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By W. C. Schroeder

During the post-war period, and particularly during the past few years, coal production has been maintained at a reasonably constant level. This is in contrast to the greatly expanded demand for oil and natural gas. Certain markets for coal, such as the railroad and for home heating, have tended to decrease, but this decline has been offset by an increase in demand for other uses, particularly for electric power. Since the United States has very large reserves of coal and relatively limited reserves of natural gas and oil, from the conservation viewpoint, it would be better if the increased demand were to fall more heavily on coal. Where coal has lost certain markets, the decision has not always been made on the basis of price, and, in fact, in many instances, the markets have been lost where coal could show a price advantage. There are various reasons for this situation but it can be attributed in the main to the preference of certain consumers for the convenience offered by liquid and gaseous fuels. In the production of chemicals such as benzene, phenol, or ammonia, coal still plays an important role. As co-products from coke-oven operations, a wide variety of aromatic chemicals are available. In recent years, however, the production has not been sufficient to supply the demand, and it is not profitable to build coke ovens to make chemicals unless there is a market for the coke as well. As a result, the petroleum industry is beginning to take a stronger part in the production of aromatic chemicals. Natural gas has almost displaced the coke-oven water-gas machine for the production of hydrogen for the synthesis of ammonia, as well as for the synthesis of methyl alcohol and other oxygenated compounds. This information is not new and is given here only as a basis for the discussion of the broad significance of the development of the gasification process. It is clear that if coal is to regain some of its old fuel markets, as well as to maintain a position in the field of chemical synthesis, processes must be available for converting coal to the type of fuel the customer wants, and for a cheap method of furnishing gaseous raw material to the chemical industry. The operation of coke ovens and water-gas machines is not the answer to this problem for at least two important reasons: (1) the limited supply and relatively high price of good coking coals, and (2) the relatively high costs of the combined operations of coking and manufacture of water gas.

Jan 1, 1953

By R. C. Buehl, M. B. Royer

A three ton per day blast furnace using blast temperatures up to 2200°F was operated to recover manganese from open-hearth slag and manganiferous iron ore. The spiegel product containing 12 to 24 pct Mn was blown in a basic converter to high manganese oxide slag as described in the paper which follows this one. HE steel industry, which uses over 900,000 short tons of contained manganese yearly, depends on the maintenance of supplies of manganese from foreign sources such as India, Gold Coast, and Union of South Africa. Domestic ores furnish less than 10 pct of the yearly requirements of metallurgical ores and, unfortunately, the United States has no large, or even moderate, grade deposits that could supply a major portion of the requirements for many years. It may be necessary to obtain manganese from low grade materials, even though the cost is appreciably higher than when imported ores are used. An American Iron and Steel Institute questionnaire prepared in 1949 revealed the startling fact that open-hearth slags contained about as much manganese as is imported annually. The quantity of slag produced each year by integrated steel plants (not including cold-melt shops) and the manganese contained in the slag follows: Flush slag, 4,500,000 net tons a year containing 408,000 net tons Mn; tap slag, 7,230,000 net tons a year containing 364,000 net tons Mn; for a total of 772,000 net tons Mn. Some of this slag is returned to blast furnaces but about 75 pct would be available for the recovery of manganese. In several decades, when many of the present sources of high manganese ores have been depleted, open-hearth slag and manganiferous iron ore may become the major source of the manganese required for steel production. In 1948, manganese-ore imports from the U.S.S.R. were 427,000 net tons or 34 pct of the foreign ore. Imports from this source were only 81,000 tons in 1949. It became evident that adequate stockpiles of manganese could not be accumulated for many years. The Bureau of Mines initiated an extensive research program on methods for increasing domestic production of manganese and entered into a cooperative agreement with the American Iron and Steel Institute for recovering manganese from open-hearth slags whereby the Institute provided additional research funds and trained operating personnel. Description of Process and Equipment Numerous pyrometallurgical and hydrometallur-gical processes and combinations of the two can be applied to the recovery of manganese from open-hearth slag and manganiferous iron ore. The process being developed at the Pittsburgh Station of the Bureau of Mines consists of: 1—Reduction of open-hearth slag in a blast furnace to recover the iron and manganese as spiegel-eisen with 12 to 24 pct Mn. 2—Selective oxidation of the manganese from the blast-furnace metal in a basic-lined converter to produce a high manganese slag with up to 60 pct Mn content, which is a synthetic ore for the production of ferromanganese. This process has the advantage over other processes in that the equipment which would be used, such as blast furnaces and converters, has been highly

Jan 1, 1953

By J. Jones-Parra, J. C. Calhoun

INTRODUCTION The purpose of this paper is to present the results obtained by solving the fractional flow' and frontal advance' equations to obtain oil recovery at water breakthrough as a function of the length of the system being flooded, the linear velocity of injection and the displacing phase viscosity. The method of solution makes use of the stabilized zone concept first presented by Terwilliger, et al3 when calculating saturation distributions in a gravity drainage system. In order to check the calculated results, the equations and method of solution were applied to the system on which Rapoport and Leas' reported experimental data. METHOD OF SOLUTION The solution of the fractional flow equation and the frontal advance equation is obtained by assuming that a water front forms to sweep the oil out ahead of it. There is ample evidence that under the proper conditions a water 'front does form. If this water front is not to dissipate, the water saturations which comprise it must have equal linear velocities. These water saturations are said to comprise the stabilized zone. Equation (2) indicates that for all these saturations and hence fw must plot as a straight line against saturation for those water saturations comprising the stabilized zone. The water saturations lying between the highest in the stabilized zone and the highest that can be achieved in the porous medium comprise the variable zone. Regardless of the numerical value of the length of the system, the variable zone must eventually span all of it, so that for long enough systems in Equation (1) will be small enough to be neglected. Hence, for the saturations in the variable zone Equation (1) can be simplified to In order to determine the composite fw function applicable to the entire range of saturations in the porous medium, it is necessary to find the water saturation which separates the stabilized zone from the variable zone. This dividing saturation must be on the curve defined by Equation (4), and a tangent curve at that point must pass through the initial water saturation to satisfy Equation (3). Hence, the valid fw curve is given by a straight line starting at the initial water saturation, tangent to the curve of Equation (4): and along the curve of Equation (4) from the point of tangency on. The point of tangency determines the water saturation dividing the zones. The length and shape of the stabilized zone can be found by solving Equation (1) for Integrating this expression numerically between any two saturations in the stabilized zone gives the distance separating these two saturations. By repeated integration, the saturation distribution of the stabilized zone can be determined. The total length of the stabilized zone is given by The integral appearing in Equation (5) is a function of the viscosity ratio, the capillary properties of the rockfluid system, the relative permeabilities, and the initial water saturation. Considering these variables fixed and designating the value of the integral by writing caw for and v/60 for q/A; Equation (5) becomes The saturation distribution of the stabilized zone can be integrated over its length and divided by the length to obtain the average water saturation The volume of water in the stabilized zone is then given by The average water saturation in the variable zone can be found by extending the straight line segment of (the segment joining Sw and Sw) until it intersects fw = 1.00. The saturation at the intersection is. This method of finding is nothing more than the graphical solution of the equation The volume of water in the variable zone at breakthrough is then given by Assuming no initial water saturation, the recovery at breakthrough expressed as percent pore volume is given by

Jan 1, 1953

By Pol Duwez, Paul Pietrokowsky

Titanium and vanadium form a complete series of solid solutions at temperatures above 885°C. Below 885°C, vanadium is slightly soluble in a titanium (about 1.5 pct V at 650°C) and a two-phase a plus ß region extends to 18.5 pct V at 650°C. The alloys up to 15.0 pct V transform into a supersaturated a solid solution upon rapid cooling from the ß phase. Above 15 pct V the ß phase may be retained. The temperature at which the ß to a' martensite-type transformation takes place decreases steadily from 850°C for 0.5 pct V to 325°C for 12.7 pct V. IN the transition series of the periodic table, the six elements that have a body-centered cubic structure at all temperatures, namely chromium, vanadium, molybdenum, columbium, tungsten, and tantalum, fulfill the conditions required for the existence of complete series of solid solutions with the high temperature (ß) form of titanium. Up to the present time, complete solubility at temperatures above the a to ß transformation of titanium has been observed in the systems Ti-MO,1,2 Ti-Cb,2 Ti-W,³ and Ti-Ta.³ The two remaining elements, vanadium and chromium, have atomic diameters which are not as near that of titanium as the atomic diameters of the four other elements. Both are smaller than titanium and the difference, expressed in percentage of the titanium atomic diameter, is 12.3 pct for chromium and 8.2 pct for vanadium. On this basis, the least favorable conditions for solid-solution formation are therefore encountered in the Ti-Cr system. The early work on the Ti-Cr system4 revealed that up to about 1100°C the solubility of chromium in ß titanium is limited, and an intermetallic phase exists near the stoichiometric composition TiCr2. It was found later' that a continuous series of solid solutions extends across the diagram at higher temperatures, and TiCr2 forms by solid state reaction. It became apparent therefore that complete solubility would also be present in the Ti-V system. The present investigation confirms this possibility. The iodide-refined titanium used in this investigation was purchased from the New Jersey Zinc Co., New York. According to the manufacturer, a typical analysis of this product is 0.0065 pct Mn, 0.0022 pct Fe, 0.0015 pct Cu, and 0.0042 pct Pb. The Vickers hardness number (10 kg load) of the crystalline bar varies between 55 and 80. The vanadium metal was purchased from the Westinghouse Electric Corp., Lamp Div., Bloomfield, N. J. The purity of this metal is probably above 99 pct V. The oxygen content must have been quite low, since a bar about 1/4 in. square could be cold rolled into a ribbon 0.020 in. thick. To prepare the various alloys on the titanium-rich side of the diagram, the titanium rod was machined into cups 1 cm in diam and about 1.5 cm high. Pieces of vanadium, of the proper weight, were cut from the square bars and placed within the cups prior to melting. On the vanadium-rich end of the diagram, single pieces of the metals, in the proper weight pro-

Jan 1, 1953

By G. K. Manning, W. E. Few

T has been known for some time that both'inter-granular carbide and intergranular oxide phases cause brittleness in molybdenum. Parke and Ham' indicated that 0.0025 pct 0 present in molybdenum after solidification from the melt was sufficient to induce intergranular brittleness during forging. However, material containing 0.06 pct C could still be forged. However, adding this amount of carbon to insure deoxidation causes the formation of carbides on freezing. These carbides are precipitated at grain boundaries, and Rengstorff and Fischer' have shown they have an unfavorable effect on the room-temperature ductility of molybdenum. Take? in 1928 proposed that the solubility of carbon was a constant value of 0.30 pct from room temperature up to 1800°C. In 1935, Sykes, Van Horn, and Tucker' obtained X-ray data suggesting that the solid solubility of carbon in molybdenum was between 0.07 and 0.09 pct at temperatures from 1500" to 2100°C. The a-solubility line for carbon was included in the Mo-C diagram given in the Metals Handbook as a tentative line based on the data of Sykes, Van Horn, and Tucker. In order to determine the partial phase diagrams for these systems, it was necessary to construct a high-temperature furnace suitable for heat treating molybdenum at temperatures up to 4000°F. A molybdenum resistance furnace was built for this purpose in which samples could be heat treated in a purified atmosphere and quenched from any desired temperature.' Experimental Work Solubility of Carbon: Arc-cast molybdenum supplied by the Climax Molybdenum Co. and 18-gage molybdenum wire samples produced by powder metallurgy at the Fansteel Metallurgical Co. were used in determining the a-solubility line for the MO-C system. The cast molybdenum contained 0.032 pct C initially. Two lots of 18-gage wire were used, one containing 0.011 pct C and the other 0.005 pct C initially. All material contained a carbide phase as received. Fig. 1 illustrates the carbides found in the untreated material. Heat treatment in a purified hydrogen atmosphere was found to reduce the carbon content in the as-cast molybdenum. Purified argonT also decarburized molybdenum samples at temperatures above 3500°F; however, the carbon content remained constant during heat treatment in purified argon at lower tem- peratures. The argon was purified by passing it over titanium at 750 °C and then through a magnesium perchlorate drying tower. The hydrogen was purified by passing it through a commercial hydrogen deoxidizer, followed by a drying tower. Specimens having different initial carbon contents were heat treated in argon at 3500°F for periods ranging from 5 min to 5 hr and were analyzed for carbon. Samples of the same final carbon content had the same microstructures regardless of time at temperature. Furthermore, a gradient between center and surface in the amount of undissolved carbide particles present was never observed. It was concluded that at these low carbon levels, and at the high temperatures involved, diffusion proceeds so rapidly that the specimen is always substantially homogeneous in carbon content, in spite of the gradual loss in carbon. Based on the above findings, the following procedure was used to determine the carbon-solubility limit at 3000°, 3500°, and 4000°F. At each of these temperatures, a number of samples were heat treated, as shown in Table I, and rapidly cooled to room temperature. Since the samples lost carbon in proportion to the length of time heated, a series of samples were obtained of varying carbon contents. By use of a rapid cooling rate, the phases present at the high temperature were retained at room temperature. All samples were examined microscopically. Those found to contain either no excess carbide phase or only a very small amount were then analyzed for carbon. The samples actually analyzed for carbon

Jan 1, 1953

By Wesley A. Grosh

The Cuyuna range in central Minnesota has been the source of substantial tonnages of, manganiferous iron ores for almost four decades. To Increase the Nation's self-sufficiency in manganese reserves, the Bureau of Mines initiated a comprehensive investigative program to determine and develop the potential manganese reserves in the region. In the course of compiling all available information on the Cuyuna range, the Scallop-Todd lease appeared to be an area having favorable possibilities for developing substantial reserves of manganese. Early drilling on this lease indicated considerable tonnages of material relatively high in manganese. More recent drilling substantiated the size of the deposit but Indicated lower manganese values. However, beneficiation tests of samples obtained from the recent drilling indicated that the material was amenable to concentration.

Jan 1, 1953

By Charles Wert

THE diffusion and precipitation of carbon and nitrogen in a iron have previously been investigated using the internal friction as a measuring tool.' Most of this work has been done on rather pure iron; no effect was observed which would indicate that either of these phenomena is affected by the rather small amounts of impurity found in these samples of iron. Fastz observed, however, that both the diffusion rate and the aging properties of nitrogen in iron were sensibly changed by the addition of Vz pet Mn. The diffusion rate at a given temperature is reduced and the nucleation of nitrides is apparently changed somewhat. He observed no such changes for carbon in this alloy. Later Dijkstra and Sladek" extended these observations on nitrogen to other alloys of iron. They found that metals other than manganese also influence the behavior of nitrogen in iron; chromium, molybdenum and especially vanadium affect the diffusion and precipitation of nitrogen even more than manganese does. Their results have been verified in all essential details by this author, who finds in addition that small additions of nickel have about the same effect on the diffusion of nitrogen as the same amount of manganese. The present work was undertaken to study the effect on carbon in iron of these alloying elements. The alloys used had two sources. The material used as a "standard" (designated Fe in this paper) in the measurements was some iron supplied by J. K. Stanley, of Westinghouse Electric Corp., who reported 0.01 pct 0, as the only major impurity. He also made up an alloy of 0.26 pct Ni and one of 0.9 pct Mo using this same iron as a base. They were supplied by him in 2 lb billets, which were sawed into rods and cold formed into 0.030 in. wires for measurement. The alloys of chromium, manganese, and vanadium were prepared by the metallurgy section of the Institute for the Study of Metals, University of Chicago, by adding these metals in turn to vacuum melts of National Research Corp. iron. The small castings prepared in this way were also cold formed into 0.030 in. wires. After these wires had been prepared they were decarburized for 30 min at 730°C in wet Hz. After this treatment, no trace of carbon (as measured by internal friction) could be found. All specimens were then carburized for about 15 min at 710°C and water quenched. By this treatment the internal friction at 40°C was raised to a Q-' ~ 0.015. The diffusion of carbon in these alloys was studied by observing the shape and position of the internal friction peak at 0.9 cycles per sec. These measurements were made using a torsional pendulum in a manner described earlier.' The data are plotted in Fig. 1. It is seen that there is no apparent difference in internal friction between the various alloys. This is in marked distinction to the broadening and shift-

Jan 1, 1953

By A. L. Engel

This report is a compilation of results of preliminary concentration tests of seven manganese-ore samples. Six of the seven samples were submitted through the Mining Division, and 1 from Mexico was submitted by H. A. Doerner, formerly chief metallurgist, Region III. These investigations were made to assist development of mineral resources and particularly to aid economical exploitation of marginal or complex ores, from which strategic or critical minerals may be recovered.

Jan 1, 1953

By J. H. Kittel

THE properties of the metal molybdenum have been the subject of recent investigations1,2 = which have included studies of the changes that occur in the metal when it is annealed after having been cold worked. Most of the data which have been reported have pertained to only one aspect of annealing, that is, the conditions under which recrys-tallization has been observecl. The process of recovery which may precede recrystallization docs not appear to have been investigated, and it is the purpose of this note to report observations on the recovery process in cold-worked molybdenum as determined by changes ill the thermoelectric power which occur as the metal is annealed. The measurements were made on commercially pure molybdenum wires which, after annealing at 1035°C in dried hydrogen for 1 hr, were swaged to give a series of reductions up to a maximum of 84.5 pct. The variously cold-worked wires were then annea1c.d in dried hydrogen for periods of 16 hr at progrc:ssively highel. temperatures from 200" to 1000 c with a final annealing treatment of 70 hr at. 1100°C. After each annealing treatment the ther.ma1 emf's were determined against a length of original unwo~,ked material that had received the initial hydrogen anrit,aling treatment. The difference in temperature between the hot and cold junctions was maintained at about 75'C. and. the thermal emf's were measured with a potentiometer that could be read. to 0.01 microvolt. Fig. 1 shows the thermoelectric power. (dE/dT) in microvolts per C between annclalcd and cold-worked molybdenum as a function of the degree of cold work. The effect of annealing is shown in Fig. 2. The general shape of the curves in both figures is similar to results which have been obtained for copper." It was observed that after annealing at temperatures as low as 200°C recovery was well under way. The rapid changes irt thermoelectric power observed near 900 C are probably associated with recrystallization, since such a relation has been observed with copper. Beyond 900°C the thermal emf's changed in polarity. indicating that from this point or1 the specimens were more highly annealed than the standard. Annealing treatments could not be given at temperatures higher than 1100°C due to limitations of the furnace, and it is evident that, since equilibrium values of thermoelectric powers were far from having been attained, temperatures considerably higher are required to fully anneal molybdenum. References Robert M. Parke: Molybdenum, A New High-Temperature Material. Metal Progress (1951) 60, pp. 81-96. * R. A. Long, K. C. Dike, and H. R. Bear: Some Properties of High-Purity Sintered Wrought Molybdenum Metal at Temperatures up to 2400 °F. NACA TN 2319 (March 1951): G. W. Brindley: A Thern-io-Electric Study of the Cold-Rolling and Heat-Treatment of Copper, Report of a Conference on the Strength of Solids. Physical Society, London (1948) pp. 95-106.

Jan 1, 1953

By Bunting S. Crocker

DISCUSSION Fred C. Bond (Allis-Chalmers Manufacturing Co., Milwaukee)—This is a very complete description of the screened ore fine grinding installation at Lake Shore. The only important data which might be desired are the operating screen analyses and power consumption in each stage. The statement that the energy consumption, or kw-hr per ton, remains constant for all mill diameters is of great interest, but the opinion is widely held that the kw-hr per ton decreases as the mill diameter increases. More definite test work is needed to establish this point. Screened ore fine minding has been successful on hard Lake Shore ore &d on about equally hard South African Rand ore. However, it is still not determined whether it would be successful on ores of average or less than average hardness. It is possible that with softer ores the consumption of ore pebbles might be exceedingly high, or might even exceed the available supply. Also, the softer feed might result in a rapid buildup of harmful intermediate sizes in the mill circuit. These factors can be determined only by a full scale or long pilot mill test. In any case the Lake Shore staff is to be congratulated for this pioneering work. Bunting. S. Crocker (author's reply)—As requested, the operating screen analyses and Bower consumption for each of the four stages of pebble milling are given, see Table XII. The fist three stages are in series circuit; the last stage is in closed circuit. The primary circuit had rock feed averaging 124 g per piece and the final stages rock feed weighing 63 g. The intermediate stages had mixtures of the two. Regarding Mr. Bond's statement that "the opinion is widely held that the kw-hr per ton decreases as the mill diameter increases," I would say that I have frequently been told this but have never yet been shown any evidence or seen any evidence published that would prove this statement. It may be true that some of the big mills recently installed have mechanical power savers such as micarta bearings and better lubrication, but as far as the power consumed inside the mill is concerned, we at Lake Shore think that it varies as D2 .", and that is all. We published extensive information on this point in our 1939 paper. Recently Mr. Banks at Consolidated published the figures on his 10 ft 8 in. x 12 ft 0 in. rod mill. As reported in this discussion by the writer: we calculated the power necessary to run this mill based on our 7x6-ft rod mill to within 1 pct of the actual power reported by Mr.

Jan 1, 1953

By G. R. Speich, S. A. Kulin

The isothermal formation of martensite at subzero temperatures has been studied in an austenitic stainless steel. The amount of martensite formed isothermally in a given time was found to follow a C-curve behavior with decreasing temperature. Since isothermal rnartensitic transformation occurs at temperatures above the true M. temperature of the olloy, the observed M. temperature is dependent on the cooling rate. It is believed that a general martensite theory must include the basic concepts of the strain embryo theory, and also the important role of thermal fluctuations. UNTIL recently the isothermal component of the martensitic transformation had been considered as a trivial effect in theoretical considerations of this type of transformation. One of the postulates used in defining a martensitic transformation was that the reaction was temperature dependent but not time dependent. Cohen and his associates1'2 were the first to report the isothermal formation of mar-tensite. They obsel-ved the time dependency of the martensite reaction at room temperature in plain carbon steels and certain tool steels. They found that a small amount of additional transformation occurred after the specimen reached the quenching temperature and that the rate of this isothermal transformation decreased rapidly with time. These authors considered this phenomenon to be a "tailing-off" of the main athermal reaction. Kurdjumov and MaksimovaL 5 studied the isothermal formation of martensite at subatmospheric temperatures in steels containing 0.6 pct C-6 pct Mn, 1.6 pct C, and in an iron-base alloy containing 23 pct Ni and 3.4 pct Mn. In each case it was found that both the initial rate and the total amount of isothermal transformation exhibited sharp maxima with decreasing temperature. They stated that it was possible to completely suppress the martensitic transformation in the 0.6 pct C-6 pct Mn steel by drastic quenching in liquid nitrogen. They interpreted their results in terms of a thermally activated process. The maximum in the rate of nucleation vs. temperature curve was assumed to be a result of the temperature dependence of the rate of growth of the martensite plates. It has been demonstrated," however, that martensite plates can form with great rapidity even at temperatures approaching absolute zero. In addition," attempts to confirm the reported suppression of the martensitic transformation by rapid cooling of a 0.6 pct C-6 pct Mn steel have proved unsuccessful. On this basis, and on other theoretical grounds, the validity of some of Kurd-jumov's results and conclusions is open to serious question. Cohen, Machlin, and Paranjpe' have proposed a theory of martensite formation based on the nucleation of strain embryos and a growth mechanism involving cooperative atomic displacements. According to this theory thermal fluctuations can make a strain embryo supercritical and thereby produce martensite isothermally. Das Gupta and Lement' have investigated the isothermal formation of martensite in a 17 pct Cr-0.7 pct C steel at temperatures below the ambient. They found that partial suppression of the martensitic reaction occurred on quenching into liquid nitrogen. That part of the reaction which can be suppressed is taken to correspond to the isothermal rather than the athermal part of the rnartensitic transformation. The initial rate of isothermal transformation for this steel was found to go through a maximum with decreasing temperature. This is in conformity with the findings of Kurdjumov and Maksimova for the steels used in their investigation. Das Gupta and Lement conclude that isothermal martensite formation occurs by the nucleation of new plates and is always preceded by some athermal transformation. An iron-base alloy containing 14 pct Cr-9 pct Ni was used in this investigation to study further the kinetics of the austenite to martensite transforma-

Jan 1, 1953

By H. F. Bishop, F. A. Brandt, W. S. Pellini

M. S. Fisher and D. R. F. West (Imperial College of Science and Technology, London, England)—It may be of value to compare certain features of the results recorded in this very interesting paper with those of an investigation11 involving determinations of temperature gradients and rates of solidification of steel blocks of 3 in. sq section, cast horizontally in sand molds, some of which contained chills. Castings in plain carbon steels containing up to 0.8 pct C were made and, throughout this range of compositions, both inverse-rate and direct cooling curves, obtained from thermocouples placed within the mold cavity, showed a major arrest, the temperature of which was taken as the "effective liquidus" for the particular steel in question, solidifying under the conditions of the investigation. At the completion of the arrest, the curves showed a comparatively rapid de- crease in temperature. Some of the steels investigated lay within the peritectic region, and a second arrest at 1485°C was detected. In Fig. 15, which shows the effective liquidus temperatures, the limit of the 8 + liquid field has been placed at approximately 0.5 pct C. In inverse-rate curves corresponding to the thermal center of each casting, there was always a discontinuity, viz: an abrupt change of slope, at a temperature about 10 to 20°C below the "liquidus arrest," after which there seemed to be no significant irregularity in the rate of cooling. Curves corresponding to other positions in the casting generally showed some irregularities below the main arrest, probably as a result of heat flow from the solidifying interior. Even the reproducible discontinuity in the curves for the central positions appeared to have no theoretical or practical significance, though it probably corresponded to a stage in the solidification process at which only a relatively small amount of interdendritic liquid remained. Its temperature, rela-

Jan 1, 1953

By Maurice J. Peterson

THE VISUAL-ARC spectroscopic method of rapid qualitative analysis of complex inorganic compounds has been popularized in the past few years and is being employed by an increasing number of laboratories. The mineralogy and chemistry departments of several universities recently have added visual spectroscopy to their laboratory curricula. This revival of interest in a somewhat dormant analytical method has been stimulated through the publication of three papers 4 by members of the College Park staff of the Bureau of Mines. These virtually are the only recent sources of information on visual-arc spectroscopic analysis. They include data on the spectroscopic assembly, the analytical procedure, and the practical application of the method to determinative mineralogy and related fields. Requests for reprints of these papers continue to be received; at present only a limited number of copies are available for distribution. In order that these requests may be adequately answered, material from the three papers has been combined and, with some additional data, is presented in this bulletin. Numerous specific inquiries have been received regarding types of equipment available, problems in instrumentation, and information on the approximate sensitivity limits of the elements that can be detected by this method. Some of this material was not included in the original papers. Accordingly, the table of wavelengths has been revised to include the approximate visual-arc spectroscopic sensitivities, and a section on commercially available equipment has been added.

Jan 1, 1953

By D. C. McDonald

"IntroductionTHE GIANT YELLOWKNIFE property is on the west side of Yellowknife bay, Great Slave lake, N.W.T., some 600 air miles north of Edmonton. This paper deals with the underground development and mining of the complex system of orebodies which have produced, in the first fifty-six months of operation (May, 1948, to December, 1952), 652,464 tons of ore with an average grade of 0.80 ounces of •gold per ton (1).The mine has been developed from three vertical shafts designated A, B, and C. Figure l shows the positions of these openings with respect to the known ore-bearing zones and the surface plant.A shaft was sunk to a depth of 522 feet in 1945-46, primarily as a prospect shaft for investigation and development of the East Zone orebody. Drifting was carried out on the 200-and 325-foot levels. Before this development had been completed it was clear that the funds immediately available made it imperative to get revenue from production as soon as possible. By the beginning of 1946, the remarkably high-grade character of the ore in the present B Shaft area had been established by surface drilling, and the decision was made to obtain initial production from this source. Since known orebodies at shallow horizons were to be developed quickly, the choice of a suitable rock outcrop for the shaft was something of a problem."

Jan 1, 1953

By R. W. Geehan

The Bureau of Mines has been investigating deposits of critical and essential minerals in the United States since 1939. Bureau engineers made a preliminary examination of the Morefield mine early in 1943 and recommended investigation by trenching and diamond drilling, The Bureau of Mines conducted work from August to December of 1943, which indicated that the Morefield mine was a favorable location for an experimental mining program. The Bureau of Mines carried on such a program from September 1947 to March 1949. The property investigated is 30 miles southwest of Richmond in Amelia County, Va. (fig. 1). During World War II mica and beryl were shipped from the Morefield mine, but after the high prices and premiums paid during the war years were not available the mine was closed.

Jan 1, 1953

By H. N. Dunning

A comprehensive research program designed to aid development of new and improved methods for more complete production of petroleum from partly depleted reservoirs is being conducted at the Bureau of Mines Petroleum Experiment Station, Bartlesville, Okla. Water flooding has accounted for much of the petroleum produced by secondary-recovery methods; however, a considerable portion of the crude oil commonly remains in place after water flooding has been terminated. In recent years the possibility of increasing the efficiency of water flooding by using surface-active additives has received wide attention. In general, the results of laboratory research have shown that use of detergents as water-flooding additives will reduce the residual petroleum in porous media (1).3/ Some less extensive field tests have supported this conclusion but have not been entirely conclusive (2). Later studies (3, 4) have given conflicting evidence as to the relative worth of detergent additives for water floods in water-wet (hydrophilic) or oil-wet (hydrophobic or lipophilic) reservoir materials. The results of these studies emphasize the need for a more complete understanding of the fundamental principles involved in displacing petroleum from reservoir surfaces by injected fluids. Accordingly, a comprehensive research program was initiated to investigate the practical and fundamental aspects of detergency in petroleum production.

Jan 1, 1953

By S. Beatty

RECENT experimental results' on the superconductive properties of vanadium indicate that the magnetic behavior of the metal is greatly affected by internal strains caused by mechanical work, and particularly by oxygen and nitrogen impurities. These result in an increase in the hardness of the metal such that metallurgists' have used hardness as a measure of the impurities. An increase in the impurities should also be reflected in a change of lattice parameter with increasing impurity content. The lattice parameter of vanadium prepared by the thermal decomposition of the iodide has been determined by two workers. Neuburger3 obtained a value of a, =3.0338 ± 0.0003A for the body-centered cubic lattice by means of the powder method. The work of Katelaar is referred to by van Arkel4 in which a value of a0 = 3.025 is given. Four samples were used for this investigation. Sample A, the vanadium of the highest purity in the group, was obtained by means of the thermal decomposition of vanadium diiodide and deposited on a 3 mil diam tungsten filament in the form of crystals. The second sample, labeled B, was obtained by the calcium reduction of the pentaoxide at a sufficiently high temperature to give a melt. A third sample, C, was obtained in the same manner as B but remelted in a pure argon atmosphere. The last sample, D, was prepared by the calcium reduction method and the fine powdered vanadium was then sintered by means of applied heat and pressure. Samples A, B, and C were thus essentially free of mechanical strain in their preparation. Sample D was annealed in a high vacuum at 800°C. The samples were prepared for X-ray diffraction analysis such that all additional strain by cold work or by contamination with oxygen and nitrogen was kept at a minimum. Powder obtained from filings was deemed unsuitable since this would require annealing to get rid of the cold work. A heat treatment up to 1000°C at 10-6 m pressure might still increase the impurity content by means of adsorbed oxygen from residual gas in the vacuum chamber. The most satisfactory samples were prepared for back-reflection film techniques. Samples were cut to size, etched with hydrobromic acid, and mounted in Bakelite. They were then lightly polished on 3-0 paper and lightly etched. Chemical and Hardness Analysis of Samples Spectrographic analyses were made of the four samples and indicated similar metallic impurities for the group. The major metallic impurity in each sample was iron, which was less than 0.01 pct. The sum of the other metallic impurities was approximately 0.1 pct. The carbon content was assumed low by virtue of the methods of sample preparation. The principal impurity difference between the samples was in the oxygen and nitrogen content.

Jan 1, 1953

By J. J. Gilman, T. A. Read

S URFACE effects in the cleavage of brittle crystals have been known for some oftime,1, 2 but our knowledge of surface effects in the plastic deformation of crystals is of relatively recent origin. In 1936, Roscoe9 eported his observations comparing oxidized and clean cadmium crystals. He found that cadmium crystals 1/2 mm in diam when covered by an oxide film less than 1200 atoms thick had critical shear stresses about twice those for clean crystals. This effect is anomalous in that it cannot be caused by the inherent shear strength of a normal oxide film. Either an interaction between the film and the crystal causes the large increase in strength, or the oxide film has an abnormal mechanical strength. Several authors since Roscoe have studied surface effects in crystal plasticity. A complete review of the literature will not be presented, but most of the results may be summarized as follows: 1—The critical shear stress for slip is increased markedly by very thin oxide films on zinc4 and cadmium crystals;" ' also, the entire stress-strain curve is raised by an oxide coating;3,4 both effects increase with decreasing specimen radius. 2—Surface active substances such as oleic acid destroy the hardening effect of oxide films.4, 6-8 The time required for the reduction of the hardening effect to begin increases with the viscosity of the solvent4~ 3—There has been dispute in recent years about the effects of surface active substances themselves on plastic deformation. Rehbinder, Lichtmann, and Maslenikov9 state that surface active substances reduce the strength of metal monocrystals markedly and increase the number of slip lines per unit length at a given strain. The effect varies with orientation for tin crystals being smallest for x, = 0, largest for x, = 45", and intermediate as x, + 90°.10 Several workers claim to have disproved the results of Rehbinder')"." but Rehbinder and Lichtmann9 have defended themselves and Masing with his collaborators" has confirmed some of Rehbinder's results. 4—Immersion of metal specimens in electrolytes such as sodium chloride reduces their strength12,13' and subsequent cathodic polarization increases the strength reduction. For noble metals, the strength reduction occurs for both anodic and cathodic polarization," increasing with increasing polarizing voltage. 5—Electroplated copper coatings effect the creep rates of zinc monocrystals. Poly crystals are not affected." 6—Immersion in dilute acid destroys the hardening effect of an hydroxide film. When an acid solution is applied to a steadily creeping crystal, the creep rate jumps to a very high value and then drops gradually to a steady value which is higher than the initial steady rate.*' " If the hydroxide film to be removed is very thin (about 100A thick), the creep rate does not change measurably, but a small rapid strain-increment is observed when dilute acid is applied." 7—Crystal plasticity depends on specimen dimensions. This was observed by Lichtmann and Ven-stroml" for monocrystalline tin and by Andrade and Kennedy" for polycrystalline lead. 8—Immerson of copper crystals in mercury has no effect on their stress-strain curves.'" 9—Bombardment of creeping cadmium crystals with a particles which penetrate the surface to only 0.005 mm may increase their creep rates as much as five times.''' The experiments which will be described in this paper pertain to: (a) the effect of a crystal's shape on its plastic deformation, and (b) the effect of metallic surface films on plastic deformation. For the work pertaining to (a), crystals of zinc, tin, and lead were grown which had various shapes. These were tested in simple tension. Macroscopic rotations about the tension axis which are unpredicted by the classical theory of slip were observed, and serrated edges were observed in tin crystals. For the work pertaining to (b), the effects of evaporated and electrodeposited films of copper, nickel, gold, and zinc on the mechanical properties of zinc, tin, and lead crystals were determined. The films influenced both slip and twinning of the crystals in creep and tensile tests. Experimental Details Chemically pure zinc, tin, and lead were used in this investigation. The zinc was 99.999t pct pure;

Jan 1, 1953

By J. L. Lummus, Frank O. Jones

A field procedure for determining graphite in drilling mud is presented which is sensitive to 0.25 lbs/bbl and accurate to 20 per cent. The method, utilizing oil flotation principles, is suitable for use in all oil-free water base muds except those containing ligno-sulfonates, lignites, or surface active agents. INTRODUCTION Graphite was proposed as a drilling lubricant as early as 1940, but has not been used extensively until recently.' Graphite has been substituted for oil in certain instances to avoid oil contamination of core samples since it has been found that graphite does not interfere with routine core analysis. A major difficulty in using graphite is the lack of a satisfactory field test for determining the concentration of graphite in mud. DISCUSSION OF METHOD Several possible methods of analysis were investigated, including chemical separation, density fractionation, radioactive tracers, and oil flotation.', ' The investigation indicated that a satisfactory method for field use could be devised using an oil flotation method. It was found that toluene shaken with a highly diluted mud sample would recover sufficient graphite to be apparent in the oil phase. Refinement and standardization of technique made it possible to detect as little as 0.25 lb/bbl graphite and to estimate graphite content to within 20 per cent by using a visual comparison method. The test is limited to oil-free water base muds. Quebracho, phosphates, or barytes in the mud do not interfere with the test but surface active agents, lignosulfonates' and lignites evidently render !he graphite water-wet so that none may be recovered by oil-flotation. PROCEDURE Instructions for determining graphite in mud: 1. Collect representative one gallon sample.- from mud stream. Transfer immediately 350 ml portions of this Sample into four mixing cans labeled A, B, C, and D. Measure out graphite (same as is used to treat mud) for addition to cans as indicated below, using either a specially designed scoop or a balance. Can: A B C D Grams Graphite to Add: none 2 4 6 Stir samples B, C, and D for 15 minutes with propeller type mixer. 2. Clean and rinse well with water four 250 ml volumetric flasks labeled I, 11, 111, and IV. Using a 5 ml hypodermic syringe, transfer the indicated volume of samples from cans A, B, C, and D into designated flasks as follows: From Can: A B C D To Flask: I II III IV Add This Volume of Mud: 4 ml 2 ml 2 ml 2 ml 3. Measure 100 ml fresh or distilled water to each flask and swirl gently to disperse mud. Add exactly 5 ml toluene to each flask. Stopper and shake each

Jan 1, 1953

By Ruddle R. W.

Solid mattes are generally held to be either (a) eutectiferous mixtures of the component sulphides Cu2S and FeS or (b) mixtures of complex sulphides. This chapter shows that liquid mattes consist essentially of a homogeneous phase in which iron, copper and sulphur are present. The amount of sulphur is generally less than that required to account for all the metals as stoichiometric sulphides; mattes cannot therefore be regarded as mixtures of FeS and Cu2S. Some iron oxide may be dissolved in the sulphide phase and magnetite is often present as a second phase. If the sulphur content of the matte is reduced the composition enters the miscibility gap in the ternary system and either an iron- or copper-rich solution (depending upon the composition of the matte) separates as a new phase. On solidification any one of four phases (iron, copper, Cu2S and FeS solid solutions) may crystallize as primaries. The remainder of the matte solidifies as a ternary eutectic. It is possible that iron oxides enter into this eutectic. Knowledge of the ternary Cu-Fe-S system is far from complete and nothing is known of the quaternary system Cu-Fe-S-O

Jan 1, 1953