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By G. S. Rice

The subject of dust explosions in coad mines first appears in the Transactions of this Institute following the first great mine disaster that happened in…

Jan 1, 1915

By H. Kenyon Burch

INTRODUCTION THE Inspiration Consolidated Copper Co.'s plant at Miami, Ariz., was designed and built to make possible the profitable working of a low-grade, finely disseminated copper deposit containing 100,000,000 tons of ore averaging 1.64 per cent. in copper. From the-beginning it was evident that the-plant could not, be kept integral but that a break would have to be made somewhere in the flow-sheet, removing at least the concentrator to a site more suitable than any available near the mine. It was finally decided, after considering numerous arrangements, to do the coarse crushing at the mine, to store the crushed ore in a bin from which it could be loaded into railroad cars and to haul it to the concentrator, an excellent site for which was available about 1 ¾ miles from the mine. The original intention was to equip a plant to treat 7,500 tons of ore per clay, but through the acquisition and proving up of additional ore reserves, the introduction of the Ohio caving system, and the excellent results obtained in the test mill (which made it possible to treat a lower-grade ore than had been thought possible) it was evident that a plant of much greater capacity should be supplied. It was, therefore, decided to treat approximately 15,000 tons of ore per day, the duties of the four main divisions to be as follows:

Jan 9, 1916

By M. R. J. Wyllie

The relationship between the electromotive force (E.M.F.) across a shale barrier and the concentrations of sodium chloride solutions on either side has been investigated. It is shown that the action of a shale barrier is analogous to a glass membrane separating two acid solutions of different hydrogen ion concentrations. The shale behaves as a sodium electrode and is responsive to the activities of the sodium ions in the two solutions in such a way that the potential can be calculated by means of the Nernst equation. This conclusion is confirmed by laboratory experiments. In a borehole the total E.M.F. of a shale cell is the algebraic sum of the ~otential across the shale and a boundary potential. The relationship between total E.M.F. and the resistivity ratio of two sodium chloride solutions is indicated for a number of formation temperatures. The E.M.F. thus predicted is then compared with the .elf potential read from an electric log and good agreement is demonstrated. Based on both the self potential and resistivity curves of the electrical log. a method is given for calculating connate water content in a bed having in-tergranular porosity and containing both connate water and hydrocarbons. INTRODUCTION The first paper on electrical well logging by C. and M. Schlumberger and E. G. Leonardon in 1934' attributed the self potential curve principally to streaming potentials, i.e. to electroki-netic effects. Almost immediately great difficulties were encountered in reconciling many of the curves they obtained with this interpretation. and a ~econd paper' by the same authors soon appeared. In this second paper self potentials were attributed to the combined effects of streaming potentials and electrochemical potentials, the electrochemical potential being considered the result mainly of the interaction of fluids of differing salt concentrations, i.e. a boundary potential, and partly of potentials set up at the faces of impermeable materials. Some experiments involving a gray clay for the impermeable material were quated. The Schlumbergers and Leonardon deduced from the equation for a simple boundary ~otential that the electrochemical potential, as opposed to the electrokinetic potential, could be expressed in the form E=Klog- .......1 pe where K is a constant, pm the mud resistivity. p, the resistivity of the connate water in a porous bed. However, no general expression for the constant K was obtained. Although the literature between 1934 and 1943 contains a number of quotations of their results, the valuable work of the Schlumbergers and Leonardon was not extended so that the electrochemical potential has been generally attributed wholly to boundary potentials between the mud in the borehole and the connate waters in porous formations. Unfortunately, however, the fundamental premise of all these papers, that a boundary potential can give rise to current flow in a borehole, is thermodynamically untenable. As will be shown. the fact that the electrochemical potential can be fairly accurately express as E = K log pm/pc, a form in which a boundary potential may also be written, is partly fortuitous. The boundary potential is indeed an integral part of the expression for the electrochemical potential in a horehole, but in magnitude it represents only about 20% of the total potential. In 1943 an important step in the elucidation of electrochemical potentials was made by Mounce and Rust3 who showed that if a wall of shale separated two compartments which contained saline solutions of different concentrations, and if the two solutions were themselves brought into contact in the pores of a porous inert membrane (such as unglazed porcelain) a current flowed through the shale and saline solutions. The direction of positive current was from the shale into the more dilute solution. The paper of Mounce and Rust, while repeating some of the observations of the Schlumbergers and Leonardon, seems to be the first to show that the shale was the seat of a genuine electrochemical effect capable of causing current flow. In the same paper Mounce and Rust pointed out the similarity between the fundamental conditions of their experiment and the conditions which existed when a bed of shale in the ground was simultaneously in contact with a porous sand containing saline connate water and mud fluid of salinity different from that of the water in the sand. Since it is now generally recognized that the S.P. curve measures ohmic potential changes in the mud fluid in the well bore resulting from changes in current flow, it is apparent that currents having their origin in the electrochemical interaction of mud filtrate and connate waters with shale beds are a very important portion of the total S.P. The work of Mounce and Rusta and others appears to indicate that, in general, the electrochemical portion of a particular kick on a S.P. curve far exceeds any electrokinetic potentials resulting either from streaming potentials or Dorn effects. The Dorn effect, or sedimentation potential. arises when small particles are allowed to fall through certain fluids under the influence of gravity. a difference of potential being observe? between two electrodes placed at different levels in the stream of falling particles. The Dorn effect is unlikely to affect seriously the S.P. curve as now measured. A successful analysis of the electrochemical aspects of the S.P. log should

Jan 1, 1949

By M. R. J. Wyllie

The relationship between the electromotive force (E.M.F.) across a shale barrier and the concentrations of sodium chloride solutions on either side has been investigated. It is shown that the action of a shale barrier is analogous to a glass membrane separating two acid solutions of different hydrogen ion concentrations. The shale behaves as a sodium electrode and is responsive to the activities of the sodium ions in the two solutions in such a way that the potential can be calculated by means of the Nernst equation. This conclusion is confirmed by laboratory experiments. In a borehole the total E.M.F. of a shale cell is the algebraic sum of the ~otential across the shale and a boundary potential. The relationship between total E.M.F. and the resistivity ratio of two sodium chloride solutions is indicated for a number of formation temperatures. The E.M.F. thus predicted is then compared with the .elf potential read from an electric log and good agreement is demonstrated. Based on both the self potential and resistivity curves of the electrical log. a method is given for calculating connate water content in a bed having in-tergranular porosity and containing both connate water and hydrocarbons. INTRODUCTION The first paper on electrical well logging by C. and M. Schlumberger and E. G. Leonardon in 1934' attributed the self potential curve principally to streaming potentials, i.e. to electroki-netic effects. Almost immediately great difficulties were encountered in reconciling many of the curves they obtained with this interpretation. and a ~econd paper' by the same authors soon appeared. In this second paper self potentials were attributed to the combined effects of streaming potentials and electrochemical potentials, the electrochemical potential being considered the result mainly of the interaction of fluids of differing salt concentrations, i.e. a boundary potential, and partly of potentials set up at the faces of impermeable materials. Some experiments involving a gray clay for the impermeable material were quated. The Schlumbergers and Leonardon deduced from the equation for a simple boundary ~otential that the electrochemical potential, as opposed to the electrokinetic potential, could be expressed in the form E=Klog- .......1 pe where K is a constant, pm the mud resistivity. p, the resistivity of the connate water in a porous bed. However, no general expression for the constant K was obtained. Although the literature between 1934 and 1943 contains a number of quotations of their results, the valuable work of the Schlumbergers and Leonardon was not extended so that the electrochemical potential has been generally attributed wholly to boundary potentials between the mud in the borehole and the connate waters in porous formations. Unfortunately, however, the fundamental premise of all these papers, that a boundary potential can give rise to current flow in a borehole, is thermodynamically untenable. As will be shown. the fact that the electrochemical potential can be fairly accurately express as E = K log pm/pc, a form in which a boundary potential may also be written, is partly fortuitous. The boundary potential is indeed an integral part of the expression for the electrochemical potential in a horehole, but in magnitude it represents only about 20% of the total potential. In 1943 an important step in the elucidation of electrochemical potentials was made by Mounce and Rust3 who showed that if a wall of shale separated two compartments which contained saline solutions of different concentrations, and if the two solutions were themselves brought into contact in the pores of a porous inert membrane (such as unglazed porcelain) a current flowed through the shale and saline solutions. The direction of positive current was from the shale into the more dilute solution. The paper of Mounce and Rust, while repeating some of the observations of the Schlumbergers and Leonardon, seems to be the first to show that the shale was the seat of a genuine electrochemical effect capable of causing current flow. In the same paper Mounce and Rust pointed out the similarity between the fundamental conditions of their experiment and the conditions which existed when a bed of shale in the ground was simultaneously in contact with a porous sand containing saline connate water and mud fluid of salinity different from that of the water in the sand. Since it is now generally recognized that the S.P. curve measures ohmic potential changes in the mud fluid in the well bore resulting from changes in current flow, it is apparent that currents having their origin in the electrochemical interaction of mud filtrate and connate waters with shale beds are a very important portion of the total S.P. The work of Mounce and Rusta and others appears to indicate that, in general, the electrochemical portion of a particular kick on a S.P. curve far exceeds any electrokinetic potentials resulting either from streaming potentials or Dorn effects. The Dorn effect, or sedimentation potential. arises when small particles are allowed to fall through certain fluids under the influence of gravity. a difference of potential being observe? between two electrodes placed at different levels in the stream of falling particles. The Dorn effect is unlikely to affect seriously the S.P. curve as now measured. A successful analysis of the electrochemical aspects of the S.P. log should

Jan 1, 1949

By R. R. Boucher, O. J. C. Runnalls

A pronounced thermal effect has been observed on heating or cooling a1wninum-rich Al-U and Al-Pu alloys. From microscopic and X-ray diffractionstudies, the effectl has been attributed to trnsfor)nations in the inlemetallic phases UAl, and PuAl , involuing rearrangement or cluslering of vacancies The transformation obsrved in Al-20 wi oct U alloys occurred near the a Al-UAl4 eutectic tem-perature of 646°C making it difjicult to detect from heating curves. When cooling, howeoer, thermal mad X-ray analyses indicnted that the high-temperati~re phase labeled p UAL, precipitated initially during euitectic solidification. As solidification continued and after an induction period o-f 5 lo 20 tnin the nu-cleatiorz and growth of the low- twmperature phase, a UAl4 produced an euolution of energy which raised the observed alloy temperature by 1° to 2°C. in Al-Pu alloys the transformation occurred at 645°C, 5 deg below the eutectic solidification temperccture. The eslimated latent heat of transformation was 25 +5 cnl per g PuAl,. The high-tetnpevcl-ture forms of UAl, and PuAl, were easily 9-etccined by chill casting Al-U and Al-Pu alloys and on reheating the alloys the trcltzsforrnation to the a phase was sluggish even above 600°C. Separated single cryslals o-f UAl4, joy example, showed no evidence Of transformalion after heating for 16 hr at 620°C. The transformation rates increased yapidly enough with increasing temperature, however, that a a spontaneous liberation of energy lens observed on occasion when bealing cast Al-20 wt pet U to neal- the RECENT phase studies on A1-Pu alloys have indicated that earlier reported equilibrium diagrams should be modified to take account of several poly- morphic transformations in the intermetallic compound PuAl,.' During the course of the latter work an unexpected heat evolution was observed while cooling a solid alloy consisting of a mixture of a aluminum and PuA1,. The evolution occurred at 645°C, y below the a A1-Pu A1, eutectic solidification temperature. Subsequent thermal-analysis experiments with A1-U alloys showed that heat was evolved there also at a temperature nearly coincident with the a A1-UA1, eutectic solidification temperature of 646°. A search of the literature revealed that similar thermal effects had been observed before for both A1-U and A1-Pu but had never been fully explained.2,3 The purpose of the present paper is to describe thermal-analysis and X-ray diffraction experiments which have led to the conclusion that the thermal effects are due to transformations which involve the rearrangement of vacancies in the intermetallic compounds UA1, and PuA1,. EXPERIMENTAL PROCEDURE The A1-U alloys were prepared by heating super-pure aluminum (99.99 pct +) obtained from the Aluminum Co. of Canada in a graphite crucible surrounded by an induction coil. At 1000°C high-purity uranium metal produced by the Eldorado Mining and Refining Co., Ltd. was dropped into the liquid aluminum and was dissolved completely within 15 min. The impurities in the uranium were A1—4 ppm, Ca-4, C-70, Cr-3, Cu-6, Fe-30, Mg-2, Mn-10, Ni-25, Si-25, and Zn-2. The A1-Pu alloys were prepared by reacting plutonium dioxide with liquid aluminum under cryolite (3 NaF . AlF,) for 10 min at 1100°C in graphite crucibles exposed to the air. The plutonium was 99.8 pct pure, containing trace impurities of Ca, Cu, Fe, Pb, Si, and Zn. The liquid alloys were usually poured into water-cooled molds to provide castings of uniform composition from which samples could be cut for heat treatment and thermal-analysis experiments.

Jan 1, 1965

By V. V. J. Sarma

Interpretation of earth resistivity data involves not only obtaining depth to interfaces but also determining the nature of formations from their resistivity characteristics. Moore's method of interpretation envisages obtaining depths to the interfaces alone. A simple method of estimating the true resistivity values of formations by applying Hummel's formula of average resistivities is proposed. The method would increase the interpretative value of Moore's method as originally proposed. For most of the earth resistivity measurements, the four-electrode configuration developed by Wennerl is employed. In principal, the method consists of energizing (Current I) the ground through two outer electrodes and measuring the resultant potential (v) between the two inner electrodes. The configuration is such that the separation (a) between any two successive electrodes is equal. The apparent resistivity (pa) for such a configuration is given by 2p- a (V/I). By increasing the electrode separation (pa vs a) curves are obtained. Ideally, a homogeneous isotropic formation underground has a characteristic resistivity. However, the field conditions do not present such ideal cases. Almost invariably, even in the same geological bed, the physical conditions are widely different at different parts in the bed. It is further shown that the penetration of the current into the ground for a given horizontal electrode separation, a, is roughly down to a depth, equal to a. It is therefore, evident that the apparent resistivity calculated from the field observations is a weighted average of the resistivities of the materials present down to this depth. With some prior knowledge about the relative dispositions of the geological formations and their physical conditions, it would be possible, by resistivity surveys, to obtain characteristic resistivities for these formations. It is, thus, that the apparent resistivity-electrode separation curves enable one to decipher the resis- tivity distribution at various depth levels and therefore the nature of the geological formations present. Both empirical and theoretical methods have been developed for determining resistivity characteristics of the various formations. The theoretical methods proposed by Tagg2 and Roman3 are derived from studies of the potential distribution on the surface due to the presence of layers of widely differing resistivities underground. The more recent methods of Wetzel and McMurry4 and Wetzel and Mooney5 are but extensions of the original Roman method of superposition. These methods suffer from lack of similarity of the actual field conditions with those of assumed conditions in developing the theory. The empirical methods such as the one developed by Gish and rooneY6 depend purely on personal observation and local peculiarities, and are applicable only for those limited areas. Out of the empirical methods, moore's7 cumulative resistivity method is still found to be applicable in several localities of differing conditions. While Reudy in 1945 adduced some theoretical justification for the method (Eve and Keys),8 Muskat9 and Mooney 10 tried to show the lack of theoretical basis for the same. It is, however, observed that the method in practice "forms a valuable means of successfully attacking the apparent resistivity curves which fail to respond to the Gish-Rooney, the Tagg or the Roman logarithmic methods" (Ramachandra Rao). 11 Comparatively good results are also reported by Melbyel2 by employing Moore's method in interpreting the resistivity results obtained for ground water in the city of Gunnison, Colo. MOORE'S METHOD As has already been pointed out, the application of the theoretical methods is time-consuming, laborious and sometimes not applicable for quick and accurate interpretation of the field data. moore7 has developed a quick method for obtaining depths to interfaces by plotting the cumulative sums of resistivities, against the corresponding electrode separations a instead of plotting the usual Pa — a curve. In this process of continuous integration, corrections for small variations in resistivities, arising due to local surface conditions or adjacent layers, are made, while large consistent variations are brought out

Jan 1, 1963

By R. H. Thurston

Jan 1, 1879

By John Jermain Porter

PAGE. I. INtroduction............ 191 I1. Derivation of Formula foR Fuel-RequiRements.... 192 1. Heat Available in the Hearth........193 a. Method of Calculation..193 b. Data for the Determination of Critical Temperature.. 195 2. Heat Necessary in the Hearth ...... 197 a. To Care for Slag..197 b. To Care for Pig-Iron...198 c. To Reduce Silicon........198 d. For Other Items.........199 3. The Effects of Rate of Driving ..... 199 4. Loss of Carbon Between Throat and Hearth.....201 a. Solubility of Coke..201 b. Carbon-Loss Due to Flux....201 c. Effects of Reducibility of Ore..202 5. The Formula as Used........203 III. The LImitations of the Formula........ 204 1. Through Effects of Irregular Furnace-Work.....204 2. Through Ratio Between Heat-Requirements in Shaft and Hearth. 20.5 IV. The Formula Applied to Actual Furnace-Records,.. 209 1. Description of Furnace-Stock........ 209 2. Furnace Dam..........210 3. Application of Formula..211 4. Average Furnace-Practice..213 V. Sources of Error........... 214 VI. SuggesTions for Practical Methods of Fuel-Economy... 215 VII. Efficiency as a Factor in Furnace-Management.... 219 1. The Efficiency Principle........ 219 2. The Application to the Blast-Furnace..220 I. Introduction. The heat-balance of the blast-furnace has been a favorite subject for discussion for many years. and its study has contributed much to our knowledge. and still possesses a certain academic interest. As a means of accounting for differences in fuel-consumption, however. it has failed utterly. and it is evident that we must look elsewhere for the means of accomplishing this end.

Jan 1, 1912

By E. C. IBBOTSON

THIS process was reported upon by the Canadian Commission in 1904, and much detailed information was also given in a paper by Chief Engineer V. Engelhardt.1 Believing that some of the latest particulars of the process will be of interest, I submit the following data. At Gysinge in Sweden during the year ending May 31, 1906, from a fixed furnace giving 1 ton (2,240 lb.) of steel per tap, there were produced 950 tons of tool-steel and special steel ingots. . In carbon and iron tool-steels all the usual tempers were made. The bulk of this steel was made from charges composed of about 80 per cent of Swedish white pig-iron and 20 per cent. of steel-scrap. The percentage of carbon was regulated by the addition of briquettes. Other charges were made from Swedish white iron and steel-scrap. The average time taken per charge, for the year, when adding briquettes, was 7* hr., and the electric energy consumed was 1,128 units (kilowatt-hours) per ton. The average time per charge for white-iron and scrap charges was 5.5 hr., and the electric energy consumed was 886 units per ton. These consumptions include all time and energy lost from various causes, such as bad water-supply, ice, etc. It is quite ordinary practice to complete the charges with briquettes in 6.5 hr., and without briquettes in 5 hr., as shown by the following typical charges White pig-iron, 1,457; steel-scrap, 439; briquettes, 220; ferrosilicon (50 per cent. of silicon), 17 ; ferromanganese (80 per cent. of manganese), 15 lb. ; and aluminum, 1 oz.=

Nov 1, 1906

By A. Taylor

NICKEL-RICH alloys hardened with small additions of titanium and aluminum and centered around that region of face-centered-cubic primary solid solution, 7, where the atomic ratio of nickel chromium is about 3 to 1, form an important series of high temperature materials because of their resistance to oxidation, high temperature strength, and excellent creep characteristics at elevated temperatures.' With suitable heat treatment it is possible to precipitate a phase based on the ordered face-centered-cubic y' phase, Ni,,Al, from the randomly ordered nickel-rich y face-centered-cubic primary solid solution. By adjusting the ratio of aluminum to titanium the precipitation of needles of the hexagonal intermetallic compound n-NiaTi may be effected. In the present investigation, the main interest was focused on the interrelationships among the y, y, and 7 phases. By using alloying elements of high purity and a suitable melting technique the presence of carbides and nitrides could be completely obviated, although it is realized that their presence is probably essential in alloys of commercial importance. As a preliminary to the study of the Ni-Cr-Ti-A1 system, it was necessary to establish the constitutional diagrams of the three contiguous systems, Ni-Cr-Al, Ni-Ti-Al, and Ni-Cr-Ti, which together form the nickel-rich corner of the Ni-Cr-Ti-A1 quaternary tetrahedron. Accounts of this work on the ternary systems have already been published by the author. A preliminary disclosure of the author's investigations on the ternary and quaternary systems has been made by Hignett2 and has since stimulated work in the same field by Nordheim and Grant." Before the detailed account of the quaternary system, a brief description will be given of the three contiguous ternary diagrams on which it is ultimately founded. Ni-Cr-Ti System The 750° and 1000°C temperature isothermals of the Ni-Cr-Ti system as determined by Taylor and Floyd' are shown in Figs. 1 and 2. The single phase fields of greatest interest are occupied by the extensive face-centered-cubic y primary solid solution of chromium and titanium in nickel, and the close-packed-hexagonal Daltonide, n-Ni3Ti, from which tie-lines radiate across the very wide y+n two-phase field. The chromium-rich primary solid solution is represented by a. As may be seen from the diagrams, the extent of the y phase field increases quite appreciably as the temperature is raised from 750" to 1000°C. Isoparametric lines for the y phase are shown in Fig. 1. They are interesting in that they are almost parallel to the y/r+n boundary. Thus the determination of the tie-line directions is entirely dependent on the exact stoichiometry of composition of the 7 phase. Ni-Ti-Al System The 750°C isothermal section of the nickel-rich portion of the system Ni-Ti-A1 as determined by Taylor and Floyd is shown in Fig. 3.' The regions of greatest interest are the extensive y primary solid solution of titanium and aluminum in nickel, the y' Berthollide phase field based on the ordered face-centered-cubic structure of Ni3Al, and the hexagonal Daltonide phase, n-Ni3Ti. As may be seen from Figs. 3 and 4 the area occupied by the y phase is substantially the same at 750°C as at 1000°C, but the area of the 7 phase is considerably greater at the higher temperature. The tie-lines radiate from n-Ni3Ti across the y+v and y' + v two-phase fields and are evenly distributed

Jan 1, 1957

By F. Paredes, W. R. Holman, R. W. Crawford

The diffusion coefficient for hydrogen in the ß titanium alloy containing 13 pct V, 11 pct CY, and 3 pct A1 was measured over the temperature range 20° to 500°C. Results fit the expression: D= 1.58 x lgs exp-------==-----) cm2,sec THE diffusion coefficient for hydrogen in the metastable ß-phase titanium alloy containing 13 pct V, 11 pct Cr, and 3 pct A1 was measured as part of an investigation of the effects of hydrogen on the mechanical properties of titanium alloys. Several theories on the mechanisms of hydrogen embrittle-ment include diffusion of hydrogen at ambient temperature as an important step in the embrittling process.'-5 In hydrogen-contaminated a-ß titanium alloys, it has been postulated that the rate-controlling step may be the rate at which hydrogen diffuses from the ß phase to stress- or strain-nucleated brittle hydride platelets at the a-ß interface.' However, embrittlement of the all-ß alloy investigated in this work may proceed by a different mechanism, since this alloy can be embrittled without the formation of detectable hydride platelets.6 Troiano has suggested that in this case the mechanism of delayed failure or embrittlement is similar to that proposed for high-strength steel, i.e., repeated crack initiation caused by a decrease in bonding energy as hydrogen diffuses to points of high tri-axial stress at the root of a notch. In both types of alloy the rate of embrittlement is believed to be controlled by diffusion of hydrogen in the ß phase. Accurate hydrogen-diffusion data in the vicinity of room temperature should therefore be of some assistance in understanding the mechanisms of embrittlement in these two classes of titanium alloys. Diffusion of hydrogen in pure titanium has been studied by Wasilewski and Kehl7 at temperatures above 500°C. Their measurements on diffusion in the ß phase were extended below the ß-a transformation temperature (882°C) to approximately 600°C. This was possible because of the 8 stabilizing effect of hydrogen. No results at lower temperatures have been published and there are no data in the literature on hydrogen diffusion in the ß -phase alloy used in this program. Hydrogen diffusion in metals is generally investigated by measuring the rate of transport of hydrogen past a solid-gas interface, i.e., by absorption, permeation, or degassing-rate measurements. These methods produce accurate diffusion data when bulk diffusion is the rate-determining step in the over-all process. However, at the lower temperatures of interest in hydrogen-embrittlement studies or under conditions where surface films are present, the measured rates may be surface-controlled and the calculated diffusion coefficients will be in error. Surface effects were eliminated in the present work by using a modification of the common welded-couple technique m which two bars with uniform but different compositions are joined before the diffusion anneal." The same type of step change in the initial concentration vs distance curve was produced by electrolytically hydrogenating thin-strip specimens which had been electrically insulated over half of their length. Concentration vs distance curves were determined, after appropriate diffusion-annealing treatments, by vacuum-extraction analyses of transverse samples sheared from the strips. Diffusion coefficients were calculated by the methods of Grube.M This technique was feasible because of the large concentrations of hydrogen which can be charged into p -phase alloys without the formation of hydrides15'16 and because of the extremely low degassing rates observed when hydrogenated titanium alloys are heated in air. EXPERIMENTAL WORK The diffusion couples were cut from a 0.022-in.-thick mi ll-annealed sheet.* Strips 8 in. long by 1/2

Jan 1, 1965

By Stuart S. Forbes

Changes and additions made to the Canadian Copper Refiners Ltd. electrolytic refinery between 1949 and 1955 are reviewed. The effect of high current density on current efficiency and section work is discussed. OPERATING and physical changes which have been made to the electrolytic tank house of Canadian Copper Refiners Ltd. suggest a review of present conditions. Previous papers1 a have described the general arrangement. Since then, expansion, closer anode spacing, and higher current densities have increased annual cathode capacity from 112,000 to 182,000 tons. A recent extension to the tank house, begun in the spring of 1954 and completed in August 1955, was undertaken to handle the monthly production of about 3,000 tons of anodes from Gasp6 Copper Mines. The anticipation of these additional receipts and large stocks of unrefined copper caused by the increase in custom smelting at Noranda made it necessary to increase production without immediately available additional cell capacity. Accordingly, from December 1954 through March 1955, the tank house was operated successfully at a current density of 24.0 amp per sq ft. Again, as of September 1955, one of the two tank house circuits is being operated at this high density. Although other refineries may operate at current densities higher than 24 amp per sq ft, none is doing so with anodes which contain silver and gold content as high as those being refined at Canadian Copper Refiners Ltd. General Arrangement The original building consisted of two parallel bays, each 660 ft long and 60 ft wide, with a 24 ft pump bay extending along the west side of the building. A previous expansion, completed in 1939, was to the west of the original building and consisted of two 60 ft parallel bays 240 ft long. The length of these two bays was extended in 1954 to 540 ft, adding one stripper and 12 commercial sections to No. 2 electrical circuit. Space is still available for an additional six commercial sections and one stripper section. Construction on these seven sections started in September 1955, and will be completed early in 1956. The tank house capacity will then be 206,000 tons of cathodes per year. In the two tank houses there is a total of 900 cells distributed as follows—commercial, 468; stripper, 36; total, 504 in the No. 1 tank house (No. 1 circuit): commercial, 360; stripper, 36; total, 396 in the No. 2 tank house (No. 2 circuit). Section arrangement consists of nine cells to a tier and two tiers or 18 cells to a section. Anodes, weighing 620 lb each, are cast with a Baltimore groove and are refined by the multiple system. Solution enters each cell through a bottom inlet at one end and overflows at the top of the opposite end. Rate of solution flow through the cells is controlled by valves at each section to 4.5 gpm. Electrical power to the tank house is now provided by nine 675 kw motor generator sets. Each set consists of a 135-12 v 5000 amp dc generator, driven by a 980 hp 2300 v synchronous motor. When No. 1 circuit is operated at 22,000 amp, five sets, at 4400 amp each, are connected in parallel. As the maximum allowable current on No. 2 electrical circuit has recently been set at 18,000 amp, only four sets are connected in parallel on No. 2 circuit. A tenth set, now being installed, will be reserved as a spare, for use in either circuit as required. Recent Changes In 1949, the annual capacity of the tank house was increased from 112,000 to 132,000 tons by closing the

Jan 1, 1957

By M. C. Flemings, A. A. Tzavaras

Analytical and experimental procedures are descrihed for quantitative determination of volume-fraction microporosity in metals by mimorarlio-graphg. The analysis assumes spherical pores but allows for the observed fact that pores or portions of pores smaller than a given thickness do not project an image on the film. Volume-fraction microporosity was measuured in cast low-alloy steel and shown to vary from 0.6 x 10-4 to 10 x 10 depending on mode of solidification and on whether the material was air- or vacuum-cast. The aim of work described herein was to develop a method of quantitative measurement of the volume fraction of microporosity in cast metals. Microporosity, present in nearly all castings and ingots, is always interdendritic in nature and may be large enough to be seen on a polished surface with the naked eye. More generally, it is smaller in size, and its detection more difficult. Three techniques might be considered for measurement of microporosity: 1) lineal analysis of a polished metallographic surface, 2) density measurement, or 3) quantitative microradiography. As will be shown later, volume fractions of porosity in directionally solidified castings may be the order of 10-4 to 10-3; such small amounts of porosity are difficult to identify and measure on a polished surface. Density measurement is also not a suitable technique (for alloys) when the volume fraction of porosity is low. This is because the density of the base metal is often not known within the necessary accuracy, due to microsegregation or partial phase transformations. In general, it is not possible to completely eliminate microsegregation without also altering the porosity. Because of the limitations of the foregoing techniques, quantitative microradiography was employed to determine amount of porosity. In recent work, microradiography has been found to be useful for qualitative measurement of porosity, including determination of size and shape of individual pores;&apos;)&apos; however, quantitative determination of amount of porosity has not been attempted. I) CALCULATION OF VOLUME-FRACTION POROSITY The following analysis employs procedures similar to those of Cahn and Nutting3 and Hilliard.4 Major simplifications are that pores are assumed to be spherical and to be present in sufficiently small quantities that no overlapping occurs. A basic difference from the previous treatments is that the limited "sensitivity" of microradiography is considered. Assume first 1) cavities are spherical and of uniform diameter, 2) cavities are randomly distributed, 3) volume-fraction porosity and specimen thickness to pore radius ratio are sufficiently small that overlapping of the projected images of cavities is negligible, 4) sensitivity is limited (i.e., holes or portions of holes of less than a given thickness do not project an image on the film). The sensitivity, is defined as: where 5 = minimum thickness of void from which an image will be projected on the film and t = specimen thickness. Now, from Fig. 1, it is possible to distinguish between two different types of holes. These are 1) holes whose centers lie within the region t/2 > X > 6/2, where X is distance from one surface of the specimen (positive into the specimen), and 2) holes whose centers lie within the region (6 — r) < X < 6/2, Holes whose centers lie outside X = (6 -r) project no image on the film. These two types of pores are considered separately below. Type 1 Pores. When 6 is greater than 0, the image of a spherical cavity of radius r appears on the film as a circle of radius a which is smaller than r. From geometry, Fig. 1: a2=r2-52/4 [2] where a = radius of image of pore on film and r = radius of pore. Since the pores are randomly distributed and spherical V =4/3pr2Nv [3] where V = volume fraction of voids and Nv = number of pores per unit volume and the number of images of Type 1 pores per unit area of film, N&apos;A, is

Jan 1, 1965

By G. A. Vissac

The only fine coal washer with proved automatic controls, the feldspar jig is capable of good efficiencies even at low separating gravities, handles a variety of products, and treats 150 tph and over. IN continental Europe the feldspar jig is used almost exclusively for cleaning the fine sizes of coal; it operates with an artificial bed, made up generally of pieces of feldspar or of any other hard and heavy rock with good cleavages. A primitive form of this machine requiring close supervision was used in this country years ago, but output was small. The modern machines are generally air-pulsated Baum-type jigs, with capacities up to 150 tph, and treat sizes from % in. to 0, usually previously dedusted or deslimed. These jigs are equipped with very accurate and sensitive automatic controls insuring satisfactory operation even at low separating gravity and with feeds irregular in quality and quantity. This paper will deal more particularly with coal cleaning separation, but the technical studies apply equally to all minerals. Theory of the Feldspar Jig To understand fully the operation of the feldspar jig and to appreciate its potential value, it is necessary to measure and analyze the motion of small particles of various specific gravities, falling in various media, under various conditions. As no practical formulas were available for that purpose, the writer has developed new theories and established new sets of formulas, which cannot be demonstrated here. They are applicable to all minerals and to many problems of coal or mineral concentration. These formulas do not pretend to absolute accuracy, but results, tested by comparison with experimentally recorded data, are sufficient for practical purposes, as they give definite indications of trends, relative values, and order of magnitude of the many factors involved. For pulsating motions no earlier formulas are available. In the case of continuous currents or motions, such formulas as Rittinger&apos;s, Allen&apos;s, or Stokes&apos;, over a hundred years old, apply only to special shapes and sizes of particles, involve factors and coefficients difficult to measure or appreciate, and deal only with free motions. They are of little use in solving practical problems. Units used with the formulas presented here are in the CGS system. Lateral friction and suction have been taken into account according- to methods currently used in aerodynamics, and only hindered motion is dealt with. As the feldspar jig is primarily intended to create a fluid bed condition, the mixture of fluids and solids obtained is homogeneous, and the apparent specific gravity of the separating medium is calculated accordingly. For instance, if 20 pct of the volume is coal and shale, with an average of 1.60 sp gr, in a liquid of 1.10 sp gr, the actual specific gravity of the separating fluid is 0.80 x 1.1 + 0.20 X 1.6 = 1.20. The fundamental equations are as follows: The general motion of a particle falling in a medium of specific gravity equal to u, hindered motion. is dv/dt = g/Ls [ L (s-u) - u/g v2 [1] g = 981 cm per sec, acceleration of gravity, and L = thickness of the particle of specific gravity (s) and velocity (v). The initial acceleration dv/dt = g (1-u/s ) [2] is a function of the specific gravity of the particle, only for a given medium, and independent of its dimensions—an ideal separating condition. The terminal velocity Vt = gxL- (s-u)/u, [3] for a given value of u, is a function of s and L. Two particles, L, s, and L2 s2, are said to be equivalent if they have the same terminal velocity, and accordingly L1/L2=s2-u/s1-u. [4] Two such particles cannot be separated by continuous currents, in any concentrating device. Because the initial accelerated motion, which provides for efficient separation, is followed by a constant velocity, which has a limiting effect, it is essen-

Jan 1, 1956

By O. J. C. Runnals

The intermetallic compounds NpAl2, NpAl3, and NpAl have been prepared, and examined by X-ray diffraction methods. The compounds are isostructural with the corresponding U-Al compounds. NpAl3 is face-centered cubic with a = 7.785A and has the MgCu2 structure. NpAl is simple cubic with a = 4.2624 and has the AuCU3 structure. NpAl4 is body-centered orthorhombic with a = 4.428, b = 6.268, and c = 13.71A. The published description for the atomic positions in UAl, applies also to NpAl4 THE U-Al system has been examined by Gordon and Kaufmann.1 They identified the following intermetallic compounds: UAI2, UAl3, and a third, tentatively identified as UAl5. A structure analysis of the latter compound by Borie2 proved that the formula UAl4 was more consistent with the X-ray data. The crystal structures of UAl2 and UA have been reported by Rundle and Wilson.3 UAl2 was found to be isostructural with MgCu. The atomic positions in the simple cubic UA1, cell were found similar to those in the AuCu3 structure. Three analogous compounds exist in the binary system Np-Al. X-ray data for the compounds NpAl2, NpAl3, and NpAl4 are reported below. The neptunium used in the investigation was supplied through the courtesy of the Argonne National Laboratory as neptunium (V) nitrate. It was stated to have a radioactive content of 99.25 pct Np237. The impurity limits had been established by a spectrographic analysis given in Table I. Any titanium, boron, or bismuth impurity should be effectively removed during the fluorination of NpO2 to NpF4, and sodium, lithium, magnesium or strontium during the alloying procedure. The oxalate ignition technique, described by Westrum for the preparation of finely-divided reactive PuO2, was used.The neptunium (V) nitrate solution, containing 100 mg Np, was evaporated to dryness on oxalic acid crystals. The resulting oxalate was calcined to NpO, by heating in platinum at 650°C for 2 hr. An equimolar mixture of anhydrous hydrogen fluoride and purified hydrogen was passed over the NpO2 for 2 hr at 500°C. According to Fried and Davidson" the above fluorination conditions should produce the purple-black fluoride, NpF3 However, the light-green product showed only NpF4 lines on an X-ray diffraction pattern and contained only an estimated 5 pct of finely dispersed black NpF3 particles on microscopic examination. NpAl3: An intimate mixture of 50 mg of neptunium fluoride and aluminum powder (99.99 pct pure, —28 to $60 mesh) was heated to 900°C in a BeO crucible in vacuum by a tungsten coil for 2 hr, to allow the following reaction to proceed: NPF4 + 7Al + NpAl, + 4AlF. [1] The formation and sublimation of aluminum mono-fluoride in this system was verified from an X-ray diffraction analysis of the sublimate. The diffraction pattern was similar to one obtained in the aluminum reduction of UF4 to UF3,6 showing both Al and AlF3 lines. The resulting alloy was sintered at 1100°C for 1 hr. A powdered specimen of the crystalline product was sealed in a thin-walled quartz capillary for X-ray examination. The photograph was taken on a 14.32 cm General Electric powder diffraction camera, using filtered copper radiation. The films were calibrated in terms of a NaCl standard pattern. The wavelengths used in the calculations were 1.5418A for Cu K and 1.5405A for Cu K The powder diffraction pattern showed that NpAl is simple cubic with a = 4.262 % 0.005A, and is isostructural with UA13 where a = 4.27A1 or a =

Jan 1, 1954

By A. G. Guy

In a special type of electrodiffusion experiment the entire specimen is at constant temperature. The vacancies are then created at one end of the specimen and flow to the other end where they are destroyed. The energy required to operate the corresponding sources and sinks results in a super saturation of vacancies at one end of the specimen and an under -saturation at the other end. This gradient in vacancy concentration produces a chemical-diffusion flux, J(D), of vacancies in addition to the flux, J(E), caused by the electric current. Using the experimental data of Ch. Herzig,5 it is shown that a super saturation of 1 pct can cause J(D) to be about 25 pct of J(E), and thus account for the anomalous behavior of short specimens. THERE are advantages in a phenomenological treatment as contrasted to an atomistic one. For example, there are many reactions involving the element copper that are quantitatively and usefully understood from a phenomenological viewpoint, even though electron theory is not yet able to predict whether copper should be fcc or cph.&apos; Similarly, the lack of a complete atomic theory of vacancies need not prevent the development of a treatment based on thermodynamics and chemical kinetics. In the following discussion, models will be used for the vacancies and for the mechanisms by which they move or are created or destroyed, but the phenomenological treatments are not dependent on the details of these models. The important product of a phenomenological analysis is an equation that describes the relation among the measurable quantities determining the behavior of the system. Based on such an equation, experiments can be performed to study these quantities in detail. Eventually atomic theory will supply an adequate theoretical base for the phenomena in question. A chemical species whose chemical potential was invariant during reactions in binary and ternary systems of varying composition would indeed be an anomaly. Yet this is the role that has frequently been assigned to the vacancies in pure metals, in dilute solutions, and even in ordinary alloys. The weight of available evidence supports the view that supersatu-rations of vacancies are on the order of 1 pct in usual diffusion processes.&apos; Although it may seem strange that such a small deviation from equilibrium could significantly affect the thermodynamic properties of the vacancies, it is well known that the driving force for an ordinary chemical reaction is the departure of the components from their equilibrium state. Similarly, the reaction of vacancies that results in the formation of pores in various types of diffusion3 can reasonably be attributed to the supersaturation of vacancies. In the present paper, it will be shown that small degrees of supersaturation can significantly affect the kinetics of the diffusion process itself. ISOTHERMAL ELECTRODIFFUSION Two different experimental techniques are convenient for studying the behavior of vacancies in a pure metal in the presence of an electric field. Gilder and Lazarus4 studied self-electrodiffusion in a gold specimen in which only the central portion was at high temperatures. In this case the significant vacancy sources operate inside the specimen in the presence of a temperature gradient. In the laboratory of Th. Heumann a method has been devised for studying self-electrodiffusion at constant temperature.5 In principle, there is then no effect of thermodiffusion. It will now be shown why in this case the significant ATungsten disks \^^ ^^ ^Gold disks^^ ^^"T>.... "TTZA ? Up Iy&apos;7 markers ///// ////// initial plane p I y/y/y of joining \I 7//// V7//A_________I_________V//// -I 0 +I Distance from center of specimen (a) -— Direction of flow of electrons —Direction of flw of vacancies %yy} Matano I z~irkendall /%W, vy/A inlerfacej "interface ///// -} HfiK- +/ 0 Distance from center of specimen (6) Fig. 1—-Schematic illustration of the essential features of isothermal self-electrodiffusion. (a) Initial condition of specimen. (b) Condition of specimen after electrodiffusion.

Jan 1, 1970

By J. P. G. Farr, R. Brownsword

THE role of solute segregation in the formation of cellular solidification substructures in tin and its dilute alloys is well-established, see, e.g., Ref. 1. Segregation has been shown to persist during cooling, enabling solidification structures to be studied from sections taken at some distance behind the interface. In the present work, a single crystal of commercial nickel, 99.965 pct, was examined in this way. The crystal was cut from the center of a rod given a single pass in an electron beam floating zone melter. Polished sections of a nickel specimen taken normal to the growth direction showed a very fine precipitate phase, the distribution of which varied over the section. The identification of the phase proved difficult because of the small amount present and the small particle size, about 1 p: but it was shown by probe microanalysis to contain only nickel and oxygen in detectable concentrations and was probably nickel oxide, NiO. Bulk analysis of the material before melting showed there to be only 3 to 4 ppm of oxygen present, thus demonstrating a very considerable segregation concentration effect. In some areas of the section the precipitate formed a discontinuous hexagonal network suggesting decoration of the cellular boundaries known to be present in the sample2 whereas in a restricted region the precipitate formed small clusters. Occasionally it could be seen that the clusters were at the intersections of an hexagonal network of cellular dimension. It was suggested3 that this was the result of enhanced segregation to the cell boundary intersections whereas general cell boundary segregation was insufficient to give a precipitate. Enhanced nodal segregation has since been demonstrated in a number of systems.1, 4-8 The development of a suitable electrolytic etching technique (perchloric acid 20 pct v/v; ethyl alcohol 70 pct; glycerol 10 pct; current below electropolishing plateau; 1 to 2 sec etching) suggested the association of the phase with regions of solute segregation (where ko < 1); in these regions anodic attack produced grooves or depressions. In a study of the variation of solidification substructures with degree of constitutional supercooling, Biloni et a1.&apos; appear to have used standard growth conditions and varied the solute concentration. They were able to produce in a series of individual tin crystals examples of substructure ranging from planar interface through various cellular structures to den- Fig. 1—Electroetched section taken normal to the rod axis; the center of the rod lies to the left and the periphery to the right of the micrograph. The variation of structure across the section is evident. Magnification 60 times. drites. It was possible in the present nickel crystal to observe a continuous range of substructures varying with degree of supercooling across a single section as shown in Fig. 1. Growth rate, 13 mm per min, and temperature gradient were essentially constant; the variation in structure is thought to be due to a radial gradient in solute concentration ahead of the solid interface. The liquid at the interface is likely to have been richer in solute toward the periphery of the zone, the result of curvature of this interface. The type of substructure was seen to vary with increasing constitutional supercooling as follows: a) region free of precipitate. top left, Fig. 1: 6) region of nodal precipitates which became arranged in hexagons on passing from the center of the rod: c) irregular hexagonal cells with incomplete boundary precipitation; d) regular hexagonal cells of decreasing size with complete boundary precipitation. Fig. 2 shows the transition from stage 6 and Fig. 3 shows the structure in stage d. Within stage 0, the range of conditions over which irregularly positioned nodes occur appears to be small and the nodes are soon recognizable as taking up positions at the intersections of an hexagonal network as the supercooling increases.

Jan 1, 1970

By J. Geertsma

The relationship between porosity and the speed of propagation of acoustic waves in fluid-saturated porous rocks as measured by the Sonic log and by ultrasonic tecbniques is analyzed. Biot&apos;s continuum theory 1 is used to explain the difference in acoustic wave propagation between a dry and a liquid-saturated porous material. The porosity is a variable in this theory. However, the acoustic wave propagation in the dry rock depends too on porosity, and this dependence is not predicted by the theory. Frequently in dry sandstones, a nearly linear relationship between reciprocal acoustic wave velocity and porosity is observed in the low-porosity range. The physics behind this behavior is outlined. An empirical relationship of the form, 1/v = A + F, applies accordingly for many porous dry rocks, provided the porosity is the only variable. The presence of a liquid in the pores changes the value of B, and this change is found to be in agreement with the Biot theory. The time-average relation introduced some years ago2 results in an equation of the same type — 1/V = F/Vf + (1 - F)/Vr — but is not based on a sound physical picture. Still, this relation sometimes predicts approximately correct A and B values. Carbonate rocks with their complicated pore structures sometimes show a different relationship between wave velocity and porosity, unfavorable for log interpretation. Examples are presented. The simultaneous presence of calcite, dolomite and anhydrite, with their different grain densities and matrix compressibilities, complicates acoustic-log interpretation in carbonate rocks still further. Other complicating effects of acoustic-log interpretation are discussed. They are related to the influence of shale streaks and natural fractures on the average wave velocity observed by the logging tool and to the effect of adsorption phenomena on wave propagation in unstressed rocks particularly in sandstones. INTRODUCTION The velocity of propagation of sound waves in porous sediments as a function of depth is a quantity frequently measured. Velocity loggers of various d-sign may be used, for which velocity is defined as the. distance between a wave generator and a wave detector (one-receiver system) or the distance between two wave detectors (two-receiver system), divided by the shortest time required for a vibrational pulse to cross this distance. Velocity loggers ale used to assist in seismic prospecting, to differentiate between the various types of sedimentary rock layers, and also to determine rock porosity and pore fluid content. This paper is especially concerned with the relation between velocity and porosity and the effect of the pore fluid. Most velocity-log interpretation in terms of porosity is based on a formula advocated by Wyllie, et al,2 suggested earlier by Hughes and Jones,3 and known as the "time-average relation". This formula app1ies for a model consisting of a layered system of parallel alternating slices of a solid and a liquid, crossed by the wave path perpendicular to the interfacrbs. This must be an unsuitable model for the derivation of wave propagation properties of liquid-saturated porous media. It suggests that only rock matrix and fluid properties influence the wave velocity. The surprising fact, nevertheless, is that applications of this formula to clean sandstones under specific conditions (sufficient effective stress) results in porosity predictions which are close to reality. Other authors, such as Gassmann,4 White and Sengbush,5 Brandt,6 and Hicks and Berry,7 make use of more realistic models to arrive at a wave velocity formula for porous sediments. Their models consist of various liquid-saturated packings of frictionless spherical grains and are, therefore, also highly idealized. A number of experimental results obtained in the laboratory can be better explained with these model theories than by the time-average relation. A study of a general character, not depending a priori on a special model of the porous structure, was still lacking.

By B. T. Brady

Rock mechanics, like all engineering disciplines, must have a theoretical foundation. The subject of this chapter is the formulation of analytical methods that may aid in the rational design and determination of the stability of engineering structures in competent brittle rock materials. By an engineering structure in rock, we mean any (1) excavated sub- surface opening, (2) open surface structure, or (3) system of openings in rock that is virtually self-supporting-that is, not requiring artificial systems to carry structural stresses.

Jan 1, 1970

By John Griffen

THEORY HYDRAULIC classification as explained by Rittinger and others was largely restricted to conditions wherein the free-falling velocities of the particles were conceived as governing the separations effected (see chapter 9). The laws governing classification under free-falling conditions have been summarized by Chapman and Mott as fo1lows:l Nomenclature r represents, in a particle of irregular shape, the round-hole screen through which the particle would pass, or some other linear dimension of the particle equivalent to d, the diameter of a sphere. s, the specific gravity of the particle. 1, the specific gravity of the water used as a medium. K, a constant. W, the velocity of the water. In an Upward Current of water 1. A particle will move upward if [V > K dr(s - 1)] and, by suit- ably regulating the speed of the water current, the larger and heavier particles may be made to fall downward against the current, leaving the smaller, lighter particles in suspension in the current. 2. Particles such that [- = -] cannot be separated in an upward- current classifier with any one velocity of current. Coal particles having a specific gravity of 1.35 cannot be separated from refuse particles of [2.5 - 1 2.5 sp. gr.] unless the ratio of diameters is less than [ 4.3 to 1, 1.35 – 1] and the raw coal must be screened to size limits within this ratio if they are to be separated. Cone-shaped vessels or vessels of other shapes that allow the use of different velocities of current at different points in the flow are used to modify this limitation.

Jan 1, 1943