Search Documents

By Herbert H. Uhlig

Although the mechanical properties of high-carbon manganese-iron alloys, particularly the Hadfield manganese steels, have been established, the literature discloses discrepancies in the reported properties for the low-carbon alloys. Hadfieldla summarized the existing data up to 1927, including the investigations of Guillet, Arnold, Strauss, Burgess and Aston, and reported his own values for alloys containing for the most part from 0.06 to 0.I5 per cent carbon. He noted: From these comparisons it wil! be seen that while there is a broad and general agreement as to the character of the alloys at the different manganese percentages, there are disparities in individual cases, especially as regards the degree of toughness or brittleness displayed by an alloy with certain percentages and with particular types of treatment. These differences are not always readily explainable.lb His data showed that alloys containing 4 to 10 per cent manganese water-quenched from Iooo°C. were brittle and hard with maximum brittleness at about 7 per cent. Slight improvement in ductility was obtained with compositions from 10 to 17 per cent manganese. Alloys containing up to 17 per cent manganese slowly cooled rather than quenched from 87o°C., he found, were slightly improved in ductility with significant improvement in alloys analyzing 4.1 and 4.8 per cent manganese. Recently Walters, Kramer and Loring2 reported mechanical properties for alloys made up from electrolytic manganese and ingot iron and containing from 0.02 to 0.04 per cent carbon. They showed that a tempering treatment at 54o°C. (Iooo°F.) for one hour significantly improved the ductility of compositions ranging from 6.7 to &apos; 20.7 per cent manganese. The differences of these compared with Hadfield&apos;s results they considered to originate in this tempering treatment plus the fact that Hadfield&apos;s alloys contained higher carbon and phosphorus (0.06 to 0.I5 per cent C; 0.06 to 0.07 per cent P compared with 0.02 to 0.04 per cent C, <o.ooI per cent P). In this paper it is shown that of the low-carbon alloys (0.02 to 0.03 per cent) containing from 3.3 to 21.5 per cent manganese moderately or rapidly quenched from IOOO°C. some are brittle or ductile, depending on presence or absence of hydrogen. Hydrogen is readily absorbed at high temperatures, and much of it is retained when the alloys are cooled to room temperature. The presence of hydrogen in the range of composition from 10 to 18 per cent manganese is a major factor in determining relative ductility. At 22 per cent manganese, and also at compositions below 10 per cent manganese, factors other than or in addition to hydrogen play a role. These are discussed. Also data are presented to show that hydrogen absorbed by the high-carbon alloys of Hadfield composition is without effect on their mechanical properties.

Jan 1, 1944

By Wilfrid R. Foster

The industrial importance of the sillimanite group of minerals depends upon the beneficial properties exhibited by porcelains and refractories in which substantial amounts of these minerals are utilized as raw materials. The presence of "sillimanite" (now known to be the closely related mineral, mullite) in conventional porcelains and refractories has been known since before the turn of the century. As early as 1906 German investigators observed a direct correlation between the "sillimanite" content of a porcelain and its electrical and mechanical properties. Acting upon this discovery, U. S. Bureau of Standards investigators during World War I developed improved pyrometer tubes and spark plug porcelains, by increasing substantially the amount of "sillimanite" at the expense of quartz. The success of these experiments, first reported in 1918, at once aroused a lively interest in the location of natural sources of sillimanite and its related minerals. As a result of diligent search, the large andalusite deposits in California were discovered in 1919. Within the next several years large deposits of kyanite and sillimanite in India and kyanite in the United States had been reported. The search for these minerals in quantity, by both private and governmental agencies, has continued unabated during the ensuing forty years. A number of domestic deposits of kyanite have been worked during the past 30 years. Of these, only the Virginian and South Carolinian deposits are currently in substantial production. The only commercial andalusite production in the United States has been in California and Nevada. A dumortierite deposit in Nevada, known since 1917 but ignored for want of a commercial use, began production in 1925. A topaz occurrence in South Carolina has yielded a small production since about 1940. Domestic production of andalusite, dumortierite and topaz had virtually ceased by 1950. There has never been any commercial development of domestic sillimanite deposits. Kyanite has been mined almost continuously in India since about 1922. The remoteness of the large deposits of Indian sillimanite had caused it to be neglected until 1949. In that year sillimanite production began, and it has continued to the present. South African andalusite has been marketed from the 1930&apos;s until the present time. From 1944 to 1955 Kenya, British East Africa, was an important producer of kyanite. Commercial deposits of kyanite in Ontario, Canada should soon be in production. The first production of kyanite in Europe began in Austria in 1953. No commercial deposits of mullite are known anywhere in the world. It is of interest to note that synthetic mullite, which as "sillimanite" first elicited interest in the A12O3-rich aluminosilicate refractories, has enjoyed a marked increase in production in recent years. This is a result of the gradual depletion of known deposits of high-quality kyanite and related minerals."&apos; Composition The sillimanite group includes kyanite, andalusite, and sillimanite, all having the same chemical composition (A12O3•SiO2) but different physical properties. Two other minerals, dumortierite and topaz, are also included in

Jan 1, 1960

By Walter E. Mingramm

The construction of rescue-apparatus on the principle of furnishing the wearer with air from a tank containing it under high pressure was given up by inventors about 20 years ago. Such an apparatus must supply continuously, for not less than two hours, nearly 50 liters of pure air at atmospheric pressure per minute, or a total of 6,000 liters (210 cu. ft.); and a cylinder containing this amount of air, under 2,000 lb. pressure, would weigh 180 lb. or more. Although apparatus has been recently constructed utilizing liquefied air, no experiments have been made to determine the regularity with which the air is generated, nor has its chemical composition been determined. Moreover, the chief objection to such an apparatus is the difficulty and cost of keeping on hand a large quantity of liquefied air. The system of furnishing the wearer of a breathing-apparatus with air which has given the best results, and has found

Jan 1, 1909

By C. E. Webber

The economical recovery of the valuable constituents from the effluent of gas-con-densate wells has developed into a problem of balancing the cost of recovery against the cost of compressing the residual gas back into the formation. A possible method of extracting the gasoline and distillate from the natural gas is by oil absorption at high pressures. In order to design and evaluate an absorption plant, fundamental data on the composition of the coexisting hydro- carbon vapor and liquid phases at various temperatures and pressures are essential. A review of the literature indicated that the necessary data for the design of such plants are lacking. The nearest approach to desired published data is that of Katz and Hackmuth,~ who experimentally deter-mined the composition of the coexisting vapor and liquid phases in a natural gas-crude oil system at pressures up to 3000 lb. per sq. in. and at temperatures from 40&apos; to zoo°F. This paper presents the results of the experimental determination of the equilib-rium distribution of the hydrocarbons methane through hexane between natural gas and a typical absorber oil. The ranges of temperature and pressure chosen were from 33&apos; to r8oUF. and from 100 to 5000 lb. per sq. inch. Materials The absorber oil was a typical naturally occurring, Straw-colored distillate that had previously been steam-distilled to an initial boiling point of 300 F. The physical and chemical properties, including the results of an Engler distillation, are presented in Table I. A large volume of this oil was obtained and it was used throughout the complete set of experiments. Table i.—Properties of the Absorption Oil Gravity .......................... . . 32.5&apos; A.P.1. Molecular weight by benzene freezing- point depression.................. 183 Viscosity, poises; at 100°F........... 0.0a80 At 200°F...................... 0.0102 Composition, PeR Cent Aromatics........ 24.0 Naphthenes..... 36.7 unsaturates,Aromatics...... .I24.00.3 1 Parafins Naphthenes.....36.7 39.o EngLeR Distillation Per Cent /ncg. F. Per Cent Dez. P. Initial boilins rmint.. 300 I 60....... 523 5.................. 402 I 70....... 538 10.................. 421 180....... 557 20.................. 462 90....... 570 30.................. 480 1 95....... 623 40.................. 49 .................1 511 Residue, z .o per cent; loss, 0.3 per cent. See refrence I. The n-hexane was obtained from the Ohio Chemical and Manufacturing Co., Cleveland, Ohio. This liquid had a boiling range of from 149" to 152.6&apos;F., with a density of 0.667 at 60°F. and a molecular weight of 85 by benzene freezing-point depression. The propane, isobutane, wbu-tane, isopentane and n-pentane were ob-ta,ined from the Philgas Department of the Phillips Petroleum Co. Certified analyses of these compounds showed their purity to be in excess of 99.5 per cent and they were riot further purified.

Jan 1, 1941

By C. E. Webber

The economical recovery of the valuable constituents from the effluent of gas-con-densate wells has developed into a problem of balancing the cost of recovery against the cost of compressing the residual gas back into the formation. A possible method of extracting the gasoline and distillate from the natural gas is by oil absorption at high pressures. In order to design and evaluate an absorption plant, fundamental data on the composition of the coexisting hydro- carbon vapor and liquid phases at various temperatures and pressures are essential. A review of the literature indicated that the necessary data for the design of such plants are lacking. The nearest approach to desired published data is that of Katz and Hackmuth,~ who experimentally deter-mined the composition of the coexisting vapor and liquid phases in a natural gas-crude oil system at pressures up to 3000 lb. per sq. in. and at temperatures from 40&apos; to zoo°F. This paper presents the results of the experimental determination of the equilib-rium distribution of the hydrocarbons methane through hexane between natural gas and a typical absorber oil. The ranges of temperature and pressure chosen were from 33&apos; to r8oUF. and from 100 to 5000 lb. per sq. inch. Materials The absorber oil was a typical naturally occurring, Straw-colored distillate that had previously been steam-distilled to an initial boiling point of 300 F. The physical and chemical properties, including the results of an Engler distillation, are presented in Table I. A large volume of this oil was obtained and it was used throughout the complete set of experiments. Table i.—Properties of the Absorption Oil Gravity .......................... . . 32.5&apos; A.P.1. Molecular weight by benzene freezing- point depression.................. 183 Viscosity, poises; at 100°F........... 0.0a80 At 200°F...................... 0.0102 Composition, PeR Cent Aromatics........ 24.0 Naphthenes..... 36.7 unsaturates,Aromatics...... .I24.00.3 1 Parafins Naphthenes.....36.7 39.o EngLeR Distillation Per Cent /ncg. F. Per Cent Dez. P. Initial boilins rmint.. 300 I 60....... 523 5.................. 402 I 70....... 538 10.................. 421 180....... 557 20.................. 462 90....... 570 30.................. 480 1 95....... 623 40.................. 49 .................1 511 Residue, z .o per cent; loss, 0.3 per cent. See refrence I. The n-hexane was obtained from the Ohio Chemical and Manufacturing Co., Cleveland, Ohio. This liquid had a boiling range of from 149" to 152.6&apos;F., with a density of 0.667 at 60°F. and a molecular weight of 85 by benzene freezing-point depression. The propane, isobutane, wbu-tane, isopentane and n-pentane were ob-ta,ined from the Philgas Department of the Phillips Petroleum Co. Certified analyses of these compounds showed their purity to be in excess of 99.5 per cent and they were riot further purified.

Jan 1, 1941

By N. A. D. Parlee

The diffusion rate of hydrogen in liquid iron has been measured by a gas-liquid metal diffusion cell technique. The diffusion cell was formed by immersing an alumina tube containing hydrogen gas at 1 atm in a bath of stagnant liquid iron. The change in the composition of the melt in the cell was determined by measuring the rate of absorption of the gas in the cell. The appropriate solution to Fick&apos;s second law was used to examine the data and calculate diffusivi-ties. The absorption of hydrogen in stagnant pure liquid iron has been found to be diffusion-controlled. The results show that the chemical diffusion coefficient, D, of hydrogen in pure iron in the range of 1547" to 1726°C can be represented by the following Arrhenius relation: D(sq cnz per sec) = 3.2 x X exp(- 3300 i 1800/RT) where the uncertainty in the activation energy corresponds to the YO pct confidence level. Oxygen in the melt (above 0.015 pct 2) increased the apparent rate of absorption of hydrogen. The importance of diffusion data on liquid metals for predicting the rates of certain metallurgical processes has been recognized for a long time. Moreover, these data are much needed to test and develop theory for diffusion in liquid metals. Despite this practical and theoretical interest, however, relatively little reliable information about diffusion in liquid metals is available in the literature. This is particularly true for gas components such as hydrogen, oxygen, and nitrogen in liquid metals, where almost no data on chemical diffusion coefficients are to be found. This is probably due to a multitude of experimental difficulties particularly associated with high-temperature melts. In an effort to fill this gap in information, a research program was undertaken to study the diffusivities and rates of solution of gases in liquid metals. This paper presents the results of a study of the diffusion of hydrogen in liquid iron. EXPERIMENTAL METHOD Two methods for the study of the kinetics of dissolution of gases in liquid metals are being employed in this laboratory. Both involve the measurement of the volume of gas absorbed by the melt as a function of time and as such both avoid the uncertainties involved in chemical analyses of quenched samples for relatively small amounts of gas. In the first method, the gas dissolves in an inductively stirred melt and, in the absence of a slow surface reaction, the results are often interpreted in terms of mass transport across a liquid "boundary layer" between the homogeneous gas phase and well-stirred part of the melt. Other interpretations of the results of such experiments have also been described in the literature.1&apos;5 In the second method a gas-liquid metal diffusion cell is used.&apos; The gas dissolves in a cylindrical column of stagnant liquid metal and, in the absence of a slow surface reaction, the results are interpreted in terms of a non-steady-state diffusion solution to Fick&apos;s second law. The weakness of the first method is that while it gives information on the mechanism of absorption by stirred melts it yields an overall rate constant which even in the simplest cases depends on the nature and the thickness of the "mass transport layer" or "boundary layer". It yields no values of diffusion coefficients. The second method was used in this research because in many cases it is possible to determine the diffusion coefficient of the gas component in the liquid metal. In this research it has been utilized to measure diffusion coefficients of hydrogen in liquid iron. The apparatus used was essentially the same as that described by Mizikar, Grace, and par lee but certain modifications have been introduced to meet the elevated temperatures and special conditions of this research. Fig. 1 is a schematic drawing of the apparatus and Table I gives the identification of various parts in this figure. The diffusion cell, shown in detail in Fig. 2, was formed by immersing an impervious alumina tube (hereafter called absorption tube) in a bath of pure liquid iron contained in an alumina crucible. Two types of tubes were used, Morganite triangle RR and McDanel AP35. The crucible was contained in a vertical impervious alumina combustion tube (32 mm ID by 914 mm long) which was closed at both ends by water-cooled brass heads employing O-ring compression seals, Fig. 1. A protection tube enclosing a Pt, 5 pct Rh-Pt, 20 pct Rh thermocouple was introduced through the lower end of the combustion tube

Jan 1, 1968

By Luis Toron, Salvador Cortes-Obregon

John D. Price (Colorado Fuel and Iron Corp., Pueblo, Colo)—The paper on the coal fields of the Oaxaca district as prepared by engineers Toron and Cortes-Obregon of the staff of the Bank of Mexico bears witness to the thorough and careful way in which the men associated with this organization perform their work. There is little to be added to their paper in way of discussion other than to confirm and amplify some of their statements. Since the only extensive and well-developed field of coking coal lies in the northeastern section of the country adjacent to Sabinas in the state of Coahuila, it follows that blast furnace plants would be located in that same region. Two such plants are now operating at Monterrey and Monclova, using coke produced at the Sabinas district mines. But the nearer of these two plants is 600 miles from Mexico City and even farther from the center of population. Transportation of products from these mills to the market area is therefore expensive, both because of the distance and the difficulty of the terrain over which it must be carried. The development of an integrated steel industry closer to the center of population has therefore long been a goal toward which the Mexican technicians have been striving. While the presence of coal of some grade has been reported in many of the states, and many ideas have been advanced regarding its possible uses in iron and steel production, deposits of anthracite in Sonora and the various coals of the Oaxaca district as reported on in this paper are the only ones that have been explored in a serious manner. The coking coal from the Mix-tepec zone appears to offer promise of producing a coke which could be used in a standard blast furnace. Several problems are indicated, however: 1—The ash in the coal is high as mined, but indications are that it can be washed to an ash content of 15 pct with a recovery of 70 pct of washed coal. 2—Such washing would increase the volatile content from 17.4 pct to about 20 pct, and in a byproduct oven this should give a coke yield of close to 80 pct with an ash content of coke under 20 pct. 3—A free swelling index of 5 appears low for a good coking coal, and below that of the coals from the Sabinas district, which show between 6 and 9. But washing of the coal should result in an improvement in this regard; in the United States coals from Utah with an index even lower than 5 have made a usable coke. 4—A coal with volatile as low as 17.4 in raw coal and 20 in washed coal would come close to being classed as a low-volatile rather than medium-volatile coal, and low-volatile coals are notorious for their high expansion properties. Several plants in the United States are making coke from straight medium-volatile coal of 26 to 28 volatile content, and one at Rosita,, Mexico, from coal of 25 volatile. But no plants to my knowledge are using coal as low as 20 volatile. Since the Rosita coal appears to be a borderline coal from the angle of its expansion properties the coking of one of the straight lower volatile must be approached with caution. 5—There are few coals possessing any degree of coking properties which cannot be used in coke production by careful attention to its preparation and blending. The fact that coals of other types are available in this same region make improvement through blending very possible. 6—There are other workable methods of reducing iron ore other than the conventional coke-blast-furnace method. These will not be discussed here but it is known that their use has been considered. The technicians of not only Mexico but also of the other Latin American countries are keenly aware of their natural resources and their national needs. This paper emphasizes the fact that the Mexican technicians are working on their problem and attempting to speed the day of self-sufficiency for their country. Salvatore Cortes-Obregon (author&apos;s reply)—I wish to thank Mr. Price for his kind remarks. The Mixtepec coal as shown in Table II has 30 pct ash and a free swelling index of 5, but when the same coal is washed to 15 pct ash it has a free swelling index of 8 to 9 and the volatiles increased from 17.4 to 20.7 pct. A satisfactory coke has been produced from blends made in the Mexican laboratory using at least 40 pct of the Mixtepec coking coals with the other Oaxaca non-coking coals. Koppers in Germany report good coke obtained from the Oaxaca coal with a blend of 80 pct Mixtepec coal. Consideration is being given the possibility of using methods other than the conventional blast furnace for the reduction of iron ore near the Oaxaca area; electric furnaces appear promising. The non-coking coals could be used to produce cheap electric energy and the coking coals to make metallurgical coke.

Jan 1, 1955

By R. W. Bartlett

The rates of oxidation of tungsten have been determined at temperatures between 1320" and 3170°C and oxygen pressures to 1 amn using a surface -recession measurement technique. Above approximately 2000°C and 10-6 atm the rate is independent of temperature and can be calculated from gas collision theory assuming a constant reaction probability, e, of 0.06. Oxygen molecules react at surface sites where oxygen atoms have previously chemisorbed. This provides a direct pressure dependence at low pressures but at high pressures tungsten oxide molecule s form an adjacent gas boundary layer which lowers the PO2 at the tungsten surface. A correction for this effect using free-convection theory fits the rate data over the entire oxygen-pressure range from 10-8 to 1 atrn as well as data using O2-A mixtures. Below 10-6 atrn and above 2000°C, e decreases with increasing temperature because of desorption of oxygen atoms. Below 2000°C the rate decreases with decreasing temperature at all oxygen pressures following an apparent activation energy of 42 kcal per mole and depending on (Po2)n with n varying between 0.55 and 0.80. MOST of the previous tungsten oxidation studies have employed gravimetric methods and have been limited to temperatures below 1000°C where the weight loss associated with evaporation of tungsten oxides is negligible compared with the weight gain from oxidation.&apos; At higher temperatures, oxygen-consumption rates have been determined from pressure measurements, usually at constant flow rates, by Langmuir,2 Eisinger,3 Becker, Becker, and Brandes,4 and Anderson.5 The sensitivity of this method decreases with increasing pressure and, with the exception of Langmuir&apos;s work, these investigations were confined to pressures below 10-6 atm. Above approximately 1300°C, depending on the oxygen pressure, the rate of oxide evaporation is greater than the oxide-formation rate and the recession of the tungsten surface can be measured optically without interference from an oxide layer. This was first done by Perkins and crooks6 who heated tungsten rods in air pressures from 1 to 40 torr at temperatures between 1300" and 3000°C. The present investigation of the oxidation kinetics of tungsten at high temperatures emphasizes oxygen pressures from 10-6 to 1 atm. This is the range of interest for earth atmosphere re-entry applications of tungsten for which little data were previously available. APPARATUS The apparatus is a modification of the type used by Perkins and crooks.&apos; Ground tungsten seal rods, 6 in. long by 0.125 in. diam, were mounted vertically between two water-cooled electrodes, one fixed and the other having free vertical travel. The movable counter-weighted electrode is prevented from undergoing horizontal displacement by three sets of runners mounted at 120-deg intervals. Electrical contact is made by means of a water-cooled mercury pool. A 24-in. vacuum bell jar having a volume of approximately 267 liters was used as the reaction chamber with the sample holder mounted in the middle of the chamber. Power was supplied from an 800-amp dc variable power supply. Temperature readings were made by means of a Latronics automatic two-color recording pyrometer. With this instrument, corrections for emissivity are not necessary provided the spectral emissivi-ties at two closely spaced wavelengths are equal. Supporting measurements were made with a micro-optical pyrometer corrected for emissivity of bare tungsten and window absorptivity. The micro-optical pyrometer was calibrated against a National Bureau of Standards calibrated tungsten lamp and both pyrometers were periodically checked against the melting points of tungsten and molybdenum using the oxidation apparatus. Above 10-6 atm, pressures were measured with an Alphatron gage calibrated against a McCleod gage. At 10-6 atm, a hot-filament ionization gage was employed. A magnified image of the self-illuminated tungsten rod was formed using a 360-mm objective lens mounted outside the bell jar. When the experiment exceeded 1 hr, the image was focused on a ground-glass plate about 10 ft from the tungsten rod at about X8 and the recession of the thickness of this image was monitored with a Gaertner cathe-tometer. When faster rates were encountered, a 35-mm time-lapse cinecamera with a telephoto lens and bellows extension was substituted for the ground-glass plate and cathetometer. Diameter recession rates were determined from the photograph image projected on the screen of an analytical film reader. EXPERIMENTAL PROCEDURE After installing the rod in the apparatus and cleaning it with acetone, the system was evacuated to 5 1 x 10-5 torr. Before oxygen was introduced,

Jan 1, 1964

By T. V. Subrahmanyam, A. P. Rao

The adsorption behavior of chalcopyrite has been studied at different xanthate concentrations and flow rates in a column apparatus with potassium ethyl xanthate as the collector. Based upon the experiment results an equation of the type: 1/F = K3 + m3C + k2/t.Cm2.fm1 is proposed to account for the experimental data. Among copper minerals an early study on chalcocite by Gaudin and Schuman (Taggart, 1951) is well known for its research on the kinetics of the reaction by conventional method of mass balance between the products of reaction and xanthate consumed. The results were interpreted by the concept of ion exchange adsorption. Szeglowski (1977) conducted measurements on the adsorption of potassium ethyl xanthate on copper polarized to various potentials, the adsorption being measured by radio-tracer techniques. The adsorption in the range -1800 to 700 mv was found to be a reversible physical adsorption. The potential range in which the primary electrode process could lead to surface coverage with a minimum number of product layers was evaluated. The adsorption density of xanthate on sulfide surface was found to be related to the concentration of xanthate in solution and concentration of depressants as: [ ]

Jan 1, 1983

By E. O. Lilge, H. Siebert

A design of a multiple-bomb leaching unit particularly suited for the study of heterogeneous reactions, i.e. sol id-liquid-gas interfaces at high temperatures and pressures is presented. The component parts and overall design are described and illustrated in detail. The system has been tested by a limited number of experiments and found to work satisfactorily. Heterogeneous reactions at solid-liquid-gas interfaces, at high temperatures and pressures, are studied in either autoclaves1&apos;4 or bombs5&apos;9. Autoclaves are usually fairly large vessels which have a stirring arrangement incorporated in the design. Mechanical design limits the use of these vessels to relatively low temperatures and pressures. They are particularly well suited to rate or kinetic studies. Bombs can be designed to be operated at high temperatures and pressures, and are smaller vessels; because of this, stirring arrangements are not easily incorporated. In this paper a multiple-bomb system is described, that has been designed to incorporate the desirable features of both the autoclave and the bomb. The described unit has flexibility for an over all study of leaching. Most of the component units in this assemblage are standard equipment, designed and produced by well known manufacturers. No claim is made to the design of this equipment, and although described in some detail, this is done merely for clarity in the elucidation of the system presented. The general layout of the multiple-bomb assemblage is shown in Fig. 1A and 1B. The basic units in this system are: 1) 6 stainless steel 100 ml bombs (Fig. 4)

Jan 1, 1964

By Margaret G. Scroger, Luke L. Y. Chang, Bert Phillips

Using the sealed-system technique, isothermal sections at 1000°, 1400°, and 1700°C for the system Co-W-O hare been determined. The equilibrium data were obtained by microscopic and X-ray diffraction examination of samples winch had been equilibrated in pellet form fit sealed capsules and subsequcelly quenched. The only ternary phase in the system is CoWO, which mells congruentlly at approximately 1280°C. At 1000°C, this ternary phase exists in equilihrinm with all the allows and oxide compounds in the hounding binary systems. At 1400°C, liquid forms in thin oxygen-rick region near the CoWO4 composition and only one phase assemblage in the system (W + WO2 + H&apos;5CV7) contains no In order for tungsten to be used to its full potential as a refractory metal. it is necessary that coatings be developed which will preclude oxidation of the metal. It is true that coatings now in use do protect tungsten for short periods at temperatures near 1700 °C. but no coating has been developed which protects adequately at or above this temperature where the use of tungsten is most required. This situation exists despite the great effort in recent years to develop such coatings. and it has become evident that success in this area can be achieved only after a more fundamental knowledge of the thermochemical and therrnophysical propertics of tungsten oxidation and tungsten -metal oxidation is obtained. In our 1aboratories. a project liclrriel. At 1700°C, tungsten is the ouly solid phase which is stctble, and a large range of compositions melt to two liquids, one metallic and one oxidie. The sealed-system method of etjuilibra lion prevents the determination of the partial pressure of oxygen and the total gas pressure orer the condensed phases at equilibrium. This data is not available and can be obtained only by some other method. We can generalize on these unknowns and indicate that both partial pressure of oxygen and total pressure of the gas phase must increase as compositions change from the W-Co binary toward the oxygen apex and as temperatures increase. has been initiated which is directed at providing some of this fundamental information through a study of metal-tungsten-oxygen reactions and equilibria and the properties of any intermediate phases which result. This paper is based on a part of this program in which the system Co-W-O was studied between 1000° and 1700°C. I) RELEVANT INFORMATION FROM THE LITERATURE A) The Notable Lack of High-Temperature Work on Metal-Tungsten-Oxygen Systems. It should be pointed out that there has been no published report (of which we are aware) which deals with the study of a metal-metal-oxygen system at 1700°C. Also, there has been no report on a complete metal-luugsten-oxgen system at any temperature. As a matter of fact. before this program started. The

Jan 1, 1965

By B. G. Langston, R. D. MacDonald, F. M. Stephens

WITH the development of uranium ores that contain substantial amounts of acid-consuming compounds, the alkaline leach has become an attractive method for extraction. Considerable work has been done on both atmospheric and pressure-leaching with aqueous solutions of sodium carbonate and sodium bicarbonate as the lixiviants.1,2,3 For the treatment of uranium-bearing limestones and other high-lime (CaO) ores, the sodium carbonate leach has proven attractive because it avoids the high reagent consumption incurred by the reaction of sulfuric acid with lime. In addition, the corrosion problems with sodium carbonate are negligible as compared with those encountered in the acid-leach system. The sodium carbonate leach, however, does not yield as high an extraction of the uranium as the acid leach and is not attractive for economic reasons when treating ores that are high in sulfates or sulfides.

Jan 9, 1957

By J. R. Mihalisin, J. S. Iwanski

The response of Inconel "700" to heat treatment has been studied by light and electron microscopy combined with X-ray and electron diffraction techniques. A heat treatment which vesults in low ductility for this alloy appears to be associated with the formation of MC carbide in a Widmanstdtten distribution. This type of precipitation can be suppressed by suitable heat treatment with concurrent increase in ductility. Various other phases precipitated in this alloy are also identified. RECENT studies of commercial nickel base su peralloys have demonstrated the importance of the morphology of carbide phases upon physical properties.&apos; For example, empirical heat treatment studies applied to Nimonic "80" and Inconel "X" have resulted in prescribing double aging treatments for optimum physical properties. These treatments have subsequently been related micro-structurally to grain boundary carbide morphology.2 The purpose of this study was to obtain information about the morphology and identity of some of the phases precipitated in Inconel "700" after heat treatment. It was hoped that some correlation could be made of micro structure with heat treatment similar to that observed with Inconel "X" and Nimonic "80." EXPERIMENTAL PROCEDURE Specimens were obtained from a hot-rolled bar of Inconel "700" of the following composition: C Mn Fe S Si 0.10 0707 0.42 0.007 0.12 Cu Cr -A1 -Ti- Co Mo Ni 0.02 -14.90 TM 2.22 27.61 2.92-- Bal. Specimens were prepared in the following heat-treated conditions: (A) 2275°F for 2 hr WQ (B) 2275°F for 2 hr WQ + 2000°F for 1 hr (C) 2275°F for 2 hr WQ + 1600°F for 48 hr. (D) 2275°F for 2 hr WQ + 2000°F for 1 hr + 1600°F for 48 hr. Empirical stress-rupture studies had shown that treatment (D) resulted in optimum stress-rupture life and ductility. Treatment (C), although giving a good aging response, resulted in low ductility. Treatments (A) and (B), respresenting individual. steps in treatments (C) and (D) were added here for microstructural comparison studies. The procedure was to make an optical and electron microscopic investigation supplemented by X-ray diffraction analysis of electrolytically extracted residues. Electron diffraction studies were made utilizing selected area diffraction techniques with extraction

Jan 1, 1960

By N. A. Zeigler

GRaphitization phenomena occurring in solid cast iron have principally been studied from the angle of the reactions taking place during annealing of white castings in the manufacturing of malleable iron. The selected bibliography at the end of this paper presents the high spots of the published information in this field. Graph-itization of gray iron upon reheating has received much less attention, primarily because only on rare occasions is this material subjected to any kind of industrial heat-treating. Moreovcr, articles made from gray iron are seldom used commercially at temperatures when any graphitization can take place. When used in such conditions, it is assumed that the articles can be replaced at frequent intervals, which can be afforded because of the low cost of gray iron. However, there is at least one commercial process in which articles made from gray iron, during their manufacturing processing, are subjectcd to rather high temperatures; that is, manufacturing of cast-iron enamelware, which is glazed at about 1600° to 1700°F. (870&apos; to 930°C.) From practical experience, it has been found that one of the convenient and economical compositions of gray iron suitable for enameling is, in round figures, as follows: Si, 2.50 per cent; Mn, 0.35; S, 0.07; P, 0.80; T.C., 3.35; C.C., 0.70. Since this iron usually is cast into thin-walled sections, the percentage of com- bined carbon in it is relatively high. Upon heating in the enameling furnaces, this combined carbon graphitizes, which causes permanent dimensional changes of the articles. Obviously, from practical considerations, it is desirable to maintain these dimensional changes as constant as possible. In the course of experimentation with this iron, two series of experimental heats were prepared in which the manganese to sulphur ratio of the standard cupola metal was offset by ladle additions of: (I) progressively larger amounts of sulphur, and (2) progressively larger amounts of manganese. Each one of these ladle charges was cast into experimental plates 8 by 4 in. and about 5/16 in. thick. All told, 13 ladle charges were thus treated. All of them are listed in Table I, together with their chemical analyses. It may be noted that the manganese to sulphur ratio in these samples ranges between 1.2 and 30.2. Every one of these compositions was subjected to thermal allalysis, using an automatic, self-recording differential dila-tometer. The specimens used in this instrument are 50 mm. long and 4 mm. in diameter. During the dilatometer cycle they are kept under a vacuum of about 3 microns. Each one of them was subjected to a thermal cycle by heating it to I830°F. (1000°C.) in 3 hr. and cooling to room temperaturc in 5 hr. Figs. I, 2 and 3 present three automatically recorded dilatometer curves for irons: Serial No. I (normal composition), Serial No. 6 (high sulphur), and Serial No. 13 (high manganese). All three of these figures are

Jan 1, 1945

By J. H. Polhems, R. B. Brackin, D. B. Grove

THE heavy media separation process plays an outstanding role in the concentration of 4000 tons of zinc ore per day at the Mascot mill of the American Zinc Co. of Tennessee. Of the total tonnage, 72 pct is treated in the heavy media separation plant to reject 56 pct of the ore as a coarse tailing, which has a ready market. Concentrates from this separation are beneficiated further by jigging and flotation. Approximately 25 pct of the total zinc concentrate production is made in the jig mill. Jig tailings are ground and pumped to the flotation circuit where the balance of the production is made. Fig. 1 shows a generalized flowsheet of the mill. The Mascot ore is a lead-free, honey-colored sphalerite in dolomitic limestone, with lesser amounts of chert and some pyrite. A mineralogical analysis is given in Table I. After 10 years of successful operation with galena medium and treatment of nearly 10,000,000 tons of ore, a decision to convert to ferrosilicon was made early in 1948 because of the increasing price of galena and consequent high operating costs. The conversion was made on Nov. 6, 1948, and the results obtained since that time have shown remarkable improvement over those made with galena. The Table I. Mineralogical Analysis of Mill Feed, Pct Calcium carbonate 49.5 Magnesium carbonate 35.2 Iron oxide and aluminum oxide 1.5 Zinc sulphide 4.5 Insoluble 9.3 100.0 Table II. Comparative Data, Galena and Ferrosilicon Ferro- Diner-Gelenaa siliconb ence Operating costs per ton milled, ct. 21.21 9.12 12.09 Medium consumption per ton milled, lb 0.80c 0.15 0.65 Reagent consumption per ton milled, lb 0.45 0.02 0.43 Tailing assay, pct Zn 0.310 0.297 0.013 Concentrate. oct Zn 12.08 10.33 1.75 Heavy medla ieparatlon recovery. pct 89.38 90.22 0.84 Mill feed rate, tons per hr 153 166 13 Heavy mesa separation feed rate. tons per hr 100 10 0 Tons milled per heavy media separation man shift 350 620 270 Mill feed to coarse tailings, pct 51.0 56.7 5.7 Lost mill time, pct 5.6 5.0 0.6 Power consumption, kw-hr per ton 2.06 1.92 0.14 a 1947. " First 6 months of 1950. c Net consumption after deducting credit for reclaimed waste galena. Consumption of new galena was 1.320 lb per ton milled. For entire life of galena operation, a credit of 40 pct of the value of the new galena added was realized from the sale of waste galena. comparisons given in this report cover the first 6 months of 1950 as representing the ferrosilicon operation, and the year 1947 as representing the galena operation. This was the last full year in which galena was used exclusively and is representative of the best work done during the 10 years of operation with this medium. After only 2 years&apos; operating experience, with ferrosilicon and treatment of 1,807,585 tons many advantages have been revealed and are summarized in Table 11. Development Prior to the introduction of the heavy media process, all the mill feed was crushed through 5/8 in. and treated by jigging. A finished tailing assaying 0.66 pct Zn was made on rougher bull jigs, and cleaner jig tailings were ground for treatment by flotation. The first test work on the sink-and-float method of mineral beneficiation was carried out at Mascot in 1935, using a 3-ft cone and galena medium for batch tests. The following year a 6-ft cone was installed for pilot-plant work. This unit became a part of the mill circuit on March 1, 1936, and handled a gradually increasing tonnage in the next 2 years as the process developed to the point where it could treat all the + 3/8-in. material in the mill feed. Coarse jigging was then discontinued on March 1, 1939, and all coarse tailings have been made by the heavy media separation plant since that time. Feed Preparation: The original feed preparation plant consisted of a drag washer followed by two 4x10-ft Allis-Chalmers washing screens. A surge bin and two additional 5x12-ft AC washing screens were added in 1943. Use of primary and secondary washing screens was found essential to provide the cleanest possible feed for the cone and thereby avoid excessive contamination of the galena medium. Improved washing was obtained by replacing the drag washer with a 7x20-ft Allis-Chalmers scrubber, shown in Fig. 2, which has been in service since May 1944. Throughout the life of the galena operation, delivery of extremely muddy ore to the mill overloaded the medium cleaning system, and it frequently was necessary to cut off the feed and clean the medium for several hours until its normal viscosity had been re-established. The cleaning circuit

Jan 1, 1952

By E. V. Potter

For a nurnber of years, it has been known that manganese made by electro-deposition under certain conditions is ductile while under other conditions it is very brittle. The ductile metal is gamma manganese normally stable only between 1100 and 1138°C1; the brittle metal is alpha manganese, stable up to 727OC. The ductile metal is not stable, but gradually changes to the brittle form; the time required to complete the transfornlation is about 20 days at room temperature. Other observations have indicated that the transformation is completed in 10 to 15 min. at about 125°C, while at — 10°C, no appreciable change occurs in 9 months. The properties of gainma and alpha Illanganese in the pure state are ordinarilj difficult to determine because the gamma structure cannot be retained by normal quenching procedures and alpha manganese is so brittle, it is difficult to obtain specimens free from flaws. In a recent investigation2 some properties of gamma and alpha manganese were determined by studying the ductile electrolytic metal and determining the changes in its properties as it transformed to the brittle alpha form. These investigations provided an excellent opportunity for following the progress of the transition and studying its mechanism. The results of a series of such investigations are reported in this paper. Procedure Various properties of manganese were determined starting with the metal in the original ductile gamma form and following the subsequent changes in its properties as the metal transformed to the brittle alpha form. These observations were made at various temperatures, the data providing information regartling the mechanism of the transformation as well as the effect of temperature 011 the transition rate. Structure and resistivity values gave the most significant results, so this paper is concerned primarily with them. The structure was studied microscopically as well as by X ray diffraction. The resistivity was determined on strips of the metal by measuring the potential drop across a given length of the specimen. Current was passed through the specimen by wires soldered to its ends, and the potential connections were made by wires looped around the specimen near its center. The current was determined by the potential drop across a standard resistor connected in series with the specimen, the potential drop being measured on a potentiometer. In the temperature range from room temperature to 100°C an ordinary drying oven was used to heat the specimen. This was entirely satisfactory except at 100°C, where the time required to heat the specimen was long compared to the transition time, making the initial section of the resistivity curve unsatisfactory. To overcome this limitation, at 100°C and higher a thermostatically controlled oil bath was used to heat the specimens. The block on which the specimen was mountetl was plunged into the hot oil at the start of each test. The heating time was thereby reduced from 5 min. to about 6 sec, and dependable resistivity values could be obtained through 160°C. At this point the whole transition, including the warm-up time for the specimen, required only about 20 sec and it was not considered worth while trying to extend the temperature range further. Aside from the heating problem, the problem of making a sufficient number of accurate resistivity determinations became more and more difficult as the temperature was raised. Using the manually operated potentiometer, 100°C was about as far as it was possible to go. At this temperature and above, a self-balancing photoelectric recording potentiometer was used. Its response was quite rapid, and it proved to be entirely satisfactory all the way through 160°C, where the tests were stopped because of the specimen heating problem rather than any limitation of the potentiometer recorder. The metal used in these tests was prepared at the Salt Lake City laboratory of the Bureau of Mines. The method of preparation is discussed in a paper by Schlain and Prater.3 The sheets were about 2 3/8 by 5 3/16 in. and varied from 10 to 16 mils in thickness. They could be cut readily into pieces suitable for the various tests. X ray and microstructure determinations were made on pieces about 1/8 to 1/4 in. wide and about 1 in. long, while resistivity measurements were made on strips as long as possible and about 55 in. wide. The thickness of each sheet was not uniform over all its surface. This had no bearing on the X ray and microstructure determinations, but sections as nearly uniform and free from flaws as possible were chosen for the resistivity determinations. The gamma manganese was electro-deposited at 30°C, the time of deposition ranging from 5 to 12 hr for each sheet. Whenever possible, the tests were started directly after the metal was stripped from the cathode; otherwise the sheet was placed immediately

Jan 1, 1950

By M. Cohen, D. J. Blickwede

Quantitative observations concerning the carbide phases in high speed steel are of importance for two general reasons: (1) the carbides, being inevitable constituents of the final structure, exert a direct influence on the properties of the steel; and (2) a substantial proportion of the total alloy content is tied-up in the carbides, and hence the extent of their solution on austenitizing governs the composition of the steel matrix. The latter relationship has a vital bearing on the response of the steel to tempering as well as on its performance in subsequent service. Accordingly, in the course of a long-term study of the behavior of high speed steels, the authors were confronted with the problem of securing quantitative data on the carbide phases. The obvious method for acquiring such information is to isolate the car-bides from the steel and subject them to chemical, X ray diffraction and other measurements. There are well-known extraction techniques which involve the chemical or electrolytic solution of the less noble matrix (ferrite, marten-site or austenite), thus leaving a residue of the carbide phases. However, the results obtained must be scrutinized carefully1,2 since the carbides may be affected by the chemical or electrolytic action. It is the purpose of the present paper to describe the experiments leading to an electrolytic-extraction technique for quantitatively isolating the carbides from both I and hardened high speed steel. Particular attention is paid to the amount, as well as the composition, of the carbides so that the matrix analysis becomes ascertainable by subtraction from the overall steel composition. Illustrative results are given for the M-2 grade of tungsten-molybdenum steel. Review of the Literature The chemical method of dissolving the matrix selectively with respect to the carbides makes use of dilute non- oxidizing reagents such as hydrochloric or sulphuric acid. Although this simple procedure has led to the determination of the cementite composition,3,4 it achieved only limited success because of the interaction between the acid and the carbide residue. Some of the carbides may not only be destroyed in this way, but the hydrogen released is likely to remove part of their carbon as hydrocarbon gases. The electrolytic technique of isolating carbides has the advantage of rapidly dissolving the specimen (anode) in the presence of less reactive solutions than are practicable with the chemical method. This reduces the possibility of chemical attack on the carbides, and furthermore, the hydrogen evolved during the electrolysis is released at the cathode which is not in close proximity to the carbides. The common electrolytes adopted for this purpose are hydrochloric and sulphuric acids.5-l1 Aqueous solutions of ferrous salts have also been used.12,13 A considerable advance in experimental technique was introduced by Treje and Benedicks14 who developed a double-compartment cell for electrolytic extraction, the anode and cathode chambers being separated by a porous diaphragm. A solution of 15 pct sodium citrate, 2 pct potassium bromide and 1 pct potassium iodide was selected for the anolyte, while the catholyte consisted of a 10 pct solution of copper sulphate, with copper serving as the cathode. This type of cell has a number of desirable characteristics: 1. The anolyte has a pH value close to 7, at least at the beginning of the run. 2. The iron that dissolves from the anode-specimen forms a water-soluble complex ion with the citrate, thereby preventing the precipitation of iron hydroxide (which would contaminate the carbide residue) despite the neutrality of the solution. 3. Copper deposition instead of hydrogen evolution occurs at the cathode, and this avoids an increasing concentration of hy-droxyl ions which (in an otherwise neutral solution) might cause the precipitation of insoluble hydroxides. 4. Contamination of the anode chamber by copper sulphate is inhibited by the porous diaphragm. Houdremont and coworkers15 applied the above method (with the further refinement of excluding oxygen during the electrolysis, washing and drying) to the extraction of carbides from a series of plain carbon steels after various heat treatments. They had quantitative success only with specimens in the annealed condition, and concluded that the size and shape of the carbide particles play an important role in the isolation process, with large spheroids exhibiting the least tendency to decompose during the electrolysis. Up to the present time, the citrate double-cell has not been used to any extent for isolating the carbides of high alloy steels, apparently on the grounds that the complex carbides are more resistant than cementite to attack in the simpler acid electrolytes. In particular, Bain and Grossmann7 and Gulyaev10.10a have employed the hydrochloric acid cell for their investigations of the carbides in high speed steel.* It will be demonstrated here that this type of cell is capable of yielding quantitative results in the case of high speed steel, and actually has certain advantages over the more complicated double cell. However, in order to provide a rigorous test of the quanti-tativeness of electrolytic procedures for the problem at hand, both methods were studied in considerable detail.

Jan 1, 1950

By Stanley Herold

Considerable interest has been shown, during recent years, in the possibilities of developing oil fields in the South American Republics, now that the exhaustion of our present fields can be seen in the not very distant future. The demand for fuel oil and its products has been increasing far more rapidly than our increment of production during the last few years. Increase of consumption has been largely curtailed by the lack of sufficient supply. The main factors that have contributed to our previous neglect of the southern fields have been as follows:, (a) Lack of sufficient demand for the product. (b) Competition with producing fields, having large production, low cost, and better geographical position, such as Tampico, Mexico. (c) Greater interest in home fields with ready market at hand. (d) Our ignorance of southern economic and geologic conditions, clue to the distance between those areas and our financial centers. (e) Economic conditions in the southern countries, necessitating high costs of exploration and exploitation of the fields.

Jan 9, 1918

By K. Tangri, B. Swaroop

Simultaneous measurements of lattice (elastic) strain by X-ray line shift method and total strain with an electrical strain gage have been carried out on polycrystalli,ne nickel with the help of a specially designed tensometer attachment for the X-ray dif-fractometer. During the initial stages of deformation, the rate of increase in lattice strain closely follows the total strain until the plastic strain sets in. From then onwards, the two strains deviate from each other and with further increase in afiplied stress the rate of increase of lattice strain eventually decreases. Depending upon the mode of unloading, both compressive and tensile strains have been observed in nickel deformed up to 0.29 pct strain. These results have been explained on the basis of the effects of clustering of dislocations and also the production and behavior of point defects during loading and unloading, respectively. POLYCRYSTALS deformed plastically in a uniaxial tension test show residual lattice strains (hereafter referred to as RLS), which broaden the X-ray line profiles and shift their peak positions.&apos;&apos;4 It is known that uniform straining of a crystal lattice (macrostrain) produced movement of ddfraction line peaks, whereas nonuniform straining (microstrain) causes line broadening.= Though the nature and origin of RLS in deformed metals is not yet clearly understood, these are believed to be due to the presence of some form of a locked-up stress system. Several possible detailed interpretations6&apos;" of the stress system have been proposed by various workers and common to all these interpretations is the assumption that different parts of the aggregate have different tensile yield stresses; e.g., that a part A yields under a lower applied stress than a part B. Therefore, during the deformation process, the elastic strain in A will be less than that in B, and, after completion of deformation, B will tend to contract further than A but will be prevented from doing so by the restraining influence of A. Thus, when equilibrium is reached, A will be in compression while B is in tension. Although there is general agreement on the correctness of this argument, controversy still exists as to the exact nature of the parts A and B in a deformed metal. In an alternative approach to the creation of parts A and B, many other investigators have assumed that the RLS observed in unloaded specimens are in some way connected with the lack of proportionality between lattice strain and applied stress in the region above the yield stress." cullity13 has prepared a schematic summary of the results of previous workers, mainly Smith and Wood,2&apos;11 which suggests that, above the elastic limit, the lattice strain may increase less rapidly with respect to strain, or may even decrease with increase in applied stress. If the applied stress is then decreased, the lattice strain would decrease along a line parallel to the loading line in the elastic region and thus produce a compressive residual lattice strain after unloading. At equilibrium, to balance these compressive stresses? there would have to be regions under tensile stress which may well be the grain boundaries or the substructure walls formed during deformation. The present investigation was undertaken to gain a better understanding of the nature and origin of RLS and also to experimentally verify the salient features of this hypothesis. EXPERIMENTAL Stress and strain determinations were made with a specially constructed tensometer attachment for the X-ray diffractometer, Fig. 1: which permits the following measurements simultaneously on a sheet specimen under uniaxial tension at various stress levels during loading and unloading: a) lattice strains, E=. in a direction perpendicular to the direction of pulling (x direction) from shifts in X-ray line peak positions; b) the total strain, ex, in the direction of pulling. with the help of an electrical strain gage affixed to the back of the specimen directly below the area irradiated by X-rays: and c) the applied stress, with the help of a load cell which consisted of a calibrated stainless-steel sample of dimensions identical to those of the specimen under investigation, and to which it was coupled. Because of its high stacking fault energy.I4 nickel

Jan 1, 1970

By Mungo Park, C. Baring Horwood

This paper is intended, in the light of recent investigations, to call attention to some of the essential features of good practice in sampling and mine-valuation. Mine-sampling may be divided broadly into two classes: (1) development-sampling and cornputatioll of ore-reserves; and, (2) stope-sampling and estimation of stope-values. Development-Sampling. It is with development-sampling only that this paper deals— the term development being taken to mean the opening-up of a mine by cross-cuts, drives, connections, etc., preparatory to actual extraction of the ore for milling. In development-sampling the work of the sampler and the consequent estima-

Jan 1, 1909