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By George A. Packard

THE experiments here described were made under my supervision while temporarily acting as head of the Department of Metallurgy at the Missouri School of Mines, at Rolla. The work was done by Messrs. W. E. Brown, W. C. Richards, and F. L. L. Wilson, and the description of the results forms a portion of a thesis presented for the degree of Bachelor of Science. These results are submitted because I have seen no description of the application of pot roasting to the treatment of a copper-concentrate. This work followed that already described in the discussion of the ' Lime-Roasting of a Galena-Concentrate,"' and was similarly occasioned by the lack of a furnace of the reverberatory type in which the copper-concentrates could be smelted. The material for the tests was a mixture of three lots available. The first consisted of 8-mm. jig-concentrates and the second of 0.5 mm. table-concentrates, from the San Juan district, Colo. Both contained pyrite, chalcopyrite and galena. The third was a lot of copper-ore, found in the laboratory, which had been crushed through 8-mm. screen, and had at some previous time, before the laboratory roasting-furnace was torn down, received a partial roasting. The analyses of these ores are given in Table I. In order to determine the applicability of pot-roasting as to each lot of ore, and the effect of varying proportions of lime, six preliminary tests were made in a " size N " Battersea crucible, 9 in. high by 6 in. in diameter at top, with a 5/8 in. hole bored through the bottom. The crucible was set in the upturned elbow of a 2-in. pipe, the joint being luted with clay; and air was obtained from a receiver supplied by a compressor. The

Jan 1, 1908

By K. A. Gschneidner, O. D. McMasters, T. J. O’Keefe

X-ray diffraction, differential thermal, ad rnetallo-graphic methods were used to establish the Dy-Pb Phase diagram. Lead additions lower the 1377°C transformation temperature of dysprosium to 1360°C leading to an inverted peritectic reaction. The 327°C melting point of lead is lowered by dysprosium additions to about 326°C yielding a eutectic reaction. A second eutectic reaction occurs at 13.3 at. pct Pb and 1200°C. The dysprosium-richest intermetallic compound DysPb3 melts congruently at 1695°C and crystallizes in the hexagonal Mn5Si3 (D8,) type structure. The peritectic decomposition temperatures for the remaining compounds are Dy5Pb, at 1555C, DyPb2 at 955C, and DyPb3 at 880°C. A fifth compound near the DyPb stoichiometry exists over a 310°C temperature range decomposing at 1130°C by means of an inverted peritectic reaction and melting incongruently at 1440°C. The crystal structures of the compounds are discussed. A systematic study of the rare earth-lead alloy systems is underway in an effort to supply information concerning the alloying behavior of the rare earth metals. The Dy-Pb phase diagram is the fourth system to be investigated in this study. The Yb-Pb,1 Y-Pb,2 and Eu-Pb 3 diagrams have been published recently. Utilization of the rare earth series of metals as a research tool in this manner should yield a better understanding of alloy formation. EXPERIMENTAL PROCEDURE Materials. The lead used in this investigation was obtained from Cominco Products, Inc., and was specified to be 99.99 pct pure. The dysprosium was prepared in this Laboratory by the calcium reduction of the fluoride followed by distillation of the dysprosium. The major impurities in the dysprosium in ppm are: A1 (<40), Ca (400), Er (<50), Gd (<200), Ho (<200), Mg (<50), Si (30), Ta (400), Tb (<100), Y (<50), 0 (651, H (15), N (not detected), F (430), C (35). Alloy Preparation. Most of the alloys were prepared by melting weighed amounts of dysprosium and lead in sealed tantalum crucibles. The tantalum crucibles were sealed by are-welding in a He-Ar atmosphere welding chamber. Thus the alloys are in contact with He-Ar at about 1 atm pressure. Homogenization was achieved by holding them in the liquid state for about 1 hr, cooling, inverting the crucibles, remelting, and repeating the process at least twice. Since these alloys were prepared in sealed tantalum crucibles, chemical analysis for final composition was thought to be unnecessary. No detectable reaction of these alloys with the tantalum crucible was observed by metallographic examination. Metallographic evidence was also used to confirm the homogeneity of some of the alloys prepared in this manner. The compositions of a few alloys, which were prepared by nonconsum-able are-melting, were corrected for the small weight losses involved by assuming that the weight loss is due to vaporization of lead. The specimens obtained from the alloy samples were prepared under a dry-argon atmosphere because they were rapidly attacked by air and moisture. Thermal Analysis. Differential thermal analysis methods were used to determine the liquidus curves and reaction horizontals of the system. Both Pt vs Pt + 13 pct Rh and W + 5 pct Re vs W + 26 pct Re thermocouples were used to measure the temperature. An X- Y recorder was used to record the specimen temperature and differential electromotive force between the specimen and molybdenum standard. The arrest temperatures were measured potentiometri-cally. The accuracy limits (* values) associated with the reaction temperatures obtained by this method were estimated on the basis of both the reproducibility of the particular temperature value and the accuracy of the thermocouple at a given temperature. Liquidus temperatures were obtained from cooling arrest data while both heating and cooling arrest data were used to establish the horizontals of the diagram. Heat treatments during the thermal analyses of the alloys between 40 and 70 at. pct Pb were necessary in order to approach equilibrium conditions. The samples were held at temperatures between the various peritectic horizontals for l to 2 hr before the thermal analyses were continued. The entire range of compositions was investigated at the expense of a minimum amount of materials by adding appropriate amounts of lead to master alloys. More than sixty alloys were analyzed by this differential thermal method and for each alloy the results given herein are taken from two or three heating and cooling cycles. X-Ray and Metallographic Methods. Slice specimens for metallography and powder specimens for X-ray diffraction were prepared from rod-shaped samples which had been melted in sealed 0.62 5-cm-diam tantalum crucibles. The specimens were heat-treated in sealed tantalum crucibles which were protected by sealing them in argon-filled quartz ampules. Quenching was accomplished by breaking the ampules in ice water after heat treatment. X-ray powder specimens were sealed in 0.3-mm-diam glass capillaries under a dry-argon atmosphere. Copper, iron, and chromium radiation were used to obtain the powder patterns for these alloys. More than 150 powder patterns were obtained for specimens of various compositions and heat treatments. Included in these were several patterns for specimens which had purposely been oxidized. Patterns from specimens which had been accidentally exposed

Jan 1, 1969

As already said Pattin&apos;s map and the later one of Evans&apos; showed coal in several places in Ohio as early as 1750, and possibly 1748; the reference on the latter map was&apos; to an exposure near Bolivar, in Tuscarawas County, as well as along the Hocking River. So far. as now known, it &apos;was not mined in either place until 1810. George Croghan, in descending the Ohio with his party in 1765, mentions an "Alum Hill" which they saw near the present site of Pomeroy, probably an exposure of saline deposits, but does not mention coal. As settlement north of the Ohio River was prohibited until 1787, no coal was mined until long after that date. In 1785 a survey of seven ranges in the Ohio country was made, the line running west from a point on the north bank of &apos;the Ohio River, due north of the western termination of the southern boundary of Pennsylvania. The surveyors noted, "from hence to Stoney Brook between two very steep and high Ridges; it is eight yards wide, its bottom is of Slate and Sand Stone, and in many parts of it are large pieces of excellent Coal washed by, the Rains from the Neighboring Hills."&apos; This was the present Yellow Creek, and the coal was from some of the lower measures. The Scioto Company published a pamphlet in French in 1787, to promote the sale of their lands and emigration to them, in which was said,

Jan 1, 1942

By A. E. Bibb, F. W. Kunz

A platelet form of zirconium hydride was found in zirconium and ZY-1 wt pct U single crystals containing hydvogen in the range of 50 to 100 ppm. The habit planes for the hydride plateletg in the zirconium crystals were found to be {1012}, {1121}, and (1122) while the habit planes in the ZY-1 wt pct U crystals were {1121), {1123}, and (1.231). With the exception of the {1231} plane, these have been identified as the twin planes in zirconium. The different effect of hydridc on the mechanical puoperlies of zirconium at high and low strain rates has been explained in terms of the defornzation mechanism and the habit planes of the hydride. ZIRCONIUM and zirconium-base alloys are considered for many nuclear reactor applications, where the pick-up of hydrogen is a distinct possibility, if not an unavoidable occurrence. An excellent example of this is the absorption of hydrogen by zirconium and its alloys during aqueous corrosion, where as much as 30 pct of the hydrogen produced by the corrosion reaction is picked up by the metal. Under the proper conditions, the absorbed hydrogen would precipitate as zirconium hydride and consequently alter the mechanical and physical properties of the zirconium-base alloys. The knowledge obtained from a study of the crystallographic aspects of the hydride precipitation is necessary for the interpretation of the observed changes in the mechanical and physical properties. The deleterious effect of hydrogen on zirconium-base materials is not always observed in normal slow tensile loadings at or above room temperature, but becomes immediately obvious under impact loading, where the energy absorbed decreases with increasing hydrogen content,&apos; and in notched specimens where triaxial loadings are attained.2 This effect is of serious consequence in the applications of Zr where shock loads or high strain rates are experienced. The purpose of this investigation was to determine the crystallographic planes of the Zr and Zr-1 wt pct U matrices upon which zirconium hydride will precipitate and to correlate these with the observed mechanical property data. PROCEDURE Crystal Growth—Single crystals of Zr and Zr-1 wt pct U alloy were used in this investigation. The Zr crystals were made from sponge that had a typical analysis as shown in Table I. Large grains were grown in this material by rapid cooling an arc-melted charge in a button furnace. This operation undoubtedly lowered the volatile impurity concentration below those listed in Table I. Back-reflection Laue patterns of these large grains showed the presence of considerable substructure and lattice distortion within each grain. It was found that an 18-day anneal in an argon atmosphere at 840°C (a high a heat-treatment) followed by furnace cooling, resulted in the further growth of the large grains and removed the detectable substructure ana lattice distortion. Equiaxed crystals with a cube edge of approximately 1/4 in. were produced in this manner. Large crystals of Zircaloy-2 (1.5 wt pct Sn, 0.15 wt pct Fe, 0.1 wt pct Cr, 0.05 wt pct Ni) also were produced by this technique but the large amount of substructure formed could not be removed by annealing. The Zr-1 wt pct U solid solution crystals were produced from an alloy rod consisting of Westing-house-Foote hafnium-free crystal bar zirconium and depleted uranium. The chemical analysis of the alloy is also given in Table I. Three-inch sections were cut from an 0.120-in.-diameter alloy rod and tapered to a fine point on each end. The samples were sealed in evacuated Vycor tubes, homogenized for 5 hr at 1000°C in the ß-phase field, and slowly lowered in a gradient furnace into the a phase (800°C), annealed for 60 hr at this temperature to produce grain growth and furnace cooled. This technique produced large grains approximately 1/2 to 3/4 in. long over the entire cross section of the rod, which were free of observable substructure. Metallographic examination up to X1000 did not show the existence of any second phase in these grains. Crystal Orientation—All crystals were abraded on fine emery paper to produce two flat surfaces 90 deg to each other. The crystals were analyzed by the standard Back-Reflection Laue technique to obtain the crystal orientation with respect to the abraded surfaces. The Back-Reflection Laue Photograms of all crystals used were clear and sharp indicating that the crystals were free from any substructure that could be detected by these means. Hydriding—Only samples containing four to five grains were used for hydriding. Samples that exhibited fine grained patches were discarded. The samples were hydrided using the following technique. After etching in 48 vol. pct HNO3, 48 vol. pct H2O, and 4 vol. pct HF (48 pct) solution, the specimens

Jan 1, 1961

By F. N. Rhines

STUDIES upon the sintering of metal powders, in the solid state, have led to the proposal that the surface energy of the powder particles provides the driving force that causes points of contact between pairs of particles to grow into broad welds which isolate the residual vacant space into pores that tend to spheroidize and gradually to diminish in total volume.&apos; Investigators differ with regard to the mechanism of the movement of the metal, under the influence of surface energy, to accomplish these changes. One school asserts that there is a mass movement of the metal, referred to as a "viscous flow," while the other school prefers to view the movement as a self diffusion process, wherein individual atoms are, transferred without disturbance of the basic pattern of the crystal lattice. Extensive experimental studies upon the sintering of copper, conducted recently by A. J. Shaler,2 have been in- terpreted by their author as support for the viscous flow mechanism of transport, the theory of which was developed originally by J. Frenkel.3 Duplicating a portion of this work with minor changes, G. C. Kuczynski4 is led to the alternate view, namely, that the initial stages of sintering, at least, proceed as a self-diffusion process. Both of these investigations were designed to deal with an isolated unit of sintering, i.e., with the shrinkage of a single pore, or with the growth of a single point weld. It remains to ascertain the behavior of a typical metal powder compact composed of a large number of particles of varying size and sintering to a body with a multiplicity of pores. The observation of density changes alone during sintering is not sufficient in such a case; it is essential to know how the internal geometry of the compact changes. This has been the object of the present investigation, the results of which are used to support the self-diffusion mechanism of sintering. The present studies consist in the measurement of the number of pores as a function of size and time at temperature during the sintering of a copper compact made from a commercial copper powder lightly pressed and sintered in several different atmospheres. A brief survey was made also of the change in shape of the pores, under the influence of the same variables. All of this was done by direct observation with the microscope. Densities were measured on the same sample. It is found that, while the compact is exhibiting an overall shrink-

Jan 1, 1951

By M. Cohen, B. L. Averbach

Many hardened steels contain significant quantities of retained austenite even in cases where the carbon and alloy contents are low. In fact austenite has been detected in plain carbon steels containing as little as 0.50 pct carbon.1 Although the austenite may not be visible metallographically it causes definite dilatometric and magnetic effects during subsequent tempering or sub-atmospheric coo1ing.l,2,3 Therefore if the reactions which hardened steels undergo during later treatment are to be understood in quantitative fashion it is most essential to have some kind of absolute analysis for the austenite content in hardened steels. Once this analysis has been made, the austenite transformations can be followed precisely by observing such sensitive phenomena as changes in length or in magnetization but the latter techniques can only determine differences in the amount of retained austenite and usually an independent method must be found to put these differences on an absolute basis. In certain instances the microscope can be used advantageously to determine the percentage of retained austenite. The quenched sample is tempered to "darken" the martensite with minimum decomposition of the coexisting austenite, and then is polished and etched in the usual fashion. If the austenite is clearly distinguishable from the tempered martensite and other possible constituents its volume percentage can be measured quantitatively by point counting or lineal analysis.4 Such microscopic methods, however, depend on the etch being sufficiently discriminatory. In fairly coarse structures, if the austenite content is greater than 10-15 pct, there is probably little smearing of the etch, and point counting or lineal analysis seems to be quite accurate. On the other hand if the structure is difficult to resolve, as in commercially treated fine-grained . steels which contain less than 10-15 pct retained austenite, the latter may be completely obliterated by the dark etching martensite or it may appear disproportionately low as the interfaces between the two constituents become difficult to distinguish. Another disadvantage of the metallographic method is the need for "darkening" the martensite and hence the determination cannot be applied to as-hardened steels. The required tempering may spoil the structure for other tests or may even remove a small part of the austenite which is being sought. X ray methods hold more promise for covering the range under 15 pct retained austenite. Although austenite and martensite in the hardened steel may be chemically identical, their crystal structures and lattice parameters differ, and the intensity of an austenite diffraction line is some continuous function of the percentage of re-

Jan 1, 1949

By B. L. Averbach, M. Cohen

Many hardened steels contain significant quantities of retained austenite even in cases where the carbon and alloy contents are low. In fact austenite has been detected in plain carbon steels containing as little as 0.50 pct carbon.1 Although the austenite may not be visible metallographically it causes definite dilatometric and magnetic effects during subsequent tempering or sub-atmospheric coo1ing.l,2,3 Therefore if the reactions which hardened steels undergo during later treatment are to be understood in quantitative fashion it is most essential to have some kind of absolute analysis for the austenite content in hardened steels. Once this analysis has been made, the austenite transformations can be followed precisely by observing such sensitive phenomena as changes in length or in magnetization but the latter techniques can only determine differences in the amount of retained austenite and usually an independent method must be found to put these differences on an absolute basis. In certain instances the microscope can be used advantageously to determine the percentage of retained austenite. The quenched sample is tempered to "darken" the martensite with minimum decomposition of the coexisting austenite, and then is polished and etched in the usual fashion. If the austenite is clearly distinguishable from the tempered martensite and other possible constituents its volume percentage can be measured quantitatively by point counting or lineal analysis.4 Such microscopic methods, however, depend on the etch being sufficiently discriminatory. In fairly coarse structures, if the austenite content is greater than 10-15 pct, there is probably little smearing of the etch, and point counting or lineal analysis seems to be quite accurate. On the other hand if the structure is difficult to resolve, as in commercially treated fine-grained . steels which contain less than 10-15 pct retained austenite, the latter may be completely obliterated by the dark etching martensite or it may appear disproportionately low as the interfaces between the two constituents become difficult to distinguish. Another disadvantage of the metallographic method is the need for "darkening" the martensite and hence the determination cannot be applied to as-hardened steels. The required tempering may spoil the structure for other tests or may even remove a small part of the austenite which is being sought. X ray methods hold more promise for covering the range under 15 pct retained austenite. Although austenite and martensite in the hardened steel may be chemically identical, their crystal structures and lattice parameters differ, and the intensity of an austenite diffraction line is some continuous function of the percentage of re-

Jan 1, 1949

By Joseph W. Leonard, T. S. Spicer

INTRODUCTION Reasons for Thermal Drying The continuing increase in the percentage of minus %-inch coal produced as a result of the increased use of mechanical mining methods has, over the years, tended to shift considerable portions of the work of producing saleable coal to the fine coal cleaning section of the preparation plant. Because a given weight of fine coal will contain substantially greater surface area than an equivalent weight of coarse coal, it follows that, when subjected to wet cleaning processes, the fines will absorb and retain consider- ably more moisture than coarser fractions. Increased moisture pickup in the finer sizes complicates fine coal cleaning since beneficiation may not be limited to the removal of ash and sulfur but often must be expanded to include the additional step of thermal drying to remove excessive moisture. Thus, water which provides the medium for cleaning fine coal is in itself detrimental and, like ash and sulfur, reduces coal quality. Removal of surface moisture by drying is done for one or more of the following 1 reasons: (1) To avoid freezing difficulties and to facilitate handling during shipment, storage and transfer to the points of use; (2) to maintain high pulverizer capacity; (3) to reduce heat loss due to evaporation of surface moisture from the coal in the burning process, thus increasing heating efficiency; (4) to improve the quality of coal used for special purposes, such as in the production of coke, briquettes, and chemicals; (5) to decrease transportation costs; and (6) to facilitate dry coal-cleaning processes. Because benefits to coal transportation and utilization are the most common reasons for thermal drying, the following sections will examine these areas in greater detail. Benefits to Transportation Initial benefits from drying are the reduction of shipping costs from the mine to the point of utilization since more coal can be concentrated into a given weight of product when worthless moisture is removed. Non- combustible~ such as water and mineral matter in railroad shipments of coal are billed the same as coal at $3.32 per ton, according to the recent average costs. Savings of 10 to 20 dollars from drying on the shipment cost of each 50 to 60 tons of coal contained in a typical railroad car is common. Savings on coal shipments from individual mines which result from coal drying can be expressed in terms of hundreds of thousands of dollars and more each year. For example, a reduction of shipping charges of only 5 percent on one million tons per year would mean a savings of 166,000

Jan 1, 1968

By Harold M. Feder, Irving Johnson

Tkermodynamic functions for dilute solutions of uranium in liquid cadmium were obtained from galvanic cell measurements. Deviations from Henvy&apos;s law were observed at concentvations down to 2 x 10-3 atom fraction. Unusually large negative values of the pavtial molal relative enthalpy and excess entvopy of uranium, suggestive of the occu,vvenctwe of partial ovdering of cadmium around uranium in these solutions, were found. The negative relative partial molal enthalpy of uranium at the liquidus accounts for the observed retrogvade solubility of metallic uranium between 473" and about 630°C. The standard free enevgy of formation of UCd,, from a-uranium and liquid cadmium is given by F,° THE constitutional diagram of the U-Cd system,&apos; Fig. 1, is unusual in several respects. The near equality of the Goldschmidt atomic radii2 (Cd, 1.52A U, 1.56A) might be expected to give rise to extensive mutual solubility of the elements except for the restrictions imposed by differences in valence and electronegativity.3 The latter factors must be strongly influential because mutual solubilities in the terminal solid phases are probably negligible, and the solubility of uranium in liquid cadmium in the readily accessible range is only about 1 at. pct. Interestingly, the solubility of uranium in liquid cadmium actually decveases slightly with increasing temperature from 473" to about 630°C. Such a retrograde solubility in a liquid phase is a rare phenomenon in metallic systems; no other authenticated examples were found among the nearly 700 binary phase diagrams compiled by Hansen and Anderko.2 These observations suggested the existence of some unusual interaction between uranium and cadmium. Greater insight into the nature of this interaction was sought by measurement of the thermodynamic properties of the system. EXPERIMENTAL PROCEDURE The emf of cells denoted by the scheme was measured. Each cell consisted of two uranium and two alloy electrodes immersed in a molten lithium chloride-potassium chloride eutectic mixture containing uranium trichloride. The physical arrangement is shown in Fig. 2. The potential between any pair of electrodes could be measured with a Leeds and Northrup Type K-3 potentiometer. The measurements were made at points marked in Fig. 1. It should be noted that points on the phase boundaries represent the concentrations of uranium in the saturated liquid phases of heterogeneous alloys. Uranium Electrodes. Uranium, which is not a particularly soft metal, is capable of retaining residual stresses, and its potential may depend upon its physical condition. Electrodes were prepared from 3-mm diam rods of hot-rolled high-purity4

Jan 1, 1962

By B. L. Averbach, M. Cohen

THE PROBLEM MANY hardened steels contain significant quantities of retained austenite even in cases where the carbon and alloy contents are low. In fact austenite has been detected in plain carbon steels containing as little as 0.50 pct carbon.1 Although the austenite may not be visible metallographically it causes definite dilatometric and magnetic effects during subsequent tempering or subatmospheric cooling.1,2,3 Therefore if the reactions which hardened steels undergo during later treatment are to be understood in quantitative fashion it is most essential to have some kind of absolute analysis for the austenite content in hardened steels. Once this analysis has been made, the austenite transformations can be followed precisely by observing such sensitive phenomena as changes in length or in magnetization but the latter techniques can only determine differences in the amount of retained austenite and usually an independent method must be found to put these differences on an absolute basis. In certain instances the microscope can be used advantageously to determine the percentage of retained austenite. The quenched sample is tempered to "darken" the martensite with minimum decomposition of the coexisting austenite, and then is polished and etched in the usual fashion. If the austenite is clearly distinguishable from the tempered martensite and other possible constituents its volume percentage can be measured quantitatively by point counting or lineal analysis.4 Such microscopic methods, however, depend on the etch being sufficiently discriminatory. In fairly coarse structures, if the austenite content is greater than 10-15 pct, there is probably little smearing of the etch, and point counting or lineal analysis seems to be quite accurate. On the other hand if the structure is difficult to resolve, as in commercially treated fine-grained steels which contain less than 10-15 pct retained austenite, the latter may be completely obliterated by the dark etching martensite or it may appear disproportionately low as the interfaces between the two constituents become difficult to distinguish. Another disadvantage of the metallographic method is the need for "darkening" the martensite and hence the determination cannot be applied to as-hardened steels. The required tempering may spoil the structure for other tests or may even remove a small part of the austenite which is being sought. X ray methods hold more promise for covering the range under 15 pct retained austenite. Although austenite and martensite in the hardened steel may be chemically identical, their crystal structures and lattice parameters differ, and the intensity of an austenite diffraction line is some continuous function of the percentage of re-

Jan 1, 1948

By Ta M. Li

Recent economic and environmental setbacks have not slowed Occidental Oil Shale, Inc.&apos;s program aimed at the commercialization of oil shale. In fact, the firm expects to have a 795 MI (500C) bbl) per day production unit working by the end of 1976. The key to Occidental&apos;s ambitious program is an in situ method that extracts the valuable oil by retorting the shale in place. The process will require practically no water and will leave the spent shale in place underground. Additionally, all plant operations are to be located within the mine. These factors thus serve to make the operation attractive from an environmental viewpoint, in contrast to proposed conventional schemes which call for extensive underground mining, crushing and grinding at the surface, and construction of a massive surface retorting facility.

Jan 12, 1976

By A. J. Shaler, J. Prieto Isaza, J. Wulff

Tantalum metal has a number of unique properties which give it widespread application in modern technology and in research. In electronic apparatus involwing high temperatures in vacuo some of the refractory metals 6ecome brittle. Tantalum retains its ductility at elevated temperatures, and this property, together with its low vapor pressure and its ability to absorb gases, make it important in this field. Its chemical inertness in the presence of acids, halogens, and other corrosive media, makes it useful in chemical apparatus and in neuro and orthopedic surgical applications. As an addition to tungsten carbide in steel-cutting grades of cemented-carbide tools, the carbides of tantalum and of its sister element colum-bium have found considerable use. The present-day method1 of manufacturing tantalum is to sinter a powder compact of the metal in vacuo. Because tantalum-columbium alloys are difficult to work and since tantalum ores almost always contain columbium, the two metals must be separated chemically, the products of the separation being generally in the form of potassium tantalum fluoride and potassium columbium oxyfluoride. These salts are used in fused-salt electrolytic baths from which coarse metallic powder is deposited as a sponge at the cathode. Finer powder can be made from the coarse product or from tantalum scrap by first submitting it to an embrittling heat treatment in hydrogen and then crushing it. The fine hydrogen-containing powder may subsequently be degassed in vacuo at a high temperature. Prompted by the success of others2,3 in the magnesium reduction of titanium and zirconium halides; one of the authors undertook4 an investigation of the thermochemistry of the reaction between solid magnesium and gaseous tantalum penta-chloride, a subject which had not previously been studied. He found that the heat of formation of tantalum pentachloride is approximately 364,250 cal per mol at temperatures lower than the melting point of magnesium. A value of 83 units was found for the standard entropy at these temperatures. With these values, it was shown that magnesium and tantalum pentachloride are capable of reacting exo-thermically at temperatures less than the melting point of magnesium, and that no great violence is to be expected when these substances are heated together. The exothermic nature of the reaction indicated that the Drocess should be efficient and should not require much externally applied energy. Tantalum pentachloride is not commonly made commercially, and any process using it therefore involves the subsidiary problem of producing and handling this substance. A series of experiments was carried out in which dried chlorine saturated with carbon tetrachloride was passed over heated tanta-

Jan 1, 1949

By E. W. Shaw

Continued discussion of the paper of Roswell H. JOHNSON, presented at the New York meeting, February, 1915, and printed in Bulletin No. 98, February, 1915, pp. 221 to 226. See also Bulletin No. 101, May, 1915, pp. 1157 to 1162. E. W. SHAW, Washington, D. C. (communication to the Secretary+). -With the word petrology-literally the science of rocks-being used primarily for igneous rocks, and with geophysics coming to mean the study of lavas and the rocks into which they solidify, contributions to the knowledge of the physical chemistry of sedimentary rocks, even though only ideas which may be used as working hypotheses, become most welcome. The forces which control the formation and subsequent history of the stratified portions of the earth&apos;s crust are so little known that no one has yet been able to settle finally the questions as to whether petroleum is of organic or inorganic origin; whether it originated far from its present position, or nearby. Yet both the chemical and physical problems of the rocks in which oil occurs seem to be more simple than those of the igneous rocks. The oil-bearing rocks of western Pennsylvania, for example, have in all probability never been subjected to a pressure exceeding 3,000 or 4,000 lb. to the square inch, nor to a temperature higher than 100° or 200° C. These pressures are considerably below the crushing strength of rocks, and the temperature far below their melting point. The igneous rocks,, on the other hand, have been affected by enormous pressures and very high temperatures and yet steady progress is being made in reproducing in the laboratory the conditions of their formation and subsequent modification within the earth. The solution of the sedimentary-rock problems would seem to be fully as important as those of igneous rocks, and yet we must content ourselves with reasoning backward and our inferences as to what has happened are oftentimes little more than guesses.1 One of the fundamental problems is the origin of the salt water in oil fields. Is the salt water fossil sea water; has it been formed by the solution o-f salts of various kinds from distinct beds, from disseminated par-ticles, and from the weathering of suitable grains in the rock; or is it of deep-seated origin? Its general resemblance to sea water points to the first, but the principles held by some concerning the free circulation of water throughout the earth&apos;s crust, and certain peculiarities of composition indicated by the few analyses available, seem out of harmony with such an explanation.

Jan 7, 1915

By Irving Cadoff, Jack Medoff

THE linear thermal expansions of oriented single crystals of zinc were measured in the range from 20" to 416°C using a Leitz HTV optical lever differential dilatometer. The single crystals, supplied by Dr. J. J. Gilman, General Electric Research Laboratory, Schenectady, N.Y., were prepared from 99.999 pct-purity zinc, and were in the form of rods approximately 2 in. long by 0.15 in. in diameter having the following orientations: x = 1.5, 12, 20, 30, 37.5, 49, 60, 73, and 82 deg where x is the angle between the specimen axis and the (0001) plane of the crystal. From the family of expansion vs temperature curves, the instantaneous expansion coefficients were calculated at 100°C intervals, and Fig. 1 shows a plot of these derived coefficients for each orientation. Coefficients were obtained from the raw data using the chord-slope method. The curves in Fig. 1 indicate a positive temperature coefficient for low x, a negative temperature coefficient for high X, and an expansion coefficient invariant with temperature, amounting to about 43 x 106, for a crystal orientation of approximately 52 deg. From the available data, it is possible to arrive at the values for the axial thermal-expansion coef- ficients a, and a, by extrapolating the curve of the expansion coefficient vs orientation to zero and 90 deg orientations. More precise values for a, and a, are obtained if the instantaneous coefficients are plotted against the square of the cosine of the orientation angle, as shown in Fig. 2. The extrapolated terminal points of the best straight line through the data points of such a plot define the axial coefficients at that temperature. The theoretical justification for the linearity of this curve comes from inspection of a rearranged form of the general anisotropic equation for expansion: ax=a, + (a, -a,)cosZx [1I in which a, is the expansion coefficient in the "c" or [0001] direction and a, the expansion coefficient in the "a" or [ll50] direction. From Fig. 2, the axial coefficients at 100°C, for example, were found to be a, = 13.9 x 10&apos;6 and a, = 62.4 x 10"6 per "C. In the same way, the coefficients were determined for 20", 200°, 300°, and 400°C. This data is summarized in Fig. 3. It is of interest to observe the common intersection of the curves in Fig. 3, which seems to bear out the earlier observation, from Fig. 1, of a

Jan 1, 1964

By Allan Martin, R. A. Swalin

Diffusion rates of manganese, aluminum, titanium, and tungsten in nickel were measured at temperatures between 1100° and 1300°C. Activation energies, Q, and values of the frequency factor, Do, were calculated for each system. Values of Q were found to be within 15 pet of that for self-diffusion of nickel in agreement with present theories of diffusion. ONE of the most interesting problems in diffusion concerns factors governing the order of diffusion coefficients of various solutes in a common solvent metal at low solute concentrations. An early suggestion by Rhines and Mehl&apos; was that diffusion coefficients might each approach that of the self-diffusion coefficient of the solvent itself. Later Thomas and Birchenall&apos; pointed out correlations between the order of the diffusion coefficients and the freezing point depressions of the solvent by the various solutes. Other correlations have been sought. To settle this question it seems likely that much more data will be needed and, in particular, data collected at low solute concentrations. This type can be obtained by special analytical techniques as well as by use of radioactive tracers. The following study was made of diffusion of manganese, aluminum, titanium, and tungsten in a common solvent, nickel, at relatively low solute concentrations: 1—Production of alloys of nickel with manganese, aluminum, titanium. and tungsten at concentrations of the order of 1 atomic pet. 2—Use of pressure-welded diffusion couples in cylindrical form. 3—Diffusion anneals in the temperature range of 1100" to 1300°C. 4—Lathe sectioning of the diffused couples. 5—Spectrophotometric analyses of lathe turnings for the solute being studied. 6—Calculation of the diffusion coefficient for each of the solutes as a function of temperature. 7—Interpretation of results with current theories of diffusion. Experimental Work Materials—Two types of nickel were used in this research. The grade designated as Vacuum melted Mond nickel was used for all diffusion systems except the Mn-Ni system for which the Vacuum melted electrolytic nickel was used. Analyses of the two grades are given in Table I. The manganese used in making alloys was 99.9 + pet pure, aluminum 99.99 pet pure, titanium 99.9 pet pure, and tungsten of C.P. grade powder. Alloys used in this investigation were prepared by melting in vacuo or under a low pressure of argon. After melting, all heats except those of nickel-manganese were poured into a cylindrical copper mold 3 in. long and 1 in. ID. In the case of nickel-manganese, the alloys were solidified in the melting crucible. For nickel-aluminum heats alumina crucibles were used and for all other heats, zirconia crucibles.

Jan 1, 1957

By D. F. Stoneburner

The thermoelectric power and electrical conductivity of a series of liquid alloys of thallium were determined in order to study the relation of chemical bonding to semiconduction in liquids. The results indicate metallic behavior for the alloys of thallium with arsenic, antimony, and bismuth, while the sulfides, selenides, and tellurides indicate semiconduction. The results are compared with the Properties of the same alloys in the solid state. This work supports the observation that long-range order is not a necessary requirement for semiconduction. PREVIOUS work1,5 has shown that some sulfides and oxides behave as semiconductors in the liquid state. Although the band theory has been of great help in understanding the properties of solid semiconductors, its quantitative application to liquids is difficult. The very existence of liquid electronic semiconductors shows that ascribing the discrete structure of the energy spectrum to strict lattice periodicity, or long-range order, is not always satisfactory. Rather, the short-range order determines the structure of energy levels and the width of the forbidden gap and, consequently, the concentration of free holes and electrons. This is borne out by the analysis of data accumulated by Regel and coworkers.6 The similarity of electronic structure of liquid and solid phases of certain liquid metals was pointed out by Knight et a1.,7 who examined nuclear resonance in solid and liquid Li, Na, Rb, Cs, Mg, Al, Ga, Sn, and Bi. They found noticeable changes in the electronic structure upon melting only in the cases of bismuth and gallium. They concluded that "a liquid metal possesses a band structure which is very like that of the solid, provided the short-range structure is not altered during melting." In semiconductors in which the near-neighbor arrangement remains the same on fusion, the material would be expected to retain its semiconducting properties. The quantum theory of semiconductors, with its band structure of energy levels, is linked exclusively to long-range order. Furthermore, it has limited usefulness in predicting new semiconductors. Many sulfide8-12 have made comparisons of properties on the basis of crystal structure or the position in the periodic table, both methods involving the same factors as chemical bonding. Mooser and Pearson8"10 have pointed out that crystal structure depends on chemical bonding, and that this bonding is a property of the atoms themselves. As the periodic arrangement of the atoms offers an easy comparison of such factors as atomic weight and number of valence electrons it provides clues to expected similarities of bonding for various elements or groups of elements. This approach has led Mooser and Pearson to formulate their valence-bond theory of semiconduction, in which they define a semiconducting bond. These authors state that "semiconductivity is the result of the presence in a solid of predominantly covalent bonds. These lead, through the process of electron sharing, to completely filled s and p orbi-tals in the valence shells of all atoms of elemental semiconductors while in semiconducting compounds only one atom of any two bonded together need acquire closed s and p orbitals. The presence of empty &apos;metallic&apos; orbitals in some atoms of a compound does not destroy the semiconductivity provided that these atoms are not bonded together; it may, however, give rise to pivoting resonance in

Jan 1, 1965

By William L. Fink, Kent R. Van Horn

Zinc is one of the effective elements introduced to enhance the strength of aluminum. This strengthening is principally attributable to the high solid solubility of zinc in aluminum and the pronounced variation of solubility with temperature. Consequently an accurate determination of the solid solubility curve is desirable. The solid solubility relations have been studied by numerous investigators. Shepherd1 first established the existence of a solid solution region at the aluminum end of the diagram (-v phase) by specific volume and microscopic determinations. Bauer and Voge12 published a constitutional diagram which showed the limits of solid solubility as determined by thermal and microscopic methods. Hanson and Gayler3 presented the aluminum-zinc diagram which is now most generally accepted (Fig. 1). Chill-cast samples were given thermal treatments designed to obtain equilibrium conditions, quenched, and microscopically examined. The solubility was placed between 15 to 20 per cent at 60" C., 20 to 22 per cent at 140" C. and 36 to 38 per cent at 270" C. Sander and Meissner decidedly modified the limits of the -y phase field of Hanson and Gayler&apos;s diagram by using similar methods on chill-cast specimens annealed for a shorter period of time. Tanabe,s utilizing dynamic hard-ness, electrical conductivity and dilatometric measurements of specimens at temperature, obtained values comparable to Hanson and Gayler&apos;s at room temperature, but appreciably lower at higher temperatures. Nishimura6 concluded from age-hardening results of aluminum-zinc alloy chill castings, which had been quenched from 400" to 500" C., that the solubility of zinc in aluminum at room temperature is less than 5 * Metallurgical Division, Aluminum Research Laboratories. 1 E. S. Shepherd: Aluminum-Zinc Alloys, Jnl, phys. Chem. (1905) 9, 504. 2 0. Bauer and 0. Vogel: Aluminum-Zinc Alloys, Int. Jn1. Melallog. (1916) 8, 101. 3 D. Hanson and M. V. L. Gayler: A Further Study of the Alloys of Aluminum and Zinc. Jnl. Inst. Met. (1922) 27, 267. 4 W. Sander and K. L. Meissner: ZII~ Kenntnis der Konstitution der Aluminium-Zinklegierungen. Ztsch. f. Metallkunde (1922) 14, 385. 4 T. Tanabe: Studies in the Aluminum-Zinc System, Jnl. Inst. Met. (1924) 32, 415 6 H. Nishimura: On the Age-Hardening of Aluminum-Rich Al-Zn Alloys. Mem. Kyoto Imp. Univ. (1924) 3, 133.

Jan 1, 1932

By W. L. Phillips

Stress-strain data are reported for sodium chloride, lithium fluoride, and magnesium oxide tested in compression at diffevent strain rates in the telrlperature range from 70° to 873°K. Quantitative equations are given for the stvain-rate dependence of the critical resolved shear stress and the initial rate of work havdening. The properties so determined are compared with results previously reported for metals. ALTHOUGH the effects of strain rate and temperature on the stress-strain characteristics of metals have been extensively investigated1,2 these effects have not been studied in detail in ionic crystals. In the only previous investigations on the effect of strain rate on the deformation of ionic crystals. Gilman and gohnston3 and Hulse and pask4 have shown that the yield stress of lithium fluoride and magnesium oxide at room temperature is proportional to the ninth or tenth root of the strain rate. CRYSTAL PREPARATION Lithium fluoride, sodium chloride. and magnesium oxide single crystals were purchased from the Har-shaw Chemical Co. The compression fixture and sample preparation have been described in detail previously.5 The detectable impurities in MgO were eight parts in 105 of Fe and six parts in 105 of Si; in LiF, six parts in 105 of Mg; and in NaC1, two parts in 105 of Fe and four parts in 10&apos; of Mg. The cleaved samples measured - 0.1 in. by 0.1 in. by 0.3 in. Prior to testing all samples were annealed at -0.8 of their melting point and cooled to room tempera- ture at 50 C per hr.&apos; Samples were strained at rates (<) of 0.1, 0.01, 0.002, and 0.0002 in. per in. per min. EXPERIMENTAL RESULTS Fig. 1 is a plot of the critical resolved shear stress a,. (extrapolation of slope of easy glide region to zero strain) of sodium chloride, lithium fluoride, and magnesium oxide tested at different strain rates as a function of temperature. In all crystals at all strain rates a, decreases with increasing temperature according to an equation of the type397 where uo is a stress constant, K is a constant, and T is the absolute temperature. The points in Fig. 1 are the average of six tests. It is evident that there is a break in the log 0,- temperature plots at a characteristic temperature T,. The constant K of Eq. [I] is dependent on strain rate, Fig. 2. The relationship

Jan 1, 1962

By G. Thodos, E. M. Phillips

A reduced density correlation for the gaseous and liquid regions of ethane has been developed from all the experimental PVT data available in the literature for this substance. Saturated vapor and liquid densities reported for methane, propane and n-butane were utilized to establish the rectilinear-diameter line for ethane. This line was then used with the saturated-vapor data for ethane to produce the saturated envelope for this substance. Most of the saturated liquid data reported for ethane were found to be inconsistent with the saturated-liquid curve resulting from this study. The correlation covers the regions 0.65 < TR <6.0 and 0 < PR < 15. For regions for which no experimental data have been reported, the isobars of the correlation were extended by the use of the theorem of corresponding states. This correlation is presented both on rectilinear and log-log coordinates. INTRODUCTION At the present time, there is considerable interest in the exact PVT behavior of pure hydrocarbons. Matschke and Thodos12 recently have developed a comprehensive compilation of experimental vapor and liquid density data for methane. Similar studies have been conducted for other pure substances.4, 7 In the present study the density data available in the literature for gaseous and liquid ethane have been critically reviewed and utilized to develop a reduced density correlation for this substance. SATURATED LIQUID AND VAPOR DENSITIES The rectilinear-diameter rule proposed by Cailletet and Mathias5 states that the sum of the saturated liquid and vapor densities of a pure substance is a linear function of temperature which passes through the critical point. This law, although empirical, has been well established by continued verification since its conception in 1886. This rule has been applied to the saturated density data of methane,6 propane 17 and n-butane8 to produce the straight lines presented in Fig. 1 which pass through the critical point TR = 1.00, Pr = 2.00. The rectilinear-diameter relationship for ethane was established from the lines for the other substances in Fig. 1 by plotting the quantity p~, + PR against zc for different reduced temperatures. A critical analysis of the saturated vapor and liquid densities reported for ethane by Kuenen,10 Maass and McIntosh,11 and Sage, Webster and Lacey18 revealed that the values of PR1 + pr resulting from these studies were inconsistent with the rectilinear-diameter line obtained from the reliable density data of the other substances, as shown in Fig. 1. In the analysis of these data, reduced quantities were calculated using the critical con-

By W. H. Meyer

During the seventeen years Fairchild has been making aerial surveys and aerial photographic equipment many changes and improvements have been made in the equipment and in the technique of using it. Aerial photographic operations have been developed from the crude methods and apparatus of wartime to a science upon which exact engineering calculations can be based. In the early days there was no airplane specially designed to meet aerial photographic requirements. One type of camera was used in all types of operations. Projects were made to conform to the products we could make and deliver. Obviously this entailed definite limitations. We now have airplanes designed specially for aerial photographic operations in accordance with the conditions encountered in actual service experience. We have cameras for every photographic purpose and our laboratory technique and equipment have been developed to the point where it is possible to make contour maps from vertical aerial photographs with contour intervals as close as five feet. Therefore, the selection of equipment now can be made in accordance with the time at our disposal, the justifiable cost, the scale desired, and the general requirements of the client. This does not mean, however, that arbitrary deliveries can be set for aerial photographic products. The factors in each project vary and each job must be considered in accordance with the factors involved. This accounts for the fact that products of aerial surveys may readily vary from $1.25 to $200 a square mile. Sherman M. Fairchild became interested in the design of a radically different aerial camera during the war. At its close he was about ready to demonstrate his design to the War Department. By 1920, he was able to bring out his first completed model. It had a number of radical features, one of which was the first dependable high-speed between-the-lens shutter, which makes for accuracy in aerial photographic work. Another feature was the use of metal throughout, eliminating the wooden parts that had been employed in wartime cameras. Another feature was the interchangeability of parts.

Jan 1, 1937