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By Joseph G. Debanné

Foreword The three case histories and the liquid fuels planning scenario presented in this paper span a twenty year period, from the pioneering days of computers in the petroleum producing industry during the mid-fifties, to the energy crisis era of the seventies. Inasmuch as two of the main actors, Ian McKinnon and I, are featured in all three case histories, while I am currently involved in the fossil fuels scenario, this paper provides four related and personal spot readings along an evolutionary path: from the one dimensional technical domain to the multi-dimensional techno-socio-economic domain of computer applications in the petroleum industry. Coincident with this evolution in the direction of increasingly comprehensive and powerful computer applications, the evolution in hardware/software capability and in analytical power are also kept in perspective. The three case histories are: 1. The Bonnie Glen-Wizard Lake Case (Calgary, Alberta, 1955-1957); 2. The TransCanada-Great Lakes Gas Transmission Case (Ottawa-Washington, 1966); 3. The Westcoast Transmission - El Paso Pipelines Gas Export/ Import Case (Ottawa-Vancouver-Washington, 1966-1967). The liquid fuels planning scenario is a demonstration exercise rather than a case history; however, it represents an important point on the evolutionary curve and, provides a concrete example of tech-

Jan 1, 1977

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 O. J. C. Runnalls, L. M. Pidgeon

J. M. Blocher, Jr. and I. E. Campbell (Battelle Memorial Institute, Columbus, Ohio)—Since the de Boer-Van Arkel process for making titanium metal involves a number of steps in a fairly compact unit, it is difficult to determine simply which of the steps is rate controlling. In any statement as to which step constitutes the rate-controlling process, qualifications appear to be in order. It is possible to design a reaction bulb in which any one of a number of steps is made to be controlling. I—With the filament removed some distance from the crude, as in the case of the authors' experiments, the interdiffusion of iodine and iodide may be controlling. 2—If, as is usually done, the crude metal is placed in a perforated cylindrical basket, or as a briquetted mass, in close proximity to the filament, the rate of deposition is increased (we obtained rates of deposition 5 to 10 times those cited in the authors' paper), and another rate-limiting factor, such as the reactivity of the crude, may take over. In this regard, we have noticed radically different rates of deposition with different crudes, and with crudes in various stages of exhaustion. 3—With a very reactive crude metal and with optimum practical geometry, still another process may be controlling. It is felt that this is a diffusion process in the immediate vicinity of the filament involving the fundamentally adverse situation of a net flow of particles away from the filament. The separate experiments on the reactivity of iodine with titanium are interesting but somewhat inconclusive. Data is still needed on the partial pressure of iodine in an operating decomposition bulb. A knowledge of the gradient of iodine partial pressure from the crude to the filament would be particularly enlightening. Optical absorption may be a useful technique here. Accurate measurements of the total pressure within a decomposition bulb under various conditions would be quite revealing. Preliminary measurements have been made at Battelle in following this line of attack. It is interesting to note that the authors' data on the temperature dependence of deposition rate indicate that the overall rate is not controlled by the kinetics of the decomposition reaction at the filament: TiI1 ? Ti + 4I Any reasonable estimate of the activation energy of this reaction would, if its kinetics were controlling, dictate a much greater temperature dependence than is observed here. The authors apparently attribute the drop in deposition rate (eventually to zero) with increased TiI4 pressure solely to a decrease in diffusion rate. However, there is an equilibrium factor involved here that must not be overlooked. As the partial pressure of TiI4 is increased, a point is reached where, due to the competing reaction of the tetraiodide with titanium to form lower iodides, the equilibrium partial pressure of titanium is reduced to the point that it equals the vapor pressure of titanium at the filament temperature and the deposition rate falls to zero. This effect would

Jan 1, 1953

By P. Greenfield, C. C. Smith, A. M. Taylor

J. E. Harris (Berkeley Nucclear Laboratories, England)—Greenfield et al.11 attribute abrupt changes in slope of their log o/log i curves for heat-treated Mg/0.5 pet Zr alloy (zA) to &apos;atmosphere&apos; locking. It is proposed here that a more reasonable explanation of the apparent strengthening at low rates of strain can be based on precipitation either during the preanneal or during the creep tests. All the tests were carried out above 0.5 Tm where solute atmospheres are likely to be largely evaporated2 and can migrate sufficiently rapidly so as not to impose any &apos;drag&apos; on the moving dislocations. McLean3 has derived an expression for determining the temperature Tc above which, due to the high-migration rate of the atmospheres, Cottrell or Suzuki locking can play no part in determining creep strength. This expression, which holds for an applied shear stress of not greater than 5 X 107 dynes per sq cm is: Tc/Tm= 7/6.8 - log10? where i = secondary creep rate The values for T, corresponding to the maximum and minimum reported creep rates at each temperature have been calculated from the data of Greenfield et al. These are given in Table VII. All the test temperatures were above T,, the margin being greater for the higher temperatures and for the lower strain rates where the breaks in the log s/log ? curves occurred. Dorn and his collaborators14, 17 have studied systematically the effect of solute hardening on the creep properties of an A1/3.2 at. pet Mg alloy. In the temperature range where strain aging occurred in tensile tests, abnormally high-activation energies for secondary creep were obtained but at temperatures above 0.43 Tm, solute alloying did not have any effect on the creep parameters. Moreover, there have been no reports of any strain aging phenomenon during elevated temperature tensile tests with ZA material.18 Instead of the observed strengthening being due to atmosphere locking, it is now proposed that precipitates play an important role in enhancing the creep strength of the material. There are two possibilities—precipitation of zirconium hydride during the high-temperature preanneal and/or precipitation of the hydride or a-zirconium during creep. On the basis of the former the results can be interpreted in terms of a critical stress being necessary to force the dislocations through or over preexisting precipitates. From the latter, if the strengthening is due to pre- cipitation during the test then hardening should be associated with a critical strain rate. At low rates of strain, time is available during the tests for precipitation to occur either directly onto dislocations (thus pinning them) or generally throughout the matrix (which would impede dislocation movements). Examination of the data of Greenfield et al. suggests that both mechanisms may be operative since they observed precipitation during creep and also found that their alloys exhibited high-creep strength in the early stages of the low-stress tests, i.e., before creep-induced precipitation had time to occur. It is not easy to understand why they considered that precipitation of zirconium hydride is unlikely to occur at 600°C while it can take place in tests in air at as low a temperature as 200°C. Precipitation of the hydride during the preanneal cannot be ruled out merely on the basis of metallographic examination. Hydride precipitates in ZA type alloys are very small and can only be accurately resolved in the electron microscope.9 For example, in this laboratory20 hydride platelets with major dimensions <(1/10) µ have been observed by electron transmission through thin film specimens of hy-drogenated ZA material. Complex interactions between dislocations and such particles are illustrated in Fig. 12. Additional evidence for precipitation during pre-annealing is provided by the data presented in Greenfield&apos;s Fig. 1 and Table IT. These show that the creep strength at 200o and 400°C increases with the time of preanneal at 600°C. Such increases cannot be explained on the basis of increases in grain size alone for further improvements in strength were observed when the material was annealed for longer times than that required to stabilize the grains. Although the main discussion is confined to ZA material, similar arguments can be used against the strain aging hypothesis proposed to explain the binary Mg/Mn alloy data. In this case no precipitation is possible during the preanneal, but precipitation-hardening during creep can occur.

Jan 1, 1962

By Hsun Hu

Direct observations were made on the recrystalli-zntion of a cold-rolled (110) [001] crystal of 3 pct Si-Fe by annealing thin sections of the specimen inside the electron microscope during examination. Subgrain formation, presumably by polygonization, occurs rapidly, followed by a slow increase in the subgrain size before recrystallization can be detected. No migration of the subgrain boundaries was observed, and the formation of recrystallization nuclei by coalescence of subgrains is suggested. Re-c~ystallization characteristics of various texture components were individually examined. AS reported in a previous paper: orientations of the various deformation texture components in a 70 pct cold-rolled (110) [0011 crystal of 3 pct Si-Fe were completely confirmed by transmission electron diffraction patterns taken at various areas of the specimen. These orientations can be summarized as follows: Over most areas of the deformed crystal (111) planes are parallel to the surface. These areas correspond to either $- the two main defor: mation textures, the (111) [112] or the (111) [112].2-5 Within a few areas, (100) planes parallel to the surface are frequently found. These areas represent the minor deformation texture component, the (100) [Oll] type, which is derived from rotated Neumann bands.2&apos;4&apos;5 Only in very rare instances are (110) planes found parallel to the surface. This orientation corresponds to the very weak texture component of the (110) [001] type. In a pole figure, this (110) [0011 orientation is located within the orientation spread between the two main (111) [1121 type textures. Usually the electron diffraction patterns taken at various areas of the specimen are very simple ones, i.e., for any one area the pattern consists only of sharply defined spots of a single orientation. In some areas, however, more or less continuous rings of weaker intensities are superimposed on a simple pattern, indicating the presence of a wide range of additional orientations. In order to understand in detail the recrystallization of this cold-worked crystal, the recrywtallization characteristics of each of the various deformation texture components must be examined. This can best be done by using a high-temperature stage and transmission electron microscopy techniques, whereby small areas corresponding to the various texture components can be selected individually for examination. The present paper presents results obtained by this method. MATERIAL AND METHOD Specimens were prepared from a previously studied1 single crystal of a commercial grade 3 pct Si-Fe alloy with an initial orientation (110) [00l], cold-rolled 70 pct from 0.014 in. to 0.004 in. in thickness. Thin foils were prepared by electrolytic polishing as described in the earlier paper.&apos; Specimens of this thin foil were then mounted in a high temperature stage similar to the one designed by Whelan.6 A direct current was used as the heating source. The temperature of the heating grid was calibrated by means of a Pt vs Pt-10 pct Rh thermocouple in a vacuum chamber (0.01 to 0.02µHg). Maximum variation within the temperature range of 250o to 000°C was about ± 25°C. After the desired areas were selected for examination, the specimen was heated to a low temperature for some time while the selected area was constantly watched. When no further change in structure and orientation could be observed, a higher temperature was applied. Photomicrographs and diffraction patterns were taken from time to time during examination, with the heater temporarily turned off* while the photographs were

Jan 1, 1962

By G. S. Jenkins

The statistics set forth by Professor Mitchell in a proceding paper very carefully brought out the points that indicate that a marked amount of consideration must be given to" the haulage problem to adapt it to local conditions as encountered. Professor Mitchell&apos;s paper showed a spread of from 10 tons per man to 50 tons per man on the production crews, which spread can be recognized as entirely too large when one considers that the product is being sold at a price within very close limits. While a portion of this spread may be explained by different methods in cost accounting as to what employees are applicable to the production crew, it cannot all be blamed on an accounting method. A good portion must be explained by the improper application of equipment to the needs incurred by the local conditions. It is in an endeavor to go into this phase that this paper is given. It will be necessary to qualify the points covered in order to keep the subject from becoming too wide in scope. Along this line, conditions will be only those involved in bituminous coal mine practices and only the haulage of coal that is loaded with mobile loading machines in seams 4 ft thick and better. Haulage Methods Employed The Consolidated Coal Co. (Illinois) has been operating on a modernized basis for about 20 yr. By modernized we mean the loading of coal with mobile loading equipment. In review of haulage methods, it must be remembered that the main line electric haulage locomotive has been in service for some 40 or jo years. To augment this main line haulage, the mule did a quite satisfactory job during hand-loading days, but was later replaced by the gathering locomotive, either battery or cable-reel operated. This type of haulage was the method in common use at the time the mechanical loading of coal became of major importance and the success or failure of loading machine installations may be largely accredited to haulage facilities in the early days; that is, in the period around 1930. The Consolidated Coal Co. had its struggle with this problem beginning in about 1927 or 1928. We were somewhat fortunate in that we were already using gathering locomotives powered by storage batteries at the time we introduced mechanical loading. This meant that we did not have to spend as much time training motormen and trip riders as many mines did that utilized only mules for their secondary haulage. This was all advantage, and our efforts could be focused on ways and means of providing adequate car service to the loading machine. Like most operations, we endeavored to gear the car service to the capacity of the machine, with a large crew endeavoring to load the maximum tonnage that the machine would handle. Toward that end our first move was to install switches

Jan 1, 1949

By R. T. DeHoff, F. N. Rhines

The problem of determining the number of particles of a phase distributed randomly in unit volume c an opaque matrix from measurements made on random plane sections is closely investigated. A formalized derivation for the general case is presented. Applications of this formal result are made to specific types of aggregates dispersed in a matrix; circles, particles with flat circular ends, cylinders, and constant shape aggregates of ellipsoids of revolution. Quantitative measurements of the average geometric properties of these aggregates are developed. In 1953 R L. ullman&apos; developed a technique for determining, from measurements made on random plane sections, the number per unit volume, Nv, of particles imbedded in an opaque matrix. Using meas urements previously developed for volume fraction, vV,&apos; and surface area per unit volume, .SV,= he was able to determine average volume, average surface area, and average dimensions of particles, independent of size distribution, for spheres and circular disks,&apos; as well as for uniformly sized cylinders of any axial ratio.4 The technique is mathematically rigorous for the cases studied. Recent studies of this problem have yielded rigorous solutions for the general case of cylinders, permitting evaluation of NV independent of size distribution and with all axial ratios intermixed. Generalization to shapes having flat, circular ends has been deduced. A solution has also been obtained for the ellipsoid of revolution, independent of size distribution, but requiring a constant axial ratio in the generating ellipses. In the following derivations, as in Fullman&apos;s work, it is assumed that the problem is purely a combination of geometry and probability theory,that is,eithe the particles to be measured are imbedded randomly in the matrix, or a sufficient number of random plane sections are taken to make the sample representative. A relationship exists between the number of par- ticles of a given size and shape that may be situated in unit volume (Ny) and the number of intersections a random plane can be expected to make with these particles (Na). It is the purpose of the following section to derive this relationship. The probability of Intersecting Convex Bodies. Consider a convex, closed surface, that is, one for which no two surface normals point in the same direction, situated at some arbitrary position and orientation in a cube of material that is one unit long at each edge. It is not necessary to assume that this surface is symmetrical. Let planes be constructed in the cube parallel to the top face and at random distances from it. Those planes which lie between the two planes which are just tangent to the top and bottom of the surface will intersect it. The probability that a plane will intersect the body may be defined as the limit of the fraction of planes that lie between the two tangent planes as the total number of planes constructed becomes infinite. This fraction, in the limit, is equal to the distance between the two tangent planes, DV, divided by the total length over which planes are constructed, which has been taken as unity. If the body is now rotated to a new orientation, applying the same argument, the probability of intersection is again numerically equal to the distance between tangent planes. Let DV ($, 0) be defined as the distance between tangent planes of a convex body as a function of orientation, Fig. 1. The probability, Pr, of intersecting the body with a randomly oriented and randomly positioned plane, is then equal to the average value of DV (0, $) over all possible orientations. It may be easily shown that for a system of spherical coordinates the probability of finding an orientation between Q and Q + de, $ and $ + d$ is (1/4n) sin $ dB d$, so that This relationship may be applied to each body in an aggregate of convex bodies. In particular, if the bodies in an aggregate are classified according to size and shape, and the ithsuch class is considered, Eq. 111 may be applied to this entire class, the probability of intersecting any body in this class being

Jan 1, 1962

By T. A. Rickard

The function of a preposition is to show the relation of one thing to another; it is necessary therefore for the writer to select the preposition that indicates the particular relation, otherwise he will fail to express himself clearly. Is it against common sense&apos; to suggest that a Government is justified, morally as well as constitutionally, in preventing the decay of an industry by insisting upon the amalgamation of the prosperous with the needy? All these seven prepositions are used correctly. With the first dredge introduced in Russia, of Werf Conrad, Haarlem, make, this method of alluvial dining became important. Here the prepositions "with", "in", and "of" are used wrongly. He means: "This method of a1lu;ial mining sprang into importance shortly after the first dredge, made at the Werf Conrad, Haarlem, was introduced into ;Russia." The statement itself ii not true, but for that I am not responsible. Once, while I was serving with him, we were frozen in out of sight of land in the Gulf of Pichili in the North of China. Admiral Fisher wrote thus. He has used nine prepositions in making this brief statement. The sequence of three prepositions "in out of" is particularly awkward.

Jan 1, 1931

By L. W. Blau

RESEARCH work in exploration and production was further reduced during 1943 owing, partly, to difficulties in the acquisition of apparatus and, principally, to the exodus of research men to governmental agencies conducting research and to the armed forces.

Jan 1, 1944

By R. E. Miner, J. K. Jackson, D. F. Gibbons

Internal-friction measurements were made during isothermal aging treatments of 18 pct Ni maraging-steel wires between 420° and 612°C. A sharp initial drop in the internal-friction level was interpreted in terms of a rapid dislocation recovery reaction. The rate of the recovery was found to be independent of temperature. Truncation of the recovery reaction was apparent in those systems that exhibited the rapid age-hardening characteristics of the maraging steels. It is proposed that this initial hardening response is the result of a low activation energy preprecipitation reaction involving molybdenum. A gradual rise in the internal-friction level at longer aging times was associated with the precipitation of a molybdenum-containing precipitate. CONSIDERABLE research effort has recently been devoted to the mechanisms responsible for the high strength and toughness of 18 pct Ni maraging steels. These bcc martensitic alloys are found to harden during aging at temperatures between 400° and 600°C. The aging response is very rapid with more than half the total hardness increase occurring within the first few minutes of aging, Fig. 1. Precipitate particles have been observed in the later stages of aging by a number of investigators.&apos;-&apos; While the identity of the precipitates remains the subject of some controversy, one or more of the intermetallic compounds, Ni3Mo, Ni3Ti, and Fe2Mo, are almost certainly involved. Heterogeneous nucleation of precipitates at dislocations has been noted8 and cobalt is believed to enhance the formation of fine, homogeneously distributed particles by lowering the solubility of the alloying elements in the martensitic matrix.3,7 Transmission electron microscopy studies of the initial hardening behavior have not been fruitful. Strengthening mechanisms based on atomic ordering have not been generally supported by X-ray and neutron-diffraction experiments.9 In the present investigation, the aging reaction was studied using isothermal-aging internal-friction measurements. The marked sensitivity of internal friction to short-range diffusion and precipitation processes has provided a convenient tool for the elucidation of the strengthening mechanisms operative in the maraging steels. EXPERIMENTAL PROCEDURE An upright torsion pendulum was used to measure the internal friction of several maraging steels during isothermal aging. The pendulum was placed in an atmosphere of helium at a pressure slightly less than atmospheric. To permit measurement of internal friction during the first minutes of aging, the specimens were rapidly heated by passing a current through them in a manner similar to that described by Ang and Wert.10 Thermal gradients in the specimen were largely eliminated by using specially designed specimen grips11 which produced temperature variations of less than 1 pct over 90 pct of the specimen length and less than 3 pct over the entire length at aging temperatures up to 620°C. A proportioning strip-chart program controller was employed to maintain constant specimen temperature during treatments of up to 36 hr duration. A number of vacuum-melted laboratory heats having compositions near that of a typical commercial 18Ni-7Co-5Mo-0.4Ti alloy were investigated. The amount of cobalt was varied from 0 to 7 wt pct in five of the heats. Either molybdenum or titanium was omitted in the remaining two heats. The alloy desig-

Jan 1, 1967

By Willard P. Ward

HAVING been engaged during the past year in the manufacture of ferro-manganese in a blast furnace, I have imagined that some further information on this subject might be of interest to that large number of members of the Institute who are engaged in the iron and steel industries. The great question of the economical production of good steel, ingot metal, or homogeneous iron (we scarcely know now what to call it) from good materials, and at reasonable prices, has, thanks to the intelligence and energy of a few American engineers, been successfully solved in this country. Nearly all first-class railroads, and many that would riot rank so high, have adopted the Bessemer rail. Martin boiler-plates are rapidly gaining ground, in competition with

Jan 1, 1877

By P. Marier, T. R. lngraham

The kinetics of the sulfation of MnO,, MnzO3, and Mn3O4 in SO,, SO3, and O, mixtures was examined and the descending order of sulfation rates at temperatures near 400°C was found to be Mn,O3 > MnO, > Mn3O4. The respective activation energies for the thermal decomposition of MnO, and Mn,O, are 39 and 47 kcal. At 900°C, the thernzal decomposition of MnSO, to MnzO3 is slower than that to Mn3O4. The respective activation energies are 62 and 51 kcal, respectitely. MANGANESE is used to improve the hot workability of steel in the proportions of approximately 13.5 Ib of ferromanganese per ton of steel produced. This requirement accounts for about 95 pct of its large industrial market in North America. The remaining 5 pct is used in the battery and chemical industries. In most North American ores, the percentage of manganese and the manganese-to-iron ratio are not suitable for the direct production of ferromanganese. Hence, most of the North American requirements for manganese are satisfied by importing ore. Typically, many of the studies done on native low-grade manganese resources have been directed toward the production of ore substittes" and the recovery of manganese from open-hearth slags.3 Of the wide variety of processes which have been proposed, the most popular involve compounds in the Mn-S-O system. The thermodynamic properties of manganese and its compounds were reviewed by ah&apos; in 1960 and, more recently, lngrahams discussed the thermodynamics of some of the reactions involved in the Mn-S-O system at normal roasting temperatures. The conditions for producing manganese sulfide during the reduction roasting of manganese sulfate are discussed by Fuller and Edlund.9 A novel scheme was proposed recently by zimmerley7 for utilizing waste sulfur dioxide from stack gases to recover the manganese from ocean-mined manganese nodules. Very little of the work published on manganese compounds has been related to reaction rates. Singleton et 1.&apos; studied the rates of reaction on the MnO-C and Mn7C3-3MnO systems and observed linear and parabolic kinetics respectively in the systems. Tatievskaya et a1.&apos; studied the low-temperature reduction of Mn&, MnO,, and Mn& in HZ and CO, and reported activation energies in the range 1628 kcal. In this paper, the rates of some of the decomposition and formation reactions involving MnSO4, MnOz, MnzO3, and Mn3O4 will be examined after the conditions for the thermodynamic stability of the individual compounds have been designated. CONDITIONS FOR STABILITY OF MnSO4, MnOz, MnZO3, AND Mn3O4 The areas of stability for h&apos;hSO4, MnOz, MnzO3, and h3O4 were established from the data of Mah4 and Ingrahams and are shown in the predominance area diagram,10 logpq- logpsq, in Fig. 1. The diagram is drawn for two temperatures, 700°K, solid lines, and 1100°K, dotted lines. The sketch for the lower temperature includes the conditions likely to prevail in the Zimmerley patent7 when manganese nodules react with sulfur dioxide and that for the higher temperature indicates the conditions for recovering MnzO3 or Mn3O4 from MnSO4 during a roasting reaction. From the fact that the boundary between the areas of stability of MnOz and hSO4 at 700°K is parallel to the abscissa, it is evident that MnOz and SO2 should react together to produce MnSO4, irrespective of the oxygen pressure in the system. If the source of sulfur for sulfation were from waste flue gases, it is likely that the oxygen content of the gas stream would be more than sufficient to oxidize any MnsO4 to MnzO3, 107 atm of O2 required, or even to convert any Mnz03 to MnOz, 0.02 atm OZ required, prior to sulfation. At 1100°K, the diagram indicates that MnSO4 may be converted directly to either MnzO3 of Mn3O4, depending upon the prevailing partial pressure of oxygen. When the gas stream contains more than 1 pct Oz, logpq = -2, only MnzO3 would be recovered from an experiment done under equilibrium conditions. At oxygen partial pressures of less than 1 pct, one would expect to bring about a reversible exchange between MnSO4 and Mn3O4 by appropriate adjustment of the partial pressure of SOZ. These various reactions will be described in the subsequent kinetic experiments.

Jan 1, 1969

By R. W. Guard, M. E. Fine

By treating the dislocation like a surface and ap-plying the usual thermodynamic treatment to the adsorption process a Gibbs adsorption equation for dislocations was derived. For extended dislocations in binary solutions the adsorbed concentration on the fault, X2a, may be computed from (jo/da2b) where a2b is the activity of the solute in the bulk material and s is the stacking-fault energy. Using the data of Howie and Swann for s the adsorption concentration goes through a maximum at 2 at. pct Al in Ag-Al, 10 at. pct Zn in Cu-Zn, and 8 at. pct A1 in Cu-Al. The pinning stress calculated from this concentration difference goes Ihrough a maximum at the same concentration us the peak in X2 a. The computed pinning stress thus does not vary with composition in the manner predicted by Suzuki, as was also pointed out by Hendrickson. The results are compared with the stress increment which can be attributed to Suzuki locking in Cu-Zn and Cu-Al stress-strain curves. They both agree in magnitude and in the location of the maximum. The predicted and observed maximum values for the Cu-Zn system (where activity data are available) are 700 g per sq mm (predicted) and 1000 g per sq mm (measured, laking into account the orientation factor of 2.2 to convert poly-crystalline to single-crystal data). CERTAIN simple internal surfaces may be regarded as dislocation grids. This fact suggested that it might be profitable to consider certain phenomena related to segregation of solute atoms at dislocations from the point of view of the thermodynamics of surfaces and surface adsorption. A general treatment of this type is given and then the results are applied to Suzuki segregation and pinning. Confirmation of the results is obtained from comparison of stress-strain behavior for copper and copper-base alloys. Two kinds of dislocations need be treated: perfect and extended dislocations. In either case the line tension of a dislocation, ?. the work which must be done to increase the length of dislocation by a unit length, is analogous to the surface tension. For an undissociated dislocation ? is the self-energy of a unit length of dislocation; for an extended dislocation where is the self-energy per unit length of a pair of partials far enough apart so that there is no interaction energy, is the interaction energy per unit length, is the stacking fault energy per unit area, and w is the equilibrium separation of the paired partials. In the absence of an applied stress the force pushing the dislocation partials apart in a close-packed structure is Gb2/12p where G is the shear modulus, b is the Burgers&apos; vector of the complete dislocation, and is the separation of the partials. At the equilibrium separation, w this force equals s. Thus

Jan 1, 1965

By E. N. Pennebaker

A PRESENT, a comprehensive account of the geology and ore deposits of the Robinson mining district, in eastern Nevada, is not warranted. Though several years&apos; work has been done, the district is so large that it will be some time before the investigation nears completion. In this paper I purpose merely to discuss methods of study and the application of geologic data to the search for ore. In the first place, the purpose of a geological depart¬ment in a mining organization is to collect and correlate all geologic and engineering data likely to be useful. In an extensive and well developed mining camp this involves a detailed study of the structure and stratigraphy of the district as a whole, as well as careful analysis of the orebodies exposed. The problem then is to find continuations or similar ore environments in other parts of the district in which like phenomena have been active, and to explore these for new orebodies. Experience gained in other similar mining districts is useful but one must always remember that a great many mining districts are unique and that exploration rules and procedure applying to one cannot always be transferred to another of apparently similar character and be made to work. One also has to be careful in moving from one to another part of the same district. The geologist must first examine the region critically to determine its individual characteristics. .

Jan 1, 1932

By M. A. Torcaso, P. Raimondi

The distribution of the oil phase in Berea sandstone resulting from increasing and decreasing the water saturation by imbibition was investigated Three types of distribution were recognized: trapped, normal and lagging. The amount of oil in each of these distributions was determined as a function of saturation by carrying out a miscible displacement in the oil phase under steady-state conditions of saturation. These conditions were maintained by flowing water and oil simultaneously in given ratios and by using a displacing solvent having essentially the same density and viscosity as the oil. A correlation shows the amount of trapped oil at any saturation to be directly proportional to the conventional residual oil saturation Sor The factor of proportionality is related to the fractional permeability to the water phase. Part of the oil which was not trapped was displaced in a piston-like manner (normal part) and part was eluted gradually (lagging part). The observed phenomena are more than of mere academic importance. Oil which is trapped may well provide the fuel essential for forward combustion and thus be beneficial. On the contrary, in tertiary recovery operations, it is this trapped oil which seems to make current techniques uneconomic. INTRODUCTION A typical oilfield may initially contain connate water and oil. After a period of primary production water often enters the field either from surrounding aquifers or from surface injection. During primary production evolution and establishment of a free gas saturation usually occurs. The effect and importance of this third phase is fully recognized. However, this investigation is limited to a two-phase system, one wetting phase (water) and one non-wetting phase (oil). The increase in water content of a water-wet system is termed imbibition. In a relative permeability-saturation diagram such as the one shown in Fig. 1, the initial conditions of the field would be represented by a point below a water saturation of about 35 per cent, i.e., where the imbibition and the drainage curves to the non-wetting phase nearly coincide. When water enters the field the relative permeability to oil decreases along the imbibition curve. At watered-out conditions the relative permeability to the oil becomes zero. At this point a considerable amount of oil. called residual oil, (about 35 per cent in Fig. 1) remains unrecovered. Any attempt to produce this oil will require that its saturation be increased. In Fig. 1 this would mean retracing the imbibition curve upwards. In addition, processes like alcohol and fire flooding, which can be employed at any stage of production, involve the complete displacement of connate water and an increase, or imbibition. of water saturation ahead of the displacing front. Thus, in several types of oil production it is the imbibition-relative permeability curve which rules the flow behavior. For this reason a knowledge of the distribution of the non-wetting phase, as obtained through imbibition, whether "coming down" or "going up" on the imbibition curve, is important.

Jan 1, 1965

By AIME AIME

THE initial meeting on Mining Methods* opened at 10 o&apos;clock Monday morning with Scott Turner as chairman and W. Spencer Hutchinson as vice- chairman; about 60 attending. After preliminary announcements Theodore Marvin was called on for his paper,, entitled "Rock Tunnel Methods," which has been appearing serially in The Explosives Engineer. Marvin read the introduction and called attention to the account of one or&apos; two particularly&apos; interesting projects, such as the. Brooklyn water supply tunnel. E. D. &apos;Gardner, Char1e.s S. Hurter, L. D. Lamont and Spencer P. Howell took part in the discussion, Howell commenting on the fact that, in one case cited, misfires had occurred through detonator wires &apos;coming in contact with the case of an unapproved flashlight, .,: and that all flashlights should be approved.

Jan 1, 1931

By Lyman H. Hart

Some of the significant facts that will affect the supply and demand for metals during the next few decades are given in this presentation. This is important because the only hope for intelligent guidance of the national destiny depends upon presenting a consistent and accurate picture of basic problems. The metals problems now fomenting are only slightly less important than those precipitating the energy crisis. Admittedly, it is difficult to generate serious thinking on this subject when the world is enjoying easy access to all metals at modest prices. This is possible because of the current world capacity to over-produce, and United States credit standing, at least up to now, has permitted buying freely on world markets. Although both these vital conditions are subject to change, there is little doubt that if the U.S. financial house is kept in order, we can muddle along for a while on a generally expanding, metal-based economy. But should our credit standing be permitted to collapse, or should there be a tightening of world supplies of metals, the nation would immediately find itself in trouble. Unfortunately, clear signals indicate that both of these conditions are threatening. The metal age started many centuries ago, and with the exception of the noble metals, barely a dent was made in world reserves until the present century. Then, as a result of the pioneering ideas of D. C. Jackling and Paul Gemmel, and the willingness of the McNeals, Penroses and Guggenheims to back ideas with money, a virtual explosion of metal production was propagated throughout the world. It is important to examine the causes of this expansion to determine whether it is a trend that may be sustained or whether it is anomalous and therefore attributable to circumstances not likely to be repeated or continued. This period of plenty is a once only phenomenon. Vast metal resources have been sitting around here for eons, while the world was unaware of or unconcerned with their existence. But when population began to grow exponentially, and ways were discovered to use metals to develop machines to do the work of men and animals, the exploitation of raw materials increased at a staggering rate. And now the realization is dawning that minerals are a wasting asset and are beginning to present supply problems that should begin to be of concern. Two main factors have caused this condition; One is the population growth, and the other is the expanding demand for irreplaceable raw materials as nations become more developed. A group of systems analysts, at Massachusetts Institute of Technology in a book Limits of Growth, has warned that at present rates of population growth and resource consumption together with environmental constraints, a point will be reached within 100 years when the world population will become totally incapable of supporting itself. The authors conclude that this end result could be avoided if a planned equilibrium could be established at a lower rate of population growth and resource consumption. Fortunately, there is evidence that the population problem is moderating. The growth rate in the U.S. has decreased from 2.3% per year in 1900 to 1.1% in 1970. But, even at the lower rate, population will double in 70 years. The world rate is greater, and if it continues, world population will rise from 3.5 billion to nearly 10 billion in 50 years. All of these projections are questionable because the dangers of growing population are now being recognized. A marked decrease in growth rate has been noted in the more developed countries-in fact, it was zero in the U.S. in 1972. The other factor affecting consumption of raw materials is the increase in per capita use of most items as individuals become more affluent. Many economists believe that developing countries such as China and India represent a vast future potential market; but there are others, with whom the author agrees, who believe over-population tends to stagnate development. Nevertheless, it is a fact that vigorously developing societies increase consumption at a rate far above their population growth rate.

Jan 1, 1974

By P. M. Kelly

TWO analytical methods for calculating the positions of matrix and twin reflections on electron-diffraction patterns of a twinned cubic crystal have recently been published.1,2 Meieran and Richman1 considered the case of twinning on (1 12) in a bcc structure, while a more general treatment, capable of analyzing twinning on any plane in a cubic crystal, was developed by Johari and Thomas.2 The latter authors applied their general rotation matrix to both (111) twinning in face-centered crystals and {112} twinning in body-centered crystals and they derived separate expressions for these two cases. This separate treatment masks the fact that in a holosymmetric cubic crystal a (111) twin is crys-tallographically equivalent to a {112} twin.3 This is analogous to the crystallographic equivalence of rotation and reflection twins in centrosymmetric crys tals. A particularly simple example of this equivalence occurs when the two twin planes are perpendicular to each other—for example (111) and (112). Then, if twinning on (111) moves a point P to a new position P1, and twinning on (112) moves P to P2, P1 and P2 will be related to each other by a 180-deg rotation about [110]— the direction normal to both (111) and (112). Since there are diad axis axis along (110) direction in a holosymmetric cubic crys tal the two positions P1 and P2 must be crystallo-graphically equivalent. In other words if a particular pole (hk l) is in a position P1 after twinning on (Ill), then after twinning on (112) a pole of the type {hkl}—but not the particular pole (hk1)—will also be in the position P1. As a result, when only the general (as opposed to the particular) indices of poles after twinning are required, twinning on (111) gives the same results as twinning on (112). To convert the results for a (111) twin to those applicable to a (112) twin, when the particular (as opposed to the general) indices of poles after twinning are required, all that is necessary is to multiply the indices of the twin poles by the matrix for 180-deg rotation about [lie], i.e., The analytical methods suffer the disadvantage that a new set of calculations must be performed for each different diffraction pattern or, as is done in the Meieran and Richman treatment,1 a lengthy list of the location of the twin spots in reciprocal space must be prepared. All the tedious computation involved in these analytical approaches can be avoided by simply plotting, on tracing paper, a stereographic projection of a crystal twinned on say (112). By superimposing this twin stereogram on a standard (001) projection (preferably with the points and indices in a different color from those on the twin stereogram) the relative positions of both matrix and twin reflections can be determined by inspection. Alternatively, a composite projection can be

Jan 1, 1965

By F. A. Veer, W. G. Burgers, B. H. Kolster

Starting-- from Cu-Si diffusion couples a study of diffusion in the intermetallic compound Cu3Si of the Cu-Si system has been made. Mmker experiments showed copper to be the diffusing element. From the rate of growth of the Cu3Si phase diffusion coefficients were derived. The activation energy for diffusion is 18.6 kcal per mole. The couples show some interesting microscopic features, for which a tentative explanation is given. THE synthesis of dimethyldichlorosilane, (CH3)2SiC12, an important compound in the manufacture of methyl-silicones, takes place at the surface of a thin Cu3Si layer deposited on a mass of silicon particles."&apos; By passing CH3C1 vapor at about 350°C, silicon atoms are consumed from Cu3Si in forming the volatile silane molecules, thus leaving copper atoms at the surface. It is well-known that copper acts as a poison for the above-mentioned reaction by catalyzing the dissociation of methylchloride.&apos; However, no poisonous effect is observed, at least not before most of the silicon from the particles is converted into silane.3 This would be understandable, if either the copper atoms diffuse through the Cu3Si deposit to the underlying silicon or silicon atoms diffuse in the reverse direction to the copper, both processes resulting in the formation of new Cu3Si and so ensuring the proceeding of the reaction. In this paper experiments are described, demonstrating copper to be the diffusing element. Also a very low activation energy for the diffusion is observed. EXPERIMENTAL The silicon used contained 1 ppm Mg and 1 ppm Cu; the copper was spectroscopically pure (Fe: 2 ppm; Ag, Mg, Si: 1 ppm). The copper and silicon samples were prepared in the form of blocks of approximately 10 by 10 by 5 mm with two parallel sides by spark-machining. The blocks were ground on emery paper (grit 600), etched (copper with nitric acid, silicon with a 4:l nitric acid:hydrofluoric acid mixture), and cleaned with alcohol. As the brittleness of the silicon did not allow a welding procedure to prepare the diffusion couples, the copper and silicon blocks were pressed together in a steel clamp. The pressure exerted by the clamp brought about contact between the parts of the couple and so ensured proceeding of the diffusion. The couples were heated in a vacuum furnace (about 10"5 Torr). The temperature was stabilized within 1 pct. After a heat treatment a section parallel to the direction of diffusion was examined in the microscope and in the X-ray scanning microanalyzer. To determine whether copper or silicon is the diffusing element marker experiments were carried out using tungsten wires with a 20-p diam. EXPERIMENTAL RESULTS Figs. 1, 2, 3, and 4 give micrographs of diffusion zones of Cu/Si couples. Analysis by the electron mi-croprobe of the Cu/Si samples after a definite heat treatment revealed the existence of only one intermetallic phase as can be seen from the line scan shown in Fig. 5. From the X-ray diffraction pattern it could be deduced that this phase was CU 3 Si.4 Even when diffusion zones of considerable width (up to 600 p) were obtained, no other phases occurring in the Cu-Si system could be detected, neither by the electron microprobe nor by X-ray diffraction analysis. The optical anisotropy of the Cu3Si phase made it possible to observe the columnar shape of the crystal-

Jan 1, 1969

By D. T. Peters, J. C. Bisseliches, J. W. Spretnak

The pain boundary relaxation phenomenon in high-purity copper, 0FHC copper, and a precipitation-hardenable alloy o-fCu-2 uit pct Co has been studied by internal ,friction and elastic aftereffect techniques. The data were analyzed by assuming the broad distribution of relaxation times observed obeys a lognormal distribution law which enables calculation of the relaxation strength. Grain size had no effect on relaxation strength, although the peak width increased with increasing grain size and decreasing temperature. A double grain boundary peak was produced in high-purity copper by annealing to produce secondary recrystallization. The activation energy measured for 99.999 pct Cu is 37.5 * 3 kcal per mol and 46.5 kcal per mole for OFHC copper. A small peak in the Cu-Co alloy at about 220°C at 1 cps was deduced to be the grain boundary peak. Its height increased and its activation energy decreased with increasing aging time. Except for erratic peak positions the observations were consistent with the theory of pain boundary sliding. BEFORE the mechanism of the grain boundary internal friction peak in metals can be satisfactorily explained, the detailed characteristics of the relaxation process must be documented. Of interest are the effect of grain size on relaxation strength, the high-temperature background, and peak width and position. The effect on the grain boundary peak of a precipitate at grain boundaries and of the change in distribution of the particles with aging time must also be explained by any existing or forthcoming theory. The model which has received the most attention was proposed by KG&apos; and zener2 and proposes that the anelastic strain results from sliding of adjacent crystals at grain boundaries. The sliding is limited by the interlocking of grain corners. It follows, according to this model, that the relaxation strength is independent of and the relaxation time is proportional to the grain size. The proportionality between grain size, D, and relaxation time, t, has been confirmed by K&&apos; and Bisseliches . In this case, the internal-friction peaks of various specimens can be superimposed by plotting Q-&apos; as a function of the parameter vD exp H/RT where v is the frequency and H the activation energy. However, the data of Starr et 01.&apos; and Leak6 fit better to a parameter containing D to an exponent near two. A meaningful relationship is not always deducible from the shift of peak temperature with grain size. KG7 demonstrated that a twofold variation in grain size obtained by varying the amount of cold work followed by identical recrystallization anneals will cause a peak shift that is too large to be accounted for even by an exponent of two. Since the decreased grain boundary area existing with a larger grain size is exactly compensated for by an increased sliding distance, the relaxation strength should not decrease with increasing grain size. The height of the internal-friction peak has generally been observed to be rather insensitive to grain size as long as the average grain diameter does not approach the specimen diameter. Exceptions have been reported by Koster, Bangert, and Lang8 for copper, and by Leak6 for iron. The observations for copper could well have been confused by the presence df 0.3 pct0. The possibility that the peaks may simply be increasing in width with increasing grain size and that the relaxation strength, which is proportional to the area under the peak, may remain constant was not examined. his point has been checked in this investigation using high-purity copper. Atomic mechanisms to account for damping by sliding at grain boundaries have been proposed by KG7 and Mott. KG predicts the activation energy to be identical to that for self-diffusion. Mott&apos;s "island" model suggests the activation energy is nL where n is the number of atoms in an island and L is the latent heat of fusion per atom. Other authors have felt that a value equal to the activa-

Jan 1, 1964