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By J. V. Gluck, Ping-Wang Chiang

The tellurium-rich region of the Sb-TI-Te ternary system was investigated by means of DTA, metallo-graphic, X-ray, and electron beam microprobe techniques on the sections Sb2Te3-T12Te3, SbTlTe2-Te, SbT1Te2-Sb2Te3, and SbTlTe2-T12Te3. The phase behavior of this region is summarized in terms of four ternary invariant reactions and a schematic reaction diagram is suggested. Isopleths for the sections SbT1Te2-Sb2Te3, Sb2Te,-T12Te3, and SbTlTe2-Te were constructed, and a schematic diagram of the projections of the liquidus lines and invariant planes is presented. No evidence was found to support the existence of the ternary compound "SbTlTe3", or pseudo-binary behavior of the section T12Te3-Sb2Te3, as reported by Borisova and Efremova. Electrical conductivity, Seebeck coefficient, and thermal conductivity measurements were made at room temperature on fully annealed samples. 1 HE phase relationships in chalcogenides are often complex and difficult to resolve, particularly since the approach to equilibrium is a rather slow process. For example, the phase diagram of the T1-Te binary system was in doubt until clarified by Rabenau et al.,1 the phase fields at compositions near Bi2Te3 in the Bi-Te binary system have only recently been satisfactorily elucidated by Glatz,2 and there may still be some question as to the extent of the Sb2Te3 field in the Sb-Te system.3-5 In ternary systems, the existence of the compound "AgFeTe2" was the subject of a number of conflicting reports6-8 and the stoichiometry of the composition "AgSbTe2" was in doubt for a period of time.9 Recently, questions have arisen regarding the existence of certain compounds in the ternary systems Bi-Tl-Te10-14 and Sb-Tl-Te.15 The impetus for studies of these latter systems stemmed from the report of Borisova et a1.10 of a congruently melting ternary compound, "BiTlTe3", which apparently had extremely favorable thermoelectric properties for room-temperature cooling applications. Attempts by other investigators to produce the compound or confirm the transport properties proved to be unsuccessful.12-14 Recently, Chiang and Gluck14 reported studies of the phase relations in the tellurium-rich region of the Bi-T1-Te system which indicated that the section T12Te3-Bi2Te3 was not pseudobinary as suggested by Borisova et a1.10 The contention of Spitzer and sykes12 was supported that the composition "BiT1Te3" was multiphase, with the primary constituent actually being BiTlTe2, a compound whose existence has been well demonstrated.16,17 The investigation reported in the present paper was prompted by a later report of Borisova and Efremova15 on a similar study of the section T12Te3-Sb2Te3 from the Sb-T1-Te system. They also claimed this section to be pseudobinary, and that a ternary compound "SbTlTe," was formed peritectically. Some "preliminary" crystallographic data were given for the compound and thermoelectric transport properties were presented. In view of the questions concerning the behavior of the Bi-T1-Te system and the existence of the compound "BiT1Te3" it was suspected that the Sb-T1-Te system might behave in a similar fashion, particularly in light of the known existence of a compound SbT1Te2, iso-structural with BiT1Te2.17 Consequently, an investigation was undertaken to clarify the phase relationships in the tellurium-rich region of the Sb-T1-Te system. It is the purpose of this paper to present the results of this study, including a representation of the phase relations, isopleths for various composition sections, and the determination of some phase compositions and transport properties. EXPERIMENTAL PROCEDURES Commercially available high-purity (99.999+ pct) elements, purchased from the American Smelting and Refining Co., were used for the sample preparation. All samples were made from thoroughly mixed powders of previously prepared master alloys: SbTlTe2, Te, Sb2Te3, and T12Te3. Stoichiometric quantities of the constituents for each 10-g sample were weighed into a specially cleaned fused silica tube and sealed under a vacuum of better than 5 x 10-5 torr. The sealed constituents were fused and reacted at 650° to 750°C for at least 4 hr under continuous agitation in a "rocking" furnace, and the resulting product was air-cooled. The tube was opened and the sample was ground to a powder. A portion of the powder was rebottled in a DTA tube under vacuum, and the rest of the material was similarly resealed in a separate tube, re-fused in the rocking furnace, and again cooled to make the ingots for electrical and microstructural studies. All samples were subjected to further heat treatments as discussed in the section on experimental results. Each DTA tube was made of 7-mm-OD fused silica tubing with a concentric 2-mm-ID depression about 4 mm long formed in the bottom to accommodate a thermocouple. The size of a DTA sample was 0.5 to 1.0 g. An Aminco Thermoanalyzer whose accuracy was within 2°C18 was used for the DTA measurements. The metallographic samples were prepared by conventional techniques. A solution of FeCL dissolved in a methanol-HC1 mixture was found to be the most satisfactory etchant. Electron beam microprobe scanning and point-count examinations were made on polished and unetched samples using an ARL Electron Microprobe at an electron beam voltage of 20 kv. The detectors were set to receive characteristic La1 radiation. Calibration standards of the pure elements were incorporated in each sample mount; quantitative point counts were calibrated by a method similar to Ziebold

Jan 1, 1969

Mr. Tays (communication to the Secretary): Mr. Wynne's criticism of my paper* brings forward a few points which are really important, and might properly have been considered in the original paper. By calling attention to them he has rendered me a service. It is quite true, as Mr. Wynne says, that, in the tests reported by me, the Bryan mill was always working at a relative disadvantage, and my comparison of the work of this mill with that of the stamp-battery should be interpreted, therefore, so much the more favorably to the mill. Of course, wire screens can be used to advantage on the Bryan mill, if they are not of smaller size than 30-mesh; but

Jan 1, 1902

By F. M. Stewart

A paper by Hurst and van Ever-dingen in 1949 led to the practical solution of many nonsteady-state flow problems.' Subsequently, applications of this material have been discussed by several authors. The purpose of this note is to outline a simplified direct procedure for water-influx pressure predictions for pressures above the bubble point. The prcposed procedure is unique in that after the "time-conversion factor" and the "influx constant" are obtained, predictions are made without trial and error. The elimination of trial and error is made possible by expressing certain PVT characteristics as explicit functions of pressure. The procedure is applicable to fields producing at pressures above the bubble point and under radial water drive from an infinite aquifer. In the usual applications it is required to predict (1) withdrawals given future pressure history or (2) reservoir pressure, given future withdrawals or production. The theory, assumptions and conditions under which the nonsteady-state solutions hold are covered in the references and are not repeated. The simplified direct procedure outlined here has been developed from published solutions for the so-called "pressure case". A similar direct procedure for the same special conditions has been developed for the "rate case"; however, in this instance the procedure is lengthy and offers no advantage over the trial-and-error solution. Consequently, this paper covers only the procedure based on the pressure case. DISCUSSION Under the pressure case prediction of withdrawals from a water-drive field, given the future pressure history, involves the use of a nonsteady-state water-influx term together with the material balance equation. The solution of a particular problem requires the following steps: (1) division of past pressure and production data into equal time intervals; (2) computation of cumulative water influx vs pressure drop for each time interval of past history using the material balance equation; (3) determination of the best values for the "time-conversion factor" and the "influx constant" by equating the nonsteady-state influx term with the influx computed in Step 2 (this requires a trial-and-error procedure); (4) prediction of influx for a given pressure drop using the influx term and the computed factors from Step 3; and (5) calculation of fluids produced using the predicted influx in the material balance equation. A forecast of the water-oil ratio or water production rate is required to complete the calculation. It is assumed that a reliable estimate of original oil in place is available, as well as the production and pressure history, and data on reservoir fluid characteristics. If the original oil in place is unknown, it may be computed simultaneously with the tinie-conversion influx factors2,3. However, the oil in place so computed may be considerably in error3; consequently, it is usually preferable to use oil in place estimated from pore-volume data unless there is considerable doubt as to its accuracy. The Material Balance Equation Above the Bubble Point Above the bubble point the simpli-

By Gerhard Derge

The extension of metallurgical control of steelmaking processes has always made it desirable to have some quick method for determining the oxygen content of molten steel. To meet the practical demands of the steel industry, this method must also be simple enough so that the sampling can be done by the regular furnace crew. This requirement was kept in mind continually in the work to be described. An oxygen value is required for proper control, whether it be of a rimming steel or of a fully killed steel. However, two factors have discouraged the development of such direct methods: i. The reaction C + FeO Fe + CO is rapid enough to make the correct sampling Of the bath a difficult problem. The most generally accepted means of circumventing this difficulty have been the aluminum-killed bomb test of McCutcheon and Rautiol and the aluminum-killed spoon test of Herty.2 The theory of these tests is that all of the oxygen in the iron is converted to Al2O3, which can then be determined by chemical methods. Even when simplified so that the analysis is made by a measurement of turbidity, this method is too slow to be used in routine control. Furthermore, the results obtained have never been entirely satisfactory, and some of the reasons for this will be discussed later in this paper. z. The ordinary chemical methods of analysis for oxygen in steel are not reliable. The only analysis that seems to possess sufficient dependability to be of value is vacuum fusion,3 and the apparatus and technique developed for this have been too complex and slow for routine work. Indirect Methods Indirect methods of estimating the oxygen have been resorted to in mill practice. Generally these depend upon the chemical equilibria involved. The oxygen in the bath is related to other components in the slag or metal that can be analyzed the readily. These methods have many difficulties in common. Steelmaking processes involve a complicated set of interrelated reactions, all of which tend to approach equilibrium at varying rates. The degree to which any particular equilibrium is approached is not well established. Moreover, a proper use of theoretical equilibrium constants requires a more extensive knowledge of the activities of the con- than we now have. This is well illustrated by the irregularities observed when trying to determine the oxygen in the metal by its ratio to the iron oxide in the slag. Equiliblium relations may be used mole readily if they are evaluated by plant experience, but the extent of approach to equilibrium remains an undetermined variable and lack of an entirely satisfactory mean, of determining oxygen for the calibration is felt keenly, For example, the statistical analysis of the relation between carbon and oxygen4.6 illustrates that even iia a single plant wide variations exist under llormal conditions of operation. Never. theless, this is one of the best methods now

Jan 1, 1943

By Gerhard Derge

The extension of metallurgical control of steelmaking processes has always made it desirable to have some quick method for determining the oxygen content of molten steel. To meet the practical demands of the steel industry, this method must also be simple enough so that the sampling can be done by the regular furnace crew. This requirement was kept in mind continually in the work to be described. An oxygen value is required for proper control, whether it be of a rimming steel or of a fully killed steel. However, two factors have discouraged the development of such direct methods: i. The reaction C + FeO Fe + CO is rapid enough to make the correct sampling Of the bath a difficult problem. The most generally accepted means of circumventing this difficulty have been the aluminum-killed bomb test of McCutcheon and Rautiol and the aluminum-killed spoon test of Herty.2 The theory of these tests is that all of the oxygen in the iron is converted to Al2O3, which can then be determined by chemical methods. Even when simplified so that the analysis is made by a measurement of turbidity, this method is too slow to be used in routine control. Furthermore, the results obtained have never been entirely satisfactory, and some of the reasons for this will be discussed later in this paper. z. The ordinary chemical methods of analysis for oxygen in steel are not reliable. The only analysis that seems to possess sufficient dependability to be of value is vacuum fusion,3 and the apparatus and technique developed for this have been too complex and slow for routine work. Indirect Methods Indirect methods of estimating the oxygen have been resorted to in mill practice. Generally these depend upon the chemical equilibria involved. The oxygen in the bath is related to other components in the slag or metal that can be analyzed the readily. These methods have many difficulties in common. Steelmaking processes involve a complicated set of interrelated reactions, all of which tend to approach equilibrium at varying rates. The degree to which any particular equilibrium is approached is not well established. Moreover, a proper use of theoretical equilibrium constants requires a more extensive knowledge of the activities of the con- than we now have. This is well illustrated by the irregularities observed when trying to determine the oxygen in the metal by its ratio to the iron oxide in the slag. Equiliblium relations may be used mole readily if they are evaluated by plant experience, but the extent of approach to equilibrium remains an undetermined variable and lack of an entirely satisfactory mean, of determining oxygen for the calibration is felt keenly, For example, the statistical analysis of the relation between carbon and oxygen4.6 illustrates that even iia a single plant wide variations exist under llormal conditions of operation. Never. theless, this is one of the best methods now

Jan 1, 1943

By L. Ekstrom, J. P. Dismukes

The homogeneity and microstrcture of zone-leveled Ge-Si alloys haw been investigated by sellera1 physical techniques and by metallography as a function of growth rate in the range 3 x 10 1x10 cm-sec', and as a system of alloy composition throughout the system. The temperature gradient at the solid-liquid interface was about 50 deg-cm-' Cellular or dendritic structures char-acteristic of constitutional supercooling were ob-served except at very slow growth rates, which ranged from about 2 x 10 cm -sec for Ge 1 sio alloy to about 2 X 10'5 cm-sec'1 for Ge .sSio.s alloy. Using a simple model similiar to that employed for dilute solid the dependence upon compo-sition over the entire system of the critical growth rate for the onset of constiutional supercooling was calculated, and was .found to he in good agreement with the experimental results. THE recent discovery of the low thermal conductivity of Ge-Si alloys' at high temperatures has revealed that these alloys have high efficiencies for thermoelectric-power generation.', Therefore, a reliable method was needed for the preparation of homogeneous samples required for definitive measurements throughout this alloy system. Due to the low diffusion rates in the solid alloys, the segregated samples obtained by quenching a melt are not readily homogenized by annealing.475 However. isothermal solidification from a melt of constant composition can produce uniform material. Of the available semiconductor crystal-growth procedures, the zone-leveling technique6 applied to a complete solid-solution alloy system by Wang and Alexander' and by others provides a simple method of doing this. In the present work, the homogeneity and microstructure of zone-leveled alloys have been correlated with growth conditions, and the conditions for preparing homogeneous Ge-Si alloys have been established. This has provided insight into the solidification process of alloy semiconductors. EXPERIMENTAL PROCEDURE Sample Preparation. The Ge-Si alloy phase diagram4 shown in Fig. l(a) consists of a complete series of solid solutions. The zone-leveling technique used to prepare most of the samples consists of moving a zone of liquidus composition (C1) through charge material of the corresponding solidus composition (C,), as is illustrated in Figs. l(b) and l(c). To prepare the charge materials, high-purity germanium and silicon were pulverized in a steel hammer mill, cleaned magnetically, and melted together to make uniform chill castings. The zone leveling was carried out in a resistance-heated furnace similar to that of Mitrenin et al.' shown in Fig. 2. However, a few specimens of high silicon content were prepared by the Czochralski technique. The growth rate ranged from 3.5 x X6 to 1.2 X 10~3 cm-sec-'. Temperature gradients in the solid and in the melt were determined by recording the temperature as the molten zone passed over a Pt-Pt 13 pct Rh thermocouple contained in a small

Jan 1, 1965

By C. E. Nelson

The purpose of this discussion is to outline briefly the practices commonly followed in this country for the melting and refining of magnesium and its alloys. The processes used for the various forms of primary magnesium, as far as there are differences in the physical shape or behavior, will be discussed. The refining of general fine scrap or secondary magnesium was presented in an earlier paper.1 Inasmuch as the use of fluxes is an essential part of all the melting and refining processes, the principal aim of this paper will be to deal with these in sufficient detail to point out their unique characteristics, in order to make their use more effective. Types oF Melting Practice All melting and refining processes for magnesium and its alloys require the use of fluxes. These fluxes have a magnesium chloride base and other halide salts or oxides are added to give a density or behavior exactly suited to the particular melting practice. The successful handling of magnesium depends upon the proper use of the correct fluxes. There are four general methods of melting, summarized in the following paragraphs and treated in more detail in the section on Melting and Refining. Open-pot Method The open-pot method makes use of No. 230 flux.2 The flux provides protection during melting and a molten pool of flux into which the solid magnesium melts. It is stirred through the molten metal bath and agglomerates oxide or similar foreign bodies; then on quiet standing separates away, leaving the refined metal ball floating in an encircling layer of molten flux. It forms only a thin fluid film over the surface of the molten metal, which may be ' parted for hand-ladling processes and tends to cover the metal again after the ladle is removed. A very light dusting of the pot surface with fresh flux immediately after the ladle is removed is usually desirable. The open-pot method is used generally in the following processes: (I) alloying and secondary smelting in the production of ingot, (2) in sand foundries for premelting and to a smaller extent for the production of small castings requiring hand ladling, (3) in permanent-mold founding for premelting and also direct ladling to castings, (4) for continuous methods of preparing metal in the production of billets or ingots from which wrought products are fabricated, (5) in general scrap recovery. Crucible Process The crucible process makes use of No. 310 flux, which has the property of being thinly fluid at the start, to provide protection and refining qualities, and then drying out or thickening after a time, leaving a protecting crust on the pot surface until the time of casting. At that time it can be readily skimmed off or held back, thus allowing the contents of the crucible to be poured out directly into castings without fear of flux contamination. This flux is not

Jan 1, 1944

By Gerhard Derge

THE extension of metallurgical control of steelmaking processes has always made it desirable to have some quick method for determining the oxygen content of molten steel. To meet the practical demands of the steel industry, this method must also be simple enough so that the sampling can be done by the regular furnace crew. This requirement was kept in mind continually in the work to be described. An oxygen value is required for proper control, whether it be of a rimming steel or of a fully killed steel. However, two factors have discouraged the development of such direct methods: I. The reaction C + FeO -+ Fe + CO is rapid enough to make the correct sampling of the bath a difficult problem. The most generally accepted means of circumventing this difficulty have been the aluminum-killed bomb test of McCutcheon and Rautio1 and the aluminum-killed spoon test of Herty.2 The theory of these tests is that all of the oxygen in the iron is converted to A1203, which can then be determined by chemical methods. Even when simplified so that the analysis is made by a measurement of turbidity, this method is too slow to be used in routine control. Furthermore, the results obtained have never been entirely satisfactory, and some of the reasons for this will be discussed later in this paper. 2. The ordinary chemical methods of analysis for oxygen in steel are not reliable. The only analysis that seems to possess sufficient dependability to be of value is vacuum fusion,3 and the apparatus and technique developed for this have been too complex and slow for routine work. INDIRECT METHODS Indirect methods of estimating the oxygen have been resorted to in mill practice. Generally these depend upon the chemical equilibria involved. The oxygen in the bath is related to other components in the slag or metal that can be analyzed more readily. These methods have many difficulties in common. Steelmaking processes involve a complicated set of interrelated reactions, all of which tend to approach equilibrium at varying rates. The degree to which any particular equilibrium is approached, is not , well established. Moreover, a proper use of theoretical equilibrium constants requires a more extensive knowledge of the activities of the reactants than we now have. This is well illustrated by the irregularities observed when trying to determine the oxygen in the metal by its ratio to the iron oxide in the slag. Equilibrium relations may be used more readily if they are evaluated by plant experience, but the extent of approach to equilibrium remains an undetermined variable and lack of an entirely satisfactory means of determining oxygen for the calibration is felt keenly. For example, the statistical analysis of the relation between carbon and oxygen4 5 illustrates that even in a single plant wide variations exist under normal conditions of operation. Nevertheless, this is one of the best methods now

Jan 1, 1943

By A. W. Bitner, A. W. Asman

An analysis is made of three different types of section production units that represent the manner in which most of the nation's bituminous coal is produced. The general delays and production characteristics of these sections are presented along with a method for evaluating section performance based on actual and theoretical production characteristics. THE forerunner of the modern mechanical loading machine first entered the mines in 1890—a Stanley header with a conveyor. Since then progress has been substantial, both in the design and application of mechanized production units. Mechanization is almost a necessity for survival in the economy of today. In this paper an analysis is made of three types of sections, and a method for evaluating section performance based on present production characteristics and theoretical characteristics is presented. In mechanical loading mining sections the loading machine is the unit directly responsible for production. If the face preparation units provide a plentiful supply of properly prepared coal and the transportation system is coordinated and adequate, the loader will be idle a minimum of time. If either of the above do not perform adequately or other delays occur, the effect on production will be reflected in the performance of the loading machine. Therefore, attention is focused on the loading machine and factors that affect the overall performance of the production unit. Three complete mechanized production units are presented for analysis: A track section, a trackless section using battery-powered shuttle cars, and a trackless section using cable-reel shuttle cars. These particular sections were chosen for the following reasons: 1—The daily tonnage and mining conditions are approximately the same. 2— Production in each is 10 to 20 pct above the daily average. 3—The production characteristics and delays are average and typical. 4—They represent the manner in which the most of the nation's bituminous coal is produced. A. W. ASMAN, and A. W. BITNER, Members AIME, are Chief, and Research Assistant, respectively, Div. of Mining, The Pennsylvania State College, State College, Pa. Discussion on this paper, TP 3140F, may be sent to AIME by Oct. 31, 1951. Manuscript, Feb. 22, 1951. St. Louis Meeting, February 1951. Section A Fig. 1 is a layout for the track mining section showing the development to date, the projected plan and the cuts loaded on the shift studied. The seam mined averages 96 in. in thickness with a fireclay bottom and a roof of 10 in. of drawslate topped by sandstone. The mineability is considered good, and roof support is not a difficult problem. Two locomotives are used in the section to minimize the losses occurred in trip changing. The places are driven 20 ft wide, and the crosscuts are angled to permit fast tramming of the equipment. Table I lists the equipment and labor that make up the section. ANALYSIS Production Characteristics: The average loading rate for eight loading machines studied of this type is 1.81 tons per min. This one at 2.78 is considerably above average.

Jan 1, 1952

By F. Keller, J. D. Edwards

The anodic treatment of aluminum presents problems of scientific as well as of commercial interest.l-3 Of particular interest is the fact that, during the anodic oxidation process, the oxide continues to form at the metal-oxide interface under any oxide previously formed. This has led to speculation as to the mechanism involved in the formation of the relatively thick oxide coatings that are used commercially for decorative or protective purposes. Furthermore, the ability of certain types of oxide coatings to adsorb dyes and other substances has stimulated research to determine the actual structure of these adsorptive coatings. It has been found that anodic oxide coatings on aluminum are composed essentially of aluminum oxide. They are formed by the action of oxygen ions penetrating to the metal surface during the electrolytic oxidation treatment. These coatings can be formed in a number of different electrolytes, as for example, those which contain sulphuric acid, chromic acid, oxalic acid, or boric acid. These are the commonest and most useful electrolytes employed commercially. Except for certain specific conditions of formation, the coatings in general have been found to be amorphous alumina, as far as can be determined by X-ray or electron-diffraction methods. Anodic oxidation processes can be arranged in three rather general classes if they are grouped in relation to the solvent action of the electrolyte on the coating.4 In the first class, the electrolyte has little or no solvent action on the coating that is formed. In general, coatings produced under such circumstances are nonporous and non-adsorptive. In the second class, the electrolyte exerts an appreciable solvent action on the coating. These coatings are porous and adsorptive. Finally, for the third class, the electrolyte tends to dissolve the coating about as rapidly as it is formed. This action produces electrolytic brightening or anodic polishing of the aluminum surface and at most leaves only a very thin film of oxide. The nonporous and nonadsorptive type of oxide film is represented by the coatings that are formed when solutions of boric acid are employed as the electrolyte. It is especially significant that these impervious films are formed in electrolytes that exert little or no solvent action on the coating. Where a boric acid electrolyte is used, the coating tends to form rapidly, with the result that the flow of current is soon reduced to substantially zero. This indicates that the growth of the coating has stopped. As a rule, the thickness of the coating is roughly proportional to the voltage employed for formation and the coatings of this type are exceedingly thin. In an electrolyte of this type, the coating has a high resistance when the aluminum is made anode; consequently, any current that may flow (leakage current) is very

Jan 1, 1944

By F. Keller, J. D. Edwards

The anodic treatment of aluminum presents problems of scientific as well as of commercial interest.l-3 Of particular interest is the fact that, during the anodic oxidation process, the oxide continues to form at the metal-oxide interface under any oxide previously formed. This has led to speculation as to the mechanism involved in the formation of the relatively thick oxide coatings that are used commercially for decorative or protective purposes. Furthermore, the ability of certain types of oxide coatings to adsorb dyes and other substances has stimulated research to determine the actual structure of these adsorptive coatings. It has been found that anodic oxide coatings on aluminum are composed essentially of aluminum oxide. They are formed by the action of oxygen ions penetrating to the metal surface during the electrolytic oxidation treatment. These coatings can be formed in a number of different electrolytes, as for example, those which contain sulphuric acid, chromic acid, oxalic acid, or boric acid. These are the commonest and most useful electrolytes employed commercially. Except for certain specific conditions of formation, the coatings in general have been found to be amorphous alumina, as far as can be determined by X-ray or electron-diffraction methods. Anodic oxidation processes can be arranged in three rather general classes if they are grouped in relation to the solvent action of the electrolyte on the coating.4 In the first class, the electrolyte has little or no solvent action on the coating that is formed. In general, coatings produced under such circumstances are nonporous and non-adsorptive. In the second class, the electrolyte exerts an appreciable solvent action on the coating. These coatings are porous and adsorptive. Finally, for the third class, the electrolyte tends to dissolve the coating about as rapidly as it is formed. This action produces electrolytic brightening or anodic polishing of the aluminum surface and at most leaves only a very thin film of oxide. The nonporous and nonadsorptive type of oxide film is represented by the coatings that are formed when solutions of boric acid are employed as the electrolyte. It is especially significant that these impervious films are formed in electrolytes that exert little or no solvent action on the coating. Where a boric acid electrolyte is used, the coating tends to form rapidly, with the result that the flow of current is soon reduced to substantially zero. This indicates that the growth of the coating has stopped. As a rule, the thickness of the coating is roughly proportional to the voltage employed for formation and the coatings of this type are exceedingly thin. In an electrolyte of this type, the coating has a high resistance when the aluminum is made anode; consequently, any current that may flow (leakage current) is very

Jan 1, 1944

By G. K. Manning, A. R. Elsea, A. B. Westerman

INTRODUCTION A CONSIDERABLE number of high-temperature alloys, that is, alloys which have load-carrying ability at elevated temperatures, have been developed on an empirical basis. In order to determine why these alloys possess this particular ability, a project was started at Battelle Memorial Institute on the fundamental factors promoting high-temperature strength of alloys. At the time of inception of this study, the cobalt-base alloy, Vitallium, was widely used because of its good high-temperature properties. One phase of this study was to include an investigation of the structures observed in Vitallium after various heat treatments. However, before investigating the structural features of Vitallium, it appeared logical to examine the phase diagrams of the related binary systems in order to develop information as to which phases- might be present in Vitallium. A preliminary survey of the pertinent alloy systems was made, with particular emphasis on the cobalt-chromium system, which is the base for the Vitallium series of alloys. The early work of Lewkonja1 and Guertler2 indicated that cobalt and chromium are completely miscible in the liquid state, and, within a narrow temperature range, in the solid state; that the liquidus shows a minimum; and that the alloys containing 45 to '85 pct chromium undergo a transformation at 1200 to 1250°C. More recently, Wever and Haschimoto,3 Wever and Lange,4 and Matsunaga5 carried out experimental work which led to the diagrams shown in Fig I and 2. Both diagrams are based on thermal analysis, metallographic, magnetic, and dilatation data; in addition, X ray diffraction results were used by Wever and Haschimoto, and electrical resistance measurements by Matsunaga. It is apparent from a comparison of the two diagrams that there was a difference of opinion as to the locations of the boundaries of the various phases, and as to the existence of a phase containing approximately 47 pct chromium. With these exceptions noted, it might be pointed out that the two diagrams are similar, and that, in general, any particular reaction which is shown on both diagrams occurs at a lower temperature on the Matsunaga diagram than on that of Wever-Haschimoto-Lange. Thus, in view of the gaps in the data and the questionable features in the published diagrams, it appeared desirable to start the fundamental study of Vitallium by determining the diagram for the cobalt-chromium system. EXPERIMENTAL WORK For the convenience of the reader, the diagram as determined by the present investigation is presented in Fig g. The liquidus and solidus data for the low-chromium alloys were taken from the work of Wever and Haschimoto,3 while the, melting point for pure chromium is the

Jan 1, 1948

By Donald T. Hawkins, Ralph Hultgren

The lorsion effusion method has been used to measure the vapor pressure of lead over pure lead and eight Pb-Sn alloys ranging from 9.1 to 87.9 at. pct Pb in the temperature range 950° to 1125°K. The resulting ?H°y 298 = 46,630 ± 200 cal per g-atow for pure lead is in excellent agreement with previous work. Deriued ?Gph values for the alloys were smoothed and correlated with previous heat of formation data to obtain entropies for the liquid alloys. values for the tin component were calculated by Gibbs-Duhem integmtion. Surfhce depletion of these liquid alloys was found to be absent, as shown by the fact that the measured pressure remained substantially constant with time in contrast with previous measurements on iron-rich solid Fe-Mn alloys. The activities and Gibbs (free) energies of the liquid Pb-Sn system are not well known although the heats of formation have been accurately determined by K1eppa.l Vapor pressure determinations of the activity of lead by Voronin and Evseev2 disagree with those of Predel.3 Elliott and chipman4 measured activities by the electromotive -force technique in the ternary Pb-Sn-Cd system. From the resulting values of the activity of cadmium, they were able to calculate the activities of lead and tin for the binary Pb-Sn system at the compositions xsn = 0.33 and 0.67. Atarashiya, Uta, Shimoji, and Niwa5 determined the activity of tin from Hz-H2O equilibrium measurements, but their results are subject to question due to uncertainty in the final state of their samples. To resolve these differences, measurements of the activity of lead were made using a torsion-effusion apparatus. Among other advantages, this apparatus rapidly detects errors caused by surface depletion, which tends to reduce the apparent vapor pressure of the more volatile component. If the measured torques remain nearly constant with time, only bulk depletion is occurring. This contrasts with the rapid decrease in torque found in solid Fe-Mn alloys at high temperatures and low manganese contents.6 EXPERIMENTAL 99.999+ pct Pb was obtained from the American Smelting and Refining Co. and 99.999 pct Sn from Vulcan Detinning Co. Eight Pb-Sn alloys were prepared by melting together weighed amounts of the pure metals in evacuated Pyrex tubes and quenching the melts in water. Loss of weight in preparation was less than 0.02 pct in all cases. The effusion cells were made from high-purity, nonporous graphite. Graphite was chosen because of its resistance to reaction with lead and tin and because it can be accurately machined with precision orifices. Two cells were used with overall dimensions as shown in Fig. 1. The orifices of cells 1 and 2 were, respectively, 1 and 1.5 mm in diam.

Jan 1, 1968

By W. W. Schmittroth, A. Y. Bethune

THE commercial analysis of Special High-Grade zinc usually involves the determination of lead, iron, copper and cadmium as impurities in the base metal. Over the past 20 years, as the result of metallurgical improvements in the art of producing Special High-Grade zinc metal there has taken place a gradual exclusion of almost all extraneous elements, and the few that do remain in the final product have been virtually reduced to the vanishing point. Thousands of tons of zinc .are now commercially produced annually and made available to the trade, in which impurities are present only in the order of 0.0010 per cent or less and the sum total of all impurities does not exceed 0.0025 per cent. To such zinc the term "superpurity" might well be applied without undue exaggeration. The techniques used for production control and final analysis of Special High-Grade zinc by means of emission spectra in the laboratories of the electrolytic zinc plant of the Sullivan Mining Co. are based on the premise that self-electrodes are to be preferred over all other forms for the examination of the zinc in question. Furthermore, after a survey of the literature and considerable experimental work,1 it was decided that the spectrographic method of internal control, the principle of which was first announced by Gerlach,2 using a modification of the high-voltage alternating-current arc source introduced by Duffendack and Thompson,3 with the calibration of each photographic plate as recommended by Wolfe,4 would yield the most accurate and reproducible results. Self-electrodes were chosen in order to make use of one of the unique advantages inherent in spectrographic analysis; namely, the rapid and almost effortless detection of elements other than those being quantified by the analyst; or conversely, the proof that the zinc is free from such impurities if no spectral line of the suspected element appears. This fact was verified for certain elements, and will be discussed later. Carbon electrodes impregnated or packed with zinc salts chemically prepared from the zinc to be assayed were avoided for a number of reasons. First, the chemical manipulation was another time-consuming step, which increased the chances for contamination. Second, none of the common zinc salts, such as the chloride, nitrate or sulphate, yielded reproducible results under our conditions, nor did the spectral line of the impurity appear as readily in the low concentrations as when using zinc metal. Third, no commercial carbon, except the very expensive, was pure enough to use with this grade of zinc and the continued time, effort and expense incurred in the purification of carbon was not desirable. The use of Special High-Grade zinc self-electrodes introduces certain complications with regard to obtaining satisfactory excitation conditions, because it seems necessary to raise the temperature

Jan 1, 1946

By T&apos Ke, ing-sui

Accoriding to the classical theory of elasticity, the elastic portion of the stress-strain curve is represented by a straight line. such a representation implies that there is a linear relationship between strain and stress and also that strain is a single-valued function of stress and vice versa. Actually, such a one-to-one correspondence between strain and stress does not exist in real metals. A well-known example is the elastic after-effect on unloading. Another familiar example is damping or internal friction, that is, the dissipation of energy attending vibration. In an extensive review of such phenomena, zener1,2 has proposed the term "anelasticity" to denote that property of a solid in virtue of which strain is not a unique function of stress in the non-plastic region. The phenomena arising from anelasticity are called anelastic effects. The measurements on anelastic effects are important in many fields of metals technology. The, in precise instruments such as watch springs, difficulties often arise from the slight dimensional changes after fabrication. The internal friction or damping capacity of metals is often an important factor in deciding whether they are appropriate for instruments in which there are accompanying vibrations.3 However, for metal scientists, the study of anelastic effects furnishes a powerful tool for understanding many properties Of meta1s in terms of their microstructures or atomic interactions. In order to utilize the anelastic measurements to their fullest extent for acquiring such information, the experimental studies Of anelasticity must be interpreted by appropriate mathematical analysis. For a great many problems, however, the necessary information often Can be Obtained by general qualitative arguments. From the definition of anelasticity, any physical changes occurring in a specimen as a result Of the applied stress will cause anelastic effects if such physical changes are accompanied by a delayed change of elastic strain. Under these circumstances, we have the condition that strain lags behind the stress. We may mention the stress-induced transportation phenomena as examples. These include the stress-induced thermal diffusion,4-7 the stress-induced diffusion of particles,8-l2 and the stress-induced viscous slip along the microelements in metals.12-15 The differential equations describing the microscopic mechanism in these phenomena lead to relations in which stress is linear with respect to strain (and/or their derivatives). Thus if we Can demonstrate that the superposition principle is valid under the circumstances in which the anelastic effects are observed, we would expect in the macroscopic relation a linear relationship between stress and strain and their derivatives. This report is to describe a number of anelastic effects observed in alpha-iron, and an attempt is made to derive valuable information from a critical study of these

Jan 1, 1949

By T&apos Ke, ing-sui

Accoriding to the classical theory of elasticity, the elastic portion of the stress-strain curve is represented by a straight line. such a representation implies that there is a linear relationship between strain and stress and also that strain is a single-valued function of stress and vice versa. Actually, such a one-to-one correspondence between strain and stress does not exist in real metals. A well-known example is the elastic after-effect on unloading. Another familiar example is damping or internal friction, that is, the dissipation of energy attending vibration. In an extensive review of such phenomena, zener1,2 has proposed the term "anelasticity" to denote that property of a solid in virtue of which strain is not a unique function of stress in the non-plastic region. The phenomena arising from anelasticity are called anelastic effects. The measurements on anelastic effects are important in many fields of metals technology. The, in precise instruments such as watch springs, difficulties often arise from the slight dimensional changes after fabrication. The internal friction or damping capacity of metals is often an important factor in deciding whether they are appropriate for instruments in which there are accompanying vibrations.3 However, for metal scientists, the study of anelastic effects furnishes a powerful tool for understanding many properties Of meta1s in terms of their microstructures or atomic interactions. In order to utilize the anelastic measurements to their fullest extent for acquiring such information, the experimental studies Of anelasticity must be interpreted by appropriate mathematical analysis. For a great many problems, however, the necessary information often Can be Obtained by general qualitative arguments. From the definition of anelasticity, any physical changes occurring in a specimen as a result Of the applied stress will cause anelastic effects if such physical changes are accompanied by a delayed change of elastic strain. Under these circumstances, we have the condition that strain lags behind the stress. We may mention the stress-induced transportation phenomena as examples. These include the stress-induced thermal diffusion,4-7 the stress-induced diffusion of particles,8-l2 and the stress-induced viscous slip along the microelements in metals.12-15 The differential equations describing the microscopic mechanism in these phenomena lead to relations in which stress is linear with respect to strain (and/or their derivatives). Thus if we Can demonstrate that the superposition principle is valid under the circumstances in which the anelastic effects are observed, we would expect in the macroscopic relation a linear relationship between stress and strain and their derivatives. This report is to describe a number of anelastic effects observed in alpha-iron, and an attempt is made to derive valuable information from a critical study of these

Jan 1, 1949

By A. L. Mular

The flotability of crushed zinc oxide pellets which were doped to produce more n-type or less n-type (more p-type) properties was studied with a Halli-mond tube. Flotation data are presented to show that the pH at which 50% recovery occurs and the collector concentration for 50% recovery depends upon the concentration of doping agent added substitu-tionally for zinc in zinc oxide. The time of sintering of pellets has a slight effect on flotation behavior. A speculative model is proposed to explain the observed behavior in light of the fact that zinc oxide is a semiconductor and has a space charge region at the surface. Experimental verification is necessary before the proposed model can be established as correct. In recent years, the attachment of flotation reagents to minerals has been shown to depend upon the behavior of an electrical double layer which exists in the liquid near the mineral-liquid interface.' Thus, a mineral placed in water will undergo a surface re-arrangement, most likely be preferential dissociation of lattice atoms or by surface adsorp-tion-desorption reactions, to form a dissociation electrical double layer with the solution. Among the many factors which influence adsorption processes, the past history of the mineral itself is one of the most important. Because of trace impurities, minerals from different localities may exhibit marked differences in flotation behavior. This is not unexpected, since investigators who have studied the detailed structure of the double layer's3 have known for some time that the impurity content of many minerals may exert strong influence on double layer variables. For this reason, their studies were usually made with minerals of high purity. The precise relationship between impurities in a mineral and double layer parameters such as capacity and electrostatic potential has been obscure. However, impurities in a semiconductor type mineral which is in contact with a solution have been recently shown to produce changes in the properties of a space charge layer which extends into the bulk of the semiconductor to a distance of one micron or more.4 The double layer is influenced by the space charge layer, whose origin is best discussed in terms of the band theory of solids. A qualitative description of the behavior of impurities in the bulk of a semiconductor, from a chemical point of view, is useful at this point. Briefly, impurities or defects (lattice vacancies, interstitials, etc.) in semiconductors such as PbS, ZnS, FeS2, Cu2S, NiS, NiO, Fe2O3, ZnO, CdS, MnO2 and many others, behave somewhat like acids or bases in water. For example, water dissociates into hydrogen and hydroxyl ions according to

Jan 1, 1965

By W. M. Bertholf

IN 1945 tests were made in the coal washery of the Colorado Fuel and Iron Corporation, at Pueblo, Colo., to determine the value of the Humphreys spiral. So far we have demonstrated that it is of definite value to us in rewashing a portion of our table middlings; and we are fairly certain that this is not necessarily the only place in which it can be used to advantage. Because of manpower and material shortages, experimental work has been discontinued for the present. Three of the spirals are being installed for use in rewashing the middlings, and testing and experimental work will proceed when this installation is completed. All evidence secured so far points to the fact that the spiral can make an effective separation of heavy material below 8-mesh; but that it is ineffective in removing larger, heavy material. This, of course, will limit its use to fine coal or a classified feed containing no heavy material larger than 8-mesh. In considering the results of our tests, it should be noted that the feed was our table middling, and that any real separation of this material is a "moral victory," as there is little material that could be properly called coal and practically no heavy rock, the consequence being that previous attempts to clean the middlings have not been at all successful. Several articles dealing with the spiral and its use in treating heavy minerals have already been published,1 but for the benefit of those who have not seen these we include a brief description of the spiral and of the way it operates, taken from Bulletin 4 of The Humphreys Investment Co.: The Humphreys Spiral Concentrator consists of a spiral conduit of modified semicircular cross section. Ore pulp is fed to the top and, as it flows downward, the heavier particles concentrate in a band along the inner side of the pulp stream (Fig. I). Outlets for removal of products are located at the lowest points in the cross section of the conduit. Wash water, added at the inner edge of the stream, flows outwardly across the concentrate band. The width of concentrate band removed at the outlets is controlled by adjustable splitters. Concentrate is usually removed from the upper portion of the spiral and middling from the lower portion. Tailing is discharged from the lower end. Tests are usually made in closed circuit, since this provides a maximum of information with a minimum amount of sample. Fig. 2 shows the spiral set up for closed-circuit testing, and gives a good idea of the general arrangement of such an installation. The small cyclone separator is used to provide clean wash water without introducing additional water into the circuit.

Jan 1, 1946

By W. W. Schmittroth, A. Y. Bethune

The commercial analysis of Special High-Grade zinc usually involves the determination of lead, iron, copper and cadmium as impurities in the base metal. Over the past 20 years, as the result of metallurgical improvements in the art of producing Special High-Grade zinc metal there has taken place a gradual exclusion of almost all extraneous elements, and the few that do remain in the final product have been virtually reduced to the vanishing point. Thousands of tons of zinc are now commercially produced annually and made available to the trade, in which impurities are present only in the order of 0.0010 per cent or less and the sum total of all impurities does not exceed 0.0025 per cent. To such zinc the term "super-purity" might well be applied without undue exaggeration. The techniques used for production control and final analysis of Special High-Grade zinc by means of emission spectra in the laboratories of the electrolytic zinc plant of the Sullivan Mining Co. are based on the premise that self-electrodes are to be preferred over all other forms for the examination of the zinc in question. Furthermore, after a survey of the literature and considerable experimental work,' it was decided that the spectrographic method of internal control, the principle of which was first announced by Gerlach,2 using a modification of the high-voltage alternating-current arc source introduced by Duffendack and Thompson,3 with the calibration of each photographic plate as recommended by Wolfe,4 would yield the most accurate and reproducible results. Self-electrodes were chosen in order to make use of one of the unique advantages inherent in spectrographic analysis; namely, the rapid and almost effortless detection of elements other than those being quantified by the analyst; or conversely, the proof that the zinc is free from such impurities if no spectral line of the suspected element appears. This fact was verified for certain elements, and will be discussed later. Carbon electrodes impregnated or packed with zinc salts chemically prepared from the zinc to be assayed were avoided for a number of reasons. First, the chemical manipulation was another time-consuming step, which increased the chances for contamination. Second, none of the common zinc salts, such as the chloride, nitrate or sulphate, yielded reproducible results under our conditions, nor did the spectral line of the impurity appear as readily in the low concentrations as when using zinc metal. Third, no commercial carbon, except the very expensive, was pure enough to use with this grade of zinc and the continued time, effort and expense incurred in the purification of carbon were not desirable. The use of special High-Grade zinc self-electrodes introduces certain complications with regard to obtaining satisfactory excitation conditions, because it seems necessary to raise the temperature

Jan 1, 1949

By J. R. Long, C. E. Armantrout, A. H. Roberson, T. R. Graham

The preparation and fabrication of copper-manganese-zinc alloys and the evaluation of their engineering properties have for some time been an integral part of a research program of the Federal Bureau of Mines. In this project, the use of electrolytic manganese, along with high purity copper and zinc, has permitted the preparation of alloys which contain a minimum of impurities which are capable of producing detectable effects in the properties studied. The initial work on the physical properties of wrought alpha solid solution alloys and a general outline of the alpha solid solution area for alloys containing up to 40 pct manganese have been presented in previous reports. 1,2,3,4,5 The evidence accumulated in these investigations clearly showed that additions of manganese to the copper-zinc alloys improve the strength properties of the brasses without seriously reducing their characteristic ductility and that considerable quantities of manganese could be added to the copper-zinc alloys without exceeding the mutual solubilities of manganese and zinc in copper. In continuation of these studies, additional data have been obtained in a more extensive investigation of the phase relationships of the copper-manganese-zinc ternary system. The present report delineates the solid phase boundaries of the ternary system from the copper-zinc binary to the manganese-zinc binary for alloys containing up to 50 pct zinc. Summary The alloys used in this investigation were conditioned by working schedules designed to homogenize the structures prior to heat treatments required for the equilibrium phase sludy. The treated alloys were examined by metallographic methods including hardness and X ray data for confirmation. The composite data of the investigation are summarily presented in a series of isothermal sections of the ternary system at 1100, 1200, 1300, 1200, and 1500°F. The salient features of the system as outlined by these data are: (1) the continuous alpha solid solution which extends across the diagram to the gamma-manganese phase of the manganese-zinc system at temperatures of 1200°F and higher, (2) the beta phase of the copper-zinc system similarly forms a continuous solid solution with its counterpart the beta field of the manganese-zinc binary, (3) at 1100°F (593°C) these alpha and beta fields are greatly restricted by complications arising from the allotropic transitions of manganese and the decreasing solubility of manganese in the alpha solid solution. The alpha + beta fields intersect the alpha + alpha manganese field to produce the beta + alpha manganese field and two adjacent three phase fields consisting of alpha + beta + alpha manganese and gamma + beta + alpha manganese. Typical microstructures representative of the various phase areas at each temperature are also presented. Review of Previous Work The copper-manganese-zinc alloys have periodically been the subject of numerous investigatioris of both prac-

Jan 1, 1950