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By R. Webeler

In order to study the role of work hardening in the fatigue process, use was made of the great sensitivty of the resistivity of AuCu to cold work. A change of the resistivity of AuCu of the order of 1 to 2 pct at the temperature of liquid nitrogen was found to occur as a consequence of severe fatigue. ACCORDING to Orowan's theory,' the process of fatigue In metals 1s associated with the production of a number of small regions which have undergone strain hardening. This phenomenon is supposed to occilr even if the stress applied during fatiguing is always smaller than the yield stress. In an attempt to verity the existence of such regions, Welber and Webeler' undertook to detect the stored energy associated with severe fatigue in copper. Previous experiments" had shown that the energy stored in a sample of copper which has been cold worked by torsion is released in the temperature range between 150" and 250°C when the sample is heated from room temperature and that no more energy is released (or absorbed) between 250" and 450°C. In particular the stored energy amounted to 0.41 cal per g for a case in which the mechanical energy expended in twisting the sample was 11.9 cal per g. In the case of fatigued copper, however, no release of stored energy could be detected between 150" and 250°C, so that the experimental error of &0.02 cal per g represents an upper limit for the amount of energy stored in strain hardening., It seemed desirable to attack the problem in a new fashion. For this purpose, it was decided to make use of the fact that, if an alloy capable of undergoing the order-disorder transition is ordered and then cold worked, the resistivity, p, increases very greatly above the value for the ordered state even if the deformation is very small. Some insight into the nature of the fatigue process may be obtained then by measuring the resistivity of an ordered sample before and after subjecting it to fatigue. For reasons which will become apparent from the following remarks, considerably more can be learned by carrying out the resistivity measurements at two different temperatures. In the case of a material containing impurities, vacancies, dislocations, or other imperfections of essentially atomic dimensions, the resistivity, p, according to Matthiessen's rule, can be represented as a sum of two terms p = p, + p, where p, is the (temperature dependent) resistivity of the pure metal, and p, is the temperature independent contribution of the imperfections. Briefly, the physical basis for this rule is the following: The main contribution of the impurities in question to the resistivity results from the fact that they interrupt the periodicity of the lattice and thus scatter the conduction electrons with a probability which is almost independent of temperature. In order that this be the case, it is necessary that the' extension of the impurities be small enough—roughly less than one electron mean free path—so that their main effect on the resistivity occurs for the foregoing reason. If an alloy like AuCu is partly or completely disordered by quenching from an appropriate temperature, Matthiessen's rule also applies to a very good approximation* with p, representing in this case the resistivity po of the ordered sample and p, the additional (temperature independent) resistivity due to the disorder. In general, the disorder can be represented in terms of atoms which are displaced from their "proper" positions in the superlattice and which thus qualitatively represent the imperfections in the superlattice responsible for the term p,. Since the misplaced atoms are distributed at random throughout the super-lattice, their contribution to the resistivity still can be considered in terms of the scattering of conduction electrons by lattice defects. The situation is somewhat more complex in the case of an alloy disordered by cold work because the process of disordering here does not involve a random redistribution of the atoms; however, Matthiessen's rule also holds in this case. Whenever Matthiessen's rule does apply, the values of the quantity /3 = (p? — /(T, — T,), where p, and p, are the values of the resistivity at two fixed temperatures, T, and T,, respectively, is constant (independent of p,) for a given alloy or metal. In particular, if a sample of AuCu is subjected to ordinary cold work, the value of /3 remains equal to Po, the value for the ordered material. According to Orowan's theory,' as remarked before, a fatigued sample contains a large number of isolated severely cold-worked regions, which make up only a small proportion of the metal. Thus, if a sample of AuCu initially in the ordered state is fatigued, more or less disordered regions will be produced within the ordered material. If these regions are small enough so that Matthiessen's rule applies, then it follows from the previous discussion that /3 again will remain equal to Po. If the effect of fatigue is to produce cold-worked regions which are macroscopic—of the order of at least several electron mean free paths—the effective resistivity, p, has to be computed by use of the ordinary laws of large-scale electrodynamics. For the sake of simplicity, it will be assumed here that the cold-worked regions are completely disordered and have a resistivity, p,. For a given proportion A of disordered regions the effective resistivity, p, for the current in a given direction depends on the geometrical configuration of these regions. In any case, the value of p for such

Jan 1, 1956

By C Nucifora, M Landers, J Jones, G Maddocks, K Mandaran, A Forbes, W Wilson, S Newman

Glencore’s Mount Isa Mines Limited (MIM) operates the Mount Isa open cut and underground copper (Cu) and zinc-lead (Zn/Pb) mines near Mount Isa in Queensland, Australia. Tailings from processed Cu and Zn-Pb ore is contained in a 1,315 ha shallow (< 35 m deep) multi-cell valley fill tailings storage facility (TSF). Static geochemical testing conducted by MIM over the life of mine (LoM) verifies that the Cu, and Zn-Pb tailings has a wide range in sulfide content and diverse mineralogy with significant acid neutralising capacity (ANC) in some samples. The tailings are predominantly classified as potentially acid forming (PAF) using static analytical methods. Kinetic leach testing using free draining columns and humidity cell tests simulating tailings placed on the surface of the TSF suggest that the tailings samples are likely to remain non-acid forming (NAF) for 10 to 40 years under aerial exposure, and much longer than this under saturated conditions within the TSF. During this period of weathering, as ANC is depleted, the neutral pH drainage may contain elevated concentrations of some elements including sulfate, manganese and zinc. Only when the ANC is depleted would the tailings then begin to produce acid drainage. CITATION:Mandaran, K, Jones, J, Nucifora, C, Maddocks, G, Landers, M, Forbes, A, Wilson, W and Newman, S, 2018. Mount Isa Mines Rehabilitation Materials Sampling and Analysis program for closure planning, in Proceedings Life-of-Mine 2018, pp 138–140 (The Australasian Institute of Mining and Metallurgy: Melbourne).

Jul 25, 2018

By J. Chipman, N. J. Grant, H. L. Bishop, H. N. Lander

Data of several studies on the equilibrium between molten iron and open hearth-type slags have been combined to determine some of the chemical reactions involved in steel-making. Effects of slag composition and temperature on the iron oxide activity, distribution of sulfur between slag and metal, and the carbon content of the metal are discussed. Also, an overall reaction for the equilibrium between sulfur and oxygen is presented. DURING the past 15 years, a number of significant equilibrium studies have been carried out between liquid iron and simple basic and acid slags in an effort to throw light on the chemical reactions involved in steelmaking. This paper is a summary of the experimental reports on investigations which have been conducted at the Massachusetts Institute of Technology, and of related work in other laboratories. The investigations summarized in this paper include the works of Fetters and Chipman1 and Taylor and Chipman,' which dealt with simple slags that are similar to those found in the open hearth. The sulfur determinations of the slag-metal tests of Fetters and Chipman as reported by Grant and Chip-man" are included. Also, the investigations by Win-kler and Chipman' and Grant and ChipmanQ f more complex slag systems are included in this summary. The experimental procedure is described in detail in each of these papers and will not be discussed. Since the previous reports have been somewhat independent, it is desirable to review and combine the data of the various investigations to determine, as accurately as possible, the reactions in the slag-metal systems of the open hearth. It is the object of this report to present the combined data in such a way as to enhance their utility and applicability. Oxidizing Power of Slags of the System (CaO+MgO)-Si0,-FeO in Equilibrium with Carbon-Free lron The slags selected to determine the iron oxide activity in equilibrium with pure liquid iron were those containing less than 2 pct each of P,O,, MnO, or A1,0, on a weight percentage basis. The method used to calculate activities of iron oxide in liquid slags was that developed by Taylor and Chipman.' The solubility of oxygen in molten carbon-free iron under pure iron oxide slags can be expressed by the following eauation —6320 log (pctO)-------------— + 2.734 [1] where T is the absolute temperature. The oxygen solubility values as determined from Eq. 1 were used throughout this study to calculate the iron oxide activity. The iron oxide activities of slags of various iron oxide contents are plotted in Fig. 1 as a function of the basicity, which is defined as the ratio (pct CaO + pct MgO)/pct SiO,, and are based on molecular percentage values of the components. The percent (FeO), is the total iron content in the slag calculated to FeO. Fig. 1 shows that as the basicity increases at constant mol pct (FeO),, the iron oxide activity increases rapidly and reaches a plateau which extends on the basicity scale from about 1.3 to 2.3; the iron oxide activity then decreases rapidly until a basicity of about 3.0 is reached, where it tends to level off. The solid portions of the curves represent the experimental data of Fetters and Chipman and Win-kler and Chipman. Their experimental heats were made in magnesia crucibles, and hence the slags were saturated with magnesia. The broken lines on the left represent the experimental data of Taylor and Chipman, who used a rotating crucible. In general, these slags contained less than 3 pct MgO. The absence of data for slags containing less than about 40 mol pct (FeO), and basicity ratios greater than about 2.5 made it necessary to calculate curves using ionic concepts of slags. The broken lines on the right, which disregard the solubility limits of di and tricalcium silicate and lime, were obtained by following the treatment of Flood and Grjotheim,"

Jan 1, 1957

By Richard H. Kennedy, G. A. Swanquist, John W. King, Frank F. McGinley, Dale C. Mathews, Hans H. Adler, E. C. Peterson, Ralph M. Wilde

INTRODUCTION From the first historical records of the discovery of uranium as an element and the attempted classification of its minerals in the early 18th century-through its first uses in pigmentation and the coloring of glasses and ceramic glazes-until 1939 when it was discovered that the isotope U235, was fissionable, uranium oxide in the form of pitchblende ores and concentrates (produced mainly in Bohemia, Canada, and the former Belgian Congo) in recent times was the source of uranium compounds incidental as byproducts to the recovery of radium from this invariable associated source. In 1938 this byproduct production from pitchblende concentrates was about 471 st of U3O8, with over 90% from Canada and the Belgian Congo and only 25.85 st from carnotite ores in the United States.1 Under the impetus of the Atomic Energy Commission's (AEC now part of the Energy Research Development Administration) domestic and foreign production incentives and buying programs, and as an initial assurance of atomic armament capability of the United States and the Free World, the growth of the uranium mining and milling industry burgeoned from 1952 to 1962. After a short period of decline, in the second decade and in large commitments beyond, it has again extended its capacity to meet ever-increasing fuel demands of atomic power generation by the electric utilities industry. In 1961 the peak production in the United States alone was 17,758 st of U3O8. Peak aggregate domestic and foreign deliveries of 34,581 st of U3O8 to the AEC occurred in 1960.z Canada's maximum delivery of 13,506 st of U308 was made in 1959. These peak and continued productions in the Free World are largely from: the Mesozoic (Jurassic) and Tertiary (Eocene) sandstones in the United States; the quartz pebble conglomerates of Canada and the Witwatersrand; pegmatites, Jurassic limestones, and Precambrian complexes, with less but significant production; the phosphoria, where byproduct production is minor. This uranium production in the form of precipitated concentrates has come from the milling of ores from these sources, both directly and by retreatment of gold cyanidation tailings on the Witwatersrand. Milling of crude ore has followed these processes: conventional crushing and size preparation, ore drying when required, salt roasting for high vanadium ores and byproduct vanadium recovery, carbonate or acid-leaching processes, classification sand-dine separations or countercurrent decantation (CCD) circuits and complete liquid-solids separations, resin-in-pulp (RIP) or liquid-liquid (solvent) ion-ex- change extractions, clarification of pregnant liquors, precipitation, filtration and washing, sodium and vanadium removals, and drying or roasting and packaging of the high-grade, high-purity uranium concentrate commonly referred to as "yellowcake." Coupled with the hazards and control of dust generation incident to conventional crushing and milling operations, more stringent control of airborne respirable and ingestible radioactive particulates and the protection of personnel against definitive external radiation are inherent to uranium milling. Impoundment and control of tailings and other effluents of uranium milling are more restrictive than in conventional practice, be- cause long-term disposal and containment of the uranium series of radionuclides, whether in solution or in solid form, are requisite to uranium milling and are made manadatory under regulatory agencies of government. 2. GEOLOGY AND MINERALOGY OF URANIUM Early Uses and Byproduct Production of Uranium Uranium was discovered by Klaproth in 1789 but had little commercial importance until the discovery of uranium fission by Hahn and Strassman at the close of 1938. The well-known uranium ores of Joachimsthal, Czechoslovakia, the Congo, and the Colorado Plateau were early sources of radium. Minor quantities of uranium were used for small-scale technical and industrial applications, particularly in coloring glass and ceramics, but most of the uranium was discarded. The Colorado ores were also mined later, chiefly for vanadium. Impetus of Armament Capability and Fuel Demands for Atomic Power Following the discovery of atomic fission, uranium became critically important for military applications and, more recently, as a nuclear fuel. Prior to 1966 uranium was acquired in the United States almost solely for use in the weapons program of the AEC. By 1970 the AEC had procured approximately 325,000 st of U3O8 from domestic and foreign sources. Current and future marketability is primarily dependent upon commercial demand for reactor fuel. Estimates of

Jan 1, 1985

By Robert M. Dreyer

Although lateritic deposits have long been a principal source of bauxite and are becoming an increasingly important source of nickel, the problems in the evaluation of such deposits are not generally understood. In the evaluation of lateritic bauxite and nickel deposits, there are many similarities, but there also. are significant differences. It has long been recognized that laterites with commercial concentrations of trivalent metals represent the ultimate in the intense leaching of tropical soils. Any factors which effect-the rate of soil leaching will effect the form of local lateritic concentrations. Although the most intense leaching generally occurs on somewhat elevated areas of gentle relief where there is a free downward flow of rain water, the- effect of local rock structures in effecting varia¬tions in soil metal concentrations has-not been well understood - primarily because the laterite forms a masking blanket over the rocks from which the laterites were derived. All of the-factors which facilitate downward movement of water may effect greater surficial concentrations of trivalent metals. Such features as zones of fracturing, zones of greater rock permeability, and areas of karst topography may, therefore, be responsible for greater leaching. The variations in rock structures and the vagaries of ground water flow pat¬terns impart, to the laterites, rapid lateral and vertical variations in thickness and metal concentrations. Because of such rapid

Jan 1, 1970

By E. H. Kurt

INTRODUCTION The simplest way to drill a hole into rock is to strike a steel chisel or drill bit with a hammer. Early miners used this elementary hand technique so successfully in "single jacking" and "double jacking" that the first mechanical rock-drill designers sought to duplicate it. However, in the early developments, the designers were forced to retreat to a construction known as the "piston drill," wherein the entire drilling element is tied to the piston and reciprocates with it. It took nearly 50 years to devise a method of divorcing the two elements and to achieve the original hammer principle used in hand drilling. The Mont Cenis tunnel, drilled through the French Alps in 1861, usually is considered the birthplace of the mechanical rock drill. The Hoosac tunnel in Massa¬chusetts was drilled at about the same time, and the success of these two ventures paved the way for innova¬tions that produced the Burleigh, Ingersoll, Sergeant, and Waugh piston drills between 1870 and the turn of the century. In 1897, George Leyner of Colorado introduced what has been considered the most significant development in rock-drill history. He devised the hollow drill steel for water flushing; when combined with his free-piston hammer drill, this became the first lightweight and dust¬free underground machine. In addition, Leyner's drills introduced improvements such as automatic rifle-bar rotation of the drill steel and chuck, automatic lubrica¬tion, and an enclosed throttle control. During the 1920s and 1930s, automatic feeds, centralizers, sliding cones, and the automatic water back head were developed, laying the groundwork for all pneumatic underground drills currently in use. Since these pioneering efforts, rock-drill development has been concerned primarily with refining the designs and improving the metallurgy to make faster, lighter, and more dependable machines. Fig. 1 illustrates the progress in drilling speed during the first 125 years of rock-drill development; that progress is a credit to the persistence and inventiveness of the designers in the rock-drilling industry. ROCK-DRILL CLASSIFICATIONS To meet the variety of conditions encountered in rock drilling, several distinct types of drills have been de¬veloped. In general, rock drills may be classified as either hand-held or mounted, with the hand-held ma¬chines including the jackhammer or sinker, the jackdrill or jackleg, and the stoper. The mounted drills are com¬monly known as "drifters." Table 1 shows that each type of drill is available in several sizes from different manufacturers. Fig. 2 illustrates a typical rock drill, showing the principal components. The jackhammer or sinker, shown in Fig. 3, is used primarily for general mine utility work such as drilling anchor holes (short vertical holes to bolt or anchor machinery), pin holes (short, usually horizontal holes to fasten sheaves, etc. to side walls), popholes (for blasting large boulders), and similar applications. They also are used for shaft sinking. Jackhammers are classified ac¬cording to weight, and they range from 7 to 30 kg (15 to 65 lb). The rock drill originally known as a jackleg was made by clamping a pneumatic cylinder or leg to a jack¬hammer, both to support the weight of the machine and to feed the tool forward in horizontal or uphole work. The more modern jackdrill refined this concept to make the hinged pivot for the leg integral with the drill cylinder and to group all drill and leg controls in the drill back head for convenience. Fig. 4 illustrates a typical jackdrill. Jackdrills are classified according to cylinder bore size, ranging from 60 to 83 mm (2.375 to 3.25 in.). Because of their light weight and versatility, jack drills are very effective in small drifts, small tunnel head¬ings, and stoping. The larger machines are applied to hardrock formations and in applications where drilling speed is a primary consideration. In soft formations or

Jan 1, 1982

By R. Gibala

Internal-friction measurements on hydrogen-charged iron over the temperature range 4° to 300°K are reported. Two relaxation peaks, the hydrogen Snoek peak at 48 °K and the hydrogen cold-work peak in the range 145" to 2200K, are observed at 80 kc per sec. The effects of hydrogen-charging, aging, and deformation on the internal-friction results are determined and are used to show evidence of partitioning of hydrogen between solid solution and dislocations. The hydrogen-dislocation binding energy is estimated from the behaviors of the relaxation tiwzes and relaxation strengths of the Snoek peak and the cold-work peak. Its value is approxi,mately 6400 cal per mole. MANY investigators have demonstrated the usefulness of internal-friction measurements in determining the manner in which interstitial impurities interact with dislocations in bcc metals. Part of this success has resulted from the existence in bcc interstitial alloys of two anelastic relaxation peaks—the Snoek peak' and the cold-work or Koster peak2 (designated hereafter by SP and CWP, respectively). The SP has its origin in the redistribution of interstitials in solid solution among sites made energetically nonequivalent by an applied stress. The rate at which the redistribution occurs, measured by the relaxation time for the process, is related in a simple way to the diffusion rate of the interstitial in the free solution. The relaxation strength is proportional to the concentration of interstitial in solid solution. The CWP appears to have its origin in the relaxation of an interstitial-dislocation complex for which the relaxation time at a given temperature is much longer than that for the SP. The relaxation strength depends strongly on the concentration of interstitial and the amount of deformation at relatively low concentrations and deformations.2-8 From the dependence of the relaxation strength on interstitial concentration, the SP and CWP may serve as measures of the concentrations of interstitials in free solution and bound at dislocations, respectively. Thus their behaviors have been used to investigate interstitial-dislocation interactions in Fe-C, Fe-N, and several refractory metal systems.'-' However, the Fe-H system has not been studied extensively,? even though disputes in recent years over the mechanism of hydrogen embrittlement in steels involve argument over the extent to which lattice hydrogen and hydrogen-dislocation interactions play an important role.?-'' Previous work on Fe-H indicates the internal-friction behavior to be qualitatively consistent with that for other systems. Apparently, both a SP and a CWP are observed in the temperature ranges 30" to 50°K and 100°to 140°K, respectively (at 1 cps). However, there is neither sufficient nor accurate enough information to identify convincingly these peaks with their supposed counterparts in other systems. Nor have there been any attempts to make quantitative use of these peaks to study hydrogen diffusion, aging, or interaction processes. In this paper, an attempt is made to obtain more complete information on internal friction of hydrogen in iron than presently available. Internal-friction measurements in the range 4° to 300°K on hydrogen-charged iron show that the two peaks discussed above are in fact the hydrogen SP and CWP. Several effects of hydrogen charging, aging, and deformation on these peaks are observed and are used to determine the partitioning of hydrogen between solid solution and dislocation sites in iron. EXPERIMENTAL Materials. The starting material for this investigation was a high-purity iron supplied by National Research Corp. as a 1-in.-diam rod. The following analysis was given (inwt pct): C, 0.004; N, 0.0003; 0, 0.007; P, 0.002; S, 0.005; Si, 0.006; Mn, 0.001; Cu, 0.002; Ni, 0.005; Cr, 0.001; Mo, 0.001. After an initial vacuum anneal (-5 XTorr) at 700°C, the rod was cold-

Jan 1, 1968

By Robert E. Wood

The compressibility factors, Z, of helium, nitrogen, and helium-nitrogen mixtures in the three-dimensional space of temperature, pressure, and gas composition have been related to the Leiden form of the virial equation of state. The dependency of virial coefficients through the fifth on temperature and gas composition has been established for the temperature range 133.15° to 748.15° K. Compressibility factors, Z, have been computed from the equation of state and tabulated as functions of gas composition, pressure, and temperature. Tabular values of Z are presented for 30.00 through 100.00 percent helium for temperatures from 240° through 700° R for pressures from 14.696 through 3,050 psia and for temperatures from 720° through 1,300° R for pressures from 14.696 through 1,500 psia. Tabular values of Z are presented at increments of 5.00 percent helium and 20° R, and, for pressures greater than 50 psia, at increments of 50 psi.

Jan 1, 1967

By Joel N. Van Sant

THIS REPORT describes the occurrence, mining, and use of refractory clay in Colorado within Region III of the Federal Bureau of Mines, which includes the States of North arid South Dakota, Nebraska, Wyoming, Colorado, Utah, New Mexico, and Arizona. Field work by the Bureau of Mines, United States Department of the Interior, included examination of active and abandoned refractory-clay mines as well as a reconnaissance survey and sampling of numerous clay-bearing formations exposed in Colorado. Information from the survey and the sampling will help guide private industry in its search for virgin sources of refractory clay. Library research of published and unpublished reports from various Federal, State, and private sources was conducted during the early phase of the investigation. Most of the refractory clay mined in the Denver-Golden district of Colorado is not used for refractory purposes but is blended with other clays in the manufacture of structural clay products. The predominantly flint-clay de-posits in the Pueblo and Fremont County districts are mined and utilized chiefly in fabricating refractory products.

Jan 1, 1959

By Herbert H. Einstein

This report contains the documentation for 11 computer programs representing the entire computer documentation for the eight-volume report entitled "Risk Analysis for Rock Slopes in Open Pit Mines." A detailed summary of the programs is included.

Jan 1, 1979

By P. Chiotti, J. T. Mason

Ther?nal, X-ray, metallographic, and vapor pressure data were obtained to establish the phase diagram and standard free energy, enthalpy, and entropy of formation for the compounds in the Sw-Zn system. Four compounds, SmZn, SmZn2 , SmZn4.s, and SmZn8.5, melt congruently at 960°, 94Z°, 908°, and 940°C, respectively. The cornpounds SlnZns, Sm3Znll, and SnzZn7.3 undergo peritectic decomposition at 855", 870°, and 890C, respectively. Another compound of uncertain stoichiometry, SmZn11, undergoes peritectic decomposition at 760°C. Four entectics were observed with the following compositions in weight percent zinc and eutectic tenzperatures in degrees Centigrade: 12 pct, 680°C; 36 pct, 890°C; 58 pct, 850°C; and 72 pct, 900°C. An allotropic transformation and a composition range were observed for the SmZnz compound. The transfor)nation varies from 905" to 865°C as the zinc content increases from 16.0 to 48.5 wt pct, respectively. The free energy of formation of the compounds at 50PC varies between -15.9 kcal per mole for SmZn to -51.1 kcal per mole for SmZn,.,. Corresponding enthalpies vary between -19.2 to -78.3 kcal per mole. The ther-modynamic properties for the liquid alloys are described by the relations: A search of the literature revealed very little information on the Sm-Zn system. Chao et al.&apos; as well as Iandelli and palenzonai have reported the structure of SmZn to be cubic B2 type and Kuz&apos;ma et al3. have reported the structure of -sm2zn17 to be of the Th2Ni17 type. The purpose of this work was to establish the phase diagram of this system, to determine the zinc vapor pressure over the solid two-phase regions of the SYstem, and to calculate the thermodynamic properties of the compounds. MATERIALS AND EXPERIMENTAL PROCEDURES The metals used in this investigation were Bunker Hill slab zinc 99.99 wt pct pure and Ames Laboratory samarium. Analysis of the samarium by chemical, spectrographic, and vacuum-fusion methods gave the following average impurities in ppm: Nd, <200; Eu, <100; Gd, <100; Y, <50;Ca, 225; Ta, 400; Mg, 10; Cu, ~50; 0, 175; H, 20; and N, 15. The elements Fe, Si, Cr, Ni, Al, and W were not detected. The samarium was received as sponge metal and was kept under argon except when being cut with shears and when being weighed. Tantalum was found to be a suitable container for alloys with zinc contents up to the Sm2Znl, stoichio-metry. At higher zinc contents the grain boundaries of the tantalum containers were penetrated by the alloy and the containers failed during prolonged annealing. About 25 g of massive zinc and samarium sponge were sealed in tantalum crucibles equipped with thermocouple wells. These crucibles were in turn sealed in stainless-steel jackets. All closures were made by arc welding under an argon atmosphere. The samples were equilibrated in an oscillating furnace and in some cases were given various heat treatments in a soaking furnace. After appropriate heat treatment the steel jackets were removed and the alloy subjected to differential thermal analysis. The apparatus was calibrated against pure zinc and pure copper and found to reproduce the accepted melting points within 1°C. Alloys were subsequently subjected to metallographic examination and those of appropriate compositions were used for X-ray diffraction analysis and for zinc vapor pressure determinations. The vapor pressures were determined by the dewpoint method. Both the differential analysis and dewpoint measuring apparatuses have been described in earlier papers.4, 5 All alloy samples were etched with Nital (0.5 to 3 pct nitric acid in alcohol) except the samarium-rich alloys. These more reactive alloys were electro-polished in a 1 to 6 pct HClO4 in methanol solution at -700c at a potential of 50 v. EXPERIMENTAL RESULTS Phase Diagram. The results of thermal analysis are indicated by the points on the phase diagram, Fig. 1. Eight compounds and four eutectics were observed. The composition of the compounds and their melting or peritectic temperatures are given on the phase diagram. The four eutectic compositions in wt pct zinc and eutectic temperatures in % are: 12 pct,- 680°C; 36 pct, 890°C; 58 pct, 850°C; and 72 pct, 900°C. The stoichiometry of the most zinc-rich compound is still uncertain, but is very likely either SmZnll or SmZnlz. However, to simplify the presentation which follows it will be referred to as SmZnll. As shown on the phase diagram the phase regions for some of the samarium-rich alloys have not been unambiguously established. A sample of pure samarium was observed to transform at 924°C and to melt at 1074"C, in good agreement with corresponding val-

Jan 1, 1968

By F. C. Frischknecht

Most early development and application of electromagnetic prospecting methods took place in Scandinavia, where geological conditions favor their use. In other parts of the world these methods have aroused cycles of interest, but in Scandinavia they have been used continuously and successfully since the 1920&apos;s. Electromagnetic methods may be classified into two general groups. One group includes methods in which the source of the electromagnetic field remains stationary while the receivers are moved about to explore the area. The other includes procedures in which the energizing and receiving systems are moved together. Other classifications could be based on the size of the energizing source, the particular components of the electromagnetic field which are measured, or the mode of transporting the equipment. The difference between fixed-source and moving-source methods, however, is of such great fundamental importance that it will be emphasized in this discussion. FIXED-SOURCE METHODS Essentially, a fixed-source method consists of the measurement of electromagnetic fields about the source. The mutual coupling between the source and the earth is constant, but the mutual coupling between the receiver and the earth (unless the earth is homogeneous) and also between the source and the receiver changes at each station. The results are usually normalized by relating the field data to the calculated free space or primary field. Turam and Radio Reference Signal Methods: The turam or two-frame* (see Fig. 1A) is probably * Turam means two-coil. the most common fixed-source method. The energizing source is an insulated cable grounded at both ends or formed into a large rectangular loop. Measurements are taken along a traverse at 5 to 50-meter intervals using two small receiving coils, the lagging coil being placed at the position previously occupied by the leading coil. The complex ratio (i.e., inphase and out-of-phase ratios) of the voltages induced in the two coils is measured. Operating frequency range is about 100 to 800 cps. In a typical turam survey a straight, grounded cable several kilometers long is laid out parallel to the probable strike of the ore deposits or conducting strata being sought. An area extending 1 or 2 km on each side of the cable, and within 1 or 2 km of the ends of the cable, is surveyed. Measurements are made at stations 5 to 25 m apart along traverses perpendicular to the cable. Measurements may be made along lines parallel to the cable to serve as base lines for the traverses or for other special purposes. Commonly the receiving coils are oriented with their planes horizontal so that only the vertical component of the field is measured. If additional information is required, one of the hori- zontal components may also be measured by orienting the coils with their planes vertical. In a modified turam technique developed recently for both ground and airborne measurements (Fig. 1B) the amplitude of the complex voltage induced in a single receiving coil is measured and its phase compared with that of a reference signal transmitted from the energizing system by a radio frequency carrier. Thus the un-normalized field is obtained directly, whereas with the turam method it is obtained by calculation from the ratios. The turam method and its modifications have a greater working depth than the other electromagnetic procedures used in ore prospecting. Under favorable conditions conductors have been located at depths of 200 to 300 m. A modified turam method with one of the electrodes grounded in the upper end of a plunging orebody was used to follow the extension of this body to a depth of 200 m beneath a layer of conducting schists. Straight grounded cables are usually preferred to insulated loops because they are easier to lay out and because they often make the method more sensitive. The greater sensitivity of a grounded cable is a result of ground return currents which may flow in the orebodies in addition to the eddy currents caused by induction from the current in the cable. Anomalies in the vertical field due to eddy currents are characterized by a correspondence between high values for the inphase component and positive out-of-phase components and/or low values for the inphase component and negative out-of-phase components. Also the inphase component may approach zero, but it does not become negative. In very long continuous conductors that are parallel to a grounded cable the effect of ground return currents may far exceed the effect of eddy currents. These ground return currents cause a lack of correspondence between the inphase and out-of-phase components and may cause negative inphase or anti-phase components. It becomes difficult to carry out the measurements and often difficult to interpret the results. Such results immediately suggest the presence of graphitic strata, however, since ore deposits are rarely extensive enough to accumulate sufficient ground return current to cause these results. A cable laid out perpendicular to the strike or an insulated loop is sometimes used in areas where graphitic schists and slates are present. Anomalies are then completely or almost entirely due to eddy currents and are easier to interpret. The measured voltage ratios are normalized by either subtracting or dividing by normal field ratios calculated from free space considerations. The normalized ratios are then plotted as individual profiles. When significant anomalies occur in the ratio measurements, the actual normalized fields are calculated by beginning with a measured or an assumed value for the field at a point near the cable and successively multiplying this value by the normalized ratios. There is a similarity between this process and a numerical integration of the ratio curve. Conversely, in many respects the ratio curve is similar to the first derivative of the field curve.

Jan 1, 1960

By R. I. Jaffee, H. R. Ogden, D. J. Maykuth

IN THE past year, Jaffee and Campbell&apos; and Finlay and Snyder2 reported on the mechanical properties of titanium-base alloys, some of which were in the same ranges of composition as are covered in this paper. In this paper, evidence confirming that given by Finlay and Snyder on the effects of carbon, oxygen, and nitrogen on titanium will be presented; and, in addition, new data will be given on the effects of these elements on the flow properties and phase transformation of titanium. Materials and Preparation of Alloys The preparation and general properties of iodide titanium have been adequately described elsewhere.&apos; , As-deposited iodide titanium rod, prepared at Battelle, of Vickers hardness less than 90 was employed as the base metal in the present work. This was the same material as that used by Finlay and Snyder.2 The probable analysis reported by them for standard quality metal holds here also: N 0.005 pct, 0 0.01 pct, C 0.03 pct, Fe <0.04 pct, A1 <0.05 pct, Si <0.03 pct, and Ti 99.85 pct. Carbon was added in the form of flake graphite supplied by the Joseph Dixon Crucible Co. Oxygen was added in the form of c.p. grade TiO, powder, produced by J. T. Baker Chemical Co. Nitrogen was added in Ti3N4 powder, supplied by the Remington Arms Co. Individual ingots weighed 7 or 8 g. Carbon, oxygen, or nitrogen was added by placing the corresponding powder in a capsule made from as-deposited iodide titanium rods and melting the capsule with the balance of the charge. The charge was are-melted with a tungsten electrode on a water-cooled copper hearth under a partial vacuum of very pure argon (99.92 pct minimum). Melting was practically contamination free. Vick-ers hardness increases of less than 10 points were normal for unalloyed iodide titanium control melts. Nitrogen analyses of are-melted iodide titanium showed a nitrogen content of 0.005 pct, about the same as is present in the as-deposited rod. No tungsten pickup was found in a melt of iodide titanium analyzed for tungsten. Weight losses in melting nitrogen-free alloys were very small and varied consistently from nil to 0.015 g (0 to 0.2 pct). This permitted the use of nominal composition for these alloys. Chemical analyses made for carbon, which can be analyzed conveniently by combustion methods, justified this procedure. Where nitrogen was added, considerable splattering took place. Here it was necessary to analyze for nitrogen by the Kjeldahl method. The ingots were hot rolled at 850°C to about 0.045 in. thick. After hot rolling, the strips were descaled by mechanical grinding, and then given a cold reduction of 5 to 10 pct to insure a uniform thickness throughout the length of the specimen. The edge strips and the tensile strips were annealed in a vacuum of 1x10-4 mm Hg pressure for 3 1/2 hr at 850°C and furnace cooled. Methods of Investigation Hardness Measurements: At least five Vickers hardness measurements were taken using a 10-kg load on each sample in the following conditions: (1) top and bottom of each ingot, (2) top and bottom surface of as-rolled and annealed sheet, and (3) on cross-section of annealed sheet and all quenched specimens. Tensile Tests: Tensile tests were conducted on Baldwin-Southwark testing machines having load ranges of 600 or 2000 lb. Tests were made on 1-in. gauge-length specimens, 3 1/4-in. overall length, 1/2 in. wide, 0.040 in. thick, with a reduced section 1 1/4 in. long and 0.250 in. wide. Two SR-4, A-7 strain gauges, one mounted on each side of the specimen, were used to measure the strain over a limited range to determine the modulus of elasticity. After the modulus of elasticity readings had been taken, load vs. strain readings were taken, using only one strain gauge, at increments of 0.0001 in. until the yield points were passed and then at 0.001-in. increments to the limit of the strain-gauge indicator (0.02 in.). Strain readings above 0.02 in. per in. were taken every 0.01 in., using dividers to measure the strain between the 1-in. gauge marks until the maximum load had been reached. Crosshead speed, when using the SR-4 gauges, was 0.005 in. per min, and, when using dividers, 0.01 in. per min. Flow Curves: Flow curves were determined using the true stress-true strain data obtained during the tension test. The usefulness of this type of information has been dealt with very adequately elsewhere by L. R. Jackson,&apos; J. H. Hollomon,6 and many others. Flow curves of true stress vs. true strain could be converted to the more conventional cold-work curve of 0.2 pct offset yield strength vs. percentage of cold reduction by means of the transformation, 1/1 = 1/1-R, where R is the fraction reduction in cold working. Thus, the true strains corresponding to percentage reduction can be calculated, and the 0.2 pct offset yield strengths scaled off the — 6 curve by taking the true stresses corresponding to the values of 6 + 0.002 strain. Heat Treatment: For the transformation studies, the alloys were heat treated in a horizontal-tube furnace using a dried 99.92 pct argon atmosphere, and quenched into water. Essentially no contamination was found after several hours of heat treatment at temperatures up to 1050°C. Metallography: Specimens were prepared in the

Jan 1, 1951

By C. H. P. Lupis, Henri Gaye

There are m -I conditions for the stability of a solution of m components with respect to infinitesinzal flucturations. However, in most cases, only one of these conditions has to be considered to determine the domain of instability and the existence of this more restrictive condition greatly simplifies the calculations. It may be used advantageously for the prediction of miscibility gaps and the method is illustrated in details for the case of the Ag-Pb-Zn system. THE thermodynamic conditions for the formation of a miscibility gap may be viewed as a necessary consequence of the conditions for spinodal decomposition. A previous article1 has examined in detail the form of these conditions for multicomponent systems. There is only one condition for the stability of a binary system (with respect to infinitesimal fluctuations), but there are two conditions for a ternary system, and m — 1 conditions for an m-component system. The probability of violating a stability condition, and thus forming a miscibility gap, obviously increases with the number of components, a result which is rather intuitive since the atoms of the solution have now many more ways of redistributing themselves and introducing complexities in the form of the free energy hy-persurface. It is of interest to take advantage of this possibility of precipitating new phases and to examine which stability condition is the likeliest to be violated, that is, which stability condition is thermodynamically the most restrictive. The finding of such a condition would greatly simplify the application of the stability criteria since only one condition could then be considered, instead of m - 1. In Ref. 1, coherency strain energy terms were neglected, thus restricting the applications of the treatment to solutions where they are negligible, such as liquid alloys. In the following study the same assumption will be made. To generalize the treatment to systems where the strain energy terms are sizable, the reader is referred to Cahn&apos;s classical article on spinodal decomposition.2 Let us designate by Gij the second derivative of the Gibbs free energy with respect to the number of moles ni and n j. There are several equivalent sets of m — 1 stability conditions.&apos; The one considered here expresses that the successive diagonal determinants of order 1, 2, ... m — 1, associated with the symmetric Gij matrix (for 2 5 i, j 5 m) are positive.&apos; For a binary solution 1-2, the condition for stability is: O(u=G22^0 [1] For a ternary system 1-2-3, the condition [I.] is re- tained (the value of G22 will differ, of course, according to the concentration of 3) and another condition is introduced: £>(21 = G22G33 - Gl3 ^ 0 [2] In a composition diagram, these two conditions define two domains of instability. Starting at a point where the solution is stable (for instance at a point where the solution is very dilute) we gradually change the composition until the condition [I] or [2] is violated. As already noted in the literature, e.g., in the work of Prigogine and Defay,3 it is the boundary of the domain (2) which is first crossed. For if we assume that the boundary of the domain (1) is reached first, at this point G22 = 0 and the second condition is necessarily violated (D(2) = -& 5 0), in contradiction with our original assumption. An exhaustive study of the ternary regular solution case may be found in the work of Meijering.4 Moreover if the boundaries of the two domains have a common point, they also have a common tangent. For if the two lines were to cross each other as is illustrated in Fig. 1(a) any point M in the line QP would be such that £> = 0 and 0"&apos; > 0 which, as shown above, are incompatible results. Thus, the two lines must be tangent at their common point Q as illustrated in the example of Fig. l(b). The reasoning of Fig. l(a) implies that the point Q is not a "singular" point for either boundary line. This singularity may be of two types. First, the lines meet without crossing each other and without being tangent. Second, the tangent at Q for D"&apos; or 0"&apos; is not single-valued. Other types of singularity are unlikely because of the usual analytical forms of D"&apos; and 0"&apos;. The exception to the common tangent requirement due to the first type of singularity was pointed out by John Morral;5 it occurs when the common point, Q&apos; or (3" in Fig. l(b), is located at a boundary of the composition diagram, e.g., at the line X3 = 0. It may also be noted that at the common nonsingular point Q of D(1) and D(2), Fig. 1(b), G23 is necessarily equal to zero, whereas at a point such as Q&apos; or Q", this conclusion is no longer valid because the product G22G33 is now indefinite (of the form 0. a). The exception to the common tangent requirement due to the second type of singularity occurs when two branches of the same boundary line intersect, for example when D(1)or D(2) decomposes into a product of functions, at a point which belongs to the boundary of the other condition. It is possible to show by a simple analytical calculation that, in this case, if Q is a singular point of D(1), then it is necessarily a singular point of D(2), and that the reciprocal is true except if G33 = 0 at Q. For the present article, however, more elaboration on these singularities appears to be unwarranted. To generalize the previous results to an m -component system, we use the mathematical theorem stating that if the diagonal determinant D(r) = 0, then

Jan 1, 1970

By S. Horton, F. L. Stanley, P. J. Bethell

Introduction The McClure River Processing Plant is located at McClure in Dickenson County, VA. The plant was originally constructed in 1979 as a 600 st per hour facility. The plant is fed by coals from numerous mines in the area as well as a major longwall mine onsite. Coal is processed predominantly for the metallurgical coal market. The original plant was comprised of three separate processing circuits incorporating a heavy medium vessel for the coarse material (+10 mm). Intermediate sized material (10 x 0.6 mm) was beneficiated in heavy medium cyclones, with the remaining fines (0.6 mm x 0) passing to froth flotation for upgrading. The products from all three circuits were combined prior to thermal drying and then stored in silos or ground storage prior to shipment to the metallurgical coal markets. A middlings heavy medium cyclone circuit was also present to rewash the vessel and primary heavy medium cyclone rejects. The original circuit is as shown as Fig. 1 (Editor&apos;s note: All figures are reproduced at the end of this paper.) In reasonably close proximity to the McClure Plant is the much older, less efficient Moss 1 Plant, (Chance cone, table, water only cyclone, froth flotation, Fig. 2), which prior to the McClure Plant expansion was processing considerable tonnages of coal. At that time, the McClure River Plant was processing coal at the maximum possible feed rate, and the Moss 1 Plant was finding increasing difficulty in maintaining the stringent quality specifications on its major metallurgical coal accounts. Given the fact that many of the feeder coals to Moss 1 could be moved with minimal difficulty and cost to McClure, an exercise was conducted to evaluate the potential of expanding the McClure Plant. This would result in transferring coals from Moss 1, thereby increasing yield, reducing operating costs, and enabling customer specifications to be met more easily. After evaluating many possible ways of expanding the McClure Plant, we eventually settled on an approach based on the idea of Gallagher at German Creek in Australia (Gallagher, 1986). Our objective was to increase plant capacity by removing the coarser size fractions (0.60 x 0.15 mm) from froth flotation and at the same time eliminating the finer fractions (1.25 x 0.6 mm) from the heavy medium cyclone circuit, thereby allowing these circuits and therefore the plant as a whole to increase its capacity. These size fractions (0.60 x 0.15 mm from froth flotation and 1.25 x 0.6 mm from the heavy medium cyclone circuit) would be treated in a new spiral circuit. After desired evaluation of the various circuit capacities, including desliming screen, clean coal filter and thermal dryer capacities, etc., it was concluded that we should be able to maintain high levels of processing efficiency in the existing circuitry while at the same time expanding plant feed rate from a nominal 600 st per hour to 1000 st per hour, thereby achieving the objectives The circuit that was finally settled on is shown in Fig. 2. Several unique features were incorporated in this circuit in an attempt to maximize processing efficiency and reduce maintenance costs. First, the idea of a single-stage spiral circuit was abandoned in favor of a two-stage circuit incorporating rewashing the primary spiral middlings in a secondary spiral (Bethell, 88). The spirals selected were Mineral Deposits Model LD4 units. It was felt, after much previous testing, that spiral middlings rather than being a true middling gravity fraction were in fact a combination of true middlings with a preponderance of misplaced light coal and high-density rock. Consequently the insertion of this material directly into either clean coal or refuse streams (per normal practice) would only lead to loss of efficiency. The operating philosophy behind the design of the circuit was to produce the purest coal and rejects possible by adjusting the spiral splitters. Misplacement of refuse into the clean coal and vice versa would be minimized by taking a fairly large middlings cut. By reprocessing this material (10%-15% of primary spiral feed) in a secondary bank of spirals the misplaced material in the primary middlings would be reprocessed and its probability of reporting to the correct stream greatly enhanced. To minimize fines loading on the spirals, fine aperture sieve bends were to be included. A further novel feature of the circuitry is the desliming/ dewatering system. A philosophy of accepting inefficiency but forcing it to work in our favor was developed. The dewatering screens (Linatex Combis) were chosen not for their ultimate screening efficiency but for their ability to remove slimes (tolerating a fair quantity of oversize in the effluent) and their enhanced maintenance characteristics. Any oversize passing into the effluent, together with the fine coal centrifuge effluent, would pass to classifying cyclones, the objective of which was to reject to overflow (and hence froth flotation) as many fines as possible (-150 µm) without running the risk of losing coarse (1.25 x 0.15 mm) material to oversize. Hence, by a process of producing a "slime free" screen product coupled with a "coarse free" cyclone overflow, sizing efficiency could be maximized. Obviously, recirculating load had to be factored into the Combi Screen design capacity. The spiral circuit as shown in Fig. 2 was installed at McClure River in January 1988. The spiral circuit efficiency was very high immediately, and, after the normal debugging, plant capacity has been increased to the point at which we are currently processing of the order of 1100 st per hour. Test program The performance of the spiral circuit has been evaluated by two major samplings of the entire new circuit, coupled with routine bi-monthly tests on all other major components of the plant circuitry.

Jan 1, 1992

By Charles L. Mantell, Kurt Straler

The hydrogen reduction of Cr2O3 to chromium metal was found to be feasible at very low water-vapor concentrations, corresponding to dew points of -38° to -24°C, over a temperature range of 1130" to 1490°C. Hydrogen reduction under these conditions was predicted by the calculated equilibrium curves which also indicated that CrzOs is reduced directly to chromium without forming the intermediate oxide, CrO. This reduction path was confirmed by X-ray diffraction analysis. The percent reduction of Cr2O3 at each reaction temperature was constant with time, suggesting an inhibiting effect of water vapor. A small increase in the residual water-vapor concentration of a single temperature, 1490°C, strongly retarded the rate of reduction This effect was expressed by an empim&apos;cal equation which indicated a direct relationship between "distance from equilibrium" and the rate of reduction. me effect of temperature over the range of 1130" to 1490°C was expressed in an Arvhenius plot of log rate vs reciprocal absolute temperature. From this curve the apparent enthalpy of activation was found to be 29,600 cal. Based on the hypothesis that the rate of reductiun is contvolled at the oxide-metal interface, an over-all rate equation consistent with the experimental data and the thery of absolute reaction rates was formulated. A simplification of this expression to an Arrhenius equation was justified by the overriding effect of temperature on the rate of reaction for the minimum water-vapor concentration range. MOST of the metals in Subgroup V1 of the periodic table can be prepared commercially by direct reduction of their oxides by hydrogen or carbon monoxide, at temperatures considerably below the melting points of both the metals and their oxides. Chromium is an exception, being generally reduced from its ore, Cr2O3 . FeO, by silicon in an electric arc furnace which operates above the melting point of the Fe-Cr alloy or above the melting point of chro- mium if a chromium oxide be the starting material. In reduction of chromium oxide by hydrogen, either reduction does not occur at all or the rate of reduction is extremely slow. Theoretical considerations based on the high, exothermic, free energy of formation of Cr2O3 compared to the oxides of the other Subgroup VI metals, molybdenum, tungsten, and uranium, would also suggest a slow rate of reaction and a high activation energy. Interest in the direct gaseous reduction of fine-powdered ores in fluidized beds was considered justification for examination of this reaction. In order to develop a basis for a continuing study of the commercial feasibility of the direct gaseous reduction of chromite, a study of the kinetics of the reduction of Cr2O3 with hydrogen was undertaken. To the authors&apos; knowledge no accurate kinetic data for this reaction have been obtained. Neither has an activation energy been determined nor has an attempt been made to establish a mechanism of reaction. LITERATURE Maier10 compared the data of I. Y. Granaat,6 H. von Wartenburg and S. Aoyama, and G. Grube and M. Flad7 with that derived from calorimetric and ther-modynamic properties for the equilibria for the reduction of Cr2O3 with hydrogen. These results, plotted as the log of the equilibrium constant vs absolute temperature for the reduction of Cr2O3 and the intermediate oxide, CrO, to chromium, show agreement between the differently derived data. In both cases the equilibrium constants were extremely low. Maier showed that, over a temperature range of 1000° to 2000°K, Cr2O3 is more readily reducible than CrO. Granat assumed that CrO was preferentially formed from Cr2o3 above 1100°C. Grube and Flad&apos;s analysis of their reaction products in the 895" to 1000°C range indicated the coexistence of only Cr2O3 and chromium. The hydrogen reduction of the other Subgroup VI metals, molybdenum, tungsten, and uranium, shows that reduction of the higher oxide proceeds through all of the intermediate oxides before being reduced to the metal. Since evidence pointed to an anomaly in the reduction behavior of Cr2O3, the authors investigated the reduction path of Cr2Os.to chromium. This was done theoretically with more recently available free-energy data and experimentally by X-ray diffraction analysis. This work reinforces Maier&apos;s conclusion.

Jan 1, 1964

By D. L. Archer, W. W. Owens

Conventional waterflooding often is uneconomic in highly fractured reservoirs because of the gross bypassing of the reservoir oil by injected water. Imbibition and pressure pulse flooding have been used in at least one fractured reservoir in an attempt to achieve better oil recovery performance. This paper presents the results of laboratory flow tests conducted on large cores to evaluate the possible applicability of these methods (particularly pressure pulse flooding) to different types of reservoir systems. Test data were obtained on both water-wet and oil-wet systems, and on systems having two widely different levels of compressibility and flow capacity. Results indicate that pressure pulse recoveries from fractured reservoirs will likely not exceed 5 to 10 per cent pore space with maximum response achieved during the first pulse cycle. Improved recovery by this method is possible from both oil-wet and water-wet reservoirs. Comparable saturation distributions during imbibition and pressure pulse production suggest that an initial pressure pulse cycle to speed production response would not interfere with subsequent imbibition flooding in water-wet reservoirs. INTRODUCTION There is a steady increase in the number of fluid injection projects being initiated each year to improve oil and gas recovery over that obtained by primary production mechanisms. Experience gained in different geographical areas and with different recovery methods is teaching that reservoir anatomy is one of the more important factors controlling the success or failure of such projects. Fractured formations appear to be the rule rather than the exception, especially in carbonate reservoirs. Conventional methods of fluid injection, whether it is waterflooding, gas injection or miscible flooding, have limited applicability to highly fractured reservoirs because of the severe bypassing of reservoir fluids. The result is early breakthrough of the injected fluid and rapidly increasing ratios of injected to in-place fluid with an undesirable effect on return on investment. Thus, innovations to conventional methods must be developed if recovery from fractured reservoirs is to be optimized. One new method proposed for application to highly fractured reservoirs is pressure pulse waterflooding. Although pressure pulsing with gas has been suggested&apos; and rested in at least one reservoir; the Sohio Oil Co. is generally credited with the development and testing of pressure pulsing in conjunction with waterflooding. Publications" of Sohio&apos;s waterflood operations in the Spra-berry Trend indicate that the idea for pressure pulse flooding evolved from a critical analysis of the disappointing early performance of their flood initiated in a portion of the trend in April, 1961. This flood was planned to take advtantage of imbibiltion and high pressure gradients across the reservoir matrix blocks (unfractured Mocks of the reservoir rock which are visualized to be generally surrounded &apos;by the fracture system) evaluated in pilot tests by the Atlantic Richfield Co.5 and Humble Oil & Refining Co.&apos; However, the early recovery and pressure performance of this flood indicalted that high pressure gradients induced between the fracture system and the centers of the matrix blocks were forcing water into the periphery of the blocks and temporarily interfering with the counter-current flow of oil due to imbibition. Fill-up in the blocks was occurring with re-solution of the free gas phase as pressures climbed above the original reservoir bubble point. It appeared that cessation of water injection to permit the capillary forces to become dominant and that expansion of the rock and its contained fluids during pressure reduction might aid in expulsion of oil from the rock matrix into the fractures. Subsequent production performance. aflter cessation of injection, proved this hypotheslis correct. Thus, pressure pulse waterflooding was born. Pressure pulse flooding appears to have several advan&apos;tages over imbibition type flooding in highly fractured reservoirs. First, all wells may be used for water injection which should hasten fill-up and achieve a more rapid increase in reservoir pressure. Second, because of increased injection pressures and rates, flooding gradients will force water into the reservoir matrix more rapidly than would be achieved by imbibition alone. Third, during the pressure depletion cycle of the flood, the compressibility of the system, which has been increased by resolution of the free gas phase, provides energy for the displacement of oil at a rate greater than would correspond to countercurrent flow during imbibition. Fourth, during depletion all wells may be put on production, thus contributing to higher oil withdrawal rates on a reservoir-wide basis. One possible disadvantage of pressure pulse flooding as compared to imbibition floodling, however, is that the outer periphery of each matrix block is flooded to a residual or near residual oil saturation during the Water lnjection stage. This zone of reduced permeability to oil m&apos;ay offer greater restriction to the production of

Jan 1, 1967

By J. Lewis, J. Harper, M. F. Ashby

A grain boundary in a metal interacts with second-phase particles, which exert a pinning force (first estimated by Zener) on the boundary opposing its motion. We have computed the shape of boundaries which interact with more or less spherical second-phase particles and have constructed a soap-film model to reproduce the shape of the boundary surface. An important result is that measurement of this shape allows the pressure, or driving force, on the boundary to be measured. We hare applied this technique to grain boundaries in two alloys and hate measured the pinning force exerted by single second-phase jwrticles on the boundaries. It is in good agreement with Zener&apos;s estimate. J\. boundary between two grains, or two bulk phases, interacts with small inclusions or particles of a second phase, whether they are gas or solid. This interaction means that the boundary, forced to migrate by a difference in free energy between the material of the two grains or phases which it separates, exerts a force on a particle which it touches, tending to drag it forward. (The movement of inclusions through metals under the influence of this force, has, in fact, been observed. 1-3) Equally, the particle can be thought of as exerting a pinning force on the boundary, tending to hold it back. Zener (in a celebrated private communication4) first realized that this interaction, and the resulting pinning force, existed. His calculation of its magnitude was crude but adequate: a spherical inclusion of radius r blanks off an area nr2 of the boundary on which it sits; since the boundary has an energy of rMM x per unit area, the blanlung-olf decreases the energy of the system by MM: this energy is returned to the system if the boundary is pulled free from the inclusion— a forward movement of the boundary by a distance r will do this—so that the maximum pinning force is Trrym.M- A similar argument can be made for inter-phase boundaries. The nature of the particle itself did not enter this, or two subsequent treatments.5,6 When it is considered, tic leifthe energyoftheb a) The boundary may enter and pass through the particle if the energy of the boundary is lower within the particle than in the matrix. Fig. l(r/). Certain coherent precipitate particles behave like this. h) More usually, the boundary will bend round the particle, enveloping and bypassing it. Fig. l(b). In doing so, it changes the structure and energy of the interface between the particle and its matrix. This means that the boundary does not touch the particle surface at right angles, as early treatments assumed,5&apos;9 but at some angle a which depends on this change in surface energy of the particle, and can be calculated from the equilibrium of surface tensions. Most precipitate particles and inclusions behave like this. Gas bubbles or liquid drops can be regarded as belonging to either group. The progress of bypassing is conveniently measured by the angle shown in Fig. 1. When the nature of the particle is ignored, its maximum pinning force is exerted when - 45 deg. When it is considered, this critical value of is found to depend on a and thus on the nature of the particle. The maximum pinning force lies between nryMM and 2jtjMM (Appendix 1). not very different from Zener&apos;s result. In reality, a boundary between crystals has a specific energy and tension which varies with the orientation of the boundary. Furthermore, recent experiments7 indicate that such a boundary is not atom-ically smooth, but has steps on it: migration of the boundary corresponds to the sweeping of these steps across the boundary surface, like the Frank model of crystal growth from the vapor. This means that the interaction of a boundary with particles should really be considered in terms of the way in which particles hinder the movement of these steps. To suppose a grain boundary or interphase boundary to be smooth, and to ignore the variation of its energy with orientation, is to liken it to a soap film. The advantage of this soap film approximation, which we have used throughout this paper, is that interaction energies and boundary shapes can be calculated easily. We have done this by numerical computation and by using a soap film model, and have compared the results with grain boundaries in an aluminum-based and a copper-based alloy. It turns out that the shape of the boundary which bulges between particles allows the pressure an it to be calculated; that is, the local driving force an the boundary can be measured. This has allowed us to check the Zener relationship experimentally.

Jan 1, 1970

By M R. Lane, M L. Cramer, N P. Wines

Increasing attention is being focused by regulators and industry on the residual environmental liabilities associated with mining projects following site relinquishment (termed surrender in Queensland). Even sites that have been rehabilitated to a high standard and to the satisfaction of the regulator are not completely risk free and may require some degree of ongoing management. As well as ongoing monitoring and maintenance costs, considerations should include how costs associated with potential risk event occurrence can be quantified and, if considered material, how provisioning should be undertaken to minimise the risk to the state and to taxpayers. In Queensland for example, once a resource site is fully rehabilitated and meets its environmental authority conditions or rehabilitation completion criteria, the tenure and environmental authority can be surrendered. During the surrender process any ‘residual risks’ resulting from the use of the site for the resource activity must be considered, and, if requested, a payment given to the government to cover any ongoing management and risk costs. Accent Environmental, in conjunction with Lane Associates, was engaged by the Queensland Government as part of the government’s financial assurance framework reforms to develop an innovative, ‘one-size fits most’ Residual Risk Calculator for the Queensland resources industry. The calculator is an Excel-based tool that uses detailed user inputs to estimate post-surrender management requirements and liability at resource sites. If residual environmental risks associated with rehabilitated mine sites can be identified, quantified and managed through pragmatic regulatory tools and effective provisioning, site relinquishment/surrender can be achieved without compromising environmental and social outcomes or exposing the state to unreasonable financial risk. The effective management of residual risk can also help facilitate operations as well as relinquishment/surrender of sites where a ‘walkaway’ solution may not be otherwise technically feasible.

Aug 2, 2023

By W. W. Anderson, S. Razi

Electroluminescetrce of single crystals of terbium-(loped ZnS prepared by vapor-transport technique shows the sharp line specirum characteristic of the 4f— 4ft,ansitiotzs of the trivalent Tb3 rotz. V-I tt~easuverr~ents give evidence of space-ellarge-lirrlited curvent but the thrveshold for trap-filled law behavior is not iu agreement with Lampert&apos;s theory for. Single injection. Variations of &apos;brightness with applied voltage, the observation of double peaks its brightness because joms, and the spatial distribution oi electroLur?zir~escerrce indicate that the accelet~atiotz-collision mechanism involving the bst lattice and/ov shallow traps is most likely to be responsible fov excitation of&apos; electrolnminescence. Efficiency rtreusuver)~etits show the quantwn efficiency to be about 10 pct and powev efficiency about 0.05 pct. Effect of anr~eallng the crystal in sulfur vapor is to enluztzce llle rare-earth emission. It rs pvoposed tlzat sulfitv anr~ealing crreates acceptorr-lvpe defects with which the donor-type vare-eavtll ion can associate more readily vesulting in enhanced rare-earth emission. A&apos;o such e~zlznr~cerr~etrt is obserued when the crystal is atztrealetl in zinc vapor. Photolianinescence of ZnS doped nith a variety of rare earths also shows tile slurvp l~rze rwve-eavtlz erriission which in sorrretirr~es accompanied by broad band, stvuctureless lattice emission. Photo-atrd electrolutr~itzesce?~ce of ZIIS:Tb slw~rj do!rlit~unt rare-earth emission in the ~ticirzity of 54(3OA corre-sporrdit~g to the transition D* — Fj. Hoz~!el)er, the detailed line structuve of the luo spectvtr is cliffevet~t, irzdicutit~g that different sites are active in the two processes. Decay of rave-eartlr fluorescence in ZnS doped with any of sei!evul vuve eurtlzs car1 be described by a single exporleritial e.scepl joy ZrlS:lIo. Tl~is exceptiotr can be explaitred it~ tevrr~s of tlre closely spaced er~evgy 1e1:els Jov the HO~&apos; iorr. Decay lime measurertzekzts jov ZnS:Tb, using pulsed elect,-ical ar~d pulsed opticcll excitutiorzs, (11-e itz goor1 agrcetrier~t. LUMINESCENCE of rare-earth-doped materials has been a subject of interest for the past 20 years. Within the past few years there has been a considerable increase in rare-earth research motivated in search of new and more efficient laser materials and also due to the use of certain-rare-earth compounds in the preparation of color television screens. The purpose of this study has been to seek an understanding of some of the basic processes involved in exciting the rare-earth luminescence which is associated with transitions within the 4f shell of the trivalent rare-earth ion. Single crystals of ZnS doped with a variety of rare-earth ions have been prepared by vapor-transport technique described elsewhere.&apos; Photoluminescence was excited by a high-pressure short-arc mercury lamp together with suitable glass and chemical filters. For electroluminescence, sinusoidal and pulse excitations were used. 1) ELECTRICAL CHARACTERISTICS 1.1) V-I Measurements. Electroluminescence experiments were performed on crystals of terbium-doped ZnS. The samples were cleaned and etched and indium or In-Ga alloy contacts were alloyed on by heating in H2 atmosphere to 600°C for times ranging up to 10 min. Static voltage-current measurements were made on several samples. Fig. 1 shows the results for a typical sample. For voltage V < 20 v, the V-I relationship is linear giving a resistivity of 2.5 x 109 ohm-cm for this particular sample at room temperature. In the range of 20 to 250 v, I varies as V "3 and at still higher voltages (when electroluminescence is visible to the scotopic eye) current varies as Vs up to 600 v, all at room temperature. At 77"K, for V > 200 v, / I vge5 up to 1000 v. The V-I characteristics at room temperature follow reasonably well the behavior predicted by Lampert&apos; for one carrier space-charge-limited current in an insulator with traps although, as shown later, the expression derived by Lampert2 for the threshold for trap-filled law behavior Vtfl yields an unrealistically low value for trap density if we use the experimental value of 300 v for VtfL. Assuming the case for shallow trapping, the transition from Ohm&apos;s law behavior to space-charge-limited behavior occurs at voltage Vtr given by where no = thermally generated free carrier density, L = length of the sample, e = static dielectric constant, 6 = ratio of free to trapped electron densities, e = electron charge. For the ZnS:Tb crystal, L = 0.5 mm, E = 8.3 €0, Vtr - 20 v, and no = 5 x 10&apos; per cu cm, calculated from the ohmic behavior assuming electron mobility of 100 sq cm per v-sec. This results in 9 = 0= As more and more electrons are injected the Fermi level moves up in the forbidden gap toward the conduction band. If we assume a single-energy level for traps (which is not strictly correct, as we will show later), the current voltage characteristic is profoundly affected when the Fermi level crosses the trap level. The traps are now filled and injected carriers can no longer be immobilized in traps. Hence, current rises sharply with voltage. The transition from space-charge-limited behavior to the trap-filled behavior occurs at voltage VTFL given by

Jan 1, 1968