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By M. Duclos, A. Sawatzky

A simple model has been developed which describes the steady-state solute distribution in Ti-H type systems above the eutectoid temperature in the presence of a temperature gradient. The solute distribution is dependent on the shape of the phase boundaries. An interesting result, and one that is not observed at steady state in thermal diffusion below the eutectoid temperature, is the existence of a two-phase region. The heat of transport for hydrogen in a titanium, Q*a, over the temperature range 275" to 650.C is determined to be 4500 * 230 cal per mole. The heat of transport for hydrogen in B titanium, QB* over the temperature range 320" to 590.C is found to be 630 ± 200 cal per mole. It is also shown that thermal diffusion provides a method by which phase bounduries above the eutectoid may be determined in Ti-H type systems. IN modern technology materials are being used at constantly increasing temperatures under greater temperature gradients. Thus atomic migration in metal alloys due to a temperature gradient (thermal diffusion) may in some cases occur to an observable extent. The thermal diffusion of hydrogen in zirconium has in recent years received considerable attention1-' because of the use of zirconium alloys in nuclear power reactors. The thermal diffusion kinetics below the eutectoid (547°C) are fairly well understood. At steady state the solid solution, a, and hydride, 6, phases are completely separated with the hydride precipitating at the lower temperatures. No experimental work has been carried out in the a + B region although Droege4 suggested that a complete separation of the two phases, as observed at temperatures below the eutectoid, might not always occur. In the present investigation a simple model has been used to determine the steady-state solute distribution under a temperature gradient in Zr-H type systems heated above the eutectoid temperature. The solute distribution is shown to be dependent on the shape of the phase boundaries in the constitutional diagrams and several typical cases are discussed. The model has been applied to Ti-H. This system was chosen in preference to Zr-H because of its much lower eutectoid temperature (-300°C as compared with 547.C), thereby reducing experimental errors due to oxidation and hydriding. The heats of transport for hydrogen in the a and B phases of titanium also have been determined since they were required to compare the proposed thermal diffusion model with experiment. THEORY In the presence of a temperature gradient the atomic flux in a single-phase region of a two-com-ponent system of which the atoms of only one component are diffusing is given by:' J = - U\dx + RT3 dx) which can be written as: j-D(dn/dt +Q*n/RT2)dt/dx [11 J - -D\dT + RT2)dx [1] where D = diffusion coefficient, n = solute concentration, T = absolute temperature, R = gas constant, dT/dx = temperature gradient, and Q* = heat of transport. At steady state (J = 0) Eq. [I] leads to the solute distribution: n = noexp Q*/RT where no = a constant depending on total solute content. The heat of transport Q* can be experimentally determined from the steady-state distribution. In the present paper we shall determine the solute distribution in systems having the constitutional diagram exemplified by Ti-H shown in Fig. l.' As shown, N,(T) and NB(T) are the equilibrium solute concentrations in the a and 0 phases at temperature T. Lines AA' and CC' define the region of interest to us. The following assumptions are made: 1) Steady-state conditions prevail. 2) In a single-phase region all points on an isotherm have the same thermodynamic potential so that the composition over an isotherm is uniform. If a two-phase region exists, thermodynamic equilibrium is found only at phase interfaces. However, we assume the component of the concentration gradient along an isotherm to be small so that the composition in each phase is approximately the same as at the interface and is given by the constitutional diagram, Fig. 1. 3) There is appreciable diffusion of only one component. 4) We shall consider only the case where Qa*, QB*, and Qg*, the heats of transport for solute diffusion in the a, B, and 6 phases, respectively, are positive. This has been observed for the thermal diffusion of hydrogen in zirconium3 and titanium.10 We will show that the steady-state solute distribution above the eutectoid is primarily determined by the heats of transport and the temperature dependence of Na(T) and Np(T). It may be quite different from the steady-state distribution below the eutectoid. For example, we will see that, under certain conditions,

Jan 1, 1970

By J. J. Bowman, E. H. Dix

A LACK of experimental data illustrating the effect of composition, particularly in respect to impurities, on the mechanical properties and corrosion resistance of aluminum-alloy die castings induced the authors and their associates to undertake a limited study of these relations. A number of commercial alloys and several experimental variations of a commercial alloy were used for the investigation. Mechanical property, growth, steam, paraffin, salt spray and atmospheric exposure tests were employed. This paper deals with the more accelerated tests and the results they have produced. It is concluded that a high-silicon alloy with all impurities except iron strictly limited to small amounts will develop an excellent resistance to corrosion and retain satisfactory mechanical properties and casting characteristics. As a direct result of this investigation an alloy of this character with superior corrosion resistance is now available commercially. In general, copper increases the strength and decreases the elongation and corrosion resistance. Tin reduces the mechanical properties and the resistance to corrosion. Iron reduces the elongation and, if excessively high, may adversely affect the tensile strength. Even excessively high iron contents do not affect the corrosion resistance, which is fortunate for the die caster as it is this element that is the most difficult to control. Nickel and zinc in limited amounts do not seem to affect the properties or corrosion resistance of at least the high-silicon alloy. Growth tests have confirmed the previous common belief that dimensional changes under either dry or wet conditions at 100° C. are too small to be of practical importance.

Jan 1, 1935

By AIME AIME

SECOND only to the February Annual Meeting of the Institute are the Regional and Divisional meetings held in the fall of each year. Six such gatherings are scheduled in the next the months, with something likely to interest every member of the Institute. A brief résumé of the programs follows. Regional Meeting Vancouver T HE regional meeting of the Institute will be held at Vancouver, Sept. 13 to 20, in conjunction with the annual western meeting of the Canadian Institute of Mining and Metallurgy. The pro gram appeared on page 350 of MINING AND METALLURGY for July and-proof of careful preparation-a month later re- quires no correction and little elaboration. On the technical side there are few changes. A new item on the Wednesday morning program is the paper, "Investigation of Residential-type Stokers," by H. F. Yancey, supervising engineer, Northwest Experiment Station. U. S. Bureau of Mines, Seattle. As to entertainment the meeting is taking on some most pleasurable aspects. Two notable excursions have been arranged.

Jan 1, 1937

By Clark A. Sumner, D. Arthur Burnham

A process for recovery of greater than 99% of the copper contained in acid leach solutions by sulfide precipitation using hydrogen sulfide as a hydrometallurgical reagent has been developed. The process incorporates the concept of hydrogen sulfide addition to recycled copper sulfide solids in a turbulent flow area where further precipitation or agglomeration occurs to increase the effective particle size of the copper sulfide precipitate. Because the recycled solids provide a larger number of particles upon which momentary excesses of hydrogen sulfide are absorbed, oversulfidization of the product is prevented. Copper sulfide precipitates produced in this manner in a laboratory test reactor showed greatly improved physical characteristics compared to copper sulfide precipitates obtained by conventional direct precipitation in which H2S is bubbled directly into acid leach liquor. Copper sulfide precipitates were evaluated and compared by use of filtration tests and settling rate studies. Electron microscopic examination of the solids confirmed the presence of larger particles in reactor-precipitated copper sulfide. Flotation was examined as an alternative to filtration for recovery of CuS precipitates and was found to achieve complete CuS removal without addition of collector or frothing reagents in a period of 2 min. In the same test reactor, a rapidly floatable CuS precipitate was also formed by mixing H2S with acid liquors used to leach crushed copper oxide-copper sulfide ore (LPF process). In the presence of gangue from the crushed ore, flotation of both natural and reactor-produced copper sulfides resulted in recovery of better than 90% of the copper contained in the crushed ore.

Jan 1, 1974

By A. B. Kinzel

IT is with sincere appreciation and a deep sense of responsibility that I accept the honor of delivering the Howe Memorial Lecture. In our time metallurgical research has delved into phenomena ever more complex in character, so that much of this work must be done by organized teams. We, of the Union Carbide and Carbon Research Laboratories and the Electro Metallurgical Co., are truly a team and the lecture which is to follow is due largely to a few of the outstanding members of that team here cited and well known to you in their own right: John Lamont, whose work deserves special recognition, Walter Crafts, William Forgeng, William Binder, Robert Fowler, and David Swan. Thus it is a fitting pleasure to accept this honor for the research institution which I represent. Henry Marion Howe was truly inspirational and his breadth of view was such that he could use either the method of rigid proof or implied mechanism to further the broad understanding. But perhaps his outstanding characteristic was his sound judgment and his ability to weigh observations. The following is replete with observations and judgment as to their implication. We would like to feel that it is the type of dissertation which Howe, himself, would have enjoyed. Chromium carbides in stainless steel have, in a sense, been a key to the progress of the stainless steel industry. Brearley's first stainless steel, containing approximately 0.30 pct C, was successful because it differed from previous Fe-Cr alloys in that the carbides were present in such amount and form as to provide the stainless and cutting properties. Again, the 12 pct Cr die steels with a carbon content of 1.5 pct or more achieved their properties by virtue of the form and distribution of the chromium carbides. In the straight chromium steels with from 12 to 25 pct Cr, chromium carbide amount and distribution are once more the determinants with respect to physical properties and corrosion resistance. In each of the cases just cited the role of the carbide is in essence similar to that of iron carbide in carbon steel and this story is so well known that we need not dwell on it. In the austenitic stainless steels, the chromium carbide plays only a minor positive role with respect to mechanical properties, and for corrosion resistance the objective is to achieve maximum homogeneity. Thus the tendency has been to ever lower the carbon and correlatively the chromium carbide content of the austenitic steels. Today stainless steels with carbon less than 0.03 pct are beginning to find their true place, and this is being aided in major degree by our Company's introduction of a new type of ferrochromium having negligible carbon. The role of carbon in these austenitic steels has long been recognized, and a truly enormous amount of research has been devoted to the subject. Much has been learned about corrosion resistance, but the attack on the problem from the point of view of carbide precipitation and the nature thereof has left much to be understood. Because of its fundamental importance to the future of stainless steels, further study of the mechanism of carbide formation in austenitic steels is of interest. In the 18-8 Cr-Ni steels, which are typical of the austenitic class of steel, carbon is soluble in the aus-tenite to the extent of approximately 0.15 pct at 1832°F (1000°C). The solubility becomes less with decreasing temperature, so that at 1652°F (900°C) the solubility limit is approximately 0.06 pct, at 1472°F (800°C) it is about 0.03 pct, and at 932°F (500°C) it is approximately 0.01 pct. Obviously this is the ideal situation for the classical precipitation phenomenon. It is true that, in a sense, 18-8 austenite resulting from annealing is in a metastable state, and the phenomenon of ferritic precipitation from this austenite should be considered. However, in a so-called fully austenitic 18-8 steel this is secondary with respect to the carbides and can be neglected. A wide variety of chromium carbides is known. Only one chromium carbide, Cr,,C,,, frequently referred to as Cr,C, has been found in unmodified low carbon 18-8 steel. This, fortunately, simplifies the study of the precipitation phenomena. For this study an A.I.S.I. type 304 stainless steel of commercial quality was selected. Analysis showed C 0.07 pct, Mn 0.49 pct, Si 0.33 pct, Ni 9.34 pct, Cr 18.91 pct, and N 0.033 pct. As expected with this composition the steel was homogeneous after annealing except for a few pools of ferrite, which were disregarded in that their location was not coincident with subsequent carbide precipitation areas. On corrosion testing the steel was normal and typical of good commercial quality. Specimens 1/2xlx4 in. were annealed and subjected to precipitation heat treatment for 100 hr at 100" temperature intervals from 1000° to 1500°F and for ten selected intervals ranging from 5 min to 64 hr at 1300°F. These blocks were then cut into small pieces for metallographic studies. The first problem

Jan 1, 1953

By Kenneth M. Ritchie

Mineral wool is a term applied to man-made fibers of silicate glass with useful properties resulting from their fibrous nature. In contrast with crystalline fibrous minerals such as asbestos, mineral wool fibers are amorphous, solid filaments produced by drawing from molten liquid and subsequent cooling. Chemically they are silicate glass with varying percentages of metallic oxides, especially those of aluminum, calcium, magnesium, iron, and in glass wool, sodium, potassium and boron. Other elements such as manganese, titanium, sulfur, etc., result from their presence in the raw materials used and are not purposely added. In the United States, mineral wool is a generic term and may be applied to rock, slag or glass wool. In Europe, glass silk and silicate cotton are products in the same category, but the term mineral wool is less commonly used. Current usage is to ignore the actual source and to differentiate products on a composition basis; thus rock and slag wools have about 35-45 pct of silica, while glass wool has 54 to 60 pct. Much mineral wool of slag origin is called "rock wool," and this practice is increasing, although wool made of slag from lead or copper refining is often referred to as "lead slag wool." Its greenish-gray to greenish-black dark color, due to 5-25 pct Fe (reported as FeO), distinguishes it from "white" wools made from iron, blast furnace slag containing only 1-2 pct FeO or Fe203. Most mineral wool is used for thermal insulation against heat and cold; sound absorption and isolation are probably the next most important uses. Both its thermal and acoustic values result primarily from the physical structure of the heterogeneous mixture of fibers and air which is the form in which the fibers are first obtained and handled. For this reason, within fairly wide limits, differences in chemical composition are relatively unimportant, and for most conventional applications all types are competitive in properties and value. Mineral wool intended for extreme conditions of high temperature, acid resistance and special purposes must have a chemical composition which will insure the desired properties. This may differ greatly from that of ordinary wools; for example one product approximately 98 pct Si02 and another consisting of 50 pct A1203 and 50 pct Si02 are produced and sold for high temperature service up to 2000°F or more. These are considerably more expensive to manufacture and their cost limits their use. Historical The manufacture of mineral wool consists fundamentally of a process which subjects molten material to shear and/or tensile forces that draw them into fibers. The liquids are cooled at a rate which solidifies them quickly. As a solid glass they are technically super-cooled liquids since they have no true melting point. The drawing out of glass into thin rods, filaments and tubes was known from very early times, and present day continuous production of glass filament for textiles was evolved gradually by adapting hand methods to automatic machinery. Rock and slag wool manufacture had a somewhat different development. Early explorers reported finding filamentous material

Jan 1, 1960

One of the very simplest losses to overcome, and at small expense, is belt slip. To show the extent of the loss of money through slipping of the main belt alone, a chart, supplied us through the courtesy of the Cling-Surface Co., Buffalo, N. Y., is shown herewith, upon which this is easily ascertained. By glancing up and down column "D" of this chart it is evident that the "Cost of Avoidable Belt Slip per Year in Dollars" may vary all the way from the smallest sums into the thousands of dollars. Roughly, 2 per cent. of the potential power in the driving pulley of the engine is represented by "belt creep." Its loss is unavoidable because of the elasticity of the belt. This has been recognized and provided for in the chart, so the reader can go ahead and connect known values, while the intersection with column "D" gives the avoidable money loss. Simply zig-zag across the chart twice with a straight edge, as shown by the dotted lines and the money loss is immediately found. Thus if the total belt slip is 6 per cent. (column A) and the cost of coal per ton is $4 (column B), run a straight line through those two points and locate the intersection with column "C." Then from that point of intersection run over to the tons of coal burned per year (which in this instance has been stated as 1000 tons) and the cost of avoidable belt slip per year is shown by column "D" as being $160. To give a clear idea as to the meaning of "Total Belt Slip Per Cent." let us take an example. You find by means of a revolution counter that a given driven pulley is rotating only 940 times per minute. You figure that without slip it should rotate 1000 times per minute; 60 revolutions per minute, therefore, are absolutely lost. Dividing this 60 by the r.p.m. that pulley should make you get 0.060 or 6 per cent. which is the "Total Belt Slip." After having made this determination, it is a simple matter to apply it to the chart as has been done and determine the money loss per year due to such slip.

Jan 4, 1918

By D. I. Bardos, A. M. Bardos, Paul A. Beck

The approximate effective silicon radii in ternary Laves phase alloys with transition elements and silicon were found to range between 1.16 and 1.21A, i.e., considerably smaller than the atomic radius calculated for elemental silicon. The atomic radii were found to increase with the size of the transition element atoms in the structure. It has been noted by Aronsson1 that silicon in solid solution in iron, cobalt, and nickel has an effective CN 12 atomic radius of approximately 1.20Å, a value very much smaller than the CN 12 radius of 1.34Å derived from the interatomic distances in elemental silicon.7 The unusually short metal-silicon interatomic distances in transition element monosilicides and disilicides have been also pointed out by various investigators.1 A similar tendency was observed by Nevitt in Cr3O type silicides.2 Recent work on Laves phases in ternary systems of silicon with transition elements4"8 suggested that extensive Laves phase fields may occur in such systems.8 It has been pointed out by Laves7 that the MgCu2 and MgZn2 type structures lend themselves particularly well for the determination of the effective radii of the component atoms. In these AB2 phases the B atoms are arranged in close packed straight lines, and their distances are related in a simple manner to the lattice parameters.8 The present work was undertaken in order to find out whether or not the B transition element in such AB2 Laves phases can be replaced to an appreciable extent by silicon. In cases where extensive substitution proves to be possible, the "average atomic radius for the B site" at various silicon contents was to be determined, and the effective atomic radius of silicon calculated by extrapolation to complete replacement of the B component by silicon. The following ternary systems were studied: Ti-Mn-Si, Ti-Fe-Si, V-Co-Si, V-Ni-Si, Nb-Fe-Si, Nb-Co-Si, Ta-Fe-Si, Ta-Co-Si, and Mo-Fe-Si. In all of these alloy systems, the Laves phase solid solutions were found to extend over a considerable range of silicon content. As previously reported,4"8 in the V-Co-Si, V-Ni-Si, and Mo-Fe-Si ternary systems Laves phases do occur, even though there are no corresponding binary Laves phases. In stabilizing the Laves phase, silicon acts as if it were decreasing the effective electron concentration of the alloy.8 A more detailed study of the boundaries of the Laves phases in the V-Co-Si and V-Ni-Si systems has been made and will be published elsewhere. In both cases, the elongated Laves phase fields extend parallel to the B-Si side of the composition triangle, clearly showing that silicon is substituting for cobalt, respectively, nickel over a wide range of compositions. The binary Laves phases NbCo2 and TaCo2 have the cubic MgCu2-type structure. It was found that, in both ternary systems with silicon, again the MgZn2-type hexagonal Laves phase is stabilized and that this phase extends to high-silicon contents. In each ternary system at least three Laves phase alloys of the composition A(B1_xSix)2 were used, x here denoting the fractional substitution of the B-transition element atoms by silicon. The alloys, listed in Table I, were prepared by arc melting in argon. Each specimen was water quenched after a homogenizing anneal of 3 days at 110(FC, except for the Mo-Fe-Si alloys, which were annealed at 1200°C. Metallographic examination showed that most of the homogenized alloys consisted of a single phase, although some had minor amounts of a second phase, as shown in Table I. X-ray diffraction patterns were prepared using an asymmetrical focusing camera of large resolution and Fe Ka radiation. The patterns were indexed, and the lattice parameters of the hexagonal Laves phases were determined from the available diffraction lines of highest indices: (213), (205), and (313). The lat-

Jan 1, 1963

By H. P. Wheeler

WHEN Germany invaded Poland in September, 1939, the only operating helium plant in the United States was that near Amarillo. Texas, supplied with helium-bearing natural gas from the near-by Cliffside gas field. Today the Bureau of Mines has five plants capable of producing more than 25 times the prewar helium output of the Amarillo plant. Two of the plants have received Army-Navy "E" flags for their part in the faraway "Battle of the Atlantic," where heliumfilled Navy blimps chased Adolf Hitler's submarines away from American shores. Meteorologists, watching balloons carried high into the stratosphere by helium, determined weather conditions that influenced the selection of D-day and dates for other military operation. Demand for helium doubled overnight when the Navy decided to expand its lighter-than-air activities; and as the blimp patrol proved effective, the helium demand became ever greater. A tribute to the success of the Bureau of Mines in meeting the demand for helium was paid by the late Secretary of the Navy, Frank Knox, in a letter to the Secretary of the Interior on April 10, 1944. Secretary Knox wrote, in part,

Jan 1, 1945

By W. C. Ellis, E. S. Greiner, M. E. Fine

C. H. Samans and W. R. Ham (Chicago, Ill., and Dix-field, Maine, respectively)-—For several years we have been studying transitions of this basic type in metals, alloys, glasses, etc. Usually, however, they are not so clearly marked as those which the authors have found, and hence are much more difficult to determine accurately. Since our studies indicate that most of them occur virtually unchanged (as far as temperature is concerned) regardless of the form in which the element appears, we believe that they are a characteristic of the atom. Specifically, we believe that there is an additional rotational degree of freedom possessed by the nucleus which has not been considered heretofore. This nuclear rotation is made up of several components, each related to the several quantum shells of electrons. In chromium there are four of these shells and hence four separate series of characteristic transition temperatures. The lowest temperature at which any transition occurs, based on the present state of our computations, is 125°K, 4° higher than the authors' value of 121°K. A convergence of this series, we believe, shows up at the higher temperature of 2085 °K, surprisingly close to the transformation temperature of 2103°K recently announced by N. J. Grant of M.I.T. for a body-centered to face-centered transformation in chromium. Likewise, our computations indicate a temperature of 311°K for the second transition temperature, reported by the authors as 310 °K. A convergence of this series, we believe, shows up at a higher temperature as the melting point at 2163°K. Although our work on these series must, in a sense, still be regarded as empirical, since we do not understand fully as yet just what the series mean, it is based on a reasonably firm picture. The individual constants, from which the various series are computed for each element, comes directly from the X-ray K absorption limit. Furthermore, the same basic method has accounted for transformation and melting temperatures in about 50 of the chemical elements, which is all we have tried thus far. In many cases the only known transformation is the melting point, but in others the occurrence of transformations or other transitions, equally as well marked as those of the authors, has been pointed out by others. These observations have assisted us greatly. Consequently we were very pleased to see the authors' excellent work in finding these two transitions in chromium. With these confirming data, our picture of this element is clarified considerably, so we expect that at least some of our work can be published in the near future. R. C. Ruder (E. I. du Pont de Nemours & Cu., Wilmington, Del.)—The authors' interpretation of these transitions in terms of 3d to 4s electronic structure transitions is most interesting. It would be interesting to have additional experimental evidence of such transitions from the temperature dependence of the Hall coefficient in the neighborhood of the property changes discussed in this paper. Simple theory15 suggests the Hall coefficient as a measure of the free electron (or s electron) concentration per unit volume. It has been shown that for paramagnetic'" and ferromagnetic1? metals the simple theory is in fact too simple. However, the existence of a discontinuity in the Hall coefficient would provide information which should aid both in our understanding of these transitions and the significance of the Hall coefficient in these metals. It was rather surprising that no significant paramagnetic effects were observed. In this connection the recent work of McGuire and Kriessman18 is cited. They measured the magnetic susceptibility of chromium from 20" to 1460 °C. They also observed no large change in the susceptibility although there might be a change in slope in the vicinity of the 40 °C transition. The existence of these 3d to 4s electronic transitions has been discussed in connection with the paramagnetic susceptibility behavior of nickel and nickel alloys.'"-" Assuming a correspondence principle between classical and quantum mechanical paramagnetic theory and using classical theory to calculate the effective Bohr magneton number from the Curie constant for substances obeying the Curie-Weiss law," it is found that the effective magneton number is a function of temperature. The process of calculation involves the inverse of the differential of the 1/x4 vs. temperature curve so that good and numerous data are necessary to obtain significant results. The data of Fallot23 show a discontinuous increase of about 12 pct in the effective magneton number between 850" and 900 oC, followed by a continuous increase up to the melting point. The data of Sucksmith and Pearce24 show a possible 8 pct increase. The older data of Terry25 and Weiss and Foex26 show a continuous increase. It is possible that small amounts of impurity atoms change these electronic transitions significantly. Fallot's23 data on a nickel alloy with 4.5 atomic pct Fe indicate that the discontinuity occurs around 1300 °C. Systematic investigation of the transition metals for transitions of this nature should provide information which would be very valuable for our understanding of these metals. The absence of antiferromagnetic structures in chromium has been shown by Shull27 using neutron diffraction techniques. M. E. Fine, E. S. Greiner, and W. C. Ellis (authors' reply)—The remarks by Drs. Samans and Ham are certainly very interesting, in particular those pertaining to the close agreement between the theoretically calculated values for transition temperatures in chromium and the experimental values reported by a number of investigators. This is a remarkable achievement and we shall look forward to a more detailed presentation of the method followed in their calculations. We do not believe that the transition in pure chromium near 40 °C remains temperature invariant with alloying, as was reported by Samans and Ham for a number of the substances that they studied. We have not done any work with alloys but base our belief on the results of earlier studies in which less pure chromium was included and considerably lower transition temperatures were observed. The transition tempera-

Jan 1, 1952

By D. J. Weintritt, R. G. Hughes

Statistics show arz increase in the average depth of wells drilled in recent years. As a corollary to this trend, drilling fluids have been improved in an effort to meet the problems inherent at temperatures approaching 500°F. Of importance are (1) deterioration of mud components and (2) the effect of solids on filtration and rheological properties. High-temperature, stable water-base and oil-bare muds are discussed. Those areas in which differences exist are pointed out. Results are based on data taken from the Fann consistotneter, rheometer and shear-strength measurements, static and dynamic filtration tests, methy-lene blue test for bentonite solids and specific heat measLrrenlents of muds. INTRODUCTION Higher well temperatures go along with the fact that the average depth of wells continues to increase. Recent data by Gardner' lists 137 completions deeper than 15,000 ft for the first half of 1964 with a record second-half total of 167 wells drilling or proposed. In addition, there has been an increase in drilling for steam for power production or mineral recovery. In this application the depths are modest, but the mud may approach the critical pressure and temperature of water. Scearce and Magnon' report drilling mud used at temperatures of about 700°F in the Salton Sea area of California. Most deep wells have been drilled with water-base muds. In recent years, however, there has been a substantial increase in the use of oil-base muds because of technological advances in effective additives. The significance of this development was dealt with in considerable detail by Simpson and his co-workers.3 Additiona1 field data have now been obtained to indicate that oil muds are competitive in control, performance and cost with the best types of water muds for use at high temperaturc. This parallel offer of two very different fluid systems, each offering a similar variability in performance, cost and convenience, has created the need to evaluate the merits of these fluids under specified conditions so that the advantages and disadvantages of each can be weighed in relation to the over-all drilling program. This paper is not intended as a review of all the factors. Rather, it attempts to emphasize: (1) important condltions and facts peculiar to high-temperature drilling muds, (2) that more than one imposed test condition or testing method is necessary to describe the quality of a mud at high temperature and (3) that elaborate experimental precautions are necessary whenever laboratory data are used in selection of a mud for field use. WHAT IS A HIGH-TEMPERATURE DRILLING FLUID? For the purpose of this discussion, a high-temperature drilling fluid is any system so formulated or treated to economically minimize the effects of temperature on the properties of the fluid. Our experience in drilling fluids suggests that these effects become obvious for many mud materials at temperatures of 300F or higher. It is understood that hydrolysis of starches, depoly-merization of certain organic thinners, or irreversible chemical reactions (such as that of clay and lime) can affect filtration, viscosity and shear strength at less than 300F. However, the temperature level is not a serious point and in no way affects the precautions and techniques used in this study. An up-to-date review of the literature on high-temperature drilling fluids and the many variations was treated by Rogers'in 1963. EXPERIMENTAL REQUIREMENTS TESTING EQUIPMENT AND PROCEDURES With the advent of deeper drilling and increased demand for temperature-stable drilling fluids, new testing equipment and laboratory techniques were devised for the evaluation of drilling fluids subjected to elevated temperature and pressure. While the equipment has not been standardized, it is in widespread use. Milligan et al. Qescribe a filtration cell for determining the filtration properties of drilling fluids at temperatures in excess of 300F. They showed the effect of variations in temperature and pressure on oil and water muds filtered in the 300 to 400F range. The dynamic filtration apparatus described by Simpson6 permits the study of the filtration properties to temperatures of 350F for drilling fluids circulated over sandstone cores. Watkins et al.' describe the use of pressure bombs for studying the effect of prolonged periods of elevated temperature upon the gelation or solidification of drilling fluids. Chisholm et a1.' describe the use of a modified cement consistometer adapted for use in drilling fluid evaluations. A similar consistometer is used in this study, although the application and data-recording method have been changed. The consistency of a mud sample is measured by timing the movement of a soft iron bob which is magnetically moved up and down in the sample container.* Changer in the time of travel and the temperature of the mud at that moment are plotted with a two-point Brown Elec-tronik Recorder. A 10-in. chart with a speed of 4-in./hr is used. Fia.- 1 is a generalized internretation of the data ob-

Jan 1, 1966

By Ray W. Carpenter, Ralph Hultgren, Raymond L. Orr

Heats of formation of Au-Zn alloys of compositions Au3Zn and AuZn were rneasured at several temperatures by liquid tin solution calorimetry. The data for Au3Zn show that much smaller heat and entropy effects are associated with the a2- a1 transformation than for the a1 - a transformation. This result is consistent with reported X-ray diffraction studies which indicate that the a1 and (a2 phases have ordered structures which only slightly differ, whereas the a phase is disordered. The heat of formation of AuZn(ß') does not change significantly between 322o and 8000 K, confirming that the ß' alloy remains highly ordered to high temperatures. Not many measurements have been made of the energies of order-disorder transformations in alloy phases. In many cases these energies may be conveniently determined by measuring heats of formation as a function of temperature. Many alloy phases approximately obey Kopp's law of additivity of heat capacities; as a consequence their heats of formation do not change with temperature. In ordered alloys, however, a decrease in degree of order with increasing temperature will contribute an endothermic component to the heat of formation. Thus, for ordered phases where other anomalous contributions to heat capacity in the alloy or its pure components are absent, a measured change in the heat of formation may be attributed to the energy of disordering. A portion of the Au-Zn phase diagram1" is shown in Fig. 1. The composition AuZn(ß') has a well-ordered superlattice structure of the CsCl type at room temperature. The alloy is considered to remain ordered to its melting point,1 although, from X-ray diffraction data and electromotive force measurements of zinc activities, Terpilowski3 concluded that considerable disordering began at -673°K. The Au3Zn composition is a disordered fee solid solution (a) at high temperatures. Between 693o and 543oK, the ailoy orders to form the a1 phase, having a structure based on the L12(AuCu3) type, but with a regular distribution of ordering faults in the c direction, making it tetragonal. Below 543oK, the alloy orders further by means of slight atomic shifts, without diffusion, yielding a complex long-period orthorhom-bic superlattice structure, a2.4-7 Heats of formation of Au3Zn(a2) and AuZn(ß') were measured at 363°K by Biltz et al.8 by aqueous solution calorimetry. Heat capacities of several alloys between 14.9 and 38.4 at. pet Zn in the range from 373" to 723°K were measured by Iwasaki ef al.6 Stoichiometric Au3Zn, however, was not included in the alloys measured, the nearest composition being 26.1 at, pet Zn. Also, the heating rate used for the measurements, 2 deg per min, may not have permitted equilibrium to be reached in the neighborhood of the transformations. Heat contents of solid and liquid AuZn were measured between 488o and 1138°K by Kubaschewski.9 It was decided to determine the ordering energies of Au3Zn and to check on the possible disordering of AuZn by measuring the heats of formation of these alloys at several temperatures. The present paper reports measurements by liquid tin solution calorimetry of the heats of formation of the three phases of Au3Zn at temperatures within their regions of stability, and of AuZn at a low (322°K) and a high (800°K) temperature. EXPERIMENTAL Alloy Preparation and X-Ray Examination. Ten-gram ingots of Au3Zn and AuZn were prepared by melting weighed amounts of gold (99.95 pct Au) and zinc (99.99 pet Zn) together in sealed evacuated Vycor tubes at 1060°K, followed by rapid quenching. The resulting ingots were homogenized at 900°K for 10 days. The Au3Zn alloy lost no weight in preparation, the loss from the AuZn alloy was enough to introduce an uncertainty of only 0.1 at. pet in its composition. Filings for X-ray examination were taken from various parts of each ingot and strain-annealed at 723°K for 20 min in vacuo. The Au3Zn filings were quenched rapidly to retain the disordered phase. Diffraction patterns were determined with an X-ray dif-fractometer using copper Ka radiation.

Jan 1, 1968

By George S. Rice

DEFINITE data on the amplitude and effect of ground movement in specific mineral formations, caused by various methods used in the mining of ores, coal, and nonmetals, or in the extraction through wells of petroleum, sulphur, and soluble salts, are increasingly needed because of legal liabilities from damage to overlying or adjacent properties, and growing concern as to the conservation of national mineral resources. Not since the committee was established in 1923 has it been so difficult to get technical papers giving ground movement and subsidence data from specific mine operators. The reasons given, as above indicated, are pending or threatening lawsuits. There are three major objectives in ground movement and subsidence studies : (1) Maximum recovery of a mineral resource. (2) Minimizing damage to surface structures, highways, railroads, and agricultural lands caused by caving or subsidence, which may in some situations, as along the Gulf of Mexico shore, cause flooding by surface waters. (3) Lessening damage to overlying or adjacent mineral by back-filling of mine excavations as completely as possible.

Jan 1, 1940

By John B. Knaebel, Robert J. Grant

This paper outlines the trends in gold production since the discovery of America, in the world as a whole, and in the principal producing regions as well. World production climbed at an average rate of about 20,000,000 oz. per 5-year period until the record all-time output of 111,307,000 oz. in the period ending with 1915. Production fell off during the war period, but has been mounting since 1925, and will probably be nearly 100,000,000 oz. for the 5-year period ending in 1930. Total world production of gold from 1492 to the end of 1930, as closely as can be determined, is more than 1,061,000,000 fine ounces. More than one-half of this total, or about 575,000,000 oz., has been mined since 1900. In percentage of world production, the United States jumped from 4.8 per cent for the decade 1831-1840 to 44.5 per cent for the five years ending with 1855. This is the highest figure ever reached by this country, although, with the exception of the 10-year period ending 1865, it ranked first among the nationa from 1849 until the end of 1905. During the 5-year period ending with that year, the United States produced 24.7 per cent of the world's gold. The tremendous increase from South Africa following 1890 resulted in that country's becoming the largest contributor for the five years 1906-1910, a position it has held with increasing dominance ever since. Relegated to second place in the period 1906 to 1910, the United States produced nearly 20 per cent of the world's new gold until 1920. From 1921 to 1925 it averaged 13.6 per cent and since then it has continued to decline in relative importance, accounting for only 10.9 per cent in 1927. Final figures for 1930 may place Canada second among the gold producers of the world.

Jan 1, 1931

By E. B. Spice

Although much may be learned about the economics of cold weather operations by studying successful mining ventures in southern and central Canada, it is the purpose of this article to extend the study by considering only permafrost areas. Geographically this means most of the country north of the 60th parallel. In this area, at the present time, only five Canadian companies are carrying on routine and successful mining operations on a year-round basis. However, there have been some score of unsuccessful ventures, and a number of properties in the development stage show promise of being producers. Problems of cold weather are worthy of study. It may be pointed out that successful mines in this area face problems of isolation and costly transportation as well as cold weather. To reach valid conclusions, consider the development of a mythical mineral deposit located on the 65th parallel in the heart of the barren lands; problems of isolation and transportation will be ignored.

Jul 1, 1956

By Paul Weaver

DURING 1932 the amount of geophysical surveying carried out as a part of oil-field development in¬creased, particularly in the Gulf Coast of Texas and Louisiana. Here the most intensive geophysical activity was displayed in the discovery of domes and prospects several years ago, after which there was a period of relative inactivity. This year many of the leases required development and geophysical methods were used to obtain pictures of the detailed structures. These were almost exclusively gravity and reflection-seismograph surveys and for the first time this latter method was generally used by oil operators to construct subsurface contours. The total number of geophysical troops in this territory increased from 16 to 40 during the year.

Jan 1, 1933

By Ziebell, Howard A.

THE Washington magnesite deposits, located in the hilly and mountainous northeastern part of Washington, occur as massive lenses in a sedimentary series made up of dolomite, shale, and quartzite, into which basic dikes have intruded. The ore pattern resembles a series of disconnected chain links extending approximately 25 miles in a south-west direction. Magnesite in this district is all crystalline and closely associated with dolomite, talc, serpentine, and basic dike rock. All deposits which have been developed are near the surface so that quarry-bench mining has been possible. For over twenty years hand sorting magnesite ore at the quarry face was standard practice. Ore cars were hand trammed on 30-lb rail systems which led from the face to ore passes or raises for the magnesite ore and to the waste dumps for disposal of the rejected waste material. This system was somewhat modified by the use of Dempster Dumpster trucks. The ore was, however, still sorted by hand from the calcium and silica bearing waste rock. Power equipment. consisting of one 3/4-yd electric shovel, was

Jan 1, 1949

By K. H. Heino

Two 200 T/da Lurgi Turbulent Layer fluid-bed roasters have been in operation at Canadian Electrolytic Zinc Limited since 1966. Zinc concentrate containing 52-54% Zn, 9-11% Fe,31-33% S is treated to produce calcine containing 60-62% Zn,10-12% Fe, .l-.3% S as sulphide and .8-1.2% S as sulphate. Each roaster train comprises a waste heat boiler, two cyclones in parallel and a two-field electrostatic precipitator. Distribution of calcine collected is 10-15 percent from bed overflow, 55-65 percent from boilers, 20-25 percent from cyclones and 2-6 percent from precipitators. A Monsanto designed contact plant produces acid at a rated capacity of 365 T/da (100% H2304 basis) from roaster gases diluted to 7.0-7.5% S02. The process steps are gas cleaning and cooling by weak acid scrubbing, acid mist removal in electrostatic precipitators, gas drying in 93.5-96.5% H2304, conversion of sulphur dioxide to sulphur trioxide in a four-pass converter containing vanadium pentoxide catalyst, and absorption of the sulphur trioxide in 98.1-98.3% H2S04. Product acid is 93.2% H2S04. Conversion efficiency is 97-98 percent and overall sulphur recovery from concentrate is 87-90 percent. The adjacent fertilizer plant has a capacity of 135 T/da of P205. The products are 54 percent phosphoric acid, run-of-pile triple superphosphate, and diammonium phosphate. The plant is of Ugine-Kuhlman design and consists of an air-cooled multiple tank reactor, a tilting pan filter, and a forced circultation vacuum evaporator. Triple superphosphate is made on a continuous belt and partially cured in a rotary dryer. Diammonium phosphate is produced by ammoniating phosphoric acid in a single stage reactor. The slurry of ammonium phosphate is granulated in a blunger and dried.

Jan 1, 1970

By AIME AIME

EVEN the weather man joined in a friendly conspiracy to make the fall meeting of the Industrial Minerals Division at Rolla, Mo., Oct. 23-25. the splendid surges that it was. Following weeks of rain, the foliage of the Ozarks was still green, merely enlivened here and there by splashes of autumn coloring. In contrast to the tranquil beauty of the School of Mines campus under smiling Indian summer skies, the pace of the meeting was lively. Registration was larger than at any previous meeting and included an unusual number of prominent names and delegates from all over the country. From 125 to 150 were present throughout the three technical sessions, at the Thursday evening smoker, and also at the banquet on Friday; when students trooped in to the technical sessions the audience was augmented occasionally to over 200.

Jan 1, 1941

By S. P. Ray, B. D. Sharma

THE activation energy values for self-diffusion in pure metals have been correlated with a number of physical properties such as melting points,1 valences,' Debye temperatures,3 and cohesive energy densities.4 Extending the melting point correlation, the self-diffusion activation energy values for the alloys can be similarly correlated with the solidus temperatures. For metals and alloys which exhibit phase transformations, such a correlation is not feasible because of the uncertainty of various physical properties of the corresponding phases. Using thermodynamical approach, Ardell5 calculated the hypothetical melting points of the low melting phases of the polymorphic metals. However, these calculated melting points do not show reasonable correspondence with the activation energy of self-diffusion. Recently, a new approach treating metals and alloys as electron concentration phases has been developed by Engel6 and Brewer.7 These workers have attempted to correlate the crystal structures with the electron configurations of the atoms existing either in ground state or in an excited state of low promotion energy. The basic postulate of this theory is that whereas the contribution to the bonding of the metal comes from the interaction of both d and (s-p) electrons existing either independently or in hybridized states, the existing crystal structure is controlled by the (s-p) electrons alone. Specifically, a metal is supposed to crystallize in bcc, hcp, or fcc phase provided the metal has one, two, or three valence electrons per atom in the (s-p) configurations. The diamond, or ZnO and ZnS structures, occur with four (s-p) electrons per atom. Secondly, the contribution of d electrons to bonding is supposed to increase with atomic number

Jan 1, 1970