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By F. E. Jaumot, R. L. Smith

Self-diffusion in zinc has been used as an instrument for comparison of the absorption and sectioning techniques as a means of studying diffusion. Single crystal as well as poly-crystal samples were used asanda the temperature range of diffusion extended from 200° to 415°C. For temperatures above 200°C, the data indicate that the results obtained from the absorption technique agree with those obtained from the sectioning technique. The effect on the values of the diffusion coefficient of electroplating vs evaporation as a means of applying the tracer was investigated and no significant difference observed. It was found that an excess or deficiency of tracer did not materially affect the results obtained from the sectioning technique, but invariably caused errors with the absorption technique. NEARLY all self-diffusion experiments and many alloy diffusion experiments have employed radioisotopes as the instrument for following the diffusion. Of the various techniques in which radioisotopes are applicable, the two most widely used are the sectioning and absorption techniques. In the former, the diffusion coefficient is obtained from a curve of log concentration vs the square of the mean penetration depth. In the latter, the diffusion coefficient is calculated from a knowledge of the decrease in activity at the surface after diffusion. In spite of the importance of knowing the reliability of the diffusion data and the widespread use of these two techniques, they had not been directly compared experimentally on the same samples. Thus, such a comparison was worthwhile. The specific system chosen for this comparison was the self-diffusion of zinc, since the metal was readily obtainable in high purity, single crystals were easily grown, and the anisotropic features of the diffusion added an additional factor of interest to the comparison. Self-diffusion in both single and polycrystals was investigated, since the possibility existed that grain boundaries and grain boundary diffusion might produce different effects for the different techniques. Also, the effects of electroplating vs evaporation as a means of applying the radioactive tracer, and the effects of applying an excess or deficiency of tracer material were studied. The general experimental procedures and the mathematical analyses of both techniques have been described previously in some detail, and only those points essential to an understanding of the present work will be discussed here. The mathematical analysis of the sectioning data requires only a knowledge of the solution of Fick's equation. where C,, is the initial concentration, C is the concentration at depth x, D is the diffusion coefficient, and p is the absorption coefficient of the solvent metal for the radiation from the solute. Having obtained F from the experiment, the value of z can be read from a plot of F vs In z, and D can then be calculated if is known. The necessity of knowing the absorption coefficient causes most of the criticism of the absorption technique. It is very difficult to measure accurately under the conditions existing in the diffusion experiment, but it is absolutely necessary, as will be indicated briefly later. Portions of this problem have been discussed in detail elsewhere." The difficulties involved in the measurement of the absorption coefficient arise from three principle factors: the physical characteristics of the absorber, the geometry, and complex radiation spectra. The first two are heavily dependent upon the third. If

Jan 1, 1957

By Keats, J. L.

IN THE literature on the elimination of metalloids in basic open-hearth practice, there are a great many heats recorded in which excellent data on changes in slag and metal composition during refining are given, but in almost all of these heats either temperature data or weights and analysis of charge are unrecorded and observations on the physical charac- teristics of the slag are almost always lacking. With these points in mind, a test heat was made in which as complete as data possible on all the factors that affect the elimination of metalloids were obtained.

Jan 1, 1957

Jan 1, 1905

By E. C. W. Perryman

The recovery of X-ray line broadening, hardness, and electrical resistivity from cold worked AI-Mg alloys has been investigated. The results, together with those from density measurements, suggest that magnesium atoms freeze in the excess vacancies formed by cold working, and that this affects the climb of dislocations during the recovery process. PREVIOUS work1, " has shown that while 1 pct Mg increases the activation energy for recrystalliza-tion, it decreases the activation energy for the recovery of mechanical properties and decreases the subgrain size both after cold working and annealing. A similar result has been reported by Varley2 for an A1-2 pct Mg alloy. With plastic deformation at high temperatures, McLean and Farmer' and Rachinger have found that magnesium appears to retard the motion of dislocations and, furthermore, they find little or no effect of magnesium on the size of subgrains formed during high temperature deformation. In view of the apparent contradictions as to the effect of magnesium on subgrain size, the recovery process in Al-Mg alloys has been investigated more thoroughly by studying the annealing out of X-ray line broadening, hardness, and electrical resistivity from alloys cold worked at room temperature. Material Used—The chemical analyses of the alloys are given in Table I. Fabrication—The material used was cold rolled 20 pct at room temperature, the grain size prior to the last cold rolling operation being similar to that used in previous work; i.e., 230. The experimental procedure for annealing, determination of X-rav half-veak breadth. hardness measurement, electEica1 resistivity, and density and metallographic examination was exactly the same as previously described." Variation of X-Ray Half-Peak Breadth with Annealing Time—Isothermal annealing curves at 100°, 200°, and 250°C were obtained for material cold worked 20 pct. The half-peak breadth of the (333) Ka, line directly after cold working is shown as a function of magnesium content in Fig. 1. Only with the 2.87 pct Mg alloy was overlapping of the a, and n.. reflections observed to any appreciable extent. To separate these, Rachinger's method' was used. Typical isothermal annealing curves are shown in Figs. 2 and 3 for 100" and 200°C, respectively. These curves are similar to those obtained previously for super-purity aluminum except that the

Jan 1, 1957

By C. Kremer Bain

DURING the past several years of diamond drilling in Washington County, Mo., the St. Joseph Lead Co. has discovered a concentration of commercial lead-zinc ore at four different points within an area of 36 square miles. The largest and to date the most promising group of these orebodies is located in the Indian Creek area. It was considered to be of sufficient value to warrant development.

Jan 9, 1953

By Alan Stanley

The MacIntyre Development of the National Lead Co. is located at Tahawus, N. Y. The operations involve the mining and concentrating of a titaniferous iron ore to produce an ilmenite concentrate and a magnetite concentrate. Construction of the MacIntyre plant was commenced during the summer of 1941, when world conditions threatened to cut off the supply of Indian ilmenite. An open pit mining operation was developed and the crushing and milling equipment put in operation in July 1942. A general description of the operation was given in the Adirondack Issue of Mining and Metallurgy for November 1943. The metallurgy of the mill operation was described by Mr. Frank R. Milliken,* Plant Manager, National Lead Company, MacIntyre Development, and presented at the AIME New York Meeting, February 1948.

Jan 1, 1949

By R. W. Kraft

A back- reflection precession-type X-yay camera for determining the crystallographic orientation of the crystallites of both phases in small areas of thick specimens of polyphase alloys is described ad the geometry, advantages, and limitations of the apparatus are discussed. Metallographic obseg-vations of interfacial angles (or habit planes or growth direction are made on the same specimen so that the crystallographic and metallographzc orientation data call be directly correlated. An example of the application of tile technique to a unidi-~~ectionally solidified CuA12-A1 eutectic specimen is presented. The interfacial planes ad growth directions of each phase were established, and the orientation relationship between the phases was observed and found to be approximately intermediate between two previously reported relationships. The crystallographic interfacial relationship between two solid phases is an important parameter in a variety of metallurgical phenomena because of the energy associated with the interface and because this energy is at least partly associated with the way in which the two space lattices are in contact along the interface. In order to describe the interfacial planes in the crystallites of both phases it is necessary to determine the crystallographic orientation of each phase in a specimen relative to each other, and to directly correlate these data with met-allographic measurements from which the interfacial planes can be determined on the same specimen. The back-reflection Laue technique is the easiest way to determine the orientation of thick single crystals or large grains and the method can be combined with metallographic techniques to provide the necessary data, provided the reflections from each phase can be distinguished from one another. However, if the crystallites are small or of varying orientation or if one or both phases has a unit cell with less than the maximum symmetry, many overlapping and complex Laue patterns are recorded simultaneously and it becomes impractical if not impossible to interpret the photographs. All of these complexities were present in a unidirectionally so- lidified A1-CuA12 eutectic alloy1 for which a crystallographic analysis was desired. Consequently the method described here was developed since no known X-ray or electron diffraction technique had all of the following attributes which were required. 1) Method should yield data from which the crys-tallographic orientation of every crystallite or diffracting unit in the irradiated area can be determined. 2) Method should be adaptable to the study of small areas. Depending upon the degree of preferred orientation in the specimens, it should be possible to obtain reliable data in a reasonable length of time on irradiated areas as small as 1.0 or even 0.1 mm in diam. 3) Method should permit direct correlation of crystallographic data with microscopic orientation data pertaining to crystallite axes, habit, morphology, and growth directions as determined by optical microscopy. 4) method should be such that selected areas of large specimens can be easily studied. Trepanning of a small specimen (such as an electron microscope specimen) from larger specimens was undesirable since it would greatly increase the problem of correlating the crystallographic and microscopic directional data. Requirements 3 and 4 dictated that an X-ray back-reflection pinhole technique should be used on large samples, such as metallographic specimens which had previously been examined and analyzed for their microscopic characteristics. Similarly, requirement 2 could be satisfied by choosing a collimator of appropriately small diameter. Exposure times would not be excessive provided the detector were close enough to the specimen. Because of space limitations film was chosen in preference to a Geiger counter. Requirement 1 was fulfilled by using monochromatic radiation and providing enough additional degrees of freedom in specimen rotation to compensate for Bragg law restrictions on diffracted beams. DESCRIPTION OF APPARATUS The apparatus shown in Fig. 1 consists of a pin-hole collimator, (a), projecting through a rotatable circular film in a holder, (b), which records X-ray reflections in the back-reflection region. The specimen, (c), is mounted on the end of a shaft, (d), which is provided with an adjustment, (e), so that the specimen surface can be placed accurately on

Jan 1, 1962

By Paul C. Merritt

Samuel Hopkins, an 18th century inventor from Philadelphia, has been little noted nor long remembered by History, but it was he who on July 31, 1790, obtained what no other man can ever achieve -the first patent issued by the Government of the United States. Signed by President George Washington, the patent guaranteed to Hopkins the protection of the American Government for his "improvement, not known or used before, . . . in the making of Potash . . . by a new Apparatus and Process." The patent itself is no longer important, but it serves as a milestone in the development of an industry that is now rapidly moving to fulfill its role as a mineral to feed the world. Potash ranks as one of the oldest products of Man, having been used as a condiment by the habitants of Gaul a thousand years before Athens achieved its Golden Age of culture. By Hopkins' time, the uses of potash had changed considerably, going primarily into glass-making, tanning, soap, and explosives, yet the same sources and techniques of manufacturing potash used during the earlier 2000 years-that is, leaching of plant ashes in iron pots with water, followed by water evaporation and crystallization of the potassium salts-were still being used.

Jan 10, 1966

By Gilbert Santoro

In this study tantalum carbide filaments of various compositions in the fcc region were prepared by heating a tantalum wire in a measured amount of hydrocarbon vapor. Such properties as tensile strength, transverse-rupture strength, microhard-ness, lattice parameter, electrical resistivity, and magnetic susceptibility were measured as a function of carbon content. Some of these properties showed a maximum or a minimum between a carbon-to-tantalum molar ratio of 0.80 and 0.85, the composition range at which the color changes from metallic gray to gold. The recent literature has shown that in the large homogeneity range for the fcc phase of the Ta-C system there is a marked variation for such properties as microhardness,' electrical resistivity, ' thermodynamic properties,z'3 lattice parameter and superconductivity. In addition to the technological interest of these variations within a single phase, important theoretical benefits may ensue from a continuous investigation of properties vs stoichiometry in tantalum carbide and other refractory defect compounds, for example the effect of the metal-metal distance and crystal structure upon bond formation and electronic structure. Whether there is a similar variation of the tensile strength is of practical importance. Of theoretical interest would be the knowledge of how the magnetic susceptibility varies with carbon composition. Both of these properties, as well as the transverse-rupture strength, were determined for tantalum carbide filaments in the fcc phase region. The lattice parameter, the electrical resistivity, and the microhardness were also investigated and compared with values appearing in the literature. EXPERIMENTAL PROCEDURE Material Preparation. Tantalum carbide specimens of various carbon content were prepared by statically carburizing high-purity tantalum filaments in measured quantities of pure hydrocarbon gas. The filaments, which were 10 mil in diameter and 20 or 40 cm long, were heated by their own resistance at temperatures from 1800" to 2200°C using alternating current in some cases and direct current in others. Tantalum wire from two sources was used. One had a reported purity of 99.96 wt pct Ta. The ingot from which this wire was drawn had been electron beam-melted as the final step in its purification. The reported purity of the other wire, which was prepared by a powder metallurgical process, was 99.88 wt pct Ta. The impurities of both tantalum sources are listed in Table I. Spec-trographic-grade toluene or research-grade propane was used as the source of carbon. The apparatus for the carburization of the filaments is shown schematically in Fig. 1. The system was evacuated to 1 x l0-' mm of Hg when using the electron beam-melted tantalum and to less than 1 p when using the less-pure tantalum. Neither the difference in the base vacuum, nor in the hydrocarbon gas, nor in the tantalum filaments resulted in any detectable difference in the properties studied in this work. However, only the carbides prepared from the higher-purity tantalum were used in the magnetic-susceptibility determinations. Once the base vacuum had been reached, the system was flushed with the hydrocarbon and re-evacuated. For any desired composition of the carbide, hydrocarbon gas was allowed to leak into a constant-volume flask to a predetermined pressure. These pressures were measured by a Cartesian diver-type mercury gage with a range from 0 to 20 mm and with a scale expanded to nine times. The hydrocarbon gas was allowed into the reaction tube and the filament was quickly raised to the reaction temperature. The slack in the filament due to thermal expansion was taken up by drawing out the movable electrode with a screw mechanism. The filaments were kept at temperature from a few minutes to 200 hr. In the majority of cases the heating time was 6 hr. The reaction tube was cooled by cascading water on its outer surface. By means of an ammeter and a voltmeter the electrical resistance at the reaction

Jan 1, 1963

By David Cole

THE New Cornelia Copper Co. is mining and treating a 'monzonite " porphyry" copper deposit that is all hard rock. The oxidized surface shell, which constitutes the leachable part of the orebody, is measurably more resistent to crushing and comminution processes than is the underlying sulfide portion. The siliceous ribs running through the whole orebody are harder to crush than the main mass and there is no soft crumbly material to furnish the large volume of primary fines that features the crusher feeds of most other porphyry properties. New Cornelia ore reaches the primary crushers with a greater. proportion of large 'pieces. When the New Cornelia company first equipped its 'property, it used the following machines and flow , scheme to reduce the ore to leaching size:

Jan 1, 1925

By Wing L. Lew

LEAD, silver, and zinc, in quantities of economic importance are found in the Aguilar ore. The lead occurs as galena and the zinc as sphalerite and marmatite. The silver occurrence is more complex. Pyrargyrite and proustite have been identified only occasionally. Galena is silver-bearing and so are the various other sulphides, though to a lesser degree. The principal nonsulphide gangue minerals include calcite, quartz, wollastonite, rhodonite, and various calcium, aluminum, and iron silicates. A typical analysis of, the ore is: Pb, 11.2; Zn, 12.3; Fe, 4.4; Mn, 2.2; Cu, 0.15; S, 11.2; CaO. 7.6; "Insoluble," 50.1 percent; and Ag 263 g per ton. Crushing is done in three stages. The primary crusher at the mine is set to deliver about a 5-in. product. The crushed ore is then transported to the secondary crushing plant by a 3-km cableway where the general practice is to hold the product of the first Symons to about 1 in., and of the second Symons to about 1/2 in. When the ore is soft and rich the product of the first Symons is by-passed directly to the ball-mill bins. Dust control in the secondary crushing plant is effected by enclosing the dust-emanating sources and exhausting the enclosures with a Clarage No. 18 fan driven at 1300 rpm by a 20-hp motor. Use is also made of spray water at one or two critical places. Every effort is made to keep the air free from visible dust. Dust counts taken at the working places show dust concentrations of less than six million particles ner cu ft. The composition

Jan 1, 1947

By C. C. Nitchie, G. S. Brooks

With the gradual depletion of the natural-gas pools of the Kansas district, together with the uncertainty of further cheap fuel developments, some of the western zinc companies turned to the coal fields, attracted by their permanency and the success of the Matthiessen & Hegeler Co. and the lllinois Zinc Co. Being then confronted with the problem of using a relatively high-priced fuel, although the ultimate supply was very great, the fuel economies of the kilns and furnaces became of far more importance, and the more modern equipments, as a result, embodied distinct gaias in this phase of the business. In addition, there have been some pronounced advances in the actual making of gas from these coals. Increased efficiency in gas making has contributed its hare to lowering costs and those plants located in the higher priced fuel districts have probably been obliged to study these economies somewhat more closely. Naturally, many beneficial changes have resulted in both practice and apparatus in these sections. On certain western coals, for instance, the actual saving in fuel consumption has been 50 per cent. By this is meant that, where about 1.75 tons were burned to smelt 1 ton of oxidized ore, 0.7 to 0.9 ton is now required. While comparisons by T. R. Ingalls1 of fuel economies in smelting in this country and Germany before the war may, in general, be correct, they do not appear to do justice to the more progressive American practice. It is doubtful whether German plants were substantially bettering these fuel ratios. Data furnished by Bender and Frams do not afford records averaging less than 0.9 ton coal per ton ore on materials from 40 per cent. to 50 per cent. zinc. Fuels As producer fuel, Illinois, Indiana, and Kansas coah offer a wide range of material, although varying much in their amenability to gasscation. The proper fuel for each plant can only be determined after com-

Jan 1, 1920

By J. J. Tietien, R. O. Clough

A technique previously used to prepare alloys of InAs1-xPx and GaAsl-x Px, miry: the gaseous hydrides arsine and phosphine, has been extended to grow single -crystalline GaAs 1-x Sb x by replacing the phos-phine with stibine. Procedures were developed for handling and storing stibine which now make this chemical useful for vapor phase growth. This represents the first time that this series of alloys has been grown from the vapor phase. Layers of P -type GaSb and GaSb-rich alloys have been grown with the carrier concentrations comparable to the lowest ever reported. In addition, a p-type alloy containing 4 pct GaSb exhibited a mobility of 400 sq cm per v-sec which is equivalent to the highest reported for GaAs. RECENTLY, interest has been shown in the preparation and properties of GaAs1-xSbx alloys, since it was predicted1 that for compositions in the range of 0.1 < x < 0.5, they might provide improved Gunn devices. However, preparation of these alloys presents fundamental difficulties. In the case of liquid phase growth, the large concentration difference between the liquidus and solidus in the phase diagram, at any given temperature, introduces constitutional supercooling problems. It is likely that, for this reason, virtually no description of the preparation of GaAs1-xSbx by this technique has been reported. In the case of vapor phase growth, problems are presented by the low vapor pressure of antimony, and the low melting point of GaSb and many of these alloys. In previous attempts1 at the vapor phase growth of these materials, using antimony pentachloride as the source of antimony vapor, alloy compositions were limited to those containing less than about 2 pct GaSb. This was in part due to the difficulty of avoiding condensation of antimony on introducing it to the growth zone. A growth technique has recently been described2 for the preparation of III-V compounds in which the hydrides of arsenic and phosphorous (AsH3 and pH3) are used as the source of the group V element. With this method, GaAs1-xPx and InAs1-xPx have been prepared2&apos;3 across both alloy series with very good electrical properties. Since the use of stibine (SbH3) affords the potential for effective introduction of antimony to the growth apparatus, in analogy with the other group V hydrides, this growth method has been explored for the preparation of GaAs1-xSbx alloys. In addition to GaSb, these alloys have now been prepared with values of x as high as 0.8. In the case of GaSb, undoped p-type layers were grown with carrier concentrations equivalent to the lowest reported in the literature. Thus it has been demonstrated that, with this growth technique, all of the alloys in this series can be prepared. EXPERIMENTAL PROCEDURE A) Growth Technique. The growth apparatus, shown schematically in Fig. 1, and procedure are virtually identical to that described2 for the growth of GaAs1-xPx alloys, with the exception that phosphine is replaced by stibine.* HCl is introduced over the gallium boat to *Purchased from Matheson Co., E. Rutherford,N+J. transport the gallium predominantly via its subchlo-ride to the reaction zone, where it reacts with arsenic and antimony on the substrate surface to form an alloy layer. The fundamental limiting factors to the growth of GaAs1-xSbx alloys from the vapor phase, especially GaSb-rich alloys, are the low melting point of GaSb (712°C) and the low vapor pressure of antimony at this temperature (<l mm). Thus, relatively low antimony pressures must be employed, which, however, imply low growth rates. To provide low antimony pressures, very dilute concentrations of arsine and stibine in a hydrogen carrier gas were used. Typical flow rates (referred to stp) were about 4 cm3 per min of HC1 (0.06 mole pct)+ from 0.1 to 1 cm3 per min of ASH, (0.002 to 0.02 mole pct), and from 1 to 10 cn13 per min of SbH3 (0.02 to 0.2 mole pct), with a total hydrogen carrier gas flow rate of about 6000 cm3 per min. Although no precise data on decomposition. kinetics exist, it is known4 that stibine decomposes extremely rapidly at elevated temperatures. However, the high linear velocities attendent with the high total flow rate (about 2000 cm per sec) delays cracking of the stibine until it reaches the reaction zone and prevents condensation of antimony in the system. To improve the growth rates of the GaSb-rich alloys, growth temperatures just below the alloy solidus are main-

Jan 1, 1970

By L. Zwell, H. A. Wriedt

X-ray Lattice parameter and bulk density measurements were made at room temperature on solid solutions of nitrogen in purified a, iron, containing from 0 to 0.053 wt pct N. When nitrogen is dissolved in a, iron, the fractional increase in unit cell volume (X-ray diffraction) and the fractional increase in volume per gram of iron (bulk density measurement) are the same within experimental error. The two sets of results when averaged show that the unit cell edge of a, iron increases linearly by 3.2 X 10-2 A per wt pct N dissolved and that the partial gram-atomic volume of nitrogen at infinite dilution in a, iron is the same as it is in nitrogen-martensite, that is, 5.90 cm3. RECENT reviews17&apos; of literature dealing with the lattice parameter of ferritic iron-nitrogen alloys indicate that the dilating effect of dissolved nitrogen on the bcc unit cell of a iron is not known with confidence. Five investigations3-7 either revealed no effect of nitrogen or were inconclusive. Among other investigations, where quantitative data were obtained, the results of Osawa and Iwaizumi8 indicate too large an effect, and those of Eisenhut and Kaupp9 show the lattice parameter of ferrite varying with the nitrogen content at concentrations far beyond the known solubility limit. It is not clear in Burns&apos;10 data what value should be used for the lattice parameter of nitrogen-free ferrite in calculating the dilation. Burdese11 shares with Burns the shortcoming that the iron-nitrogen alloys were solution-treated and quenched with undissolved nitride present. The consequence is that the un- certainties in the solubility limit1 are added to those in the lattice parameter measurements when the variation of lattice parameter with nitrogen content is computed. For a system of such widespread interest, we felt that a new investigation was merited. Both X-ray diffraction and bulk density measurements were used to determine the dilation of the , a iron lattice by dissolved nitrogen. EXPERIMENTAL PROCEDURE Material. The bulk density and X-ray diffraction experiments were both made with specimens of a purified iron (denoted as "B iron")- from Battelle Memorial Institute. The impurity contents were as follows: As, C, Cu and Pb—50 ppm; Ag, Al, Co, Ga, 0, Ti-11 to 50 ppm; B, Be, Ca, Cd, Cr, Mg, Mn, Mo, N, Ni, S, Sb, Si, Sn, V, W-10 ppm or less. The vacuum-cast ingot was hot-forged and annealed. Pieces of the forged stock were machined and cold-rolled to give strip stock 0.08 and 0.002 in. thick for density and for X-ray measurements, respectively. Preparation of Specimens. Starting with a piece of the cold-rolled iron stock, the general sequence of operations, after an initial recrystallizing anneal, was to measure the density or lattice parameter, nitrogenize, remeasure the property, age or denitrogenize, and again measure the property. Duplicate analyses for nitrogen were made by a modified Kjeldahl method on portions of the actual density specimens and on pieces nitrogenized to equilibrium alongside the X-ray specimens. Annealing of the density specimens was performed by sealing the pieces with the as-rolled surfaces removed by filing into evacuated "Vycor" capsules and treating for 1 hr at 750°C followed by furnace cooling. (TO check the effect, if any, of annealing procedure, a specimen also was

Jan 1, 1962

By Donald M. Liddell

From a commercial standpoint, the only beryllium mineral warranting attention is beryl, 3Be.Al2O3.6SiO2, which is of fairly widespread occurrence. The chief deposits are in Brazil, Argentina, India, Canada and Portugal. When pure this contains about 14 per cent of beryllium oxide. The mineral richest in beryllium is phenacite, (BeO)2SiO2, or beryllium orth-osilicate, which contains 45.55 per cent beryllium oxide when pure, and if anyone is ever fortunate enough to discover a large deposit of it, it will revolutionize beryllium metallurgy. Gadoljnite, zBe0.Fe0.2Yz0~.zSi0~, is also often referred to as a beryllium mineral, though the occurrences are comparatively scant and it is of more interest as a source of yttrium than it is of beryllium. There has been a good deal of talk recently regarding some occurrences of helvite in the United States. Helvite is a complex manganese-iron beryllium silicate and, apart from difficulties that would arise in its treatment because of its compo-sition, the beryllium content of the known deposits is not high. Early Metallurgy The elemcnt beryllium was first isolated by L. N. Vauquelin in 1797.~ He crushed and heated beryl, having the idea that this heating made it more readily amenable to attack by chemicals, and then mixed the mineral with three times its weight of caustic potash and fused the mixture. The melt after cooling was dissolved in hydrochloric acid: dehydrated, and again taken up with hydrochloric acid and filtered to separate the silica. The filtrate was treated with an excess of potassium carbonate and the precipitate after draining was leached with a solution of caustic potash, which dissolved the alumina. The undissolved material was, in Vauquelin&apos;s own words, "une terre nouvelle." He dissolved the precipitate with nitric acid and evaporated it to dryness, took up with hydrochloric acid and threw the iron out with potassium hydrosulphide, though he found that to make a complete separation of the iron involved a second treatment. The solution, after throwing out of the iron, had a pronounced sweet taste, and though Vauquelin always speaks of working on "terre du beril" he suggests that the new element should be known as "glucine" (glucinum) from the Greek word for sweet, because of this outstanding property. Vauquelin did considerable work on the comparison of aluminum and beryllium, working out a separation of most of the aluminum based on its precipitation as alum. His work is reviewed at some length, since ordinarily his procedure is incorrectly stated. It will also be recognized by those who have studied beryllium metallurgy that a good many technicians have followed his ideas since, including preheating the beryl before treatment. The fusion with

Jan 1, 1944

By Charles L. Mantell, Kurt Straler

The hydrogen reduction of Cr2O3 to chromium metal was found to be feasible at very low water-vapor concentrations, corresponding to dew points of -38° to -24°C, over a temperature range of 1130" to 1490°C. Hydrogen reduction under these conditions was predicted by the calculated equilibrium curves which also indicated that CrzOs is reduced directly to chromium without forming the intermediate oxide, CrO. This reduction path was confirmed by X-ray diffraction analysis. The percent reduction of Cr2O3 at each reaction temperature was constant with time, suggesting an inhibiting effect of water vapor. A small increase in the residual water-vapor concentration of a single temperature, 1490°C, strongly retarded the rate of reduction This effect was expressed by an empim&apos;cal equation which indicated a direct relationship between "distance from equilibrium" and the rate of reduction. me effect of temperature over the range of 1130" to 1490°C was expressed in an Arvhenius plot of log rate vs reciprocal absolute temperature. From this curve the apparent enthalpy of activation was found to be 29,600 cal. Based on the hypothesis that the rate of reductiun is contvolled at the oxide-metal interface, an over-all rate equation consistent with the experimental data and the thery of absolute reaction rates was formulated. A simplification of this expression to an Arrhenius equation was justified by the overriding effect of temperature on the rate of reaction for the minimum water-vapor concentration range. MOST of the metals in Subgroup V1 of the periodic table can be prepared commercially by direct reduction of their oxides by hydrogen or carbon monoxide, at temperatures considerably below the melting points of both the metals and their oxides. Chromium is an exception, being generally reduced from its ore, Cr2O3 . FeO, by silicon in an electric arc furnace which operates above the melting point of the Fe-Cr alloy or above the melting point of chro- mium if a chromium oxide be the starting material. In reduction of chromium oxide by hydrogen, either reduction does not occur at all or the rate of reduction is extremely slow. Theoretical considerations based on the high, exothermic, free energy of formation of Cr2O3 compared to the oxides of the other Subgroup VI metals, molybdenum, tungsten, and uranium, would also suggest a slow rate of reaction and a high activation energy. Interest in the direct gaseous reduction of fine-powdered ores in fluidized beds was considered justification for examination of this reaction. In order to develop a basis for a continuing study of the commercial feasibility of the direct gaseous reduction of chromite, a study of the kinetics of the reduction of Cr2O3 with hydrogen was undertaken. To the authors&apos; knowledge no accurate kinetic data for this reaction have been obtained. Neither has an activation energy been determined nor has an attempt been made to establish a mechanism of reaction. LITERATURE Maier10 compared the data of I. Y. Granaat,6 H. von Wartenburg and S. Aoyama, and G. Grube and M. Flad7 with that derived from calorimetric and ther-modynamic properties for the equilibria for the reduction of Cr2O3 with hydrogen. These results, plotted as the log of the equilibrium constant vs absolute temperature for the reduction of Cr2O3 and the intermediate oxide, CrO, to chromium, show agreement between the differently derived data. In both cases the equilibrium constants were extremely low. Maier showed that, over a temperature range of 1000° to 2000°K, Cr2O3 is more readily reducible than CrO. Granat assumed that CrO was preferentially formed from Cr2o3 above 1100°C. Grube and Flad&apos;s analysis of their reaction products in the 895" to 1000°C range indicated the coexistence of only Cr2O3 and chromium. The hydrogen reduction of the other Subgroup VI metals, molybdenum, tungsten, and uranium, shows that reduction of the higher oxide proceeds through all of the intermediate oxides before being reduced to the metal. Since evidence pointed to an anomaly in the reduction behavior of Cr2O3, the authors investigated the reduction path of Cr2Os.to chromium. This was done theoretically with more recently available free-energy data and experimentally by X-ray diffraction analysis. This work reinforces Maier&apos;s conclusion.

Jan 1, 1964

By Johnston, T. L.

BISMUTH is found as native metal associated with tin, copper, cobalt, silver, gold, or other metals and in a variety of ores. The more important ones are: bismuthinite (bismuth glance), Bi2S3; bismite (bismuth ochre), Bi2O3.3H2O; and bismutite (bismuth carbonate), Bi2O3CO3?H2O. Of lesser importance are the arsenate, telluride, and vanadate. The sulfide is the most common; the others are often oxidation products from this mineral. Bismuth minerals have been found in various places in the United States, principally in Colorado and Utah, but no ores are mined solely for bismuth. In the Granite mining district of Beaver County, Utah, a stratum of limestone about 6 ft. thick has been almost completely replaced by contact minerals in which bismuthinite associated with pyrite and molybdenite was found intergrown with silicate minerals. In the early days a few small lots of ore assaying 7 to 10 per cent bismuth were shipped from this district. Native bismuth has been found in the Clifton and Tintic districts of Utah. Bismuth is produced as a byproduct in the refining of lead, copper, gold and silver ores, it being recovered from the anode mud from the Betts process. Deposits of bismuth minerals exist in Argentina, Aus¬tralia, China, Japan, Germany, Spain, Peru, Bolivia, and Canada, but Bolivia is the principal, producer and could easily supply all of the present world&apos;s demand.

Jan 1, 1933

By Ulick R. Evans

I Should like to commence by saying how much I appreciate the honor which the American Institute of Mining and Metallurgical Engineers has done me in inviting me to visit your country, and to deliver this lecture before you. In choosing a subject, and in deciding what to include and what to omit, I have endeavored to discuss as far as possible work carried out recently in Europe with which you may not be unduly familiar. It would be poor return for your hospitality, and a mistaken sort of compliment indeed, if I were to load the lecture with accounts of researches carried out in your own country—researches with which you are probably better acquainted than I. Not that I have in any way excluded work done on this side of the Atlantic from my survey; one would indeed find it difficult to write on this, or on any other branch of science, without mentioning American work. But I have endeavored as far as possible to concentrate on aspects of the case which will, I hope, be comparatively fresh to you, and I feel fairly certain that this will be in accordance with your own wishes. Films Produced at Elevated Temperatures If a strip of iron is heated strongly at one end, the other end remaining cold, there is produced over the heated portion a layer of oxide scale, the thickness of which diminishes steadily with the distance from the hot end. Somewhere in the middle of the strip, the thickness of the oxidized layer will become comparable to the wave length of light, and over this region the thin films give rise to a series of beautiful interference tints, commonly known as "temper colors." The colors are caused by the fact that two trains of light waves are reflected respectively from the outer and inner surfaces of the oxide film, and the possibility arises that the "crests" of one series of waves may coincide with the "troughs" of the other, thus diminishing the intensity of the light of some particular wave length. The state of affairs in this part of the strip is shown diagrammatically in Fig. 1, in which the film thickness is enormously exaggerated, of course, in comparison with the length of the strip; the

Jan 1, 1929

By Ulick R. Evans

I Should like to commence by saying how much I appreciate the honor which the American Institute of Mining and Metallurgical Engineers has done me in inviting me to visit your country, and to deliver this lecture before you. In choosing a subject, and in deciding what to include and what to omit, I have endeavored to discuss as far as possible work carried out recently in Europe with which you may not be unduly familiar. It would be poor return for your hospitality, and a mistaken sort of compliment indeed, if I were to load the lecture with accounts of researches carried out in your own country—researches with which you are probably better acquainted than I. Not that I have in any way excluded work done on this side of the Atlantic from my survey; one would indeed find it difficult to write on this, or on any other branch of science, without mentioning American work. But I have endeavored as far as possible to concentrate on aspects of the case which will, I hope, be comparatively fresh to you, and I feel fairly certain that this will be in accordance with your own wishes. Films Produced at Elevated Temperatures If a strip of iron is heated strongly at one end, the other end remaining cold, there is produced over the heated portion a layer of oxide scale, the thickness of which diminishes steadily with the distance from the hot end. Somewhere in the middle of the strip, the thickness of the oxidized layer will become comparable to the wave length of light, and over this region the thin films give rise to a series of beautiful interference tints, commonly known as "temper colors." The colors are caused by the fact that two trains of light waves are reflected respectively from the outer and inner surfaces of the oxide film, and the possibility arises that the "crests" of one series of waves may coincide with the "troughs" of the other, thus diminishing the intensity of the light of some particular wave length. The state of affairs in this part of the strip is shown diagrammatically in Fig. 1, in which the film thickness is enormously exaggerated, of course, in comparison with the length of the strip; the

Jan 1, 1929

By Arthur R. Kommel, Robert F. Mehl, Gerhard Derge

The orientation relationships resulting from allotropic transformations and the formation of segregate structures in metals and alloys have been the subject of the eight earlier papers in this series&apos;. A brief summary of orientation studies has also been given by Sachs2. A survey of these papers discloses that the factors that determine the orientation relationship of a precipitated phase to its parent solid solution, as well as the outward form and appearance of the new phase, are not completely understood. It is now evident that crystallographically analogous systems, as a rule, exhibit the same type of Widmanstatten figure and orientation relations, so that useful information is not to be expected from examination of a new alloy involving lattice combinations of which the orientation relationships are already known. Therefore, the determination of the relations existing between lattice types that have not already been studied seems to be the most promising mode of attack upon the problem; both of the systems reported in this paper represent new combinations of lattice types. A. The Mg-Mg2Sn System The magnesium-tin equilibrium diagram given by Hansen3 shows the phase Mg2Sn to be the only intermediate phase. The solid solubility of Sn in Mg decreases from 14.8 weight per cent at the eutectic temperature, 561&apos; C., to 2.3 per cent at 450°, while no solid solubility of Mg in Mg2Sn has been observed. The crystal structur: of Mg is close-packed hexagonal with a0 = 3.202 A. and co = 5.199 A.4, while Mg2Sn is of the CaF2 type with a. = 6.78 A., with four molecules in a unit ce115,6. Alloys from two different sources have been used: (1) those supplied by the Dow Chemical Co., which contain 6 and 8 weight per cent Sn, and (2) those prepared in this laboratory, containing 8 and 13.5 per cent Sn. The latter were made from Dow high-purity Mg and Baker chemically

Jan 1, 1937