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R. Schuhmann, Jr. (Purdue University)— Fulton and Chipman's results on rate of silica reduction from slags are analogous in many was to the results of Parlee, Seagle, and Schuhmann10 on rate of alumina reduction from alumina crucibles. Both investigations have given comparably low rates of reduction and slow approaches to equilibrium. Accordingly, we may hypothesize that the rate-determining step is the same in both kinds of experiments; that is, oxygen diffusion across the stagnant boundary layer on the liquid-metal side of the interface between the liquid metal and the oxide phase (slag or solid oxide). I suggest that silica reduction involves the following consecutive steps: I) At the slag-metal interface: SiO2(slag) Si+ 20 II) Transport of oxygen from slag-metal to gas-metal interface: a) diffusion across liquid-metal boundary layer at slag-metal interface. b) convection within the body of liquid metal. c) diffusion across boundary layer at metal-gas interface. 111) At the metal-gas interface: C +O- CO (gas) Iv) At the graphite-metal interface: C (graphite) -C At steelmaking temperatures it is reasonable to assume that equilibrium is attained in all three chemical reactions (I, 111, and IV) right at the respective interfaces. Convection within the stirred liquid metal (step IIb) is also rapid. Transport of Si and C should be orders of magnitude easier than transport of 0, because of the relatively high concentrations of Si and C. Accordingly, we might expect the overall reaction rate to be determined by boundary-layer diffusion of oxygen, either IIa or IIc. Fulton and Chipman's demonstration that bubbling CO through the system had no major effect on reaction rate indicates that IIc is not the slowest step. Therefore, it becomes logical to estimate the maximum rate for step IIa and to compare this theoretical estimate with Fulton and Chipman's experimental data. If oxygen diffusion across the liquid metal boundary layer at the slag metal interface (step IIa) is rate-determining, In this equation, dn sio, /dt is the rate of silica reduction in moles per sec,A is the area of slag-metal interface in sq cm, Do is the diffusivity of oxygen in sq cm per sec, 6, is the boundary layer thickness in cm, c,* is the oxygen concentration right at the slag-metal interface in moles per cubic cm, and co is the oxygen concentration in the body of the liquid metal, also in moles per cubic cm. Equilibrium data" on the silicon deoxidation reaction in liquid iron and steel at 1600°C indicate that the oxygen contents of the liquid metal in Fulton and Chipman's experiments at 1600°C probably fell in the range of 0.5 x10-3 x10-3wt pct. That is, the maximum conceivable value of co*-co for the system under consideration was on the order of 10"5 mole oxygen per cubic cm. On the basis of previously published data,1O,11 it is estimated that Do/0 will fall somewhere in the range from 10-3 to 10-1 cm per sec. The surface area A in Fulton and Chipman's experiments was approximately 20 sq cm, and the weight of metal involved was about 500 grams. Combination of all these figures with the above rate equation leads to an estimate that the rate of silica reduction should fall within the range from 0.002 to 0.2 wt pct Si per hr. This estimate is consistent with the experimental data. For example, Fulton and Chipman's Fig. 2 shows a change of about 0.3 pct Si in 10 hr, corresponding to an average rate of 0.03 pct per hr. According to the proposed hypothesis, increasing the temperature will increase the reaction rate ill two ways: 1) by increasing oxygen diffusivity and 2) by increasing the oxygen concentration (oxygen solubility) in the liquid metal. The combination of these two effects accounts for the high value of the observed activation energy. Summarizing, I propose that the rate of silica reduction, like that of the carbon-oxygen reaction, is diffusion controlled and that low oxygen concentration in the liquid metal is the major factor accounting for the very low observed rates of silica reduction. John Chipman (author's reply)—The authors thank Professor Schuhmann for his interesting contribution. His proposed explanation may well prove to be the correct one. There is clearly a need for much further experimental work on this problem, and further research is in progress.

Jan 1, 1961

By Shiou-Chuan Sun

THIS paper presents the design and operation of a frothmeter capable of measuring the frothing characteristics of pine oils and other frothing reagents. The experimental data show that the froth-ability of pine oil is governed by: 1—rate of aeration, 2—time of aeration, 3—height of liquid column, 4—chemical composition of pine oil, 5—pH value of solution, 6—temperature of solution, and 7—concentration of pine oil in solution. The effect of mineral particles on the behavior of froth also was studied, and the results can be found in a separate paper.' The results also show that the relative froth-abilities of pine oils in the frothmeter generally correlate with those in actual flotation, provided that other factors are kept constant. In addition to pine oils, the other well-established flotation frothers were tested, and the results are included. In this paper, compressed air frothing is the frothing process performed by means of purified compressed air, whereas sucked air frothing is the frothing process accomplished by purified air sucked into the glass cylinder by a vacuum system. The term vacuum frothing denotes that froth was formed by degassing of the air-saturated liquid under a closed vacuum system. Apparatus The frothmeter, shown in Fig. 1, is capable of re-producibly measuring the volume and persistence of froth as well as the volume of air bubbles entrapped in the liquid and is capable of being used for compressed air frothing, sucked air frothing, and vacuum frothing. Fig. la shows that for compressed air frothing, the apparatus consists of an airflow regulating system, 1-3; a purifying and drying system, 4-8; a standardized flowmeter to measure the rate of airflow from zero to 500 cc per sec, 9; and a graduated glass cylinder, 13; equipped with an air regulating stopcock, 10; an air chamber, 11; and a fritted glass disk to produce froth, 12. The fritted glass disk, 5 cm in diam and 0.3 cm thick, has an average pore diameter of 85 to 145 microns. The pyrex glass cylinder has a uniform ID of 5.588 cm and an effective height of 63 cm. The inside cross-sectional area of the glass cylinder was calculated to be 24.53 sq cm, or 3.8 sq in. For sucked air frothing, Fig. lb shows that the apparatus for compressed air frothing is used again, with the following modifications: 1—compressed air and its regulating system, 1-3, are eliminated; and 2—a vacuum system, 16, equipped with a vapor trap, 15, and a vacuum manometer, 17, is added. The vacuum system can be either a water aspirator or a laboratory vacuum pump. Any desired rate of airflow can be drawn into the glass cylinder, 13, by adjusting the opening of the air regulating stopcock, 10. The sucked air stream is cleaned by the purifying and drying system, 4-8, before entering the glass cylinder, 13. When this setup is used for vacuum frothing, the air regulating stopcock is closed. The frothmeter has been used for almost 3 years and has proved to give reproducible results, as illustrated in Table I. With a magnifying glass and suitable illumination, the frothmeter also can be used to study the attachment of air bubbles to coarse mineral particles.' Experimental Procedures Except where otherwise stated, the data presented were established by means of the compressed air method. The volume and persistence of froth were recorded respectively at the end of 4 and 6 min of aeration at a constant rate of airflow of 29.3 cc per sec, which is equivalent to 71.6 cc per sq cm per min, or 462.6 cc per sq in. per min. The aqueous solution for each test, containing 1000 cc of distilled water and 19.2 ± 0.5 mg frothing reagent, was adjusted to a pH of 6.9 0.2. The volume of froth is expressed as cubic centimeter per square centimeter and is equivalent to the height of the froth column (the distance between the bottom and the meniscus of the froth). The volume of froth was obtained by multiplying the height of froth by the cross-sectional area of the glass cylinder, 24.53 sq cm. Before each test, the glass cylinder, 13, was cleaned thoroughly with jets of tap water, ethyl alcohol, tap water, cleaning solution, tap water, and finally distilled water. The cylinder with stopcock,

Jan 1, 1953

By Shiou-Chuan Sun

THIS paper presents the design and operation of a frothmeter capable of measuring the frothing characteristics of pine oils and other frothing reagents. The experimental data show that the froth-ability of pine oil is governed by: 1—rate of aeration, 2—time of aeration, 3—height of liquid column, 4—chemical composition of pine oil, 5—pH value of solution, 6—temperature of solution, and 7—concentration of pine oil in solution. The effect of mineral particles on the behavior of froth also was studied, and the results can be found in a separate paper.' The results also show that the relative froth-abilities of pine oils in the frothmeter generally correlate with those in actual flotation, provided that other factors are kept constant. In addition to pine oils, the other well-established flotation frothers were tested, and the results are included. In this paper, compressed air frothing is the frothing process performed by means of purified compressed air, whereas sucked air frothing is the frothing process accomplished by purified air sucked into the glass cylinder by a vacuum system. The term vacuum frothing denotes that froth was formed by degassing of the air-saturated liquid under a closed vacuum system. Apparatus The frothmeter, shown in Fig. 1, is capable of re-producibly measuring the volume and persistence of froth as well as the volume of air bubbles entrapped in the liquid and is capable of being used for compressed air frothing, sucked air frothing, and vacuum frothing. Fig. la shows that for compressed air frothing, the apparatus consists of an airflow regulating system, 1-3; a purifying and drying system, 4-8; a standardized flowmeter to measure the rate of airflow from zero to 500 cc per sec, 9; and a graduated glass cylinder, 13; equipped with an air regulating stopcock, 10; an air chamber, 11; and a fritted glass disk to produce froth, 12. The fritted glass disk, 5 cm in diam and 0.3 cm thick, has an average pore diameter of 85 to 145 microns. The pyrex glass cylinder has a uniform ID of 5.588 cm and an effective height of 63 cm. The inside cross-sectional area of the glass cylinder was calculated to be 24.53 sq cm, or 3.8 sq in. For sucked air frothing, Fig. lb shows that the apparatus for compressed air frothing is used again, with the following modifications: 1—compressed air and its regulating system, 1-3, are eliminated; and 2—a vacuum system, 16, equipped with a vapor trap, 15, and a vacuum manometer, 17, is added. The vacuum system can be either a water aspirator or a laboratory vacuum pump. Any desired rate of airflow can be drawn into the glass cylinder, 13, by adjusting the opening of the air regulating stopcock, 10. The sucked air stream is cleaned by the purifying and drying system, 4-8, before entering the glass cylinder, 13. When this setup is used for vacuum frothing, the air regulating stopcock is closed. The frothmeter has been used for almost 3 years and has proved to give reproducible results, as illustrated in Table I. With a magnifying glass and suitable illumination, the frothmeter also can be used to study the attachment of air bubbles to coarse mineral particles.' Experimental Procedures Except where otherwise stated, the data presented were established by means of the compressed air method. The volume and persistence of froth were recorded respectively at the end of 4 and 6 min of aeration at a constant rate of airflow of 29.3 cc per sec, which is equivalent to 71.6 cc per sq cm per min, or 462.6 cc per sq in. per min. The aqueous solution for each test, containing 1000 cc of distilled water and 19.2 ± 0.5 mg frothing reagent, was adjusted to a pH of 6.9 0.2. The volume of froth is expressed as cubic centimeter per square centimeter and is equivalent to the height of the froth column (the distance between the bottom and the meniscus of the froth). The volume of froth was obtained by multiplying the height of froth by the cross-sectional area of the glass cylinder, 24.53 sq cm. Before each test, the glass cylinder, 13, was cleaned thoroughly with jets of tap water, ethyl alcohol, tap water, cleaning solution, tap water, and finally distilled water. The cylinder with stopcock,

Jan 1, 1953

By A. E. Blakeslee

Morphological and electrical properties of GaAs epitaxial layers are influenced not only by changes in the nominal substrate orientation but also by small amounts of misorientation from the exact crystal planes. Deviations up to 5 deg from {11IA}, {11IB}, and (100) planes were investigated. Growth rates increase progressively with angle, approximately I u per hr per deg. Size and density of growth pyramids fall off with increasing angle, but other effects that are deleterious to the surface may occur which are heightened by increased misorientation. Carrier concentration decreases and electron mobility consequently increases as the angular offset increases, except in the case of strong compensation, where the mobility trend is reversed. It has long been known that changes in the crystallo-graphic orientation of the substrate may cause pronounced effects on the morphological properties of vapor grown semiconductor films. Reports of orienta-tion-dependent growth rates and surface characteristics are as old as the literature on epitaxy itself. shawl has recently published a comprehensive study of the dependence of growth rate on substrate temperature and orientation in epitaxial GaAs. It is also well-known that misorienting the substrate surface a few degrees away from the nominal low-index crystal-lographic plane often produces a much smoother epitaxial surface. This was reported by Tung2 for silicon, Reisman and Berkenblit3 for germanium, and by Kontrimas and Blakeslee4 for GaAs, and use is commonly made of this fact in the semiconductor industry to help guarantee smooth vapor deposits. The effects of substrate orientation on the carrier concentration and mobility of vapor grown GaAs were first documented by williams5 in 1964 and have been observed by several other authors since then,6,7 but no one has yet reported a careful study of how small changes influence these properties. We have made such a study and have found that sizable differences in growth rate, morphology, carrier concentration, and mobility can indeed be observed for epitaxial films grown on substrates that are oriented by progressive small increments away from the exact crystal plane. EXPERIMENTAL Early in the investigation an arsine synthesis system of conventional design8 was employed to produce growths on {111A}-oriented GaAs substrate crystals. In that early work, pronounced effects on carrier concentration and electron mobility were observed as a function of slight misorientation from this low index plane. That observation led to the more careful study that is reported here. An AsC13 system, differing in major aspect from those commonly in use today9 only in that the reactor is vertical rather than horizontal, was used for the detailed study. The gallium source was at 900°C and the substrates were at 750°C. The flow rate of pal-ladium-diffused H2 through the AsCl3 bubbler was 200 cu cm per min, and the flow rate of bypass H2 was also 200 cu cm per min. The substrates consisted of chro-mium-doped semiinsulating GaAs to facilitate elec-trical evaluation of the overgrowth by means of Hall and conductivity measurements on conventional eight-legged Hall bridges. They were misoriented by 0 to 5 deg from the {111A}, {111B}, and (100) planes, toward the (100) from the {111A} and {111B} and randomly toward the <111A> or <111B> from the {loo). The crystals were oriented for sawing by the Laue back-re-flection technique, which is good only to about ±1/2 deg; but after polishing or sometimes after epitaxial growth the wafers were checked by a diffractometer technique which is accurate to about * 0.1 deg. After lapping, the wafers were polished with NaOCl after the technique of Reisman and Rohr,10 and just before use they were cleaned in NaOC1, thoroughly rinsed with de-ionized water, and blown dry with nitrogen. Each run employed four wafers, each misoriented by differing amounts from one of the three major faces, and at least two runs were made for each orientation. The runs were continued long enough to provide at least a 15-µ or thicker layer. SURFACE MORPHOLOGY The appearance of all the films that were grown in a given run always changed from wafer to wafer as a function of increasing misorientation, but not always in the same regular fashion. At least three different trends were observed. These are more easily seen than described, and reference to the series of photo-

Jan 1, 1970

By H. C. Gatos, J. T. A. Pollock

It is well known that the superconducting critical current densities of many alloy superconductors may be increased by cold working and in some cases further enhanced by a short heat treatment. This latter enhancement has been attributed to the redistribution of dislocations into cell-like networks&apos; and to the precipitation of second phase particles,2&apos;3 which act as flux pinning centers. In a manner analogous to dislocation pinning in precipitation hardening alloys,4 it is expected that here also a critical distribution of the pinning centers should result in maximum pinning effect. Concentration inhomogeneities exist in most or all commercial alloys yet there have been only a few attempts made to determine their effect on critical current capacity in the absence of cold working. Sutton and Baker,5 and Kramer and Rhodes6 have found that the complex precipitation processes occurring during the aging of Ti-Nb alloys can result in critical current density enhancement. Livingston7-10 has clearly shown, for lead and indium based alloys, that the distribution of precipitated second phase particles is of critical importance in determining magnetization characteristics. However, these &apos;(soft" alloys age at room temperature and the time involved in specimen preparation prevents metallographic examination in the state in which the superconducting measurements are made. Thus results with such alloys are expected to be biased towards larger precipitates and interpar-ticle spacing. The present study of Ta-Zr alloys was undertaken to examine the influence of second phase precipitation, as controlled by heat treatment, on the critical current capacity of well annealed polycrystalline material. A study of the published phase diagram11 indicated that annealing supersaturated samples containing up to 9 at. pct Zr at suitable temperatures would result in the precipitation of a zirconium-rich second phase. It was MATERIALS AND PROCEDURE The alloys were prepared from spectrochemically pure tantalum and zirconium. Analysis was carried out by the supplier. Major impurities in the tantalum were: 12 pprn of 02, 17 pprn of N2, 19 pprn of C, and less than 10 ppm each of Mo, Nb, Al, Cr, Ni, Si, Ti. The crystal bar zirconium was pure except for the following concentrations: 15 pprn of 02, 17 ppm of C, 23 ppm of Fe, 11 ppm of Cu, and less than 10 pprn each of Al, Ca, N2, Ti, and Sn. Samples were prepared in the form of 8 to 10 g but-tons by arc melting using a nonconsumable electrode on a water-cooled copper hearth in a high purity ar-gon atmosphere. Each button was inverted and re-melted three times to ensure an even distribution of the component elements. The samples were then homogenized at temperatures close to their melting points for 3 days in a vacuum furnace maintained at 5 x 10-7 mm Hg. After this treatment the buttons were cold rolled to sheets approximately 0.020 in. thick from which specimens were cut, 0.040 in, wide and 1 in. long suitable for critical current density (J,) and critical temperature (T,) measurements. These strips were then recrystallized and further grain growth was allowed by an additional vacuum heat treatment at 1800°C for 60 hr. Some second phase precipitation occurred during cooling of the furnace and a solution treatment was necessary to produce single phase supersaturated samples. This treatment was successfully carried out by sealing the samples together with some zirconium chips in quartz tubes under a vacuum of 5 x 10-7 mm Hg, heating at 1000°C for 5 hr and then quenching into water or liquid nitrogen. The samples were then heat treated at either 350" or 550°C and quenched into water or liquid nitrogen. All samples which were heat treated at 350°C were quenched in both cases by cracking the capsules in liquid nitrogen. The samples treated at 550°C were quenched by dropping the capsules into water. Analysis for oxygen in randomly selected samples indicated that the oxygen content was in the range of 175 to 225 ppm. Values of Tc were determined by employing a self-inductance technique. Jc measurements were made at 4.2oK by increasing the direct current through the wire in a perpendicularly applied field until a voltage of 1 pv was detected with a null meter. The risk of resistive heating at the soldered joints during these latter measurements was reduced by first plating the ends of the wires with indium and then soldering to the copper current leads using tin. Metallographic examinations were performed after mechanical polishing of the same samples and etching in a 4H20:3HN03 (conc):lHF(conc) solution.

Jan 1, 1970

By P. A. Laxen, H. R. Spedden

WHEN a mineral particle is fractured, bonds between the atoms are broken. The unsatisfied forces that appear at the newly formed surface are considered to be responsible for the adsorption of ions at the mineral surface. A knowledge of the mechanism and extent of ion sorption from solution onto a mineral surface is of interest in the development of the theory of flotation.&apos;*&apos; Study of the adsorption of sodium from an aqueous solution oftheon quartz offers a simple approach to this complicated problem. The availability of a radioisotope as a tracer element meant that accurate data could be obtained."." Three main factors which appeared likely to affect the adsorption of sodium are: l—concentration of sodium in the solution, 2—concentration of onotherof cations in the solution, and 3—anions present in the solution. Hydrogen and hydroxyl ions are always present in an aqueous solution. By controlling the pH, the concentration of these two ions was kept constant. The variation in thesethe amount of sodium adsorbed with variation in sodium concentration was then determined under conditions standardized in regard to hydrogen ion. The effect of concentration of hydrogen ions and of other cations was also measured. A few experiments were made to get a preliminary idea on the effect of anions. The active isotope of sodium was available as sodium nitrate. Standard sodium nitrate solutions were used throughout these experiments except when the effects of other anions were studied. It was found that sodium adsorption increased with sodium-ion concentration, but less rapidly than in proportion to it. Increasing hydrogen-ion concentration, or conversely decreasing hydroxyl-ion, brings about a comparatively slight decrease in sodium-ion adsorption. Increasing the concentration of cations other than hydrogen or sodium decreases somewhat the adsorption of sodium ion. It would appear as if the kind of anion is a secondary factor in guiding the amount of sodium ion that is adsorbed. Materials and Methods Quartz The quartz was prepared as in previous work in the Robert H. Richards Mineral Engineering Laboratory&apos; except for the refinement of using de-ionized distilled water for the final washing of the sized quartz, prior to drying." To minimize the laborious preparation of quartz, experiments were made to determine .whether the sodium-covered quartz could be washed free of sodium and re-used. The experiments were successful as indicated by lack of Na" activity on the repurified material and by its characteristic sodium adsorption. Table I gives the spectrographic analyses of the quartz used. The quartz ranged from 16 to 40 microns in size, averaging about 23 microns (microscope measurement), and had a surface of 1850 sq cm per g (lot I), 2210 (lot 11) and 2000 (lot 111) as determined by the Bloecher method." Radioactive Sodium Method of Beta Counting for Adsorbed Sodium: Na22, the radioisotope of sodium, possesses convenient properties.&apos; It has a half-life of 3 years, thus requiring no allowance for decay during an experiment. On decay it emits a 0.575 mev ß+ radiation and a 1.30 mev r radiation. The decay scheme is illustrated in the following equation: ß+ NaR-------&apos;8&apos;77NeZ2 3 years The /3 radiation is sufficiently strong to penetrate an end-window type of Geiger-Mueller counting tube. This, in turn, makes it possible to use external counting, a great advantage in technique. Furthermore, it permits the assaying of solids arranged in infinite thickness, while assaying evaporated liquors on standardized planchets. The equipment used was standard and similar to that employed by Chang.R The original active material was 1 ml of solution containing 1 millicurie of Na" as nitrate. This active solution was diluted to 1000 ml. Five milliliters of this diluted active solution was found to give a quartz sample a sufficiently high activity for accurate evaluation of the sodium partition in the adsorption measurements. Also, 1 ml of final solution gave a sufficiently high count for precision on the liquor analyses. The sodium concentration of the diluted active solution was 1.2 mg per liter, so that 6 mg of sodium for 60 ml of test solution and 12 g of quartz was the minimum amount used. The active solution was stored in a Saftepak bottle. Procedure for Adsorption Tests: The method consisted of agitating 12 g of quartz with 60 ml of solution of known sodium concentration for enough time to establish equilibrium between the solution and the quartz surface. The quartz was separated as completely as possible from the solution by filtering and centrifuging. The activity on the quartz and in the equilibrium solution was measured and the partition of the sodium was calculated from the resulting data. The detailed procedure for the adsorption test is set forth in a thesis by Laxen." In brief, it included the following steps: 1—Ascertainment of linearity between concentration of Na" and activity measured. 2—Evaluation of factor to translate activity on solid of infinite thickness in terms of activity on an evaporated active film of minute thickness, on the various shelves of the counter shield. 3—Taking precautions to avoid evaporation of water during centrifuging

Jan 1, 1953

By P. A. Laxen, H. R. Spedden

WHEN a mineral particle is fractured, bonds between the atoms are broken. The unsatisfied forces that appear at the newly formed surface are considered to be responsible for the adsorption of ions at the mineral surface. A knowledge of the mechanism and extent of ion sorption from solution onto a mineral surface is of interest in the development of the theory of flotation.&apos;*&apos; Study of the adsorption of sodium from an aqueous solution oftheon quartz offers a simple approach to this complicated problem. The availability of a radioisotope as a tracer element meant that accurate data could be obtained."." Three main factors which appeared likely to affect the adsorption of sodium are: l—concentration of sodium in the solution, 2—concentration of onotherof cations in the solution, and 3—anions present in the solution. Hydrogen and hydroxyl ions are always present in an aqueous solution. By controlling the pH, the concentration of these two ions was kept constant. The variation in thesethe amount of sodium adsorbed with variation in sodium concentration was then determined under conditions standardized in regard to hydrogen ion. The effect of concentration of hydrogen ions and of other cations was also measured. A few experiments were made to get a preliminary idea on the effect of anions. The active isotope of sodium was available as sodium nitrate. Standard sodium nitrate solutions were used throughout these experiments except when the effects of other anions were studied. It was found that sodium adsorption increased with sodium-ion concentration, but less rapidly than in proportion to it. Increasing hydrogen-ion concentration, or conversely decreasing hydroxyl-ion, brings about a comparatively slight decrease in sodium-ion adsorption. Increasing the concentration of cations other than hydrogen or sodium decreases somewhat the adsorption of sodium ion. It would appear as if the kind of anion is a secondary factor in guiding the amount of sodium ion that is adsorbed. Materials and Methods Quartz The quartz was prepared as in previous work in the Robert H. Richards Mineral Engineering Laboratory&apos; except for the refinement of using de-ionized distilled water for the final washing of the sized quartz, prior to drying." To minimize the laborious preparation of quartz, experiments were made to determine .whether the sodium-covered quartz could be washed free of sodium and re-used. The experiments were successful as indicated by lack of Na" activity on the repurified material and by its characteristic sodium adsorption. Table I gives the spectrographic analyses of the quartz used. The quartz ranged from 16 to 40 microns in size, averaging about 23 microns (microscope measurement), and had a surface of 1850 sq cm per g (lot I), 2210 (lot 11) and 2000 (lot 111) as determined by the Bloecher method." Radioactive Sodium Method of Beta Counting for Adsorbed Sodium: Na22, the radioisotope of sodium, possesses convenient properties.&apos; It has a half-life of 3 years, thus requiring no allowance for decay during an experiment. On decay it emits a 0.575 mev ß+ radiation and a 1.30 mev r radiation. The decay scheme is illustrated in the following equation: ß+ NaR-------&apos;8&apos;77NeZ2 3 years The /3 radiation is sufficiently strong to penetrate an end-window type of Geiger-Mueller counting tube. This, in turn, makes it possible to use external counting, a great advantage in technique. Furthermore, it permits the assaying of solids arranged in infinite thickness, while assaying evaporated liquors on standardized planchets. The equipment used was standard and similar to that employed by Chang.R The original active material was 1 ml of solution containing 1 millicurie of Na" as nitrate. This active solution was diluted to 1000 ml. Five milliliters of this diluted active solution was found to give a quartz sample a sufficiently high activity for accurate evaluation of the sodium partition in the adsorption measurements. Also, 1 ml of final solution gave a sufficiently high count for precision on the liquor analyses. The sodium concentration of the diluted active solution was 1.2 mg per liter, so that 6 mg of sodium for 60 ml of test solution and 12 g of quartz was the minimum amount used. The active solution was stored in a Saftepak bottle. Procedure for Adsorption Tests: The method consisted of agitating 12 g of quartz with 60 ml of solution of known sodium concentration for enough time to establish equilibrium between the solution and the quartz surface. The quartz was separated as completely as possible from the solution by filtering and centrifuging. The activity on the quartz and in the equilibrium solution was measured and the partition of the sodium was calculated from the resulting data. The detailed procedure for the adsorption test is set forth in a thesis by Laxen." In brief, it included the following steps: 1—Ascertainment of linearity between concentration of Na" and activity measured. 2—Evaluation of factor to translate activity on solid of infinite thickness in terms of activity on an evaporated active film of minute thickness, on the various shelves of the counter shield. 3—Taking precautions to avoid evaporation of water during centrifuging

Jan 1, 1953

By Enrique Touceda

The question as to the proper amount of total carbon that the malleable founder would prefer to have in pig iron for use in the production of air-furnace, white iron castings, must be considered from different angles, that is, whether it is desirable or advantageous from an economic standpoint to use some kind of low-carbon scrap on his mixture, or make use of pig and sprue only. Whereas silicon is the acknowledged scrap carrier in the case of cupola gray iron castings, carbon performs this role for the most part in malleable iron practice, irrespective of the character of furnace used for the production of the white iron castings. In this particular, the advantage lies with the maker of gray iron castings in that the silicon content in pig iron through a regulation of furnace temperature is under very easy control by the blast-furnace manager, whereas he has little or no control over the resultant percentage of carbon, as this is dependent on the quantity of coke in the hearth, and hearth temperature, coupled with the amount of hearth slag and its particular composition. As perhaps more than 95 per cent. of white iron castings are made in air furnaces the following statements are intended to cover that situation particularly: In the malleable process the composition of the hard iron castings (that is determined upon as best suited for the work in hand) is the one factor that must control the composition of the mixture to be used; because if the elements are not between certain definite limits individually and collectively the annealed or finished product will be unsoitable, due, perhaps, to lack of sufficient strength or because it is too hard, to machine easily. The annealed product can be divided into two classes, one of which greatly predominates, that is, by far the largest tonnage is used for machine parts where high strength and ductility are essential requisites, while a far smaller amount, light in weight and thin in section, is used for other manufactured products in which castings of any reasonable degree of strength and ductility have proved satisfactory.

Jan 1, 1927

By A. J. Langhammer

A. J. Langhammer.—That is rather asking a question of the wrong man. However, I will reply to the question from our point of view. There is a considerable amount of iron powder available but the properties vary over a wide range. Powder metallurgy has progressed to the stage where we recognize certain requirements in powdered iron, and what may be a good powdered iron for one application will not necessarily fit the picture for the next one. Further, I believe that there is room for great improvement in the properties of powdered iron. Also, that there is only a limited quantity of powdered iron available having certain specific properties in which we are at the moment interested. F. P. Peters.—May I have a word? With all possible respect to the contributions of the Chrysler Corporation (and they have been tremendous) to the war effort, I think it is easy to get from part of Mr. Langhammer&apos;s discussion a false impression of vaster possibilities than really exist. It would be well if in addition to Mr. Langhammer some other manufacturers of machine parts&apos; might tell us in the next few minutes some of the limitations they have found. For example, what is the maximum tensile strength that is being produced in a commercial part in production today? And what is the actual size limitation on bearings that are in operation and are standing up well? We should always bear in mind the fact—and I think Mr. Langhammer will agree with me— that quoting on a particular part does not necessarily mean placing it in production. In many cases it may be several months before the quotation is resolved and we know whether the part can be made. Let us open up this thing for a little free-for-all discussion of some of the ceilings that do exist in the design of machine parts made by powder metallurgy. The ceiling is not unlimited, and Mr. Langhsmmer will agree with that, 3 am sure. H. Hendriks.*—I do not think that there is so much limitation in the making of powder metallurgic manufactured parts as mentioned. Last year we had the problem of making dies for a special machine used in the manufacturing of slide fasteners. This part was wearing out very fast. It was very hard to make, it had to be hobbed out of a special steel and it was a difficult thing to manufacture in general. The tolerances were one half of one thousandth of one inch on all dimensions. We submitted this die to a manufacturer of powder-metal parts. He thought that it was impossible, but we were not as skeptical as he was and decided to try it anyway. The Canadian General Electric Carboloy Division, in Toronto, gave us then the design for the dies, which we made to their specifications. When the first part was delivered, we submitted it to our Inspection Department and its check showed that all the tolerances were right on the dot. They delivered I9 parts of exact specification, then they went off the beam; they could not keep to the tolerances. It took them a long time to get back again. We do not know what happened, but the main point I want to&apos; make is that if a problem is attacked in the right may, the dies are made right and corrected as to dimensions found out by experiment, I do not think that there is so much diffculty in making powder-metal parts to close tolerances.

Jan 1, 1945

By G. Carman Ridland

IN conjunction with a geological investigation of the silver-bearing veins at Contact Lake, Northwest Territories, Canada, a survey was made with a Geiger-Müller counter of the gamma-ray emissions from the rocks in the vicinity of the mine workings. Discontinuous pitchblende veins have been encountered occasionally in the silver-bearing fissures, and the geophysical survey was undertaken with the hope that abnormally high gamma-ray intensities, if detected, might lead to larger and more continuous pitchblende discoveries. Before the instrument was used at Contact Lake, preliminary tests were made, first with laboratory specimens at Princeton University, and later over known pitchblende deposits at the Eldorado property, LaBine Point, N.W.T. The Geiger-Müller counter, as adapted for field use, is described; the technique of transporting and operating the instrument is outlined; and the general precautions to be observed are discussed. The results obtained at Great Bear Lake show that the instrument is capable of detecting not only a pitchblende ore shoot in a shear zone, but also the mildly radioactive "host rock" at a considerable distance from the ore body. Hence, use of the Geiger-Müller counter is urged, not just for the detailed search for an ore body in a shear zone, but for the detection of possible radioactive "host rocks" in large-scale reconnaissance surveys of unexplored regions made by prospectors and members of federal geological survey parties.

Jan 1, 1943

By R. T. DeHoff

In any structural transfortnation which is driven by surface tension, the geometric variable of fimdamental importance is the local value of the mean surface curvatuve. Acting through the suvface free energy, this quantity determines the magtnitude of both the pressure and the chemical potential that develops in the neighborhood of an arbitrarily curved surface. A metallographic method which would permit the quaniitatiue estinzation of this propevty is of fundarnerztal irztevest to studies of such processes. In the present paper, it is shoun that the average value of the mean surface curvature in a structuve can be estimated from two simple counting measuretnents made upon a vepresentative metallograpIzic section. No simplifyirlg geonzetric assurmptions are necessary to this deviuation. It is further shoum that the result may be applied to parts of interfaces, e.g., interparticle welds in sintering, or the edge of growing platelets in a phase transformation, without loss of validity. In virtually every metallurgical process in which an interface is important, the local value of the mean surface curvature is the key structural property. This is true because the mean curvature determines the chemical potential of material adjacent to the surface, as well as the state of stress of that material. The theoretical description of such broadly different processes as sintering,1,2 grain growth,3 particle redistrib~tion4,5 and growth of Widmanstatten platelets8 all have as a central geometric variable the "local value of the mean surface curvature". The tools of quantitative metallography currently available permit the statistically precise estimation of the total or extensive geometric properties of a structure: the volume fraction of any distinguishable part:-&apos; the total extent of any observable interface,10,11 and the total length of some three-dimensional lineal feature:&apos; and, if some simplifying assumptions about particle shape are allowed, the total number of particles.&apos;2"3 The size of particles in a structure, specified by a distribution or a mean value, can only be estimated if the particles are all the same shape, and if this shape is relatively simple.14-16 The relationships involved in converting measurements made upon a metallographic section to properties of the three dimensional structure of which the section is a sample are now well-established, and their utility amply demonstrated. In the present paper, another fundamental relationship is added to the tools of quantitative metallography. This relationship is fundamental in the sense that its validity depends only upon the observation of an appropriately representative sample of the structure, and not upon the geometric nature of the structure itself. It involves a new sampling procedure, devised by Rhines, called the "area tangent count". It will first be shown that the "area tangent count" is simply related to the average value of the curvature of particle outline in the two-dimensional section upon which the count is performed. The average curvature of such a section will then be shown to be proportional to the average value of the Mean surface curVature of the structure of which the section is a sample. The final result of the development is thus a relationship which permits the evaluation of the average value of the mean surface curvature from relatively simple counting measurements made upon a representative metallographic section. The result is quite independent of the geometric or even topological nature of the interface being studied. QUANTITATNE EVALUATION OF AVERAGE CURVATURE IN TWO DIMENSIONS The Area Tangent Count. Consider a two-dimen-sional structure composed of two different kinds of distinguishable areas (phases), Fig. l(a). If the system is composed of more than two "phases", it is possible to focus attention upon one phase, and consider the remaining structure as the other phase. The reference phase is separated from the rest of the structure by a set of linear boundaries, of arbitrary shapes and sizes. These boundaries may be totally smooth and continuous, or piecewise smooth and continuous. An element of such a boundary, dA, is shown in Fig. l(b). One may define the "angle subtended" by this arbitrarily curved element of arc, dO, as the angle between the normals erected at its ends, Fig. l(c). Now consider the following experiment. Let a line be swept across this two-dimensional structure, and let the number of tangents that this line forms with elements of arc in the structure be counted. This procedure constitutes the Rhines Area Tangent Count. Suppose that this experiment were repeated a large number of times, with the direction of traverse of the sweeping lines distributed uniformly over the semicircle of orientation.&apos; Those test lines which ap- proach from orientations which lie in the range O to O + dO form a tangent with dA; those outside this range do not, see Fig. l(c). Since the lines are presumed to be uniformly distributed in direction of traverse, the fraction of test lines which form a tangent with dA is the fraction of the circumference of a semicircle which is contained in the orientation range, dO; i.e., vdO/nr or dB/n. If the number of test lines is N, the number forming tangents with dA is N(d0/n). Since each test line sweeps the entire area of the sample, the total area traversed by all N test lines is NL2. The number of tangents formed with dA, per unit area of structure sampled, is therefore

Jan 1, 1968

By H. O. Pickard

The Hoover and Mason Phosphate Co. made extensive tests with a rig manufactured by the Paris Manufacturing CO. as shown in Fig I. It is powered by a 20-hp Wisconsin air-cooled gasoline engine, through a single reduction gear and flexible coupling. The machine operates a 4-in. auger with a detachable cutting head, as shown in Fig I. The auger length is 3 ft 4 in. and the cutting head averages 7 in. The unit has a drilling capacity of 100 ft and can drill an average prospect hole in less than 15 min. The weight of the motor is used for the thrust feed for driving the auger and head down, aided by the spiral shape of the auger. The rate of downward motion—i.e., the feed—is regulated by a handwheel. The string of tools is withdrawn from the hole by a gear train controlled by a hand-operated clutch. In fairly dry strata, not of the consistency of mud, the action of the auger

Jan 1, 1948

By H. O. Pickard

The Hoover and Mason Phosphate Co. made extensive tests with a rig manufactured by the Paris Manufacturing CO. as shown in Fig I. It is powered by a 20-hp Wisconsin air-cooled gasoline engine, through a single reduction gear and flexible coupling. The machine operates a 4-in. auger with a detachable cutting head, as shown in Fig I. The auger length is 3 ft 4 in. and the cutting head averages 7 in. The unit has a drilling capacity of 100 ft and can drill an average prospect hole in less than 15 min. The weight of the motor is used for the thrust feed for driving the auger and head down, aided by the spiral shape of the auger. The rate of downward motion—i.e., the feed—is regulated by a handwheel. The string of tools is withdrawn from the hole by a gear train controlled by a hand-operated clutch. In fairly dry strata, not of the consistency of mud, the action of the auger

Jan 1, 1948

By Herbert Clark Hoover, Lou Henry Hoover

MANY persons hold the opinion that the metal industries are fortuitous and that the occupation is one of sordid toil, and altogether a kind of business requiring not so much skill as labour. But as for myself, when I reflect carefully upon its special points one by one, it appears to be far otherwise. For a miner must have the greatest skill in his work, that he may know first of all what mountain or hill, what valley or plain, can be prospected most profitably, or what he should leave alone ; moreover, he must understand the veins, stringers1 and seams in the rocks2. Then he must be thoroughly familiar with the many and varied species of earths, juices3, gems, stones, marbles, rocks, metals, and compounds4. He must also have a

Jan 1, 1950

By B. J. Scheiner, A. G. Smelley

The Bureau of Mines, US Department of the Interior, is conducting research on a dewatering technique for fine particles generated during the mineral beneficiation process that will recover a portion of the water now being lost using conventional waste disposal methods and significantly reduce the time required for land reclamation. The technique utilizes a flocculant, polyethylene oxide (PEO), that forms strong stable flocs that can be dewatered rapidly on static and/or rotary screens. Infield tests, phosphate clay waste has been dewatered from a nominal 2.5% solids to greater than 20% solids. In other field tests, coal-clay waste has been dewatered from a nominal 3% solids to greater than 55% solids. In addition, small-scale continuous tests have shown that bentonitic clays can be dewatered from 12% solids to 40% solids.

Jan 1, 1985

By F. E. Rizzo, L. R. Bidwell, D. F. Frank

THE use of galvanic cells for the determination of oxygen activities has spread rapidly since the suitability of calcia-stabilized zirconia as a solid electrolyte material was first demonstrated by Kiukkola and Wagner.&apos; In many of these investigations:-7 including several at ARL, the free-energy changes for various oxidation-reduction reactions involving the oxides FexO, NiO, and Cu2O have been measured as a means of assuring that a cell apparatus is functioning properly. As a result, a large quantity of data pertinent to the calculation of the high-temperature standard free energy of formation (?GO) of these oxides has been accumulated. AGFexo has been carefully measured in many independent investigations, using a variety of techniques, and consequently is accurately known. chipmans has used this informa-

Jan 1, 1968

By L. Eaton, A. W. Last, J. L. Stevens

COPPER ore from Kennecott Copper&apos;s Ray mine, about 60 miles southeast of Phoenix, Ariz., is concentrated at the company&apos;s mill at Hayden, some 18 miles south of the mine. The Hayden mill is currently treating 16,000 tons of ore per day by flotation, using raconite, a crude butyl xanthate, as a collector for the sulfide copper minerals and lime as a pyrite depressant.1 The ore contains significant amounts of nonsulfide copper minerals, but recovery of these values has been low. The Hayden mill is now being modified to provide for treatment of future ores by leach- precipitation-flotation (L-P-F). This modification, costing about $5 million, is expected to reduce the loss of nonsulfide copper values and improve overall copper recovery by an additional 2 lb per ton of ore.

Jan 11, 1957

By Lawrence Adler

The authors are to be complimented on using a novel and potentially helpful technique to analyze the effects of mine roof trusses. However, some criticisms of their application and analysis seem appropriate to further its acceptance. This discussion will deal with the normal structural analysis format covering: 1) material. 2) load, 3) structure, and 4) analysis. It will then briefly review the testing procedures and finally cover miscellaneous items. That the analytical and testing results admittedly disagreed by several orders of magnitude, indicates a need for improved understanding. The introduction of data determined previously was not assisted by references to "Interim" or "Preliminary" reports. This material should have been concisely reformulated for the open discussions that Transactions encourage. In addition, many important simplifying assumptions are tacitly made without recognition, and much less, an attempted justification.

Jan 1, 1979

By R. A. Anderson, T. E. Tietz, J. E. Dorn

Recent investigations1,2,3,4 have conclusively shown that the strain hardened state of metals depends upon the temperature and strain rate of pre-straining as well as on the total plastic strain. A typical example of the effect of temperature of prestraining on the work hardening of metals is reproduced in Fig 1. When pure aluminum is strained at liquid nitrogen temperature the upper solid stress-strain curve (OFGH) is obtained. But when pure aluminum is prestrained to e2 = 0.153 at atmospheric temperature and the test is then completed at liquid nitrogen temperature, the curve OBCD results. Thus a prestrain E2 = 0.153 at atmospheric temperature gives a flow stress C when continued at liquid nitrogen temperature, whereas a higher flow stress G results when the specimen is strained exclusively at liquid nitrogen temperature to the same strain E2. Consequently the metal strain hardens more rapidly at the lower temperature. Obviously the strain alone is not a measure of the strain hardened state in metals. Inspection of Fig 1 reveals that the flow stress at C is identical with that at F. This fact suggests that a strain E2 = 0.153 at atmospheric temperature induces the same work hardened state as a strain E1 = 0.058 at liquid nitrogen temperature. But this concept of equivalent strains is also in error. If curve CD is shifted to the left so that point C falls on F, point D becomes D&apos;. Inspection of the curves reveals that the rate of increase of stress with strain at C is greater than the rate of increase of stress with strain at F even though the flow stresses are identical. Consequently C and F do not represent identical work hardened states. It therefore becomes important to ascer- tain how the strain hardened states at C and F might differ from each other. In a more recent report1 it was shown that straining at higher rates of strain increases the amount of strain hardening in a manner quite analogous to straining at lower temperatures. These observations suggested that the flow stress is not only a function of the strain but also a function of the strain rate-temperature history of straining, perhaps in accord with the Zener- ?H Hollomon parameter p = Ee /RT (where

Jan 1, 1950

By Stanley C. Herold

A few hates on the occurrence and significance of mud volcanoes in Colombia may be of interest at the present time, owing to the renewed activity in geological exploration of the coastal regions bordering the Caribbean Sea. The best-known volcanoes are found a few miles from the seacoast. One is situated to the south of Puerto Colombia; the second, to the east of Cartagena near the village of Turbaco; and the third, near the village of Puerto Escondido south of the Sinu River. Others are reported in more inaccessible localities. Usually they stand 2 1/2 or 3 ft. (0.762 or 0.914 m.) above the surrounding ground at the crater, though several craters from 10 to 20 ft. -(3.04 to 6.09 m.) "apart will often build up an extensive mound at low gradient. The shallow mound may cover 1/2 or 3/4 acre (0.2 to 0.3 ha.) with an elevation of 12 or 15 ft. (3.65 or 4.57 m.) at the, center. The craters are formed of hardened blue clay; the inside diameters vary from 14 to 24 in. (35.56 to 60.96 cm.). The rim is continuous, except on one side where there is usually a cut 3 or 4 in. deep, thus allowing an overflow. The craters are filled to the&apos; rim-cut with a thick mixture of blue clay mud and water, which is kept in agitation by escaping gas. Fig. 1 shows the bubble in the act of bursting and Fig. 2 the appearance of the surface of the viscous fluid a second or so later. The frequency of the explosions is determined by the weight of the column of fluid in the neck of the volcano, consequently, such explosions are not synchronous in a group of craters. Ordinarily, there arc two or three explosions in about 3 minutes. The supply of gas is small but steady and sufficient pressure must accumulate before the bubble can enter the column of fluid. The water is derived from the surface and enters the scdirnentary strata not far distant from the volcano. During long dry seasons, as the supply of water fails the volcano dries and geyser action ceases. The temperature of the muddy fluid is normal; the gas is dry and inflammable. - No petroleum products come with the gas. On the surface of the fluid, there is sometimes a dark brown streaky scum, which

Jan 1, 1920