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By K. M. Myles

The vapor pressure of palladium over a series of Rlz-Pd alloys has been measured by the torsion-effusion method. The thermodynamic properties of the alloy system at 1575=K have been calculated from the vapor pressure data. The activities and the free energies of formation exhibit large positive deviations from ideal behavior. The enthalpies of formation are endother-mic. The entropies of formation are positive and larger than the ideal entropy of mixing. All of the thermodynamic properties suggest that a strong tendency toward phase separation exists in the solid solutions. The possible origin of the phase instability and the various factors that influence the thermodynamic properties are discussed. RECENT studies of the thermodynamic properties of alloys of palladium with nontransition elements have indicated that a significant contribution to the enthalpy of formation is related to the redistribution of the conduction electrons upon alloy formation.'-' The present work was undertaken to ascertain the importance of this contribution in Pd/transition-metal alloys. The Rh-Pd system was chosen for this investigation for several reasons: 1) The thermodynamics of the system were unknown. 2) Rhodium and palladium are completely soluble at high temperatures; below 1118OK the solid solution becomes immiscible.', 3) The difference in magnitude between the vapor pressures of rhodium and palladium permitted the use of an existing effusion apparatus. 4) Additional information was known about the alloy system that would facilitate the interpretation of the thermodynamic results. EXPERIMENTAL PROCEDURE The thermodynamic properties of the Rh-Pd alloy system were calculated from the vapor pressure of palladium over solid palladium and over several solid Rh-Pd alloys. The vapor pressure was measured by means of the torsion-effusion apparatus that has been described previously. In this method, an effusion cell is suspended from a tungsten filament inside a high-temperature furnace. Two orifices are located eccentrically such that the effusion of the vapor creates a rotational torque in the filament. The angle of rotation is directly related to the total vapor pressure within the cell. As the vapor pressures of rhodium and palladium are approximately five orders of magnitude apart," the total vapor pressure was considered to be effectively equal to the equilibrium vapor pressure of palladium. The effusion cells were made from high-purity alumina since auxiliary experiments indicated that essentially no reaction occurs between alumina and solid Rh-Pd alloys. Unfortunately, because the orifices were irregular, an accurate calculation of the Free- man-Searcy correction factors" could not be made. The constants were determined in an independent experiment where the vapor pressure of copper, as measured in the alumina cell, was compared with an accurate value of the vapor pressure, which had been determined previously.4 Depletion of palladium from the surfaces of the specimens was minimal as the deflection of the cell remained constant, for at least 15 minutes, at each of the experimental temperatures. Lattice parameter measurements of the postrun alloys also indicated that no changes in the composition of the surfaces had occurred. The alloys were prepared by arc melting the requisite amounts of the 99.99 pct pure elements. The four most palladium-rich alloys were remelted in a levita-tion furnace since complete melting of the components had not occurred in the arc furnace. All of the alloys were subsequently homogenized at elevated temperatures in sealed alumina thimbles. After heat treatment, the alloys were analyzed chemically and were in essential agreement with the nominal compositions. The thermal histories and nominal compositions of the alloys are given in Table I. Lattice parameters of the heat-treated alloys were computed, by means of the method described by Mueller et a1. ,I2 from X-ray diffraction powder patterns obtained with filtered copper radiation in a 114.6-mm-diam Straumanis-type Debye-Scherrer camera. The results, which are tabulated in Table I, exhibit a slightly greater negative deviation from Vegards' law than the values reported by Raub et al.13 The diffraction lines were sharp and well-resolved and thus indicated that the alloys were homogenous. RESULTS The logarithms of the individual values of the vapor pressure of palladium were fit, by the least-squares method, as a linear function of the reciprocal of the absolute temperatures. The constants of the equations are given in Table I along with the temperature range over which the data was accumulated. The latent heat of vaporization at 298.15"K for pure palladium, calculated by the third-law method,14 showed no systematic temperature dependence. The average value of 88,920 * 20 cal per g-atom agrees favorably with the average of the results obtained in the most reliable previous investigations.15"19 The activities of palladium were computed from the vapor pressure data at 1525', 1575", and 1625OK. Consistent with the mass spectrometric study of the atomicity of palladium vapor,lg the vapor was assumed to be monoatomic. The activities of rhodium were determined by integrating the Gibbs-Duhem equation with the aid of the a function.20 In the calculations, the activities of the pure solid metals were assigned the value of unity. From the activities, the partial and integral free energies, entropies, and enthalpies of formation at 1575° K were computed; they are assembled in Table 11.

Jan 1, 1969

By Allen D. Garrison

THE chemistry of clays and shales has been assuming increasing importance in the petroleum industry, and two factors have greatly influenced this trend. The first has been the growing evidence that the marine shales are source beds, and that the petroleum compounds have migrated to the sand reservoirs overlying or underlying these shales: the second has been the demand for drilling fluids better adapted to penetrate these marine shales without difficulty and expense. ORIGIN AND GENERAL COMPOSITON OF CLAYS AND SHALES Clays, shales and surface soils are all closely related materials. They are mixtures of finely divided compounds formed during the weathering of the solid crust of the earth. Their nature is essentially colloidal; that is, their behavior is determined by the state of division of the materials and the surface reactions of the smallest grains. Many of their chemical changes affect only the exposed areas and do not involve the interior of the grains of matter. The extent of these reactions is more nearly proportional to the area of the substances than to their mass, therefore it is possible for a small amount of a material in an extremely fine state of division to completely dominate the character of the mixture. More than 83 per cent of the crust of the earth is composed of three elements-oxygen, silicon and aluminum. Consequently, the corrosion products of the crust are predominantly aluminosilicates, or compounds of aluminum, silicon and oxygen. If we add the compounds of six elements-iron, calcium, sodium, potassium, magnesium and hydrogen-more than 98 per cent of the crust has been accounted for. These six elements, together with the first three, also appear in soils, clays and shales. But direct chemical analysis is of little value in describing the nature of such materials. Many chemical individuals may be present in variable amounts, and the extreme subdivision of any one of the individuals may contribute qualities that dominate the mixture.

Jan 1, 1939

By Arthur B. Cummins, Henry Mulryan

DIATOMITE is a hydrous or opaline form of silica, commonly known as diatomaceous earth, diatomaceous silica or kieselguhr. The term "infusorial earth" has lost its original meaning and today is incorrect in view of the distinctions between diatoms and infusoria. Various locality and variety names are obsolete but some retain local significance. Moler and Celite are trade names that have become associated with diatomite products from certain deposits in Denmark and near Lompoc, California. COMPOSITION Diatomite is essentially silica with some combined water (2 to 10 pct). Frequently it contains organic matter (from traces up to over 30 pct) and varying amounts of inorganic impurities such as sand, cryptocrystalline silica, clay, volcanic ash, calcium carbonate, magnesia and soluble salts. In the natural or crude state, diatomite contains from 10 to 65 pct or more of free water. Table I gives analyses of several diatomites from deposits of different types. PROPERTIES Pure varieties, either massive or stratified, are friable and porous, of low apparent density, and somewhat chalklike in appearance. Varieties containing organic matter vary from sedimentary oozes to peatlike materials. Impure varieties may be more or less claylike, sandy, calcareous or cherty. Compacted types approach porcellanite and silicified shales. COLOR-white, cream, gray, tan, brown, greenish to nearly black. HARDNES-light-weight varieties appear 1 to 1.5 because of porosity, but microscopic particles are 4.5 to 6.5. SPECIFIC GRAVITY-1.9 to 2.35. APPARENT DENSITY---dry block form, 20 to 40 lb per cu ft; dry powder, 5 to 16 lb per cu ft. CRYSTAL SYSTEM-generally amorphous (isotropic by X-ray diffraction) but frequently showing faint cristobalite pattern.67.68,70 MELTING POINT-1400° to 1650°C. STREAK-white. LUSTER

Jan 1, 1949

By Henry Wurtz

HERACLITUS, a sage of antiquity, called the dark philosopher, who refused a throne, preferring a hermit's cell, propounded, twenty-four centuries since, the maxim : [ ] War (or strife) engenders all things. This, though probably intended by Heraclitus to apply especially to the internal forces of nature, is often said, with equal reason, of the affairs of men. Controversial strife, whether fortunately or unfortunately, is a crucible through which all new discoveries in science, and all technical applications of science must pass-a test which they must all endure before they can become so vitalized as to germinate, so to speak, take root in the human mind, grow tip, and overspread the earth. The greater the number and the power of the elements arrayed against such a growth, and of the influences hostile thereto, the greater should be the inherent vitality of the germ, the more strenuous, skilful, and persistent its cultivators and upholders. During the decade last past we have had, in spite of the severe stringency of the times, an active growth of this kind in progress, whose prospective importance it would now be difficult to overrate. This is the movement which has for its motive the idea that, generally speaking, fuel should be gaseous in form, and which has for its goal the introduction into general public use of gaseous products, made by cheap and rapid processes and on a gigantic scale, distributed throughout our cities and towns in distribution-systems which shall be proportionately gigantic, and sold at prices which will bring such fuel within the means of the poorest householders. Personally, for ten years past, the writer has never failed, on occasions public or private, to urge his belief that the realization of this idea, deemed by him a certainty of the future, will bring about

Jan 1, 1880

By AIME AIME

A PAPER recently presented before the Anthracite Section of the A. I. M. E. by S. J. Phil- lips, Mine Inspector, Fifth Anthracite District, Department of Mines of Pennsylvania, covering the water hazards in the anthracite coal mines of the Lackawanna River Valley, was especially timely because the conditions there are duplicated to a large extent in the Wyoming Valley, which is traversed by the Susquehanna River with its many large tributary streams. Also, in the southern anthracite field, where there are a number of large creeks, similar pumping problems and mine water hazards will in time be presented if mining is continued to its conclusion.

Jan 1, 1936

By F. E. Gregory

MINING methods and customs in many districts of England are to this day strangely bound about by the records and traditions of the past. In some mining fields this is more apparent than in others, yet it is everywhere in evidence, for Cornwall with her mines under the sea, Wales with her famous quartzites, and Derbyshire with her remarkable cavern deposits, are all tinctured with quaint customs that have come out of the almost forgotten past. Here, modernism has never replaced tradition, and many of the laws are woven of the woof and warp of ancient custom. Indeed, these things exist because they have come to be part and parcel of the civil laws. And these laws are observed with meticulous care and accorded all the reverence due their venerable age. All activities pertaining to the mining of metals are hedged around by curious and ofttimes clumsy laws, each minute and trivial detail being covered by the civil code, and each petty law enforced by an ofttimes pompous official.

Jan 1, 1933

By Herbert J. French

ALLOY steels have become essential to industry in meeting the rigid requirements on materials imposed by our, advanced technology. In comparison with the total ingot capacity of the steel industry, the volume of alloy steels is relatively small although for many years annual alloy-ingot tonnage has, been in seven figures. However, the monetary value of the alloy-steel production is exceedingly high and the benefits derived from the products are relatively great. The trend in total ingot production since 1932 has been generally upward with only two major interruptions. That of the year 1938 was due to a decrease in general business activity whereas that of 1946 resulted largely from work stoppages. Traditionally, the tonnage of alloy-steel ingots produced was in the neighborhood of 5 to

Jan 1, 1948

By Alan Morris

In a previous paper1 the results of cutting tests on free-cutting brass rod were reported. Investigation was made of the effects of variation in lead content, microstructure and cold drawing. The author's reply to the discussion of that paper includes a study of the directional cutting properties of drawn and annealed rod. The present paper records the results of tests made on series of samples in which the tin, iron and copper contents have been varied. The apparatus used and method of testing are described in detail in the previous paper. The machine is of the pendulum-operated milling type used and described by Airey and Oxford.2 Angular readings of the height to which the pendulum rises after falling from a fixed position, both when a cut is made and when the pendulum swings freely, give the basis for calculation of the energy consumed in making a cut. Careful weighing of the sample before and after cutting gives a measure of the amount of metal removed. The results are expressed in footpoiinds per cubic inch of metal removed, and have been called "unit cutting energy." In the course of the discussion of the author's earlier paper, W. B. Price reported large-scale tests involving some 50,000 lb. of material. These tests indicated that the addition of as much as 0.6 per cent of iron and 0.25 per cent of tin had apparently no adverse effect on the highspeed cutting characteristics of the rod. The rod also contained a small amount of nickel. The test results reported here tend to confirm his observations. Effect of Variation in Tin Content The castings for this series were made 2 by 1 by 9 in. and were processed as follows: 1. Castings were annealed at 500" C. for 7 hr. 2. Cold-rolled to 0.700 in.

Jan 1, 1933

By Philip B. Bucky

[ ]

Jan 1, 1942

Jan 1, 1969

By AIME AIME

SILVER reached a new high, with the ceiling the limit, at the annual Institute dinner at the Commodore on Washington's Birthday night. Carrying along as ballast other commodities, such as rolls, roses and ferns, souvenir boxes and table number placards, hundreds of silvery balloons, cut loose from their moorings at the tables, bounced idly against the plaster decorations high overhead. At the head table, Scott Turner, retiring President, pre- sided as toastmaster, with the new President, Frederick M. Becket, on his right, and the Chairman of the New York Section, Sydney H. Ball, on his left. Many other distinguished Institute members, medalists, and representatives of organizations and committees, ranged to the east and west. Each had the opportunity at least to rise and bow.

Jan 1, 1933

By A. Hellawell

Specitlrens of the Al-Ge eutectic alloy have been frozen unidivectionally at rates between 2.5 x 10-6 and 2.5 x 10-4 cm per sec and the structure examined by optical and X-ray methods. There is no epitaxial relationship between phases, the aluminum having random orientation and the germanium a preferred (011) fiber textuve. Lamellar colonies which are BINARY eutectic alloys occur between either silicon or germanium with the metals aluminum or silver. common in this alloy are constructed from axial and nonaxial (111) plates of germanium which are related by a variety of twin configurations. Irregular or globular regions of the microstructure are composed of continuous single crystals of each phase, the germanium being heavily twinned. There is limited solid solubility in these systems, and the eutectic phases all involve diamond cubic with fcc crystal structures. In the microstructures of these eutectic mixtures the silicon and germanium crystals exhibit an almost infinite variety of shapes which are notably sensitive to

Jan 1, 1968

Jan 1, 1899

Jan 1, 1884

By H. A. J. Wilkens, H. B. C. Nitze

From time to time papers treating of specific cases of Southern gold-mines and mining have appeared in the Transactions of this Institute, as well as in other journals and publications. Mr. George I?. Becker, of the United States Geological Survey, made a reconnaissance of the Southern Appalachian gold-belt during the fall of 1894; the results of his investigations are published under the title of "A Reconnoissance of the GoldFields of the Southern Appalachians," in the Sixteenth Annual Report of the Director of the United States Geological Survey, 1894-95 : Part III., " Mineral Resources of the United States." Mr. Becker has treated the subject mainly in a scientific geological manner. We present this paper to the members of the Institute as requested by the Secretary last May, with the object of covering the ground from a more practical and technical standpoint. The notes for this paper were made in a large measure from personal observations, gained chiefly during the past summer on a trip through the field. In connection with this trip we collected a suite of typical hand-specimens, representing the gold-ores and wall-rock from the more important localities. This collection forms a part of the exhibit

Jan 1, 1896

By A. S. Richardson

AIR conditioning, or air cooling, for the improvement of ventilation in the Butte mines has come into increasing use during the past 10 years. In part, the methods practiced have been described in previous publications of the Institute, but some improvements on earlier methods have been made and a number of new features have been developed. This paper is presented as a record of progress made, and for the sake of completeness describes all general features of the work. The need for air conditioning in the ventilation of mines in the district arises from the fact that the temperature of the ground and mine water has shown a very great increase with increase in mining depth, and has now reached a maximum of slightly over 130°F. The most difficult part of the ventilation problem is the maintenance of temperature and humidity of a satisfactory standard in the working places, especially on the lower levels. Although ordinary ventilation is adequate to maintain good conditions in most of the working places it is subject to a number of limitations at great depth. Most important among these limitations is that with increase in depth the air becomes heated before it reaches the working places, both by compression from increase in atmospheric pressure and by heat transferred to it from rock at high temperature, so that its capacity for lowering temperatures is greatly reduced before it reaches the operating zone. Increasing depth of mining also increases the distance traveled by the air in its passage through the mine, and this causes a corresponding increase in resistance to air flow, so that there is greater difficulty in maintaining even the same volume in circulation. Thus, in the face of a demand that the ventilating system have a very much greater capacity to remove heat from the mine, the tendency is for that capacity to diminish. The only evident alternatives were (I) the opening of additional air shafts to increase the volume of air in circulation, (2) an extension of the existing system that would be subject to the same limitations, or (3) the adoption of an entirely different method such as air cooling. Fortunately for an economic solution of the problem, the mean annual temperature of the surface atmosphere at Butte is about 40°F., with very low relative humidity in summer, so that there is unlimited natural cooling power at a temperature range adaptable to air-conditioning methods. METHODS Two similar methods of air conditioning are used, as necessitated by service requirements and dependent upon the equipment available. In one, which is the more important and has the greater cooling capacity, water is circulated in a closed circuit, and, alternately, first absorbs heat from warm mine air and then dissipates it in the surface atmosphere by cooling at a cooling tower. The second

Jan 1, 1941

By Henry Wurtz

Jan 1, 1880

By Charles Will Wright

Brief descriptions of the occurrence of the various deposits of strategic minerals then known in South America are published in "The Mineral Deposits of South America," by B. L. Miller and J. T. Singewald, 1919; in "Ores and Industry in South America," by H. F. Bain and T. T. Read, 1934; and in many publications on the individual countries. To give a gen.era1 idea of the situation today and possibilities for future output of strategic minerals in several of the countries, the following notes are offered. All tonnages are in metric units.

Jan 1, 1940

American Zinc Institute, 60 East 42nd St , New York, N Y. Julian D. Conover, Secretary The monthly Journal of the American Zinc Institute contains papers on zinc deposits, mining and metallurgy of zinc, as well as affairs of the Institute, statistics, and many papers on phases of the utilization of zinc It has the title "Zn " The numbers for each year are collected as volumes for that year, the first volume was issued in 1918, and the latest complete volume available is Vol 12 (1929) Copies of Indexes to the volumes will be sent upon request Back numbers of the Journal are not generally available for distribution but may be seen in most libraries For further information regarding papers, back numbers of the Journal, or volumes, address the Secretary

Jan 1, 1933

ALABAMA Alabama City.-Eddy, L. Altoona.-Cain, J. America.-Foreman, J. T. Anniston.-Foster, R. N. Ashland.-Sturdevant, J. C. Bessemer.-Ball, E. M. Calhoun, F. W. Maschmeyer, W. L. McKenzle, W. C., Jr. Birmingham.-Abbott, C. E. Aldrich, T. H. Aldrich, T. H, Jr. Ashton, J J.

Jan 1, 1923