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By H. L. Gilbert, C. T. Anderson, W. J. Kroll

In a previous paper,' the use of a split graphite tube resistor as a heater element for high-temperature furnaces has been described. The principal advantages of this type of construction are: I. The quadruple resistance or voltage compared with the top-bottom clamp resistor furnace. 2. Free expansion of the resistor. 3. The ease of protection from oxidation by air. 4. The firmness by which it may be held in the compact split clamp. This construction appeared to be well adapted for the fusion of high melting metals which require fusion in a vacuum. Zirconium metal had previously been melted at the Albany Laboratory of the Bureau of Mines in a vacuum arc furnace on a water-cooled plate, using a movable tungsten top electrode.% When larger furnace capacities were desired, this type of construction proved to have its limitations as the largest tungsten rods available were about 7/8 in. in diameter. The supply of direct current of high amperage for producing the desired arc characteristics was also not available. Considerable difficulty was also found in compensating the atmospheric pressure on the flcxible tubing of the movable electrodc, at the same time keeping its movement sufficiently free to enable the striking of an arc on any part of the metal briquet. Among the various materials used for the electrodes in conducting experiments in the vacuum arc furnace was graphite. It was found that zirconium fused in a graphite cup with a carbon arc was contaminated to only 0.2 pct carbon. It was therefore decsed to melt zirconium directly in graphite crucibles. A high-frequency furnace was first used in the attempt to melt the zirconium in graphite crucibles. The high-frequency heating coil was placed outside a silica tube which was evacuated by means of an oil diffusion pump backed up by a mechanical pump. The graphite crucible was thoroughly degassed at 19oo"C before use. Considerable difficulty was experienced in operating at such temperatures in vacuo because, as shown by Zintl,3 carbon vapor formed and reacted with silica accortling to the reaction: SiO² + C = SiO + CO. The silicon monoxide which is volatile at these high temperatures reacted with the zirconium, thereby contaminating it with silicon and oxygen. The presence of carbon monoxide was detected by means of a gas discharge tube placed in the vacuum system as indicated by the pale blue glow of the tube as soon as carbon vapor started to react with the hot silica. The reaction between the carbon vapor and hot silica was avoided by the use of split cylindrical molybdenum shields which were inserted between the graphite crucible

Jan 1, 1949

By Gordon G. Bentle, W. P. Fishel

GREINER, Marsh, and Stoughton1 have reviewed the literature in a monograph on the iron-silicon system. The lack of agreement among the various studies may be due to the difference in the purity of materials in some cases. The results of the X-ray method indicate only a general rather than a specific limit of the y loop. The iron-titanium system was investigated by Roe and Fishel,' whose results are used in determining the iron-silicon-titanium y loop. The literature indicates that no study has been made thus far of the iron-silicon-titanium system in the y loop region. Experimental Procedure The alloys were made from Armco iron, 99.86 pct Si, and 98.5 pct Ti. The titanium contains 1.07 pct Fe. The Armco iron contains 0.01 pct C, 0.005 pct Si, 0.02 pct Mn, 0.006 pct P, 0.01 pct S, and 0.04 pct Cu. A dilatation sample of Armco iron was prepared in the same manner as were the other samples. Several dilatation runs indicated that Ac3 begins at 905°C and ends at 910°C, which compares favorably with the study of Wells, Ackley, and Mehl' employing specially purified iron. All alloys were melted in an induction furnace in Alundum crucibles and were top poured into baked core sand molds. The ingots weighed about 600 g as cast. Dilatation samples of 4 in. by % in. diam were taken from the bottom end of the ingot, from which turnings for analysis were taken. Turnings from each end of two of the samples indicated that the alloys possessed uniform silicon content. A hole was drilled halfway through each end of a 4 in, dilatation sample. A chromel-alumel thermocouple was inserted in each hole and the surrounding metal peened in to hold the thermocouple in place. Fig. 1 represents the dilatation apparatus. The heating unit is an Alundum tube wound with resistance wire; the dilatation tube is a McDanel combustion tube; the push rod is zircon; the dial gage is graduated in 0.0001 in. and was vibrated to prevent sticking. A blank run over the temperature range of interest gave no significant dilatation. The thermocouples were attached to a multiple recording micromax which indicated the temperature at each end of the sample at 35 sec intervals. A Lindberg control unit governed the rate of heating of the furnace, and lowering or raising the

Jan 1, 1957

By Ralph M. Hunter

Until recent years, maintenance of surface coal handling facilities was a relatively simple task. Equipment consisted principally of conveyors, screens and crushers of comparatively simple construction. Electrical equipment consisted of motors and starters, with little, if any, interlocking. In most cases failure of any component affected only the grades of coal loaded so that even a prolonged breakdown did not affect mine operation materially. However, with the introduction of modern cleaning plants, the picture has changed. The equipment is much more complex and therefore more difficult to maintain. In many cases failure of any component of the plant prevents loading of coal. Even if provision is made to bypass, the quality of coal loaded is lowered, affecting markets. In the case of plants designed to permit full seam mining, marketable coal cannot be loaded without operation of the cleaning plant. Under these conditions it is apparent that considerable thought and effort toward better maintenance are justified. In order to assure continuous, efficient and economical operation, maintenance should receive consideration, not only after the plant is in operation, but while it is being designed. It is hardly necessary to say that the designer should strive for sturdi-ness and wearing qualities. It is sometimes not realized, however, that even the best parts will sooner or later require replacement or repair. The designer should, there- fore, give consideration to accessibility. Anyone who has had to do with cleaning plant maintenance is familiar with installations where several hours are required to get at a part that can be repaired or replaced in a few minutes, once it is accessible. As in most cases, experience is the best guide. The men who operate and maintain this equipment know the problems encountered. Whenever available, the opinions of these men should be sought and heeded. As an example, we might consider the refuse elevator on a Chance Cone. Our company is now operating three of these cones, the first of which was installed in 1941, and the latest in 1946. Exact records are not available, but well over 50 pct of delays charged to the Chance Cones have been caused by the refuse elevator. This elevator receives refuse from the cone and carries it to a point above the water level of the cone, discharging onto a dewatering and desanding screen. Since the elevator operates under water and necessarily has close clearances in the lower boot, it tends to jam on large pieces of refuse or tramp iron. The chain, buckets and boot are also subjected to the action of water, sand and refuse, which accelerate normal wear. In case of jamming or chain-breakage it is necessary to drain the elevator and the cone so that even a minor fault in the elevator causes a considerable loss of time for the cone. In our new plant, which will contain two Chance Cones, the refuse elevator has been eliminated. This was accomplished by raising the cone so that the refuse gates could discharge directly onto the dewater-

Jan 1, 1949

By A. H. Kline, E. B. Zimmer, Zay Jeffries

It is well known that many properties of a given metal vary with the size of grain or cell. For most industrial purposes, where high ultimate strength and high elastic limit are desired, the manufacturer tries to produce a fine-grained structure. For some purposes, for example in transformer iron, a coarse-grained structure is desirable. The terms fine-grained and coarse-grained are used only in a relative sense. For example, a fine-grained cast copper might have grains 100 times larger than coarse-grained high-speed steel. Similarly, a finegrained steel rail might have grains or cells 100 times larger than coarsegrained wire, which was made of steel from the same heat. In some metals, the change in grain size is more appreciable khan the changes in any of the properties determined by the tensile test. Furthermore, in metals which have been annealed or subjected to high temperatures, grain size may prove to be a better indication of the life of the metal in use than the tensile test. One of the authors was able to supplant the tensile test with grain-size determinations in the control of metal for a specific use, the latter determination being more indicative of the life of the metal part than the tensile test. A grain-size determination with a tensile stest is, of course, more valuable than either singly. At present there is a decided dearth of data on actual grain-size determinations in metals, and consequently a corresponding lack of ability to interpret the determinations after they are made. It would be desirable to have correlation made between grain size and properties of metals, comparing thousands of determinations. In this way, grain-size determinations might be interpreted in much the same manner that tensile tests are now. Several Methods of Measuring Grain Size One of the chief reasons why more grain-size measurements have not been made is the excessive work involved in making a determination.

Jan 1, 1916

By L. Kaufman

An equation is derived relating AF a", the difference in free energy between austenite and martensite, to temperature and composition in the iron-chrmnium and iron-chromium -nickel systems. This equation is used to calculate at M,for low-carbon stainless steels. A method for utilizing the energetic equations to calculate M, in stainless steels is suggested. In addition, an explanation is given for the anomalous effect of chromium in forming a y loop concurrent with the lowering of M, in iron-base alloys. It has been demonstrated that the effect of alloying elements on the Ms temperature is strongly dependent upon the influence of the alloying element on the thermodynamic properties of the y and a phases. Notwithstanding the fact that alloying elements affect the Ms temperature by changing the lattice parameters, elastic constants, and inter-facial energies of the a and y phases, their primary role is a thermodynamic one. Thermodynamic analyses have been presented for the iron-carbon'-4 and iron-nickele systems in which equations are derived for Fa and FY, the free energies of the b.c.c. (or b.c.t.) and f.c.c. phases. These equations, which can be obtained with the aid of the equilibrium diagrams, can be used to help predict the Ms vs composition curves. This paper deals with a calculation of the thermodynamic properties necessary to compute AFffLY for iron-chromium alloys. In view of the lack of direct information concerning the activity of chromium in the a and y phases of iron, the regular solution approximationa,g was utilized to bridge the gap. After the necessary equations were derived for the iron-chromium system they were used to calculate AFff— Y for stainless steels by combining them with the previous results obtained for iron-nickel alloys. The results of these calculations offer a means of rationalizing the anomalous behavior of chromium in iron-base alloys. The latter depends on the regular solution approximation in contrast to the explanation offered by zener , which is based upon the "magnetic specific heat effect." THERMODYNAMICS OF THE IRON-CHROMIUM SYSTEM If y represents the atomic fraction of chromium in an iron-chromium alloy, then the free energy of the b.c.c. phase Fa, the f.c.c. phase FY, and the difference in free energy between the f.c.c. and b.c.c. phases of the same composition are given through [3] and Fmy represent the free energies of mixing of the a and y phases; while @era -' and uFea 4Y represent the difference in free energy between f.c.c. and b.c.c. chromium and iron respectively. The values of AEFe0ff4Y in the temperature range between 0" and 900K ( .

Jan 1, 1960

By Irving Cadoff, Jack Medoff

THE linear thermal expansions of oriented single crystals of zinc were measured in the range from 20" to 416°C using a Leitz HTV optical lever differential dilatometer. The single crystals, supplied by Dr. J. J. Gilman, General Electric Research Laboratory, Schenectady, N.Y., were prepared from 99.999 pct-purity zinc, and were in the form of rods approximately 2 in. long by 0.15 in. in diameter having the following orientations: x = 1.5, 12, 20, 30, 37.5, 49, 60, 73, and 82 deg where x is the angle between the specimen axis and the (0001) plane of the crystal. From the family of expansion vs temperature curves, the instantaneous expansion coefficients were calculated at 100°C intervals, and Fig. 1 shows a plot of these derived coefficients for each orientation. Coefficients were obtained from the raw data using the chord-slope method. The curves in Fig. 1 indicate a positive temperature coefficient for low x, a negative temperature coefficient for high X, and an expansion coefficient invariant with temperature, amounting to about 43 x 106, for a crystal orientation of approximately 52 deg. From the available data, it is possible to arrive at the values for the axial thermal-expansion coef- ficients a, and a, by extrapolating the curve of the expansion coefficient vs orientation to zero and 90 deg orientations. More precise values for a, and a, are obtained if the instantaneous coefficients are plotted against the square of the cosine of the orientation angle, as shown in Fig. 2. The extrapolated terminal points of the best straight line through the data points of such a plot define the axial coefficients at that temperature. The theoretical justification for the linearity of this curve comes from inspection of a rearranged form of the general anisotropic equation for expansion: ax=a, + (a, -a,)cosZx [1I in which a, is the expansion coefficient in the "c" or [0001] direction and a, the expansion coefficient in the "a" or [ll50] direction. From Fig. 2, the axial coefficients at 100°C, for example, were found to be a, = 13.9 x 10'6 and a, = 62.4 x 10"6 per "C. In the same way, the coefficients were determined for 20", 200°, 300°, and 400°C. This data is summarized in Fig. 3. It is of interest to observe the common intersection of the curves in Fig. 3, which seems to bear out the earlier observation, from Fig. 1, of a

Jan 1, 1964

By C. W. Volek, J. E. Chappelear

The injection of a hot liquid into initially cool porous media, saturated with the same liquid and surrounded by two impermeable but heat conducting media (cap and base rock), has been studied both experimentally and theoretically. The temperature dependence of the viscosity was included in the theoretical model, but it was assumed that the specilic heats and densities of the various materials were independent of the temperature. Solutions to the theoretical model were approximated by numerical methods. Both theoretical and experimental results indicate that center-line temperatures are significantly higher than boundary temperatures. Comparison of experimental and theoretical results with a cold/hot viscosity ratio 01 19:1 were in reasonable agreement. Theoretical calculations show that the effect of the temperature dependence of viscosity was very significant at ratios of 100:l to 1000:1, which are typical of those that occur when injecting hot water to flood heavy oil reservoirs. INTRODUCTION We consider the problem of prediction of fluid flow and temperature distribution in an initially cold-fluid-filled reservoir on the injection of the same hot liquid by the use of mathematical and physical models. The results reported are for a two-dimensional rectangular section of the reservoir, as shown in Fig. 1. The injection and withdrawal faces are assumed to be equipotentials for fluid flow. The ultimate purpose of such models would be to predict hot-water injection performance. However, we note that in the work presented here, one of the most significant aspects of the problem — the instabilities resulting from two-phase, water and oil flow — is not included. We will not give a historical review, but refer instead to the paper of Spillette and Nielsen,1 which contains a rather complete bibliography and critical discussion. The physical problem is exactly the same as Spillette and Nielsen, except for certain simplifications in our assumptions. The mathematical details are somewhat different, and we will present the details of our method here. The mass flow equation, which is elliptic in character, is handled by successive overrelaxation. The heat flow equation, which is parabolic in character, is handled by a straightforward explicit approximation. Some difficulty arose in the over-all heat balance due to small errors in the solution of the mass flow equation, and we feel that a different formulation of the heat flow equation would be desirable for future work. In addition to the mathematical solutions for the temperature distributions in a porous medium due to the injection of hot liquids, experimental data are presented to check the validity of these solutions. A schematic diagram of the model is shown in Fig. 2. Certain qualitative physical conclusions were obtained from our numerical and experimental results. These are: 1. Assuming high (infinite) conductivity normal to the bedding plane in the reservoir is a poor approximation, and may lead to overestimates of the total heat losses (to cap and base rock) of as much as 50 percent. 2. More heat is retained in the reservoir (per unit of heat injected) for higher viscosity changes. 3. Any particular temperature isotherm moves more rapidly along the center line for higher viscosity changes. Consequently, the approximation of temperature independent viscosity is not suitable for obtaining quantitatively correct results. MATHEMATICAL MODEL Our mathematical model is that of a reservoir of thickness 2h. The problem is idealized from that of a linear hot-water drive, and we imagine that the input face is sufficiently far away from the injection wells that the stream lines enter it normally. Similarly the production wells are far enough from the outflow face that the flow lines leave it normally. The reservoir and surrounding cap and base rock

Jan 1, 1970

By C. A. Zapffe

BOTH the foundryman and the theoretical metallurgist are now generally agreed that the anomalous "rising" or "bleeding" of certain ferrous castings of killed metal is primarily attributable to hydrogen. How and why the phenomenon occurs, however, have not been made clear. The following discussion is intended to harmonize foundry experience with metallurgical theory so that the foundryman may possibly improve his ability to prognosticate whether a certain casting may bleed or not. BLEEDING, RISING, AND PIPING The "rising" to be discussed here is not to be confused with the action in rimming ingots as a result of the carbon-oxygen reaction, although a conclusion will be drawn that may apply to the art of controlling the rimming action. Only killed metal is considered, which includes both steels and irons. In Fig. I, three killed, chill-cast ingots are shown: a porous ingot whose evolution of gas during late stages of solidification has ejected metal through the top; an ingot in which moderate gas evolution during solidification has lifted the mushy central metal, i.e., it has "risen"; and, third, a sound ingot with good piping characteristics. The first type is referred to as "bleeding," and generally infers that a solid skin had first formed through which the liquid metal later erupted. There is no fundamental distinction between bleeding and rising in reference to killed metal.* POROSITY Hydrogen appears as a cause of bleeding because the gas evolution simultaneously leaves a porosity of a type traceable to hydrogen. Twenty years ago, Melmoth1 noted that killed steel that rose unexpectedly in the mold, if returned while liquid to the furnace and heated further under a reducing lime slag, would again rise in the mold; but that if the ingot were allowed to solidify and was then remelted no rising occurred. A critical quantity of the responsible gas is therefore removed by the rising action. Melmoth associated rising with high silicon (0.7 to 0.9 per cent) and concluded that silicon increased gas absorption. Because silicon is a strong deoxidizer, oxygen must, therefore, be eliminated from consideration of the three common gases in steel-oxygen, nitrogen, and hydrogen. Butterworth2 later decided that pinhole porosity was caused by gases dissolved in the metal and that hydrogen was obtained from steam in the mold. Allen's classical work on copper castings,3 soon followed by

Jan 1, 1942

By Roger C. Malan

The Monument Valley and White Canyon districts are in northeastern Arizona and southeastern Utah. Exploration and mining for uranium has been conducted in these districts since the late 1940's. In July 1965, ore reserves plus ore production at 174 properties were approximately 3.3 million tons of ore containing about 19 million pounds U3O8, of which about 10 per cent remained in reserves. The two largest mines, Monument No. 2 and Happy Jack, together account for about 45 per cent of the sum of production and reserves. Approximately half the deposits in these districts contain less than 1000 tons of ore. Nearly 5000 feet of Permian, Triassic, and Jurassic sedimentary rocks, mainly continental in origin, are exposed in these districts. All the important uranium deposits are in the Shinarump, the basal member of the Chinle Formation of Triassic age. The Shinarump lies on a widespread unconformity. It is composed of fluvial sediments, generally less than 100 feet thick, that were deposited by streams flowing from a source to the south. Most of the deposits are in an arcuate belt, convex to the west. This belt, 3 to 12 miles wide, extends from Monument Valley northward nearly 130 miles. It is along the western flank of the ancient Monument Valley-Monticello upland, an area that was slightly uplifted at the beginning and again at the end of deposition of the Shinarump. Erosion and subsequent reworking of the Shinarump sediments in the vicinity of this upland are postulated to have made possible the transportation, in solution, of the uranium contained in these sediments. The soluble uranium probably was carried by migrating ground water into sites favorable for precipitation in Shinarump beds bordering the upland. Thus, the original very small amounts of dispersed uranium in the early Shinarump sediments were accreted in the favorable belt where the accumulations of carbonaceous plant remains and their decay products provided a persistent reducing environment.

Jan 1, 1968

By F. V. Hicks

THE similarity of mining practices in bituminous coal fields through-out America is due to the fact that certain fundamental conditions are encountered in all fields. The problems of labor, housing and mining are somewhat similar whether the mine is in Pennsylvania, Illinois, Wyoming or the State of Washington. Each field has had its particular problems, resulting in advantages or disadvantages over a competing field. This might take the form of a wage differential, a better natural condition more favorable to cheap production, or proximity to a market that allows freight rate advantages, etc. In any event, no matter how favorably situated, the mining companies that have been slow to recog-nize and accept the advantage of mechanization, clinging too long to the old hand methods, have found themselves unable to meet competition. Throughout the Wyoming coal fields, production methods have so changed in the last decade as to be almost unrecognizable to an old-time coal miner who has had no connection with the industry during; that period. The old contract system, with its peculiar labor relationship between employer and employee, based upon the long-established custom that the miner's working place was his castle, and that it was his privilege to carry on operations within that place largely in his own way and to his own liking, is a condition that has passed away. The present-day, 100 per cent mechanized mine bears but little resemblance to the old. A change -in system has naturally altered the old-time labor relationship. Contract labor has been almost entirely eliminated and a straight day-wage basis established, with certain classes of work calling for different rates, which places the entire personnel of the underground operating force more directly under the direction and supervision of the mine foreman and his assistants. The transition from the old order to the new has gradually done away with the system of penalties, personal- rights and privileges existing under the contract system, which were so controversial in the past that the average mine management was constantly involved in labor disputes in fields where organized labor was employed.

Jan 1, 1936

By E. H. Burdick

THE difficulties inherent in table concentration operations as applied to gold, silver, lead and zinc ores, are accentuated in the scheelite mill, which has a flowsheet that is similar in general principles. The narrow "spread" in the specific gravity between scheelite and the usual gangue in which it occurs often makes its clean separation extremely difficult and in some cases impracticable. The problem is further complicated by the extreme friability of the mineral and its inordinate tendency to "slime," particularly where fine grinding is necessary and wet grinding methods are employed. The physical aspect of the occurrence of scheelite in the ores, the kind and character of the rock in which the mineral is present, its hardness, friability and the specific gravity of its constituents, as well as like characteristics of the associated minerals-pyrite, pyrrhotite, sphalerite, and others, all have a bearing on the successful milling of crude ores and the production of a concentrate that is marketable with minimum price penalty or none at all. Most tungsten deposits are considered low grade when the limiting factor of low percentage recovery by gravity methods is borne in mind. The great majority of deposits developed or in process of development carry from 0.4 to 1.0 per cent tungstic oxide. Ore carrying I per cent is considered good grade; 0.7 to 0.8 per cent, fair, and below that figure, low grade. Steady mill feed averaging upward of 1.0 per cent W03 is exceptional. Inasmuch as buying specifications demand a 60 per cent W03 content, the mineral content of the ores as mined must be concentrated to at least that degree. A few companies have constructed chemical plants for the treatment of their complex concentrates and low-grade flotation product, but the smaller operator must rely on table concentration, borrowing the tools and to a large extent the methods of his predecessors in the gold, silver, lead and zinc mills. Whether these are the best tools and methods that can be devised is an open question. Except in rare instances, table concentration, however carefully conducted, does not yield a satisfactory final recovery of the mineral content in headings as indicated by chemical determinations of tungstic oxide content. A saving of 60 to 65 per cent is considered fair, and an average 80 per cent recovery, exceptional. Each scheelite ore body is a separate problem. Details of handling that give best results in one case may not be successfully operative at a property on the same contact zone and but a short distance removed. Supplementary treatment of tailings by flotation may be successful in producing a low-grade concentrate of around 15 per cent WO3, which is adapted to further treatment chemically at a given property and entirely unsuccessful at another. This problem constitutes another of the unanswered questions. The following paragraphs relate solely to the beneficiation of scheelite ores by table concentration and supplementary methods.

Jan 1, 1942

By E. H. Burdick

THE difficulties inherent in table concentration operations as applied to gold, silver, lead and zinc ores, are accentuated in the scheelite mill, which has a flowsheet that is similar in general principles. The narrow "spread" in the specific gravity between scheelite and the usual gangue in which it occurs often makes its clean separation extremely difficult and in some cases impracticable. The problem is further complicated by the extreme friability of the mineral and its inordinate tendency to "slime," particularly where fine grinding is necessary and wet grinding methods are employed. The physical aspect of the occurrence of scheelite in the ores, the kind and character of the rock in which the mineral is present, its hardness, friability and the specific gravity of its constituents, as well as like characteristics of the associated mineral-spyrite, pyrrhotite, sphalerite, and others, all have a bearing on the successful milling of crude ores and the production of a concentrate that is marketable with minimum price penalty or none at all. Most tungsten deposits are considered low grade when the limiting factor of low percentage recovery by gravity methods is borne in mind. The great majority of deposits developed or in process of development carry from 0.4 to 1.0 per cent tungstic oxide. Ore carrying 1 per cent is considered good grade; 0.7 to o.8 per cent, fair, and below that figure, low grade. Steady mill feed averaging upward of 1.0 per cent WO3 is exceptional. Inasmuch as buying specifications demand a 60 per cent WO3 content, the mineral content of the ores as mined must be concentrated to at least that degree. A few companies have constructed chemical plants for the treatment of their complex concentrates and low-grade flotation product, but the smaller operator must rely on table concentration, borrowing the tools and to a large extent the methods of his predecessors in the gold, silver, lead and zinc mills. Whether these are the best tools and methods that can be devised is an open question. Except in rare instances, table concentration, however carefully conducted, does not yield a satisfactory final recovery of the mineral content in headings as indicated by chemical determinations of tungstic oxide content. A saving of 6o to 65 per cent is considered fair, and an average 80 per cent recovery, exceptional. Each scheelite ore body is a separate problem. Details of handling that give best results in one case may not be successfully operative at a property on the same contact zone and but a short distance removed. Supplementary treatment of tailings by flotation may be successful in producing a low-grade concentrate of around 15 per cent W03, which is adapted to further treatment chemically at a given property and entirely unsuccessful at another. This problem constitutes another of the unanswered questions. The following paragraphs relate solely to the beneficiation of scheelite ores by table concentration and supplementary methods.

Jan 1, 1942

By Thomas Crowe

Much has been written upon the precipitation of metals from cya-nide solution by zinc. We often read of the many factors that influence precipitation, such as zinc surface, purity of zinc, percentage of lead, temperature of solutions, strength of solutions in cyanide or alkali, etc. Little do we hear, however, of the part that oxygen plays in precipitation. Caldecott1 says: "As the dissolving of gold is essentially an oxidation process, so its precipitation is one of reduction." All who have studied or worked with cyanide solutions will agree that Caldecott's statement is true. In the cyanide work in the mills of the Portland Gold Mining. Co., we have always found oxygen to be the greatest enemy to precipitation. OXYGEN ANTAGONISTIC TO GOOD PRECIPITATION A few years ago, while making some experiments on the effect of pressure upon the dissolving rate of gold front our ores, to prove a point, I made some bottle tests under vacuum. The results were surprising, and showed that under vacuum practically no gold dissolved, which confirmed my belief that Elsner's equation was true and also led me to investigate the amount of dissolved air carried by solutions at atmos-pheric pressure. The experiment consisted in partly filling an acid-bottle with mill-solution and connecting it by a rubber hose to a vacuum pump. When the vacuum was suddenly applied, a cloud composed of. thousands of small air bubbles rose out of the solution, showing qualitatveily the . amount of dissolved air that was contained in the solution, and also proving that the relief of atmospheric pressure on the solution permitted this dissolved air to escape.

Jan 8, 1918

By P. D. White, J. T. Moss, J. S. McNiel

Results of experimental work on the in situ combustion process were first published in this country in 1953' when Kuhn and Koch described results of a three-well test in Jefferson County, Okla. Shortly there-after Grant and Szasz2 described field studies in Nowata County, Okla., in which several modifications of the basic combustion process were investigated by injection of various oxidizing gas mixtures other than air. In the past five years speculation concerning this method of oil recovery has continued, with a number of interesting papers on various aspects of in situ combustion appearing in the literature3,4,5,6,7. However, only one of these' provided actual engineering information on pattern-type field experiments. The primary objectives of the Oklahoma three-well test were to check operation of specially designed electrical ignition equipment and evaluate problems associated with initiation of combustion in a natural oil sand reservoir. Immediately following successful completion of this test in the Pontotoc sand, plans were activated for a second field experiment to be conducted in the same sand a short distance away. The objective of this second field test1 as to establish a relationship between field observations and information derived from laboratory experimentation and computations. Secondary objectives of the test were to develop operating tech- niques and define operating problems, and to obtain information that would assist in the economic and engineering appraisals of the process. Careful planning was required since this test was designed with the hope of providing basic information on the characteristics and operation of a combustion drive. It was necessary to include test facilities which would not only permit precise control and measurement of the process variables but would also provide sufficient flexibility of control to insure that variables in the combustion process could be studied during the course of the test under a wide range of conditions. In order to accomplish these objectives elaborate instrumentation and several control wells were included in the design of the test installation. This type installation was felt to be well suited for an experimental study, but was in no respect intended as a counterpart of a commercial-scale operation. PRELIMINARY LABORATORY WORK An important objective of the field experiment, as stated previously, has been to obtain reliable data on operating variables which might be compared with similar data obtained in laboratory combustion tests. The value of successful correlations between quantities that can be measured in the laboratory and those obtained in a full-scale commercial venture has been well established for other industrial processes. The difficulty of following a process underground should make such correlations even more essential here. Also. approaching the field test phase of development of in situ combustion, it was considered desirable to precede design of test equipment with laboratory combustion studies under a variety of conditions to establish likely ranges of variables. These included temperature, air injection rate, frontal advance rate and produced gas composition.

By P. J. Spencer, J. N. Pratt

The vapor pressure of manganese over liquid Mn-Sn alloys has been determined by a high-temperature torsion-effusion technique. Alloys containing from 8 to 100 at. pct Mn were investigated in the temperature range jrom 1280" to 1580" and the measured pressure values were used to calculate the partial and integral thermodynamic properties of the liquid alloys. The activities show small negative departures from ideality while the integral heats and excess entropies of mixing are asymmetric inform, changing from positive to negative with increasing manganese content. The possible contribution of various factors to the observed thermodynamic properties is discussed. COMPARATIVELY few thermodynamic data are available for manganese alloy systems.' Therefore, as part of a continuing program of studies of the thermodynamic properties of transition metal alloys, measurements have been made on various binary alloys involving this element. In recent publications,2~3 investigations of liquid Mn-Cu alloys and of the Mn-Au system in both solid and liquid states have been reported. For the first-mentioned system the work suggested that magnetic interactions may be responsible for the observed form of the thermodynamic properties, while in the second the influence of the electrochemical factor appears to be dominant. The present paper describes a similar study of liquid Mn-Sn alloys. Again the thermodynamic properties have been obtained from vapor pressure measurements made by use of a high-temperature torsion-effusion technique.4 A detailed description of the apparatus and of the experimental procedures used in alloy preparation and pressure measurement may be found elsewhere.2'4 EXPERIMENTAL RESULTS Sixteen alloys, ranging in composition from 8 to 100 at. pct Mn, were prepared from spectroscopically standardized manganese of 99.99 pct purity and tin of 99.999 pct purity, both supplied by Johnson-Matthey and Co., Ltd. One-gram samples of the alloys were obtained by carefully weighing appropriate amounts of the pure components into an effusion cell; this was then suspended in the apparatus and the metals melted together in situ by heating under vacuum to approximately 1550°K. After allowing sufficient time for a homogeneous liquid alloy to be formed, vapor pressure measurements were commenced. These were determined as rapidly as possible at a series of steady temperatures within the range of interest. The duration of experimental runs on individual samples was kept sufficiently short to ensure insignificant varia- tion of alloy composition during investigation. After completing pressure measurements, the alloys were rapidly cooled and their compositions checked by weighing or chemical analysis. All experiments were conducted using effusion cells machined entirely from boron nitride. Measurements were made using a variety of cells with orifice areas ranging from 0.0032 to 0.0075 sq cm and lengths of the order of 0.04 cm; the usual effusion correction factors for orifice geometry and molecular distribution were calculated using Freeman and Searcy's equation5 and had values between 0.6 and 0.75 for the orifices employed here. The vapor pressures of manganese over the alloys were measured at approximately 20°K intervals in the temperature range 1280" to 1580°K. In view of the close approximation of the measured pressures to Clausius-Clapeyron behavior in the experimental temperature range, the data for each alloy have been expressed by equations of the form: logp(atm) =-A/T + B A least-squares computer treatment was applied to the vapor pressure values in order to obtain the coefficients A and B with their associated error. The resulting equations are listed in Table I, together with the equation for pure solid manganese obtained from a previous study.4 To minimize the effect of possible apparatus calibration errors, the activities and partial free energies of manganese in the alloys were calculated by initial reference to the latter equation, obtained from identical torsion-effusion measurements. The immediately resulting thermodynamic quantities, based on a solid manganese reference state, were then converted to refer to the more appropriate supercooled pure liquid manganese standard; tabulated values of the free energies of solid and liquid manganese from Hultgren et al.' were used for this purpose. Partial entropies of solution of manganese were calculated from the temperature coefficients of the free energies and partial heats from the Gibbs-Helmholtz relationship.

Jan 1, 1969

By E. H. Burdick

The difficulties inherent in table concentration operations as applied to gold, silver, lead and zinc ores, are accentuated in the scheelite mill, which has a flowsheet that is similar in general principles. The narrow "spread" in the specific gravity between scheelite and the usual gangue in which it occurs often makes its clean separation extremely difficult and in some cases impracticable. The problem is further complicated by the extreme friability of the mineral and its inordinate tendency to "slime," particularly where fine grinding is necessary and wet grinding methods are employed. The physical aspect of the occurrence of scheelite in the ores, the kind and character of the rock in which the mineral is present, its hardness, friability and the specific gravity of its constituents, as well as like characteristics of the associated minerals— pyrite, pyrrhotite, sphalerite, and others, all have a bearing on the successful milling of crude ores and the production of a concentrate that is marketable with minimum price penalty or none at all. Most tungsten deposits are considered low grade when the limiting factor of low percentage recovery by gravity methods is borne in mind. The great majority of deposits developed or in process of development carry from 0.4 to 1.0 per cent tungstic oxide. Ore carrying I per cent is considered good grade; 0.7 to 0.8 per cent, fair, and below that figure, low grade. Steady mill feed averaging upward of I .o per cent WO3 is exceptional. Inasmuch as buying specifications demand a 60 per cent W03 content, the mineral content of the ores as mined must be concentrated to at least that degree. A few companies have constructed chemical plants for the treatment of their complex concentrates and low-grade flotation product, but the smaller operator must rely on table concentration, borrowing the tools and to a large extent the methods of his predecessors in the gold, silver, lead and zinc mills. Whether these are the best tools and methods that can be devised is an open question. Except in rare instances, table concentration, however carefully conducted, does not yield a satisfactory final recovery of the mineral content in headings as indicated by chemical determinations of tungstic oxide content. A saving of 60 to 65 per cent is considered fair, and an average 80 per cent recovery, exceptional. Each scheelite ore body is a separate problem. Details of handling that give best results in one case may not be successfully operative at a property on the same contact zone and but a short distance removed. Supplementary treatment of tailings by flotation may be successful in producing a low-grade concentrate of around 15 per cent W03, which is adapted to further treatment chemically at a given property and entirely unsuccessful at another. This problem constitutes another of the unanswered questions. The following paragraphs relate solely to the beneficiation of scheelite ores by table concentration and supplementary methods.

Jan 1, 1943

By E. H. Burdick

The difficulties inherent in table concentration operations as applied to gold, silver, lead and zinc ores, are accentuated in the scheelite mill, which has a flowsheet that is similar in general principles. The narrow "spread" in the specific gravity between scheelite and the usual gangue in which it occurs often makes its clean separation extremely difficult and in some cases impracticable. The problem is further complicated by the extreme friability of the mineral and its inordinate tendency to "slime," particularly where fine grinding is necessary and wet grinding methods are employed. The physical aspect of the occurrence of scheelite in the ores, the kind and character of the rock in which the mineral is present, its hardness, friability and the specific gravity of its constituents, as well as like characteristics of the associated minerals— pyrite, pyrrhotite, sphalerite, and others, all have a bearing on the successful milling of crude ores and the production of a concentrate that is marketable with minimum price penalty or none at all. Most tungsten deposits are considered low grade when the limiting factor of low percentage recovery by gravity methods is borne in mind. The great majority of deposits developed or in process of development carry from 0.4 to 1.0 per cent tungstic oxide. Ore carrying I per cent is considered good grade; 0.7 to 0.8 per cent, fair, and below that figure, low grade. Steady mill feed averaging upward of I .o per cent WO3 is exceptional. Inasmuch as buying specifications demand a 60 per cent W03 content, the mineral content of the ores as mined must be concentrated to at least that degree. A few companies have constructed chemical plants for the treatment of their complex concentrates and low-grade flotation product, but the smaller operator must rely on table concentration, borrowing the tools and to a large extent the methods of his predecessors in the gold, silver, lead and zinc mills. Whether these are the best tools and methods that can be devised is an open question. Except in rare instances, table concentration, however carefully conducted, does not yield a satisfactory final recovery of the mineral content in headings as indicated by chemical determinations of tungstic oxide content. A saving of 60 to 65 per cent is considered fair, and an average 80 per cent recovery, exceptional. Each scheelite ore body is a separate problem. Details of handling that give best results in one case may not be successfully operative at a property on the same contact zone and but a short distance removed. Supplementary treatment of tailings by flotation may be successful in producing a low-grade concentrate of around 15 per cent W03, which is adapted to further treatment chemically at a given property and entirely unsuccessful at another. This problem constitutes another of the unanswered questions. The following paragraphs relate solely to the beneficiation of scheelite ores by table concentration and supplementary methods.

Jan 1, 1943

By David Segura

THE Huitzuco mercury deposits have been described by C. W. Vaupell,1 therefore the general information such as location, history, production, etc. will not be repeated here. The present owners acquired the property when the deep levels of the Cruz mine were flooded, and it was believed that a relatively large tonnage of low-grade ore and fills would be encountered in the flooded section, because f the early mining methods used in the Cruz mine. The mine was partly unwatered and about 187,000 tons of fills was pit-sampled in the San Cayetano stope. These fills average 2.4 kg. Hg per. ton. During the period of maximum production at Huitzuco, the ores were sorted in the mine and cobbed into 3-in. pieces, which were treated in Scott furnaces. Large pieces of raw ore are found in the sinter, and it is indicated that both recovery and, costs were not very satisfactory. Recent practice has been to treat the ores in closed retorts made of 10-in. pipes. Because f the presence of combined antimony in the mineral livingstonite (HgS.2Sb2S3) and considerable native sulphur, little or no metallic mercury is recovered in the condensers and a second retorting of the condenser muds is-necessary. This makes the treatment of the ores expensive and tends to low recoveries of mercury. The prin-cipal costs of retorting are, in their relative order: (1) fuel, (2) low recov-ery of mercury, (3) replacement of retort pipes, (4) labor.

Jan 1, 1938

By J. E. Dutrizac, R. J. C. MacDonald, T. R. lngraham

When sintered disks of synthetic chalcopyrite (CuFeS2) were leached in acidified aqueous solutions of ferric sulfate, the following reaction stoichiometry was obtained: CuFeS2 + 2Fe2(SO4)3 = CuSO4 + 5FeSO4 + 2S Over the temperature range from 50º to 94ºC, the reaction displayed parabolic kinetics. The parabolic rate constant for the dissolution of copper is given by the equation: log.k(mg2/cm4-hr)= 11.850 - 3780/T The activation energy for the dissolution process is 17 ± 3 kcal per mole. The parabolic kinetics have been attributed to the progressive thickening of a sulfur film on the surface of the chalcopyrite. When the leaching solutions contain less than 0.01 molar Fe+3 , the Fe concentration influences the rate of leaching, probably through a mechanism involving the diffusion of ferric sulfate through the sulfur layer. At higher Fe+3 concentrations, the rate control in the leaching. reaction has been attributed to the diffusion of ferrous sulfate through the sulfur. The rate of reaction is insensitive to changes in acid concentration and in disk rotation speed. ThE reaction of acidic ferric sulfate solutions with various sulfide minerals is of practical interest for both bacterial and heap leaching. This leaching medium is generally used with low-grade ores that cannot be treated profitably by conventional means. In both bacterial leaching1-3 and heap leaching, the active agent for sulfide dissolution is ferric sulfate. Although the reactions of ferric sulfate with chalcocite, covellite, and bornite have been investigated,4*7 the kinetics of leaching chalcopyrite with ferric sulfate have not been thoroughly studied. This paper reports a study of that reaction. EXPERIMENTAL Reagent-grade sulfur was purified by the method of Bacon and FanelliB and then it was vacuum-distilled to remove any soluble magnesium salts that had been introduced during the purification procedure.9 From stoichiometric quantities of the purified sulfur and hydrogen-reduced electrolytic copper sheet (99.90 pct Cu), CuS was synthesized at 450°C in a vacuum-sealed, pyrex vessel. About 24 hr was required for the completion of the reaction. A similar procedure involving hydrogen-reduced iron wire (99.90 pct Fe) was used to synthesize FeS1.002. A 2-furnace arrangement was required. The iron was heated to 800°C while the sulfur was maintained at about 400°C. Although the reaction to consume the sulfur was rapid, the material required additional heating (1 week) in a sealed silica ampoule at 800°C before it was homogenized. X-ray powder diffraction analysis confirmed that the copper sulfide was covellite and that the iron sulfide was troilite. The composition of the iron mineral was confirmed by wet chemical analysis. The two sulfides were ground to minus 100 mesh, weighed in equimolar amounts, mixed thoroughly, and pressed into pellets at 80,000 psi. The pellets were vacuum-sealed in pyrex ampoules and then sintered for 3 days at 550°C after an initial heating at 450°C for a few hours. The pellets were then cooled, polished with 3/0 emery paper, rinsed in acetone, and stored. The material had the characteristic brassy color of chalcopyrite and was shown by X-ray diffraction to be CuFeS2. Microscopic examination of the polished surfaces revealed small inclusions of pyrite (approximately 0.5 vol pct) as the only impurity. The presence of small amounts of a second iron compound will not alter the amount of dissolved copper but might increase the amount of ferrous ion slightly. It was calculated that dissolution of all of the pyrite and 100 mg of Cu (a typical value) would change the expected ferrous concentration by only 4 pct. Microscopic examination of a pellet after leaching revealed that the pyrite was not preferentially solubilized; only those pyrite grains at the surface were attacked. Hence, the pyrite is unlikely to alter the rate of copper dissolution. The chalcopyrite disks were about 1.7 mm thick and 27 mm in diam. They were about 80 pct of theoretical density, and for this reason their true reaction area was somewhat larger than the 5.8 sq cm area presented by the polished face. The disks were cemented to lucite cylinders in such a way that only the polished face was exposed. The disks were then leached by methods previously described.6,7 RESULTS AND DISCUSSION Stoichiometry and Kinetics. The initial experiments were directed to the problem of resolving the stoichiometry of the leaching reaction. Disks of CuFeS2 were leached at 80°C for various periods of time in acidified ferric sulfate solutions that were protected from oxidation by a cover of flowing nitrogen. When the disks had been partly leached, they were removed, their soluble salts were washed out, and then they were treated with CS2 in a Soxhlet extraction apparatus. The ratio of elemental sulfur to dissolved copper thus obtained was approximately 2 to 1. After the extraction of elemental sulfur from the pellet, the residue consisted of unreacted chalcopyrite only. For runs in which an appreciable amount of copper was dissolved, the ratio of ferrous ion to cupric ion in the solution was

Jan 1, 1970

By A. J. Mcintosh

PRICE changes in competing fuels in the last three decades have reflected the changes in the consuming habits of the people of the United States. Prior to World War 11 the importance of fuel oil and fuel gas increased almost constantly while the relative importance of both bituminous and anthracite coal decreased. During this same prewar period coal prices increased to a much greater extent than oil prices. In fact, in many years, oil prices declined and in most cases are now no higher than they were back in 1925-26. During the war natural economic trends were entirely upset because of the tremendous petroleum requirements of the Army and Navy. Under these conditions many industrial plants were converted to the use of coal and the new installations in home heating and industrial plants of all kinds which might have used oil were practically eliminated. Although petroleum prices were rigidly controlled by OPA coal prices increased several times during the war. An over-all statement as to the rela-

Jan 1, 1947