Kirkendall interfaces). A convenient mathematical relation between Kirkendall coordinates, x'i, and the reference cartesian coordinates, ii, is obtained by specifying that the Kirkendall coordinate system coincide with the cartesian system at time, t = 0. After diffusion has occurred for some time, t = t, the Kirkendall coordinate system will differ from the reference system in the manner shown schematically for the one-dimensional case in Fig. 1. The third coordinate system is Darken's1 local cartesian-coordinate system, xi, which is identical with ii in orientation and units, but which moves with the point under consideration in the Kirkendall coordinate system. Even though most diffusion problems are essentially one-dimensional, there is an advantage in first carrying out the analysis of the three-dimensional problem to gain a clearer insight into the assumptions that are made in the usual one-dimen-

Jan 1, 1962

By H. S. Price, R. L. Reed, J. E. Warren

The behavior of the reverse-combustion process in a linear adiabatic system is theoretically investigated by means of an idealized physical model. T his model is described by a pair of non-linear equations involving heat and mass transfer which are coupled by a concentration-dependent reaction-rate function of the Ar-rhenius type. The differential equations governing the quasi steady-state temperature and concentration distributions are approximately solved by using either physical or mathematical simplifications. It is shown that the reverse -combustion process can be mechanistically described by simple physical models whose behavior equations can be solved formally. It is further demonstrated that the derived reverse-combustion equations can be solved numerically within the error limits for the experimental data. The theoretically predicted peak temperature-flux-velocity relationship exhibits reasonable agreement with experimental data obtained from Athabasca tar sand. The principal contribution of this work lies in its usefulness as a starting point for developing a more comprehensive theory. A description of the vaporization-coking process must be obtained; then, the theory must be extended to three dimensions to include geometrical effects and heat losses. INTRODUCTION In another paper,'" he physical processes visualized as occurring during reverse combustion have been described. In this paper, the extent to which an elementary theory can account for experimental observations is determined. Theoretical results that can be used to estimate some of the behavior characteristics of importance to this process are also presented. Since it is not possible to include all the features of the combustion mechanism of which we are currently aware, the mathematical formulation refers to the highly idealized system developed herein. This simplified physical model is based on the simultaneous transfer of mass and heat accompanied by a chemical reaction: it is described mathematically by a pair of coupled, nonlinear differential equations. Similar sets of equations have been studied extensively in the field of flame propagation; an excellent review of these investigations has been published by Evans.1 FORMULATION OF THE PROBLEM It will be recalled that the experiments are performed with a thin-walled cylindrical tube that is uniformly packed with sand and oil. The system is maintained substantially adiabatic by means of heat supplied externally in such a way that the radial temperature gradient in any plane normal to the axis of the tube approaches zero. Initially, the tube is at ambient temperature, except at one end where it is rapidly heated to a predetermined temperature. When the prescribed temperature is achieved, air is caused to flow into the cold end of the tube. As the oxygen in the air stream contacts the hot oil, a localized exothermic reaction takes place. The generated heat is conducted and convected away from the reaction zone so that definite temperature and concentration profiles are rapidly established and move uniformly in a direction opposite to that of the air flow (Fig. 1). As a consequence of this mode of oxidation, all of the oxygen in the air is consumed; then, the remaining nitrogen and the gaseous combustion products sweep out all vaporized hydrocarbons and leave an immobile hydrocarbon-coke on the sand.

By D. O. Ehrenburg, R. J. Watson

During the earlier period of electrical prospecting, the search for orebodies was by far the most important application of this method of geophysical prospecting. In the past few years, however, increasing attention has been paid to the possibilities of this method in the investigation of subsurface structures. Not only have fault zones been located, but attempts have been made to determine the depth to certain strata and thus contouring on some bed which proves to be a good "electrical marker." Many workers have published the results of field tests showing how their particular interpretations have agreed with the actual field conditions, but very few have stated their method of interpretation. Weaver, Hummel and Stefanesco and Schlumbergerl have given a more theoretical discussion of the resistivity methods. Hummel and Stefan-esco and Schlumberger have published mathematical solutions for the flow of electricity in a medium involving four layers. In this paper the authors present a solution for the flow of electricity in a medium of any number of horizontal strata. By means of this solution, curves showing the relationship between the apparent resistivity and the electrode spacing can be computed for ideal cases. Point-source in an Infinite Homogeneous Medium In resistivity measurements the current is conveyed to the earth by means of two electrodes, which can be mathematically treated as point-sources of equal and opposite strength. A point-source of strength I is defined as a point at which electricity is being generated at the constant rate of I coulombs per second, or I

Jan 1, 1932

By Thomas T. Read

The fact that certain types of ore-deposits have attained their present condition through the action of descending surface waters was, perhaps, first clearly pointed out by Posepny.l The oxidizing effects of such waters were discussed by Pen-rose,2 and many papers dealing with this phase of the subject have subsequently appeared. That secondary enrichment of sulphide ores, however, might be produced by descending surface waters was not clearly understood until after the copper-bearing veins of the Butte district, Mont., had been carefully studied by the geologists of the U. S. Geological Survey, although De Launay3 had suggested that sulphides might be transported from point to point and re-deposited in the zone above the level of ground-water. As a result of the study of the Butte district, two papers by geologists engaged in the work appeared within a short interval. The first by Weed: dealing with the enrichment of veins by later metallic sulphides ; and the second by Emmons; treating of the secondary enrichment of ore-deposits in general. In the latter paper it was pointed out that a typical vein of sulphide ores which has been subjected to the action of descending surface-waters exhibits four zones,—an upper or surface-zone, in which the changes hare been mainly of removal, the products being typically oxides; a second zone of oxide enrichment, in which the less soluble metals brought from above have been precipitated as carbonates or oxides; a third zone of sulphide enrichment,

Jan 1, 1907

By E. O. Lilge, H. Siebert

A design of a multiple-bomb leaching unit particularly suited for the study of heterogeneous reactions, i.e. sol id-liquid-gas interfaces at high temperatures and pressures is presented. The component parts and overall design are described and illustrated in detail. The system has been tested by a limited number of experiments and found to work satisfactorily. Heterogeneous reactions at solid-liquid-gas interfaces, at high temperatures and pressures, are studied in either autoclaves1'4 or bombs5'9. Autoclaves are usually fairly large vessels which have a stirring arrangement incorporated in the design. Mechanical design limits the use of these vessels to relatively low temperatures and pressures. They are particularly well suited to rate or kinetic studies. Bombs can be designed to be operated at high temperatures and pressures, and are smaller vessels; because of this, stirring arrangements are not easily incorporated. In this paper a multiple-bomb system is described, that has been designed to incorporate the desirable features of both the autoclave and the bomb. The described unit has flexibility for an over all study of leaching. Most of the component units in this assemblage are standard equipment, designed and produced by well known manufacturers. No claim is made to the design of this equipment, and although described in some detail, this is done merely for clarity in the elucidation of the system presented. The general layout of the multiple-bomb assemblage is shown in Fig. 1A and 1B. The basic units in this system are: 1) 6 stainless steel 100 ml bombs (Fig. 4)

Jan 1, 1964

By H. R. Banks

Pondering the action of a ball mill employed to carry on comminution from the product of fine crushing to the point where flotation, cyanidation or other concentrating methods are applicable, one wonders where this machine had its origin. When Henry Wadsworth Longfellow reiterated the observation of that older poet Von Logau, and wrote "Tho' the mills of God grind slowly, yet they grind exceeding small," he probably visualized the type of mill that was employed in medieval times for the production of flour, and can therefore not be considered as having gained admittance to the fraternity of millmen, on behalf of either poet. He does, however, make it quite clear that the efficiency of even these Mills of Destiny was low, and to that extent voices a characteristic of fine-grinding equipment that has been the bugbear of all metallurgical engineers. Principle of Ball Mill The principle of the ball mill probably is traceable to the action along the coast line of oceans or lakes, or in the mountain streams. Wave action on rocks and pebbles, close to the shore line, gives the potential energy to the grinding media, which, in their rolling and tossing, break down the sands, and the resultant "pulp" carried out from the shore is classified and settles out in sizes ranging downward to extremely he mesh. Surely, these are the real mills of God. If we allow our minds to dwell on the total tonnage that has been handled in this way, adding to the sands and clays at present in existence those enormous tonnages of metamorphosed sedimentaries we sense the vast quantity of rock that has been so reduced. Is it not likely, therefore, that the answer to the beginnings of pebble milling, and eventually ball milling, came through the perception of this natural mill by one of our engineering forebears? Methods of Grinding The relatively low return of mechanical input to a ball mill, in terms of useful work accomplished, has always intrigued me immensely. The potential energy absorbed by a ball raised to a high point in its path is apparently released with a very small return in useful work. Is the ball mill the most desirable means of he grinding, or is there some other method through which we can recover a reasonable amount of the energy input in terms of useful work? Some years ago, on his retirement, H. W. Hardinge was questioned as to his thoughts on the trend of fine-grinding equipment. As I recall, his prophecy at that time was that the most likely field for improvement in grinding media would be toward a charge of flat disks with some mechanical scheme to cause them to slide over each other. Undoubtedly, Mr. Hardinge went through the usual experience of the muller and bucking board, the customary introduction of the budding millman to his calling. I have often wondered, but have never got beyond the wondering stage, as to the

Jan 1, 1947

By H. R. Banks

Pondering the action of a ball mill employed to carry on comminution from the product of fine crushing to the point where flotation, cyanidation or other concentrating methods are applicable, one wonders where this machine had its origin. When Henry Wadsworth Longfellow reiterated the observation of that older poet Von Logau, and wrote "Tho' the mills of God grind slowly, yet they grind exceeding small," he probably visualized the type of mill that was employed in medieval times for the production of flour, and can therefore not be considered as having gained admittance to the fraternity of millmen, on behalf of either poet. He does, however, make it quite clear that the efficiency of even these Mills of Destiny was low, and to that extent voices a characteristic of fine-grinding equipment that has been the bugbear of all metallurgical engineers. Principle of Ball Mill The principle of the ball mill probably is traceable to the action along the coast line of oceans or lakes, or in the mountain streams. Wave action on rocks and pebbles, close to the shore line, gives the potential energy to the grinding media, which, in their rolling and tossing, break down the sands, and the resultant "pulp" carried out from the shore is classified and settles out in sizes ranging downward to extremely he mesh. Surely, these are the real mills of God. If we allow our minds to dwell on the total tonnage that has been handled in this way, adding to the sands and clays at present in existence those enormous tonnages of metamorphosed sedimentaries we sense the vast quantity of rock that has been so reduced. Is it not likely, therefore, that the answer to the beginnings of pebble milling, and eventually ball milling, came through the perception of this natural mill by one of our engineering forebears? Methods of Grinding The relatively low return of mechanical input to a ball mill, in terms of useful work accomplished, has always intrigued me immensely. The potential energy absorbed by a ball raised to a high point in its path is apparently released with a very small return in useful work. Is the ball mill the most desirable means of he grinding, or is there some other method through which we can recover a reasonable amount of the energy input in terms of useful work? Some years ago, on his retirement, H. W. Hardinge was questioned as to his thoughts on the trend of fine-grinding equipment. As I recall, his prophecy at that time was that the most likely field for improvement in grinding media would be toward a charge of flat disks with some mechanical scheme to cause them to slide over each other. Undoubtedly, Mr. Hardinge went through the usual experience of the muller and bucking board, the customary introduction of the budding millman to his calling. I have often wondered, but have never got beyond the wondering stage, as to the

Jan 1, 1947

By J. C. Wilhoit, E. M. Galle

A three-dimensional photoelastic study was made to determine the stress state around the wall and bottom of a wellbore due to fluid pressure within the wellbore and unequal principal geostatic stresses. Models simulating the wellbore were made from a phthalic anhydride-cured epoxy resin. The frozen stress technique of three-dimensional photoelastic-ity was used to determine the stresses within the model. Two separate problems were solved: (1) hydrostatic pressure on all sides of the model with the exception of the inside of the hole, and (2) uniaxial compression perpendicular to the center line of the hole. The results are presented in the form of contour curves for each stress component. The curves cover a region which extends several hole radii from the bottom and wall of the hole. By proper use of these results, the state of stress may be calculated for any point on the wall or bottom of the hole, as well as for any point within the material that surrounds the hole. A systematic method is given for calculating these stress components for any combination of fluid pressure within the wellbore and system of unequal principal geostatic stresses, provided one of the principal geostatic stresses is parallel with the wellbore. The results show that stresses around the wall and bottom of a wellbore, induced by an uneyual system of principal geostatic stresses, are appreciably different from those induced by geostatic stresses that are hydrostatic. For uneyual principal geostatic stresses, the experimentally determined stresses on the wall of the hole several radii from the bottom are in good agreement with the stresses calculated by elastic theory. INTRODUCTION Interest in the problem of determining the stresses around and near the bottom of a wellbore, due to geostatic loading and fluid pressure within the wellbore, originated in the petroleum industry. The stresses on the wall of the wellbore are of interest due to their relation to lost circulation during drilling, the fracturing of formations during squeeze cementing and hydraulic fracturing of producing formations. The stresses on the bottom of the hole are of interest to the drilling segment of the industry because to produce a hole in the earth it is necessary to remove material from the bottom of the hole. This removal of material is produced by structural failure of the rock, whatever the criterion for failure may be. Cunningham and Eeninkl have shown that for certain conditions the effect on drilling rate of the bottom-hole stresses caused by a hydrostatic overburden pressure is small compared to other effects. This question, however, needs further experimental and analytical investigation. Much information concerning the stresses on the walls of wellbores has been published considering both equal and unequal principal geostatic stresses. The problem of determining the stresses around the bottom of the wellbore is considerably more complicated. However, previous investigators have obtained numerical and experimental solutions to the problem for equal principal geostatic stresses. whitworth2 and woods3 have obtained numerical solutions. word415 obtained a three-dimensional photoelastic solution, Durelli and Deily 6 obtained surface stresses only by photoelastic means, and Cheatham and Wilhoit7 determined the stresses around the bottom of a short cylindrical cavity. While Miles and McGuire, Harrison and Kieschnick and Hubbert and Willis 10 obtained the stresses on the wall of a wellbore for unequal principal geostatic stresses, they did not concern themselves with the stresses near the bottom of the hole. The estimates made by Hubbert and Willis of the differences between the principal geostatic stresses indicate that, to obtain a satisfactory solution for the stresses around the bottom of a wellbore, unequal principal geostatic stresses should be considered. This work is directed toward obtaining such a solution. The materials in the earth's crust are nonhomo-geneous, permeable and anisotropic. Previous

By Nicholas J. Grant, David S. Bloom

An investigation of the Cr-Ni system has revealed that there exists a eutectoid transformation at about 1180°C. 'The transformation in chromium implied by the eutectoid reaction was detected at about 100°C below its melting point. Associated with the eutectoid transformation, a metastable transition structure has been found. THE Cr-Ni phase diagram is shown in current literature to be a simple eutectic system in which the high chromium end of the diagram is incompletely determined, Fig. 1. The last investigation of this system was undertaken in 1936.' Because of limitations in metal purity, especially of chromium, and temperature measuring techniques, the diagram should be accepted with some reservations, as was indicated by Hansen.V or examwle.-, the wresence of the compound Cr²Ni, with a tetragonal structure," remains unverified and incompatible with the simple eutectic diagram. The work reported here began because of discrepancies that appeared in experimental studies in the binary alloys Cr-Ni and in the ternary system Cr-Mo-Ni. The existing binary Cr-Ni diagram failed to provide a complete explanation of observations made by microscope, X-ray, and thermal analyses. Experimental Methods The materials employed were of a higher degree of purity than were available to previous investigators. The Mond nickel used had a nominal purity of 99.87 pct, while the electrolytic chromium analyzed 99.03 pct with the major impurity being 0.5 to 0.7 pct oxygen with some iron. All alloys were melted in a vacuum furnace to remove dissolved gases, sufficient carbon was added to the charge to combine with all the oxygen as CO. Final analysis determined the carbon as about 0.02 pct and the oxygen around 0.06 pct or slightly more. Stabilized zirconia crucibles and thermocouple protection tips were used throughout and contributed no detectable impurity to the melts, as long as the oxygen in the chromium was kept low. Heats averaged about 250 g, which permitted about 2 in. of the thermocouple protection tips to be submerged. The temperature drop across the thermocouple protection tip was determined to be about 3°C, a minor source of error. The alloys, after removal from the vacuum furnace, were placed in a furnace operating in a purified argon atmosphere for the thermal analyses. An- nealed wolfram-molybdenum thermocouples provided the primary means of temperature determination, though a Pt-Pt-10 pct Rh couple was employed for a check when possible. A sensitive, high-speed Leeds and Northrup Speedomax recording potentiometer indicated the thermocouple output. X-ray diffraction patterns were obtained primarily on a Norelco unit, which permitted diffraction angles only up to 45" (28 = 90"). In general, either rotated or stationary solid samples were used, because it later evolved that many samples were susceptible to transformation resulting from the cold working involved in pulverizing. It was also noted that rotating a sample sometimes suppressed weak lines, so, usually, samples were not rotated. Later a high temperature camera was adapted for use at temperatures up to 1400 °C on the Norelco unit utilizing both solid and powdered samples. Unless otherwise noted, all X-ray patterns were made with a chromium tube and a vanadium filter. Further-

Jan 1, 1952

By F. H. Buttner, E. R. Funk, H. Udin

Gold wires, 5 mil in diam, are found to creep viscously up to approximately 5.5x106 dynes per sq cm around 1300°K. Beyond this point, an additional slip mechanism appears. The average coefficient in the viscous range at these temperatures is 18.9 ± 7x10 12 poises. This observation and other visual observations made during the experiments agree with Herring's predictions. EARLY creep studies by Chalmers on single crystals of tin produced some of the first experimental evidence to suggest that metals deform viscously under very light stresses. That is to say, over a small initial stress range up to 150 g per sq mm, the single crystals of tin elongated at a rate proportional to the stress. The proportionality constant between strain rate and stress is by definition the coefficient of viscosity. Chalmers named this range of proportionality the microcreep range. One of the first theoretical attempts to explain the microcreep phenomenon was given by Kauzman,' who applied Eyring'sQ eneral statistical mechanical theory of shear rates to creep data then available. From the rate theory, he deduced the general hyperbolic sine law for shear rate on the assumption that the distortion of the reaction path due to stress is negligible and that the system is an infinite continuum. In order to fit the available data to the equation, it was necessary to assume that creep occurs by shear of rather large blocks of material, rather than by an atomistic shear process as in diffusion. The size of the shear units was shown to increase with increasing temperatures and lower stress, or lower strain rates. In applying the hyperbolic sine law equation to the microcreep data of tin, it was shown by Kauzman that the unit shear blocks became quite small, which suggested to him that microcreep might be a self-diffusion process. Making this an assumption, Kauz- man reworked the rate theory and arrived at an equation where the shear rate is proportional to the stress. In the form of viscosity coefficient, the equation is: o- _ \LkT V = 2qAlA where u is the stress; S, the shear rate; X, the distance in shear direction moved by flow units relative to one another in the unit process; L, the distance between layers of units of flow; T, the absolute temperature; k, Boltzmann's constant; qAL, a constant proportional to the size of flow units; and kT A, the diffusion coefficient = ------kTe-Q/RT = K X2 h Kauzman applied the expression to molten lead with a fair degree of success, the calculated viscosity being low by a factor of four. For solid lead the result is 5000 times too high. Taking q = 1, and X = dA = L = 21 = nearest neighbor distance, Udin, Shaler and Wulff8 found the equation low by a factor of lo7 for solid copper. On the basis of the discrepancy in lead, Kauzman indicated that microcreep is probably not a simple diffusion process of molecular shear units, but one involving preferential diffusion paths, or even that diffusion in solids does not involve shear at all. Cottrell and Jaswon4 treat the microcreep phenomenon on the basis of slow moving dislocations and apply it to Chalmers' data on tin with fair success. Nabarro Suggested a microcreep model in which mass movement in the direction of pull is effected by the diffusion of holes. The tension on the crystal effectively creates a greater hole concentration at regions near the crystal surfaces perpendicular to

Jan 1, 1953

By W. J. West, T. D. Mueller, J. E. Warren

The authors have presented valuable information on the influence of the interfacial tension and the contact angle on the recovery efficiency of the waterdrive process. It is considered, however, that the following points deserve a closer examination. 1. As pointed out by Wyllie and Spangler1 the displacement pressure PD i.e. the pressure required to initiate the displacement of the wetting phase from the core, is a measure of the maximum pore diameter dmax. If the capillary pressure Pe as a function of the wetting

Jan 1, 1956

By Wing L. Lew

LEAD, silver, and zinc, in quantities of economic importance are found in the Aguilar ore. The lead occurs as galena and the zinc as sphalerite and marmatite. The silver occurrence is more complex. Pyrargyrite and proustite have been identified only occasionally. Galena is silver-bearing and so are the various other sulphides, though to a lesser degree. The principal nonsulphide gangue minerals include calcite, quartz, wollastonite, rhodonite, and various calcium, aluminum, and iron silicates. A typical analysis of, the ore is: Pb, 11.2; Zn, 12.3; Fe, 4.4; Mn, 2.2; Cu, 0.15; S, 11.2; CaO. 7.6; "Insoluble," 50.1 percent; and Ag 263 g per ton. Crushing is done in three stages. The primary crusher at the mine is set to deliver about a 5-in. product. The crushed ore is then transported to the secondary crushing plant by a 3-km cableway where the general practice is to hold the product of the first Symons to about 1 in., and of the second Symons to about 1/2 in. When the ore is soft and rich the product of the first Symons is by-passed directly to the ball-mill bins. Dust control in the secondary crushing plant is effected by enclosing the dust-emanating sources and exhausting the enclosures with a Clarage No. 18 fan driven at 1300 rpm by a 20-hp motor. Use is also made of spray water at one or two critical places. Every effort is made to keep the air free from visible dust. Dust counts taken at the working places show dust concentrations of less than six million particles ner cu ft. The composition

Jan 1, 1947

By C. A. Kroetz, A. J. O’Neal

The Long Island Lighting Co. has operated an extensive monitoring system for over three years. Nearly 900,000 separate pieces of information have been recorded for a land area of some 600 sq miles, 15 miles north to south by 40 miles east to west. The data are composed of about a half million sulfur dioxide measurements at various locations, 290,000 of which were by the West-Gaeke method, about 160,000 pieces of weather data, and 220,000 measurements of sulfur dioxide as emitted from each of the power plant stacks on the system, all measured on an hourly basis and stored on computor cards and tapes. The computor has been programmed to collate stack emissions, weather information, and ground level sulfur dioxide measurements. The analysis shows that emissions from tall stacks do, indeed, contribute very little to ground level sulfur dioxide. For example, LILCO shows that its Northport plant contributes less than 2 ppb, hourly annual average. They also state that the plant converted to 100% natural gas or shut down, would reduce ground level sulfur dioxide by no more than 2 ppb.

Jan 1, 1973

By W. L. Batt

MODERN war means mechanization, and mechanization means raw materials, especially minerals-and lots of them. Let me recall a few events of recent history-events that constitute mile- stones down the road to the war now blazing on three continents and threatening to spread still farther. In 1932, Japan took Manchuria, largely upon the excuse that she needed raw materials; in 1935, Italy invaded Ethiopia, largely upon the excuse that Mussolini's growing nation needed raw materials-in this case oil; from 1933 to 1935, Germany cried out for a greater share of the world's natural wealth, and since 1938 has invaded or occupied ten other countries, frequently upon the excuse that she needed-and had a right to-more raw materials.

Jan 1, 1940

By Geoffrey Gilbert

THE Montana Phosphate Products Co., subsidiary of the Consolidated Mining and Smelting Company of Canada, operates three phosphate properties north and northeast of Garrison, Powell County, Mont. Production of all three is from the same phosphate bed, a 3 to 4-ft. member of the Phosphoria formation, whose outcrop is traceable across the mountains of the Garnet Range in a series of southeasterly pitching folds. Because of topographical differences and of variations in the attitude of the bed, each property has its own mining methods and problems. Most of the phosphate rock produced since I930 has been shipped to the plant of the Consolidated Mining and Smelting Co. at Trail, B.C., where it is treated with sulphuric acid for conversion to phosphoric acid, which in turn is used to produce various fertilizers. HISTORY The occurrence of rock phosphate in Montana has been known. since 1910, and the Garrison area was mapped by the United States Geological Survey in 1913In the nineteen twenties William Anderson, owner of a ranch 8 miles north of Garrison, discovered phosphate on his land, and the Montana Phosphate Co., which later became the Montana Phosphate Products Co., was formed to work the deposit. Montana Phosphate Products Co. later obtained United States leases on two adjoining parcels of ground, and this combined property, known as the Anderson mine, has been the main source of Consolidated's phosphate rock. The mine now includes an adjoining parcel leased from Anaconda and mined from the Anderson workings. In 1940, the Graveley mine, a small privately owned property 6 miles east of the Anderson, was leased from the owner by Montana Phosphate Products Co., and a U. S. lease held by Graveley on some adjoining ground was subleased. In 1943 the Luke mine, on the Mineral Hill property, 1 ¾ miles south-southwest of the Graveley, a U. S. lease, which previously had produced a few thousand tons, was optioned from the lessees by Montana Phosphate Products Co., and is now being developed. At both these mines the rock is appreciably higher grade than at the Anderson mine. GEOLOGY The Phosphoria formation is the Permian member of an extensive sequence of Paleozoic and Mesozoic rocks. It is underlain by Pennsylvanian (Quadrant) quartzite and Mississippian limestone, and overlain without any marked unconformity by Jurassic (Ellis) shale and Cretaceous shale and sandstone. In the Garrison area, the Phosphoria itself consists mainly of about 50 ft. Of gray to yellow chert. Immediately below the chert is the phosphate, usually 3 to 4 ft. thick. Below the phosphate occur a few

Jan 1, 1945

IlAbad, Leopoldo F , Min Engr , Div of Mines, Bureau of Science, Manda, P I '23 ||Abadilla, Quince, A , Cia Minera de Petrolco El Aguila, S A Box 86, Puerto Mexico, Ver , Mexico '20 ||Abarquez, Ramon F , Met , Bureau of Science Manila, P I '24 ||Abbey, Robert Graham, Student, Case School of Applied Science Cleveland, Ohio '21 Abbott, A N , Mines Supt, Mazapil Copper Co , Ltd Concepcion del Oro, Zac , Mexico '23 Abbott, Clarence E , Gen'l Supt , Iron Mines Div , Tenn Coal, Iron & R R Co , 1405 Minnesota Ave , Bessemer, Ala '04 Abbott, Louis Benjamin, Chief Engr , Consolidation Coal Co , Elkhorn Div Jenkins, Ky '15 Abbott, Robert R , Met Engr , Peerless Motor Car Co Cle veland, Ohio '12 ||Abbott, Wells Osborn, Ray Consolidated Copper Co Hayden, Ariz '23 Abeel, George H , Jr, Cons Min Engr 4612 W 17th St, Los Angeles, Cal '18 Abel, Albert E, Asst to Pres, Valley Mould & Iron Corpn Sharpsville, Pa '19 Abernathy, George Elmer, Prof Geol & Min , Kansas State Teachers College Pittsburg, Kans '20 Abey, Hiroshi, Min & Met Engr, Takata & Co , 2 Yeirakucho, Nichome, ICojimachi-ku, - Tokyo, Japan '17 ||Aborn, Robert H 24 Groveland St , Auburndale, Mass '19 Abouchar, Sylvain Sley, Min Engr & Geol , Care of S H Sekaly, 13 Rue El Nimr, Cairo, Egypt '17 ?Abraham, Arthur W 1626 N Alexandria Ave, Los Angeles, Cal '21 Abrahams, Alexander I, Gen'l Mgr, Ricon Electrical Co Slough, London, England '13 ||Abrahamson, C Walter, Min Engr, Brule Min Co Stambaugh, Mich '21 Abrams, Charles Jackson, Mill Supt, Utah Apex Min Co Bingham Canyon, Utah '21 Abrams, David H, Cons Min Engr 182 Worth St, Johnstown, Pa '20 ?Acker, E O'C , Met 128 East Washington Lane, Germantown, Philadelphia, Pa '86

Jan 1, 1923

By David R. Mitchell

IF you are the owner of a mine, or a mine executive, or just an ordinary miner, and have a son about to go to college, do you urge him to take up mining engineering or do you try to dissuade him from such a course? If you live in the East, or the Middle West and your interest has been in coal rather than metal mining, the chances are that your young hopeful will be urged to do almost anything else rather than follow in father's footsteps.

Jan 1, 1939

By M. J. Marcinkowski, A. Szirmae, R. M. Fisher

Room -temperature hardness measurements obtained from single and polycrystalline samples of a 47.8 at, pet Cr-Fe alloy which were aged for various times al 500°C show a two-fold increase over that of the unaged alloy after annealing for 1000 hr. A detailed examination of the deformation markings in the neighborhood of the hardness imbressions reveals that twinning becomes an increasingly more important mode of deformation as aging proceeds. this observation is shown to be inconsistent with the Proposals that the transformation is eve of order-disorder On the other hand, the results are in agreement with previous observations of Fisher et al. of a coherent chromium-rich precipitate which forms in an iron-rich matrix as a result of a miscibility gap in this alloy system as proposed by Williams . Using the coherent precipitate hypotlzesis as a model, a detailed analysis of the various possible strengthening contributions to both the slip mid twinning stresses is made. In the case of' slip, lattice friction within the chromium-rich phase and the chemical energy associated with the interface between the two phases contribute about 60pet to the total strength. The contributions from coherency strains and modulus differences are thought to contribute the remaining 40 pet of the strength but are difficult to evaluate because of uncertainties regarding the flexibility of the dislocation line. All of the factors have nearly the same or else a smaller effect on the twinning stress in the aged alloy. Twinning is never observed in the unaged alloy because the twinning stress is much higher- than that for slip. With increased aging times, the various contributions to the total stress for both twinning and slip increase, but most of those for slip increase much more rapidly, so that, in the fully aged alloy, it surpasses the stress for twin propagation. When a twin is nucleated by the chance occurrence of an internal stress concentration during a test, the subsequent twin burst results in a low hardness reading. FeRNTIC Fe-Cr alloys from about 15 to 80 at. pet Cr content show considerable change in properties such as hardness, electrical resistivity, saturation magnetization, and so forth, after aging in the vicinity of 500°C.* The most marked change is a large increase in hardness accompanied by a sharp decrease in ductility, so the phenomenon has often been referred to as the 475°C (885°F) em-brittlement problem. Changes in microstructure are rather subtle and most investigators have not been able to observe any X-ray diffraction or metal-lographic changes during aging. There is little doubt that the phenomenon is inherent to the Fe-Cr binary system and is not directly related to the formation of a phase. Two distinct schools of thought have developed during the past decade concerning this problem. Masumoto, Saito, and sugiharal have concluded, from their own specific-heat measurements, that atomic ordering occurs in this temperature range. Pomey and Bastien2 have also attributed the changes in physical properties with aging in the neighborhood of 500°C to atomic ordering. In addition, Takeda and Nagai3 claimed to have found X-ray verification for superlattices corresponding to the compositions FesCr, FeCr, and FeCr3. However, all known attempts to observe superlattices in Fe-Cr alloys using neutron diffraction, which should be much more sensitive, have been unsuccessful. These have been reported by Shull et al.4 for 25 at. pet Cr, williams5 for 75 at. pet Cr, and Tisinai and samans6 for a 28.5 at. pet Cr. steel. The second and more prevalent opinion ascribes the 475°C embrittlement phenomenon to the formation of a coherent precipitate due to the occurrence of a miscibility gap in the Fe-Cr system below about 550°C. This latter concept was first indicated by the results of Fisher, Dulis, and Carroll,7 who were able to extract fine particles about 200Å in diameter from samples of 28.5 at. pet Cr steels aged from 1 to 3 years at 475°C. The extracted material was found to be nonmagnetic, to have a bee structure with a lattice parameter between that of iron and chromium, and to contain about 80 at. pet Cr. Williams and paxton8 and williams5 confirmed these results and first explicitly proposed the existence of a miscibility gap below the a region in the equilibrium diagram. Alloys aged within this gap

Jan 1, 1964

By N. Mungan

Formation damage, i.e.. reduclion in permeability, has been generally attribuled to clay minerals which expand or disperse upon contact with water that is less saline than the connate water. Luboratory, studies show that penneahility reduction can also occur in formalions containing only nonexpandable clays such as illite or kaolinite, and can be caused also by changes in pH. Furthermore, pH changes can damage even formations that are essentially free of clays. It is suggested that permeability reduction is due to the small passages being blocked by particles, which may be dispersed clays, cemenlion material or other fine parricles. These particles are dislodged by dispersion of clays due to changes in salinity or by dissolution of calcareous cement by acids, or of silicaceous cement by alkaline solutions. In working with reservoir cores, it was found that extracted cores damaged more easily and extensively than nonextracted cores. The extent of damage depended also on tenlperatltre. INTRODUCTION Permeability is an important property of porous media and has been the subject of many studies by engineers and geologists. Many of these studies are conccrned with formation damage, i.e., reduction in permeability, resulting from exposure of oil-producing formations to water substantially less saline than the connate water. This effect causes understandable concern since during drilling, completion and production phases formations are often exposed to fresh water. The damage resulting from contact with relatively fresh water has been attributed to expansion and dispersion oF clay minerals. During laboratory investigation of the use of NaOH as a wettability reversal agent to increase oil recovery from oil-wet reservoirs, several cores used in the displacement studies suffered loss in permeability. Despite the traditional usage of NaOH for conditioning aqueous mud systems, the role of the caustic filtrate in wellbore damage seems to have been overlooked. Browning2 as recently reported on the effects of NaOH in dispersing clay minerals but he was concerned only with complications that may arise in drilling massive shale beds. The following study was made to examine the role of pH and salinity changes in core damage. Where cores from reservoirs were used, tests were performed with extracted and nonextracted cores both at room and reser- voir temperatures, since it was felt that the test environment and core condition may affect the results. Because of its limited coverage and exploratory nature, this study is not intended to provide answers to field formation damage problems. It is hoped that it will encourage research into new aspects of the permeability reduction problems, particularly those allied to new recovery and production processes. PROCEDURE In all permeability tests, fluids were pumped through the cores at a constant volumetric rate. Only deaerated fluids and reagent grade chemicals were used. The fluids were passed through two ultrafine filters before injection to remove any entrained particles. The cores, with the exception of the unconsolidated cores, were mounted in Hassler holders. Water was used to transmit pressure to the sleeve. The inlet endpiece had two entry ports which permitted scavenging one fluid with another to avoid any mixing in the small holdup volume. The cores were flushed with CO2 gas, evacuated for 5 to 6 hours and saturated with the first liquid at a pressure of 1,000 psi for 24 hours to eliminate any free gas from the cores. Pressure differences up to 20 psi were measured by transducers, calibrated in inches of water and continuously recorded. For greater pressure drops, gauges were used. All reservoir cores were cleaned with a light refined mineral oil, then with heptane, and finally dried with CO2. Compatibility tests showed that no precipitates formed when mineral oil and the crudes were mixed. Some cores were extracted in Dean-Stark-type solvent extractors using xylene and trichloroethane and dried in a vacuum oven at 450F. Each test consisted of a sequence of water, test solution, and again water flow. RESULTS AND DISCUSSION STUDIES IN BEREA CORES Salinity Contrast Berea cores 2-in. in diameter and 12-in. long were cut from sandstone quarried in Cleveland, Ohio. The clay minerals were identified by X-ray diffraction to be chlorite, kaolinite, illite and incerlayered illite. Flow of fresh water or 30,000 ppm brinc does not cause any permeability reduction (Fig. 1). However, after injection of brine the core is readily damaged by fresh water. Damage starts almost instantly as the fresh water injection is begun, and at a cumulative injection of 1.2 PV fresh water, the permeability has dropped from 190 to 0.9 md. Upon continued injection, the effluent contains clay minerals dislodged from the core. The final core per-

Jan 1, 1966

By B. H. Kear, B. J. Piearcey

The orientation and temperature dependence of the tensile and creep propevties oj Mav-M200 crystals halle been determined. Crystals oriented for single slip exhibit ,maximum ductility, minimum work hardening, and least creep resistance, whereas crystals in multiple slip orientations show nzinimu~n ductility, strongest work hardening, and greatest creep resistance. At 1400" and 1600°F there is a marked improzlenzent in creep strength for orientations approaching [001] and [111], indicating that interactions between dislocations gliding in intersecting octahedral slip systems play an important role in creep resistance. At 1800°F the creep strength is much less dependent on orientation, which is rationalized in terms of slip in cube planes as well as octahedral A frequent mode of failure in high-strength cast nickel-base superalloys is by intergranular fracture, particularly along those grain boundaries oriented transverse to the major stress axis. VerSnyder and ~uard' demonstrated that this problem could be overcome by eliminating transverse grain boundaries through unidirectional solidification. Piearcey and versnyder2 made use of this principle in the development of unidirectionally solidified gas turbine blades and vanes, where the growth direction of the columnar grain structure coincides with the axis of principal stress under operating conditions. The present investigation was undertaken to determine if further improvement in properties may be obtained by eliminating grain boundaries altogether, so as to take advantage of the well-known dependence of mechanical properties of single crystals upon the orientation. 1) EXPERIMENTAL PROCEDURE Single crystals of Mar-M200* were grown from the melt under vacuum by a modified Bridgman method. The melt was poured into a preheated alumina mold, and crystal growth was promoted from one end by appropriate gradient cooling. Tensile and creep specimens (2 in. diam by $ in. gage length) were prepared by a series of operations involving electrical discharge machining, precision grinding, and electropolishing. The orientations of the specimens were determined by the Laue X-ray back-reflection method. Tensile tests were carried out in aWiedemann machine with furnace attachment, using a strain rate planes. In all orientations imzpvouement in the strength charactevistics of the material can be induced by heat treatment. Creep ad stress rupture data for (001) oriented crystals are compared with similar data obtailted previously joy random polycvystalline material, and also columnar grained material having a prejevved (001) orientation. The single-crystal )material exhibits both longer rupture life and lower minimum creep rate at all temperatuves, and the rupture elongation is comparable with that in the columnar grained material. From these results it is concluded that single crystals should and useful application in gas-turbine blades and tanes. The optimum orientation for a blade is considered to be with its axis of principal stvess parallel to (001) ou (111). of 0.0001 sec-'. Load and extension were recorded directly on an X-Y recorder. The strain measuring device consisted of extension arms attached to the grips at one end and leading out of the furnace to an LVDT (linear variable differential transformer) at the other. Creep tests were performed using a standard constant load creep frame. 2) DISCUSSION OF RESULTS 2.1) Structure of Alloy. The structure and segregation in as-cast and heat-treated Mar-M200 has been described in detail else where.~ The main features are as follows: the as-cast material is heavily cored, due to pronounced dendritic segregation during solidification; the dendrites are rich in tungsten and cobalt whereas the interdendritic regions are rich in chromium, titanium, nickel, and carbon. The structure consists of -60 vol pct coherent precipitate of y', basically Ni3(A1,Ti), in a matrix of y (nickel-base solid solution), interspersed in the interdendritic regions with minor MC carbides and -y' eutectic. The y' particles, and y-y' eutectic, contain more titanium, aluminum, and nickel, and less tungsten, cobalt, and chromium than the y matrix. Heat treatment partially removes segregation, eliminates the eutectic, refines the y' dispersion in y, and gives additional partially coherent M23Cs carbide. An as-cast crystal, therefore, is composed primarily of two oriented phases (y + y'), whereas the normally heat-treated crystal consists of three oriented phases (y + y' + MZ3Cs). Typical electron transmission micrographs of the y + y' structure are shown in Fig. 1. Crystals grown in the (100) orientation develop a simple unidirectional dendritic structure, Fig. 2, since (100) happens to be the preferred direction of growth for dendrites in this material. Crystals grown in the {110) and (111) orientations, however, tend to promote equal growth, generally in separate colonies, in the two and three geometrically favored (100) growth directions, respectively. In other orientations of growth, a single (100) dendrite direction generally pre-

Jan 1, 1968