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By Arnulf Muan, Carlos Landolt

Equilibria involving Cu-Pt alloys, copper oxides, and atmospheres of known ox2gen pressures have been determined at 1000' and 1200 C. The data obtained have been used to calculate activity-composition relations in the alloys. A moderate negative deviation from ideality is found. At high copper concentrations, the results of the present study are in good agreement with those of previous investigators, whereas at low copper concentrations the activities obtained in this investigation are slightly higher than those reported previously. The present study is part of a research program dealing with the determination of phase relations and thermodynamic properties of copper-containing systems at high temperatures. The information available for such systems is very scanty, particularly for copper oxides and their combinations with other oxide components. Platinum is commonly used as a container in studies of oxide equilibria. To evaluate quantitatively the extent of reaction between the oxide and the container, a knowledge of activity-composition relations in Cu-Pt alloys is necessary. Such data are not available for Cu-Pt alloys in the temperature range of particular interest in the present research program, and particularly for alloys low in copper. Studies of various aspects of the systems Cu-Pt and Cu-0 have been reported in previous literature. The system Cu-Pt is known1 to form a continuous solid-solution series above 812.C, whereas ordered phases are present in certain composition ranges at lower temperatures. Thermodynamic data for the system have been reviewed by Hultgren et al.,' who presented free energies of mixing at 65Oo C, mainly derived from electromotive force cell measurements by Weibke and Matthes.3 Enthalpies of mixing at 640°C have been obtained by Oriani and Murphy4 with liquid tin calorime-try. Their results differ considerably from those derived from the temperature dependence of the data of Weibke and Matthes. Thermodynamic data for the disordered alloys have been obtained by Assayag,5 and more recently by Schmahl and Minzl,6 by Myles and Darby,7 and by McCormack, Myers, and Saxer.8 The two latter sets of data7'' became available after the present study was completed. In the system Cu-0+ two oxides are stable at high temperatures, CuO and CuzO+ each having only minor deviations from stoichiometry. Equilibria in the liquidus temperature region of the system Cu2O-CuO have been studied by Roberts and systemsmyth,9'10CuzO-CuO by Vogel and ocher,I1 by Osterwald,12 and recently the the present authors.13 The system is of the eutectic type with a eutectic temperature of 1083.C The composition of the eutectic liquid corresponds to Xcu0 = °.44, and the oxygen pressure of the coexisting gas phase is Po2 = 0.55 atm.13 Equilibrium oxygen pressures for coexistence of solid CuO and solid Cu2O have been determined by Schmahl and Muller,l4 by Gadalla, Ford, and white,l5 by Bidwell,16 and recently by the present authors.13 There is reasonably good agreement among the various sets of data. Free energies of formation of Cu2O(s) from the elements have been derived by Tretyakov,17 by Bidwell,16 by Kiukkola and wagner,18 by Pal'guev and Neuimin," and by Steele and Alcock,20 There is particularly good agreement among the latter three1'-20 sets of data. THEORETICAL BASIS Consider a subsolidus isothermal section of the system Cu-Pt-0, as shown in Fig. 1. Two phase as-

Jan 1, 1970

By Robert W. Thomas

LEACHING of mined-out areas at the Arizona property of the Ray Mines Division, Kennecott Copper Corp., was started on Jan. 20, 1.937, and by July 1, 1938, 10,000,000 lb. of copper had been produced by this method. Leaching operations at present are confined to the western portion of the ore body and over an area of approximately ten acres. The ore in this area was extremely high in pyrite and the copper content, which averaged slightly in excess of 1 per cent, was the result of incomplete secondary enrichment by solutions which apparently worked laterally from the main ore body. Above the ore was an unaltered zone of primary or protore averaging 125 ft. in thickness and containing approximately 0.6 per cent copper. Above this was the capping or leached zone averaging 50 ft. thick.

Jan 1, 1938

By R. Q. Shotts

Data are presented which show that fractions of varying densities from the same coals are oxidized at different rates by nitric acid. From oxidation data, the approximate quantity of "bright" and "dull" components may be calculated. Definite relationships between oxidation rate and rank are shown for density fractions from at least two bituminous coals. IN 1945, the Alabama State Mine Experiment Station initiated a program on the determination of fusain in certain coals of the state.1 Because of the lack of equipment and personnel necessary for microscopic examination, the chemical method2 was used exclusively. During studies of the distribution of fusain in fractions of various sizes and densities on a medium volatile coal, the author noted a higher rate of oxidation of the nonfusain part of the coal in the lower density fractions and the difference in rate became more marked the shorter the oxidation period used. Since durain and other "dull" components of coal have been reported3,4,5 to have higher densities than vitrain and the bright components, it appeared probable that the observed differences in rates of oxidation in the different density fractions were due to variations in petro-graphic composition. Such effects have been noticed by other workers.2,3 In order to obtain further evidence on this point, several Alabama coals of different rank have been separated into three or more fractions on the basis of density and their rates of oxidation determined, using the procedure specified for the determination of fusain, except that measurements were made at short time intervals as well as for the longer periods specified in the regular procedure. Significant differences in the rates of oxidation of the nonfusain part of the various fractions have been observed, and it is believed that studies of this type may make possible the identification of individual petrographic components or lead to methods for their semiquan-titative estimation. Properties of the Coals: Analyses and some properties of the whole coals studied are given in table I. The range in rank of the coals is not the widest possible within the state, but samples of the low volatile coals that occur in thin beds in the northeastern part of the state, were unavailable. The Clements bed is not, at present, considered workable. The coal is of medium volatile rank, quite friable, and very strongly swelling. Analyses of different size fractions show that the larger sizes are of higher rank than the smaller ones. Material passing the No. 50 sieve (all sieve sizes refer to the U. S. Standard Series) is close to high volatile A in rank, except for the size passing a No. 200 sieve, in which fusain is partially concentrated. Because of the variation in rank of the sizes of Clements coal, oxidation studies were made of two widely different size ranges. The + 1-in. material was crushed on rolls to about 1/8 in. and separated into five fractions by float-and-sink treatment in a benzene-carbon tetrachloride mixture. The — No. 4 + No. 8 and the — No. 4 + No. 50 size ranges tested overlap but the latter size was studied last with the expectation that it would include more oxidizable material than the first size. This proved not to be the case. Yields and properties of the specific gravity fractions oxidized are shown in table II. Milldale bed coal probably represents, as nearly as it is possible to do so, the "average" coal of the state. The material passing a No. 4 sieve was the only size range oxidized. It was divided into four specific gravity fractions. As in every case the heaviest fraction, which was essentially rock, was discarded. The Black Creek is the most extensive in area of

Jan 1, 1951

By R. Q. Shotts

Data are presented which show that fractions of varying densities from the same coals are oxidized at different rates by nitric acid. From oxidation data, the approximate quantity of "bright" and "dull" components may be calculated. Definite relationships between oxidation rate and rank are shown for density fractions from at least two bituminous coals. IN 1945, the Alabama State Mine Experiment Station initiated a program on the determination of fusain in certain coals of the state.1 Because of the lack of equipment and personnel necessary for microscopic examination, the chemical method2 was used exclusively. During studies of the distribution of fusain in fractions of various sizes and densities on a medium volatile coal, the author noted a higher rate of oxidation of the nonfusain part of the coal in the lower density fractions and the difference in rate became more marked the shorter the oxidation period used. Since durain and other "dull" components of coal have been reported3,4,5 to have higher densities than vitrain and the bright components, it appeared probable that the observed differences in rates of oxidation in the different density fractions were due to variations in petro-graphic composition. Such effects have been noticed by other workers.2,3 In order to obtain further evidence on this point, several Alabama coals of different rank have been separated into three or more fractions on the basis of density and their rates of oxidation determined, using the procedure specified for the determination of fusain, except that measurements were made at short time intervals as well as for the longer periods specified in the regular procedure. Significant differences in the rates of oxidation of the nonfusain part of the various fractions have been observed, and it is believed that studies of this type may make possible the identification of individual petrographic components or lead to methods for their semiquan-titative estimation. Properties of the Coals: Analyses and some properties of the whole coals studied are given in table I. The range in rank of the coals is not the widest possible within the state, but samples of the low volatile coals that occur in thin beds in the northeastern part of the state, were unavailable. The Clements bed is not, at present, considered workable. The coal is of medium volatile rank, quite friable, and very strongly swelling. Analyses of different size fractions show that the larger sizes are of higher rank than the smaller ones. Material passing the No. 50 sieve (all sieve sizes refer to the U. S. Standard Series) is close to high volatile A in rank, except for the size passing a No. 200 sieve, in which fusain is partially concentrated. Because of the variation in rank of the sizes of Clements coal, oxidation studies were made of two widely different size ranges. The + 1-in. material was crushed on rolls to about 1/8 in. and separated into five fractions by float-and-sink treatment in a benzene-carbon tetrachloride mixture. The — No. 4 + No. 8 and the — No. 4 + No. 50 size ranges tested overlap but the latter size was studied last with the expectation that it would include more oxidizable material than the first size. This proved not to be the case. Yields and properties of the specific gravity fractions oxidized are shown in table II. Milldale bed coal probably represents, as nearly as it is possible to do so, the "average" coal of the state. The material passing a No. 4 sieve was the only size range oxidized. It was divided into four specific gravity fractions. As in every case the heaviest fraction, which was essentially rock, was discarded. The Black Creek is the most extensive in area of

Jan 1, 1951

By Paul Gordon

The distribution coefficient, k, of interest in zone refining is generally defined as the ratio of the solid to the liquid solubilities of one element in another at the normal melting point of the solvent. In practice, distribution coefficients are frequently calculated from solubilities at temperatures well below the melting point of the solvent, e.g., at a eutectic temperature. This is done because of the general lack of accurate data on the liquidus and solidus curves in most phase diagrams. The practice is equivalent to assuming that the liquidus and solidus curves are straight lines in the temperature range between the melting point of the solvent and the temperature at which data for the solubilities are known. It is recognized that the k values so derived may be in serious error; we have found evidence in recent zone-refining operations that a case in point is silicon in aluminum. The phase diagram found in the literature for silicon in aluminum indicates a eutectic on the aluminum-rich side at 12.5 at. pct Si and at 577°C,1 and a solid solubility of silicon in aluminum at this temperature of 1.59 pct.2 It also shows the liquidus and solidus as nearly straight lines from 577°C to the melting point of aluminum (660°C)1,2 The k value obtained from this data is 0.13. This is almost exactly the same as the k value (about 0.14)' obtained in a similar way for copper in aluminum. Yet we have found by mass-spectrograph analyses* of three bars of zone-refined aluminum that copper is efficiently removed from aluminum by zone refining but silicon is not. Two of the three bars of aluminum were zone-refined in our laboratories, the other in the laboratories of AIAG Metals, Inc. The former two bars, designated bars PG2 and PG3, were 30 in. long by 1 in. in diameter during refining; each was processed in a high-purity graphite boat* and kept under refining stage of the process consisted of thirty unidirectional zone traverses at rates of about 1 to 2 in. per hr, with a zone length of 1 to 2 in. At approximately the middle of the refining period a 6-in. piece of the impurity-laden finishing end of the bar* was cut off and replaced with new start- ing material. Following refining, the purest 20-in. section of the bar (obtained by discarding approximately 2 in. of the starting end and 8 in. of the finishing end of the bar) was leveled and then analyzed. The AIAG bar was 16 in. long and about 1.2 in. in diameter; it was purified by eight passes of a 2-in. zone at a rate of 1.6 in. per hr, the bar being contained in a sintered alumina boat lined with loose alumina powder of the highest purity. Data for the silicon and copper contents of the three refined bars are given in Table I. Derived data for the efficiencies of the zone-refining operations are listed in Table 11. It is clear from these two tables that the copper is removed much more efficiently—by a factor of 10 to 50 times—from aluminum during zone refining than is silicon. For example, in bar PG3 the thirty zone passes reduced the copper content from 10 to 0.02 ppm, i.e., by 500 times, whereas the same treatment lowered the silicon content by only a factor of about 16. It seem virtually certain, therefore, that the distribution co efficient, k, for silicon in aluminum is well above that for copper and is very likely not much below unity. This also implies that the solidus line on the aluminum-rich side of the A1-Si phase diagram is very probably appreciably curved near the aluminum melting point since the phase-diagram data indicate such curvature is unlikely in the liquidus.

Jan 1, 1965

By H. Larson, J. Chipman

The ferrous and ferric oxide concentrations of slags, expressed as j = Fe+++/(Fe+++ + Fe++), have been established through gas-slag equilibrium at 1550°C in a range of oxygen pressure of 10-I to 10-9 equilibriumatm. The value of j is increased by basic additions (BaO, CaO, MgO, MnO) and decreased by acidic oxides (SiO2 and TiO2). Oxygen pressure is shown graphically as a function of composition for slags which are analogous to those at the slag-gas interface of the open hearth furnace. THE progress which has been made in recent years in understanding the chemistry of metallurgical slags has been based largely on studies of slag-metal and slag-gas equilibria. There is a considerable body of knowledge which is applicable to reactions occurring at the slag-metal interface in open hearth steelmaking. There is little information concerning reactions of the slag with the furnace atmosphere and hence little basis for an understanding of the transfer of oxygen, sulphur, or hydrogen between gas and slag. The oxygen pressure of the open hearth atmosphere is normally of the order of 10-1 to 10-3 atm which differs by several orders of magnitude from that of about 10" atm at the slag-metal interface. The chemical properties of the slag, for example, the ratio of ferric to ferrous iron and the ability of the slag to hold sulphur in solution, are greatly affected by changes in oxygen pressure. This investigation was undertaken to enlarge our knowledge of the effect of oxygen Pressure on steel-making slags. Using air or controlled mixtures of CO a CO2 a range of oxygen Pressures from 10.' to 10.' was covered. Review of the Literature There are only a few references in the literature which pertain directly to this investigation. The most important is that of Darken and Gurry1,2 on the system iron-oxygen. This work included the determination of the phase diagram of the system and also a study of the field of homogeneous melts and their oxygen pressures. Their apparatus and procedure were very similar to that used in this study. Iron oxide was melted in a platinum crucible under an atmosphere of CO2:CO, CO2:H2, H2O, CO2, air or O2 depending upon the partial pressure of oxygen desired. After equilibrium was reached, the sample was quenched and analyzed for ferrous and ferric oxide. By appropriate calculations these authors were able to determine the oxygen and iron activities in the various slags, heats of formation of the oxides of iron, and heats of solution of iron and oxygen in the liquid slags. In a subsequent paper' the same authors made a less thorough investigation of the effects of additions of lime and manganese oxide on the composition of iron oxide melts. Only a few experiments were made and those in a narrower range of temperature and oxygen pressure. Darken' has investigated the fusion temperature of iron oxide in contact with silica under various atmospheres. He found that the temperature changes from 1120° to 1447°C as the gas composition changes from CO2/CO equal to 20.8 to pure oxygen. A comprehensive paper by White" predates the work of Darken and Gurry. The decomposition of ferric oxide into oxygen and lower oxides of iron was studied from 1000° to 1650°C and under oxygen pressures from 2 to 76 cm of mercury. The effect of

Jan 1, 1954

By SAM YOUR

PROCESSING, technology and application of non- ferrous metals-copper, lead, zinc, aluminum, nickel, precious metals, foundry metallurgy, less common metals, secondary metals-are the special field of the Institute of Metals Division. New developments in this field during 1930 are more or less briefly out- lined in this review prepared by the papers and publications committee of the Institute of Metals Division as follows:

Jan 1, 1931

By D. H. Gray, G. Bergamini, I. Fatt

A method developed by soil scientists for measuring permeability anisotropy of soils has been adapted for use in studies of sandstone permeability aniso-tmpy. Studies on Berea and Bandera sandstone show that permeability of these materials decreases upon application of simulated overburden pressure. Permeability reduction of Berea and Grubb sandstone cores subjected to simulated overburden pressure is shown to be a function of the ratio of radial to axial stress. INTRODUCTION The effects of mechanical stress on reservoir rock parameters are now generally accepted as being important in reservoir engineering calculations. In several oil fields the unique behavior of the reservoir has been attributed to the influence of overburden pressure or internal fluid pressure on rock permeability or fluid content. l Although the gross effects of overburden pressure on permeability, porosity, waterflood efficiency, electrical resistance and sonic velocity have now been established,3-9 there are some very interesting, and perhaps important, details of rock behavior under stress that have not heretofore been studied. In this paper we will show that permeability anistropy of several sandstones is a function of overburden pressure. We will also show that permeability reduction of cylindrical samples of two sandstones, when subjected to mechanical stress, is a function of the ratio of radial to axial stress. Most studies of overburden pressure effects made in the past have attempted to duplicate reservoir conditions by applying hydrostatic external pressure on all surfaces of the sample. Assuming perfect elasticity, that is, no viscoelastic flow during geological time, reservoir rock in situ cannot be under hydrostatic stress as is apparent from the value of 0.25 for Poisson's ratio for most rock. In the absence of tectonic forces the horizontal stress component If there are directional permeability effects, as has been reported from field and laboratory studies, l0,11 then one would expect hydrostatic stress as used in the laboratory to give a different permeability reduction from that occurring under reservoir stress conditions. The influence of stress on directional permeability was measured by a modification of the method first described by Maasland and Kirkham for use on soil samples.12 Their method permits calculation of the permeabilities along each of the three mutually perpendicular axes of a cubic sample. The modification reported in this paper extends the method to observing these permeabilities when the sample is under hydrostatic stress. The Hassler sleeve type of core holder is satisfactory for studying overburden pressure effects on permeability if a known force is applied to the end plugs. Wyble6 used a sleeve core holder but did not load the end plugs. In this paper we combine sleeve pressure and axial force to give permeability changes which we believe are close to those occurring in reservoirs when reservoir pressure changes. The combination of sleeve pressure and axial force assumes, however, that the sleeve pressure simulates both vertical stress and horizontal stress in one direction. METHOD PERMEABILITY ANISOTROPY The Maasland and Kirkhaml2 method of measuring permeability anisotropy uses a cube of porous material which is Open On three faces and has discs with a Center hole for an air inlet cemented to the other three mutually perpendicular faces (Fig. 1). The rate at which air pressure falls in a bottle of known volume, and pressure slightly above atmospheric, when the bottle discharges through each disc, is

By C. A. Heiland

IN the third year of war, geophysical oil exploration broke all records to keep pace with the demand for increased reserves. Geophysical prospecting for strategic and other minerals also grew in scope. The trend of geophysical oil exploration throughout the war is indicated in Fig. 1. This figure resembles the one presented in the last annual review issue of M&M (February 1944, p. 62), corrected for data on-operations in the last months of 1943 and extended into 1944. The average number of geophysical oil prospecting crews in the field in 1944 was 451, whereas the total in 1943 was 340. An upward trend in the use of all geophysical methods is clearly evident throughout the year. Seismic operations were 67 per cent, gravimeter surveys 28 per cent, and other methods 5 per cent of the total. Seismic reflection and refraction crews increased 181/2 per cent over the 1943 average, gravimeter operations increased 73 per cent, and other methods gained 92 per cent. The increase in seismic and gravimeter operations, particularly the latter, is probably due to an increased production of equipment and the organization of new service companies. Miscellaneous methods gained largely through a revival of magnetometer work, and an increase in the use of torsion balances and electrical equipment. In comparison with the prewar average of 1941, it is noteworthy that seismic operations increased 58 per cent, gravimeter operations 88 per cent, and miscellaneous other methods gained as much as 283 per cent. Unfortunately the expansion in the number of geophysical crews does not indicate a proportionate increase in efficiency or in areal coverage, as will be brought out later.

Jan 1, 1945

By Carl Scholz

Discussion of the paper of Carl Scholz, published in Bi-monthly Bulletin, No. 22, July, 1908, pp. 551 to 559. HOWARD N. EAVENSON, Gary, W. Va. (communication to the Secretary*) :-For some time before the publication of Mr. Scholz's paper, I had been collecting data bearing upon its subject, and I now take pleasure in presenting my results to the Institute in the form of a discussion. It has long been a matter of common opinion among mining-men that mice-explosions are, more frequent during the colder, or winter months, than during the warmer ones, and it is a matter of common knowledge among them that the air-ways and road-ways in most mines are much drier and are more in¬clined to be dusty during the winter than during the summer. In many mines, places which are wet and sloppy in the summer are dry and sometimes dusty during the winter. These changes, of course, can only be due to atmospheric conditions, and are caused by differences in temperature and humidity. Until recently, however, very little attention has been paid to the part that atmospheric conditions may play in mine-explosions, or, rather, to the effect they may have in rendering mine-conditions peculiarly dangerous, and in spreading and rendering more disastrous the effects of what would otherwise probably have been .small explosions. To show the difference in mine-conditions during sunnier .and winter months, I have tabulated in Table I. the results of 24 observations of hygrometric conditions in several different mines at different times of the year. Mines Nos. 1, 2, and 6 are located in the Pocahontas.coal -region, in McDowell couuty, W.Va., the first one being a shaft-mine shaft mine and the others drift. Mines 1A and 2A are drift-mines located in Logan county, W. Va. All of these are mines of fair size, but none of them has been in operation more than six years,

Jun 1, 1909

By J. MURRAY RIDDLELL

AN increase of 18 per cent in the production and consumption of all metals last year was readily met by the mines, but more than an average amount of development work was made necessary. Mining methods were improved appreciably; open-pit operations ad¬vanced more than underground practice: and the transportation phase of mining progressed to a greater extent than the other related functions. A new belt-conveyor system of mining was placed in operation at the Spruce open-pit iron ore mine at Eveleth, Minn. The gathering portion of the belt system was installed beneath the surface of the open pit, following closely the bottom rock, in especially provided drifts; beyond it inclined upward to the surface and finally discharged into a 500-ton shipping pocket. Length of the belt was 4500 ft. net vertical lift 386 ft. and capacity 750 long tons per hour. The mined ore found its way to the belt through one of three vertical raises, whose horizontal section was 10 by 10 ft. Each raise was equipped with a grizzly, crusher, pan-type feeder, and auxiliary equipment. Transportation of the ore from the working faces of the pit was accomplished as follows: (1) Two raises were equipped with tower and anchor stations, 3-cu.yd. drag scrapers, and related power units; (2) the remaining raise was provided with electrically driven power shovels and 20-ton trucks mounted on pneumatic tires. This installation has entirely replaced railway pit haulage and partly eliminated power shovels. In a similar

Jan 1, 1938

By Felix E. Wormser

REGISTRATION started bright and early Monday morning in the Silver Corridor at the Waldorf-Astoria with Mrs. W. H. Bassett as chairman. What a registration-over 200 ladies! Several joined us from as far away as California and Washington State. Apparently they enjoy our meetings so much that present travel inconveniences didn't discourage their coming. At noon the ladies joined the men at the All-Institute Luncheon and Monday evening we had our informal dance, which is separately reported. Tuesday morning was devoted to our annual meeting at which all Section annual reports were read. At noon we were all the guests of the W.A.A.I.M.E. at a luncheon at the Port Arthur Restaurant on Mott St. in Chinatown. Many of us rode down on the old 3d Ave. elevated railway-the last of four. It, too, is soon to be torn down. The luncheon was delightfully unusual, with huge dishes of delicious Chinese food on each table. Our chairman, Mrs. Read, who lived in China in her youth chose our menu, and she chose it well, for most of us indulged so heartily that as we arose from the table we felt we couldn't eat again for 24 hours. Someone donated sherry wine, and boxes of Chinese pencils as favors. We wonder who? All owe a big vote of thanks for this lovely party to Mrs. T. T. Read and Mrs. H. A. Prosser, chairmen, and Mrs. H. W. Hardinge, Mrs. R. Hursh, and Mrs. R. L. Lloyd, vice-chairmen.

Jan 1, 1944

By Dorsey Hager

THE rapid increase of water troubles in the Mid-Continent oil fields is causing much alarm. Troubles occur at Towanda, Eldorado, Augusta, Cushing, Blackwell, and Healdton, although they had, not been acute in the Mid-Continent field until about two years ago, when the unusual conditions in the deeper oil fields were first encountered. California faced the same situation, but, thanks to aggressive measures, has largely overcome the dangers. The following analysis of water trouble may throw some light on the subject and be of assistance in solving the problems involved. WATER TROUBLES CLASSIFIED The presence of water in large quantities in oil sands has the following results: 1. Diminishes oil production. 2. Diminishes casing-head gasoline production: (a) By curtailing the gas flow. (b) By making the use of vacuum pumps unsuccessful. 3. Increases lifting costs: (a) By making it necessary to pump large quantities of water, which requires. a fast motion and long stroke (third hole). (b) By requiring the use of compressors for air lift. (c) By causing break-downs and delays due to the high speed necessary to pump water. (d) By making it necessary to treat "cut" or emulsified oil. Oil production is seriously curtailed by the presence of large quantities of water. Lease records show that wells are shut down 40 to 60 per cent. of the pumping time where serious water trouble occurs. While a small quantity of salt water may cut the paraffine and keep the oil moving, several hundred feet, or a hole full of water, effectually "kills" the oil

Jan 10, 1918

By B. A. Wilcox, A. H. Clauer

The steady-state creep of TD Nickel NL + 2 001 pct TltOz) has been studied orer the telirperatve range 325&apos; to 1100O and the stress range 15,000 to 36,000 psi. At high temperatures (aboue 0.5 T& gran-boundary slzding is the )nost znportant )node of creep deformation, and the steady-state creep rate, is, can be related to stress and temperature by: where Q = 190 kcal pev mole and n has an unusually high value of 40. A creep mechanism based on cross slip of dislocations around The O2 particles can satisfactovily explain the low-temperature (T < 0.5 T,) cveep behavior, and the follo wing relation is applicable: Q, (a) is found to decrease from 57 to 46 kcal per mole as the stress is increased from 32,000 to 36,000 psi. THERE have been a variety of theories proposed to explain the influence of dispersed second-phase particles on the yield strength and flow stress of metals, and these have been reviewed recently by Kelly and icholson.&apos; However, only several attempts2"4 have been made to develop mechanistic treatments which characterize the creep behavior of dispersion-strengthened metals, and to date these have not been fully evaluated experimentally. weertman2 and Ansell and weertman3 proposed a quantitative creep theory for coarse-grairzed dispersion-strengthened metals, based on the concept that the rate-controlling process for steady-state creep was the climb of dislocations over second-phase particles, as suggested by choeck. The theory predicted that the steady-state creep rate, <,, was proportional to the applied stress, a, for low stresses and that is a4 o for high stresses. The activation energy for creep, Q,, was equivalent to that for self-diffusion, Qs.d., in the matrix. Some limited experimental evidence in support of this theory was obtained on a recrystallized Al-Alz03 S.A.P.-type alloy by Ansell and Lenel.6 Ansell and weertman3 also developed a semiquanti-tative theory for high-temperature creep of lineg-rained dispersion-strengthened metals in order to explain their results on an extruded S:A.P.-type alloy, which had a fine-grained fibrous structure. They suggested that the rate of dislocation generation from grain boundaries was the rate-controlling process, and fitted their results to the equation: where Q, was found to be 150 kcal per mole, i.e., QC- 4Q,.d. in aluminum. Similar high activation energies for creep7-&apos;&apos; and tensile deformation" of dispersion-strengthened alloys have been observed by other investigators for S.A.P.,&apos;" indium-glass bead omosites, and Ni + A1203 alls.&apos; There is no general agreement regarding the mechanisms involved in the creep of dispersion-strengthened metals, and this is due in part to the lack of detailed studies relating the structures of crept specimens to the mechanical behavior. The present investigation on thoriated nickel was undertaken with the aim of studying the structural changes which occur during creep of a dispersion-strengthened alloy and rationalizing the observed mechanical behavior in terms of the creep structures. EXPERIMENTAL METHODS The material used in this investigation was 1/2-in.-diam TD Nickel bar, which contained 2.3 vol pct Tho,. Obtained from E. I. duPont de Nemours & Co., Inc. The final fabrication treatment by DuPont consisted of -95 pct reduction by swaging followed by a 1-hr anneal at 1000°C. Transmission and replica electron microscopy revealed that the material had a fine-grained fibered structure with an average transverse grain size of -1 p and a longitudinal grain size of 10 to 15 p. Selected-area diffraction indicated that the fiber axis was parallel to (OOl), in agreement with the results of Inman eta1." All creep specimens were vacuum-annealed at 1300°C for 3 hr prior to testing. Transmission electron microscopy showed that the only structural change due to annealing was a slight decrease in dislocation density, confirming the reported high degree of structural stability.13 Furthermore, recrys-tallization or grain growth during creep was never observed. The structure typical of uncrept material (after the 1300 C, 3-hr anneal) is shown in Fig. 1. The grain boundaries are predominantly high angle and. although some areas show a tangled cell structure, the grain interiors are relatively dislocation-free. Individual dislocations are strongly pinned by the Tho2 particles; i.e., very rarely did dislocations move within a thin foil. The grey "halos" around some of the larger particles which protrude out of the foil surface arise from contamination in the electron microscoge. The Tho, particle size ranged from -100 to IOOOA, and the distribution is shown in Fig. 2. The technique used to obtain the data in Fig. 2 consisted of dissolving the nickel matrix in acid, collecting the Tho2 particles on cellulose acetate, and measuring about 1000 particle diameters in the electron microscope. Similar results were obtained by measuring about 600 particles in thin foils, an; the average particle size was found to be 2r, = 370A. Using the data in Fig. 2 (annealed structure), the mean planar center-to-center particle

Jan 1, 1967

Jan 1, 1934

By P. C. Johnson, B. A. Stein

This paper describes a study of the effects of combined heat treatment and explosive loading on the mechanical properties of high-strength steels. nis program investigated two distinct areas: 1) the effect of shock waves, without gross irreversible defmmution, on a 3-Cr steel at various stages of heat treatment; and 2) the effect of rapid deformation (explosive forming) on H-11 and D6-AC steels in the metastable austenitic state. The mechanical properties of these steels were improved, in some cases markedly, as a result of these treatments. ,AUSFORMWG, which requires the plastic deformation of metastable austenite, is a process which can appreciably improve the properties of selected alloy stee1s.l,2 The Ausform process significantly increases the strength of these steels without decreasing their ductility. The properties at high temperatures are also improved through a change in the response of the steels to tempering. Although the mechanism by which ausforming alters the properties of these steels is not fully understood, it appears that the dislocation arrays produced by deformation of the metastable austenite influence the structure of the martensite on subsequent transformation. This, in turn, affects the strength, ductility, and tempering response of the martensite. This research used chemical explosives to deform steels at various stages in their heat treatment in order to improve the properties of these steels. The explosive energy is used in two ways; 1) high-pressure shock waves are propagated through the steel to produce extensive microscopic shear strain without causing a large irreversible change in shape, and 2) explosive energy is used to cause extensive macroscopic plastic strain in the metastable austenitic state (explosive forming). I) AUSFORMING WITH INTENSE SHOCK WAVES The steel used in this phase of the research was an alloy having a nominal composition 0.43 pct C, 3.0 pct Cr, 1.5 pct Ni, and 1.5 pct Si. The steel was subjected to intense shock waves in three conditions: 1) in the metastable austenitic state, 2) in the tempered mar tens itic state, and 3) in the tempered martensitic state after ausforming by conventional techniques. The specimens were in the form of disks 2.75 in. in diam and 5/16 in. thick. These were incorporated into a specimen assembly consisting of two disks pressed into a 5 by 5 by 1 in. block of stainless steel, Fig. 1. Spalling (or scabbing) is confined to the front disk. The specimen is protected from oxidation and decarburization by the surrounding metal. The temperature of the assembly is monitored by a thermocouple inserted into one side of the stainless steel block. The assembly is positioned over an oil reservoir which serves both as a means of catching the disks and as quenching medium for the disks shocked under ausforming conditions. Plane shock waves are introduced into the assembly by a metal driver plate impacting the top surface of the block. The driver plate is accelerated by a chemical explosive sheet supplied by E. I. du Pont de Nemours & Co. All the specimens were subjected to plane shock waves having a peak pressure of approximately 430 kbar. The pressure is that quoted by G. E. Dieter for the plane wave generator used in this work.&apos; The driver plate used was 1/4 in. thick, so that the initial pulse was essentially a l/2-in.-wide square wave. The attenuation of the peak pressure during the subsequent 1/4 in. is estimated to be less than 5 pct. The shock front induces a temperature rise, a portion of which is irreversible. Rough estimates (+25 pct) of this temperature rise have been made for iron shocked at room temperature.4 For a 500-kbar shock wave, the temperature rise in the shock front is about 700°F, and is held for a time of the order of microseconds. The irreversible temperature rise, which remains after the shock wave passes, is about 450°F.4 The disks are quenched to room temperature within a few seconds of the shock treatment. It should be emphasized that the temperature rises given above are estimates for pure iron at room temperature, and are not necessarily true for the tests made in this work. The disks shocked at temperatures in the metastable austenitic range were austenitized in the stainless steel assembly in a furnace protected from the firing area. The assembly was removed from the furnace and placed over the recovery reservoir. The plane wave generator was then positioned and

Jan 1, 1963

By P. N. Richards, M. K. Ormay

The present Paper extends the previous work on cold reduced, low carbon steels to preferred orientations developed after various heat treatments. In recrystal-lized rimmed steel, cube-on-comer orientations increased with cold reductions up to 80 pct. Above that {111}<112> and a partial fiber texture with (1,6,11) in the rolling direction dominated. During grain growth, cube-on-corner orientations have been observed to grow at the expense of {210}<00l>. In re-crystallized Si-Fe (111) (112) and cube-on-edge type orientations are dominant near the surface and the (1,6,11) texture near the midplane for reductions up to 60 pct. With larger reductions {111)}<112> and the (1,6,11) texture are dominant. In cross rolled capped steel a relationship of 30 deg rotation was observed between the (100)[011] of the rolling texture and the main orientations after re crystallization. Most orientations present in recrystallized specimens can be related to components of the rolling texture by one of the following rotations: a) 25 to 35 deg about a (110) b) 55 deg about a (110) C) 30 deg about a (Ill) THE orientation texture of recrystallized steel is of interest where the product is to be deep drawn, because preferred orientation is related to anisotropy of mechanical properties such as the plastic strain ratio (r value);1,2 and in electrical steel applications where a high concentration of [loo] directions in the plane of the sheet improves the magnetic properties of the material. It is interesting to note that both these aims are to a large extent achieved commercially, even though the orientation texture of cold rolled steel does not show large variation3 and the recrystallized orientations are generally given as being related to the as rolled orientations mostly by 25 to 35 deg rotations about common (110) directions.4-6 There is, as yet, no single completely accepted theory on recrystallization. The three mechanisms that have been investigated and discussed are: a) Oriented growth b) Oriented nucleation c) Oriented nucleation, selective growth Largely from the observations of the recrystalliza-tion process by means of the electron microscope,7-11 there is now considerable evidence that the "nucleus" of the recrystallized grain is produced by the coalescence of a few subgrains to form a larger composite subgrain, which finally grows by high angle boundary migration into the deformed matrix. From the intensive work on the recrystallization of rolled single crystals of iron, Fe-A1 and Fe-Si al-loys4-" he following observations have been made: 1) The change in orientation during primary recrys-tallization can usually be described as a rotation of 25 to 36 deg about one of the (110) directions. 2) The (110) axes of rotation often coincide with poles of active (110) slip planes. 3) If several orientations are present in the cold rolled structure, the (110) axis of rotation will preferably be a (110) direction that is common to two or more of the orientations. 4) With larger amounts of cold reduction (70 pct or more) departure from these observations became more frequent. 5) After larger cold reductions, rotations on re-crystallization about (111) and (100) directions have been observed. K. Detert12 infers that a rotation relationship of 55 deg about (110) directions is also possible, by stating that the recrystallized orientation {111}<112> can form from the orientation {100}<011> of cold reduced partial fiber texture A.3 The observation by Michalak and schoone13 that (lll)[l10] formed during recrys-tallization in fully killed steel containing (111)[112],— as well as (001)[ 110] which is related to the {111}<011> by a 55 deg rotation about <110>-implies a possible 30 deg rotation relationship about the common [Ill]. Heyer, McCabe, and Elias14 have recrystallized rimmed steel after various amounts of cold reduction, by a rapid and by a slow heating cycle and found that the preferred orientations strengthened with increased cold reduction. The most pronounced orientation up to about 70 pct cold reduction was found to be {1 11}< 110>, after 80 pct cold reduction both {111}<110> and {111}<112>, after 85 and 90 pct cold reduction, {111}<112>, and after 97.5 pct cold reduction it was {111}<112> and (100)(012). In the present work, the orientation textures of the recrystallized specimens are examined under various conditions of steel composition, amount and method of cold reduction, and method of recrystallization. The relationships between the preferred orientations of the as rolled and recrystallized specimens, and the conditions for the formation of the various orientations during recrystallization are investigated.

Jan 1, 1970

By E. W. Filer, R. P. Smith, L. S. Darken

The solubility of nitrogen gas in purified iron and low alloy steels is determined for the y region (930° to 1350°C). The diffusivtiy of nitrogen is estimated from the rate of approach to equilibrium. The investigation of aluminum-killed steels, held in nitrogen, discloses precipitation of aluminum nitride, the solubility of which is determined. ALTHOUGH several investigations of the solu-bility of nitrogen gas in y iron have been reported, all have made use of the method adopted by Sieverts in his classic work, whereby the solubility is determined by the pressure or volume change of the gas. The agreement between different investigators* is rather poor, particularly as compared to the self-consistency of results of several individual investigators. The present report represents a portion of our investigation of the equilibrium of nitrogen and nitrogenous atmospheres with iron and steels. The method adopted in this temperature region (910" to 1400°C) consists of holding the specimen in gaseous nitrogen, quenching (or cooling), and determining the nitrogen content by direct analysis (solution in acid followed by distillation and titra-tion of the ammonia).** Up to 1050°C a 20 in. vertical wire-wound (Kan-thal) furnace was used; this was wound in three sections so that by proper adjustment of relative currents, and use of a modulator1 and a commercial controller (using a chromel-alumel control couple), a zone almost 6 in. long could be maintained uniform within a few tenths of a degree. Since the temperature coefficient of the nitrogen solubility is low, the full precision was not utilized and a variation of l° to 2" was tolerated; a variation of a similar amount also occurred occasionally between the beginning and end of the experiment. At higher temperature a vertically mounted, tubular Globar furnace and control unit was used; the zone of uniformity (l° to 2"C) was here limited to about 2 in.; fluctuations with time were comparable to those in the wire-wound furnace. Reported temperatures were measured by use of a platinum-platinum-rhodium thermocouple, which was frequently com- pared with a similar standard couple which was calibrated at the gold and palladium points and also compared with one certified by the Bureau of Standards; error from this source is believed to be less than 1 "C. Nitrogen gas from a commercial cylinder was mixed with slightly over 1 pct H by use of a gas mixer described previously.&apos; This mixture was passed over hot copper and through ascarite and phosphorus pentoxide to remove oxygen and water vapor. The purified gas contained 1.05 pct H. This procedure was adopted to prevent the formation on the specimens of oxide film, which is well known to be nearly impervious to nitrogen; its success was attested by

Jan 1, 1952

By B. B. A. Luzzat

ALUMINUM is today the most widely used of the nonferrous metals. The technical literature on the aluminum smelting process is, nevertheless, very meager, so that anyone interested in the subject cannot rely on more than a couple of dozen publications.&apos; The patent literature is equally scarce; most patents refer to the production of alumina from aluminum-bearing ores, while not more than a few score significant patents deal with the electrolytic reduction of alumina, which is the real core of the aluminum smelting industry. The "reduction phase" is, from a technical and a scientific point of view, much more interesting than the "alumina phase", which, in effect, is only a combination of such well-known chemical operations as dissolving, precipitating, filtering, drying, and calcining. The electrolytic reduction of alumina, on the other hand, has features which do not appear in any other metal smelting operation. Some of them are of great technical and scientific interest even for those not directly engaged in the production of aluminum. The purpose of this paper is to describe in some detail the basic facts and developments of the reduction phase of aluminum smelting. Two Aspects of the Electrolytic Process The raw material for the reduction process is alumina (Al2O3) . Its purity in general runs as high as 99.50 pct or more. Small differences in the chemical composition generally do not affect the reduction process.* Of more importance are the physical prop- erties of the alumina, since they affect not only its rate of solution in the molten bath but also its heat insulating power.† In the following pages, un- less otherwise stated, it is assumed that a standard "Bayer" alumina is used. The reduction process, by which alumina is broken down into its components, may be roughly defined as its electrolysis in molten cryolite. The oxygen separates at the anode, and the aluminum at the cathode, which forms the bottom of the electrolytic cell. The electrolytic cell (or pot) where the process is carried out is a strongly reinforced steel box. The

Jan 1, 1951

By G. Richards Gwinn

THE mineral graphite has been known for hundreds of years and was first used commercially as a coloring agent. Its true identity, however, was not recognized until the end of the eighteenth century and its commercial development did not become extensive until near the close of the nineteenth century. The common names for this mineral are graphite, plumbago, and black lead; others less frequently used are potelot, crayon noir, carbo mineralis, and kish. Graphite was named by Johann Gottlieb Werner in 1789 from the Greek word graphein, to write, and this name was applied primarily to the large crystalline, flake variety. Plumbago is a trade term used primarily for massive graphite as found in Ceylon. Black lead is also a trade term and, like plumbago, is based upon the idea that prevailed throughout the Middle Ages that graphite was a form of lead, or at least contained that metal. Graphite is a soft, black, unctuous form of carbon that crystallizes in the hexagonal system with rhombohedra1 symmetry. It occurs occasionally in six-sided tabular crystals but usually is found in foliated masses, minute disseminated scales, or earthy lumps. It has perfect basal cleavage, is gray to black, has a metallic luster and a gray streak. The specific gravity is 2.1 and hardness is 1 to 2. It is opaque even in finest particles; extremely resistant to the action of acid or heat; and a good conductor of both heat and electricity. Graphite may be separated into three classes: ( ) natural, (2) manufactured (which is sometime called artificial), and (3) colloidal. Natural graphite is divided into two classes, "crystalline" and "amorphous." Crystalline graphite may occur as flake, lump, chip or dust. Amorphous graphite is a commercial term only, as all graphite is crystalline, but grades in which the individual grains cannot be distinguished are classified by the trade as amorphous. Natural mixtures of crystalline and amorphous occur in all proportions. The term "artificial graphite" is a misnomer; "manufactured graphite" is a better term, because it actually is pure crystalline graphite,

Jan 1, 1949