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By N. D. Jagger, I. M. Arbuthnot

Introduction Over the last five years, a large number of small- to medium-sized carbon-in-pulp treatment plants have been built in Australia, most designed to treat between 250,000 t/a and 1.5 Mt/a of ore. Because of the limited capital resources and tight cash-flow positions of these relatively small mining companies, the primary requirement was often to get a plant built and operating in a short period of time and at minimal capital cost. Therefore, since the inclusion of both pre-leach and tailings thickeners represents an obvious and significant capital cost, most of these plants were built without thickeners or even detailed, cost-benefit analyses on their inclusion. In some cases, the increasing use of High Rate Thickeners (HRTs) in the mineral processing industries has, however, resulted in a reassessment, because of their considerably lower cost. This reassessment was triggered primarily by the need to conserve water in arid mining areas where borefields are costly to install and water is limited. With the startup and operation of these installations, the resulting significant savings in cyanide consumption has been recognized, in many situations, as a primary justification for the installation of HRTs. Solution balances Degradation of cyanide occurs in the tailings water discharge to slime dams. The degree of degradation (cyanide loss) in the water recovered depends on a number of factors, but it is usually assumed to be about 90%. The most important mechanisms of CN loss are through HCN losses and oxidation by oxygen in the air, which also assists in the hydrolysis of CN. These mechanisms are supported by the large dam surface area and the long retention time of the tailings water in the dam. By thickening the CIP tailings at the plant and recovering as much tailings water as immediately possible, these losses are avoided. The retention time in an HRT is less than three hours, and the surface area is relatively small. Therefore, CN losses are negligible, which is not necessarily the case in conventionally-sized thickeners. Fig. I shows a block diagram of a 100-t/h gold plant without a thickener. In this example, 50% of the tailings water pumped to the tailings dam is recovered, and the CN concentration of the returned water is 10% of the tailings CN concentration of 150 ppm. Fig. 2 represents a plant with an HRT on tailings, thickening to 55% w/w solids. In this case, the thickened tailings are pumped to the dam, and 25% of the contained water is recovered. The recovered water and the mill make-up water are not sent directly to the mill; instead, they are added to the thickener feed and mixed with it prior to thickening. By doing this, the tailings are effectively washed, and the additional cyanide is recovered. Solution balances over these two circuits show cyanide recoveries of 5% and 65%, respectively. Thus, the thickener use increases cyanide recovery by 60%. Fig. 3 shows a two-stage HRT circuit in a countercurrent decantation (CCD) configuration. In this example, an additional 13% of cyanide is recovered through the use of the second-stage unit. This configuration can be justified when residual cyanide levels are high. Capital and operating costs - Case study 1 Illustrative cost figures are based on a CIP tailings thickener installed, in early 1988, as part of Dominion Mining's treatment plant at Paddy's Flat near Meekatharra. (All costs within this paper, unless stated otherwise, are in Australian dollars.) [Assumptions: Feed rate 150 t/h Ore moisture content 5% Leach density 40% solids Underflow density 55% solids Residual cyanide in tailings 150 g/m3 Flocculant dosage 15 g/t Consumable costs: Water $ 0.40/m3 Cyanide$ 2.00/kg Flocculant$ 4.50/kg Power$ 0.12/kWh Length of tailings pipeline2,500 m Capital costs of the major items involved in the thickener installation are given below: Thickener unit, 15-m diam $ 230,000 Water return pumps 12,000 Water recirculation pumps 28,000 Feed box 5,000 Flocculant make-up system 18,000 Flocculant storage tank and dosing pumps 11,000 Piping and valves 85,000 Electrics and instruments 47,000 Civil works 29,000 Installation 69,000 Total cost$ 534,000] Savings in capital costs that can be attributed to the

Jan 1, 1993

By G. Venturello, C. Antonione, G. Della Gatta

Results from work on the effect of inferstitials on recovery and recrystallization of' very pure iron (99.995 pet) doped with nilrogen up to 400 ppm are reported. Nitrided specimens were obtained by heating the iron in a static atmosphere of NH3 + H2. The samples were cold-rolled 80 pet, subjected to a series of isochronal and isothermal anneals, and submitted to examination by X-rays, micrographs, and hardness tests. Small additions of nitrogen show a strong effect in reducing recovery of' the mechanical properties of high-purity iron. At the temperatures of. the experiments, this effect proved greater than in the case of carbon. At 400°C pure iron recovers more than 50 pet of the total hardness increase, carburized iron vecovers 25 pet, and nitrided iron only 10 pet. On the other hand. the addition of nitrogen has, similarly to carbon, a very small effect on recrystallization; the effect is, however, slightly higher than that of carbon. When the concentration Of nitrogen is above the solubility limit in a iron at the temperattue of the experiments, an increase in the frequency of nu -cleation is also observed. THE object of the present work is to improve knowledge on the effect of interstitials both on recovery and on primary recrystallization of pure iron. In fact. at present there are no available data on the effect of nitrogen on high-purity iron. The only work which at present can be somewhat related to this problem is a work of Leak et al.1 in which grain boundary internal friction at high temperature in the presence of increasing amounts of nitrogen is studied by a torsion pendulum. The present work is a continuation of a previous one2 on the effects of carbon. EXPERIMENTAL PART Preparation of the Material. Pure iron was prepared following the same methods used in the pre- vious work2 and was nitrided using controlled quantities of ammonia in an apparatus similar to that used for carburizing. The apparatus consists essentially of a gas-tight quartz tube containing the specimens. The tube, maintained at constant pressure by means of a mercury seal, is placed in a resistance furnace. For nitriding, the NH3 + H2 atmosphere with a suitable concentration of NH3 was introduced into the tube, which had been previously carefully evacuated and degassed by heating at 600°C. The hydrogen used was carefully purified by passing it through a palladium filter. The ammonia required was prepared with the following reaction: CaO + 2NH4CI —CaCl2 + H2O + 2NH3 by heating the mixture of CaO and NH4C1 in a glass flask and then collecting the ammonia in a graduated Hempel burette. For each nitriding program a given amount of NH3 prepared by this method was introduced together with the H2 into the tube previously evacuated. Nitriding of the sample was then performed at 570°C for 48 hr. After this, to ensure a homogeneous distribution of nitrogen, the samples were further heated for 72 hr at 800°C. With this method which uses a static nitriding atmosphere, carefully controlled conditions of purity are obtained. Contrarily, with the conventional continuous-flow methods, using large quantities of circulating gas, there is a greater risk of introducing impurities into the samples. Furthermore, the required nitrogen concentration in the specimen is easily predetermined and obtained. A plot of the relation observed between the initial concentration of NH3 in the gas and the quantity of nitrogen introduced into the iron samples is given in Fig. 1. The data refer to samples of 1.2-mm thickness and to the nitriding conditions previously described. Furthermore, as a comparison, the data relative to two 0.5-mm-thick samples are reported. The presence of a reservoir in the cold zone of the reaction bulb made possible the gradual dissociation of ammonia on the sample in the hot zone. Internal-friction methods were used to determine the content of nitrogen dissolved in the iron samples. Some analyses were also carried out with chemical methods. The following table, Table I, shows a comparison of data obtained with chemical and internal-friction methods. The correspondence between chemical methods and internal-friction

Jan 1, 1964

By Arnulf Muan, D. P. Masse

PHASE relations in the system CoO-SiO2 have been determined as a basis for further investigations of thermodynamic properties of olivine solid solutions involving Co2SiO4 as a component. Previous data on the system CoO-SiO2 are incomplete or uncertain. Biltz and Lemke1 determined the melting point of cobalt orthosilicate as 1345°C , but Asanti and Kohlmeyer2 have later found a considerably higher temperature, 1420°C. The latter authors also studied melting relations of one mixture on the CO side and two mixtures on the SiO2 side of the orthosilicate composition and sketched a tentative phase diagram for a limited composition range of the system. However, no phase identification was carried out, and the authors left unanswered the question of the possible existence of a stable meta-silicate phase. Greig3 showed that a 90 wt pct SiO2-10 wt pct Co mixture at 1725°C consists of two immiscible liquid phases. The quenching technique was used in the present investigation. Mixtures of high-purity cobalt oxide ("Fisher Certified") and dehydrated silicic acid ("Baker Analyzed") were equilibrated in air atmosphere. The samples were then quenched to room temperature and the phases present were identified by microscopic and X-ray examination. The samples were kept in small envelopes made from thin (0.0004 in.) platinum foil. Thermodynamic data which have become available recently for Pt-Co alloys4 were used to check that the losses of COO from the oxide samples by alloying of cobalt with platinum in the present investigation were too small to change significantly the compositions of the oxide material during the equilibration. A vertical tube furnace with an 80 pct Pt 20 pct Rh resistance winding was used in runs up to 1510°C. Temperatures in these runs were measured with a Pt vs 90 pct Pt 10 pct Rh thermocouple calibrated against the melting point of diopside (CaMgSi2O6, 1391.5?C). The given temperatures as measured by this technique are estimated to be accurate to *5°C. Quench runs at temperatures above 1650°C were made with a modified Roberts and Morey5 strip furnace, using strip resistors composed of a 60 pct Pt-40 pct Rh alloy. Temperatures were measured with an optical pyrometer which was calibrated against the liquidus temperature of a mixture composed of 10 wt pct CaO, 90 wt pct SiO2 (1707°C). The temperatures measured with this technique have an estimated accuracy of +15°C. The results are shown graphically in Fig. 1. Only one intermediate phase, the orthosilicate Co2SiO4 with olivine-type structure, is stable in addition to the end members cobalt oxide and silica. The melting point of the orthosilicate was found to be 1415" ± 5°C. The metastilicate CoSiO3 is not stable at the temperatures of the present investigation. The two eutectic points in the system CoO-SiO2 where COO plus olivine, and olivine plus silica, coexist with liquid were found to be 72 wt pct COO and 1407°C and 63 wt pct COO and 1381°C, respectively. The melting point of cobalt oxide in air was taken as 1745?C, based on the previous data of Aukrust and Muan.6 Within limits of error (+ 5?C), identical eutectic temperatures to those determined in air were found when two representative mixtures were equilibrated at 1 atm O2 pressure and in an atmosphere of 84 vol pct CO2, 16 vol pct H2. This suggests that changes in oxidation state of cobalt in the condensed phases are not significant as far as their effect on the phase relations are concerned. This inference was substantiated by failure to detect7 any "excess oxygen" (i.e., oxygen in excess of that contained in Co2SiO4) in a sample of orthosilicate composition equilibrated in air 10°C above the liquidus temperature and subsequently quenched to room temperature. This work was carried out as part of a research program sponsored by the U.S. Atomic Energy Commission under Contract No. AT(30-1)-2781.

Jan 1, 1965

CHAIR: I see a great many safety men in the audience and I hope you will all take part in using up the time that we have left. The point brought up by all was the necessity of education. It is very hard to know just how this is going to be done. We get very little encouragement to do this. At a recent meeting at Rock Springs, 100 in attendance, and most of them mine officials. Another condition which contributes to accidents is the labor turnover in many of our States. With many companies I am told from actual statistics the labor turnover is 125 per cent. Each field has different mining conditions so that men coming from one field are not always familiar with the mine conditions in the field they come to. These are conditions which have to be overcome. WM. LITTLEJOHN: Mr. Harrington brought up the subject of sprinkling. I will try to tell what we are doing at the Utah Fuel Company camps. Our dust at Castle Gate is the most inflammable gas that has yet been tested at the Pittsburgh station of the Bureau of Mines, so it is up to us to use every precaution to keep it down. I will try to tell what we are doing regarding sprinkling from tanks. We now have in operation two tanks in our locomotive roads, one in Castle Gate, one in Sunnyside. These tanks are something like 500-gallon tanks with pump on one end of truck which gets its power from the power wire and has a half circle perforated pipe on the other end of tank. This is simply hooked on to the locomotive. When the pump is started up it throws a fine spray of water all around which wets the roof, the sides and floor. We found this very successful from an economical as well as a working standpoint. A roadway that we probably would have had to pay a man at least two shifts for, covering the full distance, with the ordinary hose and spray, we can do in half a day and do it more thoroughly. We are also figuring on at the present time using the same system on rope haulage ways, which of course will have to be run by a reel from the feed lines, handling say four hundred feet each way before reconnecting. We haven't got it finished, but are working on it at the present time. MR. COLBURN: I would like to say a few words -about this question of education. Education was mentioned by all three sections of the Safety Committee. Education regarding safety might be divided into two branches. One branch is for the official at the mine to keep him acquainted with the latest developments in safety equipment and safety methods. The other part of education is for the workmen. The United States Bureau of Mines is co-operating in both directions. Safety Clubs are organized around the Bureau of Mines First Aid Training, but it is the idea to expand those clubs and teach the miner the advantage of such-things as the closed safety lamp, and also the regulations that have been made for his safety. In Illinois we can't operate with the closed lamp, because the miners in that section of the country are not educated to the advantages of the safety lamp. Another form of education has been taken up by the National Safety Council, consisting of voluntary organizations similar to the Institute, to which all mining men are invited to attend. Such conferences nave been held in the Lake Superior district, in Butte, and in Globe, Arizona, this year. These are to be extended throughout the coal mining regions. CHAIRMAN PRYDE: The Union Pacific Coal Company has also built two tank cars of 600 gallons capacity each. The tanks are connected with hose, so that water can flow from one tank to the other. A centrifugal pump is mounted on a truck, and connected to the front tank. This pump takes its power from the trolley wire. The discharge from the pump is perforated, so that it sprays the floor and sides of the entries. We expect to use this water train on main haulage ways where we have no sprinkling line.

Jan 1, 1923

By T. M. Morris

A SEARCH of the literature reveals that no measurements have been made of the forces acting between a small solid particle whose surface is hydrophobic, and an air bubble to which the solid adheres, both immersed in water. Analyses have been made of the forces acting to support a greased solid on the surface of water, and the forces acting to cause a solid, whose surface is hydrophobic, to adhere to an air bubble in water. The latter analysis T. M. MORRIS, Junior Member AIME, is in the Department of Metallurgical Engineering and Mineral Dressing, School of Mines and Metallurgy, Rolla, Mo. New York Meeting, February 1950. TP 2734 B. Discussion of this paper (2 copies) may be sent to Transactions AIME before Feb. 28, 1950. Manuscript received May 16, 1949. This paper is the result of work done for part of a doctor's thesis at the Missouri School of Mines and Metallurgy. is often incomplete, however, because the internal pressure of the bubble has been neglected. It will be demonstrated that the internal gas pressure is not a negligible factor when dealing with bubbles of the size encountered in flotation. A study of the forces acting between an air bubble attached to a large flat surface is informative. It must be borne in mind, however, that this is not the condition present in a flotation cell, where the particle is small compared to the size of the bubble. The bubble is allowed to spread to its maximum contact angle on a large flat surface in the first case, whereas in the second case, the spread of the bubble is limited to the surface of the small particle which is presented to the bubble. Kabanov and Frumkinl studied the forces acting to cause adhesion of bubbles of hydrogen to a large surface of mercury, which served as an electrode in a dilute sulphuric acid solution. The force acting to hold the bubble to the mercury surface was found to be the vertical component of the surface tension between hydrogen and the sulphuric acid solution. The forces tending to cause the bubble to separate from the mercury surface were found to be: (1) the force exerted due to the internal pressure of the bubble acting upon the area of contact between the bubble and the mercury surface, and (2) the buoyant force of the bubble minus the hydrostatic force acting at the base of the bubble. These investigators photographed bubbles that were just on the verge of separating from the mercury surface. From these photographs, they measured the contact angle between the mercury surface and the tangent to the hydrogen-solution interface at the point of contact between bubble and mercury surface. They calculated the volume of the bubble and the internal pressure of the bubble. The equivalence between the upward acting and downward acting forces was remarkable. Wark2 pursued an investigation similar to that of Kabanov and Frumkin, and at the same time. His deductions verified those of Kabanov and Frumkin. He also considered the conditions present in flotation and was aware of the effect of the internal pressure of the bubble. Further, he proposed several conditions under which a small solid particle would adhere to an air bubble in water. In 1922, Edser," an English physicist, made the following statement. "It must be remembered that no particle could float stably, but for the possibility of variation of the contact angle, for if this were a constant, a slight tilt would inevitably cause the particle to sink." Wark criticized this statement, maintaining that the contact angle does not vary. The experimental data to be presented indicates that Edser was correct. Experimental Procedure: Briefly, the experimental procedure was as follows. A bubble of air was generated in distilled water. A rod of known diameter, one end of which was water repellent, was attached to this bubble. The weight of the 'rod was measured. The internal pressure of the bubble was measured with a manometer. The hydrostatic head from the surface of the water to the bottom of the rod was measured. The angle between the horizontal projection of the end of the rod and the tangent to the bubble at the circle of contact be-

Jan 1, 1951

By Paul J. Fopiano

SOME relationships between the flow characteristics of iron single crystals of 99.9 pct purity and the behavior of imperfections have been investigated. X-ray rocking-curve measurements and etch-pit counts were made as a function of plastic strain, and compared to the stress-strain curve obtained on a modified Polyani tensile machine. Crystals grown from rolled strips of vacuum-melted iron by the strain-anneal method1 had a high preference for a (110) longitudinal direction and a (211) face normal. The tensile specimens were prepared from 2 by i by 0.040 in. single crystals having a gage area of 3 by \ in. Rocking-curve measurements were carried out with a highly perfect germanium monochromating crystal in which the dazz spacing was matched to that of the dZl1 in the ir0n.l Well-collimated CuKal radiation was used throughout. These procedures practically eliminated errors due to geometrical and wavelength resolution. Inasmuch as the rocking-curve half breadth may vary markedly from point to point in the specimen being irradiated, the crystals were strained in place by mounting a hydraulic loading device on the double-crystal spectrometer. The rocking curves were taken after each increment of strain in the unloaded condition, since no observable difference was found in the rocking-curves between the loaded and unloaded states. The rocking-curve half breadths of the as-grown specimens were in the range 90 to 120 sec of arc when the beam irradiated an area of about -£ by -& in. on the specimen. DeMarco and weiss3 have shown that, for a well-colli- mated X-ray beam, irradiating about 10"! sq in. of the very same material, half breadths within 10 pct of the Darwin natural half breadth were observed. Since the rocking-curve specimens were stressed by the load-unload technique, the strain achieved at any given stress depended on the time of holding because of low-temperature creep. Fig. 1 shows the rocking-curve half breadth (also area/peak height) as a function of plastic strain for a relatively short holding time (2 to 5 min) at each stress level. For strains less than 0.1 pct the rocking-curve breadth is essentially constant; it is only for larger strains that there occurs a significant increase in this breadth. Where the holding times at each stress level were longer (by well over an order of magnitude) there occurs a significant increase in the rocking-curve breadth only after plastic strains of the order of 0.6 pct had been introduced into the specimen. This observation is related to the time dependence of creep phenomena and emphasizes the difficulty in comparing data obtained by two such different straining methods. Etch-pit results were obtained using a 2 pct nital etch on specimens strained in the range of 0 to 1 pct. Prior to etching, all specimens were annealed for 3 hr at 150°C, the carbon content being sufficient to decorate the dislocations for strains of at least 1 p~t.~ The data points were all taken from parts of the same single crystal which had been strained with short holding times at stress in increments of strain of the order of tenths of 1 pct. The (211) plane is particularly difficult to etch-pit in vacuum-melted iron and therefore it is felt that these values are as much as an order of magnitude low. Fig. 2 shows the etch-pit density as a function of plastic strain. The smooth curve passing through the data points is not meant to infer a quantitative correlation with the rocking-curve data. What is of interest, however, is the change in etch-pit density in the region of 0.2 pct plastic strain. The first three increments in strain (points 2,3, and 4) did not produce a measurable change in the etch-pit density while subsequent increments did produce a measurable change. While the absolute values of these results do not appear to be cor-

Jan 1, 1967

By Carl Wagner

AT elevated temperatures. most metals react with oxygen, sulphur, or halogen rather rapidly, although a coherent layer of the reaction product is formed and separates the two reactants from each other. The reaction proceeds, since one of the reactants or both dissolve and diffuse across the reaction product. In many cases the rate is diffusion-controlled as is indicated by the validity of the parabolic rate law of Tammann' and Pilling and Bed-worth. wott and Gurney' have suggested that diffusion processes also play an important part in the case of reduction reactions. This is confirmed by observations reported below. In general, however, the rate of reduction reactions is determined not exclusively by diffusion processes. Reduction of Silver Sulphide Above 179°C silver reacts with liquid sulphur very rapidly. Since the volume of silver sulphide is much greater than that of the equivalent amount of silver, a coherent layer of silver sulphide is formed in accordance with a rule established by Pilling and Bedworth.' According to Wagner','' silver ions and electrons migrate from the Ag-Ag,S interface across the silver sulphide layer to the Ag,S-S interface where the following chemical reaction takes place: 2 Ag +2 e + S Ag,S If silver sulphide is reduced by means of hydrogen, the equivalent volume of the reaction product, silver, is less than that of the initial substance. Accordingly, no coherent layer of silver is formed. Instead, fine filaments of silver grow from the silver sulphide surface into the ambient gas. This phenomenon has been investigated by many authors, especially by Kohlschiitter," who has also reviewed previous literature. Kohlschiitter has interpreted the observed phenomena by migration of "silver" dissolved in silver sulphide. According to Wagner,' silver ions and electrons are the migrating particles. The sequence of consecutive steps involved in the reduction of silver sulphide is shown in Fig. 1. Every- where at the silver sulphide surface, hydrogen reacts with sulphur so that excess silver ions and electrons are formed, which migrate at random until they are captured by a nucleus of metallic silver. If such a nucleus lies on the surface and material is furnished only from the base, the original nucleus is pushed outward and thus a filament grows. Removal of sulphur and formation of metallic silver may also take place at different points when silver sulphide is reduced by copper. The reaction is usually formulated as: AgL,S + 2 Cu = Cu.S + 2 Ag but the actual reaction products are silver and a solid solution of the two sulphides. Primarily, excess silver and electrons dissolved in silver sulphide are formed. After a certain degree of supersaturation has been reached, nuclei of metallic silver may form. If, however, a silver foil is in contact with the silver-sulphide phase, as is shown in Fig. 2, silver ions and electrons will migrate to the Ag,S-Ag interface where they are captured. To confirm this scheme, a composite sample, with the geometry shown in Fig. 2, was made by pressing silver sulphide tablets 0.6 cm in diam and 0.4 cm high together with a copper cylinder and a silver foil in crucibles of iron, which does not react appreciably with silver sulphide at 400°C. After heating for 3 to 7 hr at 400°C. the specimens were cut normal to the phase boundaries. It was found that the thickness of the silver foil had increased from 0.01 cm as initial value to a maximum value of 0.06 cm. In the interior of the silver sulphide tablets only traces of metallic silver were observed. These observations show clearly that silver ions and electrons may migrate over distances of several millimeters before they form metallic silver. Reduction of Cuprous Sulphide by Iron The behavior of cuprous sulphide is very similar to that of silver sulphide, since the lattices of the high temperature modifications are identical, but in Cu.S there is a variable deficit rather than an excess of metal. To investigate the displacement of copper by iron, cuprous sulphide powder covered by a copper foil was pressed in iron crucibles and heated up to 800 °C for 3 to 7 hr. The thickness of the copper foil increased from an initial value of 0.005 cm to a nlaximum value of 0.029 cm. In the interior of the

Jan 1, 1953

By Y. Kondo, S. Yamazaki, Z. Asaki

Thermal deco7nposition of Pyrite particles in a fluidized bed with inert gas stream was studied. Assuming that heat transfer from the surroundings to the fluidized particles controls the overall decomposition rate, rate equations for the batch process and for the continuous process were derived. In the batch experiment, a linear rate equation satisfies the experimental results and the overall heat transfer coefficient calculated from the rate constant agrees fairly well with that obtained by Leva.l1 For the continuous process, two rate equations were derived, one on the assumption of complete mixing of particles and another on the upward piston flow of particles in a fluidized bed. The former holds for a bed containing a higher fraction of decomposed pyrite realized at lower feeding rates. The latter can be applied for a bed at higher feeding rates. Thus, segregation of particles in the fluidized bed was indicated at higher feeding rates. Bed temperatures also correspond to these conditions. ThERMAL decomposition of pyrite may be represented by Eq. [I]. The pressure of diatomic sulfur gas reaches 1 atm at about 690°C. The thermodynamics,' kinetics,2'3 composition, and properties3-5 of decomposed products of such a reaction have been studied. Pyrite is a very common sul-fide mineral and is often accompanied with other sul-fides. It is of basic interest in nonferrous metallurgy to clarify the behavior of pyrite in the pyrometallur-gical processes of sulfide minerals of metals such as copper, lead, zinc, nickel, and so forth. Interest in this reaction increased recently because of possible elimination of arsenic from pyrite in processing highly purified iron oxide pellets. Producing elemental sulfur from pyrite, instead of sulfuric acid, also aroused interest in this reaction. It is indicated that the thermal decomposition of solid particles, such as calcium carbonate, proceeds through three major sequential steps: heat transfer, interfacial chemical reaction, and mass transfer.637 It is known that the decomposed product of pyrite is very porous2, 3 and the diatomic sulfur gas evolved can easily escape through this layer of decomposed product. It depends upon the circumstances, therefore, whether the heat transfer to the interface within particles or the chemical reaction at the interface determines the overall decomposition rate. The enthalpy change in the decomposition of pyrite is about 33 kcal per mole FeS2 which is comparable to that of calcium carbonate. The decomposition of calcium car- bonate becomes more and more dependent on the rate of transport of heat when reaction temperature increases, such as occurs in a fluidized bed.6'7 It is reasonable to presume, therefore, that the thermal decomposition of pyrite, an endothermic process, carried out in a fluidized bed may be analyzed according to the heat transfer controlling model. This work intends, first, to propose a mathematical model that determines the overall rate in a fluidized bed for the decomposition process and, second, to investigate a few characteristics of the fluidized bed based upon the experimental results obtained. KINETICS OF THERMAL DECOMPOSITION IN A FLUIDIZED BED It is intended in this section to obtain rate equations for thermal decomposition of pyrite in a fluidized bed by assuming that the overall rate is determined by heat transfer from the surroundings to the particles. Both batch and continuous processes are considered. 1) Batch Process. To obtain the rate equation in the batch process, the following two additional assumptions are made. First, the temperature of preheated inert gas, tg, blown into the fluidized bed is assumed to be the same as the temperature of the fluidized bed, tf. Thus, no heat exchange occurs between the gas and particles in the bed and only the heat transfer from the reactor wall kept at tw to the particles is to be considered. Second, the decomposition is assumed to start at the outer surface of the particles and to proceed toward the center. At any given time during decomposition, undecomposed pyrite remains in the tori at a temperature: td. The decomposed shell is composed of FeS1+x whose outer surface is at tp Diatomic sulfur gas evolving at the interface is heated to tf during its escape through the decomposed shell. This is illustrated in Fig. 1. With the above-mentioned assumptions of heat transfer, we have:

Jan 1, 1969

By D. Akers, R. Dospoy

Introduction The geological processes that form coal can also concentrate trace elements in the coal. For example, the average concentration of arsenic in bituminous coal (20 ppm) is ten times the average concentration found in all the other rocks that make up the earth's crust (2 ppm). Similarly, other elements, such as antimony, cadmium, mercury and selenium, are more concentrated in coal than in the earth's crust. When coal is burned, trace elements can be further concentrated. Although no new constraints on trace clement emissions were placed on the power generation industry under the 1990 Clean Air Act Amendments, the act does mandate a three-year study of air toxics. Any new regulations aimed at electric utilities as a result of this Federally-mandated study will almost assuredly be very costly-an estimated $1 billion per year. Many trace elements in coal are associated with mineral matter. For example, arsenic is commonly associated with pyrite, cadmium with sphalerite, chromium with clay minerals, mercury with pyrite and cinnabar, nickel with millerite, pyrite and other sulfides, and selenium with lead selenide, pyrite and other sulfides (Finkelman, 1980). There are also cases in which some of these elements are organically bound. Just as both organic and pyritic sulfur can be found in the same coal, the same trace element may be both organically bound and present as part of a mineral in the sane coal. Physical coal cleaning techniques are effective in removing mineral matter from coal and can potentially remove at least some of the trace elements associated with specific minerals, thereby reducing the release of these elements into the atmosphere. Conventional coal cleaning to remove trace elements As part of a project funded by the Electric Power Research Institute, CQ Inc., a wholly-owned EPRI subsidiary located in western Pennsylvania, has demonstrated that large reductions in the concentration of many trace elements are possible if conventional coal cleaning techniques are properly applied. Four examples are given in Tables 1 to 4. In each example, the results shown were generated by cleaning the coal at CQ Inc.'s commercial-scale cleaning test facility. Cleaning results for Upper Freeport Seam coal from Northern Appalachia are provided in Table 1. Data are presented in the table in two ways: as a weight-based concentration (parts per million) and as a concentration per heat unit (grams per billion Btu). Grams per billion Btu is analogous to pounds per million Btu, but avoids the use of numbers with many decimal places. The heat-based concentration provides a better measure of boiler impacts, because the increased heating value obtained through coal cleaning reduces the number of tons that must be burned to produce a given thermal output. Reducing the quantity of coal burned reduces the quantity of trace elements entering the boiler. This raw coal is relatively high in several trace elements of environmental concern, including arsenic, cadmium and chromium. Cleaning provided large reductions in the quantity of arsenic, barium, cadmium, chromium, fluorine, lead, mercury, nickel, silver and zinc. The results for tests with a Powder River Basin coal, Rosebud/McKay, are presented in Table 2. Large reductions in arsenic, barium, cadmium, fluorine, mercury, nickel, selenium and zinc were observed with cleaning. The concentration of chromium increased with cleaning, while lead concentration increased in one test and decreased in another. Table 3 presents test results for Croweburg Seam coal from Oklahoma. Large reductions in arsenic, barium, cadmium, chromium and zinc were obtained with cleaning. Smaller reductions were obtained with lead and nickel, while chromium, fluorine and mercury increased in at least one of the tests. Table 4 presents cleaning test data for Kentucky No.11 Seam coal. In this case, large reductions were obtained with all elements measured. In general, these data indicate that physical coal cleaning is effective in reducing the concentration of many trace elements, especially if they are present in the coal at relatively high concentrations. The degree of reduction achieved is coal-specific, relating in part to the degree of mineral association of the specific trace element and the degree of liberation of the trace element-bearing mineral. The extent of trace element removal also depends on the method of cleaning the coal. Figure 1 is a washability plot, by size fraction, of arsenic vs. ash content for Upper Freeport

Jan 1, 1994

By E. J. Ripling

A NY mechanism proposed to explain hydrogen embrittlement in titanium and its alloys must, of course, be consistent with the experimental data that characterize this embrittlement. Unfortunately, however, the mechanical behavior of hydrogen-bearing titanium, at least a-ß titanium, has not been unequivocally defined. Lenning, Craighead, and Jaffee have clearly shown that hydrogen cmbrittles a-titanium by elevating its transition temperature, probably as the result of the formation of titanium hydrides. Therefore, in these alloys, hydrogen acts like at least one other interstitial contaminant, namely, nitrogen.&apos; On the other hand, ß-titanium has been shown by these same investigators to tolerate very large amounts of hydrogen without suffering severe mechanical damage.2 Mixing these two phases, however, to form the most important class of commercial alloys, the a-ß alloys, again results in severe hydrogen embrittlement, although the mechanism by which the embrittlement is produced is not of the same type as that which causes brittleness in a alloys. Ductility damage due to hydrogen increases as the strain rate is reduced in a-ß alloys, while embrittlement in a alloys increases as the strain rate is increased, since the latter is a transition temperature behavior. Steel, like the a-ß alloys, becomes more hydrogen sensitive at slow strain rates, suggesting that the mechanism producing the embrittlement in these two metals is similar. Brown and Baldwin&apos; described the hydrogen-produced ductility depression in steel as a function of testing temperature and strain rate by defining the slope of the two surfaces that produced the depression in a three dimensional chart, Fig. 1. One of these surfaces was given by the equations (de/de)4 > 0 (de/dT) < 0 [1] while the other was defined by the pair of equations Surfaces of the type given by Eq. 1 are suggested in two ways. One is an embrittlement mechanism wherein the diffusion rate of hydrogen is competitive with the rate at which the material is being deformed, as suggested by the planar pressure theory of Zapffe and his co-workers.&apos; The other is the diffusion controlled extension of Orowan&apos;s theory on delayed fracture in glass by Petch and Stables.&apos;&apos; Surfaces of the type given by Eq. 2 are also compatible with a mechanism of pressure build up in voids, according to de Kazinczy,&apos; since the solubility of hydrogen in the metal increases with testing temperature so that as the temperature is raised, the pressure in the voids is reduced. Kotfila and Erbin recently presented some data on the dependence of ductility on testing temperature and strain rate for the a-ß 3 pet Mn complex alloy at four different hydrogen levels.H Although data were presented for only three testing temperatures at three different strain rates, their results indicated that surfaces of the types defined in Eqs. 1 and 2 are produced in the alloy when the hydrogen level is sufficiently high—200 and 300 ppm—Fig. 2. Jaffee and his co-workers presented data on a number of different a-ß alloys which indicated the existence of surfaces of the type described by Eq. 2, but the ductility recovery at low temperatures as given by Eq. 1 was not found." In an attempt to aid in crystallizing this description of the ductility dependence of hydrogen-bearing a-ß alloys, tests were conducted by the author on a-ß titanium 140A with three different hydrogen contents. The tensile properties of two as-received rods and one vacuum annealed rod* were obtained over a range of testing temperatures and strain rates as shown in Figs. 3 and 4. Hydrogen analyses were made by the Battelle Memorial Institute on four pieces of the rod whose properties are shown as solid circles in Fig. 4. The hydrogen content of these pieces, taken at widely spaced intervals within the rod, were 280, 270, 289, and 270 ppm, indicating that the hydrogen content within a single as-received rod was quite uniform. One of the broken test pieces whose properties are shown in Fig. 3 as solid circles was also analyzed, and found to have a hydrogen content of 310 ppm. The analyses obtained on two of the vacuum annealed specimens were 92 and 170 ppm.

Jan 1, 1957

By Kenneth Schellinger

THE terms surface tension and surface energy are well known when applied to liquids and are generally described by referring to the excess energy of the air: liquid interface as a result of unsaturated molecular forces surrounding the surface molecules of the liquid due to the presence of the air phase on one side. Such unbalanced forces produce the familiar water droplet of spherical form and are generally summed up as a surface tension measured in dynes per centimeter which can be shown mathematically to be equal numerically to a corresponding surface energy expressed in ergs per square centimeter. A specific surface energy, however, is best thought of as the energy necessary to produce one unit, of new surface on a substance. Hence, in producing a bubble in a flotation cell the impeller must supply surface energy corresponding to the air: liquid interfacial area on the interior of the bubble. Inasmuch as it is relatively easy to extend or contract the surface of a liquid, there are a number of successful methods for liquid surface tension, or energy, measurement based upon surface deformation. This happy state of affairs does not, however, extend to solids, which are considered to possess surface energies for the same reasons as do liquids, i.e. because of unsaturated ionic bonds at the solid: gas interface. As in the case of the flotation cell producing surface on liquids as new bubbles, it takes energy to produce new surface on solids as new particles. As every mill man knows, this surface is produced on mineral solids in a grinding mill by the action of a tumbling mass of iron balls. But here so much energy usually is wasted by the inefficient action of these balls that a large amount of heat is generated, and the surface energy production may be easily confused with the energy necessary to produce this ineffective heat. The tumbling balls and fracturing minerals ultimately take their energy from a rather large electric motor. It has been variously estimated that from 10 to 20 pct&apos;" only of this energy from the motor does not appear as heat and may be presumed to appear as surface energy on the min- erals present. Such a production of new surface on the mineral phases is accompanied, of course, by a size reduction that is inevitable as more and more mineral interior molecules become surface molecules by the fracture exposure. This size reduction of mineral particles, although the most obvious feature and perhaps the sole object of the milling operation, is from this energy viewpoint the outward manifestation of the production of surface energy only. Measurement of the characteristic surface energies of pure minerals and their various mixtures in ores would be a step towards understanding of the energetics of the commercial grinding operation. In addition, the characteristic surface energy of a mineral is probably a physical property specific for that mineral, and therefore, from a scientific standpoint, should be measured. It is interesting to note that, in contrast to the large body of work on the surface tensions of liquid systems and biological systems, the field of solid surface energies has been neglected. Prior to 1920 it is difficult to find more than one or two references to work on solid surface energies in Chemical Abstracts. Since 1920 such references number somewhat less than 100, while those on liquid systems are numbered in the thousands. Much of this apparent neglect of the field of solid surface energies (the term is intended to be somewhat inclusive at this point and refers both to the solid: gas, and the solid:liquid interface) is because of the lack of a reliable method of measurement rather than any lack of scientific curiosity. It was, and still is, difficult to produce new surface on a solid without the simultaneous production of interior changes in the same solid which may consume part of the energy used. The extension in the surface area can be measured, but the interior crystal-

Jan 1, 1953

By C. P. Lawhon, J. P. Simpson, W. M. Evans

Data obtained under controlled test conditions using a microbit drilling machine showed that oil emulsified in water muds may either increase or decrease the drilling rate, depending upon drilling conditions. A low-viscosity oil such as diesel fuel can give drilling rates in limestone almost equal to that of water. Data obtained for water emulsified in oil muds showed little decrease in the drilling rate in water-saturated cores as the water percentage of the mud was increased above the 5- to 10-percent range. Changes in drilling rate were found to be dependent upon the oil or water concentration of the mud and upon the type of formation drilled. Changes in static filtration on paper (API filtrate) did not correlate with filtration while the mud was circulated across rock. INTRODUCTION Oil additions to water muds have been reported to increase drilling rates, provide hole stability and improve filtration control. Eckel&apos; showed that water-base emulsion muds used in the West Texas area increased drilling rate with increasing oil concentration up to 15 percent oil by volume, but drilling rate decreased at a concentration of 20 percent by volume. Based on laboratory tests using water muds to drill shale, Cunningham and Goins&apos; reported that drilling rates increased and tendency for the bit to ballup decreased with the addition of oil. Percentage increase in drilling rate varied with the particular formation. They showed oil additions to improve drilling rates ap proximately 75 percent in Vicksburg shale and as much as 150 percent in Miocene shale. Each investigation showed an optimum oil content for the particular formation. Most data that indicated improved filtration control due to oil additions were based on static API Eltrates through paper rather than dynamic filtration through permeable rocks. Some types of dynamic test give a better representation of filtration down-hole while drilling and might be more likely to show some correlation with drilling rate. Static filtration would be important, of course, in relation to hole stability and formation damage. This laboratory&apos;s drilling tests, conducted on water-raturated Berea sandstone, indicated that improvements in drilling rate were not evident with increasing oil concentration in water-base muds. Investigation also showed similarity between oil-emulsion (water-in-oil) muds and water-emulsion (oil-in-water) muds while drilling these formations. In Lueders limestone high concentration of water-in-oil muds and high concentration of oil-in-water muds provided the same relative drilling rates. In Berea sandstone there was a large reduction in relative drilling rate with both the oil and water muds that contained low percentages of emulsified fluid. Dynamic filtration rates of water muds on rock did not always decrease with increasing oil percentages even though the static API filtration rates on paper did decrease. Data observed in laboratory drilling of limestone and sandstone indicate that improvements in field drilling operations when water- or oil-emulsion muds are wed may not be the result of increased drilling rates but of improved hole conditions. In some cases, actual drilling rates might be slower but improved hole conditions will result in less total time on the hole. DEFINITIONS Mud pressure—Pressure of drilling fluid as measured after leaving the drilling chamber. This is considered as the approximate mud pressure just past the bit and at the face of the formation. Terrastatic pressure—Pressure representing weight of overburden. Formation pressure—Pressure of formation fluid as measured at outlet of drilling chamber. This is considered as approximate pressure of fluid in the pores of the formation. Differential pressure—Difference between the mud pressure and formation pressure. Relative drilling rate, percent—Drilling rate with experimental fluid divided by drilling rate with water times 100 equals percent. LABORATORY EQUiPMENT AND TESTING PROCEDURES The drilling equipment has been described in previous publications The microbit drill is a closed system (capacity, approximately 7 gal) that can be pressurized to 15.000 psi and heated to 500F. Main components are a drilling chamber, filter-heater, rotary-drive and variable-speed cir-

By T. S. Plaskett

A striated structure perpendicular to the growth axis was observed by the copper-decoration tech-nique in dislocation-free, .float-zoned silicon crystals. The striations, which were spaced about 100 p apart, fitted the relationship d = f/u , where d is the spacing, f is the growth rate, and u is the crystal rotation rate. Each stria was resolved into an UNDOPED silicon crystals pulled from quartz crucibles by the Czochralski technique usually exhibit a striated structure perpendicular to the growth axis.&apos;-&apos; This structure has been attributed to oxygen segregation, with the oxygen being introduced from the quartz crucible. If the crucible is rotated, the level of oxygen contamination has been reported as high as 10° atoms per cu cm.10 These striations are similar to solute striations commonly observed in doped Czochralski-grown crystals. The periodic nature of the striations is caused by a periodic variation in the growth rate",12 which is attributed mainly to thermal gradients in the melt.13 A finer striated structure14 attributed to constitutional supercooling is sometimes observed between the coarse striae. The oxygen striations have been observed by infrared transmission techniques,&apos; by the copper-decoration technique,&apos; by X-ray diffraction microscopy,6-8 and by 9 p absorption measurements3 on crystals pulled from the melt both with and without dislocations. In this investigation float-zoned dislocation-free crystals were examined by the copper-decoration technique. The level of oxygen for float-zone material is less than 1016 atoms per cu cm the lower limit of detection by 9 p absorption measurement. EXPERIMENTAL TECHNIQUE The crystals were grown by the float-zone process with the rf heating coil outside of the quartz envelope containing the silicon. All float zoning was done under an atmosphere of purified helium. The Dash technique15 was used to grow the crystal dislocation-free. This involves growing the crystal initially with a diameter between 2 and 3 mm and at array of starlike precipitates of copper. The strucLure was not .found at the surface tor a depth of about 1.5 mm, or in a region of similar width ahead of a dislocation network. The structure is postulated to consist of vacancy clusterings or dislocation loops. very rapid rates, about 20 mm per min, for a distance of about 3 cm. The diameter of the crystal is then increased to the diameter of the source of silicon, which in this case was about 19 mm. Because of the arrangement of the apparatus, the zone was passed downward rather than upward, contrary to the standard float-zoning practice. Also, the source was rotated rather than the seed. ziegler17 has made dislocation-free crystals by a similar technique but has passed the zone upwards. The starting material was zone-refined and had a p-type resistivity of 150 ohm-cm. The major impurity was boron; the total impurity excluding the boron was reported by the supplier (Dow-Corning) to be typically less than 2 x 1013 atoms per cu cm. The crystals were examined by the Dash copper-decoration technique18&apos;19—a method in which about 10" atoms per cu cm of copper are diffused at a temperature between 900" and 1000°C into silicon which is then quenched to room temperature. On quenching, the copper precipitates on crystalline defects which are then visible when viewed by transmission infrared microscopy. The photomicrographs shown were taken either of the infrared image tube screen or directly on infrared film. All sections prior to decorating were chemically polished and, for some sections, given a sirtlZ0 dislocation etch-pit examination. After decorating, the samples were mechanically polished. RESULTS A photomicrograph, taken in transmission of a decorated cross section, is shown in Fig. 1. The portion of the section shown is near the surface of the crystal. The entire cross section showed no dislocation etch pits after being given a Sirtl etch treatment. It is seen that the copper precipitated randomly. Each precipitate, as has been reported by others, was found to have a starlike structure.

Jan 1, 1965

By W. A. Hoyer

A pulsed high-energy neturon-induced spectral logging tool has been built and field-tested. The reaction of deuterium on tritium is used to generate pulses of 14-Mev neutrons. By detecting only the prompt gamma rays produced by neutron inelastic reactions in the formation, the presence and relative abundance of carbon, oxygen, calcium, silicon and other important elements may be ascertained from a gamma-ray spectrum. Gamma-ray spectra obtained in a shallow test well and in experimental field use show that it is possible to identify formations and their contained fluids. INTRODUCTION The penetrating gamma rays from naturally occurring radioactive elements in subsurface formations have been used for a number of years in well logging as a means of characterizing and distinguishing strata. Still another nuclear logging method which has been employed for some years consists of the bombardment of strata with neutrons and the measurement of the number of gamma rays produced by neutron capture reactions involving elements in subsurface strata.&apos; Since one of the principal elements entering into capture reactions is hydrogen, the latter procedure essentially results in a hydrogen log, whether the hydrogen be in combined form in either oil or water; thus, the log gives an indirect measure of porosity. These methods, with various refinements, have been developed to such an extent that they have become routine procedures in formation evaluation. Neither gamma-ray logging nor conventional neutron logging, however, yields sufficient information to permit unequivocal identification of the mineralogic composition of formations, and neither method gives information which may be used for the positive identification of hydrocarbons in strata. Accordingly, a number of efforts have been made in recent years to gain additional information from nuclear logs. Brannon and Osoba have shown that it is possible to identify naturally occurring radioactive elements in subsurface formations by spectral analysis of gamma rays emanating from these elements. Such an identification is of value in the characterization of strata. A simplified form of spectral analysis of gamma radiation resulting from neutron capture reactions between elements in earth materials and bombarding neutrons has been used with some suc- cess under favorable conditions to differentiate between petroleum and water. This method relies upon the relatively high energy of gamma radiation from neutron capture by chlorine and, in effect, furnishes a chlorine log. In areas in which interstitial water is of sufficiently high salinity, this log can give valuable information on water saturation and, thus, indirectly on hydrocarbon saturation. Still another approach to obtaining more information by nuclear techniques is "activation logging", in which certain elements yield short-lived radioactive isotopes on neutron activation and, thus, can be detected by gamma-ray spectral analysis. From the standpoint of determining by nuclear logging methods the mineralogic composition of strata and the presence or absence of hydrocarbons, it is essential that information be obtained on the presence and relative amounts of several elements such as carbon, oxygen, hydrogen, calcium, silica and others. Some elements, such as hydrogen, chlorine and sulfur, can be determined by spectral analysis of gamma radiation resulting from neutron capture reactions."" Others — carbon and oxygen, for example — do not enter readily into capture reactions but do yield gamma rays of characteristic energies from inelastic scattering reactions with high-energy neutrons. Accordingly, the latter reactions are of particular interest as a means of identifying hydrocarbons in subsurface strata. Several years ago it was recognized that information requisite to the identification of subsurface strata and of contained fluids could be obtained by pulsed operation of a subsurface neutron generator and associated gamma-ray detector. It was contemplated that pulsed operation would be effective in discriminating in time that gamma radiation which results predominantly from inelastic scattering reactions from that gamma radiation arising from neutron capture reactions. Accordingly, research was continued and construction of such a device was initiated. Although many problems were encountered, they were solved successfully. The following sections describe the tool which has evolved, its performance and the results which have been obtained with it to date. THEORY OF OPERATION OF NEUTRON-INDUCED GAMMA-RAY SPECTRAL LOGGING TOOL THEORY OF INDUCED NUCLEAR REACTIONS Of fundamental importance is the fact that an element, when bombarded with neutrons, emits gamma radiation of energy characteristic of that element. In theory, therefore, an element may be identified by

By J. Lohrenz, C. R. Clark, B. G. Bray

Procedures to calculate the viscosities of in situ reservoir gases and liquids from their composition have been developed and evaluated. Given a composition expressed in methane through heptanes-plus, hydrogen sulfide, nitrogen and carbon dioxide together with the molecular weight and specific gravity of the heptanes-plus fraction, the procedures are capable of calculating the viscosity of the gas or liquid at the desired temperature and pressure. The procedure for reservoir liquids was developed using the residual viscosity concept and the theory of corresponding states, and was evaluated by comparing experimental and calculated results for 260 different reservoir oils ranging from black to highly volatile. The average absolute deviation was 16 per cent. This is the first known procedure for calculating the viscosity of reservoir liquids from their compositions as normally available, i.e., including the heptanes-plus fraction. The procedure for reservoir gases uses a sequence of previously published correlations. Evaluation of the procedure was accomplished by comparison of 300 calculated and experimental viscosities for high-pressure gar mixtures in the literature. The average absolute deviation was 4 per cent. The calculations are useful for (I) determining viscosities in compositional material balance computations and (2) predicting the viscosity decrease which occurs when gases, LPG, or carbon dioxide dissolve in reservoir oils. INTRODUCTION Methods to predict viscosities of reservoir fluids from the normally available field-measured variables have been presented. Beal,1 Standing,2 and Chew and Connally3 orrelated oil viscosities with temperature, pressure, oil gravity and gas-oil ratio. Carr, Kobayashi, and Burrows4 and Katz et al.5 have presented correlations for reservoir gas viscosities as a function of temperature, pressure and gas gravity. Lie all intensive physical properties, viscosity is completely described by the following function: Eq. 1 simply states that viscosity is a function of pressure, temperature and composition. These previous correlations1- hay be viewed as modifications of Eq. 1, wherein one assumes more simple functions may be used. The assumptions are practical, because the composition is frequently not known. Further, the assumptions are sufficiently valid so that these correlations are frequently used for reservoir engineering computations. In compositional material balance"&apos; computations, the compositions of the reservoir gases and oils are known. The calculation of the viscosities of these fluids using this composition information is required for a true and complete compositional material balance. For reservoir gases, Carr, Kobayashi and Burrows4 have presented a suitable compositional correlation. For reservoir oils, no correlation is available, and data from reservoir fluid analyses have been used7-9 for compositional material balance calculations.* From a theoretical point of view, this is entirely invalid. The reservoir fluid analysis, whether flash, differential, or other process, does not duplicate the compositions which occur during the actual reservoir depletion process, therefore the viscosities measured during reservoir fluid analysis are not those which occur in the reservoir. From a practical point of view, the "error" of using viscosities from reservoir fluid analysis is of varying and unknown significance. One can say qualitatively that the error is greatest where compositional effects are greatest, i.e., for volatile oil and gas condensate reservoirs and pressure maintenance operations. The first requirement to obtain a quantitative estimate of the significance of the error is to develop a reliable compositional correlation for the viscmities of reservoir oils. No such correlation has been available. Consistent with this requirement, the objective of this study was to develop a procedure to predict the viscosity of reservoir fluids from their compositions. Normally, the compositions of reservoir fluids are available expressed as mole fractions of hydrogen sulfide, nitrogen, carbon dioxide and the hydrocarbons methane through the heptane-plus fraction, with the average molecular weight and specific gravity of the latter. The final correlation was to use the composition in this form. While the more challenging objective of the study was the development of a correlation for the viscosities of reservoir oils, the viscosities of reservoir gases were also studied. The end result of the study was a procedure to calculate the viscosities of reservoir gases and liquids suitable

Jan 1, 1965

By James Boyd

Scientists and engineers must concern themselves not only with technical problems, but with the socio-economic difficulties of our scciety. The author states that raw materials are basic to the economic process and that mineral raw materials occur naturally in nearly limitless quantities. He feels that the economic pocess will provide sufficient raw materials for man&apos;s needs, and discusses in some detail the world economic environment. As our society grows in complexity, it becomes more urgently incumbent upon scientists and engineers to bring their experiences to bear on the solution, not only of technical problems, but also on socio-economic difficulties. It is to this field that I have directed a large part of my energies. RAW MATERIALS BASIC TO THE ECONOMIC PROCESS There are certain premises, frequently overlooked, which bear emphasis. As economics concerns the production, distribution, and consumption of goods, so our whole society is based on raw materials. Without the basic extractive industries of agriculture and mining, there would be no economic problems with which to deal. This principle has been expressed as "All productivity is based on three factors: 1) natural resources, whose form, place, and condition are changed by the expenditure of 2) human energy (both muscular and mental), with the aid of 3) tools.77* It seems strange that such an obvious statement needs to be made. It is forgotten by all of us, however, at one time or another when we get involved in the complicated theories of economics dealing with the financial and fiscal policies of the various governments, in the financing of enterprises, in marketing, and in labor relations. Unless decisions in all of these fields are made with this, and the rest of the "Ten Pillars of Economic Wisdom," consciously in mind, the resultant policies are doomed to eventual failure, whether these are policies of individuals, companies, or governments. The economic process is basic to society. But economics and the social aspects of humanity are inevitably intertwined. If human needs are not provided for within the basic economic structure, conflicts arise to disrupt the most carefully laid social plans. Similarly, it is the failure of society to cope with basic economic prerequisites that leads to discord within the body politic and thus to eventual economic disaster. We who are engaged in the various aspects of the mineral industry, therefore, have a large part to play in society&apos;s future development. MINERAL RAW MATERIALS OCCUR NATURALLY IN NEARLY LIMITLESS QUANTITIES Throughout my career in and out of government, I have formed my decisions on two principles: 1) Fundamentally, all mineral raw materials exist within the earth&apos;s crust in quantities greatly exceeding man&apos;s needs; 2) Any problems of supply of these materials are primarily economic in nature. With respect to my first assumption, analyses by geochemists enable them to estimate the quantities in which each of the known elements exist in the earth&apos;s crust. One of the most cautious and famous suggests that the average copper content of the lithosphere to a depth of ten miles is about 55 ppm. If this is valid, then the lithosphere contains about 1.4 quadrillion (1.4 x 10 ") tons of copper metal — an unimaginable quantity. This is 8,500,000-fold that which has been consumed by man in his existence. To illustrate further, consider that the deepest copper mine in history went to about 9000 ft below the surface; the present copper mines of the world now average less than 1500 ft in depth. We can assume that in most continental land areas of the world it is technically feasible to mine to a depth of at least one mile. The land areas of the world to an average depth of one mile, then, contain 343 billion tons (343 x 10&apos;) of copper metal, or 2000 times that which has been extracted to date. I don&apos;t believe man will ever expend his energies to extract copper from rocks which contain only a few parts per million, but he knows that each element

Jan 1, 1968

forated, allowing the completion of the removal of wash water. When discharged into the washed nut bin, the coal is moist but carries so little water as to not be objectionable to the trade, nor to give any difficulty from freezing during the coldest weather. The rock and bone from the primary jigs is elevated to a 15-ton bin by means of a single strand scraper conveyor 40 feet center to center operating on a 45 degree incline, carrying 12" x 5" scrapers every two feet. This conveyor travels at a speed of 100 feet per minute and has a capacity of 17 tons per hour. From this bin, this material falls into the third or rewash jig similar in all respects to the first two, which discharges the rock waste directly into a 15-ton refuse bin below and the bone into a short dewatering conveyor which delivers into a similar 15-ton bin from which the bone is taken to the powerhouse. The oversize and water from the shaker screen, the water from the dewatering conveyor for both the washed nut and bone, and the sludge and wash water from the three jigs, are delivered by launders to the first compartment of a three-compartment settling tank. Most of the coarser broken coal is deposited in this tank, from which is it continually removed by a bucket elevator carrying 8" x 5" perforated buckets operated on a 60 degree incline at 200 feet per minute, capable of delivering 25 tons per hour to the 50-ton washed coarse slack bin. The water passes successively through the three compartments of the settling tank and from thence through a six-inch pipe to a centrifugal pump, circulating 900 gallons per minute against a 32-foot head. A four-mesh screen 30" x 72" in the third compartment of the settling tank removes the chips of wood, paper, and the other trash, which otherwise would accumulate in the water. Water is provided from the camp water system, deriving water from the well located in an arroyo bed. During the summer months just passed, the water used, has been 108 gallons per ton of raw nut, or 146 gallons per ton of washed nut. The water meter had not been installed last winter, but it is estimated that operating at capacity, the washery will be found to require only about 75 to 100 gallons per ton of raw nut. It has not been found necessary, nor advisable, to attempt to dry the sludge from the settling tank, nor to save the water from leakage of the tanks and bins. The sludge from the jigs is washed into the settling tank and the sludge from the settling tank is washed through a tile drain to the arroyo. The jigs, shaker screen, circulating pump, washed slack elevator, and the rock handling conveyor, are all driven from line shafts driven by one 40 H. P. motor, each jig driven through a clutch. The belt conveyor and the washed nut conveyor, have separate motor drives of five and seven and a half H. P. respectively. The washer is housed in a corrugated iron building, which is partially heated by steam coils. One attendant is required for operation, regulating the feed of the jigs, the supply of water, removal of the rock, and oiling and maintaining the machinery. The rewash jig is operated only intermittently. About eleven per cent by weight of raw nut is removed as waste and four per cent goes to the washed slack bin. No control analyses of the products have been made; the efficiency of the plant being determined only by the physical appearance of the products; but the washery has been a source of pride and satisfaction to all those connected with it. As mentioned before, it has caused no interruption of operation and it has assisted materially in creating an unprecedented demand for ALAMO nut. MR. CHARLES: If there are any questions, I shall be pleased to endeavor to answer them. MR. LITTLEJOHN: Mr. Charles, do I understand it is the nut only that is washed there? MR. CHARLES: Yes, sir. MR. LITTLEJOHN: What did you say the size was? MR. CHARLES: Through three inch round perforations, retained on

Jan 1, 1926

By C. G. Dunn, P. K. Koh

THE primary recrystallization texture in cold-rolled silicon iron, which is the matrix texture for developing the Goss texture or the cube-on-edge texture by secondary recrystallization at temperatures near 900°C,1-5,21 has not been adequately described. Thus from the present available information, it is not possible to explain satisfactorily both the grain-growth selectivity of the matrix and the often observed magnetic torque curve, which itself provides some information on the texture. Also lacking is information on the special annealing texture that develops in this material when the annealing temperature is 1200°C or higher and the rate of rise to temperature is extremely rapid. From the work of May and Turnbull5 and from unpublished work, it was known that isothermal annealing near 1200°C tends to reduce the extent of secondary recrystallization and that a much weaker cube-on-edge texture results if appreciable normal grain growth replaces secondary recrystallization. Koh and Dunn6,7 have obtained additional information on complex primary recrystallization textures from further studies made after normal grain growth. In these instances the initial textures were retained during normal grain growth. A similar result reasonably could be expected in the present study except for the presence of a grain growth ihibitor1-5,8,9.21 and its tendency to allow only a few grains to grow. However, any information on the orientations of grains in the special annealing texture, even if far from representative of the initial matrix texture, would provide useful information on the nature of the matrix texture. In the present texture study the method of Newkirk and Bruce,10 which is based on the methods of Geisler" and Schwartz, 12 is used to obtain a complete (110) pole figure of the primary recrystallization texture. The high-temperature annealing texture is determined simply from the orientations of a large number of selected grains. The kinetic nature of the process that produces the annealing texture is treated elsewhere13 and it is shown that a form of secondary recrystallization with a very high rate of nucleation occurs during rapid annealing at high temperatures. EXPERIMENTAL PROCEDURE Commercial 0.014-in. cold-rolled silicon iron strip (3.16 wt pct Si), prepared by two stages of cold rolling with an intermediate short anneal, was given a decarburizing 3-min anneal at 800°C. Me-tallographic studies indicated complete recrystallization. Short-time anneals at 900° C and at higher temperatures proved that secondary recrystallization had not begun at 800°C, in fact, the short additional anneals were still in the induction period of secondary recrystallization. A rapid rise to an annealing temperature of 1260°C (2300°F) was obtained in a BaC12and NaCl fused salt bath. The structures that resulted from anneals in the range 12- to 1000-sec duration were relatively finegrained, even though the growth was a form of exaggerated grain growth13 or secondary recrystallization with a high nucleation frequency.= Many of the grains were large enough for an X-ray study using a 5-mil X-ray beam. A transmission Laue Camera and an optical-mechanical stage for moving the grains into the X-ray beam were used. A total of 325 grains were X-rayed in this manner and the grain orientations determined. Complete (110) pole figures were obtained for the primary recrystallization texture using CoKa radiation at 30 kv in the back-reflection range, such as (220) for (110) poles, as described recently by Newkirk and Bruce.10 The low voltage serves to reduce the spurious white radiation to a minimum. A filter of 0.001-inch iron foil was located in front of the detector slit for transmission and in front of the beam slit for back reflection. A new and improved specimen holder extended the useful tilting angle range for transmission to 70 deg instead of 60 deg as previously reported.&apos; A torque magnetometer was used to obtain the magnetic torque curves for a number of l-in. diam disk specimens. RESULTS The (110) pole figure of the material after recrystallization at 800°C is shown in Fig. 1. The positions of the pole concentrations are found to be

Jan 1, 1961

By Bernard L. Cohen

INTRODUCTION The most serious occupational radiation episode in U.S. history was the exposure of uranium miners to radon daughters in the 1945-1968 time period. Although the maximum permissible dose at that time was 12 WLM (working level months) per year, average exposures were several times that figure, and ten times higher exposures were not uncommon. Starting in the early 1960s, mounting epidemiological evidence appeared for an excess incidence of lung cancer among these miners; up to 1974, there was an excess of 134 cases (159 observed vs 25 expected) among the 4000 in the group under study (NAS-1980). When this excess became apparent, the Federal Government took jurisdiction, greatly tightened enforcement, and in 1969 lowered the maximum permissible exposure to 4 WLM per year. These standards were met largely by a great improvement in ventilation. As a result of these measures, average miner exposures were reduced 5-fold from 1965 to 1968 and by another factor of 3 by 1970. In 1978, the 4 WLM/year maximum permissible exposure was exceeded by only 37 of 7500 underground miners, for only 16 wars it exceeded by more than 25%, and for only 8 was it exceeded by 502 (AIF-1980). The average exposures to the various groups are listed in Table 1. We see that the average exposure for all miners was 1.03 WLM, and for those who worked essentially full time underground it was 1.45 WLM. For purpose of later discussion, it will be convenient to choose a single value for average exposures. In view of the fact that employment situations and job categories are bound to vary over a lifetime of work, we take this to be 1.3 WLM/year. The purpose of this paper is not to dwell on history, but rather to address the question of whether or not this present situation is satisfactory. This question was considered recently by a study group under the auspices of National Institue of Occupational Safety and Health (NIOSH-1980) and it answered the question in the negative, concluding that the maximum permissible exposure should be substantially reduced. However, their arguments were incomplete and were lacking in perspective. The principal thrust of this paper is to provide some of the material overlooked. RISK TO URANIUM MINERS FROM RADON EXPOSURE In order to quantify the risk to uranium miners under present working conditions, it is first necessary to estimate the risk of lung cancer per WLM of exposure. The most straightforward way of doing this is to use the data on the group of uranium miners under study. These are listed in Table 2 for 8 exposure ranges and for the total group (NAS-1980). If all data are given equal weight, the risk is seen to be 3.5 x 10-6 per year per WLM. Much can be said in favor of using this value for the risk as dose independent; it is within one standard deviation (SD) of the observations in 5 of the 8 dose categories (as expected from the definition of SD), and within 2 SD for all 8, and for the three cases differing from the mean by more than one SD, two are above and one is below. However, the uranium miner exposures in the present situation will be far below those covered in Table 2, so it is worth considering the possibility that the risk differs from this at low doses. From the last column of Table 2 we see that the experience from all exposures below 600 WLM indicates a risk higher than the mean for the entire group by more than two standard deviations (the value 600 WLM in this comparison was deliberately chosen to maximize this deviation; for exposures below 360 WLM and 840 WLM, the excess is only 1.0 and 1.6 standard deviations respectively). In view of this tendency for the risk to be higher at lower dose, we will take the risk to be 5.0 x 10-6 per year per WLM in what we will refer to as model A. This risk estimate is based entirely on exposures much [higher] than those that will be experienced by

Jan 1, 1981

By William D. Cassity, Batric Pesic

Introduction Gold mining on an industrial scale is becoming increasingly dependent on low-grade refractory sulfide ores that contain large amounts of pyrite (FeS2) and arsenopyrite (FeAsS). Gold is usually present as sub-microscopic particles dispersed evenly throughout the sulfide matrix. Without some form of preoxidation, efficient recovery of this finely disseminated gold through cyanide leaching is hampered because the surface of the sulfide particle becomes passivated and impervious to penetration of the cyanide. Traditional methods for recovery of refractory gold from arsenopyrite ores include roasting and autoclave leaching. A modem alternative method is to preoxidize the mineral using the bacterium Thiobacillus ferrooxidans prior to attempting to re- cover the gold through cyanidation. The bioleaching of arsenopyrite ores presents a problem in the mobilization of large quantities of arsenic, present both in the +5 and +3 ionic states. Dissolved arsenic species pose a dual problem: they are -1 to the bioleaching process itself through inhibition of bacterial activity, and they also pose an environmental threat. The arsenate anion (AsO2) has been shown to be more toxic to living organisms, including Thiobacillus ferrooxidans, than the arsenate anion (AsO43) (Collinet and Morin, 1989). There is some disagreement as to the fate of arsenite in bioleaching solution. Mandl, Matulova, and Docekalova (1992) reported that dissolved arsenite concentration was constant during a long-term bioleaching study of chalcopyrite using Thiobacillus ferrooxidans. Torma and Oolman (1992) report that Thiobacillus ferrooxidans has been found capable of oxidizing As3+ to As5+. The solid products of arsenopyrite/pyrite bioleaching include jarosite (MFe3(SO4)2(OH)6 where M can be K+, Na+, NH4+ or H3O+), scorodite (FeAsO4.2H2O), ferric hydroxides, and ferric hydroxysufites (Carlson et. al., 1992; Van Breemen, 1982; Lazaroff et. al., 1982). The particular species formed is a function mainly of pH. Little study has been performed on the effect of solid products on bioleaching. Pesic and Kim (1993) showed that Thiobacillus ferrooridans cells served as a nucleation sites for jarosite particles, which grew rapidly and eventually killed the cell. Most bioleaching studies are performed at low pH&apos;s (<2.0) under uncontrolled conditions. By studying bioleaching of arsenopyrite under controlled pH conditions and at higher pH&apos;s (2.0 to 3.0), the distribution of iron and arsenic between the solid and liquid phases can be controlled, and their effects studied. The objective is to develop a bioleaching process that operates at high efficiency while keeping amounts of dissolved heavy metals low. Pesic, Stohok, and Torma (1993) demonstrated the usefulness of this approach in the leaching of cobaltite (CoAsS) concentrates. Materials and Methods The focus of this study was the bioleaching of arsenopyrite ore by Thiobacillus ferrooxidans. The parameters studied included the effects of pH, and the effects of arsenate (AsO43 and arsenite (AsO2). pH studies included pH set initially but not controlled, and pH controlled continuously with NaOH or LiOH. Bioleaching results from two strains of Thiobacillus ferrooxidans with different adaptation histories were compared. Bioleaching experiments were conducted in 150 ml stirred glass reactors using a strain of Thiobacillus ferrooxidans adapted to arsenopyrite ore, supplied by the U.S. Bureau of Mines. These bioreactors were innoculated with stock cells grown on arsenopyrite ore for 14-16 days. Typical elemental breakdown for this ore was: As, 9.90%; Fe, 18.60%, Stot, 9.26%; Suifide, 7.50%; SiO2, 25.90%. Mineralogically, the ore contained both arsenopyrite and pyrite. Bioleaching efficiency was measured by withdrawing bioleach solution samples at selected intervals, filtering, and measuring the amount of dissolved cobalt, iron, and arsenic by atomic absorption spectroscopy. Because the precipitation of iron and arsenic at higher pH&apos;s would lead to unreliable results, a 100 mg tracer of cobaltite concentrate from the Blackbird mine in southern Idaho was added to solution. Dissolution of the cobaltite tracer was used to indicate bioleaching of the bulk arsenopyrite ore. Cobalt has been shown to be stable in solution even when iron and arsenic were precipitated (Pesic, Storhok, and Tonna, 1993). The pa-

Jan 1, 1995