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By E. N. Skinner, Arthur Philliops

During the course of an experimental program concerned with the hydrogen embrittlement of copper containing oxygen in concentrations within the solubility limits it became necessary to make a critical appraisal of the literature dealing with the solubility relationships of oxygen and solid copper. The latest determinations, and perhaps the only data obtained on "spectroscopically" pure copper, are those of Rhines and Mathewson' who reported that the solid solubility increases from 0.007 per cent oxygen at 600°C. to about 0.01; per cent at 1500ºC. Hanson, Marryat and Ford2 had previously placed the solubility limit at less than 0.009 per cent oxygen at 1000ºC. and Allen and Street3 had suggested, on the basis of an unpublished research by T. Hemitt, not over 0.005 per cent oxygen at 500°C. In the introductory stages of the investigation indirect evidence accumulated to suggest that the solubility limits were significantly lower than those previously reported. For this reason it was deemed essential to clarify this point before proceeding with a program intended to establish a quantitative relationship between hydrogen embrittlement and oxygen concentrations positively known to be within the solid solution range. Furthermore, the increasing production and the highly selective applications of the commercial "oxygen-free" coppers inevitably direct attention to the practical necessity for exact knowledge regarding the effects of mini-tie concentrations of the elements ordinarily found in the high-purity coppers now available. Of these elements oxygen occupies a unique position, not only by virtue of its specific effects on copper but more particularly in view of its important reactive tendencies toward the other impurities with which it is associated. Rhines and Mathewson considered several methods for measuring the solubility of oxygen and finally adopted the simple plan of saturating the specimens, obtained from redeposited cathode copper, by heating at the desired temperature in air. After the removal of surface oxide by mechanical and chemical means, the oxygen content was determined in the underlying metal. In general, this process of saturation, with a few modifications, was followed by the present writers. Although the procedure is direct and has obvious advantages, its effectiveness, unfortunately, is reduced by an excessive scaling of the copper, particularly at the higher temperatures. After saturation treatments above 900°C. the writers found that the specimens, necessarily rather thin in the original condition, consisted largely of scale and yielded too little metal for a satisfactory analytical sample. Furthermore, great difficulty was experienced in effecting complete removal of the scale. Needless to say, it is necessary to exercise extraordinary care in the preparation of the surface of the analytical sample in order to eliminate submicro-scopic fragments of cuprous oxide which ordinarily are lodged in the crevasses and

Jan 1, 1941

By Yanping Xiao, Ton van Sandwijk, Gus Van Weert, Larry McHugh, Thomas Zabev

"All attempts to remove significant amounts of arsenic from enargite via neutral or reductive pyro routes have required operating temperatures between 600 and 700 º C, too high to propose an equipment development program. Operating at reduced pressures, or using hydrogen or elemental sulphur as a sweeping gas did not help to lower these temperatures. Admixing iron powder gave excellent results, but still required 700 º C. By fortuity, in recent experiments to produce tennantite from an enargite mineral sample, it was observed that enargite was completely converted to bornite, chalcopyrite with minor residual tennantite within an hour at 400-450 ºC. This is believed to be due to the presence of pyrite in the mineral sample treated. All earlier decomposition work appears to have been done on predominantly enargite (i.e. low pyrite) samples, or at high operating temperatures, ignoring possible reactions at lower temperature. The decomposition of enargite into iron substituted tennantite plus some bornite under evolution of liquid elemental sulphur, followed by further decomposition of this tennantite into bornite and volatile arsenic sulphides, appears experimentally feasible at these low temperatures and mimics described ore genesis pathways at > 250 ºC in saline solutions. We suggest two pathways to describe the observed experimental results:20 Cu3AsS4 + 12 FeS2 ???5 Cu10Fe2As4S13 + 2 Cu5FeS4 + 31 S(l)31 S(l) ???31 S(g) (evaporation)5 Cu10Fe2As4S13 ???10 Cu5FeS4 + 10 AsS(g) + 5 As2S3(g)"

Jan 1, 2014

By J. Bruce Wagner, Roger L. Levin

Integrated forms of two solutions of Fick's second law for the movement of a plane interface through a sample of wustite, and for diffusion into a semi-infinite slab of wustite, are shown to yield nearly identical values of the chemical diffusion coeffcients of cation vacancies in wustite, over the temperature range 900° to 1100°C. The chemical diffusion coefficients, the values of D obtained for the propagation of a concentration gradient through samples of undoped and doped wustite, are obtained from the equations It is becoming increasingly important in metallurgical practices to understand the role of the chemical diffusion coefficient, i.e., the diffusion coefficient of a species across a concentration gradient. During the first stages of sintering, one of the mechanisms by which the bonds between neighboring particles develop is by volume or bulk diffusion. This diffusion coefficient as deter- where ?m is the weight change at any time t, ?W is the total weight change at t =8, A is the area of the specimen, and AC is the total change in the cation concentration after the establishment of equilibrium, as determined by reduction experiments in different carbon monoxide -carbon dioxide mixtures within the limits of existence of the single-phase field. mined from the standard equations for volume diffusion during sintering is actually a chemical diffusion coefficient, and it has been observed to be many times larger than the self-diffusion coefficient as determined on the same materials by experiments using radioactive tracer techniques. Kuczyn-ski1 has noted that, if the controlling mechanism of sintering of A12O3 in an oxidizing atmosphere is the diffusion of oxygen, then this diffusion coefficient as measured from sintering rates is about 2.2 x 104 higher than the self-diffusion measurements obtained by tracer techniques. He has also reported the diffusion coefficient obtained from the rate of sintering of Fe2O3 powder to be about 10 6 times faster than the self-diffusion coefficient of

Jan 1, 1965

By Chander S

Properties of surface films on chalcopyrite and pyrite differ due to variations in the mechanism of oxidation of the two minerals. In the case of chalcopyrite the first step in the oxidation is the release of iron as ferric ions, which hydrolyse depending upon conditions prevalent in solution. The iron oxide/hydroxide layer formed by hydrolysis of ferric ions is quite porous and easily detachable from the surface of chalcopyrite. When the surface oxide layer is detached a sulphur-rich layer is exposed making chalcopyrite hydrophobic. The thickness and properties of the sulphur-rich layer determine its flotation response, both in the absence and presence of collectors. In the case of pyrite, on the other hand, iron is released as ferrous ions which require much higher pHs to hydrolyse. These ions remain adsorbed on the surface of pyrite making the surface hydrophilic. When the iron species are complexed with chelating agents such as ethylene diamine tetra acetic acid, pyrite was hydrophobic. Siderite forms in the presence of carbonate ions, which might be present in several flotation systems. Siderite nucleated on isolated sites at the surface. The presence of such a precipitate is likely to influence the interaction of pyrite with various reagents thereby altering its flotation behavior. To determine the mechanism of oxidation, kinetics of oxidation of chalcopyrite and pyrite was studied using several electrochemical techniques, namely, cyclic voltammetry, polarisation and impedance spectroscopy. Floatability of the minerals was investigated by measurement of contact angles on mineral electrodes and by Halimond tube flotation. Impedance spectroscopy was especially useful for estimating various properties of surface film for both the minerals. Properties such as charge transfer resistance, porosity, and capacitances of the surface films on the two minerals are compared under several conditions of oxidation. These properties were found to be a strong function of the rate and the extent of oxidation.

Jan 1, 1993

By C. G. Dunn

Identification of the kinds of orientation relationships that may exist among crystals is an important problem in the metallurgical field. As an aid to its solution standard orientations of several orders of twins would be very useful for rapid analyses to discover high-order as well as low-order twin relationships. Although data have been published that give orientations for three generations of twins, these data are not readily useful in the form presented; i.e., in a stereo-graphic projection with one pole per orientation.' However, accurate data based on calculations of the positions of all {1001 planes for such groups would be very useful when presented in tabular form. Therefore, calculations have been made for a group of four orders of twins and the data are listed in Table 3. Illustrative applications are considered briefly, with the idea of pointing out what may be done with large groups of orientations. Method of Computing Orientation OF a Twin It is common practice to describe the orientation of a crystal in terms of the positions on a stereographic net of the poles of certain planes of the crystal. A single position on a net may be given in terms of two angle variables, two sets of which appear in the following equations: Polar Net Wulff Net x = , sin ?p cos Fbp x = r COS ?w y = r sin ?p sin Fp y = r sin ?w cos Fw % = r cos ?p z = r sin ?w, sin +, The three numbers z, y and z determine a length r as well as a direction (0, 4) in an X, Y, Z coordinate system. In the present case, r will be set equal to (h2 + k2 + L2)1/2, where h, k and I are the usual Miller indices for a crystallographic plane, a restriction that facilitates determination of the positions of poles of new planes from those of old or known ones,2 as will become evident later. Furthermore, since twinned lattices have certain planes in common, it is an easy matter to determine the orientation of a twin of a crystal if the orientation of the crystal itself is known. We start therefore with a crystal of known orientation (positions of three {Ioo} poles given) and determine where the cube poles occur in first, second, third and fourth-order twins. Methods for identifying twinned lattices and for making the calculations to find the orientation of a twin have been published.3,4' Reference 4 will be illustrated in the calculation of the orientation of a twin, even though this method differs from the one used by the writer in obtaining the following data on four orders of twins. Consider a crystal S and its twin A1, A' being one of the four {112} or {III} type* first-order twills of S. The orientation of S—i.e., the positions of poles of (I00)

Jan 1, 1945

By Christopher Bambridge

The Washington State Department of Transportation (WSDOT) is constructing a new tunneled route under Seattle to replace the existing State Route 99, Alaskan Way Viaduct (AWV), which follows the historic waterfront for several miles. The viaduct separates the businesses that rely upon the tourist trade from the down-town area. The reconnection of the city to the waterfront areas will occur following the completion of the SR99 Re-placement program that replaces the aging structure that was severely impacted by the 2001 Nisqually earthquake, with a state-of-the-art, twin-deck highway with a world record-breaking 17.4-m (57.3-ft) bored tunnel. Constructed in the 1950s, the double-tiered viaduct is nearly 3.2 km (2 miles) long and runs parallel to city?s waterfront. The viaduct, which is partially supported by the seawall, is a vital local and regional transportation link and carries about 110,000 vehicles each day. The seawall, built from concrete and timber in the 1930s, extends along Seattle?s waterfront and supports the soil behind it. Studies in the 1990s showed that the viaduct was nearing the end of its useful life, apparent by its exposed rebar and weakened columns. The 2001 Nisqually earth-quake further damaged the viaduct, forcing WSDOT to temporarily close it for inspection and limited repairs. The viaduct and nearby seawall are vulnerable to an-other earthquake and continue to show signs of age and deterioration. Following a collaborative process, WSDOT developed the following guiding principles to the viaduct replace-ment:

Sep 1, 2013

By David W. Mitchell

WHILE pure magnesium does not corrode rapidly the presence of even very small quantities of certain other metals accelerates corrosion remarkably. Because magnesium is such an electropositive metal (E° = +2.34 volts)' the presence of substances that permit galvanic activity is extremely undesirable. It is stated that as little as 0.017 pct of iron in magnesium causes a marked increase in the corrosion rate.2 Magnesium and its alloys are commonly melted in iron or steel pots; consequently the commercial metal has the opportunity to pick up iron if it has that tendency. Quantitative data on the solubility of iron in magnesium are of practical as well as of academic interest. Some magnesium alloy castings tend to have large grain size unless suitable treatment is given to the liquid metal just prior to casting. One method of grain refinement consists of "superheating" the metal just prior to casting. "Superheating" is heating to a temperature 100 to 200°C above the casting temperature and holding for a short period of time. Superheated metal has a much finer grain than unsuperheated metal. A satisfactory explanation of this phenomenon has not been forthcoming. One hypothesis attributes the grain refinement in the superheated metal to precipitation of some phase that is miscible at the temperature of superheat but not miscible just below the casting temperature and which is thought to provide nucleating centers for crystallization. This phase, if the foregoing hypothesis is correct, would probably be a metal or an intermetallic compound. Of the metals likely to be found in magnesium alloys, iron is one of the most likely candidates for the role of grain refiner for iron occurs in small quantities in all commercial magnesium and magnesium alloys. A. Beck' states that magnesium, in either the liquid or the solid state, cannot dissolve iron and that iron exists as a finely divided suspension which does not settle out because of its extreme fineness. Beck also presents a micrograph showing a large iron dendrite in magnesium but does not comment on the crystallization of iron from a solution supposed to contain none. It is doubtful that dendrite formation from suspended iron would be possible. This suspension theory is the basis of patents4 covering the removal of iron from magnesium by allowing the iron particles to act as nuclei for the formation of primary magnesium crystals which can be separated by segregation. Also covered by patents is the removal of iron by the addition of another metal to form an intermetallic compound with the iron which, because of its increased particle size, is able to settle out of the molten metal. Here, too, quantitative information on the extent of iron solubility in liquid magnesium is of more than theoretical interest. M. Hansen,5 in his critical collection of the data on binary alloys, states that iron is not soluble in liquid magnesium. W. R. D. Jones6 who studied the physical properties of low iron magnesium alloys observed a

Jan 1, 1948

By D. H. Polonis, M. B. Kasen

AN unusual thermal etching phenomenon has been observed on the surface of a Cu-Si alloy. The observations were made during studies of vacancy condensation pit formation which were reported in previous papers.1,2 Figs. 1 and 2 are photomicrographs of the surface of a Cu-4.8 pct Si alloy after heating in vacuo (3 x X mm Hg) to 525°C and subsequently holding at that temperature for 16 hr in an impure (air-contaminated) argon atmosphere. Under these conditions preferential removal of silicon from the matrix by oxidation results in a surface which is entirely a phase overlying an a plus y structure. The light areas of Fig. 1 are regions in which very little thermal etching has occurred, while the majority of the surface has experienced severe etching. Similar regions in Fig. 2 are seen as plateaus above contours produced by net transfer of material from the specimen surface. Twin boundaries are also visible in Fig. 2. The difference in matrix mi-crostructure between Figs. l and 2 reflects the par- ticular orientation of low-index planes with respect to the surface of observation. Thermal etching contours of this type have been studied in detail by Hondros and Moore Both of the photomicrographs show that one or more dark spots are located approximately at the center of every protected area; where two spots are in close proximity, the protected areas have merged. The microstructures indicate that the anomalous resistance to thermal etching is related to the presence of these spots. Williams and Hayfield have shown that local regions of unusually high oxidation resistance can be caused by a surface monolayer of atoms with a work function higher than that of the base material. The result is an inhibition of the rate of electron removal from the base material and a decrease in the oxidation rate. The source of the protected layer may be either surface diffusion from contaminants on the specimen surface or pipe diffusion of solute atoms followed by migration across the surface. In the latter case the driving force is a difference in chemical potential resulting in a Gibbs adsorption phenomenon. In the present case, chemical polishing of the specimen surface precluded contaminants of a strictly surface nature. Consequently, diffusion of impurity atoms from within the lattice appears to be the most tenable explanation of the observed phenomena. The authors propose that the structures of Figs. 1 and 2 reflect the diffusion of impurity atoms along extended dislocations within the individual a phase grains prior to surface oxidation. The central spots within the protected regions are seen as sites of dislocation emergence which have become locally decorated with oxide in the manner discussed in Ref. 1. Williams and Hayfield observed protected regions adjacent to the grain boundaries of iron-contaminated copper which they attributed to the segregation of iron to the grain boundaries coupled with high dif-fusivity along the complex dislocation array at such boundaries. No evidence of such grain boundary protection was observed in the Cu-Si alloy; this

Jan 1, 1964

By T. D. Guldem, J. L. Kaae

ALLOYS with nominal composition of 45-Fe 35-Ni 20-Cr, ASTM-B-163, known under the commercial names of Incoloy 800 and Sanicro 31 (Alloy 800), are often employed at elevated temperatures for extended periods. Therefore, knowledge of the aging behavior of these alloys is of considerable importance. Significant decreases in ductility and increases in yield strength have been observed in the 45-Fe 35-Ni 20-Cr alloys containing about 0.4 pct Ti and 0.4 pct A1 after long-term aging at 540" to 700"~."~ However, no direct evidence has been presented for precipitation phenomena that might result in such changes. Strengthening effects have been attributed to the effects of local or-dering.3 Since y' precipitation (Ni3A1, Ti) is known to occur in similar alloys which contain more titanium and aluminum,4-7 it was decided to explore the possibility that y' might precipitate in these alloys and might be responsible for the changes in mechanical properties on aging. This note reports some observations of two distict types of matrix precipitates made by means of transmission electron microscopy, in a 45-Fe 35-Ni 20-Cr alloy containing 0.31 pct Ti and 0.4 pct Al. The steel used in this investigation was obtained from the Sand-vik Steel Works; it is designated Sanicro-31 (Alloy 800). The chemical composition of the alloy is given in Table I. Aging of solution-treated material at 700" and 800°C for 130 and 100 hr, respectively, produced the matrix precipitates shown in Figs. l(a) and l(b). It is apparent from these micrographs that the precipitate particles occurred in the form of thin square plates parallel to the matrix cube planes. Extraction replication and selected-area electron diffraction showed that the precipitates were M23C6. Coherency strains, consistent with the semicoherent nature of small M23C6 precipitates,' were evident for certain imaging conditions. In addition to matrix precipitation, preferential precipitation of M23C6 on dislocations was common, as has been reported previously for austenitic stainless steels.'" Specimens aged for longer times (-300 hr) at 700°C exhibited a different type of coherent matrix precipitate in addition to the M23C6. An example is shown in Figs. 2(a) and 2(b). In addition to the few large M23C6 precipitates, small precipitates exhibiting strain contrastl0,ll are present. The "line of no contrast" of the strain field of a given precipitate lies along differ-

Jan 1, 1970

By N. A. D. Parlee

THE gas-liquid metal diffusion cell technique1-3 has been used to study the diffusion of nitrogen in Fe-C alloys. The actual apparatus and technique were the same as employed by the authors to study the diffusion of hydrogen in liquid iron.' The diffusion cell' was formed by immersing an alumina tube in a stagnant melt contained in an alumina crucible. The tube (hereafter called absorption tube) contained nitrogen gas at 1 atm and was connected to a sensitive gas-measuring system. The change in the average concentration of nitrogen in the melt in the absorption tube was determined by measuring the rate of absorption of nitrogen in the diffusion cell. Eq. [I], 1-3 derived from the appropriate solution of Fick's second law, was used to examine the data and to calculate chemical diffusion coefficients (D) in situations where the absorption appeared to be controlled by diffusion in the liquid: where V is the stp volume in cu cm, d is the diffusion cell diameter in cm, p, is the density of the melt in g per cu cm, pg is the stp density of nitrogen in g per cu cm, C, is expressed in wt pct, D is in sq cm per sec, and t is in min. According to Eq. [I], a plot of v vs vt should yield a straight line passing through the origin if absorption is controlled by diffusion in the liquid. The slope of this line could be used to determine the value of D under appropriate conditions. As discussed in earlier reports,1,2 the initial thermal expansion of the gas upon immersing the absorption tube distorts the line in the initial stages of a diffusion experiment. However, this is not a serious problem since the slope of V vs 6 plots can be determined from the data points obtained after the initial expansion ceases. The volumes reported on the data plot presented here represent absorption after this thermal expansion ceased. Several preliminary diffusion experiments were attempted with melts of pure iron and with Fe-C alloys containing up to 0.6 pct C. In these cases, no or very little absorption was observed. The only data obtained were for an Fe-C melt which was in addition thoroughly deoxidized by successive hydrogen and vacuum-degassing treatments. These treatments introduced an appreciable amount of aluminum into the melt and reduced its omgen content. The original charge material for this melt contained 0.23 pct s and approximately 0.001 pct &. After repeated hydrogen and vacuum-degassing treatments two diffusion experiments were performed. The analysis of the melt

Jan 1, 1968

By R. C. Ruder, C. E. Birchenall

The method of decrease in surface activity was used to determine the rates of diffusion of Co" into cobalt and into nickel. Since the absorption curves for cobalt radiation were quite complex under the conditions of these experiments, the effects of geometry and surface preparation on the diffusion results were investigated. The cobalt self-diffusion coefficients obey the equation DCoco = e-61100/RT cm2 per sec. For dilute cobalt diffusing in nickel, DConi, == 1.46 e-/R' cm2 er sec. AS part of the general program to measure the self-diffusion and dilute-solution diffusion rates of the iron-group metals, the diffusion coefficients of cobalt into cobalt and nickel have been measured using the radioactive isotope Co"'. Self-diffusion studies in iron have been previously reported by Birchenall and Mehl.' The technique of measurement used was the decrease in surface activity method described by Steigman, Shockley, and Nix.' It has been determined that scattering of the measured beta radiation by the specimen matrix is significantly influenced by the condition of the surface and the counting geometry. Accurate diffusion coefficients can be calculated from the activity data provided that the specimens have plane diffusion surfaces and that the absorption properties of the emitted radiation are determined under geometrical conditions duplicating with external absorbers the absorption and scattering in a thin film at the specimen surface as nearly as possible. The cobalt used in this research was originally in the form of hydrogen reduced rondels 99.9+ pct pure. The nickel had been prepared by the carbonyl process and was found by spectrographic analysis to contain 0.03 pct Fe, 0.04 pct Co and smaller traces of other metallic elements for a balance purity of 99.9+ pet Ni. Both materials were vacuum melted and cast in rectangular ingots. Specimens 7/8x7/8x1/4 in. were machined from these ingots. The specimens were then ground to 4-0 emery paper and annealed in hydrogen for at least a day at 1200°C. Some of the specimens were used in preliminary experimentation after which their diffusion faces were machined to remove the radioactive material from the previous diffusion experiments. After grinding, the specimens were polished using an electrolytic lapping technique described by Mazia." This lapping was continued until at least 0.005 in. was removed from the diffusion surface. The final surfaces were metallographically smooth except for a few fine scratches caused by the glass cloth. A large percentage of the area was undisturbed as determined by microscopic examination. The grain diameters of the diffusion specimens varied from 0.1 to 5 mm. There were no effects due to grain boundary diffusion in the experiments

Jan 1, 1952

By G. W. Nabor, H. J. Ramey

A blotter-type electrolytic model was utilized to prepare flow diagrams for a field test of the in-situ combustion process. It is pointed out that the areal sweep of a combustion pattern is similar to sweep patterns that would be developed at an infinite mobility ratio, which exists (approximately) across a combustion front because of the complete removal of liquids from the sand behind it. The precision of the blotter method was tested by comparison with results obtained by other techniques and was found to be satisfactory. The blotter-type model will not furnish as much information as more elaborate and expensive potentiometric models, but its speed of operation and ease of construction make it a highly satisfactory tool to determine areal sweep patterns. A tabulation of sweep efficiency and mobility ratio is furnished for various well geometries. INTRODUCTION In connection with the first field experiment with the in-situ combustion method of oil recovery," flow diagrams for the unique well geometry and boundary conditions involved in the subject test were developed. From these diagrams, information concerning the areal sweep and distribution of flow was obtained. A survev of the literature on potentiometric models, utilized to solve two-dimensional flow problems,1,2,3,4,5,6,8,9,10 indicated that the information desired could be obtained by means of a blotter-type model by making certain modifications in the technique. The following discussion describes the application of the modified blotter-type electrolytic model to the solution of the problem of the flow of gases in an oil reservoir for an engineering appraisal of the progress of the combustion front during the first field experiment. Considerable information has been published on the theoretical aspects of electrical model techniques. One author stated that:' "The models are based on the observation that since the velocity of an ion in an electrolytic system is proportional to the potential gradient, just as the velocity of a fluid particle in a porous medium is proportional to the pressure gradient, the paths of the ions in the electrolytic systems must be similar to those of the fluid particles in a porous medium with the same geometry and equivalent boundary conditions." This suggestion of a real analogy has been established repeatedly by comparisons of analytic derivations with model results. The analogy between the movement of a combustion front and the model results is not as apparent, since the combustion process differs from water flooding and gas cycling in that the velocity of the burning front is different from the velocity of the injected fluid at the front in combustion. Analogy between electric current flow and movement of the burning front exists because the local velocity of the burning front is proportional to the air (mass) velocity at this point (assuming frontal temperatures are at least as high as the ignition temperature of the fuel). Most model studies fall into one of two categories: (1) electron conduction, or (2) ionic conduction models. Examples of these are models which employ as flow media either a thin metal sheet, or a porous blotter saturated with an electrolyte, respectively. Of the two, the porous blotter model, an ionic conduction model, appears to be the most adaptable to the flow problem that results when using in-situ combustion. This problem requires that the mobility of the particles in the model be controlled analogous to the mobility of gas flowing through burned sand of high permeability to gas and then through oil sand of lower permeability to gas. Although the blotter model has heretofore been

Jan 1, 1955

By R. P. Smith

The carbon content of a number of alloys ranging (before carburitation) from purified iron to purified cobalt was determined for fixed activities of carbon by equilibration with each of six CO-CO2 atmosphere at 1000°C. At fixed carbon activity, the carbon content decreases continuously with increasing cobalt content. For concentrations of 0 to 50 at. pct Co the results can be expressed by a linear interaction equation of the type In y2 = 7.76n2/(n1+n3)+ 2.30 n3/(n1+n3) where y2 is the activity coefficient of carbon (standard state such that y2— 1 as n2 — 0 in the Fe-C binary) and n1, n2, and n3 are the number of atoms of iron, carbon, and cobalt per unit weight of alloy. The results are also given in terms of the a functions. In the same concentration range, the results are in accord with the regular solution theory of Alcock and Richardson. THE carbon content of Fe-Si, Fe-Mn, and Fe-Ni alloys at fixed activities of carbon has been reported previously.'-, The present work extends R. P. SMITH, Member AIME, is Research Chemist, E. C. Bain Laboratory for Fundamental Research, United States Steel Corp., Research Center, Monroeville, Pa. these measurements to a series of Fe-Co alloys. These alloys, like the Fe-Ni alloys, are fcc ("aus-tenitic") over the entire range of composition at 1000°C. EXPERIMENTAL PROCEDURE The alloys were made from electrolytic cobalt and Plast-Iron in a small vacuum-melting furnace. A small amount of graphite was added to each melt to keep the oxygen content low. The ingots were analyzed for iron and carbon: the amount of cobalt was obtained by difference. Analysis of the top and bottom of the ingots indicated that they were uniform in alloy content. Except for the pure cobalt the ingots were hot-rolled to approximately 0.15 cm thickness, cleaned by sandblasting, then cold-rolled to about 0.045 cm. We were not successful in cold rolling the pure cobalt; therefore it was hot-rolled to the final thickness. The last traces of surface oxide were removed by acid pickel, then the samples were treated in a hydrogen-2 pct water vapor mixture at 1100°C to remove carbon and most of the oxygen. The carburizing procedure was similar to that previously described.1,2,4 The alloys in the form of strips about 1.7 cm wide, 7.5 cm long, and 0.04 cm thick, together with a similar specimen of purified iron, were equilibrated with each of six CO-CO2 mixtures of fixed composition, then quenched in the

Jan 1, 1965

By Parke A. Dickey

Potential differences between strata of shale and sandstone have been recognized for about years, and they form the basis of the electrical logging of oil wells. Hitherto these potentials have been ascribed solely to electrochemical reactions caused by the disturbing effects of the water in the drill hole through which they are generally measured. Observations by the author in wells empty of water and in a mine shaft suggest that potential differences between sandstones and shales are natural and specific properties of the rocks, although they are modified in measurement by the disturbing effects of the water in the drill hole. The cause of these potentials probably is to be sought in the relative polar adsorptive capacities of quartz and clay particles. Introduction The existence of potential differences in the surface of the earth has been known for some time, and their measurement has facilitated the discovery of geological discontinuities such as ore bodies. The technique of measurement has been well established.'-a In measurements in oil wells, it has been found that the potential of shales with respect to some arbitrary reference is very nearly constant in any one well, at least below the zone to which meteoric water has gained access. Sandstones and some other types of sedimentary rocks have a difference of potential with respect to shale that is negative and may attain a value of 200 millivolts or more. The difference of potential, as usually measured commercially with water in the hole, is distributed over about one foot vertically at the top and bottom contacts of the sandstones. The sharpness of the curve at the formation contacts can be improved by using a short electrode that is close to the wall of the hole. These potentials generally have been ascribed to the disturbing effects of the water in the drill hole. Potentials have been found, however, in wells in which no water was present. In the course of experiments in electrical logging in Pennsylvania, carried out by the Pennsylvania Geological Survey, observations were made of several phenomena that hitherto have not been described, to the author's knowledge, in the published literature. The potential differences across the contacts of sandstone and shale are called in this paper "natural potentials," as distinguished from the potentials caused by electroendosmosis (electrofiltration) and concentration differences, which will be discussed subsequently. Potentials in Cored Well In the spring of 1942, the author measured the potentials in an exploratory well (Day 13, near Grand Valley, Pa.) which had been cored with diamond tools. The potentials were first measured with fresh water in the hole. A null balance potentiometer was used in this and all the other measurements described in this paper. One nonpolarizing porous pot electrode, containing copper sulphate solution and crystals surrounding a pure copper elec-

Jan 1, 1944

By Parke A. Dickey

Potential differences between strata of shale and sandstone have been recognized for about years, and they form the basis of the electrical logging of oil wells. Hitherto these potentials have been ascribed solely to electrochemical reactions caused by the disturbing effects of the water in the drill hole through which they are generally measured. Observations by the author in wells empty of water and in a mine shaft suggest that potential differences between sandstones and shales are natural and specific properties of the rocks, although they are modified in measurement by the disturbing effects of the water in the drill hole. The cause of these potentials probably is to be sought in the relative polar adsorptive capacities of quartz and clay particles. Introduction The existence of potential differences in the surface of the earth has been known for some time, and their measurement has facilitated the discovery of geological discontinuities such as ore bodies. The technique of measurement has been well established.'-a In measurements in oil wells, it has been found that the potential of shales with respect to some arbitrary reference is very nearly constant in any one well, at least below the zone to which meteoric water has gained access. Sandstones and some other types of sedimentary rocks have a difference of potential with respect to shale that is negative and may attain a value of 200 millivolts or more. The difference of potential, as usually measured commercially with water in the hole, is distributed over about one foot vertically at the top and bottom contacts of the sandstones. The sharpness of the curve at the formation contacts can be improved by using a short electrode that is close to the wall of the hole. These potentials generally have been ascribed to the disturbing effects of the water in the drill hole. Potentials have been found, however, in wells in which no water was present. In the course of experiments in electrical logging in Pennsylvania, carried out by the Pennsylvania Geological Survey, observations were made of several phenomena that hitherto have not been described, to the author's knowledge, in the published literature. The potential differences across the contacts of sandstone and shale are called in this paper "natural potentials," as distinguished from the potentials caused by electroendosmosis (electrofiltration) and concentration differences, which will be discussed subsequently. Potentials in Cored Well In the spring of 1942, the author measured the potentials in an exploratory well (Day 13, near Grand Valley, Pa.) which had been cored with diamond tools. The potentials were first measured with fresh water in the hole. A null balance potentiometer was used in this and all the other measurements described in this paper. One nonpolarizing porous pot electrode, containing copper sulphate solution and crystals surrounding a pure copper elec-

Jan 1, 1944

By Nitin Bhavsar, Kaushik Vakil, Lakshmikanth Reddy, Sanjay Sarkar, Tathavadkar. Vilas, Bhavin Desai, Raghavendra Adiga

Gold and platinum group metals (PGM) do not dissolve in sulfate electrolyte from anode during electro-refining of primary copper. The PGM form solid ‘slimes’ which accumulates at bottom of the electrolytic cell. Typically, 8 to 10 ppm silver is present in copper cathodes, which is equivalent to almost 2% of silver loss during electro-refining. The silver can be cemented with cathode copper as soon as it is dissolved into the electrolyte from anode or during entrapment of slime particles in cathode. Over a period of time, the concentrates grade has deteriorated and change in type & amount of impurities in concentrate has resulted in higher silver loss during refining process. Therefore, an in-depth investigation was carried out in both fire- and electro-refining processes to understand the root causes of higher silver loss in copper cathodes. The detailed characterization and the plant data analysis were carried out. The results of study revealed that higher silver loss in 3rd crop cathodes as compared to 1st and 2nd crop cathodes from same anode. In anode silver was present in two forms, dissolved in copper (solid solution) and in slime phases such as Cu2-xAgxSeTe. SEM-EDX study of anode cross section confirmed higher silver and oxygen content in central region (core) of anode as compared that in both air and mold sides. This is due to non-uniform cooling of anode which was confirmed by the solidification modeling. Higher concentration of oxygen & silver at core of anode rised Ag+ concentration in electrolyte and slime particles during 3rd crop. The results of study were used to optimize the anode cooling process and also electrolyte chemistry to reduce the silver loss. The details of study carried out are discussed in this paper using the results of modeling, characterization and experimental studies. INTRODUCTION In the electrolytic refining of copper, fire refined copper anodes are used as raw material. Anodes contains copper of the range 99.5 to 99.6%, rest being the impurities. Hence, the purpose of the refining is (1) to remove the impurities so that final cathode conforms to the LME specifications and also (2) to recover the precious metal from the anode copper. When anode is dissolved, most of the impurities reports to the anode slime settled at the bottom of the cell, and rest dissolves in the electrolyte. Dissolved impurities remains in electrolyte and are removed during electrolyte recycling. However, sometime dissolved impurities and slime particles get entrapped in cathode due to disturbances in operational conditions. Metals dissolving in the electrolyte are the elements such as Ni, Co, Fe, Zn. The electrode potential of As, Sb and Bi being close to that of copper, these elements partly dissolve in the electrolyte. Noble metals like Ag, Au, Pt and Pd are generally insoluble and are thus expected to report to the anode slime. A small amount of the sliver content from the anode is dissolved in the electrolyte. Because the dissolved silver electroplates on the cathode at a smaller applied potential than copper, the cathode typically contains up to 8 ppm of silver. This is referred to as ‘silver loss’ in cathode (Cooper, 1987). Fortunately, silver is a rather benign impurity in copper due to its electrical conductivity being higher than copper. However, higher silver loss in cathode is loss of revenue for Copper smelter due to significant difference in their LME price.

Jan 1, 2019

By R. N. Chakravorty, R. J. Kolada

Introduction Spontaneous combustion in coal mining is recognized as a major hazard in terms of safety and economics. A survey by Olaf (1979) revealed that 80% of coal mine fires were caused by spontaneous combustion. Modern mining methods demand a high capital investment. Closure of a working face may then result in a huge loss. Even a short production interruption can prove expensive. Spontaneous combustion may also produce lethal amounts of carbon monoxide, thus posing a serious threat to the health and safety of underground miners. The worldwide recession in the early 1980s resulted in a number of mine closures and production cutbacks. So large stockpiles at mine sites were common. Experience has shown that stockpile fires are difficult to extinguish. Critical factors influencing spontaneous combustion There is no simple method of predicting whether a particular mining method applied to a specific coal seam will result in spontaneous combustion. Under favorable conditions of heat accumulation, spontaneous combustion can occur with any type of coal. It is known that subbituminous coals are more susceptible compared to low volatility bituminous coals, and that a high ratio of exinite increases the risk. However, the inherent moisture content of the coal and the exposed surface area may be more significant. Actual mining and ventilation conditions also strongly influence susceptibility. In practice, the experience gained with the mining method applied to a particular type of coal seam must be carefully evaluated with respect to the factors responsible for spontaneous combustion. Feng, Chakravorty, and Cochrane (1973) summarized the critical factors influencing spontaneous combustion in coal mines (Table 1). Prevention methods and strategies Mine layout is the most important factor preventing spontaneous heating. Working districts should be designed so that a particular section can be isolated on short notice without affecting production in others. Sites for preparatory seals should be identified and marked during planning. With coal seams that are highly susceptible to spontaneous combustion, the retreat method of working is preferred. This is because the gob is not subjected to a large difference in ventilation pressure. Coal pillars should be designed to resist excessive crush. The panel system of working is preferred, particularly for mining coals susceptible to spontaneous combustion. The size of each panel is calculated based on the incubation period and the rate of extraction. Controlling air leakage is also important for controlling spontaneous combustion. This is usually achieved by minimizing ventilation pressure difference, proper siting of doors, and avoiding unnecessary stopping and starting of fans. Air leakage is also reduced by sealant coating, injection of cements in cracks and crevices, and by maintaining good gateside packs. Application of inhibitors to control spontaneous combustion met with limited success. Chamberlain and Hall (1973) concluded that borate solution or Montan powder sprayed in the gob area or infused into a low rank coal would reduce the possibility of spontaneous combustion. Early detection of heating Significant research is being conducted worldwide to develop methods for early detection of heating. Monitoring combustion products during the early stage of heating is the most suitable method for detecting spontaneous combustion. The major gaseous products resulting from low temperature oxidation of coal are carbon dioxide, carbon monoxide, and water vapor. In mining operations, carbon dioxide monitoring is considered unsuitable because there are sources other than spontaneous heating from which this gas may originate. Carbon monoxide, however, is a more specific product of combustion during low temperature oxidation of coal. Over the years,

Jan 10, 1988

By J. W. Stewart

The aim of this paper is to point out the various ways in which design is taught in standard four-year mining engineering curricula in American colleges and universities; to discuss the reasons apparently justifying the great diversity of procedure that exists along this line; and to indicate possible solutions to the difficulties now attending the teaching of design. A study was made of typical four-year mining engineering curricula in 15 colleges and universities of the United States (Table I). Great diversity in content of the various design courses, if taught as described, became apparent immediately. It appeared that it might be both interesting and instructive if the cause for this colorful variety could be found. Was the cause local mining conditions, departmental individuality, or actual necessity? Study of the school catalogues revealed that the various design courses could be classified into two fairly distinct types; namely, (I) those dealing with mine equipment or structures, and (2) those dealing with underground layout of mine workings. It seemed reasonable to label the first type of course "mining design" and the second type "mine design." Some such distinction must have been in the minds of mining educators, for we find both names (i.e., mine design and mining design) used to designate the design courses included in the various mining curricula Unhappily, the name and the apparent content of such courses do not, in all instances, conform to the classification made here, although in most instances such conformation does obtain (Table I). It is possible that in the exceptional case the method of teaching a design course, and consequently the content of it, may have been changed at some time without change in the name of the course. Apparently only 3 of the 15 schools made an effort to cover both types of design in their curricula (Table I). Two other schools did not list or describe any course of study that could with certainty be taken as a design course. Of the remaining 10 schools, 9 gave a mining-design type of course and one gave a strictly mine-design type. Obviously, the preponderance of design courses afforded are of the mining-design type. Why? To answer this question, it is necessary to make a study of the prerequisites for the two types of design courses taught. In all schools the design courses were taught in the senior year; in eight, design was taught throughout both semesters; in two, it was taught during the first semester only; and in three it was taught during the second semester only. Consequently, excepting the last three cases noted, it is obvious that all prerequisites for a design course should be completed by the end of the junior year PREREQUISITES What are the probable prerequisites for the different kinds of design courses as they appear to be taught? Let us take first the case of the mine-design type of course, having to do with layout of underground workings. Here it would seem that logical

Jan 1, 1943

By J. W. Stewart

The aim of this paper is to point out the various ways in which design is taught in standard four-year mining engineering curricula in American colleges and universities; to discuss the reasons apparently justifying the great diversity of procedure that exists along this line; and to indicate possible solutions to the difficulties now attending the teaching of design. A study was made of typical four-year mining engineering curricula in 15 colleges and universities of the United States (Table I). Great diversity in content of the various design courses, if taught as described, became apparent immediately. It appeared that it might be both interesting and instructive if the cause for this colorful variety could be found. Was the cause local mining conditions, departmental individuality, or actual necessity? Study of the school catalogues revealed that the various design courses could be classified into two fairly distinct types; namely, (I) those dealing with mine equipment or structures, and (2) those dealing with underground layout of mine workings. It seemed reasonable to label the first type of course "mining design" and the second type "mine design." Some such distinction must have been in the minds of mining educators, for we find both names (i.e., mine design and mining design) used to designate the design courses included in the various mining curricula Unhappily, the name and the apparent content of such courses do not, in all instances, conform to the classification made here, although in most instances such conformation does obtain (Table I). It is possible that in the exceptional case the method of teaching a design course, and consequently the content of it, may have been changed at some time without change in the name of the course. Apparently only 3 of the 15 schools made an effort to cover both types of design in their curricula (Table I). Two other schools did not list or describe any course of study that could with certainty be taken as a design course. Of the remaining 10 schools, 9 gave a mining-design type of course and one gave a strictly mine-design type. Obviously, the preponderance of design courses afforded are of the mining-design type. Why? To answer this question, it is necessary to make a study of the prerequisites for the two types of design courses taught. In all schools the design courses were taught in the senior year; in eight, design was taught throughout both semesters; in two, it was taught during the first semester only; and in three it was taught during the second semester only. Consequently, excepting the last three cases noted, it is obvious that all prerequisites for a design course should be completed by the end of the junior year PREREQUISITES What are the probable prerequisites for the different kinds of design courses as they appear to be taught? Let us take first the case of the mine-design type of course, having to do with layout of underground workings. Here it would seem that logical

Jan 1, 1943

By E. H. Edwards, J. Washburn

Zinc crystals were deformed in simple shear and it was found that anisotropic strain hardening occurred in which the inactive slip systems were hardened more than the active system. The formation of dislocation barriers by dislocation interaction was discussed as a possible explanation of the hardening of the latent systems. STRAIN hardening which accompanies slip in a metal crystal is not limited to the slip systems actively contributing to the plastic strain. There is also a strengthening of the latent slip systems which are crystallographically equivalent to the active system. In the case of aluminum deformed in tension, Taylor and Elam1 found that plastic flow on one set of octahedral planes caused either the same or a slightly greater hardening on an inactive set. Similar results have been obtained for crystals of a brass2 and of Cu-A1 solid solutions.3 Experiments by Rohm and Kochendorfer4 indicated that the hardening of the active system exceeded the hardening of any latent system for aluminum crystals deformed in shear. On the other hand, strain hardening in zinc and cadmium crystals tested in simple shear at —196°C was recently found to be greater in the latent than in the active slip direction." When the strain direction was shifted during testing to a direction 60" from the original, a higher stress was required for glide to continue than would have been needed for flow to proceed in the original direction. The relation between the hardening of active and latent systems must be complex, depending upon the relative orientations of the systems and upon the experimental techniques used to deform the crystal. A detailed knowledge of the hardening produced in latent systems would be valuable in choosing between possible dislocation models of the strain-hardening process. The experimental data now available are incomplete and even contradictory. The present study was undertaken to provide quantitative information regarding the relative amount of hardening of active and latent systems for a particularly simple case. Zinc crystals were deformed in simple shear along one of the three crystallographically equivalent directions [250], [1210], and [1120] in the slip plane, and the relative hardening produced in each of these directions was compared. Experimental Procedure and Results The single crystals of 99.99 pct purity zinc used in this investigation were grown from the melt in the form of 1 in. diam spheres. Shear specimens were acid-machined from the crystals by a method which has been described previously. The gage section of the test specimen was a cylinder having a height of 1/8 in. and a cross-sectional area of approximately 1/3 sq in. All specimens were machined with the axis of this cylindrical gage section aligned with the [0001] axis of the crystal. An innovation in the design of the shearing apparatus for these tests was the provision for a rapid shift in the direction of the applied stress from one slip direction to any other slip direction lying in the same slip plane. Fig. 1 shows a section through the specimen and shearing apparatus, and Fig. 2 is a

Jan 1, 1955