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By R. D. Russell, R. M. Farquhar

ISOTOPIC tracers have become an important aid in following the progress of chemical processes in the laboratory. It has recently been found possible to utilize a system of naturally existing isotopic tracers to obtain information about the geo- logical history of lead ores. Common lead, such as is found in lead deposits, is a mixture of four stable isotopes having atomic weights 204, 206, 207, and 208. Of these, the last three are identical with the lead isotopes produced as stable end products of the radioactive decays of uranium and thorium: the first, lead-204, is not known to be produced on the surface of the earth by any process. Since uranium and thorium occur in the surface regions of the earth in amounts comparable with lead, and since the half-lives of uranium and thorium isotopes are of the same order as the age of the earth, they produce the radiogenic lead isotopes in amounts com- parable to the amount of nonradiogenic lead present. Every significant exposure of a sample of lead to uranium and thorium will therefore lead to the permanent alteration of the lead isotope ratios in that sample.

Jan 5, 1957

By Janshi Sen

Vertical-intensity magnetometers, for instance the Hotchkiss Superdip and the Askania vertical field balance, are now widely used, because vertical-intensity charts give definite information for the location of upper pole, dip and strike, and approximate shape of the deposit. Again, a slow and steady increase of dip over a large area indicates a large deep-lying deposit, while a large dip limited to a small area and falling away rapidly suggests a small and shallow one. The complication comes more from the richness of the ore. A large body of lean ore near the surface might produce the same vertical-intensity chart as a rich ore at depth. This paper presents a method for calculating the maximum depth of a single-pole deposit and another for a two-pole mineral body, by utilizing data of both vertical and horizontal intensities as obtained by a Thalen-Tiberg magnetometer. As shown on the left side of Fig. I, lean ore, rich ore and a single pole produce the same magnetic field. The depth of the pole, where G is the vertical intensity at point A due to the pole; F, the horizontal intensity of the same; and a, the distance from the point of maximum vertical intensity or the vertical projection of the pole on the surface to the point of observation A. If an entirely covered deposit is indicated by magnetic measurements and boring cost estimated from the calculated depth is so reasonable as to encourage drilling, the ore should be struck somewhere within the limit of the calculated depth by the borehole. A number of such points as A should be taken for calculation, erratic results should be rejected and the average figure used for cost estimation.

Jan 1, 1946

By Janshi Sen

Vertical-intensity magnetometers, for instance the Hotchkiss Superdip and the Askania vertical field balance, are now widely used, because vertical-intensity charts give definite information for the location of upper pole, dip and strike, and approximate shape of the deposit. Again, a slow and steady increase of dip over a large area indicates a large deep-lying deposit, while a large dip limited to a small area and falling away rapidly suggests a small and shallow one. The complication comes more from the richness of the ore. A large body of lean ore near the surface might produce the same vertical-intensity chart as a rich ore at depth. This paper presents a method for calculating the maximum depth of a single-pole deposit and another for a two-pole mineral body, by utilizing data of both vertical and horizontal intensities as obtained by a Thalen-Tiberg magnetometer. As shown on the left side of Fig. I, lean ore, rich ore and a single pole produce the same magnetic field. The depth of the pole, where G is the vertical intensity at point A due to the pole; F, the horizontal intensity of the same; and a, the distance from the point of maximum vertical intensity or the vertical projection of the pole on the surface to the point of observation A. If an entirely covered deposit is indicated by magnetic measurements and boring cost estimated from the calculated depth is so reasonable as to encourage drilling, the ore should be struck somewhere within the limit of the calculated depth by the borehole. A number of such points as A should be taken for calculation, erratic results should be rejected and the average figure used for cost estimation.

Jan 1, 1946

By W. B. Morrison

Anderson, King, and Spreadborough present detailed evidence to show what ~aldwin~' has already pointed out, that, over a relatively small grain-size range (Ad"1/2 ^ 10 mm-'I2, d is average grain diameter), yield point data can fit a number of relationships. Part of the difficulty in obtaining data which reflect only the effect of change in grain size on yielding arises from the fact that in varying the grain size, even though great care is taken, other structural changes are almost certain to occur. In iron alloys, these changes may consist of variations in subgrain size, grain boundary ledge density, and degree of carbon and nitrogen segregation at grain boundaries, all of which are difficult to detect and which may affect yielding, primarily through their effect on dislocation generation. Because of the inherent inaccuracy associated with yield point measurements there is little point in using relatively complex equations to fit data, as was done by Anderson et mnl., rather than the simpler, widely used Hall-Petch equation. In compiling their table of data, it is surprising that they did not include results from certain low-carbon steels,31 in which, as illustrated in Fig. 2, the grain-size range is very much larger than in their Armco Iron. The very fine grains in these steels were obtained by a thermomechanical process. Examination by electron microscopy showed that the grains were separated by high-angle boundarie and contained only an occasional subboundary. The data from these steels obeyed the Hall-Petch equation, and it was shown quite conclusively that they did not fit a d-l or (1-lJ3 relationship. Obviously, a much wider range in grain size than used by Anderson et al. is desirable if we are to determine the true relation between lower yield stress and grain size.

Jan 1, 1969

PRESIDENT AND DIRECTOR SCOTT TURNER WASHINGTON, D. C. PAST PRESIDENTS AND DIRECTORS WILLIAM H. BASSETT WATERBURY, CONN. ROBERT E. TALLY JEROME, ARIZ. TREASURER AND DIRECTOR KARL EILERS NEW YORK, N. Y.

Jan 1, 1932

By R. J. Walter, W. T. Chandler

The Ch-H phase diagram was determined for by-drogen concentrations up to ChHo.9 at temperatures below 400°P'. The phase diagram includes a mis-cibility gap and a eutectoid transformation. A peri-tectoid transformation is postulated at the hydrogen-rich end of the diagram, Phase diagrams were determined for two levels oj purity, of the columbium. A single solid solution exists in the Cb-H system above 400°F. There has been considcrable disagreement among investigators concerning the system at temperatures below 400°F. Albrecht, Goode, and ~allett' proposed a miscibility gap containing two bcc phases with the two lattice parameters converging at about 140°C (285-F), and Brauer and ~erman' found a two-phase room-temperature region between 10 and 41 at. pct H. At sufficiently high hydrogen concentrations in the one-phase region, the hydrogen-rich phase was found to be face-centered orthorhombic. Wainwright, Cook, and Hopkills3 recently reported that the face centered orthorhombic hydride phase is derived from a unit cell which is slightly tetragonal with a small departure from 90 deg of the angle (y) opposite the r axis. The orthorhombic hydride phase was observed for hydrogen concentrations between 0.2 and 0.8 H/Cb atom ratio. Paxton and coworkers4 found that needlelike hydride plates formed in a hydrogen-charged columbium single crystal and suggested that this transformation possessed the characteristics of a diffusionless phase transformation. On the basis of room-temperature, X-ray diffraction data, komjathy' suggested that an order-disorder or martensitic transformation occurs. In the present study, the Cb-H system was investigated to resolve the discrepancies found in the literature for this system. PROCEDURE The columbium specimens were prepared from two heats of wrought 1/2-in.-diameter electron-beam melted columbium rod and from two columbium powders of -80 mesh size of different impurity contents. The columbium bar stock was pur chased from Urah Chmg Corp.; the 99 and 99.5 pct purity colulnbium powders were obtained from Fansteel Metallurgical Corp. and Kern Chemical Co.. respectively. The chemical analyses of the columbium bar and powders are listed in Table I. Hydrogen charging was performed by exposing the columbium specimens to hydrogen at 1 atm pressure at various temperatures. After exposure the specimens were quenched to prevent the hydrogen pickup which would take place if cooled in hydrogen, or the hydrogen loss that would occur if cooled in an inert gas. Adequate hydrogen purity was achieved by passing high-purity tank hydrogen (maximum 5 ppm total impurities) through an Engelhard catalytic Deoxo unit, magnesium per chlorate desiccant, and finally through activated charcoal at the temperature of boiling nitrogen. Activated charcoal at -321°F has been reported6 to remove impurities from hydrogen to a nondetectable level. A schematic representation of the heat-treating apparatus is shown in Fig. 1. A metal-sheathed thermocouple embedded in the colun~bium specimen was used to control the temperature during heat treatment and to pull the specimen boat into

Jan 1, 1965

By A. Lee Barrett

SO commonplace that they are seldom noticed, mining-machinr, bits have a definite and important bearing on the cost of coal production. At the average mine many thousands of bits are used during the year. The actual cost represented by the purchase of the bits used, as well as that of sharpening and handling them, represents a considerable sum of money. From the point of view of indirect costs they are important, as the lack of good bits at a mining machine can seriously impair production. Good bits tend to ensure an adequate supply of coal. Classes OF Bits Mining-machine bits may be divided into three general classes, based on shape and method of use: (I) chisel, (2) pick-point and (3) one-use. The chisel and pick-point bits are shown in Fig. I. The so-called "chisel" bits were made of steel of various sizes and were sharpened to a wide chisel cutting edge. Few of this type of bit are used, except in places where coring is very bad. Sometimes chisel bits are used with standard bits to help cut out the core. The "pick-point" bit is widely used today. Normally it is made from ½ by I-in. steel, is about 4½ in. long when new, has a rake angle of about 25°, a front clearance of about 23O, a side clearance of approximsteji 8".' There are many variations in the shape of this bit, depending on the ideas of the individual that may be dressing the dies of the bit machine. This bit has been generally used for many years and at present, in one form or another, is by far the most popular bit used in coal mines. This bit usually is made from 0.85 carbon steel, although in recent years some alloy-steel bits have made their appearance. At present, carbon-steel bits are frequently tipped in. hard facing materials. A third class of bits might be called the L'one-use" bit; that is, a small bit that is used once and then thrown away. These bits have two or three points, are usually made from 0.85 carbon steel and sometimes from higher alloys. Recently some. of them have been tipped with hard facing material. Most of them were used at first with special

Jan 1, 1942

By A. Lee Barrett

SO commonplace that they are seldom noticed, mining-machinr, bits have a definite and important bearing on the cost of coal production. At the average mine many thousands of bits are used during the year. The actual cost represented by the purchase of the bits used, as well as that of sharpening and handling them, represents a considerable sum of money. From the point of view of indirect costs they are important, as the lack of good bits at a mining machine can seriously impair production. Good bits tend to ensure an adequate supply of coal. Classes OF Bits Mining-machine bits may be divided into three general classes, based on shape and method of use: (I) chisel, (2) pick-point and (3) one-use. The chisel and pick-point bits are shown in Fig. I. The so-called "chisel" bits were made of steel of various sizes and were sharpened to a wide chisel cutting edge. Few of this type of bit are used, except in places where coring is very bad. Sometimes chisel bits are used with standard bits to help cut out the core. The "pick-point" bit is widely used today. Normally it is made from ½ by I-in. steel, is about 4½ in. long when new, has a rake angle of about 25°, a front clearance of about 23O, a side clearance of approximsteji 8".' There are many variations in the shape of this bit, depending on the ideas of the individual that may be dressing the dies of the bit machine. This bit has been generally used for many years and at present, in one form or another, is by far the most popular bit used in coal mines. This bit usually is made from 0.85 carbon steel, although in recent years some alloy-steel bits have made their appearance. At present, carbon-steel bits are frequently tipped in. hard facing materials. A third class of bits might be called the L'one-use" bit; that is, a small bit that is used once and then thrown away. These bits have two or three points, are usually made from 0.85 carbon steel and sometimes from higher alloys. Recently some. of them have been tipped with hard facing material. Most of them were used at first with special

Jan 1, 1942

University of Alabama University, Alabama Mining and Metallurgical Society ROBERT H WHELFSS, President JOHN WINEFORDNER, Vice-President DORACE DODD, Secretary KARL STARK, Treasurer GEORGE T BATOR, Faculty Sponsor PERCY G COWIN, Counselor

Jan 1, 1952

By Ravitz, S. F

76-B Unpublished manuscript. Not available in printed form. An experimental and Theoretical investigation of Quantitative Microscopic Mineralogical Analysis. By S.F.Ravitz and H.A.Steane. Manuscript in Engineering Societies Library.

Jan 1, 1935

H. M. BOYLSTON E. B. YOUNG SECRETARY-TREASURER OF SECRETARY-TREASURER OF BOSTON SECTION MONTANA SECTION R. M. KEENEY F. G. MOSES SECRETARY-TREASURER OF SECRETARY-TREASURER OF COLORADO SECTION UTAH SECTION

Jan 7, 1919

By Milton E. Wadsworth, W. Martin Fassell, William H. Dresher

A study of the rate of dissolution of molybdenite (MoS2) in alkaline solution was carried out under carefully controlled conditions. Effects of temperature, oxygen over-pressure, and KOH concentration were evaluated. Studies were made in the temperature range 100°C to 175°C and in the pressure range 0 to 700 psia of oxygen. Under these conditions molybdenite was found to leach according to a linear mechanism. Both oxygen over-pressure and KOH concentration were found to control the rate of leaching. The mechanism has been explained in terms of adsorption of oxygen at the molybdenite surface followed by configurational rearrangement of the adsorbed molecules. The hydroxyl ion dependency is believed to be diffusion-controlled. Laboratory batch studies have shown that molybdenite can be readily dissolved in alkaline solutions under moderate conditions of temperature and pressure. Commercial application of this process to the production of ferro-molybdenum and molybdenum chemicals is promising in view of the ease of dissolution of molybdenite and the relatively noncorrosive conditions involved in the process. HIGH temperature-high pressure techniques have long been used to great advantage in the organic chemical industry, the petroleum industry, and the paper industry. Only recently, however, have these methods been used to extract metals from their ores on a commercial scale. The Chemical Construction Corp., together with interested producers of nickel and cobalt, has done much to develop methods of producing nickel and cobalt powders by the use of high temperature-high pressure techniques.' The Howe Sound Co. is currently operating a plant near Salt Lake City in which the new Chemical Construction Corp. technique is applied to cobalt-arsenic sulfide concentrates. In this method the concentrates are leached in a dilute solution of sulfuric acid under air pressure at a high temperature. Near Edmonton, in Alberta, Canada, the Sherritt Gordon Co. is also using the new method in conjunction with its ammoniacal leach process.' National Lead Co., at Fredricktown, Mo., is operating a process similar to that of Howe Sound. In spite of the rapid growth of high temperature-high pressure hydrometallurgical processes, there has been very little work done on fundamental principles involved in this type of process. Conse- quently the literature lacks any significant data in this field. Oxidation of pyrite,3 phalerite,4 galena,5 and recently molybdenite" in alkaline solutions has been reported to some extent. This investigation was initiated, therefore, to broaden the application of high temperature-high pressure hydrometallurgy and also to contribute some insight into the basic mechanisms of oxidation in an aqueous medium under these conditions. In addition to the immediate consequences of these processes much valuable information remains to be learned about fundamental reactions when they are carried out at temperatures and pressures slightly higher than those normally encountered. Leaching of molybdenite by alkaline solutions under oxygen pressure has recently been reported in the Russian literature by E. S. Usataya,8 who found that leaching rate increased with an increase in the pH of the solution—the strongest effects being observed at a pH of 10—and also with an increase in temperature. Usataya also has reported the formation of a protective film on the surface of the molybdenite when the leaching solution was weakly alkaline, neutral, or acidic. He believes that this oxidation process explains the migration of Mo+ + in the oxidation zones of molybdenite ore deposits and the subsequent impoverishment of the ores. Equipment: The high temperature-high pressure reaction unit used in this work was especially designed for kinetic studies of this nature, emphasis being placed on accuracy of measurement and precision of control. As details of the unit's construction and operation have been discussed elsewhere,7 Only basic features and principles of operation will be discussed at this point.

Jan 1, 1957

By Thomas C. Wilder

ALTHOUGH there is an abundance of thermodynamic information available in the literature today, no experimental data on the standard molar properties of formation of zinc oxide have ever been reported for the temperature range 419.5" to 908°C. This is the temperature range for which zinc metal is a liquid. so that the formation reaction is: Data have been reported for Reaction [I] where zinc is a solid or a gas. Maier. Parks, and nderson' measured the electromotive force of the cell: in order to obtain the free energy of the reaction: over a limited temperature range. With the known properties of H2O, those of ZnO were calculated. These workers found that t;j of ZnO is -75,930 ± 150 cal per gfw and Mtf is-83,000 300 cal per gfw at 25°C. akolkin made similar measurements to obtain ilF7 and AH; of -75,870 and -82,540 cal per dw respectively at the same temperature. Truesdale and arirlg and Kitchener and 1gnatowicz4 measured the equilibrium of the reactions: respectively, in order to determine Ff of ZnO from the known values of CO, CO2, and H/X The thermodynamic properties of ZnO, presumably taken from the above investigations, are tabulated by Kubaschewski and vans' and Wicks and Block" The latter reference also gives values for the range where zinc is a liquid. These numbers are probably acquired from the known extremities of the range plus Cp data of the components. In the present work the electromotive force of the cell: was measured in order to calculate the properties of ZnO from the well known values of NiO for the temperature range where zinc is a liquid. In Cell [B] the cathode reaction is: and at the anode: The overall reaction is: for which the free energy change is: where is the electromotive force in volts of cell [B] after correction for the Pt-Ta thermocouple. The standard molar free energy of formation of NiO is very well known as a function of temperature. Kiukkola and agner's data are used in most tabulations. The error is probably less than I00 cal per gfw, The latter authors were the first to use solid mixed oxide electrolytes in galvanic cells. Their work with NiO and other oxides was performed with cells similar to Cell [B] using a variety of reference electrodes of fixed oxygen potential. There may be a small composition range for which either NiO, ZnO or both exist. If nonstoichiometry does exist for these oxides, then the properties described herein are those for the metal saturated compositions. The simple cell design was the same as described elsewheres except that the molten metal electrode was about 125 g of pure zinc including a small (0.25 to 0.50 g) amount of ZnO. The mixture of pure nickel and NiO powders making up the reference electrode was contained in a tube of the ZrOl + CaO electrolyte which was immersed in the molten zinc. A platinum contact was made to the reference electrode; tantalum to the zinc. A refractory cement plug was necessary at the open end of the electrolyte tube in order to prevent zinc vapor from contaminating the reference electrode. Experimental details such as the vessel containing the cell, furnace, temperature control and measurement, and electromotive force determinations of the cell have all been outlined previously. The temperature was varied randomly in the range between the freezing and boiling points of zinc. After each temperature change, time was allowed for the drift at the new temperature to be less than +;"c whereupon a series of three cell readings was taken at least 10

Jan 1, 1970

By P. B. Mee

The secondary re crystallization behavior of two vacuum-melted, nominally 3 pct Si-Fe alloys has been studied, one alloy being produced from pure electrolytic iron and semiconductor-grade silicon and the other from commercial-purity hot band. The vacuum-melted and vacuum-remelted alloys were found to develop {110}(hhl) and {lll)(hkl), respectively, on annealing in high vacuum and {100}(0kl) and {11l}(hkl), respectively on annealing in pure hydrogen of dew point, < — 60°C. H2S doping of the hydrogen or annealing in commercial argon was found to effect a reversal for the vacuum-remelted alloy from (111) to (100) secondary recrys-tallization, while prolonged vacuum annealing at 2 x 10-6 Tow resulted in a tertiary re crystallization from (111} to (110). The growth selection of the {lll}(hkl) component was found to be governed predominantly by the {111}/planar misorientation, the maximum deviation of the resulting secondaries being 5 deg. It is considered that the driving force for {111}(hkl) secondary recrystallization arises from the preferential lowering of ?111, possibly by phosphorus or nitrogen diffusion, just as oxygen and sulfur under certain conditions have been found to preferentially lower ?100. When heavily cold-rolled metals are annealed at high temperatures, primary recrystallization usually occurs rapidly and may be followed by considerable grain growth. However, in the presence of a fine dispersion of inclusions1"3 or with a strong matrix preferred orientation4&apos;&apos; the matrix may be stabilized and a secondary recrystallization may then be effected. Also, in vacuum-melted Si-Fe it has been shown possible to develop {100}(001) and {110}(001)6 surface energy driven secondary recrystallization textures. Further, it has been found that, on annealing very pure metals, grain growth normally ceases when a grain size approximately twice the strip thickness is acquired, due to the formation of V-shaped thermal grooves which result in an equilibrium being set up between surface and grain boundary stresses. If, however, a surface energy difference ??s, exists between adjacent grains (of the order of a few percent of the grain boundary energy ?b), then according to Mullins8 a secondary recrystallization may be effected, since the grains having lowest ?s would grow at the expense of their higher-energy neighbors. For clean bee metal surfaces ?110 should be lowest; however, for 3 pct Fe-Si (100) secondary structures have frequently been developed and have been attributed by Walter and Dunn9 to an alteration of the relative surface energies due to the preferential chemisorption of oxygen on (100) planes. Kohler,10 however, indicated that this reversal may be achieved by employing minute quantities of highly polar compounds in the annealing atmosphere, i.e., sulfur compounds, in par- ticular H2S being beneficial in (100) growth. This work has been verified by Kramer" using {100)/{110} bicrystals, while Mager12 demonstrated the importance of sulfur diffusion within the strip. Detert13 has intimated that carbon may be responsible for the preferential lowering of ?110 although no direct evidence has appeared yet to support this supposition. It must , be appreciated that the above-mentioned examples of surface energy driven secondary recrystallization were obtained with very pure vacuum-melted materials with oxygen contents (which is now known to be a critical factor") less than 35 ppm. During the course of a textural study on Si-Fe it has been found that under certain conditions (111) secondary recrystallization can be obtained by what is believed to be a surface energy growth selection mechanism. The purpose of the present paper is to briefly describe this result and to try and postulate the possible causes. EXPERIMENTAL Two vacuum-induction-melted, nominally 3 pct Si-Fe alloys were produced, one from pure electrolytic iron and semiconductor-grade silicon designated A and the other from commercial-purity hot band, designated B.

Jan 1, 1969

By H. E. Cline

A criterion for stability of a lamellar structure in two-phase alloys ulas derived froflr perturbation analysis of the steady-state solutions for eutectic growth. Both the mass and thermal diffusion were considered with boundary conditions for coupled lamellar growth. The concept of an effective liquidus slope was introduced. Excellent agreement was found with the experiments of Mollard and Flemings and the theory predicted a range of compositions on one side of the eulectic composition in which stable growth may occur with zero temperature gradient. The lamellar structure was found to be more stable than predicted by simple constitutional supercooling. The effect of impurity additions was also considered. DIRECTIONALLY solidified eutectic alloys may have a structure consisting of parallel plates or rods. It is important to know the range of composition and growth conditions that produce this ideal composite structure. Breakdown of the planar solid-liquid interface during growth may lead to a dendritic or cellular structure as in single-phase alloys. In the case of single-phase alloys, the concept of constitutional supercooling1 may explain breakdown, but in two-phase alloys the concept is no longer valid because the melting point is not given by the liquidus of one phase. Both phases must be considered in the mass and thermal diffusion problem. In the following theory a boundary condition at the solid-liquid interface was determined by using the steady-state equations of Jackson and ~unt&apos; to relate the average temperature and composition of the liquid at the interface. Then a sinusoidal perturbation in the shape of the interface was introduced to test for stability as in the analysis of Mullins and ~ekerka.~ The wavelength of the important perturbation was assumed to be much larger than the lamellar spacing, h, and the perturbation was assumed not to change the lamellar spacing, A. Both the mass and thermal diffusion equation were used with averaged quantities at the boundary to determine whether the perturbation grows or shrinks in time. A stability criterion was determined by considering the case in which the perturbation remains stationary. An example of Pb-Sn alloys was used to illustrate the validity of this theory. I) THEORY A) Temperature at the Interface. The temperature of the interface in coupled two-phase growth is close to the eutectic temperature TE even for alloys off eutectic composition. It is assumed that the interface is in local equilibrium and one expects the temperature at the intersection of the liquid phase and the solid phases a and 0 to be near the eutectic temperature. The interface is undercooled because of curvature and the deviation of the composition in the liquid from the eutectic composition. The average interface temperature Ti for steady-state growth of a lamellar eutectic with a plane interface was determined by Jackson and Hunt&apos; as given in their Eq. [17c]. Instead of using the ratio of the lamellar widths hp/h, as a parameter, the volume fraction of the 0 phase, +, will be used as it simplifies the algebra. The average interface temperature using this notation becomes: The average temperature of the interface depends on the volume fraction of the 0 phase, +, which may be related to the composition of the solid or the bulk composition of the liquid Co by: where C, and Cp are the average compositions of the solid phases. In steady-state growth, the composition of the solid is equal to the composition in the liquid far from the interface. The variation of the average interface temperature with composition is illustrated in Fig. 1 for the case of Pb-Sn alloys with a 10"4 cm lamellar spacing as calculated from Eqs. [I] and [2]. The interface temperature goes through a maximum at a composition near but not exactly at the eutectic composition. There is no reason why the composition corresponding to the maximum temperature should be equal to the eutectic

Jan 1, 1969

By R. S. Rickard, M. C. Fuerstenau

Anodic polarization curves for iron dissolution and cathodic polarization curves for copper deposition and ferric and hydrogen ion reduction were studied. These results were used to predict the relative rates of the reactions: The rates of the first two reactions were found to be first order with respect to the reacting ion, and the rale-controlling step was diffusion of the ions to the callzode surface. The rate of hydrogen ion reduction in an oxygen-free solution is dependent on the reciprocal of the square root of the hydrogen ion activity. In solutions containing oxygen, the rate of hydrogen reduction becomes dependent on the square root of the partial pressure of oxygen. At equal concentrations copper precipitation occurs about twice as fast as ferric ion reduction. In an air-saturated solution containing 0.01 M cupric ion at pH 2, the rate of hydrogen ion reduction zs about 10 times slower than that of copper precipitation. At pH values below 3, the rate of hydrogen reduction in oxygen-free solutions is very slozu. COPPER cementation has been utilized industrially for many years as a means of recovering copper from aqueous solutions. There are many different types of cementation plants, but all simply provide a means of contacting iron with relatively dilute copper solutions. In the past little or no attention has been paid to rates or mechanisms of the reactions involved. As a result, this and other studies&apos;-3 have been undertaken recently to establish the important parameters in this system. The reactions involved in copper cementation by iron are: Since transfer of charge is involved in every case, these reactions should be considered from an electrochemical point of view. In any electrochemical system involving electrolytic conduction, passage of electrons necessitates ion transfer to the respective electrodes according to Faraday&apos;s law. The current in the system will be proportional to the rate of ion transfer, and, therefore, when the current in the galvanic cell is known, the rates of the reactions involved can be determined. Galvanostatic electrode measurements5" are applicable for these electrochemical studies, in that with this technique polarization curves (current density vs electrode potential) are established by impressing a constant current through an electrode and measuring the electrode potential. Once the current density, electrode potential, and reacting area are known for each reaction in this cementation system, the rates of the iron-consuming reactions can be determined. EXPERIMENTAL MATERIALS Several metal electrodes were used in this investigation; they are shown in Table I. Solutions were made with reagent-grade salts and conductivity water. Air, nitrogen, and oxygen were employed. All of these gases were saturated with water and degreased prior to use. EXPERIMENTAL PROCEDURE The experimental work was divided into two general areas. The first area involved galvanostatic measurements, which were used to determine the rates of reactions as a function of various parameters. The second area comprised actual cementation experiments to check the rates predicted from the electrode measurements. Galvanostatic Electrode Experiments. Polarization curves were obtained using a standard galvanostatic technique5&apos;= with the apparatus shown in Fig. 1. The various electrode polarization experiments were run the same way except for changes in solution composition, polarity, and type of measured electrode. The general procedure involved the following steps: 1) a solution was made 0.5 M in sulfate ion and to the desired cation concentrations; this solution was placed in a constant-temperature bath and saturated with the desired gas; 2) the electrodes were cleaned and placed in the electrode holder; 3) the previously cleaned apparatus was assembled and immersed in a constant-temperature water bath (temperature controlled to ± 0.05"C); 4) the electrode was then positioned; the solutions were introduced, and the polarization meas-

Jan 1, 1969

By A. J. Sedriks

ALTHOUGH the occurrence of a readily visible tarnish on the stress-corrosion fracture surfaces of titanium alloys tested in oxygenated nitrogen tetrox-ide solutions has been reported,&apos; the possibility that the formation of this tarnish is a requirement for cracking to proceed does not appear to have been considered. It has been proposed that failure occurs in this system as a result of some electrochemical-mechanical process.2 However, recent studies3-6 of the stress-corrosion cracking of a brass in certain ammoniacal solutions, which also cause visible tarnishing, have led to the view that failure occurs by the repeated formation and fracture of a brittle surface film of cuprous oxide. The purpose of this note is to point out the similarities which exist between the tarnish which forms on a brass and that found on titanium alloys failed in nitrogen tetroxide, and to suggest, by analogy, that a similar tarnish-rupture mechanism may be operative in the latter case. The titanium alloy selected for the present study contained 5.2 pct Al, 2.5 pct Sn, 0.025 pct C, 0.16 pct Fe, 0.014 pct N, 0.012 pct H, 0.07 pct 0, and 0.002 pct Mn by weight. Vacuum-annealed alloy strips measuring 4 by 0.25 by 0.04 in. were used to prepare self-stressed test specimens. Each specimen was made from two strips by bending the end portions and spot welding them together to produce curved sections of uniform bending stress. (The exact details of preparing such specimens have been described by Lisagor el al.7) The curvature in the strips determines the ma-magnitude of the outer fiber stress, which in the present specimens was 100,000 psi (yield stress = 120,000 psi). The specimen surface in the spot-welded end regions was shot-peened to induce compressive stresses and thereby eliminate the possibility of stress-corrosion cracking in these regions. The test environment was nitrogen tetroxide, initially containing 99.5 pct N2O4, 0.1 pct H2O, and 0.08 pct C1, through which oxygen had been bubbled for 30 min. During testing the tetroxide was subject to an oxygen pressure of 250 psi. The duration of the test was 96 hr, and during this time stress-corrosion cracks propagated through some 50 pct of the thickness of the specimens. After testing, the tarnish was liberated from the fracture surface by immersion in a methanol-5 pct bromine solution, and then examined by electron dif- fraction and transmission electron microscopy using a JEM-7 electron microscope. The possibility that the bromine solution had affected the structure of the tarnish was investigated by an "in silu" examination of the stress-corrosion fracture surface using a reflection electron diffraction attachment designed for handling bulk specimens. Typical areas of the tarnish liberated by the me-thanol-bromine solution are shown in Fig. 1. Fig. l(a) reveals that the tarnish consists of individual platelets, and from Fig. l(b) it can be seen that the platelets are joined together to form a semicontinuous film, the boundaries of the titanium substrate grains being retained in the tarnish. Electron-diffraction patterns taken from these areas exhibited diffraction spots typical of a monocrystal. The diffraction pattern shown in Fig. 2 was taken from the central area in Fig. l(n). Monocrystal patterns obtained from areas containing numerous individual platelets can only be explained by assuming that their growth is governed by the titanium substrate (i.e., their growth is epitaxial). In other areas, the tarnish had folded over or became mechanically damaged, and these areas gave diffraction patterns consisting of "spotted" rings, enabling interplanar spacings of the tarnish lattice to be determined. These spacings, measured using a

Jan 1, 1968

Planning for a surface coal mine includes selecting the best means and equipment for uncovering the coal, loading it, and transporting it to the preparation plant. The machines and methods that will ensure optimum production will depend upon the location and characteristics of the seam to be mined. Stripping Techniques The choice of stripping units is influenced primarily by the system of mining, such as contour or out-crop mining as contrasted to mining in a region of rolling terrain with relatively flat upland surfaces. Factors such as the life of the mining operations production requirements, types of overburden, local and regional dip of coal, and land reclamation are other important considerations.

Jan 10, 1967

Elected Died 1895 ABBOTT, AI ATTHUR 1908 1882 ABBOTT, ARTHUR V 1906 1905 ABE, MASAYOSHI 1909 1903 ADAMS, CHARLES C. 1905 1903 ADAMS, HARRY C 1917 1906 ADAMS, JOHN C. 1913 1917 ADAMS, LLOYD D. 1918 1905 ADAMS, WILLAMS 1909 1903 ADAMS, W. EDWARDS 1910 1884 ADDY, MATTHEW 1896 1906 AFFLECK, WILLIAM A. 1911 1889 AKERS, WILLIAMS A. 1906 1905 ALABASTER, RUPPERT C. 1911 1899 ALBERGER, LOUIS R. 1911 1895 ALLAN, THOMAS A. 1894 ALLEN R B 1896 1905 ALLEN, R. SCOTT 1906 1886 ALLISON, ROBERT 1916 1874 AMIOT, H. 1892 1886 AMSLER, CARL 1894 1898 ANDRSON, JOHN W 1905 1895 ÅNGSTROM, CARL 1901 1887 ARCHBALD, JAMES 1910 1900 ARLETT, GEORGE H 1906 1895 ARMSTRONG, JOHN F 1898 1905 ARNOLDS, LEO F. 1917 1882 ARNOLDS, HUGO 1886 1875 ASHBURNER, CHARLES A 1889 1872 ASIIBURNER, WILLIAM 1887 1883 ATKINS, C M , JR 1885 1875 ATTWOOD, GEORGE 1912

Jan 1, 1923

By Daryl R. Tweeton, William H. Engelmann, Orin M. Peterson, Jon K. Ahlness, Gregory R. Anderson

The Bureau of Mines measured the geochemical changes as H2SO4 was used for in situ uranium leaching by Rocky Mountain Energy Company near Casper, Wyoming. Cores and ground water were analyzed before leaching. Water samples were taken from observation wells located between injection and production wells as the leach solution was brought up to full strength in several steps. Measurements were made of pH, Eh, temperature, conductivity, total dissolved solids, dissolved oxygen,HC03, U. V, Na, K, Ca, Mg,S04, CI, Mo, Mn, Fe, AI, Si, F, P, As, and Se. The data were gathered to assist in geochemical modeling of leaching and to study the potential environmental effects of acid leaching. Environmental considerations appear favorable. For example, the concentration of Se, a toxic element often found in uranium deposits, stayed below the EPA standard for drinking water.

Jan 1, 1979