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By L. D. Ricketts

Discussion of the paper of L. D. RICKETTS, presented at the San Francisco meeting, September, 1915, and printed in Bulletin No. 100, April, 1915, pp. 711 to 737. FREDERICK LAIST, Anaconda, Mont.-I am going to tell you of some of the results we have been getting in Anaconda during the past two or three months in a large plant which was finished in May. We commenced work in Anaconda a year and a half ago on the construction of a leaching plant which was to have a capacity of 2,000 tons per day. The plant was to treat tailings from the concentrator, containing about 12 1b. of copper to the ton. During the past year we changed our plans and decided to use the flotation process on the tailings from the concentrator, which contained no oxidized copper, and apply the leaching process only to tailings which had accumulated in a large dump below the works. This dump contains about 15,000,000 tons of tailings, and since some of the copper in it is oxidized, we felt that the application of the flotation process would result in the loss of too much of the oxidized copper, particularly as time went on. In starting up we had a number of difficulties to overcome, as is usually the case. They were not of a serious character. The results obtained, so far, have been decidedly encouraging. During July the plant treated a total of 50,000 tons of tailings, or an average of 1,610 tons per clay. The extraction was about 83 per cent., which, on material of the grade treated, meant a. tailing assaying under 0.1 per cent. copper. The acid consumption was about 65 lb. per ton, and the fuel percentage in. roasting was about 4 ¼ . We expect to cut the fuel percentage in the next month or two to about 3 per cent., the high percentage during July being clue to starting up and shutting clown furnaces. We find that iron builds up in the solution to a marked degree. This is not a serious platter with us, because we have cheap sulphuric acid and can reject solution whenever it gets too foul. The extraction of silver has been remarkably good in the large plant. It has averaged better than 75 per cent. It seems that so long as we maintain salt in the solution to a percentage of 10 per cent., the extraction is good. We allowed the salt to fall off in order to find how low a percentage we could use. At about 7 per cent. the silver extraction fell to 65 per cent. This was to be expected, because silver chloride is soluble in strong brine, but not in weak brine.

Jan 12, 1915

By T. G. Richardson, F. M. Perkins

In the recent paper of Richardson and Perkins entitled "A Laboratory Investigation of the Effect of Rate on Recovery of Oil by Water Flooding,"' the authors found very little appzrent effect on oil recovery of having free gas saturation present prior to water flooding in unconsolidated sands. We agree that the effect in this particular system was small but do not feel that the data presented should be regarded as disproving work of others which has shown an appreciable effect. The authors do not make such a claim, but neither do they advance an explanation of the difference. In our experience the following factors must be carefully considered when studying the relation between residual oil saturation after water flooding and initial free gas saturation: (1) the magnitude of the inherent residual oil saturation, i.e., the residual oil saturation with no free gas; (2) the increase in oil-water viscosity ratio with pressure lowering if the gas saturation is obtained by solution gas drive; and (3) the oil shrinkage which occurs with pressure lowering and gas evolution. The system studied by Richardson and Perkins gave residual oil saturations as low as 20 per cent without free gas present, and one should perhaps not expect much further lowering. As an illustration of the magnitude of the effect when the residual oil saturation is inherently higher we submit the accompanying figure. These data were obtained on an unconsolidated sand under elevated pressure in a system similar to the one described by Richardson and Perkins. Gas saturation was established by gas drive before water flooding. The viscosity ratio was 600:1 under the conditions of the displacement. Here the gas was extremely effective in reducing residual oil saturation. This fact was also indicated by Kyte, et al.2 Their plots of residual oil saturation vs initial gas saturation show trends of greater free gas effect with higher oil viscosities. The pressure-dependent effects were not discussed by Richardson and Perkins. They should be separated from the free gas effect if the objective of the study is a correlation of residual oil saturation vs initial free gas saturation. The increase in oil viscosity when gas is released from solution tends to increase residual oil saturation. This effect is rather small in the viscosity range of kerosene. A Buckley-Leverett calculation, assuming an increase in viscosity ratio from 1.2 to 1.8, indicates an increase in residual oil saturation of about 1 per cent of pore volume. Thus, one would expect this system, if operated at constant viscosity ratio, to show a slightly greater free gas effect. As Dyes- as shown, oil shrinkage can offset the beneficial effect of free gas on waterflood oil recovery, if the gas saturation is established by depletion. Since

Jan 1, 1958

By M. W. Dumais, E. P. Abrahamson

In a paper by Abrahamson and Alexander concerning a series of correlations between electronic structure and property changes, it was hypothesized that each solute atom in a dilute solution had a characteristic volume of solvent atoms over which some form of electronic interaction occurred. From this description it is possible to picture the solute atoms as occurring in an ordered array for the most efficient arrangement. A recent review article2 has shown that some form of anomaly exists for a whole series of properties when dilute additions of tungsten are made to iron, of. Fig. 1. Any mechanism to fit one property must also be amenable to mechanisms for the other properties. The possibility of some structural change in this region appears to offer the best hope. The system chosen for investigation was the iron tungsten system. Zone-refined iron with zone-leveled tungsten additions were supplied by Materials Research Corp. as 3/8-in.-diam bars. Transmission electron microscopy was used to study the structure. One-quarter inch specimens of each alloy were cold-rolled to 10-mil sheets, cleaned, punched to electron-microscope specimen-holder size, and annealed in vacuum for 2 hr at 800°C and 2 hr at 700°C followed by a furnace cool. The specimens were attached to a platinum wire and the specimen edge and wire were painted prior to thinning in a solution of 10 pct perchloric acid in glacial acetic acid. It was believed that if ordering were present due to electronic interactions the polishing procedure chosen would provide a simultaneous combination of chemical attack and electropolishing to exhibit the ordered structure. The chemical attack would be expected to penetrate those areas equidistant from the tungsten atoms, while the electropolishing would serve to "plane off" the volumes where the chemical attack had taken place. If one of the ordered tungsten planes were parallel to the specimen face at the edge of the thinned hole, a plate or micalike structure would be expected. A typical result of this polishing is shown in Fig. 2. Here a series of plates can be seen lying one upon the other. In several other specimens the plates parallel to the electron beam have been observed, behaving like slices of bread in a loaf. These edge views coupled with moire patterns indicate that the minimum plate thickness is 37 to 42A. This is equivalent to a concentration of 455 at. ppm of W if a simple cubic superlat-tice exists, or one tungsten atom every twelve iron atoms on the ordered plane. It was further noted that the base iron exhibited no signs of platelike structure. As the concentrations increased above 100 at. ppm W the amount of plate material increased. Among the specimens investigated was that shown

Jan 1, 1967

By AIME AIME

THE value to the engineering profession of a liaison between the engineering societies of Russia and America, through Engineering Council, was the subject of a meeting in the Engineering Societies Building attended by over 500 persons. In introducing the subject, Mr. N. A. Stephanoff, President of the Russian Society of America, said: In Russia, engineers were divided into two classes: those who had graduated from the high technical schools and the practical engineers who had graduated from special technical schools. These technical schools were divided into three groups: The first corresponded to the German polytechnical schools with many departments, mechanical, chemical, metallurgical, mining, etc. The second group corresponded to the French special schools of the "Écoles des Ponts et Chaussées." "École des Mines." The third group was formed by the Military and Naval Academies of Engineers. In 1910, Russia's high technical schools had about 45,000 students, whose training covered a period of not less than five years, and who enjoyed all opportunities afforded by laboratories in no way inferior to those of Germany.

Jan 1, 1920

Beverley S. Randolph, Frostburg, Md. (communication to the Secretary): It has always appeared to me that each coalseam has its peculiar character or habit, due to the conditions of its formation, by virtue of which it is either persistent or variable in its section over extended areas. One seam will hold its thickness, chemical character, number and position of partings, beds of slate, etc., over a large area, while another will be found to vary in some of these characteristics every few feet. As the position of the outcrop is an accident of the topography, depending on folding and erosion which have taken place since the bed was formed, no one opening in the outcrop, or, in fact, anywhere else, can supply reliable evidence as to the general character of the seam. To determine the character of an untried seam, a number of sections are necessary from widely separated points, in order to show such variations as may exist. Should material variations be developed, more numerous sections are necessary, in

Jan 1, 1901

By C. B. Alcock, M. G. Hocking

The kinetics of the growth of sulfate layers on blocks of Cu20 has been studied between 688" and 800°C. At 788c the over-all weight increases followed the parabolic rate law, with k = 216 30 sq mg per cm4 min, using a 1:1 entering gas mixture of SO2:02. At 757 after an initial linear period the parabolic rate law was followed, with k = 57.8 10 sq mg per cm4 min. The gas mixture required a platinum catalyst to produce the maximum SOs pressure. The sulfation rate at 757' and 788c was high until all the CUZO had changed into a core of CuO, when it became very much lower. At 757°C marker experiments showed that the sulfates (CuO. CuS04 and CuSO4) grow outwards from the oxide surface, but CuO. CuS04 mixed with CuO was found beneath the markers. At 688 markers were found at the CuO. CuS04/CuS04 interface. Visual observations at 757 showed a liquid eutectic moving beneath the sulfate surface. causing very rapid sulfation and extruding to solidify as thick 'needles" up to 8 mm long. Marker experiments have shown conclusi.cely that CuO grows on Cu20 in air by the outward migration of copper. ThermODYNAMIC measurements on the sulfate and basic sulfate of copper, reported recently,' are followed here by measurements of the rates of formation of these sulfates on cuprous oxide, in order to provide a background for the understanding of roasting processes. peretti2 and McCabe and Morgan3 have shown that the phase Cu20 lies next to Cu2S when the sulfide is roasted under conditions where sulfates will be formed. Since this would present too complex a system for kinetic study, the present work4 has been based on the kinetics of sulfation of the oxide phase. The results of a study of the kinetics and mechanism of the sulfation of cobaltous oxide have recently been reported.4,5 Results on the sulfation of cuprous oxide have also appeared,6 but are at variance with those to be reported here. This seems to be because the previous workers6 did not obtain constant SO3 pressures from the SO2/O2 sulfating gas mixtures used, as will be discussed later. Wadsworth, Leiter, Porter, and Lewis found that the sulfates produced when SO2/O2 mixtures are passed over Cu20 at red heats are CuS04 and the basic sulfate CuO.CuSO4. When the decomposition of CuS04 was followed' by differential thermal analysis, a stage corresponding to CuO .CuS04 was reached before decomposition into the oxide occurred. APPARATUS The vertical furnace used for quantitative studies was a conventional resistance-heated and propor- tionately controlled furnace with an even zone (1 deg) which was 4 cm long. The gas mixtures of SO2 and 02 were made by mixing measured flows from capillary flowmeters and drying over phosphorous pentoxide before passing them into the Pyrex top-piece of the furnace assembly. A mullite tube of bore 2% cm was used as reaction vessel and at the bottom of this tube was a trap for SO3, which condensed as a colorless liquid. The residual gas was led into a fume cupboard for ventilation to the atmosphere. The furnace used for visual observations of needle growth and other phenomena consisted of a transparent silica reaction tube of bore 3 cm, having an optically flat silica window sealed into its wall. The reaction tube was clamped vertically, inside a mullite tube of bore 4 cm and length 42 cm which was heated by Kanthal windings. The window in the silica reaction tube was arranged opposite a hole 3 cm wide and 2 cm tall which had been cut in the wall of the mullite winding tube 19 cm from its top end. A binocular microscope was used to look through the window, illumination being provided by a focusing microscope-lamp offset sideways and downwards. The oxide block to be sulfated was suspended from the removable Pyrex top-piece to the reaction tube, by means of which it was inserted at the start of the experiment, and through which entered the S02/02 gas mixture. The variation of the temperature inside the reaction tube with horizontal and vertical displacement from the window was investigated, and, while it can be said that the temperature was constant 1 deg, its value at a given position was known only to 12 deg. In both furnaces, the oxide block to be sulfated was suspended from a small silica hook immediately downstream from a platinum thimble used as catalyst, which was held on a long silica rod from a Pyrex spring attached to the removable Pyrex top-piece of the furnace. The spring was only included in the quantitative sulfating furnace; its sensitivity was 1.4 cm per g and it was found to be free from creep in a 16-hr test when carrying the working load. The extensions were followed by a cathetometer which could be read to 0.001 cm, corresponding to i0.7 mg. Extensions of the spring were measured on adding weights between 5 and 500 mg to the working load (thimble + oxide block), and Hooke's law was closely obeyed. SAMPLES Cuprous oxide blocks were prepared by oxidizing Johnson Matthey "Specpure" copper sheet of 1 mm thickness (impurities: iron at 3 ppm, silver at 2 ppm, lead, nickel, sodium, and silicon each at 1 ppm, calcium, chromium, magnesium, and manganese each at less than 1 ppm) for 6 days in air at 1000°C in a re-crystallized alumina boat. It has been reported7 that when Cu20 is prepared by heating copper sheet for 1 day the central plane of the blocks produced consists

Jan 1, 1967

By J. Holms Pollok

The determination of specific gravity dates from such antiquity, and the various published methods of determining it are so numerous, that one may well be skeptical as to the value of a new means of obtaining so well-known a quantity. I make no claim to any great novelty for the little device here described, the principles, though not the convenient details, of which are more or less embodied in the publications of Mr.

Jan 1, 1900

By Charles L. Elliot

Data on mining applications of geophysical activity in the Free World in 1964 have been made available to SME again this year by the Society of Exploration Geophysicists. Worldwide data were collected as part of an annual service to the mining industry by the Committee for Geophysical Activity of SEG. Data are taken from 245 voluntary responses (53%) to questionnaires circulated to 463 company, government and university organizations engaged in mining geophysical operations and research all over the world. WORLD ACTIVITY Worldwide manpower utilization totalled 9323 professional man-months and $14.5 million was reported spent in mining geophysical activity in 1964. This is up from 9078 man-months and $12.6 million in 1963 and 8065 man-months and $12.8 million in 1962. Worldwide geophysical activity in terms of manpower utilization and expenditures is presented in the accompanying table.

Jan 9, 1965

By George T. Hansen

WHY try to find oil in Utah? Why try to find oil anywhere? Isn't there too much oil already? Answers to these questions involve general oil conditions but are pertinent to my subject. In the first place oil produced in Utah up to the total amount of local consumption would not be subject to nor concerned with the national oil situation. An oil field in this State capable of producing up to 15,000 bbl. per day would have a large value and prompt realization. In the sec¬ond place, there is not too much oil nationally although the markets have been upset temporarily from time to time. Petroleum is so necessary and is in such general demand that an oil field anywhere, anytime, is a valuable and live asset. The oil business in general shows the best condition of any major industry. It has never been hit as hard as most industries and 1932 was a large improvement over its low spot of 1931. It can be and probably will be the one to lead the country back into business stability. Consumption of its products has been reduced less than that of any other important commodity. There are good and valid reasons why it should have been making a normal profit continuously. It has the oil and the processes and the facilities and the policies and the consumption of its products. There is only one reason why it has not been profitable recently and that is the lack of intelligence of from five to ten per cent of the producers. An op¬erator lacks intelligence when he cannot see that it is better for him to sell one barrel of oil at $1 than two or three barrels at 25 or 35c. per bbl.

Jan 1, 1933

By P. E. Phillips

INTRODUCTION Rocky Mountain Energy is the mining subsidiary of the Union Pacific Corporation, and has been active m uranium exploration since 1966. Since 1970, RME's uranium activities have been funded 50% by Mono Power, the fuels supply division of Southern California Edision. RME and Mono recognized the need for development of new methods for recovering low grade uranium deposits, and contacted Halliburton Services in regard to in situ leaching, because of Halliburton oil industry experience. As a result, a joint venture between the three parties was formed in 1974. BEAR CREEK The first ISL test was at the Bear Creek deposit in the Powder River Basin of Wyoming, about 60 miles north of Douglas. The mineralized sand is the tertiary Wasatch formation, which is an arkosic sandstone. The sand typically contains about 10% clay. The predominant clay being montmorillonite with some kaolin and illite. The roll front type trends occur along the flanks of old stream channels. This deposit was being considered for exploitation as an open pit mine. Routine amenability testing indicated it was quite amenable to a conventional acid leach, consuming about 50 lbs. of sulfuric acid per ton of ore in an agitation leach, while recovering more than 95% of the uranium. Hydrology testing indicated a permeability of about 1 darcy. The groundwater has a pH of about 8. 0 and TDS of about 1200. Test Facility The Bear Creek test was a summer-only operation, with no effort towards weather-proofing. Uranium was removed from the recovered leach solution by fixed bed ion-exchange columns. Loaded resin was eluted with strong sulfuric acid. The recovery plant was designed for simplicity of operation, with little concern for the grade or form of the yellowcake product. The plant was constructed of PVC piping and valves, fiberglass reinforced tanks, and stainless steel pumps. All waste streams were directed toward a lined evaporation pond. Wellfield The test pattern was a 30 foot radius 5 spot, with wells fully penetrating the 30 foot ore sand to a total depth of about 165 feet. The injection wells were three-inch PVC with slotted casing, while the producer was eight-inch I. D. , with a stainless steel screen. The eight-inch well was necessary in order to accommodate a six-inch stainless steel pump. Wells were cemented using cement baskets, at the top of the sand, to contain a latex acid resistant cement. Leach Conditions The lixiviant generally contained from five to seven gpl sulfuric acid, and about 0. 5 gpl hydrogen peroxide. The pH was generally 1.4 and EMF was usually -550 millivolts. Injection rates were rather variable from well to well, with a total injection rate between 12 and 25 GPM. Production rate was set at 25 GPM, since the production pump could not be throttled more than that. Approximately two pore volumes of solution were injected during the three-month test. Leach Results Injectivity was quite variable, but was generally rather poor, because of poor completion techniques. The problem stemmed from injecting before the injection wells had been completely cleaned of drilling mud. Pregnant solutions averaged about 50 ppm U308, with groundwater dilution varying from 10 to 50%, depending on the injection rate. Injectivity did decline with time, probably as a result of contamination of the well faces. A total of 1000 lbs U308 had been recovered when the test was shut down. This probably represented about 10% of the mineral under leach.

Jan 1, 1979

By C. H. Samans, G. F. Tisinai, J. K. Stanley

The addition of nitrogen (0.10 to 0.20 pct) to Fe-Cr-Ni alloys of simulated commercial purity results in a real displacement of the u phase boundaries to higher chromium contents. The effect is small for the (Y + s)? boundary, but is pronounced for the (y + a +s)/(y + a) boundary. Although there is an indication of an exceptionally large shift of the n boundaries to higher chromium contents, especially in steels with nitrogen over 0.2 pct, the major portion of this apparent shift results from the fact that carbide and nitride precipitation cause "chromium impoverishment" of the matrices. The effect of combined additions of nitrogen and silicon to the Fe-Cr-Ni phase diagram is demonstrated also. Nitrogen can nullify the effect of about 1 pct Si in shifting the (y + o)/? phase boundary to lower values of chromium at all nickel levels from 8 to 20 pct. NItrogen can nullify this U-forming effect of about 2 pct Si at the 8 pct Ni level, but not at the 20 pct Ni level. The alloys studied were in both the cast and the wrought conditions. There are indications that the u phase forms more slowly in the cast alloys than in the wrought alloys if both are in the completely austenitic state. The presence of 6 ferrite in the cast alloys accelerates the formation of U. Cold working increases the rate of o formation in both cast and wrought alloys. THE major improvement in Fe-Cr-Ni austenitic alloys in recent years has been in the addition or removal of minor alloying elements to facilitate better control of corrosion resistance, sensitization, and heat resistance. One shortcoming of the austenitic Fe-Cr-Ni alloys, which never has been completely circumvented, is their propensity toward u formation. In the AISI-type 310 (25 pct Cr-20 pct Ni) and type 309 (25 pct Cr-12 pct Ni) steels, sufficient amounts of u phase can form, if service or treatment is in a suitable temperature range, to cause severe embrittlement. Also, there is a growing conviction that this phase may be contributory to some unexpected decreases in the corrosion resistance of certain of the 18 pct Cr-8 pct Ni-type steels. The present paper discusses the effect of nitrogen additions on the location of the (r+u)/d and the (y+a+u)/(y+a) phase boundaries in the ternary Fe-Cr-Ni system, for cast and wrought alloys of simulated commercial purity, and in similar alloys containing up to about 2.5 pct Si. The objective is to define compositional limits for alloys which will not be susceptible to u formation when used near 1200°F (650°C). An excellent review of the early studies of the u phase in the Fe-Cr-Ni system has been compiled by Foley.1 Rees, Burns, and Cook2 have determined a high purity phase diagram for the ternary system, whereas Nicholson, Samans, and Shortsleeve3 are- stricted themselves to a portion of the simulated commercial-purity phase diagram. Both groups of investigators show almost an identical position for the commercially significant (y+u)/y phase boundary. Further comparison of the work of the two groups indicates that, below the 8 pct Ni level, the commercial alloys have a decidedly greater propensity toward u formation than the high purity alloys. The two groups of workers agreed that both the AISI-type 310 (25 pct Cr-20 pct Ni) and the type 309 (25 pct Cr-12 pct Ni) steels are well within the (y+~) region and that the 18 pct Cr-8 pct Ni-type alloys straddle the U-forming phase boundaries. Nicholson et al.3 showed, in addition, that these boundaries shift toward lower chromium contents if greater than nominal amounts of silicon or molybdenum are added. The effect of nitrogen on the location of the s phase boundaries in the Fe-Cr-Ni system has not been known with any certainty. In 1942, an approach to this problem was made by Krainer and Leoville-Nowak,' but at that time they apparently were unaware of the slow rate of s formation in strain-free samples and aged their samples for insufficient times, e.g., 100 hr at 650°C (1200°F) and 800°C (1470°F). For this reason, it would be expected that their (y+ u) /y boundary would be shifted toward lower chromium contents (restricted ?-field) when equilibrium conditions were approximated more closely. Procedure for Studying the Alloys The alloys used were prepared in the following way: Heats of 200 lb each were melted in an induction furnace. A 5 lb portion of each heat was poured into a ladle containing an aluminum slug for de-

Jan 1, 1955

By J. E. Flinn, S. A. Duran

The steady-state creep behavior of poly crystalline cad mi inn was studied over a temperature range of (1.56 to 0.94 Tm. Two distinct mechanisms were found to occur over this temperature range. They were described by: where and represerqt the minimum strain rates corresponding to the low- and high-temperature regions, respectirely. The two regions of constant acti11ation energy were connected by a transition region where the strain rate was controlled by both mechanisms acting in parallel. At temperatures below a transition temperature of about 0.7 Tm the agreement between the activation energy value for creep and that for self-diffiision suggests a rate-controlling mechanism of dislocation climb. For cadwzium, steady-state creep at temperatures above 0. 7 Tm appears to be controlled by another mechanism, perhaps involving the behavior of dislocation jogs. FRENKEL et al.1 studied the high-temperature creep of polycrystalline cadmium and reported an activation energy of 21 kcal per mole for the 0.5 Tm < T < 0.8 Tm range. Based on observations of creep rate at only two temperatures, a value of 22.1 kcal per mole was determined by Medbury. These two investigations were for the purpose of showing agreement between the activation energy for creep and that for self-diffusion, reported3 as 18.2 and 19.1 kcal per mole, respectively, for diffusion parallel and perpendicular to the hexagonal axis. Gilman4 investigated prismatic glide in single crystals of cadmium over a higher-temperature range of 0.72 to 0.93 Tm, and found an activation energy of 29 kcal per mole. He also reported5 an activation energy higher than that of self-diffusion for prismatic glide in zinc single crystals deformed at temperatures near the melting point. This value was in good agreement with those found for an equivalent temperature range by Flinn and Munson6 and by Tegart and sherby7 for polycrystalline zinc. These two independent studies also disclosed at lower temperatures another value of activation energy near that for self-diffusion. It would be expected from the creep results on zinc and single-crystal cadmium that creep studies on polycrystalline cadmium, extended to temperatures near the melting point, might yield an activation-energy value higher than the 22 kcal per mole value found in earlier studies. The purpose of this paper is to report the steady-creep behavior of polycrystalline cadmium over a temperature range of approximately 0.5 to 0.9 Tm EXPERIMENTAL METHOD The cadmium used in this study was obtained in the form of as-cast rods, 0.5 in. diam, through the courtesy of the Bunker Hill Mining Co. The material was of 99.995 pct purity, as determined by spectro-chemical analysis. The creep specimens, which were 0.250 in. diam by 0.400 in. long and annealed at 300°C for 45 min to produce a stable average grain diameter 0.25 mm, were tested in compression using an apparatus similar to that described by Sherby.8 The specimen temperature was controlled to within ±0.5°C with the help of appropriate constant-temperature baths. The applied stress was maintained within 1.0 pct of the desired value by the additions of lead shot at fixed strain increments. No barreling was observed over the strains encountered during testing. Isothermal creep tests9 were used in the study with only a few differential temperature tests10 run for comparison purposes. Steady-state creep data were obtained over a temperature range of 60 to 287°C (0.56 to 0.94 Tm) at five stress levels ranging from 28.1 to 140.6 kg per sq cm. RESULTS The minimum or steady-state creep rate may be described by an equation of the following form:" where i is the minimum strain rate, S is the structure factor, F is a stress function, Qc is the energy of activation, T is the absolute temperature, and R is the gas constant. The minimum strain rates obtained in this study for cadmium were recorded on a semilogarithm plot as a function of the reciprocal absolute temperatures for the various stress levels, as shown in Fig. 1. This figure shows a characteristic transitional behavior" with a parallel interaction of two mechanisms. It is obvious that the activation energies corresponding to the individual processes are insensitive to stress because the curves are parallel. The discrete activation-energies values for the low- and high-temperature regions for the various stress levels are reported in Table I, and were determined by the least-mean-square method. For the low-temperature region, an activation energy of 20.7 ± 0.6 kcal per mole was obtained, and for the

Jan 1, 1967

By David Turnbull

IN isothermal recrystallization processes, new crystals generally grow into the matrix until they impinge upon other new crystals or an external surface, at constant linear rates G. Before impingement the perceptible course of growth can be described by the equation: 1 = G(t-7) C1I where, G = dl/dt, 1 is a crystal dimension measured in a constant direction, t is the time, and 7, the nucleation period, is a positive intercept on the time axis. Fig. 1 is a schematic representation of I as a function of time for a recrystallizing grain. G is dependent upon temperature, driving energy (strain or surface energy), relative grain and boundary orientations, but is generally independent of time. The frequency of nucleation, fi, (time" volume") can be defined by the equation: N = 1/fV [2] where ? is the mean nucleation period and V is the volume of the specimen that has not recrystallized. The kinetics of primary and secondary recrystallization generally can be described satisfactorily in terms of the parameters N and G only.&apos;-" After recrystallization is complete the average grain size 7 increases with time by "normal grain growth;" didt, the average rate of grain growth, is strongly time dependent and has not yet been precisely related to G for the motion of the individual grain boundaries constituting the system. It has been suggested4* " that the elementary act in grain boundary migration is closely related to the elementary act in grain boundary self-diffusion. Although the distance of atom movement in the two processes may be somewhat different, there is reason to expect that the activated states may be very similar, so that the free energy of activation for grain boundary migration should be of the same order of magnitude as for grain boundary self-diffusion. Therefore, it is desirable to develop a satisfactory basis for comparing data on self-diffusion and grain boundary migration and to make such comparisons where possible. Theory The formal theory of grain boundary migration rates is analogous to the theory for the rate of growth of crystals into supercooled liquids reviewed elsewhere 6-8. Boreliuss has shown that the latter theory describes, within the theoretical uncertainty, the growth of selenium crystals into supercooled liquid selenium. Motto and more recently Smolu-chowski" have derived expressions for the rate of boundary migration in recrystallization. The treatment to be presented is similar to Mott&apos;s excepting that the formalism of the absolute reaction rate theory will be used. The atomic mobility, M, in grain boundary migration is defined by: G = -M6p/6x where p is the chemical potential per atom and x is the coordinate measured in the direction of grain boundary movement. Let AF be the free energy difference per gram atom on the two sides of the boundary and k the thickness of the boundary. For RT>>AF the potential gradient across the boundary (6p/6x) is essentially linear and it follows that: SF/8x = - aF/N\ [4] where N is Avogadro&apos;s number. According to the Nernst-Einstein equation, M is related to a diffusion coefficient, Do, for matter transport in grain boundary migration by the equation: M = Da/kT [5] Substituting eqs 4 and 5 into eq 3 gives the basic relation between Do and G: G = DoaF/\RT [6] Do values may be calculated from experimental values of G from eq 6 and directly compared with the coefficient of self-diffusion within the crystal, DL, or the grain boundary self-diffusion coefficient D,. However, a more convenient, though equivalent, basis for comparing atomic mobility in grain boundary migration and self-diffusion is through the constants of the absolute reaction rate theory. According to this theory diffusion coefficients may be written:" D = k2(kT/h) exp [-AF,/RT] 171 aFa, the free energy of activation, is related to the measured energy of activation, Q, by the equation: AFA = Q - T aSx - RT [8] where aSa is the entropy of activation. Substituting eqs 8 and 7 into eq 6 gives: G = ek(kT/h) (aF/RT) exp [(AS,,)C/R] exp C-Qc/RTI C91 where the subscript G refers to boundary migration. The relationship between the driving free energy and the free energy of activation in boundary migration is indicated schematically in Fig. 2. Experience indicates that the variation of G with temperature can be described by: G= Go exp [- Qc/RT] [10] where Go and Qc are generally temperature independent over wide ranges of temperature. Comparison of eq 9 with eq 10 gives:

Jan 1, 1952

By J. Alfred Berger, O. M. Katz

Selected samples of hydrided Zr-Hf alloys were rapidly quenched to voom temperature and exrtrnined metallographically, by X-ray diffraction, and through micro hardness studies to confirm high-temperutuve data Confirming experiments sllowed that there were five phases in this Lernary system: 1) hextrgonal with lattice parameters similar to that of the initia1 Zr-Hf alloy but slightly enlarged due to dissolved hydrogen; 2) fee with properties of a brittle, intermediate, hydride compound; 3) fct with c/a crvoltnd 1.07 and which appeared as a neetilelike precipitale; 4) hexagonal, designated ?, with c/a ratio of 2.37; and 5) orthorhombic, designated X, with a = 4.67, b = 4.49, and c = 5.093 and whose tnicro-st?ruct~ival nppetrl-nnce depcncled o/i, heat lvecrt~r~ent. The tetragonrrl phase never crppeal-erl witkorct the cubic hydricle. Abpecrrtrnce of 0 and A also tlependet on the hafnium content of the zirconium. A previous paper&apos; on the Zr-Hf-H system described the thermochemical data obtained with a high-vacuum, high-sensitivity mirrogravimetric apparatus. This data presented a fairly complete picture of the phase relationships at elevated temperatures. However, it could not establish the actual crystal structures, lattice parameters, or metallographic disposition of the hydride phases. The present complementary study utilizes X-ray powder patterns along with light and electron microscopy to characterize completely the five hydrided phases found in Zr-Hf-H alloys quenched to room temperature. Crystallographic features of the zr-Hf,2,4 zr-H,5-7 and Hf-H8 systems have been summarized in Table I. Designations of a, ß, and ? were retained in the Zr-Hf-H system for the phase regions through which the pressure-composition isotherms always sloped. However, it was not firmly agreed that these were single-phase regions.&apos; In fact, the region designated y always contained a cubic as well as a tetragonal phase after quenching to -196°C. MATERIALS Preparation of the high-purity Zr-Hf alloys has been described.&apos; The four zirconium alloys which were hydrided contained 37 wt pct Hf (23 at. pct), 51 wt pct Hf (37 at. pct), 73 wt pct Hf (58 at. pct), and 91 wt pct Hf (82 at. pct), respectively. These were designated B-2, B-4, B-6, and B-8. Photomicrographs of the initial alloys showed the material to be quite clean as would be expected from the precautions exercised in producing them. However, there were a number of annealing twins but no other subgrain structure. In addition to the four original alloys, fifteen hydrided samples were observed at room temperature. Hydrogen compositions are given at the top of Tables I1 to V. APPARATUS The phases present at elevated temperatures were studied by quenching hydrided samples to room temperature by two different methods, both under vacuum: 1) fast cooling of the sample tubes of the microgravimetric apparatus1&apos;9 with flowing air and 2) rapid quenching into liquid nitrogen. The cooling rate for 1) was 750° to 250°C in 30 sec. Since the microbalance chamber was not designed to permit very rapid cooling of a hydride sample, all liquid-nitrogen quenching was done in an auxiliary experiment. The auxiliary quenching apparatus consisted of a small-bore, high-temperature furnace, a sealed SiO2 tube containing the sample, and a dewar quenching flask filled with liquid nitrogen. The hydrided sample, previously quenched in the microgravimetric reaction chamber, was placed in a platinum boat in a vacuum-degassed SiO2 tube. A zirconium wire getter and degassed SiO2 rod, to reduce the internal volume, were also in the tube. After sealing the tube under vacuum the zirconium getter was heated to absorb the last traces of gas. Only the sample was heated at the reaction temperature for the desired length of time, and then the tube dropped through the opposite end of the furnace into the dewar. A quenching rate of 200" to 400° C per sec was estimated. Analyses of samples after the auxiliary experiment also showed practically no increase in oxygen or nitrogen content from heating in the SiO2 tube. All of the samples were examined at room temperature by the X-ray powder method. The majority of the powder patterns were obtained with double nickel-filtered CuKa radiation after 8- and 16-hr exposures in an 11.48-cm-diam camera. Cobalt and chromium radiation were also used to spread out the high d value end of the Pattern. Such patterns readily identified the minor phases. NO oxide or nitride lines were found. Where sharp back-reflection lines existed it was possible to reduce the

Jan 1, 1965

R. Schuhmann, Jr. (Purdue University)— Fulton and Chipman&apos;s results on rate of silica reduction from slags are analogous in many was to the results of Parlee, Seagle, and Schuhmann10 on rate of alumina reduction from alumina crucibles. Both investigations have given comparably low rates of reduction and slow approaches to equilibrium. Accordingly, we may hypothesize that the rate-determining step is the same in both kinds of experiments; that is, oxygen diffusion across the stagnant boundary layer on the liquid-metal side of the interface between the liquid metal and the oxide phase (slag or solid oxide). I suggest that silica reduction involves the following consecutive steps: I) At the slag-metal interface: SiO2(slag) Si+ 20 II) Transport of oxygen from slag-metal to gas-metal interface: a) diffusion across liquid-metal boundary layer at slag-metal interface. b) convection within the body of liquid metal. c) diffusion across boundary layer at metal-gas interface. 111) At the metal-gas interface: C +O- CO (gas) Iv) At the graphite-metal interface: C (graphite) -C At steelmaking temperatures it is reasonable to assume that equilibrium is attained in all three chemical reactions (I, 111, and IV) right at the respective interfaces. Convection within the stirred liquid metal (step IIb) is also rapid. Transport of Si and C should be orders of magnitude easier than transport of 0, because of the relatively high concentrations of Si and C. Accordingly, we might expect the overall reaction rate to be determined by boundary-layer diffusion of oxygen, either IIa or IIc. Fulton and Chipman&apos;s demonstration that bubbling CO through the system had no major effect on reaction rate indicates that IIc is not the slowest step. Therefore, it becomes logical to estimate the maximum rate for step IIa and to compare this theoretical estimate with Fulton and Chipman&apos;s experimental data. If oxygen diffusion across the liquid metal boundary layer at the slag metal interface (step IIa) is rate-determining, In this equation, dn sio, /dt is the rate of silica reduction in moles per sec,A is the area of slag-metal interface in sq cm, Do is the diffusivity of oxygen in sq cm per sec, 6, is the boundary layer thickness in cm, c,* is the oxygen concentration right at the slag-metal interface in moles per cubic cm, and co is the oxygen concentration in the body of the liquid metal, also in moles per cubic cm. Equilibrium data" on the silicon deoxidation reaction in liquid iron and steel at 1600°C indicate that the oxygen contents of the liquid metal in Fulton and Chipman&apos;s experiments at 1600°C probably fell in the range of 0.5 x10-3 x10-3wt pct. That is, the maximum conceivable value of co*-co for the system under consideration was on the order of 10"5 mole oxygen per cubic cm. On the basis of previously published data,1O,11 it is estimated that Do/0 will fall somewhere in the range from 10-3 to 10-1 cm per sec. The surface area A in Fulton and Chipman&apos;s experiments was approximately 20 sq cm, and the weight of metal involved was about 500 grams. Combination of all these figures with the above rate equation leads to an estimate that the rate of silica reduction should fall within the range from 0.002 to 0.2 wt pct Si per hr. This estimate is consistent with the experimental data. For example, Fulton and Chipman&apos;s Fig. 2 shows a change of about 0.3 pct Si in 10 hr, corresponding to an average rate of 0.03 pct per hr. According to the proposed hypothesis, increasing the temperature will increase the reaction rate ill two ways: 1) by increasing oxygen diffusivity and 2) by increasing the oxygen concentration (oxygen solubility) in the liquid metal. The combination of these two effects accounts for the high value of the observed activation energy. Summarizing, I propose that the rate of silica reduction, like that of the carbon-oxygen reaction, is diffusion controlled and that low oxygen concentration in the liquid metal is the major factor accounting for the very low observed rates of silica reduction. John Chipman (author&apos;s reply)—The authors thank Professor Schuhmann for his interesting contribution. His proposed explanation may well prove to be the correct one. There is clearly a need for much further experimental work on this problem, and further research is in progress.

Jan 1, 1961

By Craig S. Hartley

Expressions are obtained for the energy changes associated with the reaction of (a& (111) slip dislocations on intersecting (110)planes in anisotropic bcc metals. An energy criterion for assessing the likelihood of dissociation of the products of such reactions is also presented. It is found that the "burrier reactions" which form a(100) dislocations at the intersection of two active {110) slip planes are more energetically favorable in metals which exhibit a high value of Zener&apos;s anisotropy factor, A, than those which have a low value. The results are presented in a form which permits the stacking fault energy to be obtained from a measurement of the separation between par-tials in a dissociated configuration. However, until accurate calculations or measurements of the stacking fault energies involved are available, it is not possible to assess the physical importance of dissociated dislocations. In a recent paper,&apos; the energy changes associated with several types of reactions between two slip dislocations, (a/2)(111){110), in bcc structures were calculated.* Isotropic elasticity and the approxima- tion v = -3- were employed. The purpose of this work is to present calculations of the energy changes for many of the same reactions using anisotropic elasticity. The problem of dissociation of a(100) and a(110) dislocations is also considered, and maximum fault energies for which dissociation will be energetically favorable are calculated for several bcc metals. Two general types of reactions are considered; those for which the reactant (a/2)(111) dislocations have long-range attractive forces and those for which the reverse is true. An example of the former is: (a/2)[lll] + (a/2)[lll]-a[l00] while the latter are typified by: (a/2)[lll] + (a/2)[111] -a[011] Only reactants lying in different slip planes are considered; therefore, the products must lie along (111) or (100) directions, which are the intersection of two {llO} planes. It will be assumed that the reactants and products are infinitely long parallel dislocations, since in this case the energy change associated with the reactions is a maximum.&apos; THEORY The self-energy per unit length of a straight mixed dislocation in an anisotropic medium can be written? where b is the Burgers vector, K is an appropriate combination of the single-crystal elastic constants, and R and ro are, respectively, outer and inner cut-off radii of the elastic solution. The energy given by Eq. [I] does not account for any variation of the core energy with orientation. This could be manifested by an orientation dependence of the core radius or, equivalently, the Peierls width, of the dislocation. However, the energy contribution due to this source is expected to be small, and current models of the dislocation core are not sufficiently accurate to justify such a refinement. It has already been shown that for the isotropic case the energy contributions due to nonzero tractions across the cores of the reactants and products exactly cancel one another in the reaction.&apos; Accordingly, it will be assumed that this contribution to the total energy change in the anisotropic case is small. In the subsequent discussion it is also assumed that the core radii of the reactant and product dislocation are the same and that, where stacking faults are formed, the faulted region is bounded by the centers of the partials. Consequently only changes in elastic energy due to the reactions will be considered. When the dislocation is parallel to either the (111) or the (100) directions, K may be written:375 K = (Ke sin2 a + Ks cos2 a) [2] where K, and Ks are the combination of elastic constants corresponding to an edge and screw dislocation lying along the same direction as the mixed dislocation, and a is the angle between the direction tangent to the dislocation line and the Burgers vector. Eq. [2] should not be confused with the isotropic approximation to the variation in energy with line Orientation.6 It should be noted that the essentially isotropic expression for K is a result of the characteristic symmetry of the (111) and (100) directions and is not, in general, valid for other dislocation directions in anisotropic cubic metals. The energy* change for a reaction in which the re- actant and product dislocations are parallel perfect dislocations can be written: where Ep and E, refer to the self-energies of the products and reactants, respectively. For dislocations parallel to (100) and (111) directions, Eq. [3] becomes:

Jan 1, 1969

By Robin O. Williams

Robin 0. Williams (Oak Ridge National Laboratory)— The authors have questioned the degree to which the coherency strains between the iron-rich and chromium-rich phases are isotropic as proposed in Ref. 5 on the basis of the difference between the elastic properties of the two phases. The relative magnitude of the stresses is determined by the moduli as shown by Eqs. [2], [3], and [4] of Ref. 34. However, the moduli of the two phases have no direct bearing on the uniformity of either the stress or strain within either phase. The idea that the strains are isotropic within each phase (but normally of different magnitude and always of different sign) is based entirely upon the experimental observation that X-ray line broadening has not been detected even when the particles become rather large. It has not proven possible to grow the particles sufficiently large that they lose coherency. Based upon this lack of line broadening one can estimate an upper limit for the nonuniformity of the strains within each phase as follows. It is considered possible to detect line broadening if it is as great as 10 pct of the separation of the K, doublet for the (211) line using chromium radiation. The doublet separation would correspond to a total strain of 0.0017 such that the total variation of lattice parameter relative to the average lattice is now k0.05x0.0017 or something less than ± * For the present case the strain in each phase is roughly 0.002 such that the variation of strain within a phase will not exceed 5 pct. It is stated that the expression derived for strengthening for the hydrostatic straining as observed in this system would substantially overestimate the magnitude due to dislocation flexure. This is contrary to the conclusion reached in the original paper34 for the present range of particle sizes. What is the lowest temperature at which a has been observed to form in this alloy? M. J. Marcinkowski, R. M. Fisher, and A. Szirmae (nutlzors&apos; reply)— -Williams&apos; arguments based on X-ray findings for a chromium-rich precipitate and an iron-rich matrix strained to a common lattice parameter are certainly convincing. This being the case, there are no shear components of strain associated with the precipitate-matrix aggregate to interact with the shear components of the dislocation stress fields, contrary to the opinion expressed by the present authors. On the other hand, the present authors, in spite of this error, did not expect the shear interactions to be significant. The chief objection to Williams&apos; model in the present case is that the various segments of the dislocation line are assumed to pass from one potential valley to the next independently of neighboring segments. This is only true for a highly flexible dislocation line, i.e., one whose radius of curvature is something less than the center to center distance between precipitate particles which amounts to about 90A in the present alloy. In order to maintain this curvature, an externally applied shear stress of at least 230,000 lb per sq in. would be required or about four times the observed stress. It is therefore concluded that the dislocation lines move rather rigidly through the lattice. This being the case, the forces on the dislocation resulting from the hydrostatic interaction between the stress fields of the edge-dislocation components and the precipitate particles should average out to zero; that is particles above the below the slip plane produce forces on the dislocation of opposite sign and therefore will cancel when averaged over the entire length of the dislocation. On the other hand, since the dislocation is not perfectly rigid, Williams&apos; model may lead to some strengthening, but far less than that predicted. A second and equally serious objective to using Williams&apos; strengthening model for the present alloys is that profuse wavy slip due to the motion of screw dislocations played a predominant role not only in the unaged alloys but in the fully aged ones as well. Since the screw dislocation has associated with it only shear components of stress the hydrostatic strengthening model no longer applies. In view of these arguments the present authors must reject Williams&apos; model of strengthening as being pertinent to the present alloy system. The present authors have made no detailed study of the lowest temperature at which a forms in the quenched ferritic alloys. None was ever observed n the alloys aged at 500°C so that forma-tion must occur at temperatures higher than this and was therefore not a factor in the present study.

Jan 1, 1965

By S. Arthur Krom

(New York Meeting, February, 1912.) THE James diagonal-plane slimer is specially adapted to handle the finest slimes, but it will also handle sands as coarse as 40-mesh. The saving efficiency of this machine is due to the original construction of the deck, and to the rapid reciprocating movement imparted to it by the head-motion. The deck consists of a plurality of connected planes, having a certain fixed ratio of inclination one to another. These planes intersect each other diagonally to the stroke-line of the table and are arranged so as to give the pulp on the table a double treatment. This double concentration performed by the diagonal-plane deck produces cleaner concentrates and tailings than those obtained by the operation of two separate machines. The action of the diagonal planes settles, combines, and holds all the concentrates in one compact mass, sharply defined from the gangue, and easily cut away without loss. Many slime-concentrating machines distribute the feed-pulp for a distance of 4 or 5 ft. only, and upon a very limited settling-surface. This results in a thick, heavy deposit, from which it is impossible to stratify the values and wash, away the gangue, the resulting products being dirty concentrates, and tailings carrying high values. The diagonal-plane slimer distributes the feed-pulp for a distance of 10 ft., and upon a settling-surface having an area of 40 sq. ft.; in other words, it spreads the pulp thinly on the table, which allows the metallic values to settle through the gangue quickly, forming a bottom stratum from which the thinly-distributed overlying stratum. of gangue is easily brushed away by the feed-water without disturbing the underlying concentrates. Referring to Fig. 1, plane A is the main settling-section, of the table. The feed pulp flows gently down this plane and is

Jun 1, 1912

By Luckie. Peter T., Deurbouck. A. W., Harold L. Lovell, E. R. Palowitch, James K. Kindig

PART 1: DENSE MEDIUM SEPARATION by E. R. PALOWITCH and A. W. DEURBROUK INTRODUCTION During 1974, 43.9% of the 603,406,000 tons (549,099,000 mt) of bituminous coal and lignite produced was cleaned mechanically, of which 82,280,000 tons (74,875,000 mt) was cleaned by dense medium processes.l The percentage of bituminous coal and lignite cleaned mechanically by dense medium processes increased from 7 to 31 % between 1938 and 1974. Dense medium separations include those coal preparation processes which clean raw coal by immersing it in a fluid having a density inter- mediate between clean coal and reject. As there is a general correlation between ash content and specific gravity, it is possible to achieve the required degree of removal of ash-forming impurities from a raw coal by regulating the specific gravity of the separating fluid. Dense medium processes offer the following advantages over other coal cleaning processes: 1) Ability to make sharp separations at any specific gravity within the range normally required even in the presence of high percentages of the feed in the range of 2 0.1 sp gr units. 2) Ability to maintain a separating gravity that can be controlled with ± 0.005 sp gr units.

Jan 1, 1979

By C. G. Brennecke, R. T. Gallagher

This paper is the result of a research program entered into cooperatively by the General Reinsurance Corporation and Lehigh University in January 1944. The research program was instituted to find a more positive method to determine the presence of hazardous roof conditions in , mining operations. The co-authors, together with Mr. R. D. Currie, Engineer for the General Reinsurance Corporation, started working on the project in January 1944, first undertaking a library search; second, a preliminary study based on some existing equipment; third, the design of new and more suitable equipment; and finally, the field testing of equipment and methods. Purpose Any study of the accident statistics of mining operations will disclose the rather startling fact that approximately 50 to 60 per cent of all fatal underground accidents in the anthracite and bituminous mines are caused by falls of roof and coal, the metal and nonmetal mines showing only a slightly smaller percentage. Advancements in safety engineering have produced definite results in the decrease of accidents due to blasting, haulage, electricity, and explosions but no such decrease is shown in those caused by falls of roof, coal, or ore. Table Il,2 is a compilation of statistics as published by the United States Bureau of Mines, showing the percentages of fatal accidents caused

Jan 1, 1947