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By Hsun Hu

Three single crystal strips of a 3 pct Si-Fe alloy with approximately (110) [001], (210) [001], and (100) [001] orientations were rolled at room temperature to 30, 50, and 70 pct reductions in thickness. Their deformation and annealing textures were studied. In most cases, the change in texture upon recrystallization and subsequent growth can be described as rotations around the <I10 > axes. A < WO > rotational relationship was also observed. The temperature dependence of recrystallization textures was discussed. WhILE considerable data have been published on the rolling and annealing textures in silicon-iron crystals, very little study has been made on the texture formation at various stages of rolling deformation, and during the process of recrystallization. Dunn&apos; in some of his early works had studied the orientation of recrystallized grains in crystals cut out from lightly rolled (10 to 20 pct reduction) large grained sheets. He found that in most cases a third-order twin relationship exists between the crystal and the recrystallized grains. This orientation relationship actually corresponds to rotations around the <110> axes. The more recent studies of Dunn &apos; and of Dunn and Koh &apos;5 on the rolling and annealing textures in various silicon-iron crystals were concerned mostly with a cold-rolling reduction of 70 pct and annealing at 980OC for recrystallization. Reductions of similar magnitude were also employed by Walter and Hibbard in rolling columnar crystal aggregates of a silicon-iron ingot. A systematic study of the effect of rolling reduction on the deforma- tion and annealing textures is still lacking. Regarding the effect of annealing temperature on the texture formation, Dunn3 has observed a change in therecrys-tallization texture by annealing a 70 pct rolled (1 10) [001] crystal first at a low temperature then atahigh temperature. But the details of texture formation during the annealing treatments were not thoroughly investigated. The present investigation was undertaken to study the texture developments at various stages of rolling deformation and of the recrystallization process, so that a better understanding on the texture formation in silicon-iron crystals may be obtained. EXPERIMENTAL PROCEDURE The three single crystals used in the present investigation were selected from the group of single crystal strips previously prepared7 from a high grade commercial Si-Fe alloy with 3 pct Si. The thickness of these single crystal strips was 0.040 in. The orientations of the three crystals as determined by the X-ray back-reflection Laue technique are shown in Table I. Each of the three crystals was rolled at room temperature along the strip direction to 30, 50, and 70

Jan 1, 1962

By E. Miller, J. M. Eldridge, K. L. Komarek

The liquidus curve of the Mg-Pb system was accurately redetermined. The compound Mg2Pb decomposes peritectically at 538.2° ± 0.3°C to liquid and to a compound p&apos; which melts congruently at 35.0 at. pct Pb and 549.0° ± 0.3°C. The solidus curve of ß&apos; was determined. X-ray diffraction studies indicate that 4&apos; has an orthorhombic structure. Activity values of magnesium calculated from the phase diagram agree with those published in the literature. EXPERIMENTAL thermodynamic properties of binary metallic systems have to be consistent with values calculated from the phase diagram. In systems forming intermetallic compounds the shape of the liquidus curve near a compound is determined by the thermodynamic properties of the coexisting solid and liquid phases. Hauffe and Wagner&apos; neglected the temperature dependence of the chemical potentials and obtained the potential differences of the components of the liquid alloys, relative to stoichiometric liquid. Their calculations were based on the liquidus curve and on the heat of fusion of the compound, and were only valid near the congruent melting point. Steiner, Miller, and Komarek2 developed equations which account for the temperature dependence and obtained the chemical potentials of liquid Mg-Sn alloys over the entire phase diagram from the liquidus and solidus curves and from enthalpy values with the pure components as the standard states. The Mg-Pb phase diagram has been studied by several investigators whose results have been compiled and critically evaluated by Hansen.3 Although the liquidus curve was poorly defined, the general features of the diagram, i.e., one congruent melting compound, Mg2Pb, of essentially stoichiometric composition, two eutectics, and limited terminal solid solubilities, seemed to be suitable for a similar thermodynamic analysis. A careful redeter-mination of the liquidus by thermal analysis revealed, however, the existence of another compound. The liquidus curve between the two eutectics was precisely delineated and the structure and solidus curve of the new compound were investigated. The revised phase diagram was thermodynamic ally analyzed to evaluate the activity of magnesium in the liquid alloys. EXPERIMENTAL PROCEDURE The magnesium metal (Dominion Magnesium Ltd., Toronto, Canada) had a purity of 99.99+ pct; lead (American Smelting and Refining Co.) contained 99.999 pct Pb. Most experiments were carried out in graphite crucibles. Several experiments were made in high-purity alumina (Triangle R.R., Mor-ganite, Inc.) and in Armco iron crucibles to test the inertness of the graphite crucibles. Chemical analysis of magnesium and detailed description of the procedure for thermal analysis have been given previously. For the determination of the solidus curve of the compounds, specimens of initial composition Mg2Pb were equilibrated in a closed isothermal system with magnesium vapor. The source of the magnesium vapor was an alloy which had a gross composition lying in the 0&apos; + L field at the temperature of equilibration. As equilibrium was approached, the specimens lost magnesium to the two-phase reservoir thereby lowering the activity of magnesium in the specimens until activity and composition equaled that of the ß&apos;/ß&apos; + L boundary. Crucibles (1.9 cm ID by 2.2 cm OD by 4.1 cm high) and tightly fitting lids were machined from a molybdenum rod; small, shallow trays were fashioned from thin (0.005 in.) molybdenum sheet, and all the molybdenum components were degreased in hot carbon tetrachloride and then dried. The pieces were then degassed in vacuum at 950°C for about 6 hr. The two-phase alloy was placed at the bottom of the crucible and small specimens of the Mg2Pb compound, weighed on an analytical balance, were placed in two molybdenum trays above the two-phase alloy. The crucible was closed by forcing its lid on and then inserted in a titanium crucible. This crucible was evacuated, flushed twice with argon, and welded under argon. The specimens were equilibrated for about 1 week in a resistance furnace regulated by a Celectray controller, and the runs were terminated by water quenching. The specimens were again weighed and the equilibrium compositions were calculated on the basis that the weight losses were solely due to a loss of magnesium to the two-phase alloy. The structure of the B&apos; phase was investigated by the Debye-Scherrer X-ray diffraction technique. Selected ingots from thermal-analysis experiments containing about 35 at. pct Pb were re-melted, slowly cooled, and crushed in an argon-filled glovebox until the entire ingot passed through a 50-mesh sieve. The powder was thoroughly

Jan 1, 1965

By Alexander Squire

A brief study of the effects of material and processing variations upon the tensile properties of steel formed from mixtures of iron and carbon was made in order to provide information regarding the properties obtainable in iron-carbon compacts as influenced by forming pressure, sintering temperature, and graphite particle size. Sintered steels formed from mixtures of iron and graphite have been studied by Stern,&apos; who investigated the effect of various percentages of graphite on compacts formed from electrolytic iron that were repressed and heat-treated after sintering. A further study, by Stern and Greenberg,l is concerned with the heat-treatment of steels formed by the car-burization of iron compacts, and Margolies3 has reported work on the simultaneous sintering and carburization of iron-powder parts. Glauch4 investigated the effect of various types of graphite on the properties of iron-carbon powder alloys but did not determine the effect of different particle sizes of the same graphite alloyed with different types of powder. In the investigation reported in this paper, powders typical of those produced by electrolytic deposition and the decar-burization of shotted steel scrap were used. The powders were mixed by tumbling in a jar mill with graphite powder ground to an average particle diameter of 2, 4, 6, and 16 microns (as determined by microscopic measurement). The properties of the iron and graphite powders are presented in tabular form as Table I. In order to obtain the maximum information from a minimum number of test specimens, the study was divided into two sections with one set of specimens treated identically in each section as a basis for comparison. In the first section, iron powder produced by the shotting and subsequent decarburization of scrap steel was mixed with 2-micron graphite powder, pressed at 50,000, 100,-000, and 200,000 psi, and sintered in hydrogen at 1200°C for the periods of time ranging from 15 to 120 minutes. In the second section of the investigation, electrolytic iron powder was mixed with graphite of an average particle diameter of 2, 4, 6, and 16 microns, pressed at 100,000 psi, and sintered at temperatures ranging from 1000° to r200°C&apos;. for periods of time of 30 to 180 minutes. By following this procedure an indication of the effect of the following variables upon the density and tensile properties of iron-carbon powder compacts was obtained: (I) forming pressure, (2) sintering time, (3) particle size of graphite powder, (4) sintering temperature, (4) type of iron powder.

Jan 1, 1947

By Alexander Squire

A brief study of the effects of material and processing variations upon the tensile properties of steel formed from mixtures of iron and carbon was made in order to provide information regarding the properties obtainable in iron-carbon compacts as influenced by forming pressure, sintering temperature, and graphite particle size. Sintered steels formed from mixtures of iron and graphite have been studied by Stern,&apos; who investigated the effect of various percentages of graphite on compacts formed from electrolytic iron that were repressed and heat-treated after sintering. A further study, by Stern and Greenberg,l is concerned with the heat-treatment of steels formed by the car-burization of iron compacts, and Margolies3 has reported work on the simultaneous sintering and carburization of iron-powder parts. Glauch4 investigated the effect of various types of graphite on the properties of iron-carbon powder alloys but did not determine the effect of different particle sizes of the same graphite alloyed with different types of powder. In the investigation reported in this paper, powders typical of those produced by electrolytic deposition and the decar-burization of shotted steel scrap were used. The powders were mixed by tumbling in a jar mill with graphite powder ground to an average particle diameter of 2, 4, 6, and 16 microns (as determined by microscopic measurement). The properties of the iron and graphite powders are presented in tabular form as Table I. In order to obtain the maximum information from a minimum number of test specimens, the study was divided into two sections with one set of specimens treated identically in each section as a basis for comparison. In the first section, iron powder produced by the shotting and subsequent decarburization of scrap steel was mixed with 2-micron graphite powder, pressed at 50,000, 100,-000, and 200,000 psi, and sintered in hydrogen at 1200°C for the periods of time ranging from 15 to 120 minutes. In the second section of the investigation, electrolytic iron powder was mixed with graphite of an average particle diameter of 2, 4, 6, and 16 microns, pressed at 100,000 psi, and sintered at temperatures ranging from 1000° to r200°C&apos;. for periods of time of 30 to 180 minutes. By following this procedure an indication of the effect of the following variables upon the density and tensile properties of iron-carbon powder compacts was obtained: (I) forming pressure, (2) sintering time, (3) particle size of graphite powder, (4) sintering temperature, (4) type of iron powder.

Jan 1, 1947

By John S. Johnson

The maintenance cost, or renewal cost, in any preparation plant is a large item of expense and reflects in the total cost of producing and preparing the ton of coal. It is given constant study to the end that ways and means of controlling and reducing this proportion of the total cost may be developed. Study of this item of cost has proceeded along usual lines, which are: proper functioning of the maintenance organization; systematic and thorough inspection to prevent breakdonns; the making of repairs before renewals are needed; maintenance work done thoroughly the first time, instead of patching, study of parts needing frequent renewal or repairs or conditions resulting in delays, thorough knowledge of cost by the mall responsible for maintenance; and the use of special equipment and materials. This paper is to deal with special equipment and materials to reduce the maintenance cost hut before going into that I want to express an opinion on the general subject. Maintenance Organization Usually maintenance is taken care of by a group of men who perform their work on the off shift. The work is arranged by the operating official who should be thoroughly familiar with maintenance, so that materials needed may be made up for the particular job and waste of time in looking up materials be prevented. To perfect the maintenance organization, all operating attendants should be thoroughly trained to be familiar with all working parts of their equipment, to make a thorough inspection and to write out the slip for the work required. This requires job analysis, but it is worth the effort, because the attendant usually is better informed than anyone else about his particular equipment. The operating official can judge the scope of the work to direct the repair and to have material ready. Lubrication is an important item in maintenance, and a subject by itself. Usually the breaker oiler is designated to perform this task. This man should be picked for his ability and put in line for promotion to machinist. He should be trained as an inspector, as he is constantly visiting most parts of the breaker and has an opportunity to observe needed maintenance. The first thing is to lay out maintenance work and arrange to have it done; the next is to check the work and see that it has been properly done. This check should be made by the operating official, and through the attendant. The cost statement showing the various items of maintenance cost is not often understood by the man in direct charge. Cost sheets should be simplified and worked up by breaker sections; e.g., the cost of

Jan 1, 1947

By John S. Johnson

The maintenance cost, or renewal cost, in any preparation plant is a large item of expense and reflects in the total cost of producing and preparing the ton of coal. It is given constant study to the end that ways and means of controlling and reducing this proportion of the total cost may be developed. Study of this item of cost has proceeded along usual lines, which are: proper functioning of the maintenance organization; systematic and thorough inspection to prevent breakdonns; the making of repairs before renewals are needed; maintenance work done thoroughly the first time, instead of patching, study of parts needing frequent renewal or repairs or conditions resulting in delays, thorough knowledge of cost by the mall responsible for maintenance; and the use of special equipment and materials. This paper is to deal with special equipment and materials to reduce the maintenance cost hut before going into that I want to express an opinion on the general subject. Maintenance Organization Usually maintenance is taken care of by a group of men who perform their work on the off shift. The work is arranged by the operating official who should be thoroughly familiar with maintenance, so that materials needed may be made up for the particular job and waste of time in looking up materials be prevented. To perfect the maintenance organization, all operating attendants should be thoroughly trained to be familiar with all working parts of their equipment, to make a thorough inspection and to write out the slip for the work required. This requires job analysis, but it is worth the effort, because the attendant usually is better informed than anyone else about his particular equipment. The operating official can judge the scope of the work to direct the repair and to have material ready. Lubrication is an important item in maintenance, and a subject by itself. Usually the breaker oiler is designated to perform this task. This man should be picked for his ability and put in line for promotion to machinist. He should be trained as an inspector, as he is constantly visiting most parts of the breaker and has an opportunity to observe needed maintenance. The first thing is to lay out maintenance work and arrange to have it done; the next is to check the work and see that it has been properly done. This check should be made by the operating official, and through the attendant. The cost statement showing the various items of maintenance cost is not often understood by the man in direct charge. Cost sheets should be simplified and worked up by breaker sections; e.g., the cost of

Jan 1, 1947

By M. E. Wadsworth, T. L. MacKay

Sintered UO, samples were leached in sulfuric acid solutions of various concentrations. A pressurized system was used so that it was possible to investigate the kinetics of the reaction to 270°C with oxygen overpressures as high as 900 psi. The rate was observed to be a function of the concentration of hydrogen ions and directly proportional to the partial pressure of oxygen. Evidences are presented which indicate that a UO2 surface site reacts with a molecule of water to form a hydroxyl complex which in turn can dissociate with the characteristics of a weak acid. A rate determining step has been proposed which involves the reaction between an oxygen molecule and the hydroxyl complex on the surface of UO,. ThE 2 principal methods for uranium dissolution are carbonate and acid leaching. The sulfuric acid leach is the more popular and is used for the treatment of the majority of the ores of Africa, Canada, and the United States. Low recoveries in basic leach circuits led investigators at the University of British columbia1 to study leaching of uranium ores in pressurized vessels. Early in the study of dissolution of uranium it was found that only uranium in the hexava-lent state could be leached in acid or basic circuits. Therefore, the use of oxygen over-pressure in an autoclave offered an interesting approach to solving the low recovery problems of carbonate leaching. UO, was used in this study because it could be obtained in high purity and also because it is representative of the most refractory of the primary uranium minerals. A pressurized system was used to provide a means whereby important temperature and pressure parameters could be varied for the evaluation of the kinetic processes. The mechanism for the dissolution of UO2 should be similar for any of the uraninite type minerals. At the present all of the kinetic studies that have been conducted have been in carbonate media. Peters and Halpern2 carried out a kinetic study of the leaching of pitchblende. Their specimens were pitchblende ores selected on the basis of high grade and homogeneity. Pearson and wadsworth3 conducted a kinetic study of the dissolution of UO2 in carbonate solutions with results very similar to those obtained by Peters and Halpern. EXPERIMENTAL The UO2 as received* was found by spectroscopic *Mallinckrodt reagent, supplied by the Atomic Energy Commission. analysis to have a purity of 99.94 pct 0.03. It was ground in a mechanical agate mortar and screened through a 400-mesh sieve. Thin flat disks of UO2 were prepared by pressing the sized powder in a specially constructed die at a total pressure of approximately 25 tons per sq in. The pressed disks were approximately 0.25 cm thick, 1.6 cm diam, and 3.5 g in weight. As pressed, the samples were approximately 65 pct of theoretical density. It was essential that a binder such as poly-vinyl alcohol be added before pressing to prevent formation of cracks when fired. It was found by trial and error that pressed disks sintered close to 1870°C in a hydrogen atmosphere, reach densities between 91 and 91.5 pct of the theoretical density. At this density the samples had no measurable porosity based upon a 2-hr emersion in boiling water. An X-ray examination of these sintered UO2 disks showed them to be identical with the original UO2 received. Reaction of UO2 with the alundum furnace core was prevented by placing molybdenum between the samples and the core according to the method of Corwin and Eyerly.4 Leaching studies were carried out in a specially designed autoclave, the details of which have been presented e1sewhere.6 The main features of the equipment as applied to a kinetic study are: 1) solution samples may be removed during the course of a single run; and 2) temperature and agitation are carefully controlled. Two-ml samples removed from the autoclave during the course of a run were analyzed for U3O8 content with a Beckman model DK-2 spectrophotometer by the method of

Jan 1, 1959

By George E. Moore, B. K. Miller

The Missouri fire clays are here divided into plastic and semiplastic clays occurring as widespread bedded deposits in east central Missouri and flint and diaspore clays occurring as isolated "sink-hole" deposits in the north central Ozark region. Visual inspection was the first method used in clay prospecting. Thin overburden, hard sandstone "rimrocks," and the occurrence of diaspore float made this method particularly applicable in the flint and diaspore fields. The first drilling tool used was a hand auger. One man can drill 25 to 50 ft. per day at a cost of about 35 cents per foot. Holes can be drilled to a depth of 150 feet. Spud drills are often used where the overburden is hard. This drill uses a slotted earth socket bit. A two-man crew can drill about 100 ft. per day at a cost of about 35 cents per foot. Mechanically powered auger drills have been used extensively in wildcat drilling in the past few years. This type of drill furnishes a continuous set of cuttings. The practical depth limit with this drill is 50 to 60 ft. Two men can drill 300 ft. per day at a cost of about 20 cents per foot. Core drilling is used mainly to prove a known &apos;lay deposit. A A crew with a No. 22 Sullivan drill can drill about 30 to 40 ft. per day in soft clay, at a cost of about $1.25 per foot. Introduction Because of the geological variations in the Occurrence of the several types of fire clay mined in Missouri, it is necessary, when discussing the prospecting methods used for discovering and proving these clays, to divide these operations into two classes, one including plastic and semi-plastic fire clays, the other flint and diaspore clays. The plastic and semiplastic fire clays in the east central and St. Louis districts are generally classified as Cheltenham clays. This formation is a more or less continuous deposit and is found Over a large area in east central Missouri. There are variations, however, in the quality and thickness of the clay, which necessitate detailed prospecting in order to determine deposits of economic value. The nature of the overburden (Fig. 1), which consists of Pennsylvanian limestone and shale beds of varying thicknesses, and a mantle of glacial drift, regu1ates the methods and equipment used in prospecting for these clays. The district in which these clays occur is a gently rolling upland region, characteristic of most of northern Missouri. Along the southern fringe of this area there are numerous deposits of flint clay lying as masses or lenses in depressions at the base of the continuous and widespread Cheltenham formation, or as outlying "sink-hole" deposits in the area marginal to that formation. South of the Missouri River in the north central Ozark region, there are high-grade flint and high-alumina clays, commonly referred to as burley and diaspore clays in sink-hole type deposits. The overburden On these deposits is thin, consisting chiefly of soil and hard-pan, which varies from a plastic

Jan 1, 1948

By B. K. Miller, George E. Moore

The Missouri fire clays are here divided into plastic and semiplastic clays occurring as widespread bedded deposits in east central Missouri and flint and diaspore clays occurring as isolated "sink-hole" deposits in the north central Ozark region. Visual inspection was the first method used in clay prospecting. Thin overburden, hard sandstone "rimrocks," and the occurrence of diaspore float made this method particularly applicable in the flint and diaspore fields. The first drilling tool used was a hand auger. One man can drill 25 to 50 ft. per day at a cost of about 35 cents per foot. Holes can be drilled to a depth of 150 feet. Spud drills are often used where the overburden is hard. This drill uses a slotted earth socket bit. A two-man crew can drill about 100 ft. per day at a cost of about 35 cents per foot. Mechanically powered auger drills have been used extensively in wildcat drilling in the past few years. This type of drill furnishes a continuous set of cuttings. The practical depth limit with this drill is 50 to 60 ft. Two men can drill 300 ft. per day at a cost of about 20 cents per foot. Core drilling is used mainly to prove a known &apos;lay deposit. A A crew with a No. 22 Sullivan drill can drill about 30 to 40 ft. per day in soft clay, at a cost of about $1.25 per foot. Introduction Because of the geological variations in the Occurrence of the several types of fire clay mined in Missouri, it is necessary, when discussing the prospecting methods used for discovering and proving these clays, to divide these operations into two classes, one including plastic and semi-plastic fire clays, the other flint and diaspore clays. The plastic and semiplastic fire clays in the east central and St. Louis districts are generally classified as Cheltenham clays. This formation is a more or less continuous deposit and is found Over a large area in east central Missouri. There are variations, however, in the quality and thickness of the clay, which necessitate detailed prospecting in order to determine deposits of economic value. The nature of the overburden (Fig. 1), which consists of Pennsylvanian limestone and shale beds of varying thicknesses, and a mantle of glacial drift, regu1ates the methods and equipment used in prospecting for these clays. The district in which these clays occur is a gently rolling upland region, characteristic of most of northern Missouri. Along the southern fringe of this area there are numerous deposits of flint clay lying as masses or lenses in depressions at the base of the continuous and widespread Cheltenham formation, or as outlying "sink-hole" deposits in the area marginal to that formation. South of the Missouri River in the north central Ozark region, there are high-grade flint and high-alumina clays, commonly referred to as burley and diaspore clays in sink-hole type deposits. The overburden On these deposits is thin, consisting chiefly of soil and hard-pan, which varies from a plastic

Jan 1, 1948

By G. R. Belton, R. J. Fruehan

The Knudsen cell-mass spectrometer combimtion has been used to study the Fe-Al and Ag-Al liquid alloys. By application of the recently developed integration technique to the measured ion-current ratios, activities have been derived for the Fe-A1 system at 1600° C and for the Ag-Al system at 1340"C. The results are partially represented by the following equations: Internal consistency between the data on silver-rich and iron-rich alloys is demonstrated by application of the literature measurements on the distribution of aluminum between the nearly immiscible liquids iron and silver. The usual restrictions on the ratio of the mean free path of the escaping atoms to the orifice diameter of the Knudsen cell are shown not to be limiting in this technique. DESPITE the importance of a knowledge of the activity of aluminum in understanding deoxidation equilibria in molten steel, no direct studies have been made of activities in liquid Fe-A1 alloys at steel-making temperatures. Lower-temperature direct studies have, however, been carried out on aluminum-rich liquid alloys by Gross, Levi, Dewing, and Eilson&apos; at 1300°C and by Coskun and Elliott&apos; at 1315°C. Apart from phase diagram calculations by Pehlke, other determinations have been indirect and were made by measurement of the distribution of aluminum between iron and silver475 and combination of these data with extrapolated activities in the Ag-A1 system.~-% ecently, however, Woolley and Elliott have made a significant contribution by directly measuring heats of solution in the Fe-A1 system at 1600°C. The present authorslo have recently employed a Knudsen cell-mass spectrometer technique in a study of activities in iron-based liquid alloys. In this technique activities and heats of solution are determined from a series of measurements of the ratio of ion currents of the components; and since ion-current ratios are used, problems caused by changes in instrument sensitivity or cell geometry are overcome. Results obtained for the Fe-Ni system were found to be in excellent agreement with previous work, thus demonstrating the reliability of the method. The present paper describes a similar study of activities in the liquid Fe-A1 and Ag-A1 systems, this latter system being included in order that a meaningful comparison can be made with the above-mentioned indirect studies. INTEGRATION EQUATIONS A detailed derivation of the equations used to determine the thermodynamic properties from the measured ion current ratios has been given elsewhere;&apos;&apos; however it is useful to summarize them here. By the combination of the Gibbs-Duhem equation with the direct proportionality between ion-current ratios and partial pressure ratios, it was shown that for a binary system at constant temperature and pressure: where al is the activity of component 1 with pure substance as the standard state, N, is the atom fraction of component 2 in the solution, and I; and t&apos;2 are ion currents of given isotopes of the components. The activity coefficient is given by: this latter equation being more suitable for graphical integration. Combination of Eq. [l] with the Gibbs-Helmholtz equation gives an expression for the partial molar heat of mixing: EXPERIMENTAL A Bendix Time-of-Flight mass spectrometer model 12! fitted with a 107 ion source and a M-105-G-6 electron multiplier, was used to analyze the vapor effusing from the Knudsen cell. The arrangement of the Knudsen cell assembly was essentially that of the commercial instrument (Bendix model 1030) but with several modifications. Instead of heating with a single tungsten filament, a cylindrical tantalum-mesh heater was employed. Up to 1400°C simple resistance heating was used but above this temperature electron bombardment between the tantalum mesh and the tantalum cell susceptor was necessary. The temperature was measured by means of a Leeds and Northrup disappear ing-filament type optical pyrometer sighted on an essentially black-body hole in the side of the cell. Details of the temperature control, temperature measurement, and in situ calibration of the optical pyrometer can be found elsewhere.I0 In the investigation of the Fe-A1 system the Knudsen cells were constructed of thoria crucibles with fitted thoria lids (Zircoa). The cells employed in investigating the Ag-A1 alloys were made up of high-purity alumina crucibles (Morganite) with lids of recrystal-lized alumina (Lucalox). The cells were 0.370 in.

Jan 1, 1970

By A. G. Guy

Zinc vapor from a reservoir of liquid zinc maintained at lower temperatures was diffused into sets of copper-zinc alloys at 759° and 870° C and into sets of silver-zinc alloys at 650° and 700° C. Each set of ,four copper-zinc alloys consisted of pure copper and 90/10, 80/20, and 70/30 brass. Similarly the set of silver-base alloys consisted of specimens containing 0, 7, 15, and 20 pct Zn. Natural markers at the initial surfaces of the specimens ware "trapped" under a thin electroplate and their depth of burying was measured after diffusion. The ratio of diffusivities of the two components determined from these data and the chemical diffusion coefficient calculated by the Matano method agreed with previously reported results. The line of markers was irregular and was often discontinuous when a grain boundary was crossed. TECHNIQUES involving the vapor phase have been widely employed in studying diffusion phenomena in metals. Many investigators have evaporated the more volatile component from an alloy, but it is generally believed that the porosity created under these conditions interferes with adequate interpretation of the experimental results. The extensive work of Gertsriken6 has been criticized on this score. Accary1 found that the diffusion coefficient for de-zincification of brass is larger by a factor of five than that for zincification, although he attributed the difference to a higher vacancy concentration under conditions of dezincification. Balluffi and siegle2 thoroughly investigated the technique of adding a more volatile component to a less volatile base metal as a means for studying diffusion. They verified that no porosity forms in a brass under these conditions and that the diffusivities of the two components can be determined from observations of the motion of markers originally placed on the surface of the specimen. The mathematical analysis that they developed for treating the experimental data was modified in a later note, but essentially it involved using the graphical Boltzmann-Matano method that is customarily applied to solid-solid diffusion couples. The experimental method used in the present research was similar to that employed by Balluffi and Siegle except for two modifications. Balluffi and Siegle used alloy chips as the source of metal vapor. This procedure has the disadvantage that the concentration of solute at the surface of the specimen changes during the diffusion experiment as the alloy content of the chips is gradually decreased. This disadvantage was overcome by employing liquid zinc as the source of zinc vapor in a manner similar to that described by Herasymenko.9 There was then no limitation on the amount of solute usefully available, and several relatively large specimens could be diffused in a given experiment. The second modification was the use of natural markers on the surface of the specimen rather than larger, artificial markers, such as the alumina powder employed by Balluffi and Siegle. It was expected that the fine, natural markers would permit more precise measurement of the buried interface as in the case of ordinary sandwich specimens.10 EXPERIMENTAL The experiments were designed so that zinc from the vapor phase would maintain a constant zinc content at the surface of pure copper (or silver) and

Jan 1, 1960

By G. N. Goldberg, Robert A. Rapp

The steady-state kinetics and microstructures of simultaneous internal oxidation and external scale formation were investigated for the oxidation of Cb-Zr and Ch-Zr-Re alloys in pure oxygen at 1000°C. For each binary alloy, a constant rate of scale formation was observed at steady state; the internal oxidatton zone reached a steady-state, time-independent thickness. The dependence of the scaling rate on zirconium content exhibited a maximum at a low zirconium colttent; more concentrated alloys oxidized at a slower rate than pure columbium. This composition dependence of the scaling rate may be partially attributed to the effect of the internal oxidation process as an intenla1 sink for oxygen, with the formation of voluminous, and relatively impermeable ZrO2 precipitates. However, the morphologies of the ZrO2 internal oxide precipitates also affected the scaling rate. The internal oxide precipitates were distributed uniformly in the external scale. The steady-state thicknesses of the internal oxidation zones were not in agreement with those predicted theoretically from an idealized simple model. However, in this particular alloy systen1 the ideal model is not satisfied experitmentally. For ternary Cb- Zr - Re alloys with Nr10e = 0.02 or 0.05, the steady-state thicknesses of the internal oxidation zones were less than those for the corresponding binary Cb-Zr alloys. For ternary alloys with NRe(0) - 0.05, a more adherent and much less porous external scale was formed, and a reduction in the kinetics of scale formation was observed. A number of authors&apos;-7 have reported linear oxidation kinetics for the reaction of pure columbium at 1000°C in air or in oxygen of about 1 atm pressure. A thin and tightly adherent oxide layer is found at the metal/oxide interface beneath a porous external layer of scale. Although the suboxides CbO and CbO2 represent thermodynamically stable phases at 100O°C, generally only Cb2O5* is identified as a reaction product in quenched specimens. Studies at 1000°C at lower oxygen pressures8,10 (Po2 - 10-4 Torr) show that both CbO and CbO2 do form and that CbO2 is a protective oxide. The growth of CbO2 results in parabolic kinetics until Cb2O5 is nucleated and grows. Apparently because of the large volume change associated with its formation, Cb2O5 is porous and does not serve as a diffusion barrier; linear kinetics prevail after the surface is covered with Cb2o5. On the basis of these observations, several authors5,9,10 have suggested that the linear oxidation of pure columbium at 1000°C in air or oxygen of 1 atm is limited by a Loriers-type mechanism,11 whereby the total rate or reaction is controlled by ionic diffusion through a thin layer of CbO2 which is maintained at a constant thickness throughout the linear oxidation. However, the concept of a Loriers model for a three-phase CbOlCbO2 Cb2O5 scale, with the only oxygen activity gradient across the NbO2 phase, is not self-consistent. Further, the suboxides CbO and CbO2 were not observed in the high-temperature X-ray diffraction study of columbium oxidation by Goldschmidt.8 From investigations in which the large PO2, dependence of the linear scaling rate was demonstrated, the importance of an oxygen adsorption or dissolution step has been suggested.4,5,7,10,12 Thus the mechanism for the linear oxidation of pure columbium remains quite controversial. Since further insight into the oxidation mechanism of pure columbium is not provided by this investigation, the authors wish to emphasize at the outset that their experimental results are not interpreted in terms of a particular rate controlling step for the oxidation of pure columbium. Previous investigations13-18 of the oxidation of Cb-Zr solid-solution alloys in air or oxygen at 1000°C suggest a remarkable dependence upon zirconium content. For an alloy of bulk zirconium mole fraction, N2r(0) equal to 0.05 or 0.10, the oxygen uptake is reported to be as high as four times greater than that for pure columbium;13,14 for alloys with NZr(0) 0.05 or 0.10 the oxygen uptake is reported to decrease with increasing NZr(0); to a minimum uptake of about one quarter that for pure columbium at NZr(0): = 0.50.13-15Since zirconium forms a more stable oxide (ZrO2) than the lowest columbium oxide (CbO), and since columbium exhibits a high solubility19,20 and diffusivity21,23 for oxygen, the internal oxidation of the zirconium component to ZrO2 is expected at a reaction front ahead of the advancing metal/scale interface. The external scale is then formed at the metal/scale interface by the inward migration of oxygen through the scale, probably through a series combination of molecular and ionic diffusion. Internal oxidation in conjunction with external scale formation has been investigated by Maak24 for the oxidation of dilute Cu-Be alloys in pure oxygen at 850°C. For cu-Be and many other binary alloys,24-27 very small, essentially uniaxial internal oxide particles are formed in the most dilute compositions; for somewhat more concentrated alloys. the internal oxide particles precipitate as platelets or needles. From pertinent solutions to the diffusion equation, Maak28

Jan 1, 1967

By S. H. Lorain, Norman L. Wimmler, S. Ricker, P. E. Oscarson, H. G. Iverson

This paper has been prepared with the principal objective of recording the results of the Bureau of Mines exploration of five major clay deposits in the Western Region. It is based mainly on data contained in unpublished Bureau of Mines reports. Acknowledgment is made to the Federal Geological Survey for its cooperative work with the Bureau of Mines, to the various State geological and mining departments, and other State and local agencies. Clay Exploration by the Bureau of Mines Much has been written and published on clays and clay deposits relating to their refractory, ceramic, and other qualities but such literature is lacking in analyses of the available alumina content of the clays and provides little indication of their possibilities as a source of alumina. With this new objective in view, a great many of the known clay deposits were reexamined and new ones discovered. The Bureau of Mines made preliminary examination of numerous areas in the western United States. Five of those most favorably indicated were systematically drilled, and in each a large amount of high-alumina clay has been found. These five major projects are Molalla and Hobart Butte, in western Oregon; Cowlitz-Castle Rock, in southwestern Washington; Ione, in California; and the Olson-Troy area in Idaho (Fig. I). Preliminary scout drilling was done in the Stockton deposit at Coeur d&apos;Alene, Idaho; the White ware deposit near Lewis-town, Mont.; and 13 areas in the Spokane or eastern Washington region, where the most favorably indicated area, known as the Excelsior, is now being drilled more systematically. Preliminary drilling was undertaken in numerous areas adjacent to the major deposits and others more remote. As a result, large additional clay possibilities were found. The Clay Deposits The clay deposits under consideration are of the sedimentary or transported types, parts of which have been altered further by the agencies of weathering, ground water, or hydrothermal action. There are extensive deposits of residual clays in northern Idaho and in eastern Washington, but they have been found to be low in the available alumina and to contain much free quartz, mica, and unaltered feldspar. To be of value, they must first be subjected to beneficiation to remove these gangue minerals. The sedimentary clays have been derived largely from the decomposition, erosion, and transportation of granites, gneisses, schists, and basalts. At Molalla, some

Jan 1, 1948

By Norman L. Wimmler, H. G. Iverson, S. Ricker, P. E. Oscarson, S. H. Lorain

This paper has been prepared with the principal objective of recording the results of the Bureau of Mines exploration of five major clay deposits in the Western Region. It is based mainly on data contained in unpublished Bureau of Mines reports. Acknowledgment is made to the Federal Geological Survey for its cooperative work with the Bureau of Mines, to the various State geological and mining departments, and other State and local agencies. Clay Exploration by the Bureau of Mines Much has been written and published on clays and clay deposits relating to their refractory, ceramic, and other qualities but such literature is lacking in analyses of the available alumina content of the clays and provides little indication of their possibilities as a source of alumina. With this new objective in view, a great many of the known clay deposits were reexamined and new ones discovered. The Bureau of Mines made preliminary examination of numerous areas in the western United States. Five of those most favorably indicated were systematically drilled, and in each a large amount of high-alumina clay has been found. These five major projects are Molalla and Hobart Butte, in western Oregon; Cowlitz-Castle Rock, in southwestern Washington; Ione, in California; and the Olson-Troy area in Idaho (Fig. I). Preliminary scout drilling was done in the Stockton deposit at Coeur d&apos;Alene, Idaho; the White ware deposit near Lewis-town, Mont.; and 13 areas in the Spokane or eastern Washington region, where the most favorably indicated area, known as the Excelsior, is now being drilled more systematically. Preliminary drilling was undertaken in numerous areas adjacent to the major deposits and others more remote. As a result, large additional clay possibilities were found. The Clay Deposits The clay deposits under consideration are of the sedimentary or transported types, parts of which have been altered further by the agencies of weathering, ground water, or hydrothermal action. There are extensive deposits of residual clays in northern Idaho and in eastern Washington, but they have been found to be low in the available alumina and to contain much free quartz, mica, and unaltered feldspar. To be of value, they must first be subjected to beneficiation to remove these gangue minerals. The sedimentary clays have been derived largely from the decomposition, erosion, and transportation of granites, gneisses, schists, and basalts. At Molalla, some

Jan 1, 1948

By E. Buehler, J. E. Kunzler

High-pu.1-ity molybdenum has been heat treated, melted, and zone refined and the physical and chemical changes that are produced by these processes have been studied by making resistance ratio measurements. Pronounced effects are observed that are associated with recrystalliza-tion at about 1200°C and with melting. Melting alone is found to result in a substantial purification by the evaporation of impurities such as iron. Zone refining is found to be reasonably effective with four passes producing a three-fold decrease in resistance ratio and a minimum ratio of 0.0003. With the aid of low temperature measurenzents, it has been shown that the build-up of a deposit of the material being zone refined on the radio frequency coil used for heating can lead to contamination of the sample. CONSIDERABLE interest in high-purity refractory metals for the study of mechanical properties has developed during recent years. Also the need for highly pure metals in certain fundamental studies, such as electronic band structure, has become quite widely appreciated. Molybdenum can now be produced with sufficiently high purity to make it attractive for such investigations. The most suitable measure of chemical purity of metals used for many of these studies is its resistance ratio, R,.,o,/Ro, During the purification of molybdenum by zone refining and its subsequent evaluation by this technique, a number of informative observations were made. These observations concern the effectiveness of zone refining, the volatilization of impurities at the melting point, and the recrystallization of molybdenum and appear to be pertinent to other refractory metals. Also, the usefulness of low-temperature resistance measurements as an analytical tool for evaluating the presence of chemical impurities and physical defects in metals is again illustrated. Samples of high-purity molybdenum of known mechanical history were heated to various temperatures between 800°c and their melting point. Resistance ratios of the samples were measured after they had been given a specified treatment. The data were used, along with mass spectrographic analysis, as an aid in interpreting the nature of the processes that occurred in conjunction with each treatment. Changes in the concentrations of chemical impurities and physical defects are typical of things that effect the low-temperature resistivity. SAMPLES The starting material was obtained from Westing-house Corp., Bloomfield, N.J. It was in the form of molybdenum rods, usually 1/8 or 3/16 in. in diameter. These had been previously processed from bars, 5/8 in, in diameter, originally reduced from 4 in. diam arc-cast ingots, by hot swaging at about 1300°c. In the final step, the temperature was lowered to about l lOO°C which resulted in the production of elongated grains. Typical grains were about 0.03 mm thick and 0.6 mm long. The molybdenum was quite pure as is indicated by the results of mass spectro-scopic analysis1 given in Column 2 of Table I. Other nongaseous elements not listed in the table were not detected. ZONE REFINING AND THERMAL TREATMENT OF SAMPLES Several sample rods, 8 to 10 in. long, were zone refined or were heat treated at several temperatures. Both types of operations were performed using 3 me-

Jan 1, 1962

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

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

Jan 1, 1935

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

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

Jan 1, 1935

By J. B. Newkirk, A. H. Geisler

Certain of the permanent magnet alloys provide ideal systems for the study of the kinetics of the precipitation reaction and the correlation of structure with properties. One such system, Cu-Ni-Fe, was found by Bradley1,2 to exhibit a coherent transition state in the precipitation process analogous to that reported for Al-Cu alloys somewhat earlier.3 The attractiveness of some perrnanent magnet alloys for study lies in the fact that vertical sections of the ternary phase diagram in certain regions of composition (Fig I) have as their prototype the binary Ni-Au diagram. Alloys of this type decompose into products that have the same crystal lattice type but only slightly different lattice parameters. The advantages that such alloy systems oA&apos;er for study over the usual in which an intermetallic compound is formed are many: 1. Since the precipitate has the same crystal strutture as the matrix, complex atomic movements are not required to form the new lattice. 2. Similarly, complex orientation relationships are not involved for both the matrix and the precipitate would be ex. petted to have the same orientation. 3, Small &,registry of the decomposition products at equilibrium (in contrast with Cu-Ag alloys) is conducive to extensive coherent growth in the transient state and thus the transition lattice can be detected by the usual X ray diffraction methods. 4. Finally, the relative quantities of precipitate and depleted matrix can be varied from 0 to 100 pet* thus permitting wide freedom for the study of the effect of cornposition on coherent growth and properties. In the Cu-Ni-Fe alloys of appropriate composition, the face-centered cubic precipitate and also the depleted matrix when first formed are coherent with the parent matrix.1&apos;2 The two have the same <Jo parameter as the original matrix but they are both tetragonal; the precipitate has an axial ratio c/a < I while that of the depleted matrix is c/a > I. When coherency is lost they assume the normal face-centered cubic structure with the depleted matrix having a lattice parameter greater than the original matrix and that of the precipitate less. Such a mechanism would also be expected for CU-Ni-CO alloys because of the similarity in constitution but this had not been demonstrated. The Present investigation was conducted on a CU-Ni-CO alloy. The constitution diagram and magnetic properties of these alloys have been fairly well established, however, no previous determinations of mechanism of precipitation and no correlation of structure with properties had been made. Thus, an alloy of this system Was chosen for a comprehensive investiga-

Jan 1, 1949

By C. A. Pierce

Studies of roof and floor movement are of interest to those actively engaged in mining. This is especially true in the case of an entirely new area where there is no precedent for guidance. The potash deposit being mined is in the southeast corner of New Mexico, about 20 miles east of Carlsbad. The deposit was formed by the land-locked, shallow, Permian Sea that extended through parts of western Texas, Oklahoma, Kansas, southeastern Colorado, and eastern New Mexico. The saline deposits vary from 500 to 4000 ft. thick. Neither of the companies operating in this area has delimited its commercial ore bodies. As all production so far has been from Federal and State leases, the Department of the Interior and the State of New Mexico have a direct interest in the development and extraction of these ore horizons. The ore is composed of an intimate mechanical mixture of sylvite (potassium chloride) and halite (sodium chloride). It lies generally in a horizontal bed varying from 5 to 12 ft, in thickness, and has a cover of approximately 1000 ft., consisting of about 500 ft. of salt beds and 500 ft. of sediments. The immediate mine roof for several feet is principally salt with some potash and clayey material. The next 500 ft. above, from the standpoint of structure, may be considered rock salt with a few inter-bedded potash members. The upper 500 ft. is of sedimentary (Permian and Triassic) origin and contains several water-bearing formations with flows varying from 10 to 500 gal. per minute. This water intensifies the interest in convergence problems as the ore and surrounding formations are water soluble. Potash salt (sylvite) and rock salt (halite) are plastic minerals. Plasticity is defined as a "property of solids by virtue of which they hold their shape permanently under the action of small shearing stresses but are readily deformed, worked, or molded under larger stresse."1

Jan 1, 1942

By C. A. Pierce

Studies of roof and floor movement are of interest to those actively engaged in mining. This is especially true in the case of an entirely new area where there is no precedent for guidance. The potash deposit being mined is in the southeast corner of New Mexico, about 20 miles east of Carlsbad. The deposit was formed by the land-locked, shallow, Permian Sea that extended through parts of western Texas, Oklahoma, Kansas, southeastern Colorado, and eastern New Mexico. The saline deposits vary from 500 to 4000 ft. thick. Neither of the companies operating in this area has delimited its commercial ore bodies. As all production so far has been from Federal and State leases, the Department of the Interior and the State of New Mexico have a direct interest in the development and extraction of these ore horizons. The ore is composed of an intimate mechanical mixture of sylvite (potassium chloride) and halite (sodium chloride). It lies generally in a horizontal bed varying from 5 to 12 ft, in thickness, and has a cover of approximately 1000 ft., consisting of about 500 ft. of salt beds and 500 ft. of sediments. The immediate mine roof for several feet is principally salt with some potash and clayey material. The next 500 ft. above, from the standpoint of structure, may be considered rock salt with a few inter-bedded potash members. The upper 500 ft. is of sedimentary (Permian and Triassic) origin and contains several water-bearing formations with flows varying from 10 to 500 gal. per minute. This water intensifies the interest in convergence problems as the ore and surrounding formations are water soluble. Potash salt (sylvite) and rock salt (halite) are plastic minerals. Plasticity is defined as a "property of solids by virtue of which they hold their shape permanently under the action of small shearing stresses but are readily deformed, worked, or molded under larger stresse."1

Jan 1, 1942