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By C. B. Richardson, R. D. Sprague

The year 1938 was the most active and successful in the history of the oil industry in southern Louisiana. Drilling showed a 16 per cent increase over that of 1937, with a total of 538 wells drilled, which yielded 315 oil wells, 19 distillate wells, 4 gas wells and 200 dry holes. Nineteen new fields were discovered during the year, all but three of which were completed by plugging back to sands previously drilled through. Electrical logging played a large part in these new discoveries as well as in the discovery of new sands during routine development of fields. Fourteen of the new discoveries produced oil, and five produced only gas and distillate. Southern Louisiana continues to lead the world in depth of drilling, which is in part due to the great thickness of comparatively young deltaic sediments near the coast and the existence of numerous sands. The present development is rather evenly distributed over a coastal strip 100 miles wide. New Fields North Tepetate, Acadia Parish.—Atlantic Refining Company's No. 1 Klumpp was completed for a new field through perforations from 7960 to 7970 ft. The initial production was 65 bbl. of 54" gravity distillate and 4 million cubic feet of gas daily through a 1/4-in. choke with tubing pressure of 2850 Ib. and casing pressure of 2930 lb. The well is in see. 12, 7 S., 2 W., just north of Tepetate field. It was drilled to a depth of 8705 ft. and plugged back for its final completion. Atlantic's NO. 2 was completed in a new sand at 8300 ft., also for distillate. South Crowley, Acadia Parish.—Humble Oil and Refining Company's No. 1 Boyd Finch was completed in July 1938, as an oil well through perforations from 7318 to 7325 ft. after plugging from a total depth of 10,222 ft. After making several hundred barrels of oil, the well went to

Jan 1, 1939

By W. A. West

ONE who attempts to collect and classify equilibrium data from various iron-alloy systems is soon struck with the absence of any quantitative theory that can serve as a general background against which to compare and contrast results from different systems, at different temperatures, and with different concentrations. It is not necessary to wait for a perfect theory; investigation of divergences of theory from observation may prove of great value in acquiring understanding of the subject. For example, one has only to think of Raoult's law as applied to aqueous solutions. The equations developed by Zener1 represent an effort to provide such a quantitative theoretical background, and it is therefore desirable to subject this theory to such tests as can be applied. The present article is intended to be an application of available tests, and may thus be considered as a supplement to Zener's paper. It is assumed that this paper is available to the reader. The equations make it possible to calculate the effect on the equilibrium concentration of one alloying element due to the presence of one or more other elements. In particular they are intended to give, for alloy steels, the carbon concentrations in alpha and gamma phases in equilibrium with each other, and in gamma in equilibrium with cementite. They may, however, be modified for use for carbon-free alloys. A summary is given later of the equations used in analyzing the data in this paper, and the symbols are there defined. About 125 papers have been examined for experimental data suitable for this investigation. An effort was made to look up all available reports of ternary systems including iron and carbon, as well as similar systems of higher order. Supplementary material was also obtained from a number of binary systems. A few noncarbon ternary systems were also found to which these methods could be applied. A comparatively small proportion of the papers read provided usable material. In many systems the number of quantitative observations made in the iron-rich region is extremely small, and the smoothed curves to be found in most published phase diagrams are entirely useless for quantitative treatment. This opinion is confirmed by the authors of the series on Alloys of Iron Research, whose remarks show clearly that they have no illusions as to the accuracy of many diagrams that they present. A further difficulty arises from the fact that these equations apply only to rather low percentages of alloying elements. The result is that at the lowest concentrations, where the best agreement might be hoped for, the errors of observation become relatively very large. The experimental difficulties in measurements of this kind of equilibrium are, of course, an old story.

Jan 1, 1946

By Leonard Bernstein, Harry Bartholomew

MANY of the properties of metals and alloys are structure dependent. Not the least of these is the grain structure. For example, in producing alloy bonds between silicon or germanium and gold-alloy foil at temperatures above their eutectics (which are, respectively, at 370" and 356°C) but below the melting points of the individual constituents, it was found that wetting was more complete with a fine-grain structure than with a coarse-grain structure. In cases where the assemblies were held together for long periods of time at elevated temperatures, wetting was not as critically dependent on the grain structure as was the case for shorter periods of time. When liquid phase forms, it first forms in the grain boundaries due to the fact that most of the impurities are concentrated at the grain boundaries and that most impurities tend to lower the melting point of the gold alloy somewhat. In addition, grain boundaries are at high-surface free-energy levels and are thus in a more favorable condition to initiate good wetting. A fine-grain structure will have more grain boundaries per unit area than coarse-grain structure thereby making wetting somewhat easier. To make the grain structure of an alloy sys- tem visible, a satisfactory method for differentiating between the different grains of which the system is composed must be employed. For the alloy bonding system previously described, the grain structure on the foil surface is of primary interest. Conventionally used etchants for the gold-alloy system will not adequately delineate grain boundaries in their structures. For this reason an alternate method is proposed for those cases where such a determination is necessary. Foil between 0.0005 and 0.005 in. thick has been used in this determination. The equipment used in this investigation was described in a previous publication.' Essentially, it employs a resistance-type filament which can be heated up very rapidly and cooled very rapidly. A thin refractory material is placed on top of the heating element. This refractory material may be molybdenum, tantalum, tungsten, or even ceramic but its thickness should be less than 0.010 in. to minimize the temperature gradient across it. The gold-alloy foil is placed on top of this refractory material. The temperature of the heating filament is raised to 900°C and cooled down to below 100°C in 5 to 10 sec. During this cycle, the foil can be observed to plastically deform due to its own weight. With no further chemical etching, this assembly is then viewed under a standard metallurgical microscope and the grain size measured. Fig. 1 is a Au-1 pct Sb alloy at 400X magnification and Fig. 2 is a Au-1 pct Ga alloy at 130X. This technique has proved to be an adequate means for controlling processing conditions in producing large quantities of gold alloy foil.

Jan 1, 1963

By W. L. Falke, A. A. Cochran

A basic problem in connection with manganese is to find economical ways to utilize domestic resources. As a part of its program to conserve domestic mineral resources and to reduce dependence of foreign sources, the Bureau of Mines had conducted extensive research to broaden manganese technology and to find economical, technically-feasible processes for recovering manganese from these low-grade resources. This paper analyzes some of the major difficulties which have been encountered in previously proposed processes for treating low-grade manganese ores and discusses a process which may circumvent many of these difficulties. Vast deposits of low-grade manganese ore exist in the U.S., yet domestic production is insignificant compared to the more than 2 million tons of ore imported yearly into this country.' A basic problem in connection with manganese is to find economical ways to utilize domestic resources.2 As a part of its program to conserve domestic mineral resources and to reduce dependence on foreign sources, the Bureau of Mines has conducted extensive research to broaden manganese technology and to find economical, technically feasible processes for recovering manganese from these low-grade resources. Although a great many processes have been proposed for treating domestic manganese resources, a failing of many of them is that too many steps are involved for economical operation.' Some of the major processes that have been proposed were reviewed by Norman and Kirby.3,4 Chlorination processes have become increasingly useful as a means of recovering valuable metals from raw materials, because the relative cost of chlorine (Cl2) and hydrogen chloride (HC1) has decreased through the years, and because the corrosion resistance of materials of construction has been improved. The objective of these processes is to form metal chlorides that are more volatile or water-soluble than are the corresponding oxides or sulfides; these compounds then can be separated from the gangue or other minerals by volatilization or leaching. Several chlorination processes for the recovery of manganese have been investigated by the Bureau of Mines5-8 and others; the major chlorination processes were reviewed in 1963, and their main features were compared.4 In all these processes, the simultaneous leaching or volatilization of iron chlorides with manganese chloride (MnCl2) is a problem, and the more iron that is present, generally the greater the problem. The leaching step is not highly selective, and the product of this step is, at best, suitable only for the production of ferromanganese or for further processing to remove iron. The product of the volatilization step is, in all cases, a mixture of iron and manganese chlorides that contains too much iron even for ferromanganese production, and must undergo additional processing steps for iron removal. THERMODYNAMIC CONSIDERATIONS The literature indicates that the desired chlorination reactions will proceed at practical rates at temperatures near 1200°K (927°C). Free energy changes at 1200°K for the critical steps of the reduction and chlorination reactions9-11 follow: Most of the research on chlorination processes for manganese recovery has been done with HC1 rather than with C12, for the following three main reasons: 1) Recycling of the chlorinating agent, which is economically vital, appeared to be easier for HC1

Jan 1, 1968

Discussion of the paper of GEORGE S. Rice, presented. at the Pittsburgh meeting, October, 1914, and printed in Bulletin No. 94, October, 1914, pp. 2459 to 2492. WILLIAM GRIFFITH, Scranton, Pa.-I notice in the discussions and literature that emphasis is placed on rock dust, shale dust, and limestone dust, and I infer that these different. sorts of rock are ground up to produce this dust. -Is that right? MR. RICE.-That is correct, but we do not have to grind the limestone dust we are using in the experimental mine, as that is obtained from a quarry, and is used just as it comes; we can get it very cheaply, as it is a by-product of the quarries. MR. GRIFFITH.-Have any experiments been made with ordinary dirt out of the fields; could not that be used as ground dust? MR. RICE.-If you dry it and powder it enough so it will float in a, strong air current it might be all right for the barriers, but if it is damp there will be a tendency for it to mat together; then it would be quite useless for making a dust cloud. There might also be another disadvantage if used through the whole mine, if it had very much free silica in it, which is bad for the lungs. Limestone and selected shale dust would not affect the health of miners. MR. GRIFFITH.-In order to do very much good with any of those barriers, they ought to be rather extensively used throughout the mines, and there are few mines that have facilities for grinding up this rock into such a fine dust. If the ordinary earth from a plowed field could be used, even if it were not quite so good, it is more accessible and very much cheaper; therefore, in using it, with the universality of the supply through-out the country, it would tend to stop explosions. MR. RICE (communication to the Secretary*).-In closing, it is well to again emphasize that I do not advocate barriers being a "cure-all" for explosions. It will be generally agreed that prevention is best, not only by means of improved methods of using explosives, and ventilation to prevent accumulations of firedamp, but also by either thoroughly wetting the dust throughout the mine, or else so treating it with rock dust or other inert dust that an explosion cannot start. From my observations I believe that rock dusting. is a practicable method, and has the merit of visibility, and remaining effective for considerable periods, whereas the watering method has to be daily followed up, and if neglected for a short period the mine may become in a dangerous condition. The Germans

Jan 4, 1915

By T. M. Chance

THE first bituminous coal cleaning-plant to use the sand-flotation process1 was placed in operation on Oct. 1, 1925, at the tipple of the East Broad Top Railroad & Coal Co., at Mt. Union, Pa. The general principles governing the design of plants of this type and typical operating results of anthracite sand-flotation units have been previously outlined.2 I will, therefore, confine myself to a description of this particular plant and to some of the elements of design it incorporates. THE ORIGINAL MT. UNION TIPPLE The plant was installed to transfer coal from steel narrow-gage cars of 60,000 and 70,000 lbs. capacity to standard-gage equipment. The coal was hauled some 30 miles from the East Broad Top field. This coal, mined by the Rockhill Coal & Iron Co. and other operators, is a low-volatile slow-coking coal with- ash of high-fusion point. It is normally a high-grade coal that does not contain an excessive amount of free impurities, but it requires careful handling to secure a fair domestic yield, and, naturally, the need for narrow-gage transshipment increases the difficulty of the problem. The narrow-gage cars were discharged into an 8-car track hopper equipped with two feeders passing the coal to two 42-in. apron intake conveyors. Twin units were installed throughout in this original plant, two lump-and-egg shaking screens, two lump picking-tables, two egg picking-tables and two stoker conveyors. The stoker coal was loaded without cleaning. The loading tracks and booms were in duplicate and with the layout as originally installed either unit could be run independently, each unit shipping a different class of coal or both units making the same product.

Jan 2, 1926

By N. A. Gokcen, M. N. Dastur

In metallurgical process industries a knowledge of true melting and casting temperatures is very essential for increasing the operating efficiency as well as improving the quality of the finished product. Optical pyrometers are widely used for the purpose because of their cheapness and ease of operation. It is an unfortunate fact, however, that this mode of measuring temperature entails a source of severe error inasmuch as with all non-black bodies, the temperature observed is always below the true temperature owing to deficient emissive power. Hence, the need for emissivity correction arises. In 1913 Bidwell1 obtained emissivity values of 0.36-0.48 for a temperature range of 1520-1800°C. He measured the true temperature of molten iron by sighting into a carbon cavity immersed in the iron under an atmosphere of hydrogen. In 1914 Burgess2 determined the emissivity of a smooth surface of liquid iron free from oxide to be 0.37 under an atmosphere of hydrogen. He claimed to have attained an accuracy of within 5°C at 1500°C with an optical pyrometer using monochromatic light. He reported that no difference appeared to exist between the emissivities of pure iron and of steels containing considerable percentages of carbon, nickel or manganese; nor was there any appreciable variation of emissivity with temperature from 1530 to 1571°C. Wensel and Roeser3 found an elnissivity value of 0.4 for temperatures above 1375°C for cast iron. The average emissivity value for carbon steels reported by Leiber,4 odd,5 Hase6 and Umino7 range from 0.4 to 0.45. Knowles and Sarjant8 made an extensive study of emissivity of molten iron and steel over a wide range of workshop and laboratory conditions. Observations of true temperature were made with immersion thermocouples, and correlated with apparent temperatures indicated by optical pyrorneter readings taken on the pouring stream as it passed over the lip of the crucible. The emissivity of Armco iron was shown to be of the order of 0.4, rising slightly with increasing temperature. But for plain carbon steels containing up to 1.0 pct carbon the emissivity was shown to fall slightly with increasing temperatures. The results of their investigation are in agreement with those of Guthmann.9 Naeser,10 Spencer," Todd5 and Hase6 in regard to the relation between emissivity and temperature for plain carbon steels. However, Goller12 has found a rise of emissivity with increasing temperature for the same steels. Results of several investigations are given in Fig 1. Measurement of True and Apparent Temperatures The necessity for an accurate optical temperature scale for liquid iron in studies of gas-metal equilibria led to this investigation. Experimental measurements were carried out in the induction furnace used by Dastur and Chipman13 in their studies of the reaction of hydrogen with oxygen in liquid iron. The furnace as modified for this work is shown in Fig 2. The atmosphere of the furnace was a mixture of purified argon with hydrogen containing a small controlled amount of water vapor. Gases were preheated by means of a platinum-10 pct rhodium resistance coil. The stream of hydrogen sweeping across the surface of niolten iron vir-

Jan 1, 1950

By David K. Mitchell

The mineral pyrite (or marcasite) occurs in coal beds as balls, lenses, veinlets and bands. Several million tons are w-asted annually on the refuse dumps from coal mining and coal-preparation activities. Sporadic attempts have been made in the United States to recover this pyrite for manufacture of sulphuric acid but only a few plants have succeeded in recovering it on a commercial scale. Shipments of pyrite from coal mines during 1941 were reported as follows: Illinois -The Midland Electric Coal Corp., Henry County, shipped 12,026 long tons containing 46 pct sulphur, at its Atkinson preparation plant. Indiana—The Snow Hill Coal Corp. produced pyrite from its Talleydalc preparation plant in Vigo County. Kansas—The Mineral Products Co. produced 3902 long tons of pyrite containing 44 pct of sulphur from picking table and washery refuse. Specifications for coal pyrite for acid manufacture rangc from 5 to 8 pct maximum carhon limit, and 42 to 45 pct minimum sulphur limit. Where flash roasting is practiced, the pyrite must be minus 100-mesh. Most companies give no size specifications. One company specifies 20- mesh or finer. Impurities in pyrite other than carbon may limit its use—for instance, arsenic, probably as arseno pyrite-—even though a concentrate can be made complying with specifications otherwise. Pyrite-recovery Plants Bradford breakers and picking tables may be used to make a marketable product where the pyrite occurs largely in sizes coarser than about I in. To make a grade of concentrate acceptable to sulphuric-acid plants the pyrite must break freely from the accompanying coal and slate, which is a rare condition to find. Most pyrite occurring in coal beds requires crushing and an abrasive type of grinding to free it of entwined coal and slate, followed by mechanical concentration by jigs, tables or other concentrating devices suitable for heavy ores, to make a satisfactory concentrate. At the Snow Hill Coal Corporation's plant in Indiana and at the Midland Electric Corporation's plant at Xtkinson, Ill., the final concentrate is made by a mechanical jig. The most recent and complete mill for concentrating pyritc from coal-mine refuse is that of the Mineral Products Co. at West Mineral, Kans., in which jigs and tables are used. Many regrinds and recirculations of products are necessary to get a concentrate of uniform grade. Trends On the whole, the economics of recovering pyritc from coal is not favorable. Cer-

Jan 1, 1948

By David K. Mitchell

The mineral pyrite (or marcasite) occurs in coal beds as balls, lenses, veinlets and bands. Several million tons are w-asted annually on the refuse dumps from coal mining and coal-preparation activities. Sporadic attempts have been made in the United States to recover this pyrite for manufacture of sulphuric acid but only a few plants have succeeded in recovering it on a commercial scale. Shipments of pyrite from coal mines during 1941 were reported as follows: Illinois -The Midland Electric Coal Corp., Henry County, shipped 12,026 long tons containing 46 pct sulphur, at its Atkinson preparation plant. Indiana—The Snow Hill Coal Corp. produced pyrite from its Talleydalc preparation plant in Vigo County. Kansas—The Mineral Products Co. produced 3902 long tons of pyrite containing 44 pct of sulphur from picking table and washery refuse. Specifications for coal pyrite for acid manufacture rangc from 5 to 8 pct maximum carhon limit, and 42 to 45 pct minimum sulphur limit. Where flash roasting is practiced, the pyrite must be minus 100-mesh. Most companies give no size specifications. One company specifies 20- mesh or finer. Impurities in pyrite other than carbon may limit its use—for instance, arsenic, probably as arseno pyrite-—even though a concentrate can be made complying with specifications otherwise. Pyrite-recovery Plants Bradford breakers and picking tables may be used to make a marketable product where the pyrite occurs largely in sizes coarser than about I in. To make a grade of concentrate acceptable to sulphuric-acid plants the pyrite must break freely from the accompanying coal and slate, which is a rare condition to find. Most pyrite occurring in coal beds requires crushing and an abrasive type of grinding to free it of entwined coal and slate, followed by mechanical concentration by jigs, tables or other concentrating devices suitable for heavy ores, to make a satisfactory concentrate. At the Snow Hill Coal Corporation's plant in Indiana and at the Midland Electric Corporation's plant at Xtkinson, Ill., the final concentrate is made by a mechanical jig. The most recent and complete mill for concentrating pyritc from coal-mine refuse is that of the Mineral Products Co. at West Mineral, Kans., in which jigs and tables are used. Many regrinds and recirculations of products are necessary to get a concentrate of uniform grade. Trends On the whole, the economics of recovering pyritc from coal is not favorable. Cer-

Jan 1, 1948

By P. Crowther, G. J. Lamprecht

The solubilities of silver, zinc, and cerium in liquid sodium, in the temperature ranges 100 to 270°C, 190° to 550°C, and 120" to 460°C, respectively, have been determined. From the solubility data the heat the entropy the partial molal enthalpy of mixing the excess entropy and the partial molal free energy of solution for the systems Nu-Ag and Na-Zn have been calculated. For the system Na-Ce the observed negative is discussed in terms of the solubility of the oxide Ce2O3. In an earlier publication the results obtained in the study of the solubility of tin' in liquid sodium are presented, as well as the detailed analytical procedures used. 1) REAGENTS Spectroscopically pure metals as supplied by Johnson Matthey and Co, were used to produce the following tracers: 253-day Ag110, 245-day zn65, and 325-day ce141. The tracers were prepared by irradiation in a thermal neutron flux of 4 x 10 13 neutrons cm-2 sek-1. To obtain a uniform amount of the required specific activity, needed for each solubility experiment, the radioactive metal was diluted with the corresponding inactive metal, by melting them together in an inert atmosphere. The liquid sodium used contained 11 ±2 ppm of O,1 determined by the vacuum distillation method.' The oxygen was assumed to be present as the oxide NaD. 2) THE SYSTEMS: SODIUM-SILVER AND SODIUM-ZINC Plots were made of the log of the mole fraction of silver, Fig. 1, and of zinc, Fig. 2, dissolved in the liquid sodium vs reciprocal absolute temperature. The equations for the solubilities, based on the least-squares fit to each plot, are: where Xi is the mole fraction metal dissolved in sodium, T is the absolute temperature, and s is the standard deviation in the value of log Xi. The heats and the entropies lution were calculated from the solubility data by In neither of the two cases was any intermetallic compound formed between sodium and the solute metal as was the case for tin.' Thus, for the silver and zinc systems the pure metal was taken as the reference phase. Since the solids in equilibrium with the liquid sodium were the pure metals, one can calculate the partial molal enthalpy of mixing and

Jan 1, 1969

By J. M. Smith, D. Kunii

Effective thermal conductivities of sandstones filled with stagnant fluids were measured using a steady-state technique. Data were obtained for seven sandstone samples, taken from four different locations and ranging in permeability from 18 to 590 md. The measurements with gases (helium, nitrogen, air and carbon dioxide) covered a pressure range from 0.039 psia to 400 psig. Data were taken for four liquids — n-heptane, methyl alcohol, 79.8 weight per cent glycerol-water solution and pure water at atmospheric pressure. The experimental results were used to evaluate the theoretical equations for predicting stagnant conductivities developed earlier 4 The low-pressure measurements permitted evaluation of the consolidation parameter bpDp/ks (necessary to utilize the theory) for the various types of sandstones. Using these characteristic values, the tbeoretical equations correlated well with the experimental conductivity data for the several fluids and rock samples. INTRODUCTION An aspect of heat transfer in solid-fluid systems of considerable current interest is the effective thermal conductivity of porous media. The stimulus for study of the subject arises from the need for sound procedures for designing thermal methods of petroleum production. The general system occurs when there exists a flow of fluid through the pores of the solid material. However, a logical starting point in developing a theory for predicting the effective thermal conductivity in the general system is to attack the special case when the porous solid is filled with stagnant fluid. Since the flow rates anticipated in thermal production processes are very low, such stagnant conductivities k,O are also of practical significance. Kunii and Smith4 recently reviewed the existing data for stagnant conductivities and proposed a theory for heat transfer in porous rocks. This leads to equations for predicting the stagnant conductivity as a function of the properties of the fluid and solid phases. The existing experimental information1-3,5,7,8 covered a range of porosities and agreed well with the theory. However, the available data were insufficient to examine critically the effects of two important properties on koe, — the thermal conductivity of the fluid and the pressure. The objectives of the present study are twofold: (1) to measure the effect on koe of (a) the pressure for gases, and (L) the thermal conductivity of the fluid kg for bloth gases and liquids; and (2) to determine for rocks of different porosities and permeabilities the apparent solid conductivity ks and the consolidation parameter bpDp/ks required in applying the theoletical equations. Measurements extrapolated to zero pressure are helpful in evaluating ks and the consolidation parameter. However, the extrapolations must be based upon data obtained at low pressures because in small pores the molecular conductivity of the fluid may be unusually depressed. This occurs when the mean free path of the molecules is of the same order of magnitude as the pore diameter, that is, in small-diameter pores at low pressures. The phenomenon has been studied recently by Schotte6in beds of unconsolidated fine particles. With particles in the size range of 45 to 200 microns, a significant reduction of kg with pressure was found even at absolute pressures greater than 1 atm. In the sandstones employed in the present investigation, pore diameters lower than those experienced by Schotte are likely, so that the effect would presumably be greater. SCOPE OF MEASUREMENTS Stagnant conductivities were measured for four types of sandstones using a total of seven samples. The characteristics of the samples, including porosity and permeability values, are given in Table

By Enid C. Plante

To extend our knowledge of the flotation behavior of sulphide minerals, the response of the following minerals to ethyl xanthate as collector was studied by captive bubble and cylinder flotation tests: antimonite (Sb2S3), arsenopyrite (FeAsS), covellite (CuS), rnarcasite (FeS2), orpiment (As&.), pyrrhotite (FeS) and tetrahedrite (4CU2S, Sb2S3). Lollingite (FeAs2) was also exarnined to determine if its behavior could be correlated with that of pyrite or rnarcasite (FeS2. Experimental Method Mineral for Flolation and Contact Tests Mineral was prepared in the manner a1ready described1 and its behavior both freshly ground and "oxidized" was studied. Tests in which the mineral was allowed to oxidize for various periods showed that a uniform response to xanthate was reached in two days or less. Oxidation Products The soluble oxidation products from most of the above minerals were measured and their effect on the flotation of the mineral studied. The mineral samples were wet ground to minus-52 mesh and deslimed, and 20 g of this material placed in 200 ml of distilled water of a measured pH value, and CO2-free air bubbled through each suspension at a constant rate (about I bubble/sec) for 5 days. It has been shown1 that the size of the mineral is unimportant in the rate of formation , oxidation products and that probably the supply of oxygen to the mineral is the rate-determining step. At the end of 5 days the pH value of the 'supernatant liquid was measured again, the mineral filtered off and the soluble products determined. Methods for estimation of sulphur acids, ferrous and ferric iron and copper have already been described.l No satisfactory method was found for antimony. Arsenic was estimated as the arsenate.2 Flotation of "Unoxidized" Minerals with Ethyl Xanthate as Collector Fig I to 3, 4. 6, show the effect of alkali and cyanide as depressants for the minerals with 25 mg potassium ethyl xanthate per liter as collector at 35°C. Wark and Cox8 have shown that with ethyl xanthate as collector, galena, pyrite and chalcopyrite show a greater tolerance to cyanide and hydroxyl ions at room temperature than at 35°C Covellite (Fig I), marcasite (Fig 2) and pyrrhotite (Fig 3) behave similarly. The independence of the curves for pyrrhotite at 35°C with respect to cyanide

Jan 1, 1949

By L. J. Buteau, R. E. Reed-Hill, W. A. Slippy

In a zirconium {1121} twins tend to have coherelzt boundaries and thus do not usually taper to a point when they intersect a grain boundary. Under the proper conditions, a (1121) twin may deform a boundary in such a manner as to clearly rcveal the twinning shear. Measurements of these grain-bounrlary rotatzons yield a value of 0.63 for the (1151) twinning shear. The magnitude of the observed shear and its shear sense are in excellent agreement with the assumption that the second undis-torted plme (K2) for this form of twinning is the basal plane (0002). The present value of the tzvinninz shear, which is approximately three limes larger than Rapperport&apos;s value? is in excellent agreement with reported results of Sokuskii and Prolsenko.5 RECENTLY westlake&apos; reported a study of the twinning modes of zirconium based on ~ap~er~ort&apos;s2 values for the twinning elements. He observed that two of the modes, (1012) and {1122), can be explained by relatively simple dislocation models. A workable model for (1121) twinning, however, proved to be very complex and questionable. Because Rapperport&apos;s second undistorted plane, (K2), for (1121) twinning has large indices, {ll2l6), it is possible that the difficulty in defining a model for (1121) twinning lies in an incorrect value for K2. A measurement of this twinning element has therefore been made, using a method based on observations of the shear displacement of grain boundaries at positions where they are intersected by (1121) twins. EXPERIMENTAL PROCEDURES The zirconium specimens were deformed in tension on an Instron machine either at the temperature of liquid nitrogen (77ºK), or prestrained at liquid nitrogen temperature and then further deformed at room temperature. Straining at 77°K was employed in order to nucleate (1 121) twins in large numbers, since simple ropm-temperature tensile deformation favors (1012) twinning. Specimens were machined from 1/2-in.-thick plate. The material was arc-melted sponge zirconium annealed to an ASTM grain size 4 and containing, in parts per million, 380 Fe, 880 0, <40 Hf, 32 N, and < 5 H. The specimen gage length and diameter were 1.25 and 0.130 in., respectively. To insure a gage section initially free of twins, the last 60 thousandths of the specimen diameter was removed by acid machining.

Jan 1, 1963

By S. H. Davis

THE pyrites used in making sulfuric acid in the United States have been largely imported from Spain and Canada, the Spanish imports amounting to nearly 1,000,000 tons per annum in the pre-war period. The greatly increased use of sulfuric acid and the cutting off of these Spanish imports, incident to war conditions, brought about a threatened shortage of sulfur supplies during the war period. The bituminous-coal mines of certain districts have, for many years, furnished a small tonnage of pyrite in the form of coal brasses. A mechanical concentrator at Danville, Ill., for a number of years, has been treating hand-picked lump pyrite and coal from the picking belt and from the mines and a small plant near Gillespie, Ill., for a few months has been recovering pyrite from washery refuse. Many mines throughout Illinois, Indiana, Western Kentucky, Ohio, and Pennsylvania have shipped an occasional car of the hand-cleaned lump pyrite. Only a very small percentage of the available pyrite has been recovered in this way, however, as usually the miners throw such lumps into the gob with slate and other impurities. It has been estimated that the western Indiana coal field could furnish more than 100,000 tons of pyrite per annum. The present production is very small. The possibility of furnishing the domestic trade with pyrites recovered as a byproduct from coal-mining operations appears attractive but there are certain features difficult to overcome. Pyrite, to be used in acid making, must meet with certain requirements as to size and purity. Lump ore for grate burners should be under 3 in. (7.6 cm.) and over 1 in. (2.5 cm.) in diameter. Fines for use in mecnanical roasters should be under quarter mesh. The material should be high in sulfur, free from arsenic and phosphorus, and as low in carbon as possible. The pyrite obtained from coal can be made to meet all the above requirements, but it is difficult to remove all the carbon. The pyrite in coal occurs as bands and nodules of varying thickness and size and of comparative purity, but mixed with this is more or less web sulfur. The web sulfur carries with it admixed coal, which may make the concen-

Jan 8, 1919

By H. K. Livingston

A technique has been developed which makes it possible to determine the spreading pressure of liquids and solids, for simple systems. Data for surface tensions, interfacial tensions, spreading pressures, and contact angles for water, heptane, and silica are tabulated.&apos; These results can be applied to the evaluation of capillary rise and displacement pressure in a petroleum reservoir. Appropriate equations are presented and the application of these equations is discussed. The presence of surface-active components affects both capillary rise and displacement pressure and also seems to influence the rate of fluid flow. The purpose of this paper is to supplement and bring up to date the last article on the subject of the surface chemistry of petroleum reservoirs, that of Garrison in the 1935 Oil and Gas Journa1.1 A discussion of the "adhesion tension" concept used by Garrison has been presented in another publication,2 together with the reasons for the recommendation that the term "adhesion tension" be abandoned. In view of the fact that some of the data used by Garrison have been superseded by more recent work, it seemed advisable to call attention to this fact and present the more important data currently believed to be correct. In the earlier paper, Garrison set up the equations that &apos;relate solid-oil and solid-water interfacial tensions to each other, and applied data from Bartell and Miller3 to these equations. However the adhesion tension measurements made by Bartell and Miller involved a confusion of symbols, so that they did not actually measure the spreading pressure, ?s — ?sf.2 The spreading pressure is a convenient method of indicating the amount by which the surface energy of a solid surface is lowered on immersion in a liquid or vapor. Since the initial value of the free surface energy is represented by the symbol ?s and the final value is ?sF, the spreading pressure is ?s — ?SF. A technique has now been developed4 that makes possible the determination of ?s — ?sF for simple systems. This method would be very difficult to carry out with a multicomponent system such as exists in the petroleum reservoir. However, already results have been obtained for ?s — ?sF for water and heptane in contact with silica and graphite. These values will be of the same order of magnitude as those in the petroleum reservoir. Accordingly, it is possible for the first time to discuss the surface-energy relations of the petroleum reservoir on a semi-quantitative basis. Preliminary Generalizations A petroleum reservoir may contain the following four phases: gas, hydrocarbon liquid, aqueous liquid, and solid. The three fluid phases are dispersed through the solid reservoir rock. If gravity were the only force acting, it is obvious that the

Jan 1, 1943

By H. K. Livingston

A technique has been developed which makes it possible to determine the spreading pressure of liquids and solids, for simple systems. Data for surface tensions, interfacial tensions, spreading pressures, and contact angles for water, heptane, and silica are tabulated.&apos; These results can be applied to the evaluation of capillary rise and displacement pressure in a petroleum reservoir. Appropriate equations are presented and the application of these equations is discussed. The presence of surface-active components affects both capillary rise and displacement pressure and also seems to influence the rate of fluid flow. The purpose of this paper is to supplement and bring up to date the last article on the subject of the surface chemistry of petroleum reservoirs, that of Garrison in the 1935 Oil and Gas Journa1.1 A discussion of the "adhesion tension" concept used by Garrison has been presented in another publication,2 together with the reasons for the recommendation that the term "adhesion tension" be abandoned. In view of the fact that some of the data used by Garrison have been superseded by more recent work, it seemed advisable to call attention to this fact and present the more important data currently believed to be correct. In the earlier paper, Garrison set up the equations that &apos;relate solid-oil and solid-water interfacial tensions to each other, and applied data from Bartell and Miller3 to these equations. However the adhesion tension measurements made by Bartell and Miller involved a confusion of symbols, so that they did not actually measure the spreading pressure, ?s — ?sf.2 The spreading pressure is a convenient method of indicating the amount by which the surface energy of a solid surface is lowered on immersion in a liquid or vapor. Since the initial value of the free surface energy is represented by the symbol ?s and the final value is ?sF, the spreading pressure is ?s — ?SF. A technique has now been developed4 that makes possible the determination of ?s — ?sF for simple systems. This method would be very difficult to carry out with a multicomponent system such as exists in the petroleum reservoir. However, already results have been obtained for ?s — ?sF for water and heptane in contact with silica and graphite. These values will be of the same order of magnitude as those in the petroleum reservoir. Accordingly, it is possible for the first time to discuss the surface-energy relations of the petroleum reservoir on a semi-quantitative basis. Preliminary Generalizations A petroleum reservoir may contain the following four phases: gas, hydrocarbon liquid, aqueous liquid, and solid. The three fluid phases are dispersed through the solid reservoir rock. If gravity were the only force acting, it is obvious that the

Jan 1, 1943

By D. J. McAdam

In a series of papers the author and associates have discussed the influence of temperature on the tensile properties of metals.11-18 These papers present much information about the influence of temperature and the stress system on the conventional indices of mechanical properties, with special attention to the fracture stress. A recent study of the data, however, has revealed much additional information about the influence of temperature on the fundamental factors involved in the flow of metals. The present paper presents results of this study. Attention will be confined almost entirely to results derived from tension tests of unnotched cylindrical specimens at strain rates a little slower than those used in ordinary tension tests. According to a concept first presented by Ludwik and elaborated in recent papers by others,8,9,22,23 the mechanical state of a metal depends on the total plastic strain, but not on the temperature during straining, provided that the only structural changes are those essential to plastic deformation. In the summer of 1948, however, the author made the previously mentioned study of results of a general investigation by the author and associates and reached the conclusion that the mechanical state depends not only on the total strain, but also on the temperature during the straining. A number of diagrams were then prepared. These conclusions were presented without diagrams in a discussion last October of a paper by Dorn, Goldberg and Tietz.2 The metals used in the investigation on which this paper is based were Monel and oxygen-free copper. The Monel was supplied by the International Nickel Co. through the courtesy of Dr. W. A. Mudge. The copper was supplied by the Scomet Engineering Co. through the courtesy of Dr. Sidney Rolle. The data to be presented are based on results of tests at temperatures ranging between 165 and — 188°C. Description of the apparatus and methods of test are given in previous papers.1011&apos;1"2 The present paper is the first part of the general discussion of the influence to temperature on the stress-strain-energy relationship for metals. The next paper will deal with metals that are subject to structural changes other than those induced solely by plastic deformation. Influence of Temperature and Plastic Strain on the Flow Stress of Monel and Copper For a study of the influence of temperature on the stress-strain relationship, flow-stress curves obtained with annealed metals at various temperatures will be compared with curves obtained with the same metals after cold drawing or cold rolling at room temperature. Diagrams thus obtained with Monel and copper are shown in Fig 1 to 8. Fig 1 to 7 show the variation of the flow stress with temperature and plastic strain; Fig 8 is a diagram of a different type, derived from Fig 4 to 7. In Fig 1 to 7 strain is expressed in terms of A0/A, in which A0, and A represent the initial and current areas of cross-section. Since values of Ao/A are represented on a logarithmic scale, abscissas are proportional to true strains; moreover, the true strains representing prior plastic deformation and those representing subsequent strain during a tension test are directly additive. Fig 1 shows flow-stress curves obtained with annealed Monel. Five of the curves are based on results of tension tests. Between yield and the maximum load, the flow was under longitudinal tensile stress; between the maximum load and fracture, the local contraction induced transverse radial tensile stress. The portions of curves designated F, therefore, represent flow with increasing radial stress ratio, the ratio of the transverse stress S3 to the longitudinal stress Si. Curve Fo is based on the ultimate stresses of specimens taken from bars that had been cold drawn various amounts.17 Since the tensile stress at the maximum load is unidirectional, curve Fo represents the course that a flow-stress curve would take if the stress during an entire tension test could be kept unidirectional. The flow-stress curve F obtained at room temperature (Fig 1) has been established accurately by numerous measurements of the diameter of the specimen during the extension from yield to fracture.17 At the time of the experiments, however, no apparatus was available for measuring the diameter during tension tests at low temperatures. Nevertheless, curves have been established to represent with sufficient accuracy the flow at low temperatures. Each flow-stress curve must be tangent to a curve U, which starts at a point representing the ultimate stress of annealed metal. Since the ultimate stress is based on the area of

Jan 1, 1950

By Eric Kula, Åke Josefsson

L. J. Dijkstra and R. Sladek, (Ontario Research Foundation, Toronto, and Institute for the Study of Metals, Chicago, respectively)—This interesting paper confirms some results obtained some years ago in collaboration with Fast: namely the broadening of the nitrogen peak by the presence of small amounts of manganese. Later on a more extensive study of this effect was made at the Institute for the Study of Metals at Chicago. As the work has not yet been submitted for publication we wish to mention here briefly some of the results. The effect of about 0.5 atomic pct manganese, chromium, molybdenum, or vanadium on the nitrogen-peak in iron was examined. The broadening found previously in the case of manganese was even found to be more pronounced for chromium. In the case of molybdenum and vanadium a double peak was observed which seemed to justify the idea that in all cases mainly two relaxation times were involved: namely, the normal relaxation time as found in pure iron and a second relaxation time related to the existence of abnormal interstitial lattice sites introduced by the foreign metallic element. The analysis showed that for the normal nitrogen-peak as a reference at 22°C the abnormal peak was found at about 32°, 47°, 75°, and 87°C in the case of manganese, chromium, molybdenum, and vanadium, respestively. In the manganese alloy the free energy difference for a nitrogen-atom at an abnormal and a normal lattice site was estimated at 2800 cal per mol. This means that for temperatures above 100°C the solid solubility and overall diffusion rate of nitrogen is not much affected by additions of 0.5 pct Mn. We believe that the difference in rate of precipitation of nitrogen in pure iron and the manganese alloy is mainly a question of the number of potential nuclei available in the different steels. In studying the effect of these alloying elements on precipitation of nitrogen, a distinction must be made between the para reaction and ortho reaction, using terminology introduced by Hultgren.7 The ortho reaction in which the alloying metallic element participates in the diffusion under formation of nitrides occurs at high temperatures such as 600°C. The para reaction in which the alloying metallic element does not diffuse and in which the nitride inherits its alloy content from the matrix occurs at lower temperatures. To prevent the ortho reaction the alloys have to be quenched rapidly from the phase. It is not surprising that the authors find that the height of the peak indicates a lower nitrogen content than chemical analysis. In the first place the peak is not a single relaxation peak and secondly, the steels were not quenched from the phase after the nitrogen was introduced at 580 °C.

Jan 1, 1953

By W. A. West

One who attempts to collect and classify equilibrium data from various iron-alloy systems is soon struck with the absence of any quantitative theory that can serve as a general background against which to compare and contrast results from different systems, at different temperatures, and with different concentrations. It is not necessary to wait for a perfect theory; investigation of divergences of theory from observation may prove of great value in acquiring understanding of the subject. For example, one has only to think of Raoult&apos;s law as applied to aqueous solutions. The equations developed by Zener1 represent an effort to provide such a quantitative theoretical background, and it is therefore desirable to subject this theory to such tests as can be applied. The present article is intended to be an application of available tests, and may thus be considered as a supplement to Zener&apos;s paper. It is assumed that this paper is available to the reader. The equations make it possible to calculate the effect on the equilibrium concentration of one alloying element due to the presence of one or more other elements. In particular. they are intended to give, for alloy steels, the carbon concentrations in alpha and gamma phases in equilibrium with each other, and in gamma in equilibrium with cementite. They may, however, be modified for use for carbon-free alloys. A summary is given later of the equations used in analyzing the data in this paper, and the symbols are there defined. About 125 papers have been examined for experimental data suitable for this investigation. An effort was made to look up all available reports of ternary systems including iron and carbon, as well as similar systems of higher order. Supplementary material was also obtained from a number of binary systems. A few noncarbon ternary systems were also found to which these methods could be applied. A comparatively small proportion oi the papers read provided usable material. In many systems the number of quantitative observations made in the iron-rich region is extremely small, and the smoothed curves to be found in most published phase diagrams are entirely useless for quantitative treatment. This opinion is confirmed by the authors of the series on Alloys of Iron Research, whose remarks show clearly that they have no illusions as to the accuracy of many diagrams that they present. A further difficulty arises from the fact that these equations apply only to rather low percentages of alloying elements. The result is that at the lowest concentrations, where the best agreement might be hoped for, the errors of observation become relatively very large. The experimental difficulties in measurements of this kind of equilibrium are, of course, an old story.

Jan 1, 1947

By W. A. West

One who attempts to collect and classify equilibrium data from various iron-alloy systems is soon struck with the absence of any quantitative theory that can serve as a general background against which to compare and contrast results from different systems, at different temperatures, and with different concentrations. It is not necessary to wait for a perfect theory; investigation of divergences of theory from observation may prove of great value in acquiring understanding of the subject. For example, one has only to think of Raoult&apos;s law as applied to aqueous solutions. The equations developed by Zener1 represent an effort to provide such a quantitative theoretical background, and it is therefore desirable to subject this theory to such tests as can be applied. The present article is intended to be an application of available tests, and may thus be considered as a supplement to Zener&apos;s paper. It is assumed that this paper is available to the reader. The equations make it possible to calculate the effect on the equilibrium concentration of one alloying element due to the presence of one or more other elements. In particular. they are intended to give, for alloy steels, the carbon concentrations in alpha and gamma phases in equilibrium with each other, and in gamma in equilibrium with cementite. They may, however, be modified for use for carbon-free alloys. A summary is given later of the equations used in analyzing the data in this paper, and the symbols are there defined. About 125 papers have been examined for experimental data suitable for this investigation. An effort was made to look up all available reports of ternary systems including iron and carbon, as well as similar systems of higher order. Supplementary material was also obtained from a number of binary systems. A few noncarbon ternary systems were also found to which these methods could be applied. A comparatively small proportion oi the papers read provided usable material. In many systems the number of quantitative observations made in the iron-rich region is extremely small, and the smoothed curves to be found in most published phase diagrams are entirely useless for quantitative treatment. This opinion is confirmed by the authors of the series on Alloys of Iron Research, whose remarks show clearly that they have no illusions as to the accuracy of many diagrams that they present. A further difficulty arises from the fact that these equations apply only to rather low percentages of alloying elements. The result is that at the lowest concentrations, where the best agreement might be hoped for, the errors of observation become relatively very large. The experimental difficulties in measurements of this kind of equilibrium are, of course, an old story.

Jan 1, 1947