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By Charles R. Cavanaugh, John F. Elliott

The activity of nickel in liquid Pb-iVi alloys which are rich in lead was measured in the temperature region of 700° to 1100°C by means of the galvanic cell: The electrolyte used was stabilized zirconia. Tlze data were correlated using the a function, and a plot of the temperature coefficient aE/aT All subsequent calculations of the thermodynamic properties are based on these two functions. The activity, activity coefficient, and molar properties of mixing of nickel are reported. Nicke1 shows extreme positive deviations frorn ideality while lead shows a very slight positive deviation in the composition range studied The study of the activity of nickel in liquid Pb-Ni alloys reported herein was undertaken to explore the use of stabilized zirconia, an oxygen-ion electrolyte, with liquid-metal electrodes, and to obtain further information on the thermodynamic properties of the liquid binary Pb-Ni system. The cell The reversible electromotive force of the cell results from the difference in the chemical potential of the oxygen at the two electrodes: po, (left) - p~ (right) = -4E5 [I] The chemical potential of oxygen on the right is fixed by the activity of nickel in the solution and pure solid nickel oxide. That on the left is set by pure solid nickel in equilibrium with pure solid NiO. By definition: Since the chemical potential of nickel is related to the chemical potential of oxygen through the equilibrium constant for the formation of NiO from nickel and oxygen gas, the electromotive force of the cell is also expressed In this case, n is 2, E is the reversible potential of the cell, and 5 is Faraday's constant. The work of Kuikkola and wagnerl and Schmalz-reid2 has shown that the stabilized zirconia electrolyte is essentially an ionic conductor at the oxygen levels encountered in the experimental arrangement of the work, i .e., PG > 10-l7 atm. THE EXPERIMENTS The advantage of this type of reversible cell over those using a liquid electrolyte is the simplicity arising because the electrolyte also functions as one of the containing crucibles. A further simplification was the choice of the Ni (sat.)-NiO electrode as the standard. This permitted a ready check on the behavior of the electrolyte, as the potential of the cell must become zero when the right electrode becomes saturated with nickel, either because of a change of temperature or because of the addition of nickel to the electrode. It also permitted the potentials being measured to lie in the most satisfactory experimental range of 0 to 100 mv. Although it was not theoretically necessary, lead was included in the standard electrode as it assured good contact between the electrode and electrolyte. Cell Design. The general arrangement of the experimental cell assembly is shown in Fig. l(a) and the details of the cell itself are contained in Fig. l(b). The anode lead wire on the interior of the cell was connected to a coil of perforated sheet nickel. Within this coil were nickel oxide pellets which were held beneath the surface of the liquid Pb-Ni alloy. A disc of nickel oxide was held at the bottom of the external crucible (alumina) by means of the thermocouple protection tube. The nickel oxide disc and pellets were compressed dry at 10,000 psi and sintered at approximately 1000°C for an hour in air. A major experimental difficulty of reversible electromotive force cells with liquid electrodes is the selection of suitable materials for connecting

Jan 1, 1964

By Charles S. Barrett

THE experiments reported in this paper have been fruitful in disclosing the mechanism of the deformation of iron in compression. They have established the nature of "deformation bands," "etch bands," or "X-bands," that have been a recognized but little understood feature in the structure of cold-worked metals since the early days of metallography, and have shown the role of the bands in the development of preferred orientations by cold-working. The work has also shown the relation of the orientation of individual grains to the preferred orientation of the aggregate. Some of the methods previously used in the determination of the indices of slip planes and slip directions are shown to be untrustworthy in the presence of deformation bands. The conclusion is reached that many slip planes and slip directions must operate during each stage in the compression of a single crystal, and that theories failing to take account of this require revision. In conducting the experiments a method of compression has been used by which extreme reductions can easily be reached, even to the limit set by the metal's capacity to deform without fracture. The work is a portion of a research program on the plastic properties of iron and steel. It is being used as a foundation for studies of orientations resulting from recrystallization and is being extended to other metals and other types of deformation. PREVIOUS WORK The previous experiments are few and have given confusing results. Ono1 compressed a polycrystalline alpha-iron specimen between two flat plates of a testing machine and found that severe deformation oriented the crystals into a duplex preferred orientation, one set of crystallites having a cube diagonal of the body-centered cubic lattice parallel to the compression axis, and another set having a cube axis parallel to the compression axis. We shall speak of this structure as a. double fiber texture of the type [111] + [100]. Wever2 also made an X-ray determination of the texture

Jan 1, 1938

By Sandip K. Mitra, John E. Dorn

The Basinki-modified Seeger equation for deformation of metals by means of thermally activated intersection of dislocations was used to ascertain the various factors responsible for the strain hardening of poly crystalline aluminum and a series of a solid solutions of magnesium in aluminum. The analyses were based principally on the rate of change of strain rate with stress and the Cottrell-Stokes ratio. From measurements of these quantities on a series of strain-hardened states, the force displacement diagram for intersection, the density of dislocations in the entanglements, and the contributions of the athermal local stress and long-range stress interactions were deduced. Poly crystalline aluminum was observed to have the same force-displacement diagram for intersection as single aluminum crystals, and the corresponding diagram for the magnesium alloys differed in a manner that suggested that small amounts of magnesium may decrease slightly the stacking fault energy of aluminum. Although poly crystalline aluminum had about the same initial density of dislocations as the single crystals, the density of dislocations increased much more rapidly with strain in the polycrystals. This factor and the higher back stresses generated in the poly crystalline aluminum were the major factors responsible for the higher strength of the poly crystalline aluminum, As the magnesium content of the alloys was increased, the initial density of the dislocations also increased. Most of the alloy strengthening arose from this factor; alloying effects due to short-range order strengthening, Suzuki locking, Cottrell pinning, and so forth, were estimated to be quite small. The gveater rate of strain hardening in the alloys was deduced to be due primarily to the greater increase in the density of the dislocations with strain as the magnesium content was increased. It is the purpose of the present investigation to shed additional light on the average plastic behavior of a grain in a polycrystalline aggregate, by analyses, based on dislocation theory, of appropriate experimental test results. These deductions when compared with those from single-crystal data will then serve to illustrate the major items of difference between the plastic behavior of single crystals and the average behavior of a grain in a

Jan 1, 1963

By J. R. Finlay

The Cæur d'Alene silver-lead mining district of northern Idaho is probably best known to the general public as a seat of labor-troubles. So far as the writer is aware, little has been written and little is known about its geology and resources. People interested in lead-smelting are, of course, cognizant of the economic importance of the region, but they have not communicated much of their knowledge to the public. Exact figures as to the total output of the district are not obtainable, but the following estimates, covering the entire output of the 15 years during which the mines have been operated, are believed to be approximately correct: Group of Mines. Product. Wardner Group, including the Bunker Hill and Sul livan, Empire State-Idaho, Last Chance, Sierra Nevada, bur d'Alene Development Co... . $17,500,000 Cafion Creek Group, including the Gem, Frisco Con solidated, Granite, Standard, Mammoth, Hecla, Tiger-Poorman, Custer and Bell,.... 35,000,000 Mullan Group, including the Morning, You Like and Gold Hunter,........7,500,000 $60,000,000 This output covers the period of discovery and early struggles, and several periods of stagnation caused by strikes and other serious labor-troubles. In 1900 the output of the district was fully $10,000,000, and this figure would have been considerably increased in 1901 had not a curtailment of production been forced by the condition of the lead-market. In 1901 the product was about 150,000 tons of concentrates, with a gross. value of $8,250,000.

Jan 1, 1903

By J. W. Furness

Before attempting any discussion of the importance of tariff enactments as applied to exhaustible resources, certain basic factors should be emphasized. First, it must be remembered that minerals differ from organic substances in that they are irreplaceable, and when once taken from the earth's crust enter into uses which ultimately dissipate them, so . that they cannot be recovered for future use. A second factor entering into the problem is the unequal distribution of the mineral deposits of the world. No industrial nation has within its political confines a sufficient quantity of all the minerals necessary for the maintenance and advancement of present civilization; hence international exchange of these commodities is inevitable. As minerals are essential to modern industry, the supply available to any given nation constitutes a factor which limits its ambition to advance industrially. A nation which has this ambition endeavors to secure not only a supply of minerals sufficient for its current needs, but also sources which will assure it expansion. Should mineral raw materials be withheld from such a nation by enactment, it seems inevitable that every effort will be made to obtain them, and that, should the nation deem itself sufficiently powerful, its ultimate recourse will be force. Thus the importance of tariff enactments, not only from the standpoint of industrial prosperity but from the standpoint of international peace, can be appreciated.

Jan 1, 1932

By PAUL DYER MERICA

PAUL DYER MERICA, who has been awarded the James Douglas Gold Medal for his achievements in non-ferrous metallurgy, is a Hoosier, having been born at Warsaw, Ind., in 1889. His father, a clergyman and educator, was president of the University of Wyoming from 1908 to 1913. After graduating from the University of Wisconsin in 1908, young Merica (not yet twenty years of age) went to China, where he was professor of chemistry in Chekiang Provincial College, Hangchow, until 1911. He then went to Germany to s t u d y and was fortunate enough to receive his Ph.D. from the University of Berlin just a few months before the outbreak of the World War in 1914. Returning to America, his first position was as special investigator at the En¬gineering Experiment Station of the University of Illinois, but before the year was out he joined the staff of the U. S. Bureau of Standards as associate physicist. Since 1918, he has been superintendent of research for the International Nickel Co. His work during those years is excellently summarized in the following quotation from the statement of Zay Jeffries recommending him for the award.

Jan 1, 1929

By E. W. Parker

THE anthracite region, from which there is produced annually about 80,000,000 tons, or approximately 15 per cent. of the total coal supply of the United States, has a combined area of a little less than 500 sq. mi. The total area occupied by the bituminous fields (including the sub-bituminous and lignite fields) is in the neighborhood of 400,000 sq. mi., so that 15 per cent. of the total output comes from this small area of only a little more than 0.1 per cent. of the coal-producing territory. of the United States. The productive anthracite area is divided into a series of basins or troughs, roughly parallel, extending. in a northeast-southwest direction through the. Counties

Jan 1, 1921

By S. R. Titley

The recent emphasis placed upon the use of molybdenum as a geochemical indicator has stimulated considerable inquiry into the behavior of molybdenum in the zone of oxidation. This paper represents a summary of recent and continuing experimental work and calculations in an investigation of a portion of the system Mo-Fe-S-H20 and treats the stability of various iron and molybdenum compounds with respect to oxidation potential and pH. Using experimentally determined free energy values for ferrimolybdite, diagrams of the stability fields of this mineral have been calculated with respect to ilsemannite (?), molybdenite, pyrite and limonite. This theoretical approach is the one utilized by Garrels3'4 in studies of the relationships of various minerals in the zone of oxidation. Use of this approach is particularly suited to the study of geochemistry in the zone of supergene processes because of the low temperatures, low pressures and other relatively easily determined and duplicated factors that exist in the near surface environment. Such a study of molybdenum, however, is complicated by several factors. One of these is the fact that the strong amphoteric behavior of molybdenum makes possible a wide variety of substances and complexes whose exact chemical natures are unknown. The second factor is the dearth of thermodynamic data for many of the simplest of the possible compounds and ions important to the study. For the purpose of this study, the problem of complexes has been approached through considering only the simpler possibilities realizing that the complexes and systems so treated may be gross oversimplifications. All the complexes considered, however, have been suggested in the chemical 2,7,9,12 or geologi-cal literature. EXPERIMENTAL WORK Studies of the behavior of molybdenum ions and ferrimolybdite have been carried out in aqueous sys- tems, and reactions have been followed by simultaneous measurement and recording of pH and oxidation potential. A major problem involved in this study was the long periods of time necessary for equilibrium to be established in some of the systems considered; in a few instances, these periods exceeded four weeks, that is, four weeks during which measured conditions changed continuously. Another problem, in some instances, was the indeterminate nature of the reactions that have taken place. Because of the tendency of molybdenum to complex, reactions which take place under some of the more extreme imposed conditions of oxidation and acidity or alkalinity are unknown. However, useful data for the present work were obtained from studies of the molybdate ion and ferrimolybdite between pH 2 and 8 and under only moderately oxidizing to nonoxidizing conditions. Instruments used in the experiments were a Hewlitt-Packard Model 412A VTVM, a modified Beckman Zeromatic pH Meter and two Varian model 11 recorders. pH was measured between glass and calomel electrodes and Eh was measured between calomel and platinum electrodes. Conditions of pH were varied with 1N H2SO4 and 1N NH4OH and 1N NaOH. Eh was varied with gaseous nitrogen, oxygen or aqueous H202. Ambient temperature was essentially uniform at 24ºC and was increased in the reaction vessel by the positioning of a magnetic stirrer whose temperature was sufficient to bring the temperature to 2S°C in the reaction. The temperatures of reaction did not vary more than 1/2ºfrom 25°C. Two reactions were investigated, the ferrimolybdite-limonite-water reaction and the reduction of molybdate ion. Studies of both reactions yielded useful data that were used in preparation of the Eh-pH diagrams. The traces of the reactions are shown on Fig. 1. Ferrimolybdite-Limonite- Water: Studies of this reaction involved analysis of the solution of ferrimolybdite and simultaneous formation of ferric hydroxide. The data are summarized on Fig. 1. In this reaction, equilibrium was attained at various pH's when coexistence of the two solid phases (ferrimolybdite and ferric hydroxide) was attained. At the proper pH, controlled by the amount of ferrimolybdite and thus the dissolved content of molybdate species, both phases were observed and reaction times to complete the transition were on the order of weeks. The reac-

Jan 1, 1963

By D. W. Gillmore, C. C. Wright

DEWATERING is a major problem in the preparation and utilization of fine-sized coals now being recovered in increasing amounts from colliery effluents, refuse banks, and silt ponds. Of the various methods which have, been proposed for dewatering fine coal, gravity drainage is probably the oldest and most widely used, and yet little information on this subject has been published. Consequently a laboratory investigation of gravity drainage phenomena was undertaken not only to provide basic data for predicting the drainage behavior of fine coals in cars, bunkers, basins, and silos, but also to obtain some understanding of the moisture retention properties of fine coal. Because of practical interest in the problem, a reproducible laboratory technique, which simulated plant conditions as closely as possible, was developed for the evaluation of drainage variables. The ap- paratus selected consisted of vertically-mounted lucite columns, nominally 4 to 8 ft in length and 2, 3 or 6 in. in diam; the bottom of the column was provided with a rubber stopper through which was inserted a -in. diam drainage tube; a wad of glass wool was placed on the upper part of this outlet tube to retain the coal and a plug was temporarily located at the lower end to prevent drainage during charging of the column, see Fig. 1. The most satisfactory testing procedure is as follows: 1—The fine coal, which has been thoroughly

Jan 1, 1953

By D. W. Gillmore, C. C. Wright

DEWATERING is a major problem in the preparation and utilization of fine-sized coals now being recovered in increasing amounts from colliery effluents, refuse banks, and silt ponds. Of the various methods which have, been proposed for dewatering fine coal, gravity drainage is probably the oldest and most widely used, and yet little information on this subject has been published. Consequently a laboratory investigation of gravity drainage phenomena was undertaken not only to provide basic data for predicting the drainage behavior of fine coals in cars, bunkers, basins, and silos, but also to obtain some understanding of the moisture retention properties of fine coal. Because of practical interest in the problem, a reproducible laboratory technique, which simulated plant conditions as closely as possible, was developed for the evaluation of drainage variables. The ap- paratus selected consisted of vertically-mounted lucite columns, nominally 4 to 8 ft in length and 2, 3 or 6 in. in diam; the bottom of the column was provided with a rubber stopper through which was inserted a -in. diam drainage tube; a wad of glass wool was placed on the upper part of this outlet tube to retain the coal and a plug was temporarily located at the lower end to prevent drainage during charging of the column, see Fig. 1. The most satisfactory testing procedure is as follows: 1—The fine coal, which has been thoroughly

Jan 1, 1953

By Fred L. Morritz, Harold M. Manasevit, Richard Nolder, Arnold Miller

Experimental evidence is presented which confirnis the epitaxial relationship between the deposited silicon and the sapphire substrate. Four distinct modes of orientation relationships have been established. These have been shown to be Single-crystal gvowth retention as a function of surfaces oriented off ideal has been qualitatively indicated. Both full-circle goniometer X-ray techniques and replica electron microscopy have indicated varying amounts of microtwinning in the silicon. film, which may he caused by the mode of silicon formation. Parameters have been found where twin density is less than I pct. The early stages of' epitaxy of silicon m sapphire have been examined by electron-microscope techniques... and mechanisms have been proposed. THE first report of the deposition of single-crystal silicon on sapphire (single-crystal aluminum oxide) was made at the American Physical Society Meeting in Canada' by one of us and was subsequently published in the Journal of Applied physics.* This paper summarizes some of the work carried on in this area since that time, in addition to reviewing some of our earlier observations. The initial single-crystal deposits of silicon on sapphire reported were obtained on sapphire planes produced by cutting a sapphire rod perpendicular to its fastest growth direction, which is approximately 60 deg from the C axis. Direct correlations between the microstructure and X-ray data as to the single crystallinity as shown in Fig. 1 are evident. These deposits were identified as (111) silicon on the substrate oriented near the (1123) of sapphire. (Sapphire notations are designated according to the c over a ratio of 2.73.) It became evident that substrate quality and surface play an important part in successful epitaxy. For example, in Fig. 2 we observe an interesting

Jan 1, 1965

By R. Floyd Farris

A method is presented for determining minimum waiting-on-cement time, which takes into account the differences that exist between types and brands of cements and such individual well conditions as depth, temperature, and pressure. The basis for the method was determined by laboratory tests. Being a laboratory development, several steps were required to prove its merit. The first step consisted of laboratory tests designed to determine the minimum cement strength required in wells. Basis was found for setting a minimum value of 8 Ib. per sq. in. tensile strength. Next, it was shown by laboratory tests that the time to 8 Ib. per sq. in. tensile strength may be expressed as a function of consistometer stirring time to loo "poises," the approximate relation being "the time to 8 Ib. per sq. in. tensile strength equals the time to I00 'poises' times three." Next, it was shown that the time of maximum temperature development in cement slurries, due to heat of hydration, is also related to consistometer stirring time to loo poises, but only by a factor of approximately two. It was shown also that the shut-in casing pressure will build up after cement is placed and register a maximum pressure at approximately the same time the slurry down the hole attains maximum temperature. From this and the relationships listed above, the general rule was established that minimum waiting-on-cement time (time to 8 Ib. per sq. in.) after casing cement jobs in any well is equal to the time when the shut-in casing pressure reaches a maximum, as measured from the initial mixing of cement, times a factor of 1.5. Cement plugs drilled in the field at the time prescribed by this formula were found to drill "firm to hard," thus confirming the laboratory tests. These tests prove that many of the present regulations for waiting on cement require a longer time than is absolutely necessary. Use of the method herein proposed offers the possibility of a saving of $1200 per well. Introduction The length of time allowed for cement to set after casing is determined either by state-wide rules, field rules, or self-imposed rules written into drilling contracts. In general, the time is dictated by experience and common practice. However, owing to differences in opinion and in experience of the various groups involved, waiting-on-cement time often varies from one area to the next. For example, an operator in an area where no rules exist may drill out of surface pipe at 24 to 36 hr., while another operator in another area may wait 48 hr. or more to comply with state or field rules, although the depth of the well, hole size, type of cement, and other data are identical. An even greater difference in practices will be found by making similar comparisons with respect to oil-string cement jobs. Differences in waiting-on-cement times of 36 to 48 hr. are common. Further complicating the picture is the rather common practice of allowing more waiting time for cement to set at the greater depths than is allowed at the shallow depths. This practice has existed for years in spite of the common knowl-edge1,2,3 that the temperature of the earth at the usual setting depths of surface

Jan 1, 1946

By R. Floyd Farris

A method is presented for determining minimum waiting-on-cement time, which takes into account the differences that exist between types and brands of cements and such individual well conditions as depth, temperature, and pressure. The basis for the method was determined by laboratory tests. Being a laboratory development, several steps were required to prove its merit. The first step consisted of laboratory tests designed to determine the minimum cement strength required in wells. Basis was found for setting a minimum value of 8 Ib. per sq. in. tensile strength. Next, it was shown by laboratory tests that the time to 8 Ib. per sq. in. tensile strength may be expressed as a function of consistometer stirring time to loo "poises," the approximate relation being "the time to 8 Ib. per sq. in. tensile strength equals the time to I00 'poises' times three." Next, it was shown that the time of maximum temperature development in cement slurries, due to heat of hydration, is also related to consistometer stirring time to loo poises, but only by a factor of approximately two. It was shown also that the shut-in casing pressure will build up after cement is placed and register a maximum pressure at approximately the same time the slurry down the hole attains maximum temperature. From this and the relationships listed above, the general rule was established that minimum waiting-on-cement time (time to 8 Ib. per sq. in.) after casing cement jobs in any well is equal to the time when the shut-in casing pressure reaches a maximum, as measured from the initial mixing of cement, times a factor of 1.5. Cement plugs drilled in the field at the time prescribed by this formula were found to drill "firm to hard," thus confirming the laboratory tests. These tests prove that many of the present regulations for waiting on cement require a longer time than is absolutely necessary. Use of the method herein proposed offers the possibility of a saving of $1200 per well. Introduction The length of time allowed for cement to set after casing is determined either by state-wide rules, field rules, or self-imposed rules written into drilling contracts. In general, the time is dictated by experience and common practice. However, owing to differences in opinion and in experience of the various groups involved, waiting-on-cement time often varies from one area to the next. For example, an operator in an area where no rules exist may drill out of surface pipe at 24 to 36 hr., while another operator in another area may wait 48 hr. or more to comply with state or field rules, although the depth of the well, hole size, type of cement, and other data are identical. An even greater difference in practices will be found by making similar comparisons with respect to oil-string cement jobs. Differences in waiting-on-cement times of 36 to 48 hr. are common. Further complicating the picture is the rather common practice of allowing more waiting time for cement to set at the greater depths than is allowed at the shallow depths. This practice has existed for years in spite of the common knowl-edge1,2,3 that the temperature of the earth at the usual setting depths of surface

Jan 1, 1946

By Robert Mehl

THE importance of the Widmanstätten structure to structure theory in metallography has been recognized by many writers.1 It is a structure produced by the precipitation of a new phase from a solid solution upon cooling as a result of changing solid solubility, and displays a characteristic appearance indicating a crystallographic relationship between the new phase and the original solid solution (Fig. 1). First discovered in 1808 by Alois de Widmanstätten2, the structure has been traced by analogy through many alloy systems. Particularly is this true of the steels. Sorby's classic work3 on the microstructure of iron and steel was in essence an attempt to explain the origin of this characteristic structure in meteoric iron. He observed in a Bessemer steel and in a cast-steel ingot structures which we now recognize as typical Widmanstätten figures.4 Osmond5 observed structures in a steel ingot analogous to those found in meteorites. Arnold and McWilliams6 obtained (and recognized) a

Jan 1, 1930

By D. R. Hay, E. Scala

Electrotransport has been superimposed on the rate-limiling- step in zone refining which is the impurity diffusion through the liquid at the solid/liquid interface. The efficiency of zone refining is increased and relative resistivity ratios (P300°k/P4 2°K) he increased by 50 pel in tungsten for a given number of posses using- the electrotransport field-aided method. The effiect of zotze refining in the presence of an electric field on the relative resistivity ratio is examined as a function of its intensity and polarity. THE effect of electrodiffusion on the effective distribution coefficient of zone refining has been discussed by Pfann and Wagner.' Control of the distribution coefficient in zone refining is of twofold interest. A distribution coefficient of unity can be increased or decreased, making possible the transfer of some previously inseparable solutes. The general efficiency of zone refining can also be increased. In the conventional zone-refining process impurities are removed by their retention in the molten zone and subsequent deposition at the end of the rod after a complete passage of the zone. In higher-melting-point systems a second mechanism may also operate, the volatilization of impurities from the molten zone. It has been suggested by schadler2 that, in refractory metals, vacuum distillation plays the predominant role in purification. In Koo's results,3 the resistivity ratio decreased beyond a zone-refined length of 6 in. from the starting end, indicating that some purification does in fact occur by true zone-refining action. Hay and scala4 showed that the degree of purity as measured by the relative resistivity ratio method depends on the square root of time in the molten zone (number of passes) and thus appears to be limited by diffusion in the boundary layer at the solidifying interface assuming good mixing in the body of the molten zone where a linear rate would prevail. The final concentration of impurities in electron-beam floating-zone purification depends very much on the operating conditions and results obtained by various investigators2,3,5 are difficult to correlate. The diameter of the starting material, operating vacuum, and rate of traverse are among the factors to be considered. There are, nevertheless, some general observations to be obtained from the literature. Lawley5 reviewed the literature up to 1962 and concluded that the major contaminants generally remaining in tungsten after electron-beam zone refining are molybdenum and carbon. Molybdenum due to its high melting point and distribution coefficient of nearly unity would be expected to be difficult to remove by either volatilization or zone refining. Carbon is not only a common contaminant in vacuum systems, but is also very difficult to remove by conventional vacuum melting. even with vacuums of 10-7 mm Hg. For each of those impurities removed by zone refining the equation of Pfann and Wagner may be applied: It relates the effective distribution coefficient k to a superimposed driving force which accelerates the solute away from the interface with a terminal velocity L" and to the more conventional zone-refining parameters; v = rate of traverse, t = thickness of the diffusion layer at the solidifying interface, D = diffusivity of the solute in the molten zone, and ko = equilibrium distribution coefficient of the impurity.

Jan 1, 1965

By E. P. Jennings

Large deposits of titaniferous iron-ore occur at Caribou, an old silver-mining camp in Boulder county, Colo., 17 miles west by south of Boulder, and a few miles northwest of the tungsten-mines. Professor Regis Chauvenet1 published a part analysis of the ore many years ago, but gave no description of the wall-rock. Caribou hill, which contains both the silver-bearing veins and the iron-ore deposits, is a low dome of gabbro surrounded by the Archæan schists and gneisses of the Front range of the Rocky mountains, the peaks of which, a few miles west of Caribou, attain an elevation exceeding 12,000 ft. The gabbro stock is roughly elliptical in outline, with approximate diameters of 1 and 3 miles. The crest of the dome is 10,500 ft. above sea-level, and the town and ore-cleposits are 500 ft. lower. Outcrops of the iron-ore occur in the town and extend NW. for 2,000 ft., where they disappear under the swampy meadows of Caribou park. Portions of the deposit are covered by drift, but one continuous outcrop is 900 ft. long and from 200 to 250 ft. wide. A second deposit is 0.25 mile south of the town along the eastern slope of the hill. It is not as well defined as the north bed, but is approximately 1,000 ft. long and from 100 to 200 ft. wide. The easily disintegrated ore does not form prominent outcrops, but the outlines of the deposits are readily traced by the large amount of ore fragments that cover the ground. Trenches and pits sunk on the outcrop expose a roughly banded magnetic iron-ore, with pyroxene as the principal gangue-mineral. The Gabbro. This rock was classified in the field as a gabbro from the presence of pyroxene and striated feldspars, and for convenience the field-name will be retained.

Jan 1, 1913

By R. J. Wasilewski

THERMAL expansion of rhenium data have been reported by Agte et al.,&apos; and Medoff and cadoff,&apos; respectively, while the linear expansion coefficient was determined by Sims et Al.3 Denoting expansion coefficients parallel and at right angle to c axis by all and Al respectively, their weighted mean should be equal to dilatometric linear coefficient of a random polycrystalline specimen. The values reported for these coefficients are tabulated below: Since these values are in poor agreement, and because of anomalous expansion behavior observed in titanium 4 and chromium, a rede termination of the axial expansion was carried out. A Unicam 19-cm-diam high-temperature camera was used, with unfiltered CuK radiation. Camera calibration was carried out using at Pt wire standarde at temperatures up to 1100oC, the variation between indicated and true temperature being within the experimental error (estimated at <3oC) above 750o C. Rhenium Johnson Matthey spectrographic standard) was vacuum annealed at 1000 oC prior to X-ray diffraction experiments. Lattice parameters were obtained by least-squares solution using the reflec- tions (1232), (1015), (2024), and (3030) for all the patterns, and the additional reflection (2133) for higher temperature (400°C and above) patterns. The relative expansion data obtained are shown in Fig. 1, lengths of the vertical bars indicating the spread in the parameter values obtained by using various combinations of three spacings from the four or five measured. The data calculated from the equation of Ref. 2 are included for comparison purposes. Several specimens were used to obtain the above data, neither of them showing a significant parameter change after completion of the high temperature runs. Some parameter data and the corresponding expansion coefficients between 25 oC and the measurement temperature are tabulated below. The comparison of the present data with those previously reported shows reasonable agreement with the results of Medoff and cadoff2 within the temperature range covered by them (up to 1000 oC). The a values are appreciably higher throughout most of the investigated temperature range. The basal expansion is—in agreement with their findings—appreciably higher than that in the direction of hexagonal axis. The expansion coefficient, al, however, decreases rather more slowly with temperature than previously reported. The expansion along the c axis up to nearly 1000°C appears in excellent agreement. However, at higher temperatures there is a marked deviation towards higher expansion, reproducible between different specimens. Furthermore, there seems to be some irregularity in the variation of all with temperature, the apparent local minimum and maximum values at 510o and 1024o C, Table II, being well outside the experimental error limits. It must be stressed that the apparent discontinuity in the c parameter expansion is still insufficient to account for the expansion value reported by Agte et al.&apos; since a total expansion of close to 2 pct would

Jan 1, 1962

By E. S. Machlin, S. Weing

GRAIN boundary stress relaxation has been the subject of several investigations in recent years, but as yet the phenomenon is not well understood. One of the major difficulties has been the lack of a sufficient amount of data with which to evaluate any proposed mechanism. Little information is available on the effect of small amounts of substitutional solutes on grain boundary stress relaxation. It is with this important phase of the problem that this investigation is concerned. The influence of substitutional solutes on grain boundary stress relaxation has been recently investigated in copper by Pearson: and in aluminum by Dorn et al.&apos; Pearson studied the effect of zinc, gallium, germanium, and arsenic on the relaxation peak of OFHC copper.* The pure OFHC copper decreased the peak intensity and a second peak appeared at a higher temperature. This latter peak was termed the alloy grain boundary peak. At the lowest binary concentration studied, approximately 1 atomic pct, the primary peak was almost completely obliterated. Pearson found that the activation energy calculated from the alloy grain boundary peak for all solutes, irrespective of the concentration, was 44,000 cal per mol. Pearson concluded that the increase in activation energy from 33 to 44 kcal per mol is not continuous but abruptly changes from the lower to the higher value. As no attempt was made to investigate the intermediate range of concentration and hence calculate the possible variation of the activation energy for the initial grain boundary peak, this conclusion is hardly valid. In contrast to these results, Dorn et al. studied the effect of zinc, silver, copper, germanium, and magnesium on the grain boundary stress relaxation of aluminum. No change in the energy of activation was observed for binary alloys of the flrst four solutes, but a linear increase was found for increasing concentration of magnesium. Saturation was not found up to the maximum of 1.6 atomic pct. The energies of activation were obtained by plotting the horizontal displacement of the dynamic modulus curve vs temperature for two vibrational frequencies. As the modulus is proportional to the square of the frequency, this requires the measurement of the torsional frequency over a range of temperature. However, the technique does not lead to an unambiguous interpretation of the grain boundary

Jan 1, 1958

By W. R. Hibbard, Ming-Kao Yen

Various rationalizations of preferred orientations in cold worked polycrystalline metals have been based on the operation of at least two three2 five, an indefinite number, and all,6 slip systems of the type occurring in single crystals. Pickus and Mathewson3 suggested that the cold rolling texture in face-centered cubic metals could be rationalized on the basis of two or more operating slip directions symmetrically disposed about the direction of flow in such a manner that the resolved shear stress factor is equal for all operating slip systems and lattice rotations cancel each other. The importance of the direction of flow, the necessity for the operation of slip systems capable of producing the required changes in external dimensions, the maintenance of a common surface between adjacent grains and a symmetrical arrangement of the operating slip systems in order to produce an end orientation which is stable under additional deformation lead to the following rationalization of textures based on the type of slip systems operative in single crystals. The rationalization is intended to explain why certain orientations are suitable for deformational flow without a change in orientation and thus are stable end orientations or ideal texture orientations. It does not attempt to explain how the grains of a randomly oriented polycrystalline aggregate will reach this orientation. The rationalization is based on the following four postulates: 1. The ideal textures for polycrystalline aggregates are the result of reorientations of individual crystals toward the same stable end orientation at which no further reorientation will occur even during additional deformation. Since, in simple slip, the relative orientations of the stress axis and the active slip system determine the change in orientation during slip, it is considered that the orientation of the stress axis with respect to the ideal texture determines what slip systems must be active to retain the stable end orientation. Therefore the stable end orientation should be a symmetrical one around the stress axis with respect to the active slip systems such that lattice rotations resulting from slip will cancel each other and prevent a resultant change in orientation. (Rotational symmetry only—not translation, inversion, nor others—is considered here.) Thus a metal under a pure stress should develop a texture consisting of one or more of the crystallographically symmetrical directions, <100>, <110> or <111> for cubic metals or <0001>, <1010> or <1120> for hexagonal close-packed metals, parallel to the stress axis. 2. Since the active slip direction is the direction of glide during simple slip and thus the direction of maximum shear movement, in the ideal texture the active slip

Jan 1, 1949

By Ming-Kao Yen, W. R. Hibbard

Various rationalizations of preferred orientations in cold worked polycrystalline metals have been based on the operation of at least two three2 five, an indefinite number, and all,6 slip systems of the type occurring in single crystals. Pickus and Mathewson3 suggested that the cold rolling texture in face-centered cubic metals could be rationalized on the basis of two or more operating slip directions symmetrically disposed about the direction of flow in such a manner that the resolved shear stress factor is equal for all operating slip systems and lattice rotations cancel each other. The importance of the direction of flow, the necessity for the operation of slip systems capable of producing the required changes in external dimensions, the maintenance of a common surface between adjacent grains and a symmetrical arrangement of the operating slip systems in order to produce an end orientation which is stable under additional deformation lead to the following rationalization of textures based on the type of slip systems operative in single crystals. The rationalization is intended to explain why certain orientations are suitable for deformational flow without a change in orientation and thus are stable end orientations or ideal texture orientations. It does not attempt to explain how the grains of a randomly oriented polycrystalline aggregate will reach this orientation. The rationalization is based on the following four postulates: 1. The ideal textures for polycrystalline aggregates are the result of reorientations of individual crystals toward the same stable end orientation at which no further reorientation will occur even during additional deformation. Since, in simple slip, the relative orientations of the stress axis and the active slip system determine the change in orientation during slip, it is considered that the orientation of the stress axis with respect to the ideal texture determines what slip systems must be active to retain the stable end orientation. Therefore the stable end orientation should be a symmetrical one around the stress axis with respect to the active slip systems such that lattice rotations resulting from slip will cancel each other and prevent a resultant change in orientation. (Rotational symmetry only—not translation, inversion, nor others—is considered here.) Thus a metal under a pure stress should develop a texture consisting of one or more of the crystallographically symmetrical directions, <100>, <110> or <111> for cubic metals or <0001>, <1010> or <1120> for hexagonal close-packed metals, parallel to the stress axis. 2. Since the active slip direction is the direction of glide during simple slip and thus the direction of maximum shear movement, in the ideal texture the active slip

Jan 1, 1949