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By Norman Lamont

The evaluation of certain reser-voir properties, such as porosity and fluid saturation, from electrical well surveys has been widely accepted in petroleum engineering. Various investigators have established relationships between these properties and certain parameters which affect the response of the electrical log. Among these are the resistivities of the mud, its filtrate, and its filter cake. In 1949, Patnode1 established a relationship between the resistivities of the mud and filtrate. The well logging service companies have contributed relationships for the mud-mud cake resistivities2,3 These have been valuable since it was the practice to measure only resistivity of mud at the well site. During the mid-1940's the industry began drilling wells with oil-emulsion drilling fluids. These were conventional aqueous muds with a dispersed oil phase. Since 1950, oil-emulsion muds have been used on an increasing number of wells each year. However, the practice of measuring only the resistivity of the mud at the well site has continued, and the mud filtrate and mud cake resistivities have been determined by the above-mentioned relationships. Service companies are now equipped to measure all three resistivities at the well site. An investigation was conducted on the resistivities of oil-emulsion muds, mud filtrates, and mud cakes to determine if these values conformed to the relationships for aqueous muds. TYPES OF MUDS Fifty-one oil-emulsion mud samples were prepared in the laboratory following a standard manual' published by a leading mud company. The diesel oil in the samples varied from 5 to 50 per cent, the majority of the samples being in the 10 per cent region. The basic aqueous mud types which were converted to oil-emulsion muds were commercial clay and bentonite muds, low pH and high pH, caustic-quebracho treated muds, and lime treated muds. The emulsions were stabilized by dispersed solids, lignins, lignosulfo-nates, sodium carboxymethyl cellulose, or sulfonated petrolatum. It is worthy of note that after a quiescent period of two weeks at room temperature all samples, regardless of emulsifying agent, remained stable. The make-up water for the muds was from the laboratory tap. Resistivities were varied by the addition of table salt to the water. A range of mud resistivities from 0.44 to 3.9 ohm-m was obtained in this way. Twenty-three field muds were tested. These covered the same range of mud types as did laboratory muds. Oil provinces of the Gulf Coast, South Texas, West Texas, Oklahoma, Montana, and Canada were represented. MUD TEST PROCEDURE Each mud was tested for density, viscosity, pH, and filter loss by standard testing techniques. The resistivity measurements were obtained with a Schlumberger EMT meter. This meter required small volumes of sample, e.g., 2 mm. Filtrate was obtained from a Standard Baroid fil-ter press at the end of a 30-minute test. The filter cake from the same test was used for cake resistivity measurements. Mud, filtrate, and cake samples were heated to 100" F in a constant temperature water bath prior to measurement of resistivities. RESULTS The relation between mud resistivity (Rm) and mud filtrate resistivity (Rmf) is shown in Fig. 1. The solid line represents an average for the data. The equation of this line is Rmf =0.876 (Rm) 1.075 . . (1) Arbitrary limits, indicated by the dashed curves, have been set. The majority of the data falls within these limits, but some points do lie outside the limits. The approximate equation Rmt = 0.88 Rm , . . . . (2) will give satisfactory results within these limits. The data on mud cake resistivity Rmc is shown in Fig. 2. The solid line is an average for the data. The equation for the line is Rmc = 1.306 (Rm)0.88 The dashed lines are arbitrary limits on the data. Within these limits, Eq. 3 may be simplified to Rmc = 1.31 Rm . . . . (4) DISCUSSION The limiting curves in Figs. 1 and 2 represent maximum deviations of ±25 per cent. Thus the use of the average curves can introduce considerable error. There is no substitute for accurate measurements of mud, mud cake, and mud filtrate resistivities at the well site. The mud sample tested should be representative of the mud opposite the formation being logged. The average mud filtrate resistivity curve of Fig. 1 is reproduced in Fig. 3 with two curves which have been published for clay-base aqueous muds2,3. The latter curves were determined from average values of a large number of drilling fluids. The three curves have essentially the same slope and the differences between them are from 7 to 22 per cent. Comparison is made only to illustrate the possibility of error

Jan 1, 1958

By Lawrence A. Roe

The magnetic reflux classifier, which utilizes the combined effects of magnetic fields and a hindered settling classifier, is a new tool for determining the quantity and quality of middlings in fine-sized magnetite concentrates. Results are given for processing a typical taconite ore, and a sketch of the apparatus is included. IN examining magnetite ores and beneficiated products it often becomes necessary to make critical studies of the amount of grinding necessary to produce the desired degree of magnetite liberation. In the past this has been accomplished by laboratory heavy-liquid tests, which provide a method for selectively removing middling particles and free magnetite from various-sized fractions. Examination of the various products under the microscope results in fairly accurate determination of the degree of liberation. The method is quite efficient on sizes coarser than 325 mesh. Thus the heavy-liquid method of middling separation was satisfactory until the advent of present day magnetic taconite studies. When magnetite concentrates ranging from 70 to 100 pct —325 mesh are studied it becomes apparent that older methods of determining liberation size are not satisfactory and that there is need for a new method. For example, some of the low-grade magnetite ores of the Wisconsin and Michigan iron ranges require grinding to 100 pct —325 mesh to produce a magnetic concentrate containing less than 12 pct silica. Examination of concentrates from such ores often reveals that many of the middling particles consist of only very minor proportions of iron mineral. Thus it becomes important to be able to determine the degree of grinding necessary not only for complete liberation, but also for liberation of only 80, 85, or 90 pct of the total iron mineral content. Actually, complete liberation is never attained, but is often used to designate that degree of liberation necessary for production of high-grade concentrates. A rougher concentrate, produced after elimination of a coarse-sized tailing, can usually be subjected to a second grinding stage and concentrated into a higher grade product than could be produced from the same crude ore with one stage of grinding resulting in the same overall size reduction. This fact adds to the importance of being able to determine partial degrees of liberation on any magnetite ore. Standard laboratory methods such as heavy-liquid separation, microscopic grain counts, Davis tube magnetic separation, magnetic flocculation, classification, flotation, and others often are not applicable, or are prohibitive because of time requirements when large numbers of fine-sized magnetite samples are investigated. The Davis tube magnetic separator is an efficient tool to use in rejecting the non-magnetic mineral particles from an ore sample. The middlings discarded by the tube separator usually are so low in iron content that they can be considered relatively unimportant in liberation studies. This condition is caused by the extremely high flux density used in the Davis tube. This flux density ranges from four to eight times the flux density produced by most of the powerful commercial machines in use today. Thus the problem resolves itself into a search for a method of selectively removing middlings from Davis tube magnetic concentrates which will be both rapid and efficient. Those methods showing most promise in the development of a process for isolating middlings from extremely fine-sized magnetic concentrates were flotation and magnetic flocculation. The use of flotation to remove middlings from magnetic concentrates is reported in the literature.'.' The flotation process is effective in removing middlings from a magnetite concentrate, but physical entrapment of fine-sized free magnetite in the silica-bearing froth is an undesirable feature. The flotation method of removing middlings requires time, effort, and precise control of many variables, and does not meet the required degree of middling isolation. Magnetic Flocculation Magnetic flocculation has long been resorted to"-" in efforts to upgrade magnetite concentrates. One of the new magnetic taconite plants now under construction on the Mesabi Range includes magnetic flocculation in the flowsheet' as an accessory process to remove high-silica middlings and free silica which has been mechanically entrapped in magnetite flocs. The use of magnetic flocculation as a laboratory method of making precise separation of middlings was further investigated, since it offered a rapid, simple method of accomplishing the desired result. Magnetic flocculation involves the subjection of a magnetic concentrate to a strong magnetic field, passing the concentrate in a highly flocculated condition to a hydroseparator or other classifiers of various types, and removing free silica and middlings as overflow products. In an attempt to utilize simple

Jan 1, 1954

By R. E. Hudrlik, G. W. Preckshot

The diffusion coefficients of silver from solid silver in molten lead were measured to within ± 0.8 pet in a columnar type diffusion cell ower, the temperature range of 326° to 530°C. Fick's law describes the process up to 530°C where the laminar mechanism appareltly breaks down. These is negligible resistance at the interface as shown by mathematical analyses. The diffusion coefficients are found concentration independent. IT would seem that diffusion in liquid metals would be free of such effects as molecular structure, dissociation. polarization. and compound formation. This view was taken by Gorman and preckshot in their study of diffusion of copper from solid copper into molten lead. They reported diffusion coefficients which were independent of the concentration over the range of 478° to 750°C. They found that the Stokes-Einstein equation with constant radius of the diffusing specie represented the diffusion data better than Eyring's rate theory equation and Sheibel's correlation. The radius of diffusion was found to be that of the doubly charged copper. There appeared to be no resistance across the solid-liquid boundary. In the present work the diffusion coefficients for silver in liquid lead were measured over a range of temperatures of 350° to 505°C. The solubility of silver in lead over the range of 303° to 630°C was also obtained. These results are compared with calculated or correlated values or with data in the literature. EXPERIMENTAL Procedure—The experimental equipment techniques and procedures were those reported in detail by Gorman and preckshot9 and will not be repeated here. Measured values of WT, Co, A. L were obtained for various diffusion times and the diffusion coefficient was computed for the case of no resistance at the interface9, 11 by: WT/CoAL = 1- 8/p2 n=1 1/(2n - 1)2 exp[-(2n - 1)2p2 Dt/4L2] [1] or where there was resistance at the interface by: WT = 1- ?n=1 2h2/ap2L [sxp [-Dan2t]/[(h2 + an2) L + h] The roots an are those of the transcendental equation3 tan (an L) = Iz/cun. The diffusion coefficient is that defined by Hartley and Crank.7 The total silver in the lead cylinder and equilibrium slug was determined by a cupellation technique' with proper correction for losses. Analysis of known samples showed that this method is surprisingly accurate. The amount of silver in the lead adhering to the silver cylinder was obtained in the same fashion as shown by Gorman and preckshot.9 The small errors involved in this determination are not critical since the silver in this adhering lead layer is only 3 to 15 pet of the total diffused. Materials—Electrolytic silver containing 99.9+ pet Ag obtained from General Refineries of Minneapolis, Minn. was used for all but runs 7 and 8. For the balance of the runs this silver was reduced with hydrogen at 1100°C and its oxygen content was found to be about 0.017 pet. For the runs. 7 and 8, phosphorous-reduced silver of the same purity was obtained from Handy and Harman Co. of Chicago, Ill. The densities of the phosphorus-reduced silver and the hydrogen-reduced electrolytic silver were 10.484 and 10.487 g per cm3, respectively. These values agree with those reported for pure silver. Silver which was reduced at 900 C had an average density of 9.998 g per cm3, indicating porosity. This silver was used for a number of runs which were not tabulated in Table I. These are indicated by crosses on Fig. 2. The 99.999 pet Pb was obtained from the National Lead Co. Research Laboratory of Brooklyn, New York. DISCUSSION OF RESULTS The diffusion and solubility results are reported in Table I for eleven runs using either phosphorus-reduced electrolytic silver or hydrogen-reduced silver at 1100° C. The solubility data shown in Fig. 1 show the excellent agreement with that reported by Heycock and Neville.8 The data of Friedrichs5 apparently are in error. The experimental solubility data of this work are reported to 0.3 pet. The experimental diffusion coefficients computed from Eq. [1] are reported within 1.2 pet of the mean and are plotted in Fig. 2. These are expressed within +0.8 pet of the experimental values over the entire temperature range by: D= 8.26 x 10 -5 e-1925/RT . [3] There appears to be little difference due to the

Jan 1, 1961

By R. J. Pindred

Discussion by R.J. Pindred In his paper, Davis presents an overview of risk. He also introduces the Capital Asset Processing Model (CAPM) as a foundation for selecting the appropriate discount rate for a mining project. While applying portfolio theory is more defensible than the ad hoc adjustment of discount rates, the CAPM is not a panacea. CAPM shortcomings [The CAPM, as Davis stated, is expressed in the equation: ri=rf+pi4) where ri is the project discount rate rf is the risk free interest rate (3i is the project beta, and 0 is the market risk premium (rm - rf)] Application of the CAPM is more difficult than Davis indicates. Valuation is prospective, while the CAPM parameters are historical. Beta is determined from a regression analysis of historical data, while the beta needed for valuation is the expected beta. Betas are known to be unstable and the regressions that generate them often have low explanatory power. The difficulty of estimating a "project" beta must also be considered. Thus, the beta that is used in the CAPM will be based on the analyst's judgment. Like Cavender's discount rate, this judgment can lead to different project NPVs. Subjectivity in valuation cannot be avoided by a mechanical application of the CAPM. The risk-free rate, which Davis identifies as a short-term real rate of 4%, is also subject to scrutiny. A mining project is not a short-term investment and no single risk-free rate is appropriate for all of the cash flows. The hypothetical mine discussed in Cavender's paper is a six-year project. One might argue for the application of a risk-free rate from the Treasury yield curve at the duration of the project (in a bond-duration sense). This, too, is inappropriate. The risk-free rate should be matched to the timing of the cash flow. These rates can be determined by calculating the implied forward rates from the yield curve using a procedure known as "bootstrapping." It is likely that each of the project's cash flows would be discounted at a different rate. Commodity prices Davis criticizes the "ad hoc adjustment to the discount rate." Yet, in his discussion of the value of stochastic simulation, he suggests that the gold price be modeled as a "random walk, with or without a trend." This is essentially an arbitrary modeling of price risk. Consider that a liquid market in gold futures exists. The futures' price curve, which is closely related to the market's estimate of future spot gold prices, should be used to provide inputs to the model. This is especially true of a relatively short six-year project. Alternatively, as Davis correctly points out, a risk-averse investor can sell the commodity short to hedge price risk. Is it any more correct, in the portfolio sense, to account for price risk at all ?? References Cavender, B., 1992, "Determination of the optimum lifetime of a mining project using discounted cash flow and option pricing techniques," Mining Engineering, Vol. 44, No. 10, pp.1262-1268 Fabozzi, F.J., 1993, Bond Markets, Analysis and Strategies, Second Edition, Prentice Hall, Inc. Higgins, R.C., 1992, Analysis for Financial Management, Third Edition, Richard D. Irwin, Inc. Solnik, B., 1991, International Investments, Second Edition, Addison Wesley Reply by G.A. Davis Pindred discusses two issues related to my paper, the shortcomings of the Capital Asset Pricing Model (CAPM) and which commodity price values to use in the valuation exercise. Even though these topics are not directly related to the use or misuse of Monte Carlo simulation, they are important points to take into consideration in valuation exercises. Since I do not appear to have addressed these issues satisfactorily in my original paper, I will comment on each here. Pindred agrees with me that applying portfolio theory, and specifically the CAPM, to the selection of project discount rates is more defensible than ad hoc methods. But he then points out that the application of the CAPM to project valuation is more difficult that I indicate. It is true that the CAPM is a difficult tool for project valuation in general,. But the application of the CAPM to mining projects is one of the easiest I can think of. The biggest problem with using the CAPM for project valuation is coming up with an expected project beta. I suggest a project beta for gold projects of 0.45. The "true" value might be 0.35, 0.55 or whatever. Pindred correctly notes that the selection of the appropriate project beta is based

Jan 1, 1996

By P. B. Baxendell, R. Thomas

Work on the calculation of vertical two-phase flow gradients by Cia. Shell de Venezuela has been based mainly on the "energy-loss" method proposed by Poett-mann and Carpenter in 1952. The "energy-loss-factor" correlation proposed by Poettmann and Carpenter was based on relatively low-rate flow data. This correlation proved inapplicable to high-rate flow conditions. In an attempt to establish a satisfactory correlation for high rates, a series of experiments was carried out at rates up to 5,000 BID in Cia. Shell de Venezuela's La Paz field in Venezuela, using tubing strings fitted with electronic surface-recording pressure elements. As a result of these experiments a correlation between energy-loss factor and mass flow rate was established which is believed to be applicable to a wide range of conduit sizes and crude types at high flow rates (e.g., above 900 BID for 27/8-in. OD tubing). It is anticipated that the resulting gradient calculations will have an accuracy of the order of % 5 per cent. At lower flow rates the energy-loss factor cannot be considered as constant for any mass rate of flow, but varies with the free gas in place and the mixture velocity. No satisfactory correlating parameter was obtained. As a practical compromise for low flow rates, a modification of the curve proposed by Poettmann and Carpenter was used. In practice this was found to give gradient accuracies of approxirnately ± 10 per cent clown to flow rates as low as 300 B/D in 27/8-in. tubing. INTRODUCTION Production operations in Cia. Shell de Venezuela's light- and medium-crude fields are principally concerned with high-rate flowing or gas-lift wells. Under these conditions the analysis of well performance, the selection of production strings and the design of gas-lift installations are vitally dependent on an accurate knowledge of the pressure gradients involved in vertical two-phase flow. Initially, attempts were made to establish the gradients empirically as done by Gilbert,' but the results were not reliable due to scarcity of data over a full range of rates and gas-oil ratios. Several methods of calculation based on energy-balance considerations were attempted, but the computations were cumbersome and the results cliscouraging. In 1952 a paper was published by Poettmann and Carpenter' which proposed a new approach. Their method was also based on an energy-balance equation. but it was original in that no attempt was made to evaluate the various components making up the total energy losses. Instead, they proposed a form of analysis which assumed that all the significant energy losses for mutiphase flow could be correlated in a form similar to that of the Fanning equation for frictional 1osses in single-phase flow. They then derived an empirical relationship linking measurable field data with a factor which, when applied to the standard form of the Fanning equation, would enable the energy losses to be determined. The basic method was applied in Venezuela to the problem of annular flow gradients in the La Paz and Mara fields" This involved establishing a new energy-loss-factor correlation to cover high flow rates and, also, some adaptation of the method to permit mechanized calculation using punch-card machines. The final result was 1 set of gradient curves for La Paz and Mara conditions which proved to be surprisingly accurate. With the encouraging results of the annular flow calculations, several attempts were made to obtain a corresponding set of curves for tubing flow. Here, unfortunately, little progress could be made. The original correlation of Poettmann and Carpenter was based on rather 1imited data derived from low-rate observations in 23/8- and 27/8-in. OD tubing. It did not cover the higher range of production rates, and extrapolation proved unsuccessful. A new correlation covering high flow rates was required, but this proved to be extremely difficult to establish since tubing flow pressure measurements at high rates did not exist—due to the difficulty of running pressure bombs against high-velocity flow. The necessity for reliable tubing flow data increased with the development of the new concessions in Lake Maracaibo, where high-rate tubing flow from depths of 10,500 ft became routine. Thus. it was decided to set up a full-scale test to establish a reliable energy-loss factor for tubing flow conditions. A La. Paz field light-oil producer with a potential of approximately 12,000 B/D on annular flow was chosen. To obtain full pressure gradients, a special tubing string was installed which was equipped with electronic surface-recording pressure measuring devices,

By A. E. Bibb, J. R. Fascia

Single-crystal wafers of zirconium have been exposed to 680°F neutral water. The single crystals were of known orientation and weight-gain data as a function of crystal orientation were obtained. These data show that all the crystal faces studied obeyed a cubic rate law out to the time of transition whereupon the crystals corroded at an approximately linear rate. The time to transition varied from 114 days for (1074) crystals to about 325 days for the (2130) faces. The epitaxial relationship be-tween metal and monoclinic oxide was found to be (0001) H (111) and [1120] 11 [101]. A black tight adherent oxide layer was formed on the crystals in the pretransition range. This black oxide was found to be monocrystalline. The white corrosion product produced after transition was found to be polycrys-talline but highly oriented. X-ray line-broadening studies found that the black oxide was a highly strained structure whereas the white oxide was relatively strain-free. These results indicate a strain-induced re crystallization or fragmentation accompanies the change from protective black oxide to nonprotective white oxide. ZIRCONIUM alloys have been used quite extensively in high-temperature aqueous environments. Alloy additions can be made to commercial sponge zirconium which enhance the corrosion resistance of the zirconium in both water and steam media, which raise the tolerance limit for certain impurities detrimental to corrosion resistance, and which reduce the amount of free hydrogen pickup during corrosion. The development of the corrosion-resistant zirconium alloys has been a long and tedious job involving trial and error methods. This technique has been necessary because of a lack of fundamental data and hence understanding of the corrosion mechanisms. The objective of the work described herein was to provide some fundamental data with respect to the aqueous corrosion of zirconium crystals as a function of the orientation of the exposed surfaces. Hg. The zirconium chunk was then cooled to below the transformation temperature (862°C) and reheated to 1200°C for 8 hr. The ultimate size of the zirconium grains increased with the number of cycles. Rapid or even furnace cooling through the transformation temperature produces a considerable amount of substructure which was intolerable in corrosion experiments as it would be in the study of any crystallographically dependent property. It was found that a high-temperature a-phase anneal for approximately 4 days reduced the substructure below the limits detectable by visual or X-ray means. Crystals so produced were carefully cut from the massive zirconium chunk and oriented by standard back-reflection Laue techniques. The crystals were then mounted in a goniometer head and, by using the three degrees of freedom available, slices on the order of 0.015 to 0.020 in. were cut parallel to any desired crystal plane. These slices were then carefully polished on both sides to produce smooth flat faces, pickled to remove about 0.002 in. per face, annealed for 1/2 hr at '750°C in a vacuum of approximately 10"5 mm Hg, flash pickled, and checked for orientation. The pickling solution was 45-45-10 vol pct HN0,-H20-HF and continuous agitation was provided to eliminate pitting of the slices. Any slice that was not within 2 deg of the desired orientation was discarded, and any evidence of substructure as indicated by the Laue spots was also grounds for discarding the sample. Thin slices were used for the corrosion tests because weight gain per area data could be obtained with only a minimum area exposed to the corrosive media that was not of the desired orientation. The thin single-crystal slices were of irregular shape and as a result the areas were determined by placing a crystal inside an inscribed square of known area, enlarging a picture of this assembly about X5, and tracing both the enlarged square and crystal with a planimeter. The zirconium used to produce these single crystals was crystal-bar grade, a typical analysis of which is given in Table I. An oxygen analysis on prepared crystals gave a concentration of 205 ppm. The hydrogen concentrations are believed to be less than 15 ppm due to the dynamic vacuum anneal given each crystal. Typical nitrogen values for zirconium treated in this manner are about 10 to 20 ppm. RESULTS AND DISCUSSION Single-crystal wafers have been exposed to de-oxygenated, deionized water in static autoclaves.

Jan 1, 1964

By H. C. Gatos, A. D. Kurtz

WITH the growing interest in the mechanism of self-diffusion of metals, the study of accurate and convenient methods for determining self-diffu-sion coefficients appears highly desirable. It was with this objective in mind that the present investigation was undertaken. Gatos and Azzam1 employed an autoradiographic technique for measuring self-diffusion coefficients of gold. This method involved sectioning of the specimen through the diffusion zone and recording the radioactivity directly on a photographic film. Because of the very short range of the emitted ß rays in gold, the activity recorded on the film was essentially the true surface activity. With proper choice of the sectioning angle, sufficient resolution could be obtained and the entire concentration-distance curve recorded in one measurement. For the boundary conditions of the experiment, where an infinitesimally thin layer of radioactive material diffuses in positive and negative directions into the end faces of a rod of infinite length, the solution of the diffusion equation is C/Cn = 1/v4pDt exp (-x2/4Dt) where C is the concentration of diffusing element (photographic density in this case), C,, is the constant (depending upon amount of radioactive material), x is the diffusion distance, D is the diffusion coefficient, and t is the time. Thus, by plotting the logarithm of the concentration vs the square of the diffusion distance, a straight line results and the slope contains the diffusion coefficient. In this manner, the self-diffusion coefficient of gold can be obtained as a function of temperature. In the present investigation the results reported by Gatos and Azzam1 have been verified, and the autoradiographic technique has been further developed and applied for the determination of the self-diffusion coefficient of gold at a number of temperatures. Furthermore, the energy of activation for the self-diffusion of gold has been conveniently determined. . Experimental Techniques Preparation of Specimens: The inert gold of high purity was received in the form of a rod from which cylinders were cut and machined to a diameter of 0.500 in. The specimens were annealed to a suitably large grain size and the faces were surface ground prior to the deposition of the radioactive layer. The radioactive isotope Au198 was chosen. It was produced in the Brookhaven pile by means of the reaction Au197 + n ? Au108. It decays by ß emission (0.96 mev) to Hg108 with the subsequent emission of a y ray (0.41 mev). 70Au 108 ? 80Hg 108 + -1e°. The half life of the Au108 is 2.7 days so that a strict time schedule had to be maintained in order to secure sufficient activity until the end of the experiments. For this reason, initial activities as high as 10,000 millicuries per gram were used. The gold arrived in the form of foil and was evaporated onto one face of each gold specimen cylinder to a thickness of about 100A. A sandwich-type specimen was formed by welding two such cylinders together. Evaporation of Gold: The gold was evaporated under vacuum from heated tantalum strips which were bent in such a way as to limit the solid angle through which the gold was allowed to vaporize, thus insuring a more efficient utilization of the gold. The specimens rested on flat brass rings which had an inner diameter of 0.475 in. The entire specimen-holding assembly could be manipulated from outside the vacuum system by means of a magnet which attracted a slug of soft iron attached to the assembly. By evaporating inert gold on glass slides under conditions identical to those employed for the radioactive gold, it was found that the thickness of the films was about 100A. Welding: The welding was performed by hot pressing in a stainless steel cylinder. The inside of the cylinder was threaded and fitted for two plugs. The specimens to be welded were placed in the middle of the cylinder and two pressing disks, one at each end, were inserted to avoid shearing stresses as the plugs were tightened. Mica disks were placed between the pressing disks and the specimens to prevent them from welding. The plugs were then tightened with a hand wrench and the entire unit was placed in an argon stream for about an hour to remove the oxygen. The unit was then inserted in the center of an argon atmosphere furnace maintained at about 700°C and left there for about an hour. Because of the difference in the temperature coefficient of expansion of the two metals, as the temperature rose. the pressure on the specimen-rollple increased and a weld resulted Welding was generally satisfactory under the conditions described.

Jan 1, 1955

By W. Rostoker, A. S. Yamamoto, K. Anderko

ALTHOUGH the corrosion resistance of magnesium and its alloys is closely related to iron content, there has been no direct measurement of the solid solubility of iron in magnesium. Bulian and Fahrenhors;1 and Mitchel]2 agree that pure iron or a limited terminal solid solution crystallizes from the Mg-rich liquid. For this reason a magnetic-moment method was selected to estimate that portion of the total iron content which is not in solid solution. Since iron in solid solution in magnesium cannot contribute to ferromagnetism, the difference between chemical and magnetic-iron analyses should yield the solid solubility. By experimentation it was found that the melting of pure sublimed magnesium (99.995 wt pet purity) in Armco-iron crucibles at about 800°C is a convenient way to introduce small amounts of iron. Melts retained 5, 10 and 20 min at 800°C analyzed 0.003,, 0.005,, and 0.018 & 0.001 weight pet Fe, respectively, after being stirred, heated to 850°C, and cast into graphite molds. The as-cast alloys were pickled in acid (dilute HC1 + HNO3), annealed at 600°C for 3 days, scalped on a lathe to remove the pitted surface, pickled again, extruded at about 100°C to 3-mm wire, reannealed 41/2 days at 500°C, and water-quenched. The specimens were again scalped, pickled, and used both for chemical and for magnetic analysis. Most of the precautions described were intended to prevent iron pickup by contact with tools or superficial iron enrichment by volatilization of magnesium during heat-treatment. It is believed that the specimens ultimately used for test were homogeneous and characteristic of phase equilibria at 500°C. Magnetic Analyses A susceptibility apparatus of the Curie type was used for magnetic analyses. Field strengths of up to 10,400 oersteds could be generated. By this method, an analytical balance measures the force of attraction which a calibrated magnetic field exerts on a suspended specimen. The force equation is as follows f/m = M dh/dy where f/m = force per unit mass of sample M = magnetic moment per unit mass dH/dy = magnetic field gradient The dH/dy characteristic of the instrument is determined by the use of a standard palladium sample, and the calibration is made independently for all values of H. Since a large finite field is required to saturate an assembly of ferromagnets, it is necessary to measure the apparent magnetic moment for increasing steps of H until a saturation value is obtained. The percentage of iron in the sample as free ferromagnetic iron may then be computed simply C= 100 (M1/M1) where C = percent content of undissolved iron in sample M1 = saturation magnetic moment of sample per unit mass M1 = saturation magnetic moment of iron per unit mass taken as 217 emu-cm per gm There is no serious difficulty in applying this method except for the unusual magnetic behavior of very fine particles of ferromagnetic substances. It has been found and is the basis for a widely accepted theory that with sufficient subdivision, the magnetic fields required to saturate and the coercive force after saturation rise to exceedingly high values. Recent work on precipitates of Fe and Co from copper solid solutions8 showed that about 5000 oersteds were necessary to approach saturation. The magnetic moments as a function of field strength measured in the present investigation are listed in Table I. Only the 0.018 wt pet Fe alloy yielded a magnetization curve with a fairly well-defined saturation plateau at 3.76x10 -2 emu-cm/ gm. This corresponds to 0.017 & 0.001 wt pet Fe in the alloy. This indicates that the solid solubility must be of the order of 0.001 wt pet Fe. The magnetic-moment data of the other two alloys are badly scattered, indicating that the amount of ferromagnetic iron in these samples is so low that the magnetic forces acting on them cannot be measured accurately by the analytical balance used. Nevertheless, the fact that even the 0.003, wt pet Fe alloy shows ferromagnetism indicates that the solid solubility must be below that value. Acknowledgment This work was sponsored by the Pitman-Dunn Laboratory of Frankford Arsenal, Philadelphia, Pa. The support and permission to publish are gratefully acknowledged. References W. Bulian and E. Fahrenhorst: Zeic. Metallkunde, 1942, vol. 34, pp. 116-170. 2 D. W. Mitchell: AIME Transactions, 1948, vol. 175, pp. 570-578. 3 G. Bate, D. Schofield, and W. Sucksmith: Philosophical Magnsine, 1955, vol. 46, pp. 621-631.

Jan 1, 1959

By Voyle R. McFarland, Robert A. Burmeister, David A. Stevenson

The distribution of lead between phases in the Ag-Sb-Te system was studied using microautoradio -graphy. Two compositions were investigated, both containing an intermediate phase Known as silver antimony telluride as the major phase, and one containing AgzTe and the other SbzTes as the minor phase. For both compositions, two thermal treatments were used: nonequilibrium solidification from the melt and long equilibration anneals of the as-solidified structure. For each composition, lead was segregated in the minor phase of the as-solidified structure, but was distributed in the matrix after anneal. The electrical resistivity and carrier type were insensitive to the distribution of lead in the two-phase structure. ThERE has been considerable interest in the Ag-Sb-Te system because of its thermoelectric properties. The major interest has been in compositions on the vertical section between AgzTe and SbzTes, particularly the 50 mole pct SbzTes composition AgSbTez (compositions are conveniently expressed as mole percent SbzTes along the AgzTe-SbzTes section). One of the major problems in the proper evaluation and utilization of this material is the inability to control the electrical properties through impurity additions: all alloys prepared to date have been p-type, even with the addition of large amounts of impurities. It has been shown Wit all the compositions previously studied contain an intermediate phase of the NaCl st'ructure as a major phase (denoted by b) and a second phase, either AgzTe or SbzTe3, as a minor phase.'-3 One explanation for the unusual electrical behavior of this material is that the impurity additions have a higher solubility in the second phase than in the matrix; the impurity would segregate to the second phase, leaving the bulk matrix essentially free of impurity.4 In order to investigate this mechanism with a specific impurity element, the distribution of lead between the two phases was determined using autoradiography. Lead 210 was chosen because of the suitability of its 0.029 mev 0 particle for autoradiography and also because of the interest in lead as an impurity in this system.5'6 EXPERIMENTAL PROCEDURE Two compositions were taken from the vertical section between AgzTe and SbzTes, 50 mole pet SbzTes (Viz. AgSbTez) and 75 mole pct SbzTes, in which AgzTe and SbzTes appear, respectively, as the minor phase. Lead containing radioactive lead (pb210) was added to the above compositions to provide a concentration of 0.1 wt pct Pb. The material was placed in a graphite crucible in a quartz tube which was then evacuated and sealed. The samples were melted and solidified by cooling at a rate of 8°C per min and then removed and prepared for microa~toradiography. After autoradiographic examination of these samples, they were again encapsulated and annealed in an isothermal bath at 300°C for a number of days and prepared for examination. An alternate method of preparation employed a zone-melting furnace; the molten zone traversed the sample at a rate of 1.2 cm per hr and the solid was maintained at a temperature of 500°C both before and after solidification. This treatment had the same effect as solidification at a slow rate followed by an anneal for several hours at 500°C. In order to obtain the best resolution, thin sections of the alloy were prepared by hand lapping to a thickness of approximately 20 p. Other samples were prepared for examination by lapping a flat surface on the bulk sample. The resolution, although somewhat better in the former procedure, was adequate in both instances and the majority of the samples were treated in the latter fashion. A piece of autoradiographic film (Kodak Experimental SP 764 Autoradiographic Permeable Base Safety Stripping Film) was stripped from its backing, care being taken to avoid fogging due to static-electrical discharge. A small amount of water was placed on the sample, the film applied emulsion side down on the surface of the sample, and the sample and the film dipped into water in order to assure smooth contact. After drying, the film was exposed for 2 to 5 days, the period of time selected to give the best resolution. The film was developed on the specimen and fixed and washed in place. Two major factors must be considered in establishing the reliability of an autoradiograph: the in-

Jan 1, 1964

By Richard R. Klimpel

Part 2 of this article continues the discussion of a 10-year, multimillion dollar research and plant testing program on slurry rheology and grinding circuits. The first part of the article (ME, Dec. 1982) presented the basic concepts identified by the research and some laboratory test results. This section Illustrates typical Industrial scale test results and Identifies some industrial operating implications of controlling rheology by different methods. At least four controllable factors decide the rheological character of a slurry-slurry density or percent solids, particle size distribution, chemical environment, and slurry temperature. The second factor has two interrelated facets: the shape of the particle size distribution which controls packing behavior of the solids, and the fineness of the distribution. Finer particles increase interparticle forces and viscosity. As indicated in Part 1, during a given grinding test it is possible for all four factors to change. However, regardless of the particular settings of the four factors in a given test, if the resulting rheological character is either dilatant, pseudoplastic, or pseudoplastic with yield, the associated breakage rate is correlated with the current rheological character. It is obvious, for example, in batch grinding tests run at constant percent solids, that the second and third factors, where appropriate, are changing during grinding because size distributions are changing and the production of fresh surface area takes up unadsorbed chemical. Thus the corresponding rheological character change in batch tests with increasing grind time would be dilatant to pseudoplastic to pseudoplastic with yield. The degree to which this transformation occurs depends on the changing setting of the four factors over grinding time. In continuous grinding tests, one might logically expect that dramatic changes in any one of the four factors will be less likely to occur. It will be shown that continuous mill operations offer some unique opportunities to take advantage of possible rheological transformation by more direct operational control of the settings for the four factors. One extra observation noted in the rheological studies was the variability in the location and extent of region B (pseudoplastic behavior) for the various coals and ores tested. The location of region B was usually in the region of 45-55% solids by volume and was of the extent of 0-8%, or 2-11% with chemical addition. The corresponding increase in net production ranged from 0-10% in region B and 0-21% in region B&apos;. When region B is small or zero (no pseudoplastic character is exhibited) no increase in production will be observed and the use of chemicals is often marginal. There are several reasons for some materials exhibiting this quick transformation from dilatancy to high yield values often at surprisingly low percent solids by volume such as 30%. One condition identified was for materials containing high levels of viscosity-producing elements such as- carbonates or clays. A second condition documented was for materials that exhibited unusually fine primary fragment distributions (fine B1,; curves). This corresponds to materials having small y values of < 0.5. Such a slurry developed a yield value quickly during grinding because of the rapid buildup of fines. A related problem can be presented by materials exhibiting excessively coarse primary fragment distributions, y values > 0.9. Breakage of this type of material produces size distributions that give poor packing efficiencies even at long grind times, thus hindering the normal rheological transformation presented earlier. A final condition that can cause the occurrance of region B to be small or zero is when the media void volume filling of slurry is < 100%. Figures 5a and 5b use previously published data of this study to demonstrate the influence of solids loading and weight percent solids on the net production of taconite ore in a laboratory batch ball mill. In particular, Fig. 5a illustrates several trends not generally recognized until this study. They include these two: • Increased slurry density allows for increased solids loading before passing through the maximum in the net production curve where the fall-off is due to non first order breakage. • The use of rheology control chemicals such as GA-4272 allows this trend to be extended to higher slurry loadings with an increase in net production over any previous condition by keeping grinding first order. Figure 5b shows the same data as Fig. 5a plotted for constant weight loadings. These various figures of net production versus percent solids show the location and extent of the regions A, B, and C presented in Part 1 as a function of solids loading. It is obvious that the rheological transformation pattern described earlier does not hold true for slurry loadings corresponding to less than the void volume of the media, which is also a region of

Jan 1, 1983

By David Turnbull

IN isothermal recrystallization processes, new crystals generally grow into the matrix until they impinge upon other new crystals or an external surface, at constant linear rates G. Before impingement the perceptible course of growth can be described by the equation: 1 = G(t-7) C1I where, G = dl/dt, 1 is a crystal dimension measured in a constant direction, t is the time, and 7, the nucleation period, is a positive intercept on the time axis. Fig. 1 is a schematic representation of I as a function of time for a recrystallizing grain. G is dependent upon temperature, driving energy (strain or surface energy), relative grain and boundary orientations, but is generally independent of time. The frequency of nucleation, fi, (time" volume") can be defined by the equation: N = 1/fV [2] where ? is the mean nucleation period and V is the volume of the specimen that has not recrystallized. The kinetics of primary and secondary recrystallization generally can be described satisfactorily in terms of the parameters N and G only.&apos;-" After recrystallization is complete the average grain size 7 increases with time by "normal grain growth;" didt, the average rate of grain growth, is strongly time dependent and has not yet been precisely related to G for the motion of the individual grain boundaries constituting the system. It has been suggested4* " that the elementary act in grain boundary migration is closely related to the elementary act in grain boundary self-diffusion. Although the distance of atom movement in the two processes may be somewhat different, there is reason to expect that the activated states may be very similar, so that the free energy of activation for grain boundary migration should be of the same order of magnitude as for grain boundary self-diffusion. Therefore, it is desirable to develop a satisfactory basis for comparing data on self-diffusion and grain boundary migration and to make such comparisons where possible. Theory The formal theory of grain boundary migration rates is analogous to the theory for the rate of growth of crystals into supercooled liquids reviewed elsewhere 6-8. Boreliuss has shown that the latter theory describes, within the theoretical uncertainty, the growth of selenium crystals into supercooled liquid selenium. Motto and more recently Smolu-chowski" have derived expressions for the rate of boundary migration in recrystallization. The treatment to be presented is similar to Mott&apos;s excepting that the formalism of the absolute reaction rate theory will be used. The atomic mobility, M, in grain boundary migration is defined by: G = -M6p/6x where p is the chemical potential per atom and x is the coordinate measured in the direction of grain boundary movement. Let AF be the free energy difference per gram atom on the two sides of the boundary and k the thickness of the boundary. For RT>>AF the potential gradient across the boundary (6p/6x) is essentially linear and it follows that: SF/8x = - aF/N\ [4] where N is Avogadro&apos;s number. According to the Nernst-Einstein equation, M is related to a diffusion coefficient, Do, for matter transport in grain boundary migration by the equation: M = Da/kT [5] Substituting eqs 4 and 5 into eq 3 gives the basic relation between Do and G: G = DoaF/\RT [6] Do values may be calculated from experimental values of G from eq 6 and directly compared with the coefficient of self-diffusion within the crystal, DL, or the grain boundary self-diffusion coefficient D,. However, a more convenient, though equivalent, basis for comparing atomic mobility in grain boundary migration and self-diffusion is through the constants of the absolute reaction rate theory. According to this theory diffusion coefficients may be written:" D = k2(kT/h) exp [-AF,/RT] 171 aFa, the free energy of activation, is related to the measured energy of activation, Q, by the equation: AFA = Q - T aSx - RT [8] where aSa is the entropy of activation. Substituting eqs 8 and 7 into eq 6 gives: G = ek(kT/h) (aF/RT) exp [(AS,,)C/R] exp C-Qc/RTI C91 where the subscript G refers to boundary migration. The relationship between the driving free energy and the free energy of activation in boundary migration is indicated schematically in Fig. 2. Experience indicates that the variation of G with temperature can be described by: G= Go exp [- Qc/RT] [10] where Go and Qc are generally temperature independent over wide ranges of temperature. Comparison of eq 9 with eq 10 gives:

Jan 1, 1952

The Annual Meeting of The Rocky Mountain Coal Mining Institute was called to order by the President, John T. Atkins, at 2:00 p.m. Tuesday, June 26, 1984 in the Colorado Ballroom of the Marriott&apos;s Mark Resort in Vail, Colorado. There were 36 members in attendance. It was moved by Bob Diederich, seconded and carried to dispense with the reading of the 1983 Annual Meeting minutes as printed on pages 105 thru 109 of the 1983 Proceedings. In keeping with the printed agenda in the convention program/ticket booklet, the President called for reports of standing committees as follow: 1. Bylaws & Resolutions - Loren Linville, Chairman Linville noted that the committee had been working for two years on bylaws changes and concluded a corporate lawyer specializing in nonprofit organizations be engaged. He then introduced Mr. Peter B. Nagle of the Denver law firm of Sherman and Howard who outlined the major changes in converting the Institute&apos;s current status of 501(c)(6) to 501(c)(3). He pointed out that such a conversion would give the Institute a proper legal status, would give individual contributors to the scholarship or other programs a personal income tax deduction, would qualify the Institute for the postal nonprofit mailing rate and the Institute would achieve the advantage of limited liability inherent in a corportion and would insulate its members, officers and directors from liability for corporate obligations. Copies of the Articles of Incorporation as well as the Bylaws were available for all members. A discussion ensued and the following resolution was moved by Bob Diederich, seconded and carried: RESOLVED, that the unincorporated association known as the Rocky Mountain Coal Mining Institute be, and hereby is, dissolved and in its place, and to carry out its objectives, shall be formed a nonprofit corporation under the laws of the State of Colorado, which corporation shall also be known as The Rocky Mountain Coal Mining Institute, and to which shall be transferred all of the assets and liabilities of this association. FURTHER RESOLVED, that the proper officers of this association are authorized and directed to execute and file with the Colorado Secretary of State, Articles of Incorporation in a form substantially similar to those prepared for this association by its counsel, and the names of the individuals identified in such Articles of Incorporation as the initial Board of Directors of such corporation, which names were proposed and recommended by the Nominating Committee of this association, are hereby approved. FURTHER RESOLVED, that the proper officers of this association are authorized and directed to do all acts necessary or convenient to carry out the terms of the preceding resolutions. (Articles of Incorporation and Bylaws as adopted are printed following these minutes.) Additional resolutions were read by Linville as follows: Item 1: WE RESOLVE herein that in the year since the last convention of the RMCMI, the Institute and the coal industry have suffered the loss, through death, and the services of: Lloyd W. Taylor Charles T. Holland THEREFORE, BE IT RESOLVED, that we record in the minutes of the RMCMI, recognition of the passing of these members who have so greatly contributed to the advancement of the industry, both nationally and in the Rocky Mountain area, and that a copy of this resolution be sent to the next of kin as evidence of the sincere sympathy and deep regard of the members of the Institute. Item 2: RESOLVED, that in recognition of their long and faithful service to the coal industry that the status of Life Member be conferred upon: Bernard Bernstrom Roy Coulson Shirl C. McArthur Item 3: RESOLVED, that we commend and express our gratitude to our Executive Secretary, officers, chairmen and committees for an outstanding job in presenting. the 80th RMCMI meeting. Item 4: RESOLVED, that the RMCMI express its gratitude to K&P, INC. of Golden, Colorado for their generous donation of office facilities and furniture for the RMCMI office and to K&P SALES ENGINEERS, INC. also of Golden, Colorado for their assistance in telephone answering, other office procedures and the use of certain office equipment. Item 5: RESOLVED, that six scholarships be awarded annually to advance the education program of the Institute to worthy students pursuing career paths in mining or other related industry in the six states in which the Institute generally operates and has members and in accordance with the criteria set forth by the Scholarship Committee. It was moved by Jim Neal, seconded and tamed

Jan 1, 1984

By F. Weinberg

The relative concentration of 1" at grain boundaries in controlled orientation bicrystals has been examined by autoradiographic techniques, and by activity measurements of grain boundary surfaces exposed by preferential ,melting. The autoradio-graphs indicate that thallium is concentrated at grain boundaries in as-grown bicrystals, but not in zcell-annealed bicrystals. They also indicate that the solute concentration and the distribution on as-grown bicrystal surfaces are markedly different than that of the bulk material. The boundary surface measurements are in agreement with the autovadiographic evidence. On the basis of these measurements, as-grown bicrystals containing approximately 100 ppm of Tl, solidified at rates between 5 and 30 cm per hr and with tilt boundaries greater than 10 deg, exhibited grain boundary segregation equivalent to roughly 10 atomic planes of pure solute. Higher solute concentrations (equivalent to 140 atomic planes of pure solute) were obtained in bicrystals solidified slowly (0.6 cm per hr); slightly higher values were obtained in specimens containing a large angle nantilt boundary. Annealing for various times over a range of temperatures eliminated grain boundary segregation within the experimental uncertainty of the results (equivalent to 1 atomic Plane of pure thallium at the boundary). The results for the as-grown bicrystals can be qualitatively accounted for by assuming the presence of a groove on the solid-1iq;id interface, at the grain boundary. SOLUTE segregation at grain boundaries may be considered in two parts, namely, nonequilibrium segregation associated with the solidification process, and equilibrium segregation in fully annealed materials.&apos; There is much indirect evidence for nonequilibrium segregation, based on preferential etching at grain boundaries and the mechanical properties of as-cast alloys. In addition, some direct observations have been reported in which radioactive tracers were used as solute additions and segregation detected at the grain boundaries by autoradiographic techniques. However, there is little detailed quantitative data on solute concentrations related to grain boundaries, particularly for different freezing conditions and grain boundary configurations. Equilibrium segregation at grain boundaries has been considered both theoretically and experimentally. cean&apos; has made an estimate of the maximum equilibrium solute concentration that might be expected at a grain boundary, based on the lattice distortions in the boundary region. He arrived at a concentration which was equivalent t a monatomic layer of pure solute. A similar value, based on thermodynamic arguments, was calculated by Cahn and Hilliard for the segregation of phosphorus in iron. Experimentally, much higher values of solute concentration at grain boundaries have been reported recently by both Inman and iler&apos; for phosphorus in iron, and Ainslie et 1.&apos; for sulfur in iron. They observed concentrations equivalent to as much as 20 to 100 atomic layers of pure solute at the grain boundaries. However, in both cases it was shown that the observed segregation was not due solely to equilibrium segregation at the grain boundary. In the former case, precipitation effectss due to trace impurities in the material were believed to account for the large amount of solute present at the grain boundary. In the latter case it was shown that a high density of dislocations in the boundary region could provide a large number of additional sites for solute atoms, other than at the grain boundary. Thomas and chalmera have reported on the equilibrium segregation of po210 in grain boundaries of Pb-5 pct Bi alloys. Using autoradiographic techniques, they observed a concentration of polonium along the boundary trace on the surface of annealed bicrystal specimens grown from the melt. The concentration only appeared after annealing, and varied with boundary angle, increasing as the boundary angle increased. Their conclusions have been questioned by Ward," who pointed out that the segregation they observed along the boundary trace was much too wide to be compatible with the usual concepts of the thickness of a grain boundary of several lattice spacings. Also, Maroun et al.,l1 with specimens similar to those of Thomas and Chalmers, found that segregation could only be detected on the specimen surface, suggesting that Thomas and Chalmers&apos; results were associated with an oxidation effect of polonium, and not equilibrium segregation. Thomas and Chalmers replied12 that they did observed segregation at the grain boundary in the bulk material and suggested further experiments were necessary to resolve the difference. The purpose of the present investigation was to examine both nonequilibrium and equilibrium grain boundary segregation in melt grown bicrystal specimens as a function of boundary angle, growth rate, and solute concentration, and to de-

Jan 1, 1963

By M. I. Sherman, J. D. H. Strickland

USE of a hydrometallurgical approach to the oxidation of sulfide ores and extraction of metals therefrom may have advantages over the more common smelting techniques when a low grade deposit is difficult to concentrate or the subsequent separation of metals, coexisting in the ore, is laborious by any known smelting operation. For economic reasons, the most promising oxidants are either atmospheric oxygen or electric power. The use of oxygen, or air under pressure, has recently been revised. Pyrrhotite has been converted to iron oxide and elementary sulfur&apos; and a variety of sulfides have been treated by Forward and co-workers.2-4 Generally sulfate is the end form of the sulfur but with galena in an acid medium, elementary sulfur can be formed." For economic reasons chlorine and ferric iron salts are about the only possible alternatives to the atmosphere as oxidizing agents for base metal sulfides. If aqueous solutions of chlorine or ferric iron are employed, the reduction products can be oxidized electrolytically in situ and used again, thus acting as catalysts for electric power as oxidant. The use of ferric salts for this purpose is established hydrometallurgical practicea but, although chlorine gas has been employed in the dry state at an elevated temperature, its use in aqueous solution at or near room temperature has not found favor. The reaction of chlorine water with the soluble sulfide ion has been studied by several workers,7-9 and both sulfate and elemental sulfur are found as end products, the latter being favored by the presence of a low concentration of oxidant relative to that of sulfide in solutions of about pH 9 to 10. Of direct bearing on the work in hand are an early American patent" and a recent Austrian patent." The former advocates stirring powdered ore with an aqueous solution of ferric chloride chlorine oxides and chlorine. In the latter it is claimed that both metal and sulfur can be obtained by electrolysis, in a diaphragm cell, of a metal ore slurry in brine. Details in these patents are scant and no data or explanation is given for the mechanism of the reaction which, in the Austrian work, is attributed to the (unlikely) action of nascent chlorine at the anode surface. No mention is made of possible differences in behaviour between various ores. Apparatus A complication encountered when working with chlorine water is that a serious loss of chlorine occurs by gas partitioning unless an enclosed system is used and any air space in the apparatus is kept very small and constant. Arrangements were made, therefore, to take out samples for analysis without letting air into the system to replace the liquid removed. For convenience in studying a heterogeneous reaction the apparatus was so designed that a reproducible controlled stirring rate could be maintained and the ratio of surface area of ore to volume of solution was approximately constant throughout any experiment. The apparatus used is shown in Fig. 1. The ground ore was placed in the horizontal cylindrical vessel, A, of about 1 liter capacity, heated by a constant temperature circulating bath pumping water through the concentric jacket, B. By adding chro-mate to this water, an ultraviolet radiation filter effectively surrounded the reaction vessel, greatly reducing any possible photochemical decomposition of chlorine solutions. Stirring was effected by glass paddles, C, attached by an axle to a magnet which was rotated by another powerful Alnico magnet, D, outside the glass end, this magnet being itself rotated by an electric motor electronically controlled to constant speed. Speed could be varied from about 150 to 900 rpm and was measured and held to within 1 pct of a given value. The end of the reaction vessel remote from the stirring magnet was closed by another one-ended glass cylinder, E, connected by thin polyethylene bellows, F, clamped by screw clamps and watertight rubber gaskets to the main vessel. Through E, a glass electrode and calomel electrode projected into the solution and a hypodermic syringe pierced a small bung and allowed acid or alkaline to be added to maintain a constant pH. By pushing the fully extended bellows until the two cylinders touched, from 50 to 100 ml of solution could be forced out through a sintered disk into the three-way tap system, G, either to waste (for flushing purposes) or up into a 10 ml burette where the solution could subsequently be measured out for analysis. The ore samples were introduced at H, the tube being stoppered by a thermometer of —1 to +52ºC range, graduated to 0.1°C intervals. To prevent ore from being ground in the end bearings of the stirrer these bearings were pro-

Jan 1, 1958

By B. B. L. Seth, H. U. Ross

A generalized rate equation for the reduction of iron oxide was derived from which two particular equations were obtained: one for rate controlled by the transportation of gas, the other for rate controlled by the phase-boundary reaction. Pellets of pure ferric oxide having diameters of 8.5 to 17.5 mm and a density of 4.8 g per cm3 were prepared and reduced by hydrogen at 750° to 900°C. From the analysis of data obtairzed, it was observed that neither the phase-houndarv reaction nor the transportation of gas controlled entirely the rate of redziction. Rather, the mechanism of reduction can he divided into three stages. In the beginning, the process seems to depend predominantly on the surJrce reaction, hut after a layer of iron is formed the diffusion of gas becomes the controlling factor. Towards the end, however, the rate falls sharply due to a decrease in porosity. The times predicted by the generalized equation for a certain degree of reduction showed an excellent agreement with those obtained experinmentally for pellets of varying sizes. WIDE interest in iron oxide reduction has resulted in many valuable studies pertaining to thermody-namical properties, equilibrium diagrams, and chemical kinetics. Although the thermodynamical properties and equilibrium diagrams are now known with a fair degree of accuracy, the mechanism and rate-controlling step in the reduction of iron oxides presents a problem to research workers which is still unsolved. This is because the field of chemical kinetics is so highly complex. Besides the chemical reaction between oxide and reducing gas, several other processes are occurring simultaneously such as solid-state diffusion of iron through intermediate oxides (FeO and Fe3O4), the diffusion of reducing gas inwards and of product gas outwards, and the sintering of iron if reduction is carried out above the sintering temperature of iron. Furthermore, there is a large number of variables, including the nature and flow rate of the reducing gas, the chemical composition and physical properties of the ore, the temperature of reaction, particle size, and so forth, all of which can affect both the mechanism and the kinetics of reduction. Despite the controversy and diversity of opinion about the mechanism of iron oxide reduction, three main schools of thought have emerged. According to the first, the rate is controlled by the diffusion of gas through the boundary layer of stagnant gas; the second claims that the rate is proportional to the area of the metal-oxide interface, while the third believes the transportation of reducing gas from the main stream to the metal-oxide interface and of product gas from the metal-oxide interface to the main stream to be the rate-controlling step. 1) The boundary-layer theory is true mainly for packed beds where the flow of gas through the bed is important. For a single particle, the boundary layer may be prevented from being the rate-controlling step if a gas flow rate of reducing gas above the critical flow rate is used. 2) Several workers have reported a linear advance of the Fe/FeO interface which provides excellent support for the belief that reduction is controlled by the surface area. McKewanl has given formal shape to this concept with mathematical derivation and has shown it to be valid for reduction of several iron ores, hematite, and magnetite, both by H2 and H2, H2O, N2 mixtures. Some other investigators, however, do not find this theory to be entirely valid. Deviations have been observed2 and further confirmedS3 Hansen4 also agrees that deviations do occur, at least in the latter stages of reduction, while from the data of several investigators summarized by Themelis and Gauvin,5 it is clear that the theory is not always applicable and further that, when it is applicable, it does not hold in the final stages of reduction. 3) Among those who claim the transportation of gas to be the rate-controlling step are Udy and Lorig,6 Bogdandy and Janke,7 and Kawasaki el a1.8 The validity of the theory has also been acknowledged indirectly by other research workers who show that the sintering and recrystallization of iron cause a decrease in reduction rate, for it is only if the transportation of gas is important that this sintering has any bearing. However, the theory has been rejected by some because they have failed to obtain

Jan 1, 1965

By Susan T. Bagley, Kenneth L. Rubow, David H. Carlson, Bruce K. Cantrell, Winthrop F. Watts

Permissible exposure limits (PELs) have been established for gaseous pollutants, carbon monoxide (CO), carbon dioxide (CO2), nitric oxide (NO), nitrogen dioxide (NO2), and some gas-phase hydrocarbons emitted in diesel exhaust. There is, as yet, no PEL recommended for diesel exhaust aerosol (DEA), nor is there a standard method for sampling this aerosol. The University of Minnesota and the U.S. Bureau of Mines have collaborated to develop a personal diesel exhaust aerosol sampler (PDEAS) which utilizes size-selective inertial impaction and gravimetric analysis. During the field tests of this sampler, numerous air quality measurements were made in underground coal mines that use diesel equipment. The mine mean DEA concentrations for the five mines surveyed, determined with the PDEAS in the haulageway, was 0.89 mg/m3 with a standard deviation of 0.44 mg/m3. DEA contributed 52 % of the respirable aerosol at this location. In three of the mines filter samples were collected for DEAassociated polynuclear aromatic hydrocarbons (PAHs) and biological activity determinations. Two of the mines were also monitored for the major gaseous constituents found in diesel exhaust. In general, the PAH and biological activity levels were similar for all three mines, and indicate that up to 25 % of the haulageway concentrations may be contributed by outby diesel vehicles. Measured concentrations of CO, C02, NO, NO2, and SO2, were well below regulated levels. INTRODUCTION Diesel exhaust contains pollutant gases, such as carbon monoxide, carbon dioxide, nitric oxide, nitrogen dioxide, and gas-phase hydrocarbons, as well as DEA. Much of the health-related concern focuses on DEA and associated organic compounds (Watts, 1992a). A wide variety of these PAHs have been identified and some are known carcinogens and/or mutagens. The U.S. Mine Safety and Health Administration (MSHA) has proposed new PELs for these and other contaminants (MSHA, 1989). MSHA has also published an advance notice of proposed rulemaking to establish a separate PEL for diesel particulate (MSHA, 1992). The U.S. Bureau of Mines has collaborated with the University of Minnesota to develop and field test a PDEAS. The PDEAS is a three stage sampler based on the MSA&apos; personal respirable dust sampler. It utilizes a respirable cyclone preclassifier followed by a 0.8 µm cut point impactor and afterfilter operating at a flow rate of 2 L/min. Respirable aerosol greater than 0.8, µm in size is collected by the impactor while DEA, less than 0.8 µm in size, is collected by the afterfilter. Hence, gravimetric analysis of the afterfilter permits measurement of DEA concentrations. This development and laboratory evaluation of the PDEAS were described previously by Cantrell (1990) and Rubow (1990). During field tests of the sampler, numerous air quality measurements were made in continuous miner sections of five underground coal mines that use diesel haulage equipment. These air quality measurements included levels of selected PAH and biological activity associated with DEA collected in the intake and haulageway areas of three of the five underground mines, and CO, CO2, NO, and NO2 in two of the mines. The objectives of this paper are to present the DEA and associated pollutant concentrations measured in these mines and to assess the impact of diesel face-haulage equipment on underground mine air quality. MINE DESCRIPTIONS The mines used for the PDEAS evaluation were designated J, K, L, N, and 0. Mines K, N, and 0 are located in the Western United States, while mines J and L are located in the East. Each mine produces high volatile, bituminous coal with shift production levels varying from 500 to 2000 tons/section. Seam heights varied from 1.5 to 3.0 m. Mines K and N use continuous mining to develop longwall panels. The others are strictly room-and-pillar operations using continuous miners. The number and types of diesel-powered vehicles used at these mines were described by Watts (1992b). Mines J, K, N, and 0 use diesel power to assist in a wide range of activities in addition to coal haulage. These included road maintenance, personnel and materials transport, lubrication, and welding. Mine L used only three diesel-powered shuttle cars to haul coal. SAMPLING AND ANALYSIS METHODS Aerosol Measurements Aerosol samples were collected in the mine portal area, the clean air intake to the continuous miner section, the haulageway one crosscut inby from the feeder breaker and belt, in the return airway, and on selected personnel. The haulageway sampling site was located near the point where the diesel-powered shuttle cars turn around to dump their loads. Additional respirable and DEA samples were collected and have been reported by Haney (1990).

Jan 1, 1993

By E. A. Swedenborg

The unit agreement for the Wertz Dome field, Wyoming, was approved by the Acting Secretary of the United States Department of the Interior on November 4, 1937, effective on December 1, 1937. The stated objectives of the agreement are to conserve and put to beneficial use all oil and gas produced; to make possible a uniform withdrawal of oil and gas in order to maintain equalized reservoir pressures; to provide for an orderly determination of the structural features of the productive horizons; and to permit the injection of gas for pressure maintenance. The purpose of this paper is to show by a discussion of the problems involved and the engineering practices employed by the unit operator, how well the objectives of the unit agreement have been accomplished in the development and production of oil and gas from the field. HISTORY AND DEVELOPMENT The Wertz Dome oil and gas field is located 88 miles southwest of Casper and 38 miles north and westerly from Rawlins, Wyoming. It is served by a state secondary oiled road connecting with U. S. Highway No. 220 at Lamont, a distance of 3 miles from the field. It has been a producing field for 27 years, first as an important producer of gas and more recently of oil. The Producers and Refiners Corp. completed Well No. 1, NE1/4SW1/4 sec. 7, T. 26 N., R. 89 W., the first productive well in the field, in September. 1921, in the Muddy sandstone of Upper Cretaceous age, at a depth of 3435 feet for an initial production of 42,000,000 cu. ft. of gas per day. In 1922 pipe lines were laid to Casper, Wyoming, for supplying fuel to the Standard of Indiana refinery, &apos;the adjoining town of Mills. and the Producers and Refiners Corp. pump station No. 6 in Mills; and to Parco (now Sinclair), Wyoming, for supplying that refinery with fuel. The gasoline content of the gas was extracted in an absorption plant located near the town of Mills. No compressors were used as the line pressure was sufficiently high to flow the gas through the absorbers. As high as 30,000,000 cu. ft. of gas per day were treated in the plant extracting 6000 gallons of gasoline. In September 1937, the pipe line was discontinued and the plant was dismantled at which time 61,000,000,000 cu. ft. of gas had been produced from the seven Muddy, Cloverly, and Sundance gas wells drilled in the field. Of this volume of gas 800,000,000 cu. ft. were produced from the Frontier formation, 34,200,000,000 cu. ft. from the Muddy sandstone, 24,000,000,000 cu. ft. from the Cloverly, locally called Dakota, and 2,000,000,000 cu. ft. from the Sundance formation. The pipe line was discontinued because of the near depletion of the gas reserves in Wertz and nearby fields, and hecause of the local field requirements demanding the retention of the remaining gas reserves. In December 1936, the Sinclair Wyoming Oil Co. completed Well No. 10, SE1/4NW1/4 sec. 7. T. 26 N., R. 89 W., at a depth of 5886 feet. as the first Tensleep sand producer with an intial of 1700 barrels of oil per day. The well was originally drilled only 14 feet into the sand and in August 1939 was deepened to a depth of 6161 feet, 289 feet in the sand, and the daily produe tion increased to 8350 barrels of oil. In February 1948 Well No. 22, SE1/4 SE1/4 sec. 1. T. 26 N., R. 90 W., was deepened from the Tensleep to the Basal Amsden sand and completed at a depth of 6635 feet for an intial of 600 barrels of oil per day in the Basal Amsden. In April 1948, Well No. 2. SW1/4 NE1/4 sec. 1, T. 26 N., R. 90 W.. was deepened from the Tensleep to the Madison limestone and was completed at a depth of 7193 feet for an intial of 1145 barrels of oil per day in the Madison. Well No. 26, SE1/4SE1/4 sec. 1, T. 26 N.. R. 90 W., was deepened from the Ten-sleep to the Cambrian and in October 1948 it was completed in the Cambrian for an intial of 277 barrels of oil per day. GEOLOGY AND PRODUCTIVE ACREAGE The surface is Steele shale of Upper Cretaceous age, covered in part by gravel beds. The topography of the field is that of a rolling hill with a steep draw or gulch along the northern edge of the field. The Steele shale lies conformably on the lower formations as

Jan 1, 1949

By E. P. Burtchaell

A method is presented for evaluating the effect of gravity drive upon the reservoir performance of a high relief pool. Conventional forms of reservoir analysis do not consider the alterations in the basic material balance data caused by gravity segregation of reservoir fluids. A procedure is outlined for structurally weighting physical and chemical data for use in the material balance equation. It is demonstrated how actual pool performance data can be utilized to evaluate the future reservoir performance of a gravity drive pool. INTRODUCTION Conventional reservoir engineering. procedure is inadequate for the analysis of an oil pool which has considerable structural relief, steep dips, and good permeability development. In, pools of this type, gravity drainage has an important part in the movement of oil to the wells and the effects of gravity on the overall pool performance should be included in any analysis of reservoir behavior. Many engineers have the opinion that the force of gravity in the movement of oil is not important until the later life of a pool.&apos; Probably the basis for this belief is that gravitational effects may not be readily discernible until a pool is nearing depletion. This would be especially true for pools not having a high degree of structural relief and permeability development. Actually the effects of gravitational forces are at a maximum when the pool pressure is high, for during this period the hydrostatic head of the oil column is at a maximum and the viscosity of the oil is at a minimum. Oil recoveries from pools having favorable gravity drive characteristics may equal or even exceed recoveries which might be expected from water displacement. Field evidence indicates that in some reservoirs gravity drive has resulted in recoveries greater than that which could have been expected from gas expansion or water drive.&apos;.3 Unfortunately, the possible effects of gravity drive on pool performance have been underestimated and other reasons have been sought to explain the high recoveries obtained. There are unquestionably many reservoirs to which the principles of gravity drainage can be effectively applied. It is the purpose of this paper to illustrate one method whereby gravity drive is included in the reservoir analysis of an oil pool. A hypothetical pool, typical of many California reservoirs, is used as an example. As used in this paper, "gravity drive" is defined as the overall effect of gravitational influences on the recovery of petroleum from the reservoir; "gravitational segregation" as the gravity separation of oil and gas within the reservoir; and "gravity drainage" as the downward movement of oil as caused by the force of gravity. SAND VOLUME DATA Fig. 1 presents a structural contour map of the pool under study. Maximum closure is 1950 feet with dips on the south flank approaching 45". The original gas-oil interface was set at -5200 feet. Average thickness of the producing sand was 200 feet. For use in subsequent calculations ill this paper, the pool was subdivided into 100-foot vertical increments and the sand-volume content of each increment was obtained. If the gross sand thickness is small, under 100 feet, the sand-volume content can be obtained by superimposing an isopachous map upon a structural contour map and planimetering the average thickness of each 100-foot increment. For sand thicknesses over 100 feet, one approacli would be to construct a sufficient number of cross-sections of the pool from which the weighted sand-volume of each 100-foot increment could be obtained. Variations in the sand body with depth, as determined by core data, can also be included in the above process. Table I presents a summary of sand-volume calculations, core data, and the original distribution of reservoir hydrocarbons in the pool. Fig. 2 illustrates the structural distribution of the sand-volume content. A total of 171,398 acre-feet is contained within the productive limits of the pool. Assuming an average porosity of 25% and an interstitial water content of 20%, the original hydrocarbon content was computed to be 227,075,000 barrels. DEPTH-PRESSURE DATA The determination of the initial vertical pressure arrangement in the pool is necessary for PVT and material balance calculations. Whenever sufficient data are available, a plot of pressure versus subsea depth of measurement should be made. From this plot a representative fluid pressure gradient can be established. Lacking sufficient initial pressure data, an initial pressure gradient may he estimated or calculated from avail-

Jan 1, 1949

By S. J. Sindeband

Prior to discussing the metallurgy of sintered chromium borides, it is pertinent to outline some of the reasoning behind this investigation and the purposes underlying the work. This study was initiated as an aproach to the ubiquitous problem of a material for service at high temperatures under oxidizing atmospheres, and it was undertaken with a view to raising the 1500°F (816°C) ceiling to 2000°F (1093°C) or better. For the reason that no small, but rather a major, lifting of the high temperature working limit was being attempted, it was felt appropriate that a completely new approach be taken to this problem. A summary of the thinking behind this approach was published recently by Schwarzkopf.&apos; In briefest terms, it was postulated that the following requirements could be set up for a material which would have high strength at high temperatures. 1. The individual crystals of the material must exhibit high strength interatomic bonds. This automatically leads to consideration of highly refractory materials, since their high energy requirements for melting are related to the strength of their atom-to-atom bonds. 2. On the polycrystalline basis, high boundary strength, superimposed on the above consideration, would also be a necessity. Since this implies control of boundary conditions, the powder metallurgy approach would hold considerable promise. Such materials actually had been fabricated for a number of years, and the cemented carbide is the best example of these. Here a highly refractory crystal was carefully bonded and resulted in a material of extremely high strength. That this strength was maintained at high temperature is exhibited by the ability of the cemented carbide tool to hold an edge for extended periods of heavy service. Nowick and Machlin2,3 have analytically approached the problem of creep and stress-rupture properties at high temperature and developed procedures whereby these properties can be approximately predicted from the room temperature physical constants of a material. The most important single constant in the provision of high temperature strength and creep resistance is shown to be the Modulus of Rigidity. On this basis, they proposed that a fertile field for investigation would be that of materials similar to cemented carbides, which have Moduli of Rigidity that are among the highest recorded. The cemented carbide, however, does not have good corrosion resistance in oxidizing atmospheres and without protection could not be used in gas turbines and similar pieces of equipment. It would be necessary then to attempt the fabrication of an allied material based upon a hard crystal which had good corrosion resistance as well. It was upon these premises that the subject study was undertaken and at an early stage it was sponsored by the U.S. Navy, Office of Naval Research. Since then, it has been carried on under contract with this agency. Chromium boride provided a logical starting point for such research, since it was relatively hard, exhibited good corrosion resistance, and, in addition, was commercially available, since it had found application in hard-surfacing alloys with iron and nickel. That chromium boride did not provide a material that met the ultimate aim of the study results from factors which are subsequently discussed. This, however, does not detract from the basis on which the study was conceived, nor from the value of reporting the results which follow. Chromium Boride While work on chromium boride proper dates back to Moissan,4 there has been a dearth of literature on borides since 1906. Subsequent to Moissan, principal investigators of chromium boride were Tucker and Moody,5 Wede-kind and Fetzer,6 du Jassoneix,7,8,9 and Andrieux." These investigators were generally limited to studies of methods of producing chromium boride and detennining its properties. Some study, however, was devoted to the chromium-boron system by du Jassoneix,7 who did this chemically and metal-lographically. This system is not amenable to normal methods of analysis by virtue of the refractory nature of the alloys involved, and the difficulties of measurement and control of temperature conditions in their range. Dilatometric apparatus is nonexistent for operation at these temperatures. Du Jassoneix made use of apparent chemical differences between two phases observed under the microscope and reported the existence of two definite compounds, namely: Cr3B2 and CrB. These two compounds, he reported, had quite similar chemical characteristics, but were sufficiently different to enable him to separate them. The easiest method for producing chromium boride is apparently the thermite process, first applied by Wede-

Jan 1, 1950

By T. S. Lovering

The use of geothermal energy is expanding very rapidly. This type of energy has proven commercially profitable for generation of electricity, for space heating, process heating, auxiliary heating of water in conventional steam power plants and for recovery of chemicals contained in natural hot water and steam. Two types of geothermal energy sources are recognized: 1) hot springs in regions of nearly normal heat flow that tap a deep reservoir through which water moves slowly to a hot springs conduit and then rapidly to the surface; 2) hyperthermal areas in which the water is heated by a relatively concentrated heat source related to volcanicity. If there is a geologic trap that provides a geologic analog to a steam boiler, as at Larderello, Italy, the hyperthermal area will have a convecting system that develops superheated water at relatively shallow depth and may provide natural steam in large quantities. If a hyperthermal area is to be productive for a long time, the underflow into the reservoir should be slow enough to allow the heat source and convective system to heat the underflow to the working temperature, and the production rate must not exceed this rate of underflow. A model based on a typical aquifer suggests that the rate of movement of water through the reservoir be such that a few years are spent in transit between isotherms that are spaced about 2°F apart. The possibility of finding blind geothermal areas is illustrated by discussion of the techniques developed in evaluating the subsurface temperatures in the East Tintic district of Utah where a map of isotherms at water level (2000 to 2000 ft below the surface) shows that a hyperthermal area may exist a short distance southeast of the mining district. Very nearly all of the energy that man currently uses comes ultimately from the sun&apos;s radiation. This includes water power, fuels such as wood, peat, coal and petroleum, the wind and all our animal power. In the paper summarizing a conference on solar energyl6 the average amount of solar energy received daily on the earth is taken at about 1 cal per m2 per min or slightly less than 2 pcal per cm2 per sec; this is almost exactly the amount of energy on the average that the earth liberates in regions of normal geothermal gradient due to its own internal heating. In many places, however, the energy released is many times the average and in some of these hyperthermal areas, geothermal steam is used for generation of electricity, and hot springs are used for heating buildings and private dwellings, process heating, auxiliary heating of water in conventional steam power plants, and chemicals may be recoverable from both hot water and steam. The use of hot springs waters for heating houses goes back hundreds of years but until recently was confined to a few dwellings close to the hot springs. In Korea, some houses had hot spring water channeled through conduits in the floor centuries ago and thus the Koreans can be credited with pioneer development of radiant heating. In Iceland at present nearly a third of the population uses natural thermal water for domestic heating." The Reykjavik system pipes hot spring water at about 94°C throughout the city and has devised insulated double pipes that allow the water to be piped for some 25 km with a drop of only 1°C for every 5 km. The actual cost to the Icelandic consumer is only one-third the cost of heating by imported coal and yet the industry is one of the most profitable in Iceland. The most profitable use of geothermal energy has been its conversion into electricity which can be transmitted economically much greater distances than hot water. The largest installation at the present time is that at Larderello, Italy, where the Count of Larderello began to experiment in the production of electricity from geothermal steam 60 years ago — in 1904. He installed his first steam turbine, with a capacity of only 250 kw, in 1912 as the result of a local quarrel with the power company which furnished the current required in the Larderello chemical industry - an industry that then dated back nearly a century. As experience was gained in drilling deep holes to tap geothermal steam and in converting it to electric power, the capacity of the installation of Larderello gradually increased, but was all destroyed by the Germans during their retreat from Italy in the closing

Jan 1, 1965