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By Kenneth A. Moon

An exact statistical treatment of a one-dimensional model is used as a basis for evoluating the reliability of certain simplified expressions for the activity of the solute in interstitial solutions, including one obtained from the exact expression by setting the repulsive interaction equal to infinity. The latter approximation is found to be satisfactory at low and moderate concentration if the repulsive interaction is large, even though not infinite. A similar expression (identical if the co-odination number is two) is derived from the quasichemical expression of Lacher, and is recommended as the best available expression for the excess configurational entropy of interstitial solutions with excluded sites. Some reasonable models are discussed, and the nature of the saturated solutions is determined by inspection. Some of the models reduce to the one -dimensional case. An analysis is given of the excess partial entropy of hydrogen in V-H; Nb-H; and To-H solutions. MOST treatments of the statistical thermodynamics of interstitial solid solutions have followed the classic paper1 of Lacher in making the simplifying assumption that the configurational entropy of the solution is ideal. However, it is becoming increasingly apparent that there are many interstitial solutions with very large so lute-solute repulsions, and for these the assumption of ideal entropy is not valid or useful. It is important to realize that with substitutional solutions large repulsions between the component atoms must lead to phase separation, whereas in interstitial solutions the free energy of the solution is not drastically increased by large solute-solute repulsions until intrinsic saturation is reached at the concentration where further solute would be forced to enter a site in which it would experience the repulsive effect of one or more solute atoms already present. In the limiting case of an infinitely large repulsive interaction, the excess free energy would be attributable entirely to excess entropy, the enthalpy of mixing being zero. AS will be shown below, even if the repulsions are less than infinite, a treatment based on an assumption of infinite repulsions may be very satisfactory up to moderately high concentrations of the interstitial component. Often in solutions where large repulsive interactions exist, there are also small interactions — often attractive—between solute atoms in configurations other than that corresponding to the large repulsion. In such cases the excess free energy will consist of an excess entropy term attributable to the large repulsive interactions, and an enthalpy term corresponding to the other small interactions. Nomenclature to differentiate succinctly between important cases would be a convenience. In this paper the nomenclature shown in Table I will be used. In Table I, and in the preceeding discussion, excess quantities are defined in terms of standard states which are pure solid solvent and pure (possibly hypothetical) solid saturated phase of the structure in question. In practice, it is more convenient to choose the interstitial element as a component, and its conventional standard state. This will add a composition-independent term to the excess entropy and the enthalpy. The earliest paper known to the present author which treats the thermodynamics of athermal interstitial solutions was given by schei12 in 1951, but the statistical derivations in that paper are open to criticism. Speiser and Spretnak were the first to give a correct statistical treatment,3 limited, however, to concentrations sufficiently low that the number of empty sites excluded from occupancy by more than one filled site is negligible. The purpose of the present paper is to extend the statistical treatment to more concentrated solutions, and to examine the magnitude of the errors introduced by assuming that the repulsive interactions are infinite when in fact they must be finite. THE QUASICHEMICAL APPROXIMATION Fortunately, a standard method already exists for taking into account the effect of large interactions upon the entropy of mixing. This is the quasi-chemical method, in which the probability of existence of a given pair of solute atoms in a certain proximate configuration is assumed to be proportional to exp(-w/kT), where w is the energy increase of the solution when the two atoms are moved from isolated locations in the solution to the configuration in question. A quasichemical treatment of interstitial solutions was given in 1937 in a widely neglected paper by Lacher.4 The result comes out

Jan 1, 1963

By D. E. Mikkola, G. E. Poquette

X-ray diffraction was used to study the growth of antiphase domains in quenched (or "disordered&apos;? Cu3Au annealed in the range 300" to 385°C. Measurements of the long-range order parameter indicate that a high degree of order is established rapidly at these annealing temperatures. Average domain sizes obtained by Fourier analysis of the superlattice peak profiles show that antiphase domain growth is analogous to classical metallurgical grain growth (i.e.,fol-lows a D2 US kt relation). The activation energy for the growth process, 44 kcal per mole, indicates diffusion control. The anisotropy in the observed effective domain sizes from seven different superlattice peaks can be best accounted for by a configuration involving antiphase domain boundaries on {100 } and (111 ) planes, where the (100) boundary is the low-energy type, {lOO} Type I. The disappearance of the (111) antiphase domain boundary during domain growth is dif-fusion-controlled with an activation energy of 48.5 kcal per mole. On the other hand, the behavior of the parameter representing the amount of (100) Type I boundary indicates that there may be a conversion of the higher-energy boundary types to (100) Type I boundary during the growth process. THE order-disorder transformation in the alloy Cu3Au has been the subject of numerous experimental investigations over the past 40 years, most of which have involved measurements of convenient physical properties such as resistivity and hardness as a function of heat treatment. The interpretation of these data is difficult because measurements of this type have the disadvantage that they yield total changes resulting from several different atomic processes which may be occurring simultaneously. The present study was undertaken to establish by means of X-ray diffraction the kinetic behavior of one of these atomic processes, namely antiphase domain growth. In the completely ordered state Cu3Au has an L12 structure which can be described as an fcc type arrangement of atoms in which the gold atoms occupy the corner sites and copper atoms the face-centered sites. Three other equivalent unit cells can be formed by allowing two gold atoms to occupy opposite face-centered sites and copper atoms to occupy the remaining corner and face-centered sites. These four different unit cells are crystallographically related by a shift of 1/2<110>. Quenching from above the critical temperature (392°C) to room temperature retains the "disordered" structure-a "random" arrangement of copper and gold atoms having the fcc structure. Annealing the disordered alloy below the critical temperature causes ordering to occur through the nucleation and growth of ordered regions at different points throughout the crystal. These small ordered regions, each based on one of the four types of unit cell, grow by consuming the disordered material until they impinge to form a domain structure in which the domains are antiphase by a shift of 4(110). The boundaries between domains are called antiphase domain boundaries (APDB) and they have been found to lie primarily on &apos; {100} planes in highly ordered Cu3Au. Two types of APDB can occur on ( 100) planes. An example of an (001)1/2[110] shear type APDB is shown in Fig. I. Because of the layer of copper atoms separating the domains in this case, there are no near-neighbor violations across the boundary and it has a low surface ener This type of APDB will be referred to as {lOO} Type I. Fig. 2 shows an (001): [011] climb type APDB, (100) Type 11. This type of APDB can be described as resulting from removal of a (200) plane followed by a shift of 1/2<110> to bring the separated regions together. Near-neighbor violations across (100) Type I1 APDB make it a high-energy boundary. There are numerous other possible APDB configurations; however, it is only worth noting that shear type APDB can be produced on the (111) plane by motion of a normal fcc dislocation with Burgers vector 1/2<110> through the ordered structure. A (111); [110] shear type APDB is shown in Fig. 3. Again, because of the near-neighbor violations this type of APDB has a higher energy than the (100) Type I APDB.

Jan 1, 1970

By A. D. LeClaire

This paper claims to provide a description of diffusion processes in solids which is said to be a reformulation of Fick&apos;s Laws and therefore, presumably, is supposed to be as general as those laws. In fact, it appears to provide no more than an atomic model of a rather restricted type leading even to results in conflict with experiment. The restriction lies in the assumption, carried throughout the paper, that even in a chemical gradient the jump frequency i of an atom of species i is a function only of the composition on the plane from which it jumps, i.e., ?i = ?i(cl, c2 ...). This means that atom jumps in opposite directions from a site would occur with equal probability. There would then be no tendency for atoms to migrate preferentially in one direction along the gradient, so the model is incapable of accommodating the well established phenomenon of atom drift in a chemical gradient.10-" A more general model that does not suffer this difficulty was discussed in a paper13 I wrote in 1958, and the results therein already contain as a special case those given by Dr. DeHoff. The simplest sufficiently general assumption is to suppose that ?i is a function ?i(a1 a2,...; wl, w2, ..-) of the concentration aj and ? ?j at the site from which and to which, respectively, a jump is made. Any such function can always be expressed as a function of the sum and difference of its arguments. Thus d is the jump distance and g a geometrical constant. Obviously this is zero, i.e., no drift, if ??ri/??j = 0. X is written in this form, revealing two components of the total drift, because it can be shown that only the second component, depending on ??&apos;i/???(?j -aj), actually contributes to the net diffusion flux Ji. This component can be shown,13 by a straightforward ther-modynamic transcription, to be responsible for the so called "thermodynamic factor" in the Darken approximation for a chemical diffusion coefficient is the activity coefficient of i. Because the jump rate ?i in DeHoff&apos;s approximation has no dependence on the concentration gradient it does not seem possible to derive the Darken equation from his Eq. [6] without the further rather arbitrary assumption that ?i = const ri. It is to be noted too that the author&apos;s derivation of Eq. [12] is only valid when ?i is in fact a function only of the cj at the plane from which the atom jumps—for only then is ci?i a unique function of position and therefore of A. Author&apos;s Reply R. T. DeHoff I am indebted to Dr. LeClaire for his penetrating discussion of my paper, "A Reformulation of Fick&apos;s First Law". I concede that it does appear initially that the relationship presented in my paper could be derived from the detail atomic model of random walk and atom drift presented in Dr. LeClaire&apos;s approach. However, there are some important differences in concept and viewpoint which deserve further amplification. Dr. LeClaire&apos;s description is penetrating, detailed, and fundamental. His approach describes an extremely complex phenomenon, the displacement of atoms in a multicomponent gradient, at a sophisticated level. For precisely these reasons, his analysis has not proved to be useful for experimental studies that have practical objectives. For example, in order to obtain the information required to complete the analysis of the jump frequency distribution in a ternary system, the following series of experiments would, I believe, be required: 1) chemical (gradient) experiments, covering the composition range;

Jan 1, 1970

By John H. Schilling

The Gabbs magnesite-brucite deposit is unique in size and is one of two magnesite deposits being exploited in the United States. It is near the town of Gabbs, which is one hundred miles southeast of Reno, in west-central Nevada. The brucite was discovered in 1927; the magnesite was found while exploring the brucite. During World War II, more than 80,000 tons of magnesium metal was produced from about 900,000 tons of magnesite ore mined from these deposits. An additional 5,000,000 tons of magnesite and 1,000,000 tons of brucite have been produced for use in making magnesia refractories and chemicals. Basic Inc., presently the only producer, mines 1.5 ± 0.25 million tons of ore and waste annually using high-selective open-pit rriethods; the ore is up-graded, calcined, and processed into a variety of products. Known reserves of highgrade (less than 5 per cent CaO) magnesite ore total more than 25,000,000 tons, and there are larger tonnages of lower-grade material; brucite reserves are small. The magnesite and brucite are in generally west-dipping dolomite of the upper member of the late Triassic Luning Formation, in the over-riding plate of the Paradise thrust fault. A great variety of dikes and a stock of Cretaceous granodiorite intrude the Luning Formation in the vicinity of the magnesite-brucite deposit. The magnesite bodies are scattered over an area of about a square mile around a prong of granodiorite which extends north from the stock. The brucite is mainly in two bodies in contact with the prong of granodiorite; at the surface and along deeper cracks the brucite has weathered to hydromagnesite and artinite. In the area of magnesite-brucite mineralization, much of the dark, fine-grained, schistose, regionally-metamorphosed dolomite of the Luning Formation has been marmorized to a lighter-colored, coarser-grained, massive dolomite that is intergrown in varying proportions with the magnesite. The magnesite and marmorized dolomite can not be distinguished visually. In addition to the two varieties of dolomite, the gangue in the magnesite and brucite bodies mainly is the various varieties of dike rock, serpentine and a variety of other "contact" minerals, and "post-ore" dolomite and calcite. The magnesite ( and recrystallized dolomite) is believed to have formed by the hydrothermal replacement of the regionally metamorphosed sedimentary dolomite; alternatively it has been suggested that the magnesite is sedimentarv and formed contemporaneously with the dolomite in an embayment of the Triassic sea. Because all the igneous rocks exposed in the immediate vicinity of the magnesite deposits appear to be younger than the magnesite, the ore-forming solutions are thought to be related to a somewhat older granite which crops out elsewhere in the area. The brucite is the result of contact-metasomatic replacement of magnesite during the emplacement of the granodiorite stock.

Jan 1, 1968

By Russell A. Carter

Alaska is a land of immense proportions and resources. Its very name, derived from an Aleut term, means "The Great Land." Yet, in a state slightly larger than Texas, California, and Montana combined, there are presently only two-large scale mines in production, excluding dredge operations. Once referred to by its territorial governor as "a storehouse of minerals," Alaska is, in the opinion of many industry observers, at least 20 years away from a healthy, productive mining industry. The mineral potential of the state is tremendous: coal deposits on the North Slope alone have been hypothetically pegged at 1.5 trillion tons. Copper-zinc deposits on the south flank of the Brooks Range are conservatively estimated to be worth $4 billion to $6 billion. However, the problems facing mineral development are of equal magnitude, and include:

Jan 11, 1976

By Tenney, J. B.

DEVELOPMENT of complex ores in the south- western part of the Rocky Mountain region has been retarded by the prohibitive distance to the nearest suitable zinc treatment plants. In the north- western and central Rocky Mountains the building, cluring tlie past decade, of electrolytic zinc plants at Anaconda, Great Falls, Trail, and Burke has tremendously stimulated the mining and exploiting of such .ores, greatly increasing the production of lead, zinc, copper, gold, and silver. Selective flotation permits the making of high-grade led, copper, and zinc concentrates. If the zinc concentrates could be made free from lead, copper, gold, and silver, they could be shipped economically to Mid- Western retort plants designed for such concentrates. Unfortunately a considerable proportion of the precious metal content accompanies the zinc blende in the ores of this region. Although some of it is saved in &apos;retort residues, the treatment cost is thereby increased so materially and the proportion saved so small, that .concentrates of ordinary grade cannot stand treatment charges and freight.

Sep 1, 1928

By John B. Hastings

THE reconnaissance of the Goldfield mining-district, described in this paper, was made in May and June, 1905, and, though this time was too short for a complete report, the work accomplished may serve as a basis for more thorough future research. Dr. Berkey has examined the rocks collected by myself, and I am using his classifications. As a result of further field-work, and Dr. Berkey&apos;s examination of the rocks, this paper is an elaboration and correction of my views expressed in the Gold-field Sun, May 12, 1905. The sketch-map, Fig. 1, illustrates the geology of the Goldfield mining-district. Goldfield is an eruptive complex, consisting of alaskite (binary granite), hornblende-andesite, hornblende-dacite, rhyolite, pyroxene-andesite, pyroxene-dacite (sometimes containing, a small quantity of olivine), quartz-felsite, olivine-pyroxene-ande¬site, and basalt. Considering this list to be arranged in the order of eruption, the age-sequence of the rocks conforms to Richthofen&apos;s law, formulated in 1868. From his observations in Europe and America, propylite, andesite, trachyte, rhyolite and basalt, occurring together, succeed one another. In a general way, the medium and more acidic rocks precede the most asic-a result supposed by some to have arisen from their relative position beneath the surface, and due to a rude stratification by gravity in the original cooling magma during the older history of the earth, or to the same differentiation occurring during a quiescent (molten ?) period preceding eruption, being aided by the ease with which acidic rocks, mixed with water vapors, become fusible. In effect, the more basic and less re-

Mar 1, 1906

By Thomas T., Read

ANY discussion of State-supported schools of mining and A metallurgy needs to be prefaced by a definition, since the first school to offer a mining curriculum, the Pennsylvania Polytechnic College, was established by a grant from the State. But, so far as can be determined, it received no further State support. It would be tiresome to go into precise details,. and it will be enough to stipulate that by State schools are meant those which derive their main financial support from regular appropriations made by a State legislature. The University of Michigan was the first of these to offer a mineral industry curriculum; its story, as well as those of Wisconsin and Illinois, has been related in the preceding chapter.* Arranging the others in chronological order involves making a decision as to what weight to attach to plans for giving instruction, as contrasted with its , effective initiation. This may appropriately be illustrated by the history of mineral industry education in California. California Among those who came to California in 1849 and the following years were many New Englanders who had a keen interest in education. Some of them, mostly Congregationalists and Presbyterians, sought to establish a school of higher education around San Francisco Bay and eventually succeeded in opening the "Scientific and Classical School at Contra Costa&apos; in Oakland, at Broadway and 5th St., on June 20, 1853. This prospered so well that it was chartered by the State as the "College of California" on April, 13, 1855. Developing so rapidly that its quarters became cramped, in 1864 it not only bought a tract of

Jan 1, 1941

By Y. A. Topkaya

The placer gold occurrences at Sart Çayl, Manisa, Turkey, the legendary River Pactolus of King Croessus, were evaluated in this study to determine if this deposit contains sufficient recoverable value to justify development and exploitation. The gold occurs both in the upper Neogene conglomerates and the alluvium derived from these conglomerates. The total reserve in the whole region is estimated to be 500 million cubic metres. Samples were taken of the upper conglomerate and in the alluvium in an attempt to determine the amount and the physical nature of the gold. The gold in samples was recovered by screening out barren oversize followed by washing the sand and gravel through riffled sluices. The resulting sluice concentrate was later panned and amalgamated at site. Laboratory cyanidation testing of some samples for control purposes was also done. The average calculated free gold was found to be about 90-100mg/m3 and the size of gold flakes found was quite small. The field as well as laboratory testing of the samples of Sart Çay1 indicated that the potential reserves in this region could only be developed as a sand and gravel operation and the gold could be recovered together with the heavy minerals as a byproduct.

Jan 1, 1984

By Sherwin F. Kelly

NEW trend in geophysics has been uncovered in these depression years, made evident through the thinning cloak of commercial activity, which, in better times, would have completely obscured it. I refer to the increasing use of these methods for geological investigations by federal and state geological surveys. This is a trend that has been gathering momentum not alone in the United States, but abroad as well. Thus, in Poland, the Geological Survey has been playing an increasing role in geophysical work since 1927, and now has- its own geophysical department. The government petroleum producing organization of Argentina has its Geophysical Commission; Brasil boasts a completely equipped geophysical department in its Mineral Production Service; the government of Chile has contracted with commercial companies for geophysical surveys; Peru is planning an intensive program of geophysical prospecting in its petroliferous regions; and Canada has, for several years, cooperated with

Jan 1, 1935

By A. C. Veatch

Jan 1, 1921

By Norman Lamont

The evaluation of certain reser-voir properties, such as porosity and fluid saturation, from electrical well surveys has been widely accepted in petroleum engineering. Various investigators have established relationships between these properties and certain parameters which affect the response of the electrical log. Among these are the resistivities of the mud, its filtrate, and its filter cake. In 1949, Patnode1 established a relationship between the resistivities of the mud and filtrate. The well logging service companies have contributed relationships for the mud-mud cake resistivities2,3 These have been valuable since it was the practice to measure only resistivity of mud at the well site. During the mid-1940&apos;s the industry began drilling wells with oil-emulsion drilling fluids. These were conventional aqueous muds with a dispersed oil phase. Since 1950, oil-emulsion muds have been used on an increasing number of wells each year. However, the practice of measuring only the resistivity of the mud at the well site has continued, and the mud filtrate and mud cake resistivities have been determined by the above-mentioned relationships. Service companies are now equipped to measure all three resistivities at the well site. An investigation was conducted on the resistivities of oil-emulsion muds, mud filtrates, and mud cakes to determine if these values conformed to the relationships for aqueous muds. TYPES OF MUDS Fifty-one oil-emulsion mud samples were prepared in the laboratory following a standard manual&apos; published by a leading mud company. The diesel oil in the samples varied from 5 to 50 per cent, the majority of the samples being in the 10 per cent region. The basic aqueous mud types which were converted to oil-emulsion muds were commercial clay and bentonite muds, low pH and high pH, caustic-quebracho treated muds, and lime treated muds. The emulsions were stabilized by dispersed solids, lignins, lignosulfo-nates, sodium carboxymethyl cellulose, or sulfonated petrolatum. It is worthy of note that after a quiescent period of two weeks at room temperature all samples, regardless of emulsifying agent, remained stable. The make-up water for the muds was from the laboratory tap. Resistivities were varied by the addition of table salt to the water. A range of mud resistivities from 0.44 to 3.9 ohm-m was obtained in this way. Twenty-three field muds were tested. These covered the same range of mud types as did laboratory muds. Oil provinces of the Gulf Coast, South Texas, West Texas, Oklahoma, Montana, and Canada were represented. MUD TEST PROCEDURE Each mud was tested for density, viscosity, pH, and filter loss by standard testing techniques. The resistivity measurements were obtained with a Schlumberger EMT meter. This meter required small volumes of sample, e.g., 2 mm. Filtrate was obtained from a Standard Baroid fil-ter press at the end of a 30-minute test. The filter cake from the same test was used for cake resistivity measurements. Mud, filtrate, and cake samples were heated to 100" F in a constant temperature water bath prior to measurement of resistivities. RESULTS The relation between mud resistivity (Rm) and mud filtrate resistivity (Rmf) is shown in Fig. 1. The solid line represents an average for the data. The equation of this line is Rmf =0.876 (Rm) 1.075 . . (1) Arbitrary limits, indicated by the dashed curves, have been set. The majority of the data falls within these limits, but some points do lie outside the limits. The approximate equation Rmt = 0.88 Rm , . . . . (2) will give satisfactory results within these limits. The data on mud cake resistivity Rmc is shown in Fig. 2. The solid line is an average for the data. The equation for the line is Rmc = 1.306 (Rm)0.88 The dashed lines are arbitrary limits on the data. Within these limits, Eq. 3 may be simplified to Rmc = 1.31 Rm . . . . (4) DISCUSSION The limiting curves in Figs. 1 and 2 represent maximum deviations of ±25 per cent. Thus the use of the average curves can introduce considerable error. There is no substitute for accurate measurements of mud, mud cake, and mud filtrate resistivities at the well site. The mud sample tested should be representative of the mud opposite the formation being logged. The average mud filtrate resistivity curve of Fig. 1 is reproduced in Fig. 3 with two curves which have been published for clay-base aqueous muds2,3. The latter curves were determined from average values of a large number of drilling fluids. The three curves have essentially the same slope and the differences between them are from 7 to 22 per cent. Comparison is made only to illustrate the possibility of error

Jan 1, 1958

By R. J. Colony

MINING geology does not lend itself - very readily to a review embracing "improvements in methods," as perhaps do shop practices or laboratory procedures. The "methods" used in mining geology are simply the application of geology to mining; winning the ore, the handling of material, mechanical appliances, all belong strictly to mining proper, and have no place in a review of geology as applied to mining. A comprehensive review would necessarily cover a .very broad field, which could be subdivided into many -parts. Only a few of these can be discussed here. .Those that have been suggested to the chairman indude :

Jan 1, 1930

By Samuel M. Dunaway

INTRODUCTION ASARCO Incorporated purchased the East Tennessee Zinc Mines of the American Zinc Company and commenced operating on November 29, 1971. Presently, three mines are operating producing 6620 t/d (7300 stpd). The ore mined is sphalerite which occurs In lower Ordovician carbonates of the upper Knox Group and occurs in open space and fracture filling. Orebodies range from 3 to 46 m (10 to 150 ft) thick with dips from flat to 20º. The mining method is random room and pillar modified by shrinkage and bench stoping. Like other mining departments, the mining group at the Tennessee Mines Division is constantly looking for methods to improve productivity and safety and to reduce mining costs. This involves testing new equipment, trying new ore extraction ideas and making mining plant alterations to meet changes in operating conditions. The areas of change that will be described in this paper are longhole raising, jumbos and LHD loading, shaft sinking, conveyor transport of ore and sublevel haulage developments. LONGHOLED RAISES Raise driving has always been a hazardous occupation for miners and today it is becoming more difficult to get competent people for this kind of work. This problem has led us to seek an easier, safer way in which to excavate raises. The first longhole raises were excavated in the early 1970&apos;s using a Gardner-Denver air trac equipped with a PR-123 rock drill. The machine used 38 mm x 244 cm (1 ½ in x 8 ft) round rods with rope

Jan 1, 1977

By Davis M. Lapham

Ore bodies at Cornwall, Pennsylvania, have been mined since 1742 principally for iron from magnetite, but also for copper (in chalcopyrite), silver (in chalcopyrite), gold (in chalcopyrite), cobalt (in pyrite), sulfur, and crushed limestone aggregate. Metallization occurs as a limestone replacement above the essentially conformable, south dipping portion of a discordant saucershaped diabase sheet. Pre-Triassic and Triassic faulting have emplaced host Cambrian limestone and two Ordovician(?) hornfels units, now for the most part resting above diabase. Thermal metamorphism of carbonate-bearing country rocks largely to calc-silicates, is ubiquitous. Metasomatism, particularly of potassium, is unique to ore zones. Associated magnetite- actinolite mineralization replaces, in a preferential sequence, all earlier metamorphic and metasomatic minerals and rarely diabase chilled margin. Mineralogical (diopside, actinolite, mica, sulfides, oxides) and chemical (Fe, Cu, S, Co) zoning of the eastern ore body is focused down dip, near its western edge, along a major vertical fault through diabase. This zoning is spatially related to magnetite veins in diabase, to an ore body within diabase, and to a shear zone that probably extends through the sheet.

Jan 1, 1968

By R. M. Waterstrat, E. C. van Reuth

BINARY- alloy phases having the A15-type crystal structure have been described as occurring at a simple and more or less invariant stoichiometric composition (A3B) which corresponds to the relative number of atoms occupying each of the two crystallographi lattice sites in this structure.1,2 It is frequently assumed, therefore, that each crystallographic site is occupied exclusively by one kind of atom. In most cases, however, there have been insufficient experimental data to establish whether atomic ordering is, in fact, complete. Recent studies have shown that binary A15-type phases are sometimes stable over an appreciable composition range3&apos;&apos;* and, occasionally, the composition range of stability does not even include the "ideal" A3B stoichiometric composition.5-7 We have observed the existence of nonstoichiometric A15-type phases in the binary systems Cr-Pt and Cr-Os. This has not been reported in previous work on these alloy systems.1,8-11 A series of alloys, each weighing approximately 30 g, was prepared by are-melting in an Ar-He atmosphere using 99.999 pct Cr, 99.999 pct Os, and 99.99 pct Pt as starting materials. Each alloy was melted four times with a total weight loss of less than 1 pct. The stoichiometric (A3B) alloys were sealed in evacuated quartz tubes and annealed at 1200°C for periods of time ranging from 3 days to 2 months. Examination of the alloy microstructures revealed that little change had occurred over this time interval and it was therefore assumed that the microstructures were fairly representative of equilibrium conditions. No evidence of contamination was observed although there was apparently some loss of chromium which was confined to a thin layer at the surface of the specimens. The quartz tubes were quenched from the annealing temperature into cold water. X-ray diffraction and metallographic examination of the stoichiometric alloys revealed an estimated 10 to 30 pct of second phases which were tentatively identified as phases previously reported in these binary-alloy systems.8-11 A second series of alloys was prepared by mixing -325 mesh metal powders having a nominal purity of 99.9 pct and compressing these mixed powders in a cylindrical die at a pressure of 43,000 psi. These alloys, each weighing 15 g, and some of the arc-melted alloys were annealed in a high-temperature vacuum furnace heated by tantalum strips at a pressure of 10-8 Torr and were rapidly cooled by turning off the furnace power. X-ray and metallographic examination of both series of alloys served to establish the composition ranges of the A15-type phases. Although some chromium losses occurred during the vacuum annealing, they were largely confined to a thin layer on the outer surfaces of the samples. It was established that the A15 phases occur in the Cr-Pt system at 21 ± 1 at. pct Pt after 1 week at 1200°C and in the Cr-Os system at 28 ± 1 at. pctOs after 1 day at 1400°C (see Table I). We also observed that an arc-melted stoichiometric (A3B) alloy in the Cr-Ir system was single-phase (A15-type) in the "as-cast" condition in agreement with previous work.8,13 In addition we obtained a sample of the Cr-Os A15-type phase from Argonne National Laboratory. This alloy contained less than 1 pct second phase12 and was submitted to a density measurement. The density measurement yielded a value of 11.14 g per cu cm in comparison to a theoretical value of 11.25 g per cu cm calculated using the observed lattice constant (4.6806Å) of this alloy. The uncertainty in measurement was 0.1 pct but the sample may have contained some cracks or minor imperfections which could account for the low experimental value. We have also studied the atomic ordering in these phases by means of integrated line intensity measurements using thick, flat, rotating powder samples and CuK a radiation in an X-ray diffractometer. We have obtained order parameters of 0.90 for the Cr-Pt phase, 0.89 for the Cr-Ir phase, and 0.64 for the Cr-Os phase using the formula: where s is the usual Bragg and Williams order parameter, ra is the fraction of chromium atoms in A sites, and FA is the fraction of chromium atoms in the alloy. The values obtained are estimated to be accurate within ±4 pct. If the unusually small value for the order parameter of the Cr-Os A15 phase were due to the existence of lattice vacancies on the "B-atom" sites, then a density of 10.04 g per cu cm would be expected in contrast to the observed value of 11.14 g per cu cm. We, therefore. conclude that the fraction of lattice vacan-

Jan 1, 1967

By W. E. Bonini, E. A. Hickok

IN the course of an investigation directed toward expanding ground-water facilities in Essex and Morris counties, New Jersey, the Board of Water Commissioners of the city of East Orange authorized a seismic-refraction survey&apos; for the purpose of de-lineating bedrock topography below unconsolidated overburden. Results of the survey were highly satisfactory and led to the preparation of a comparatively detailed bedrock contour map. Knowledge of the bedrock depth and configuration was an important aid in selection of sites for test drilling. The portion of the East Orange Water Reserve under consideration is in the flood plain of the Pas-saic River about 10 miles west of Newark, N. J. The flood plain is about 175 ft above mean sea level and is bordered by low hills rising to elevations of approximately 250 ft. The bedrock underlying the Water Reserve consists of sandstone and shale of the Triassic Brunswick formation and is covered everywhere by deposits of unconsolidated glacial outwash sand and gravel, lacustrine clay, and recent river silt as much as 150 ft thick. Yield of wells in the sandstone and shale averages 100 to 200 gpm. Since production wells constructed in the sand and gravel aquifer in the buried river valley shown on the contour map (Fig. 1) yield 300 to 1400 gpm, it was proposed to locate additional production wells in this buried valley, where the yields per well would be maximum. In 1939 and 1946 the East Orange Water Dept. had electrical-resistivity surveys made to determine depths to bedrock. From the resistivity data the exploration company prepared a bedrock contour map. A well field expansion program begun in 1955 utilized this information to locate sites for test wells along a predicted northward extension of the buried valley in which existing production wells are located. After several test wells (wells 201-205) had been drilled, it became apparent that the resistivity information was unreliable." For example, test well 201 recorded bedrock at a depth of 72 ft, whereas the resistivity depth determination was 130 ft. As a consequence, the test drilling program was temporarily suspended and a seismic survey was under- taken to determine the topography and extent of the buried valley known from well records to underlie the existing well field. In the first phase of this study, several seismic shot point locations were placed at sites where well logs had been obtained previously. This procedure is necessary in a new area to determine whether the seismic method is applicable and what degree of accuracy is to be expected. At the East Orange Water Reserve, depths obtained from the shot points near test wells 202, 203, and 204 were within 8 to 11 pct of the depths logged (Table I). With this assurance that accurate results could be obtained, additional seismic spreads were located on the Water Reserve. Using a portable refraction seismograph, in the fall of 1955 a crew of four men shot a total of 29 reversed seismic spreads in a period equivalent to six field days. Charges as heavy as 3 1b of 40 pct dynamite were necessary at a few places to overcome ground vibrations caused by traffic on nearby highways. At most other sites, a 1-1b charge was sufficient. Travel-time plots were made for all spreads, and depths and true velocities were calculated according to formulas for multiple sloping layers by Ewing, Woollard, and Vine.&apos; The plot of spread 7 (Fig. 2) is typical of the short spreads in which bedrock was shallow—about 50 ft in this case. Where there were not enough arrivals through the bedrock to define the high velocity bedrock line, the spreads were lengthened. This was done by placing shots on line several hundred feet away from each end of the line of geophones. It was then possible to construct complete reverse plots for both short and extended shot points (see spread 27, Fig. 3). Four individual depths were calculated from each extended spread. Three and in some cases four seismic layers were observed. The surficial layer had a velocity range of 900 to 1200 fps, the lowest velocity recorded. This seismic layer is above the water table and is interpreted as recent river silt. The bedrock had the highest velocities, which ranged from 10,600 to 16,400 fps. Intermediate velocities ranged from 4500 to 6800 fps. In every case the intermediate layer was within

Jan 1, 1959

By H. E. Cook

The Ising model for the internal energy of a binary alloy has been used to obtain a general equation for the critical resolved shear stress of partially ordered crystals. The equation expresses the stress in terms of the Warren "alphas " and can be used to estimate the variation in strength with order without the assumption, present in the original formulation of this problem in terms of domain size, that order is complete within each domain and that the domains are of ungorm size and shape. In addition, it is the general equation, according to the Ising model, for strengthening by short-range order. Two applications of the equation are considered: One is an estimate of the variation in strength of CkAu with long-range order. The other is an estimate of the variation in strength of FeCo with quench temperature. Reasonable agreement is found with the variations reported in the literature. When the internal energy of an alloy crystal depends upon the distribution of solute, the strength of the crystal will also depend upon it because a portion of the applied stress for plastic deformation will be: where V is the volume of the crystal and E(E) is the energy change associated with the solute redistribution caused by the plastic strain, E. We expect T to equal zero for a crystal having a random arrangement of solute because the arrangement would remain random after plastic deformation. Likewise, we expect it to equal zero when the crystal is perfectly ordered because the motion of paired dislocations found in such crystals does not disrupt order. However, when short-range order exists or when long-range order is incomplete, plastic deformation will decrease the amount of order and additional work, proportional to the ordering energy, will be expended. Fisher&apos; estimated T for crystals having short-range order by assuming an interaction energy between neighboring atoms and estimating the change in the number of unlike neighbors as a dislocation moved through the crystal. (His analysis was limited and several workers2"6 have since given more complete ones.) Fisher minimized the importance of a strengthening mechanism of this type for paired dislocations in a structure having long-range order. ~ottrell,&apos; however, pointed out that T could be appreciable for ordered crystals having antiphase domains. He attributed the strengthening to the increase in surface energy of the domains as they were cut by paired dislocations. Ardley,&apos; in his test of Cottrell&apos;s theory, found that r for Cu3Au crystals obeyed the equation: for 1 > t where 1 is the domain size, t is the domain wall thickness, and y is the surface energy of an antiphase boundary. His experiments represent the classic confirmation of the strengthening mechanism proposed by Cottrell. However, the assumptions involved in using Cottrell&apos;s theory are valid only for large domain size in CU~AU,~"~ i.e., when Eq. [2] reduces to: For small domains, ~linn~ has questioned Ardley&apos;s assumption that order was complete, and, indeed, Stoloff and ~avies" fpnd it incomplete until a size of approximately lOOA was reached. Even when the order within a domain is complete, it is not obvious how one determines the appropriate value for I in a structure where domains vary in size and are irregularly shaped. The purpose of this paper is to estimate T without restrictions upon the degree of order and domain shape. Our major assumption will be the use of a generalization of the model proposed by Bethe" (the Ising model) for the internal energy. This will in fact allow us to combine the theories for strengthening by short-range order and by antiphase domains into a single, general formalism. We will use the results to estimate the variation in strength of Cu3Au crystals with long-range order8 and the variation in flow stress of FeCo crystals with quench temperature.12&apos;13 INTERNAL ENERGY For simplicity, we restrict our considerations to those binary solid solutions which can be described as an arrangement of atoms on a Bravais lattice. An atom site will be indexed by three numbers (PI, pz, p3) determined by the vector: from the origin fixed at atom (0, 0, 0) to the atom site where a&apos;, an, and a, are the lattice translation vectors. We write: For the energy of the crystal where pi(p) is the probability (either zero or one) of finding an atom of type i (i = 1, 2) at site (p), which is shorthand for (pl, pz, p3) and pj(p + r) is that for an atom of type j (j = 1, 2) at the site (p + r), which is shorthand for (pl + rl, The coupling parameter, resents the energy associated with the pair Pi(p), Pj(p + r). The crystal is assumed large enough so that surface effects can be neglected; therefore, trans-lational and inversion symmetry require the coupling parameters to obey the relations

Jan 1, 1969

By J. R. O’Connor

Stimulated emission from Nd+3 in yttrium uanadate fYVOJ is reported. Single crystals of YVO4:Nd, obtained from Linde Col-p., have improved substantially in the last several months. Pulsed thresholds of YVO, laser rods are now approximately 2 to 3 5, cowparable to tliose for YAG:Nd. Yttrium uanadate crystalli~es irz a space group similar to zircon. All rare-earth vanadates have this structure. Rare-earth ions sucll as Nd+3 which substitutes for Y+3, aye situated irz a strong tetragonal crystal field which lacks inversion symmetry. This condition increases the p&apos;robability of the parity-forbidden f — f transitions. Yttrium anadate has strong absorption bands beyond -1000A. These are clue to Y-O, V-O charge transfer and molecular transitions. Under 2537 and 3660A irradiation pure YVO, fluroresces u bright yel-LOLO. This fli&orescence is corrzpletely quenched in YV04:Ncl crystals. This and other evidence of energy trut~sjer from the lattice is repovted. Optzcul atz 1user pvope 1-ties o! YI&apos;U4:E[t are brieJy described. THIS paper describes some of the optical and laser properties of Nd+3- and Eu+3-doped yttrium orthovana-date (YVO4). It reports laser action for the first time in this low-symmetry host. For some time we have pursued a research program concerning laser hosts&apos; wherein the rare-earth (RE) ion is situated at a site of low crystal symmetry so as to increase the probability of radiative transitions. Single crystals of doped and undoped YV04 are grown from iridium crucibles in an oxyhydrogen gas-fired furnace by a modified Czochralski technique.&apos; This material crystallizes in a D4li tetragonal space group of the zircon (ZrSiO,) type.3 All RE vanadates have the same structure and form solid solutions with YVO4. Therefore, it will be possible to investigate a variety of cross-pumped laser systems, as in the case of yttrium aluminum garnet (YAG).4 At present, ~d&apos;~-doped YAG is one of the most efficient solid-state lasers.5 Accordingly, most of the material to follow will compare the properties of YV04 to those of YAG. Fig. 1 shows the relative transmission of YAG and two types of YVO4. "Pure" YVO4 has a normal absorption edge and is colorless. A second type has a broad absorption peaking near 4200A and is yellow. Rubin and Van uitert6 suggest the yellow material is slightly reduced. Samples of each type are being investigated by electron spin resonance,7 but these studies are so far inconclusive. The pulsed laser threshold is much lower in the yellow material than in the colorless. Therefore, the absorption at 3500 to 5000.4 transfers energy to the Ndi3 ions. Photons of wave length between 2000 and 4500A cause undoped YVO4 to fluoresce at 4800, 5250, 5460, 5540, and 5750A. This emission, previously reported by Brixner and Abramsom,8 is partially quenched by EU&apos;~ and completely quenched by Ndt3 at room temperature due to energy transfer from the lattice to the RE ions. At low temperatures, some lattice fluorescence is present. This implies that the energy-transfer process is in part phonon-assisted. Although the YVO, single crystals used in this work were prepared from Y2O3 containing less than 0.01 pct rare-earth impurities, there is aopossibility that emission lines between 4800 and 5750A are due to dysprosium, terbium, and so forth. However, these lines are not observed in other compounds, prepared from Y2O3, such as YP04, Y2MoO6, and so forth. Furthermore, extensive absorption measurements on our "pure" YV04 single crystals between 0.4 and 5.0 failed to reveal any characteristic rare-earth lines. Fig. 2 compares the absorption spectra of Ndt3-doped YAG and YVO4from 0.6 to 1.0 . The Ndt3 absorptions are labeled according to free ion, R-S coupling. These term designationsQ are appropriate for YAG:Nd. They appear to be inappropriate for YV04:Nd. In YVO, neodymium must substitute for yttrium. The yttrium site is situated In a strong tetragonal field, where point symmetry is (42m) or possibly lower.1° However, the reduced splitting of the Stark components of the YV0,:Nd spectrum implies that the NdT3 ion is in a cubic site. The only plausible explanation for this discrepancy is that the Ndt3 ion is in a low-symmetry site, lacking inversion symmetry, so that a substantial admixture of 4f and 5d wave functions occurs. In this case, R-S coupling is not valid and J is no longer a good quantum number." Consistent with this view, the 4~ metastable level of YV04:Nd has an oscillator strength larger and a

Jan 1, 1968

By M. L. Rudee, R. A. Huggins

Samples of iron containing nitrogen or carbon have been given treatments similar to those used in cold-work peak (CWP) measurements and examined by transmission electron microscopy. It was observed that the unusual and nonreproducible behavior of the carbon CWP can be explained by a strong tendency for carbon to form grain boundary precipitates at temperatures below those used for CWP measurements. These precipitates dissolved at the temperatures used in the CWP measurements. There was no evidence for nitrogen precipitation at grain boundaries. There was no indication of precipitation along dislocations in either carburized or nitrided samples given treatments similar to those of CWP measurements. Although it is possible that subelectron-microscopic clustering had occurred, this observation supports the theories of the CWP that are based on continuous atmospheres rather than on individual precipitates. In an earlier paper,&apos; the present authors developed a new distribution function to predict the occupation of sites for interstitial impurity atoms around a dislocation. When this distribution was applied to the case of carbon and nitrogen in iron, it predicted that, if the temperature dependence of the concentration of solute atoms in the matrix was controlled by the presence of equilibrium carbide or nitride precipitates, the tendency for nitrogen to segregate to dislocations would be greater than that for carbon even though their binding energies to dislocations are identical. The cold-work internal-friction peak (CWP) is considered by most authors to be produced by the interaction of interstitial impurities with dislocations. Many investigators have studied the CWP in iron containing carbon and nitrogen and have observed a significant difference between its behavior in the two cases. In this paper a series of experiments will be reported that were initiated to determine whether the application of the new distribution function would explain the observed differences between the carbon and nitrogen CWP. Although it was found that the distribution function, pev se, did not explain the differences, the differences became clear, and some insight into the mechanism of the CWP was realized. Before reporting the present experiments, the literature pertaining to the differences between the carbon and nitrogen CWP in iron and the various mechanisms proposed for the CWP will be reviewed. LITERATURE REVIEW Snoek2 first observed the CWP in iron specimens containing nitrogen, but also reported a weak and unreliable peak in carburized samples. Later, Ke3 established that the CWP height was proportional to the degree of deformation. The presence of nitrogen alone would produce a peak of the same size as found in a sample containing both nitrogen and carbon, and KG concluded that the CWP was caused by nitrogen. In a discussion of G&apos;s paper it was reported that Dijkstra had investigated the CWP in samples that contained only carbon. He found it to be much smaller than the nitrogen peak and "unstable". KG et al.4 charged specimens of iron with both carbon and nitrogen. They observed that the carbon CWP was much smaller than that observed in nitrided samples, but that aging at 300°C caused the carbon peak to increase. A similar treatment produced no change in a nitrogen peak. Annealing at higher temperatures caused the height of the CWP in both the nitrogen and carbon samples to decrease. This behavior was also observed by Kamber et al. 5 who found that the activation energy for the annealing of the CWP was identical with the activation energy for the self-diffusion of iron. They concluded that the annihilation of dislocations by climb caused the reduction in the CWP height. Kamber et al. studied the "unstable" carbon peak in detail. They measured both the Snoek and CWP during various aging treatments. In carburized samples, aging at 100°C caused the Snoek peak to disappear, although the CWP peak remained small. However, a subsequent treatment for 5 hr at 240°C caused the CWP to reach a maximum. They proposed that an additional location for the carbon, other than whatever site produced the CWP, is present. In nitrided samples the CWP was completely developed as soon as a measurement was made; additional sites are not present. No explanation of either the additional site or the difference in the behavior of carbon and nitrogen was offered. petarra5 performed a systematic study of the effect of composition on the CWP. Using three kinds of "pure" iron, he showed that there was a residual CWP when the carbon and nitrogen concentrations had been reduced to less than that detectable by Snoek-peak measurements. He observed the same general annealing behavior and composition dependence as previous investigators, with the following exceptions. On first measuring the carbon CWP, it was found to be identical with the residual peak, and essentially independent of the carbon content. If the CWP was measured a second time in the same sample, it increased in size, but was still only about one-fourth the size of a CWP in a sample of the same iron nitrided to the same composition. On the other hand, a series of annealing experiments showed that the nitrogen CWP was not al-

Jan 1, 1967