Search Documents

By S. O?Connor

When one looks back and does assessments of what has been the key ingredient in achieving success in our safety efforts, there are many issues that spring to mind and cover a wide array of elements. One does not know which has the ultimate maximum effect. In his presentation yesterday, Alan Peers, our SHEQ leader, covered a lot of detail with the way we are managing safety at Modikwa. I have attempted to identify some of the key essentials in making the mine safe. Passion Safety is addressed with a passion that is unbelievable at times. When I get phoned because an incident has occurred and in reporting the incident, there are already action plans being put in place to prevent re-occurrences, you understand the commitment to put employees? safety first. You hear the disappointment in your subordinates? voices when they have to share the fact that an incident or accident has occurred.

Jan 1, 2011

The Ross Goldfield is a unique gold resource. From its discovery in 1865 there was a growing understanding of the geology of the deposit as mining moved from the surface at Jones Flat in the south to underground extraction at Ross Flat further north. Multiple layers of gold-bearing gravels were penetrated in deep shafts and six rich gold-bearing bottoms were worked. The ultimate bottom on the Old Man Group gravel surface has never been reached either at Jones Flat or at Ross Flat. Mining at Ross Flat was ultimately halted by uncontrollable flooding, by escalating costs and by a shortage of labour during the First World War. Mining at Jones Flat recommenced in the late 1980s and attention has once again been drawn to the potential magnitude of the resource at Ross Flat. Research of historic literature shows that there is potential for a bulk gold grade of 400 mg/m3 in a volume of 82 million cubic metres of gravels which lie in a basin between Jones Flat and north Ross.

Jan 1, 1993

Multiple regression analysis was used to predict elemental concentrations of copper and nickel in soils from consideration of the concentration of these elements in vegetation in an ultrabasic complex in New Zealand. Regression equations were computed from sixteen independent variables involving concentrations of ten elements in plant ash, and various physical factors such as slope and altitude of the site, and height of the tree. One elemental and one physical variable were significant for nickel at the 90 per cent level of probability and five elemental and two physical variables were significant for copper at the same level. Use of the regression equations explained 32·5 per cent and 26·5 per cent of the variance in the respective relative accumulations (amount in plant divided by amount in soil) of copper and nickel.Predicted concentrations of copper and nickel in soils agreed more closely with the observed values in the soils than did the levels of these elements in plant ash.Although the results may specifically apply only to the test area, the principles should have universal application.

Jan 1, 1972

Heap leaching for the recovery of precious metals is a comparatively new and rapidly expanding technology. The practical aspects of heap leaching are described and environmental and economic implications discussed.

Jan 1, 1984

By J. Daavittila

In the latter part of the 1980s Outokumpu Chrome in Tornio, Finland, was in a situation when its twenty-year-old ferrochrome plant was becoming too inefficient to sustain economically sound production. The company made extensive studies on the then available processing methods to find out the best possible processing route. As a result, the whole plant was practically rebuilt and expanded. When equipment was proven in practical operation, an application for FeMn production was developed. Now as the Tornio FeCr-plant is considering expansion, the same type of exercise is to be performed with today?s challenges, which will be discussed in the paper. These challenges include increasing costs or decreasing quality of raw materials, increasing energy costs, stricter environmental regulations and demand for better working conditions. The possibilities of resolving to these challenges will be discussed in the paper. The future and continuing development with FeCr includes the better utilization of process dusts and a lower consumption of energy. By adapting the latest automation tools to better control the process, even higher efficiencies can be achieved with present technology. New processes are considered for development in the future and some possible technologies will be described.

Jan 1, 2004

By Bill Cain, David F. Tsztoo, R. John Caulfield, D. Scott Kieffer

In 1994, the East Bay Municipal Utility District (EBMUD) commenced a system-wide Seismic Improvement Program to protect their facilities from catastrophic damage. A primary focus of this program has been on retrofitting the 75-year old Claremont Tunnel, which crosses the active Hayward Fault zone. A large earthquake on the Hayward Fault could generate enough right-lateral fault slip to effectively sever this important lifeline. The retrofit project involves construction of a new bypass tunnel through the Hayward Fault zone, together with systematic contact grouting and localized structural repair of the existing concrete liner. Several innovative design measures have been incorporated into the seismic retrofit design, including an oversized tunnel cross section, backfill concrete side drifts, seismic isolation of an internal structural pipe, and shear fuses in the final lining.

Jan 1, 2005

By J. M. Riley

This report summarizes Bureau of Mines experiments in purifying sulfate leach liquors, which were prepared from low-tenor beryl concentrates by modifying the Degussa process. The leach liquor was prepared from a beryl concentrate containing 2.7 percent BeO by (1) sintering the beryl concentrate with limestone in a rotary kiln at about 1,150° C. and by (2) treating the sinter first with sulfuric acid and then with water to form and extract beryllium sulfate. About 80 percent of the beryllium was dissolved. The resulting leach liquor contained 2.4 grams of BeO, 20 grams of Al203, and 6 grams of Fe203 per liter. The laboratory solution contained much more aluminum and iron than a solution derived from treating 10 percent BeO concentrate, which is the standard raw material used by industry. Tests were made to determine the behavior of the solution toward alum purification and limestone neutralization both of which were employed industrially in conventional Degussa procedure.

Jan 1, 1962

By Phil N

A large number of experiments have been carried out by many workers on the recrystallization of deformed and subsequently annealed metals and alloys. Although observations on single crystals are of great importance in the study of the recrystallization textures of deformed and annealed metals, very little of this work deals with material in this form.Since, in deformed metals, the stress concentration is greatest at the grain boundaries and along the planes of slipping, it is to be expected that recrystallization will start in these regions. For example, in polycrystalline aluminium (1),:1: (2), copper (3), a-iron (4) and brass (5), (6), which had been deformed by cold-rolling, drawing, pressing or stretching and then annealed, the new grains first appeared in the boundaries of the original crystals, whilst in the case of cupronickel (7) and iron (8), recrystallization commenced along the slip planes of the deformed material. Deformed and annealed single crystals of aluminium (9) and cadmium (10) first start to recrystallize along slip planes and in deformation twins.The present work deals with the process of recrystallization of single crystals of lead after deformatjon by creep.Two factors enter into these experiments that were not met with in other work on this subject. Firstly, lead...

Jan 1, 1940

By James R. Wait

The present final report constitutes the total productivity of a series of contracts from the U.S. Bureau of Mines and the Institute for Telecommunication Sciences over the period 1971-1979. The emphasis on the research has been analytical. In this "executive summary" we give a succinct description of each phase of the investigation. In the first phase of the investigation that was stimulated by the National Academy of Engineering, we concentrated on the analytical studies of techniques relevant to mine rescue. Several specific procedures for locating a buried source were analyzed. In the next, but overlapping phase of the investigation, we dealt with the fundemental character of how electromagnetic waves propagate in mine tunnels. At the outset we allowed for the finite conductivity of the tunnel walls and the presence of axial conductors such as cables, pipes, and tracks. The third phase of the investigation was devoted to the analyses of various specific geophysical engineering problems. The related fourth phase dealt with the general subject of non-destructive testing of wire ropes such as used for mine hoists.

Jan 1, 1980

By R. Greenwood

The advent of the space age and its promise of interplanetary flight has prompted new ideas for propulsion systems that will allow maximum energy with minimum fuel weight. The use of cesium as the source of energy for such rocket flights has been found desirable. Theoretical efficiency of a rocket fuel is measured in terms of specific impulse, defined as the number of pounds of thrust per pound of propellant consumed per second. Specific impulse is usually expressed in seconds (the number of seconds for which one pound of fuel would produce one pound of thrust) although it is really a measure of total energy, not of power. The most sophisticated chemical fuels have a specific impulse of 300 to 400 sec; liquid hydrogen heated by nuclear reactor has a specific impulse of 1000 to 1200 sec. Specific impulses as high as 20,000 sec, however, are theoretically attainable with the ion rocket, in which free cesium ions are accelerated across a voltage drop and ejected at high velocity.' Characteristics of the system have been sketched by Boden.2 The desirable properties of an ion propellant are: 1) low ionization potential, 2) low boiling point, and 3) high atomic weight. Alkali metals best fulfill these requirements, and Table I indicates the superiority of cesium. The use of heavy complex ions such as UCl3 is ruled out by their instability and other disadvantages.' Despite its enormous superiority in specific impulse, the ion rocket is inherently low-powered, capable of very small acceleration. Application of ion propulsion will be limited to large rockets and spaceships on missions requiring powered flight for weeks or months and employing a separate chemical propulsion system for escape from the earth's atmosphere where power requirements are large but of brief duration. For example, Kraemer and Larson3 considered the case of an unmanned 25,000-lb pay-load placed in a 300-mile orbit by chemical rockets, proceeding thence by ion propulsion to the vicinity of Mars, where it would go into orbit once again. Calculations provide for 8500 lb of cesium for such a voyage. The question of whether such quantities of cesium will be readily available to the space program does not appear to have been considered by geologists and mining engineers. Present Production and Uses Literature on industrial applications of cesium is scanty. The metal is used in scintillation counters, photocells, infra-red detection devices, and as a "getter" in low-voltage vacuum tubes. Production is sporadic and total figures are not published, but the annual consumption is measured in pounds rather than in tons. The few pollucite deposits known, small as they are, can easily supply the present limited demand for gram or pound lots of cesium. Until recently the price of cesium was $2 to $4 per gram, but according to Chemical Engineering, cesium salts are now available at $13 to $27.50 per lb. Geochemical Distribution As a large alkali ion, the cesium ion accompanies potassium in geological processes and tends to be concentrated in the latest crystallizing fractions of potassium minerals in much the same manner as rubidium. Most of the cesium in igneous rocks, therefore, is in the micas and potash feldspars of granites, and especially in granitic pegmatites. The cesium content rises markedly in the micas of the late by-drothermal replacement stage in complex pegmatite~.' Typically, cesium is only 0.5 to 0.01 times as abundant as rubidium in potassium minerals. Rb', with a radius of 1.47 A, is close enough in size to K' (1.33 A) so that rubidium forms no minerals of its own. Cs+ is so large (1.67 A) that only small concentrations can be taken up in potassium minerals; when cesium is present in solution in larger concentration it forms the mineral pollucite, Cs3-Na2A17Si17O48.3H2O, which is known only in pegmatites. In the weathering of igneous rocks, cesium is dissolved, carried to the ocean, and apparently in-

Jan 1, 1961

By R. L. Mauger, P. E. Damon

Potassium-argon dating of the late Mesozoic and Cenozoic intermediate to acidic plutons and volcanic rocks of Arizona and northern Sonora demonstrates the existence of two distinct magmatic episodes. The earlier episode begins in late Campanian time and dies out before the middle Eocene. Following a quiescent period in middle and late Eocene time, magmatism increases in Oligocene time, becomes most intense at the Oligocene-Miocene boundary and dies out as the Pliocene is approached. Pliocene magmatism is primarily confined to extrusion of post-orogenic basalts. The late Mesozoic-early Cenozoic magmatic pulse is essentially confined within the limits of the classical Laramide orogeny (Laramie through Wasatch time). The mid-Tertiary pulse is contemporaneous with the mid-Tertiary Basin and Range orogeny. The Laramide provides an excellent specific example of Umbgrove's concept of the pulse of the earth and in general his concept appears to be meaningful. Copper porphyry mineralization is time-congruent with Laramide magmatism and there seems to be no doubt as to the existence of a genetic relationship between the two phenomena. Two origins are tenable: direct accumulation of the copper sulfides in the copper porphyry liquid magmatic environment; or, introduction of the mineral constituents entirely from a larger source magma when the host rock is already crystalline. Transgression and regression of the epicontinental seas provide an excellent indicator of orogeny and epeirogeny. There was an overall transgression of the epicontinental seas from early Triassic time through the Turonian epoch in early late-Cretaceous time. Thereafter, there is a relatively continuous regression of the seas until the present time. Both the earlier transgressive episode and the later retreat are intermpted by temporary but distinct reversals. These interruptions can be correlated with classical orogenies. There are six distinct orogenies so indicated in the Mesozoic-Cenozoic eras. These occur at approximately 35 to 40 m.y. intervals. The regression of the epicontinental seas following the Turonian epoch was contemporaneous with the deepening of the Pacific ocean basin over the Darwin Rise. As the Darwin Rise was collapsing the East Pacific Rise was being elevated. The Western United States, situated on the eastern flank of the East Pacific Rise, was upwarped and tilted toward the east. Epeirogeny is the primary consequence of processes that operate on a global scale. Orogeny is an exothennic process that is limited in space and is treated here as a secondary consequence of epeirogenic-initiated warping. The off-campus buildings of the University of Arizona Geochronology Laboratories rest on the volcanic rocks of Tumamoc Hill. From this hill, the observer may obtain a beautiful view of typical Basin and Range topography. The city of Tucson lies below, contained within the broad Santa Cruz basin and surrounded on all sides by characteristic NW-SE trending ranges towering as much as 7000 ft above the valley floor. Since the senior author arrived in Tucson eight years ago, a great deal more has been learned about the geochronology of this and neighboring basins and ranges. For example, the volcanic rocks underlying the laboratory at Tumamoc Hill were shown on the state geologic map as Quaternary basalt. A student of the senior author has demonstrated that the so-called basalts are in fact alkali-andesites (Halva, 1961), and we now know that these alkali-andesites or doreites (Mielke, 1965) are of early Miocene age rather than Quaternary age (Bikerman and Damon, 1965). Is it any wonder then that geologists disagree on the nature and time of Basin and Range volcanism, plutonism and tec-tonism? The plain fact is that few definitive Cenozoic fossil sites were available upon which to base a chronology and geologists were forced to guess the ages of rocks in order to achieve the semblance of a time classification. We have now made considerable progress in developing a K-Ar chronology for the volcanic and plutonic rocks of the Basin and Range (Bikerman, 1965; Damon and Bikerman, 1965; Damon et al, 1964 and 1965; Mauger et al, 1965). It is the purpose of this paper to point out the main features of this chronology and to discuss the relationship of magma-tism to orogeny-epeirogeny during post-Turonian time. We will also discuss probable relationships during

Jan 1, 1967

By Takashi Ohya, George V. Keller, Richard G. Geyer

One aspect of a program to improve the chances of survival following coal mine disasters is the development of a communications system which will allow surviving miners to make their circumstances known to rescue teams. At present, it appears that an electromagnetic system may be most practical. The development and design of an effective electromagnetic communications link for signalling between mine workings and the surface requires knowledge of pertinent physical properties of the rocks overlying the mine workings and the characteristics of the ambient noise against which a communications signal must be recognized. Knowledge of the overburden electrical transmission properties is useful not only for determining a practical operating transmitter frequency at a given mine, but also for ensuring the best possible electromagnetic coupling for routine or emergency communication purposes. Field studies of the electrical transmission properties of the overburden of coal mines in Colorado, Illinois, and Pennsylvania generally show that a rela- tively uniform and unimodal electrical conductivity distribution exists provided that the region has not been subject to considerable structural or metamorphic deformation such as that observed in the Gary District of West Virginia. Measurements of ambient surface electromagnetic noise levels at several mines in Colorado, Illinois, and West Virginia were taken and analyzed and are presented in the form of amplitude histogram plots both as a function of frequency and time of day. These amplitude histograms may be used in conjunction with overburden resistivity data in implementing an uplink communications beacon system which will yield a specified signal-to-noise ratio at the surface. Numerous C.W. field transmission tests were made in various coal mining environments with use made of either a buried vertical-axis transmitting loop or a short insulated grounded current line. These transmission tests were made from 20 Hz to 20,000 Hz in frequency and at several geographic surface receiving sites. The results of these field measurements show, in general, good agreement with theoretically calculated results. Since the produced surface magnetic field from a buried vertical-axis loop source or the produced surface horizontal electric field from a buried horizontal current line show better agreement with theoretical results, they could be used for beacon location system. One criterion would be in detecting the equatorial and polar null lines of the horizontal electric field component which is normal to the direction of emplacement of a buried transmitting line current source. A second criterion would be in the surface mapping of the maximum in the vertical magnetic field directly over a vertical-axis loop transmitter and the associated null in the vertical magnetic field at a horizontal offset distance which is about 1.4 times the depth of burial of the transmitter. Finally, a third criterion would lie in the surface mapping of the null in the horizontal magnetic field directly over the vertical-axis beacon and the associated maximum in the horizontal magnetic field at an offset distance from the transmitter axis of half the depth of burial of the loop transmitter. In mapping the vertical magnetic field over a buried vertical-axis loop transmitter, the size effect of the transmitter loop must be taken into account when the separation distances between the transmitter and receiving sensor are less than ten times the effective radius of the source loop; increasing the size of the transmitting source relative to the source-receiver separation distance shifts the null in the vertical magnetic field to greater offsets. In mapping either the vertical or horizontal magnetic field over a buried vertical-axis loop transmitter, care should be exercised in ascertaining that measured nulls and maxima are along radials through the axis of the buried source loop. For the main part, coupling experiments show that ambient electromagnetic noise in coal mining districts is less of a problem above 1000 Hertz. But secondary and perhaps undesirable maxima and null phenomena (as well as penetration problems) would occur in many coal mine provinces in the behavior of the surface horizontal magnetic field (over a buried vertical-axis loop transmitter) if transmission frequencies as high as 10 kHertz were used.

By S. K. Tarby, A. E. Rathke

A series of 0.21 pci carbon steel melts was processed under conditions which sinzulated industrial vacuum degassing practices. The results indicated that the efliciency of carbon deoxidation was not significantly increased by vacuunz degassing at chamber pressures below 100 torr. The two common phenomena of vacuu?rz carbon deoxidation, i.e.,an unaccountable carbon loss and nonequilibrium deoxidation, were observed in this study. Oxygen from adsorbed and chenzically combined water of certain refractory structures was probably responsible for the unaccourttable carbon drop. The nonequzlibrium deoxida-tion phenomenon was adequalely correlated by a bubble nucleation )mechanism. Although the major limiting factor in oxygen removal from these melts contained in alumina crucibles could not be eslablished with certainty, there was some evidence that melt-refractory interactions were not the most imp-portant limiting factor. CONSIDERABLE attention has been given to the use of carbon in conjunction with vacuum degassing* as a deoxidation technique. An advantage of utilizing the reaction: for deoxidation purposes is that the reaction product is gaseous and hence can be effectively removed from the melt. The pressure dependency of Eq. [I] is illustrated by the expression for the thermodynamic equilibrium constant, K: where pco is the partial pressure of carbon monoxide, and hc and ho are, respectively, the Henrian activities of carbon and oxygen in molten steel. The thermodynamic aspects of the C-0 reaction in molten Fe-C-0 alloys have been investigated extensively. Theoretical predictions based on Eq. [2] indicate that, at the chamber pressures reached in most vacuum degassing units, carbon is the most effective deoxidizer that can be obtained. ~ornak' has compared industrial values of carbon and oxygen contents with values calculated from theory, and has shown that on a commercial basis vacuum carbon deoxidation has not achieved the degree of success that is predicted from theoretical considerations of the C-0 reaction. The use of industrial units to determine the reason for this deviation is limited by economics and the difficulty in controlling critical process variables. Therefore laboratory-sized experiments in this area should yield valuable information. Investigations on vacuum carbon deoxidation have been made in experiments conducted under vacuum induction melting conditions where pressures in the low micron range, long treatment times, exposure to highly dynamic vacuum conditions, and relatively quiescent bath conditions have been maintained. Inve~ti~ators~~~ utilizing vacuum induction melting for the production of high-purity iron by carbon deoxidation have concluded that, under high vacuum conditions, melt-refractory interactions constantly supply oxygen to the melt. Thus, it has been suggested that refractory dissociation rather than the C-0 reaction establishes the lowest possible oxygen content of a melt. Thomas and Moreau4 and Bennett, Protheroe, and ward5 have studied carbon deoxidation of Fe-C alloys melted in magnesia crucibles under reduced pressures. The results of both studies differed considerably from those predicted by theory, and the limiting factor for lower oxygen contents was attributed to melt-refractory interactions. Because the refractory material used in both investigations was magnesia, no quantitative measure of crucible reaction could be made and the amount of carbon consumed during treatment was utilized as an indirect indication of the extent of crucible reaction. Studies concerned with the determination of the minimum oxygen content attainable in pure iron and Fe-C alloy material vacuum-induction-melted in various crucible materials have also been conducted."' The suitability of a crucible refractory for use under vacuum conditions appears to depend upon the major refractory constituent, the amount and type of impurity oxides, and the composition of the melt. Meadowcroft and Elliott9 have presented a theoretical review of the type and extent of various refractory reactions which should be considered in vacuum refining. ~eadowcroft'~ considered the vacuum degassing process to be dependent upon the "carbon boil" and has proposed that a part of the difference between the experimental and theoretical results for vacuum carbon deoxidation may be explained by the fact that the pco term in Eq. [2] is not the chamber pressure. Instead, the pressure necessary for carbon monoxide

Jan 1, 1970

By Raymond L. Orr

Calorimetric measurements have been made of the heats of solution of gold axd indium in a number of liquid tin-rich alloys at a temperature of 705°K. Relative partial molar enthalpies of gold were determined as a function of dilute solute concentrations in the binary Au-Sn system and in the ternary Ag-Au-Sn and Au-In-Sn systems. Relative partial molar enthalpies of indium were determined for dilute solute concentrations in the In-Sn, Ag-In-Sn, and Au-In-Sn systems. Through application of the interaction coefficient concept introduced by Wagner and more recently extended by Lupis and Elliott, ualues have been obtained for the Au-Au, Ag-Au, Au-In, and Ag-In enthalpy interaction coefficients in liquid tin. The results are inte@reted in terms of solute atom distributions through comparisons with the predictions of dilute solution models. INTEREST in the thermodynamic behavior of dilute liquid alloys stems from two primary sources. From a practical viewpoint, it is often of importance to know or to be able to predict the effect that one solute will have on the thermodynamic properties of the other solutes in a multicomponent system. Studies of dilute solutions may also be rewarding from the theoretical point of view. Some of the difficulties arising from the more complex interactions possible in concentrated solutions are avoided, leading to easier interpretations in terms of solutibn models and bonding energies. For example, in a binary alloy the limiting values of the partial molar properties of the solute represent the case for which each solute atom is completely surrounded by atoms of the solvent, and no other interactions are possible. Solute - solute interactions in dilute solutions are conveniently treated by the interaction coefficient concept of ~agner.' Using a Taylor series expansion for the logarithm of the activity coefficient, In yi, of a component, i, in a solution consisting of dilute solutes with atomic fractions xi, xj, xk, and so forth, in a solvent, s, and neglecting the second- and higher-order terms, Wagner obtained the expression: Where Wheyz is the limiting value of yi in the pure solvent, s. The interaction coefficients, e:, e:, and so forth, are defined by: Since yi is related to the excess partial molar Gibbs energy of component i by GfS = RT In yi, E: is re- ferred to as the "Gibbs energy interaction coefficient". Lupis and Elliott~ extended Wagner's treatment to the relative partial molar enthalpy, aHi, and the excess partial molar entropy, qS. They defined the enthalpy interaction coefficient as: and the excess entropy interaction coefficient as: leading to expressions similar to Eq. [I]: The three interaction coefficients are related by? The self-interaction coefficients, E:,qf,and at, represent the effects of interactions between atoms of component i in solvent s; €3, q{, and 03 represent the effects of interactions between i and j atoms in solvent s; and so forth. From the Maxwell-type relationships between partial molar quantities, it may be shown1'2 that e{ = ej, r}\ =tj), and ai - crj. Experimental determination of the interaction coefficients requires extremely precise measurements of the appropriate properties as functions of solute concentrations in very dilute regions. Few such data exist for intermetallic alloys, even for binary systems, because of experimental difficulties. This is especially true with respect to enthalpy data for dilute alloys. Examination of the compilation of data for binary alloys by Hultgren, Orr, Anderson, and ~elle~~ reveals that determination of limiting values of &fii(Xi =0) often requires extrapolations to infinite dilution from xi = 0.05 to 0.10. Direct measurements of the enthalpy interaction coefficient, qi, for multicomponent systems are virtually nonexistent. This quantity is of course subject to direct calorimetric measurement, but its determination must be limited to cases where high experimental precision is possible. The heats of solution of gold and indium in liquid tin can be measured with relatively high precision, which makes determinations of 73 involving these metals as the measured solutes experimentally attractive. This paper presents the results of such determinations of the Au-Au, Ag-Au, Au-In, and Ag-In enthalpy interaction coefficients in liquid tin. MODELS FOR DILUTE-SOLUTION BEHAVIOR Random-Solution Behavior. In the quasi-chemical treatment of solutions, only nearest-neighbor bonds are considered, and a composition independent value

Jan 1, 1967

By Kenneth A. Moon

An exact statistical treatment of a one-dimensional model is used as a basis for evoluating the reliability of certain simplified expressions for the activity of the solute in interstitial solutions, including one obtained from the exact expression by setting the repulsive interaction equal to infinity. The latter approximation is found to be satisfactory at low and moderate concentration if the repulsive interaction is large, even though not infinite. A similar expression (identical if the co-odination number is two) is derived from the quasichemical expression of Lacher, and is recommended as the best available expression for the excess configurational entropy of interstitial solutions with excluded sites. Some reasonable models are discussed, and the nature of the saturated solutions is determined by inspection. Some of the models reduce to the one -dimensional case. An analysis is given of the excess partial entropy of hydrogen in V-H; Nb-H; and To-H solutions. MOST treatments of the statistical thermodynamics of interstitial solid solutions have followed the classic paper1 of Lacher in making the simplifying assumption that the configurational entropy of the solution is ideal. However, it is becoming increasingly apparent that there are many interstitial solutions with very large so lute-solute repulsions, and for these the assumption of ideal entropy is not valid or useful. It is important to realize that with substitutional solutions large repulsions between the component atoms must lead to phase separation, whereas in interstitial solutions the free energy of the solution is not drastically increased by large solute-solute repulsions until intrinsic saturation is reached at the concentration where further solute would be forced to enter a site in which it would experience the repulsive effect of one or more solute atoms already present. In the limiting case of an infinitely large repulsive interaction, the excess free energy would be attributable entirely to excess entropy, the enthalpy of mixing being zero. AS will be shown below, even if the repulsions are less than infinite, a treatment based on an assumption of infinite repulsions may be very satisfactory up to moderately high concentrations of the interstitial component. Often in solutions where large repulsive interactions exist, there are also small interactions — often attractive—between solute atoms in configurations other than that corresponding to the large repulsion. In such cases the excess free energy will consist of an excess entropy term attributable to the large repulsive interactions, and an enthalpy term corresponding to the other small interactions. Nomenclature to differentiate succinctly between important cases would be a convenience. In this paper the nomenclature shown in Table I will be used. In Table I, and in the preceeding discussion, excess quantities are defined in terms of standard states which are pure solid solvent and pure (possibly hypothetical) solid saturated phase of the structure in question. In practice, it is more convenient to choose the interstitial element as a component, and its conventional standard state. This will add a composition-independent term to the excess entropy and the enthalpy. The earliest paper known to the present author which treats the thermodynamics of athermal interstitial solutions was given by schei12 in 1951, but the statistical derivations in that paper are open to criticism. Speiser and Spretnak were the first to give a correct statistical treatment,3 limited, however, to concentrations sufficiently low that the number of empty sites excluded from occupancy by more than one filled site is negligible. The purpose of the present paper is to extend the statistical treatment to more concentrated solutions, and to examine the magnitude of the errors introduced by assuming that the repulsive interactions are infinite when in fact they must be finite. THE QUASICHEMICAL APPROXIMATION Fortunately, a standard method already exists for taking into account the effect of large interactions upon the entropy of mixing. This is the quasi-chemical method, in which the probability of existence of a given pair of solute atoms in a certain proximate configuration is assumed to be proportional to exp(-w/kT), where w is the energy increase of the solution when the two atoms are moved from isolated locations in the solution to the configuration in question. A quasichemical treatment of interstitial solutions was given in 1937 in a widely neglected paper by Lacher.4 The result comes out

Jan 1, 1963

By Milton E. Wadsworth, R. Ted Wimber

Cobalt sulfate solutions containing ammonium acetate and chloroplatinic acid were reduced by hydrogen in a pyrex-glass lined autoclave in the temperature range of 170o to 232°C and hydrogen partial pressure range of 115 to 830 psia. The reduction rate was directly proportional to the hydrogen partial pressure and surface area of the pyrex glass and was independent of the quantity of chloroplatinic acid added initially. Experiments involving the variation of the relative concentration of ammonium acetate indicated that the reducible cobalt complex was probably the diacetate complex of cobalt, Co(AC)4H20, or a new mononcetate complex Co Ac, which was in solubility equilibrium with a pink precipitate of CO(AC)-4HzO. THE reaction in which a metal is dissolved by an acid to produce gaseous hydrogen and a salt solution was discovered early in the history of chemistry. In 1859 Beketoff found experimentally that this reaction could be reversed; i.e., a salt solution could be reduced by gaseous hydrogen to produce a metal and an acid. A review of work done on this phenomenon since that time may be found elsewhere., The hydrogen reduction of a cobalt salt solution is facilitated by complexing the cobalt ion. An ammonia complex of cobalt has been reduced commercially in the recovery of cobalt metal. A new reducible complex of cobalt was discovered5 when it was found that a co-baltous sulfate solution containing ammonium acetate could be reduced by hydrogen at temperatures in the region of 200°C. When a cobalt sulfate-ammonium acetate solution was heated to a temperature below its normal boiling point, a violet color became apparent, indicating complex formation. The nature of this complex was investigated5 by the addition of NH4Ac to a CoSO4 solution maintained at 85o. During the first additions of NH, Ac, the pH of the solution remained fairly constant at about 5.85. However, as the ratio of NH,Ac to CoSO, approached two, the pH rose and then leveled off at about 6.05. The absorption spectra of a Co(Ac), solution and a CoSO,, NH Ac solution were obtained at 85°C and were compared and found to be the same. These findings suggested that the diacetate complex of cobalt, Co(Ac),.4H20, was formed at 85°C. When a cobalt sulfate-ammonium acetate solution was heated to a temperature above about 165o, a finely divided pink precipitate appeared. The X-ray diffraction pattern of this precipitate indicated that it was Co(Ac), - 4H,O. In addition, it was discovered that when chloroplatinic acid, H,PtCl;, was added initially to the cobalt sulfate-ammonium acetate solution, a faster reduction was obtained. The roles of the solution complex, pink precipitate and chloroplatinic acid in the reduction process were then investigated. APPARATUS The experimental work was carried out in a two-liter stainless-steel autoclave. Adetailed description of the autoclave and the auxiliary equipment used in maintaining constant temperature and pressure may be found elsewhere.= Because the stainless steel was corroded, and also because it acted as a hydrogena-tion catalyst, an all-glass liner was fabricated such that the solution came only into contact with flame-polished pyrex glass. EXPERIMENTAL PROCEDURE The solutions used in the experimental work were prepared by dissolving reagent grade chemicals in distilled water. Although variation of the brand of ammonium acetate appeared to have no effect on the experimental results, CoSO, 7H O from the J. T. Baker Chemical Co. of Phillipsburg, N. J.,was found to give faster reductions than that prepared by Allied Chemical and Dye Corp., N. Y. The former was used throughout the course of the experimental work and was weighed up at the outset of each experiment. The ammonium acetate was dissolved to form a 6M stock solution, which was stored under refrigeration. A 10 pct solution of chloroplatinic acid (J. T. Baker Chemical Co.) was diluted to a 1.15 x 1Q2 M stock solution, which was standardized by precipitation of K,PtCl, as outlined by Scott. The appropriate volume of the chloroplatinic acid, H,PtCl,, solution was pipetted into the clean, dry glass liner. The cobalt sulfate-ammonium acetate solution, which had previously been saturated with

Jan 1, 1962

By R. D. West

Miscible displacenzent recovers all oil in the area contacted by the injected .fluid, whereas water or immiscible gas drives usually leave substantial amounts of oil as residual. However, the Door mobility ratios associated with a gas-driven miscible displacement cause the sweep pattern efficiency to be much lower than that obtained with water flooding. One way in which the sweep eficiency in a miscible displacement process can be increased is by decreasing the mobility behind the flooding front. This can be achieved by injecting water along with the gas which drives the miscible slug. This water reduces the relative permeability to gas in this area and thus lowers the total mobility. The main operating conditions for the simultaneous injection -vrocess are that a zone of gas exists between the miscible slug and the leading edge of the water and that a su,@cient amount of gas be injected with the water to form the pas volume which is being left in the water zone. Laboratory model studies have shown that the ultimate sweep pattern efficiency can be as high as 90 per cent for a five-spot flooding system. If gar alone is used as the driving medium an ultimate sweep-out efficiency of about 60 per cent would be obtained in the same system. I INTRODUCTION The miscible displacement processes are a step towards total oil recovery. Conventional gas or water drives usually leave 25 to 5.0 per cent of the oil as residual in the swept portion of the reservoir. This residual can be eliminated if the oil is driven by a fluid with which it is miscible. At some reservoir conditions natural gas will become miscible with the oil. This is the "high pressure gas process".' More often, the oil does not contain enough light hydrocarbons to cause the gas to become miscible with the oil at reasonable pressures. In these cases a small band of fluid which is miscible both with the oil and gas must be kept between them2. Less than 2 per cent of the reservoir volume of the slug material is needed to keep the displacement miscible. Both processes work in the same manner, recovering all of the oil in the portion of the reservoir contacted by the injected fluids. The only difference is the manner in which the miscibility between the oil and the injected gas is obtained. Previous publications have contained detailed descriptions of these processes.1,2,3,4 However, total displacement of the oil in the swept region does not guarantee an efficient recovery process. The amount of oil to be recovered is also determined by the fraction of the reservoir contacted by the flood. This fraction is largely determined by the mobilities of the fluids. (The fluid mobility is the permeability of the rock to that fluid divided by the fluid's viscosity, k/p). This. dependence of the fraction swept on the mobility ratio has been shown in previous studies. Fig. 1 shows the ultimate fraction swept in a five-spot system as a function of the mobility ratio. The small drawings show the location of the areas left unswept for two different mobility ratios. The ultimate fraction of the reservoir swept is here considered to be attained when the producing stream contains less than 5 per cent oil at reservoir conditions. THE GAS-DRIVEN MISCIBLE DISPLACEMENT Since there is no oil left in the swept region after miscible displacement the mobility in this region is very high. It is often 50 times the mobility in the unswept regions. This means that the fraction of the reservoir contacted by the injected fluid will be less for a gas-driven miscible displacement than for a conventional water or gas drive. For a five-spot injection system, water would contact the entire reservoir volume, and the low pressure gas would contact about 90 per cent of this volume, while a gas-driven miscible displacement would only contact about 65 per cent of the reservoir. This poor sweep efficiency often offsets the benefits obtained through miscible displacement. Fig. 2 shows what the recovery curves for the three processes might look like for a five-spot system. The curves show the fraction of the in-place oil recovered as a function of reser-

By F. Weinberg, E. H. McLaren

Dilute binary alloys have been solidified under controlled thermal conditions, and solute distributions, temperatures during freezing and melting, and the position and morphology of the solid-liquid interfaces have been examined. Binary Zn, Sn, and Pb based alloys were investigated with solute additions of AgU°, AU°, Sb'24, TlZo4, snH3, and Zns5. Approximately 150 cc of metal was used in each ingot. Appreciable solute segregation occurred in most of the ingots, depending on the solute concentrations, distribution coefficients. and freezing conditions of the alloys. Measurements were made of the general solute distribution by sectioning layers of material from the ingot circumference and counting the activity of each layer. Local segregation was detected by autoradiographic techniques. Freezing and melting curves for the same alloys were obtained by precision resistance thermometry. These curves are related to the corresponding measured solute distribution curves and those calculated from theoretical expressions. The position and morphology of solid-liquid interfaces during freezing were determined by both decanting and quenching techniques. The results indicate the manner in which freezing and remelting occurred under the conditions investigated. If an isomorphous dilute binary alloy is solidified or melted under equilibrium conditions, the concentration of solute in both solid and liquid would be uniform at all stages in the freezing process. The solute concentrations during freezing could be determined from the phase diagram of the alloy, and the freezing curves would have an alloy slope defined by the solidus and liquidus points. In practice, however, solidification under equilibrium conditions rarely, if ever, occurs, primarily because of low rates of diffusion in the solid and incomplete mixing in the liquid. As a result, the solute distribution and the shape of the freezing and melting curves obtained in a given system depends on a number of factors. These include, in addition to the extent of diffusion and mixing, the initial solute distribution and concentration, the distribution coefficient, the rate of freezing or melting, supercooling of the liquid, the morphology of the solid-liquid interface, and the effect of annealing. The purpose of the present investigation was to determine, experimentally, actual solute distributions and thermal curves for a series of dilute binary alloys, using tracer techniques to determine the solute distributions and precision resistance thermometry for the temperature measurements. In addition, observations were made of the positions and morphologies of the solid-liquid interfaces during freezing and remelting. The distribution of solute in a dilute alloy, assuming complete mixing in the liquid, and negligible diffusion in the solid, is given by1 where Co is the mean solute concentration of the alloy, C, is the solute concentration in the solidg is the fraction of the ingot solidified, and ko is the equilibrium solute distribution coefficient (assumed to be independent of concentration for dilute alloys). For the case of partial mixing, ko can be replaced by an effective distribution coefficient k. If solute transport in the liquid is assumed to be entirely due to diffusion, with negligible diffusion in the solid, then the solute distribution in the solid is given by Tiller et a1.' as where R is the rate of advance of the solid-liquid interface, D is the solute diffusion coefficient in the liquid, and x is the position of the interface from the start of freezing. The temperature at the interface TI is related to the solute concentration of the solid at the interface C, by the expression where Tm is the freezing temperature of the pure solvent and ml is the slope of the liquidus for the binary alloy being considered. Accordingly, by relating TL to the actual temperatures measured in the present experiments, solute distributions can be deduced from the temperature measurements. Using the above expressions, the measured solute distribution of a given alloy may be compared to the theoretical distributions, as well as to the distribution calculated from the observed freezing curve. EXPERIMENTAL The solvent materials used in making up the binary alloys were C. P. New Jersey zinc (99.999 pct), Vulcan Extra Pure Tin (99.999 pet), and Tadanac lead (99.998 pct). The solute elements were of 99.99 pct purity or better, and were activated in the

Jan 1, 1963

By S. K. Basu, H. H. Kellogg

THE physical-chemical behavior of the system Pb-S-0 is of prime importance to the understanding of lead smelting processes, yet little accurate information is available on either equilibrium or kinetic behavior in this system. This paper is the first report of a program designed to fill gaps in our knowledge of this system. In the total ternary Pb-S-0, the region of greatest metallurgical interest is that bounded by the compositions Pb-PbS-PbS0,-PbO-Pb. Systems richer in sulfur, or richer in oxygen,* than those essentially pure SO2. This conclusion follows from the fact that all systems are in a highly reduced state, since either PbS or Pb is a constituent of all the equilibria. The content of 02, SO3, S2, S6, S8, and so forth, can be shown to be negligible compared to SO, in all such systems.* corresponding to this region can only be obtained at gas pressures exceeding 1 atm, a condition seldom met in lead smelting practice. Not only is the present study limited to condensed phases within this portion of the total system, but it is limited to temperatures at which all phases are pure solids, except for lead, which is liquid. In this limited system the following seven condensed phases are known to exist: Pb(l), PbS(c), PbO(c), PbSO,(c), PbSO,•PbO(c), PbSO4 • 2PbO(c), and PbSO, -4PbO(c). PbO exists in two crystal modifications,' but only the high-temperature yellow form is considered here. Schenck and co-workers2-4 reported the compound PbSO4 3Pb0 to be stable at high temperature, but the more recent work of Lander,5 and the present work, prove that the tetra-basic sulfate, rather than the tri-basic sulfate is stable. Fig. 1 shows the composition diagram for the binary PbO-PbSO2, based primarily on the work of Lander. In this study the univariant boundaries and invariant points existing among these seven condensed phases and the gas phase have been determined. In a ternary system, the phase rule indicates that an invariant point involves the simultaneous equilibrium of five phases—four condensed phases and the gas phase. A univariant relation involves four phases—three condensed phases and the gas phase. The gas phase in the systems studied is The following stable univariant equilibria between SOz and the condensed phases were identified: (a) PbS + 7PbS04 = 4(PbSO, - PbO) + 4SO2 (b) PbS + l0(PbS04 • PbO) = 7(PbSO4- 2PbO) + 4SO2 (c) PbS + 8(PbSO4 • 2PbO) = 5(PbSO4 . 4PbO) + 4SO2 (d) Pb + PbSO, • 4PbO = 6PbO + SO2 (e) 3PbS + PbSO4 . 4PbO = 8Pb + 4SO2 (f) 3PbS + 16(PbS04 PbO) = 7(PbSO4 . 4PbO)+ 12SO2 (g) 2PbS + PbSO,2PbO = 5Pb + 3SO2 (h) Pb + 3(PbSO4 . 2PbO) = 2(PbSO,. 4PbO) + SO, Of these eight univariant equilibria, five were measured in this work (a, b, c, d, and g) and the behavior of the other three (e, f, and h) was calculated by thermodynamic analysis of the measured data. Two invariant points were found corresponding to simultaneous equilibria as follows: Point 1: PbS, PbSO4PbO, PbSO4.2PbO, PbSO, - 4PbO, and SO2 Point 2: Pb, PbS, PbSO, . 2PbO, PbSO, - 4PbO, and SO2, From the measurements it was also possible to calculate the thermodynamic properties of the three basic sulfates of lead at 298.16°K. EXPERIMENTAL Apparatus—The experimental method consisted of the measurement of the gas pressure exerted by a given reaction mixture at a given temperature. An iridium crucible was used to contain the reaction mixture. There was no evidence of attack of the iridium,* but after use at high temperature for a week

Jan 1, 1961

By R. R. Vandervoort, W. L. Barmore

Tensile creep experiments were conducted on high-purity, poly cvystalline rhenium from 1500" to 2300°C at stresses from 1500 to I0,OOO psi in a vacuum of 10-a torr. The apparent activation energy for creep was 60 kcal per mole, and the steady-state creep rate varied directly with stress to the 3.4 power. Dislocation substructure that developed during creep was studied by transmission electron microscopy. Possible rate-controlling deformation mechanisms are discussed. The creep behavior of most metals at elevated temperature can be represented by the following equation:&apos;&apos;&apos; t = Cf(s)(^)(s/E)nD [1] where i = steady-state creep rate, C = constant, f(s) = a function involving microstructure, s = applied stress, E = the average elastic modulus at test temperature, n = constant, D = diffusion coefficient According to this well-established relationship, metals with higher elastic moduli and lower diffusion coefficients should have greater creep resistance at the same stress and temperature and equivalent mi-crostructures. While no diffusion data are available, the diffusivity of rhenium should be less than that for most other refractory metals because of its high melting point and hcp crystal structure. The Sherby-Simnad relation for calculating atomic mobility in metallic systems3 predicts that the diffusion coefficient for rhenium is less than that experimentally determined for tungsten4 in the temperature region 1500. to 2200°C. At these temperatures the elastic modulus for tungsten5 is only slightly larger than the extrapolated modulus for rhenium.6 Thus, rhenium is a good possibility for a a high-temperature structural material, but few data on the creep of rhenium have been reported. This investigation was undertaken to study the high-tempera-ture deformation behavior of rhenium in detail. EXPERIMENTAL TECHNIQUES The material used in this study was consolidated from high-purity powder. After cold pressing the powder to a plate a in. thick, the billet was sintered in hydrogen at 2250°C for 24 hr. The plate was reduced to 0.100 in. by cold cross rolling with intermediate anneals at 1650°C for 20 min between passes. The plate was further reduced to 0.060 in. by unidirectional cold rolling with similar heat treatments between passes, and then finally stress-relieved in hydrogen at 1650°C for 30 min. Specimens tested at 1900°C and below were pretest-annealed at 1900°C for 2 50 hr. Specimens tested above 1900°C were pretest-annealed at 2400°C for 5 hr. The impurity content in the "as-received" plate was quite low, table I. Essentially no change in impurity levels was detected in specimens after creep testing. All creep tests and annealing treatments were conducted in a vacuum of 10-8 torr in a test furnace heated by a tungsten mesh element. The load was applied to the specimens through a bellows, and stresses were maintained to ±1 pct of the selected value by periodic corrections for changes in specimen cross-sectional area during creep and for changes in the bellows spring force due to load column extension. One-inch-diameter tungsten force rods were used in the hot zone of the furnace. Deformation at temperature was measured by optically tracking gage marks on the specimen. Temperature was measured by a calibrated optical pyrometer and was determined to ±5"C. Grain sizes were determined by the linear intercept method and specimens were examined in the "as-polished" condition, using polarized light. Specimens annealed at 1900°C had a grain size of 52 ± 5µ , and those annealed at 2400°C had a grain size of 148 * 11 µ. Pieces were cut from the gage section of creep-tested specimens and planed to a thickness of about 0.010 in. by spark discharge machining. Thin foils for viewing by transmission electron microscopy were obtained by electropolishing in a solution of 6:3:1 ethyl alcohol, perchloric acid, and butoxy ethanol, respectively, using the window technique. Bath temperature was —4OoC, and the cell potential was 35 v. The foils were examined in Siemens Elmiskop I, operating at 100 kv. RESULTS AND DISCUSSION In order to analyze the results from creep experiments, Eq. [I] is rewritten in the following form: <=Kf(s)ne-/RT [2] where K = constant, ?// = apparent activation energy for creep,

Jan 1, 1970