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By Grant Buma

The purpose of this paper is to present arguments and evidence that there are natural processes at work which tend to minimize the impact of solution mining on the environment. The contaminants have two sources. First are elements which were present in the roll-front deposit in insoluble compounds, for example, uranium in uraninite and coffinite, molybdenum, arsenic, iron, cobalt, nickel, etc. in sulfide minerals, vanadium in micas and clays, etc. Second are elements introduced by the leach liquor. Precipitation of reduced compounds, scavenging of heavy elements and absorption by quartz and clays, can all reduce the amount of heavy elements in solution. If a roll can be demonstrated to be actively precipitating uranium and heavy metal elements, then the presence of precipitants (pyrite and carbon) can be assumed. Criteria for recognizing an active roll are described.

Jan 1, 1979

By N. A. Gokcen, John Chipman

D. C. Hilty (Union Carbide and Carbon Research Laboratories, Niagara Falls, N. Y.)—This paper is a very nicely detailed analysis of a difficult problem. I would like to point out that the results that Mr. Crafts and I published a few years ago had no reference to activity, or anything else of a similar nature; our results were strictly empirical. It is quite gratifying that we now have a case where results involving activity coefficients and results derived from direct observations on actual steel melts are practically identical. When two different laboratories, working from two entirely different approaches, come out with results in such good agreement in their major significance, that is an achievement. It is something that was not possible 15 or 20 years ago. There is one question I would like to ask Dr. Chip-man. It has to do with a very minor point of disagreement in these results. When we reported the kink in the Si-O solubility curve I think you may recall that it came at the different temperature levels at about the order of 0.015 to 0.03 pct 0 and 0.03 to 0.07 pct Si—we also pointed out that we had difficulty in obtaining data at that level, although we finally did get some. I note in going through the data for the present paper, that there are no samples in those particular silicon and oxygen ranges. I wonder if that was purely accidental or was there a reason for it. D. E. Babcock (Republic Steel Corp., Youngstown, Ohio)—Mr. Hilty, do you have any explanation for that discrepancy between Dr. Chipman's curve and your own Mr. Hilty—Our explanation for it at that time was that for some reason our system probably was not in true equilibrium with SiO, that is, in equilibrium with the silica crucible at that level. We did observe, however, that that was the level at which both the metal and the slag became saturated with SiO,. On the average, in studying inclusion formation in small ingots permitted to solidify normally from the molten state, we observed pure silica inclusions at silicon contents over about 0.05 pct and FeO type inclusions at silicon

Jan 1, 1953

By Haakon Styri

In discussion of Dr. Fitterer's paper on electrolytic separation of slag inclusions, some results from experiments on electrolyzing high-carbon steels at the SKF Research Laboratory were given. l We had been working for a number of years on chemical methods of separating the inclusions but could not find any solvent that would dissolve the steel without attacking some of the inclusions, particularly the sulfides in which we were mostly interested at the time, nor any that would dissolve all sulfide or silica in filings as fine as 300 mesh without attacking the iron. Electrolytic methods had also been tried without any real progress until we learned from the Bureau of Mines about the use of the collodion membrane around the anode. Our early difficulties were to some extent different from those of the Bureau of Mines, perhaps because of experimenting on steels of higher carbon content, but most of our difficulties were of the same nature as those of the Bureau. Formation of large quantities of basic hydroxides was traced to the use of impure and oxidized ferrous sulfate. To protect from oxidation from the atmosphere during electrolysis, after purer chemicals were obtained, a thin layer, 54 in. or less, of molten paraffin was poured over the surface of the cathode liquid, where it solidified. It was found desirable also to hold the cathode chamber slightly acid by initial addition of 0.1 per cent acid (sulfuric or hydrochloric) to prevent precipitation of the hydroxide. This acidity would decrease gradually and the cathode chamber would become neutral before the end of the electrolyzing. The increase in acidity in the anode chamber during our early experiments had appeared to cause attack of the precipitated sulfides in the residue, which originally was analyzed by volumetric method for sulfur, and for this reason a 10 per cent sodium citrate solution was substituted for the sulfate in the anode chamber. With the use of the more reliable Eschka method for sulfur determination (as in coke), there was however no serious attack on the sulfides in the anode chamber with a variety of different liquids, as shown in Tables 2 and 4. The Eschka method gives a higher sulfur value than

Jan 1, 1933

By H. J. Wasson, E. B. Hopkins

Throughout 1928, production of oil from Venezuela steadily increased, and at the close of the year, the output was at the rate of nearly 400,000 bbl. a day. The total for the year was approximately 106,500,000 bbl., representing an increase of about 66 per cent. over the 63,000,000 bbl. produced in 1927. Venezuela now stands next to the United States as the second largest oil-producing country in the world; and there is abundant evidence to suggest that this relationship will endure for a number of years. Reserves were notably increased in the Lake shore fields, and the potential output of the Maracaibo Basin is much greater than the current production. In spite of this, the percentage of production increase was comparatively moderate, and the rate of this increase continued to fall off slightly, as has been the case for the last three years. This does not suggest that further annual increases in Venezuelan output will not materialize; only that the rate of these increases appears to be on the decline, and that with every succeeding year the future tendency will be in the direction of a stabilized level of output. The following table shows the production trend of the country since 1925: 1925 increase over 1924, 132 per cent. 1926 increase over 1925, 80 per cent. 1927 increase over 1926, 75 per cent. 1928 increase over 1927, 66 per cent. Many factors will work to prevent a reversal of this trend, but the principal ones are strong ownership in large-acreage units, and the probable indisposition of the world market to absorb a more rapidly increasing Venezuelan output at prices profitable to the producers. The distress oil element is not a factor in Venezuela; also, any unforeseen jump, such as results in the United States from the discovery of a Seminole or a deep sand at Long Beach, or Santa Fe Springs, is impossible in Venezuela, on account of lack of means for transporting a sudden surplus of oil, and the slowness with which additional transportation equipment in the form of shallow-draft tankers can be obtained.

Jan 1, 1929

By Folke H. Kihlstedt

Geophysical prospecting for ore has been more or less at a standstill during the present crisis owing to the lack of interest in base-metal exploration. A notable exception is the increased use of electrical and magnetic methods in prospecting for gold, the former in Canada, United States, Sumatra, Africa and Western Australia, and the latter on the Rand. This application to gold prospecting marks a forward step in ore prospecting because it is based upon mapping the geology instead of a direct location of the ore in question, as the amount of gold in an average gold ore is far too small to have any influence upon the physical properties of the rock in which it occurs. The development has thus gone in the same direction as geophysical prospecting for oil; that is, to find geological conditions that are genetically connected with the gold ore as exemplified by known occurrences. Naturally the success of this indirect prospecting depends upon two things: (1) the soundness of the geological conclusions upon which is based the hope of discovering new deposits, because a great many geological "set-ups" are barren, and (2) the ability of geophysical methods to help the geologist to collect the pertinent geological data within reasonable cost, after which favorable structures may be drilled or trenched. The first point is one to be considered by the mining geologist. In the vicinity of producing mines or promising prospects, the chances of finding ore in quartz veins and shear zones are great, and a survey giving the location of these features will materially guide both surface and underground exploration. Even in outside exploration the chances are sometimes favorable. As an example may be taken the Northeastern Ontario-Western Quebec gold zone. Large areas are here covered with glacial and post-glacial deposits and a simple study of available maps reveals the fact that less than 30 per cent of the area can ever be even preliminarily prospected by cominonly used prospecting methods, of which the pick and shovel are the main tools. Considering the number of deposits found, it is evident that many deposits remain hidden below the overburden. The knowledge of gold geology gives a starting point

Jan 1, 1934

By Paul C. Ragland, P. Geoffrey Feiss

The Piedmont province of the southern Appalachians is the focus of interest for many exploration geologists. In the past, only those deposits with significant surface exposure were exploited. Thus, few deposits have been found and relatively little exploration has been conducted in recent years. Modern geochemical and geophysical techniques can alleviate this problem of concentrating on exposed ore bodies by allowing us to "look through" the soil and saprolite to detect the presence of significant mineralization at depth. This paper will attempt to evaluate the feasibility and effectiveness of several geochemical exploration techniques in the Piedmont province of Cabarrus and Stanly counties, N.C. The area chosen for study is shown in [Fig. 1], lying almost wholly within the Mt. Pleasant quadrangle, N.C. The area is on the eastern boundary between the Charlotte belt, a zone of plutonic and intermediate grade metamorphic rocks, and the Carolina Slate belt, a series of complexly interbedded volcanic and sedimentary rocks of predominantly low metamorphic grade. The area is considered to be an early Paleozoic active, continental margin. l As is typical of most of the piedmont, outcrop is sparse. [Figure 2] is a sketch map of the general geology of the area under study, showing the Charlotte belt rocks in the northwestern quadrant and slate belt rocks to the east. Within the area are a number of old mines and prospects, the most famous of which are the Furniss and Phoenix mines in Cabarrus County. All are reported to have contained Au and Cu. Ag and Pb were reported from some. A summary of the deposits is given in [Table 1]. Data used in this study are from three Master's theses completed at the University of North Carolina at Chapel Hi11. 3, 5, 6 In separate studies, well waters, 5 B-zone soils,3 and vein and float from the area were sampled and analyzed. Each study concluded separately that geochemical anomalies in the vicinity of the ores justify use of that specific sampling technique in a geochemical exploration program. However, no comparative study of the methods has been made. It is our intention

Jan 1, 1980

By R. M. Brick

AN increased demand for information in regard to the effect of gaseous elements in steel has accompanied the recognition of the importance of grain size. Attempts to correlate grain-size characteristics with gas con-tent, particularly oxygen in solution or in the form of included metallic oxides, have not been universally successful. Certain definite effects of dissolved gases are recognized; specifically, the role of hydrogen in causing internal cracks or "flakes" and that of nitrogen in preventing excessive grain growth of ferritic chromium steels. When irregular behavior or properties are found in a well-known steel and no definite cause for the abnormality may be assigned on the basis of chemical and metallographic tests, dissolved gases are frequently blamed as the culprits. The solubilities of hydrogen1 and nitrogen2 in pure liquid iron are known but of the ternary systems, iron-alloying element-gas, only the Fe-Si-N3 and Fe-Cr-N systems have received attention and here the study was confined to liquid alloys. Krivobok4 published a curve show-ing the solubility of nitrogen in liquid Fe-Cr alloys but gave no informa-tion on the experimental procedure employed. The considerable experimental work reported on the Cr-N binary alloys has been reviewed by Hansen.5 It is generally agreed that the nitride CrN is a stable phase although the existence of nitrides within limited temperature ranges of stability, viz., Cr3N2 and Cr2N, has been disputed, Adcock6 and others7 have reported a eutectic between Cr and CrN at 1580°C., although the supporting evidence is not complete.

Jan 1, 1940

By Francis B. Foley

In examining steel under the microscope, one is constantly confronted with structures that are difficult to interpret. Recently, in a collection of samples for exhibition purposes, the writer found a piece of open-hearth runner metal, 2 in. (50 mm.) in diameter, that had been fractured for use as a sample of cast-steel structure. On polishing and etching a section for the purpose of photographing a field to typify the microstructure of steel in the "as cast" condition, a variety of structures was found (Fig. 1) so arranged as to arouse interest at once. For a distance of about 0.065 in. (1.6 mm.) from the skin of the runner, normal ingot structure was found (Fig. 2); this was followed by a zone, about 0.215 in. (5.5 mm.) wide, of considerably lower carbon content in which occurred a most pronounced Widmannstattian structure (Fig. 3); from this point on to the center of the runner, the metal was again of normal ingot structure (Fig. 4). Representative samples taken from the metal in the three zones showed the following analysis: Carbon Nickel Chromium Per Cent. Per Cent. PeR Cent. Metal from skin........................... 0.34 1.26 0.63 Widmannstattian zone.................... 0.21 1.18 0.63 Metal from center......................... 0.34 1.32 0.67 Such a condition might result from decarburization followed by recarburization of the skin. This section came from one of the branch runners to the bottom of the mold, not from the main runner, and it is difficult to conceive of decarburization occurring in this portion of a runner. If the metal were stripped while quite hot, some oxidation would take place but the recarburization is unaccounted for. It could not occur by segregation after solidification—the tendency then is for diffusion and homogeneity. The following seems to fit the conditions and is offered as an explanation. The outside layer of normal structure 0.065 in. (1.6 mm.) thick was chilled on the walls of the runner brick when the molten metal first entered the runner. As the molten metal flows by, the outside of the stream

Jan 1, 1920

By J. E. Miller, W. E. DeVaney, L. Stroud

During a recent phase study of a natural gas, two stable equilibrium liquid phases were observed at temperatures below —200°F and pressures above 200 psi. This paper reviews the published literature on the occurrence of multiple equilibrium liquid phases and presents analytical data for the vapor and two equilibrium liquid phases of the liquefied natural gas at five experimental conditions. In addition, data for 30 conditions of two-phase equilibria are included. INTRODUCTION The low-temperature phase behavior of gases, most of which contained helium, has been investigated in the laboratories of the Helium Activity for many years. Since 1952, experimental studies of these systems have been continuous as part of the research program at Amarillo, Tex. Because of their value to private industries interested in participating in the Helium Conservation Program, several "Open File" reports containing phase equilibria data for heliurn-bearing natural gases have already been released by the Helium Activity. A paper containing information on the general phase behavior, operating criteria and extensive vapor-liquid data for two helium-containing systems was recently published.2 Additional publications presenting experimental data on the phase relationships of various gas systems are now in process and will be available in the near future. PREVIOUS EXPERIMENTAL WORK Although the formation of multiple liquids has been reported for various systems, to our knowledge this paper is the only substantiated evidence of a vapor-liquid-liquid equilibria in a naturally occurring gas. In 1940, Vink, Ames, and others13 reported the presence of two liquid phases in a hydrocarbon system consisting of mixtures of crude oils, solvents and natural gas. Eilerts and co-workers; published data on the recombined fluids from a gas-condensate well. This condensed gas, containing approximately 76 per cent methane and 24 per cent ethane-plus, exhibited two distinct liquid phases. Weinaug and Bradley 14 observed "unusual" phase behavior in a reservoir mixture. These workers postulated that the anomalous phase behavior was due to the "imminent formation of a second liquid phase". Botkin, Reamer, Sage and Lacey 1 studied two California crude oils that exhibited multiple phases. Kohn and Kuratal0 recently reported two equilibrium liquid phases in the methane-hydrogen sulfide system. Roof and Crawfordl1 and Eakin, et a16 also have reported experiments with binary systems that formed two stable equilibrium liquid phases. APPARATUS AND PROCEDURE A U. S. Bureau of Mines Phase Equilibrium Apparatus was used in conducting this study. The apparatus and procedures employed in its operation have been previously described3 and will not be repeated in detail ill this report. Briefly, the apparatus consists of a windowed cell which can be maintained within ±0.5°F for temperatures between room temperature arid -320°F. Pressure within the cell can be maintained within 0.1 per cent of gauge reading up to 800 psig. Equilibrium vapor and liquid samples are obtained in special containers4 for analysis by a mass spectrometer. Although the accuracy of the analyzer is about ±0.1 mol per cent, the reproducibility of the phase-equilibrium apparatus is considered relatively poor. Values reported from methane and nitrogen are considered accurate to ±l.0 and ±0.6 mol per cent. Data for ethane-plus in the vapor are accurate within 0.2 mol per cent; liquid-phase data for this aggregate compolnent are accurate within 1.5 mol per cent. For helium in the vapor phase, the analytical data are accurate within 0.2 mol per cent; liquid-phase analyses for this component were obtained by the charcoal adsorption method described by Frost8 and are accurate within 0.006 mol per cent. All of these references to the accuracy of reported values are conservative estimates based upon a statistical treatment of reproducibility data obtained with the apparatus.

By Chester T. Sims

RECENTLY, a new type of superalloy material called TD Nickel* has been marketed.' It is a sim- ple, two-phased alloy, consisting of thoria particles dispersed in nickel of rather high purity (Ni-2 pct Thoz). Its mechanical properties appear relatively superior to previous experimental material attempting to use the oxide nonmetallic dispersion concept (except SAP), and superior to conventional nickel-base alloys at high homologous temperatures. This is derived from an interesting method of creating the dispersion, arising during chemical processing of the nickel and thorium salts in solution while reducing the nickel to metal. An evaluation of the thoria phase was conducted at this laboratory. Material and Procedure. TD Nickel was made available, consisting of several inches of 0.470-in. rod, extruded at a ratio of 64: 1, straightened, and centerless ground. Property determinations on this rod by the supplier at 1800°F showed an ultimate tensile strength of 11,400 psi, yield strength of 9600 psi, and 6 pct elongation. Specimens were removed from the rod for as-extruded metallography, and two 1/2-in. lengths supported on high-purity Al2O9 bricks were placed in a laboratory muffle furnace for exposure at 2000° F. The furnace door was left cracked to allow a slight amount of circulation. One specimen was removed at 200 hr for examination; the other was left for 2000 hr. Metallography. The micro structures obtained for the three conditions of exposure are shown in Fig. 1. Elongation of the grain structure in the extrusion direction is readily evident. The grains appear to be up to 0.001 in. (0.003 cm) long, with a length/width ratio of about 10: 1. Allowing for modest local in-homogeneities in structure, no significant change in thoria particle size or nickel alloy grain size occurred during the 2000°F exposure. However, etching depth varies slightly from one specimen to another, changing the number of particles visible. The thoria dispersion appears to be in the order of 0.01 (min) to 0.5 (max) p diam. The minimum diameter is difficult to estimate at X10,000, and may be less. Interparticle spacing appears to be about 0.1 p. Etching effects can be seen, depending upon grain orientation. A cubic etch-pit pattern appears in certain grains, apparently when etching is started by an anodic particle of thoria, Fig. l(c). The cubic pattern appears related to crystallographic orientation, and is prominent when the [ l00 ] direction is perpendicular to the plane of polish. The grains which present a ridged appearance in the photograph appear to be oriented with the [110} direction perpendicular to the plane of polish. Analysis. The thoria particle size was measured by a line intercept method perpendicular to the extrusion direction. Only particle sizes measuring 0.001 in. at X10,000 or larger could be extimated. Within limits of experimental error, particle size distribution appears to be unaffected by exposure, Fig. 2. To check structural stability further, a grain-growth evaluation was made. The number of grain-boundary intersections was counted at X500 on each of several traces normal to the extrusion direction for each condition. It can be seen from Table I that grain diameter appears unchanged by the 2000°F exposure. The slightly finer grain diameter after 200 hr may be attributed to variations in grain size from area to area in the original extrusion. From the present rather limited study of Ni-2 Th on, it appears that: 1) for time-temperature exposure up to 2000 hr at 2000°F (Larsen-Miller parameter = 57, homologous temperature = 0.8) thoria particles of the size studied are highly thermally stable; they do not significantly react, agglomerate, or diffuse; and

Jan 1, 1963

By T. M. Geffen, J. L. Sanderlin, F. F. Craig, D. W. Moore

Scaled reservoir models have been used to study the effect of gravity on oil recovery performance in frontal-drive operations; namely, water, gas, or solvent flooding. The difference in density between the reservoir oil and the injected fluid causes their segregation, resulting in a non-uniform advance of the fluid front. In the laboratory flow tests, which simulated both five-spot and linear injection operations in flat reservoirs, the viscous, capillary, and gravity forces present in these operations were scaled. Dyed fluids were used so that the gross movement of the injected fluid could be observed. The studies covered a range of injection rates, formation thicknesses, and rock and fluid properties normally encountered in field operations. The results of the model tests indicate that the volume of the reservoir contacted by the injected fluid at its breakthrough into the producing well is less than that expected based on information which neglects gravity effects. This difference can often be as much as 80 per cent by gas or water injection in uniform sand bodies. Preliminary flow tests on a non-uniform sand body indicate that the uniformity of the flood fronts may in some situations be influenced to a much greater degree by permeability variations within the rock body than by gravity effects. The magnitude of fluid segregation due to gravity is controlled by the average injection rate, rather than day to day or week to week variations. INTRODUCTION One of the important factors controlling the oil recovery from a frontal-drive operation, such as water, gas, or solvent injection, is the volumetric sweep efficiency. This factor is a measure of the gross portion of the reservoir that is contacted by the displacing fluid. The volumetric sweep efficiency is influenced by gravity effects, well arrangements, and variations in rock permeability within the reservoir. The gravity effects are due to the displacing fluid being of different density than the reservoir oil. This causes the displacing fluid to move preferentially toward either the top or bottom of the formation. Non-uniform advance of the flood front can be caused by the relative positions of the injection and production wells. Variations in rock permeability also result in an uneven advance of the displacing fluid. Gas zones, representing paths of low resistance, may result in non-uniform movement of the injected fluid. The more uneven the advance of the displacing fluid, the lower is the volumetric sweep efficiency and thus the lower the oil recovery efficiency. The effects of well arrangement and permeability variations, upon the gross movement of the injected fluid have been the subjects of extensive investiga-ti0ns.1,2,3,4,5,6 Gravity effects have been recognized as being present in frontal-drive operations'.' but there has been little quantitative measure of their magnitude. Very likely the reason gravity effects have not been studied is that this problem does not lend itself to simple experimental or mathematical analysis. The development of reservoir modeling techniques has made possible a quantitative determination of the effect of gravity on fluid segregation and thus upon the oil recovery performance of frontal-drive operations. This paper presents a progress report on a laboratory investigation of gravity effects in fully liquid-saturated, horizontal, uniform as well as non-uniform systems. These results were obtained from scaled experiments on both linear and five-spot systems within the range of conditions normally encountered in secondary recovery operations. This study is concerned with the gross movement of the injected fluid to the time it first reaches the production wellbore. Therefore, it should be emphasized that the results of this paper can not be used to determine the effect of gravity segregation on oil recovery efficiency at abandonment conditions. MODEL SCALING The science of scaling models is relatively new as applied as petroleum production problems, Many of the scaling techniques have been adaptions of those used in basic studies of heat and fluid flow. There are

Jan 1, 1958

By W. C. Hagel, J. H. Westbrook

Usittg a sectioning technique with Agl10 as the tracer, the diffusion of silver in silver-excess (45.8 at. pct Mg), near-stoichiometric (49.8 at. pct Mg), and magnesium-excess (52.0 at. pct Mg) cylinders of CsCl-type AgMg was determined from 500" to 700°C. Diffusion coefficients conform to the expression D = Do exp (-q/RT) where the respective Do values are 1.53, 0.280, and 0.134 sq cm sec-I and the Q values are 41.3, 40.6, and 38.0 kcal g-atom-'. Lnttice-parameter and density measurements were performed on a more numerous assortment and wider range of compositions. Substitutional defects were found on both sides of stoichiometry. Activation energies for other rate processes in these alloys show related trends with changing composition, although silver may not be the rate-detemining species. KNOWLEDGE of diffusion coefficients is necessary for a quantitative understanding of the many rate processes (e.g., grain growth, precipitation, sintering, oxidation, or mechanical deformation) occurring in solids. Although these data are available for most metals and common alloys, they are quite limited for intermetallic compounds—a group of materials whose unique physical and mechanical properties are presently attracting great interest. From a fundamental viewpoint, diffusion in intermetallic compounds also offers several engaging aspects owing to: their ordering, the possibility of introducing large, stable concentrations of lattice defects, and the variety of bonding types and crystal structures which can be found. In the case of CsC1-type compounds, some previous work has been directed at examining the role of vacancy defects by changing their concentration compositionally. The diffusion of Co60 was measured in 0 NiAl1- and in P COA., Except for the results of Smoluchowski and Burgess, isothermal diffusion coefficients were found to pass through a minimum at the stoichiometric composi- they decreased sharply on what was reported by Bradley and co-wrkers' to be the vacancy-rich (aluminum excess) side of stoichiometry. This investigation of the diffusion of Agl110 in AgMg was undertaken both as an adjunct to a concurrent study of its deformation behavior and for the purpose of obtaining information on the influence of lattice defects and temperature on diffusion in another CsC1-type intermetallic compound. Bcc AgMg remains ordered up to and melts congruently at 820°C. Solubility limits at 300°C are about 41 at. pct Mg and 53 at. pct Mg. It is one of the Hume-Rothery electron compounds with a 3/2 electron-atom ratio. Previous investigations of its properties include hardress,' tenile,'-' electrical reistivity, and thermodyna-mic1',14 studies. Indications of a high bonding strength may be found in the large heat of mixing1' and in the 6-pct vol contraction on compound formaticp, as calculated using atomic radii of l.40 and l.55a for Ag and Mg. EXPERIMENTAL PROCEDURE Alloys were prepared by the induction melting of selected fine silver (99.95) and low-iron magnesium (99.95) in magnesia crucibles under 1 atm of A. Supplied by the Handy and Harmon and Dow Chemical Cos., respectivelv. Melts were poured under argon into graphite molds providing 1 1/8-in.-diarn. by 4-in.-long ingots. These were homogenized in evacuated and argon-filled fused-silica capsules by heating for 16 hr at 750'. Three 1 in.-diam. by 3/4-in.-long cylinders were machined from the mid-portion of each ingot for diffusion measurements. Three alloys, analyzing 45.8, 49.8, and 52.0 at. pct Mg were taken as representing the extremes of interest, with 49.8 at. pct Mg being very close to the stoichiometric composition of 50.0 at. pct Mg.

Jan 1, 1962

By Cuppam Dasarathy

The incidence of liquid inzmiscibility in binar)) indium alloys has been theoretically analyzed on the basis of the Hildebrand-Alott equation. Bedictions of miscibility or otherwise Imve in general been found to agree with those phase diagrams that are already publislzed in the literature. Out of a total of 27 systems, where either the complete phase diagrams are published or liquid immiscible behavior is reported, the Predictions agree with the experimental data in 25 systems, the exceptions being the Te-In and Ni-In systems. According to the equation, liquid immiscibility is also indicated in the binary alloys of indium with K, Rb, Cs, Na, Sr, Ba, Ti, Zr, V. Nb(Cb), Ta, W, U, Re, Ru, Rh, Os, and Ir. RECENT investigations by the author have shown that indium when alloyed with iron, chromium, and cobalt shows liquid immiscible behavior.1"3 The Fe-In phase diagram shows a wide range of compositions where the liquids are immiscible.4,5 No intermediate phases are present in this system. No precise information is available about the extent of liquid immiscibility in the Co-In system. However, it is certain that there is a range of compositions where the liquids are immiscible and that there are two or three intermediate phases,376 in the system. Liquid immiscibility is also strongly indicated in the Cr-In system and no evidence was obtained in the brief investigation to indicate the presence of intermediate Cr-In phases.2 The present paper deals with a theoretical analysis of binary alloys of indium with certain elements of the periodic table and indicates the systems where liquid immiscibility may be expected. The incidence of liquid immiscibility in binary systems has been theoretically examined by many workers and many excellent papers are available on the subject. In this paper, the alloy systems are examined on the basis of the more recent ideas proposed by Mott.7,8 It has been claimed8 that the Mott parameter predicts the incidence of miscibility or otherwise with reasonable accuracy and consistency. BACKGROUND TO MOTT&apos;S APPROACH Hildebrand applied his immiscibility rule for non-polar liquids to various alloy systems.9 The basis of this rule is that the equation for the excess free energy of formation of a liquid solution is rather similar to the theoretical expression for the energy of mixing of a regular solution. He postulated that when the heat of mixing is sufficiently high, separation into liquid phases will occur and the condition for complete CUPPAM DASARATHY is at the Research Centre, British Steel Corporation, (South Wales Group), Port Talbot, Glamorgan, Great Britain. Manuscript submitted March 12, 1969. IMD miscibility was shown as where VA and VB were the atomic volumes of the components A and B, and ?EV the energy of vaporization of the component. The term (?EVA/VA)1/2 was regarded as a measure of the binding energy of the component A and was called the L&apos;solubility parameter" 8A. On this basis immiscibility occurs when 1/2(VA+VB)(bA-bBf > 2RT [2] Apparently, however, there were several inconsistencies in that according to Eq. [2] several systems known to be miscible in the liquid state were predicted as immiscible. MOTT&apos;S ANALYSIS ~ott&apos;" regards that the reason for the inconsistencies arising out of Hildebrand&apos;s equation was largely due to the electrochemical attraction between the two elements, not being considered. Hence, Eqs. [I] and [2] were modified by taking into account the electro-negativities of the two elements XA and XB, and Mott arrived at an equation for immiscibility, i(VA + VB)(6A - aB)2 - 23,Q60n(XA - XBf > 2RT [3j which can be written as i **&£*&* >&apos;*°™- &apos;• HI T being the melting point of the more refractory component of the system. In Eq. [4], the numerator was called the Hildebrand term, the denominator, the electronegativity term, and their ratio, the Mott number. Mott observed that if the Mott number of a given binary system was greater than the maximum number of Pauling bonds which the two metals could form, then liquid immiscibility could be expected. The maximum number of bonds formed by a given metal was considered to be directly related to the number of bonding electrons available, i.e., to its maximum valency. Since the valencies of the elements considered vary from 1 to 6, Mott assumed that if the ratio of the Hildebrand term to the electronegativity term was >6, then immiscibility could be expected. On the contrary, if the ratio is <1, the metals should be miscible. Further, the alloying behavior is not only influenced by the valencies of the two elements but also by the relative atomic sizes that influence the types of packing and hence the coordination number. Mott considers that on average the maximum number of near neighbors of unlike atoms is 6. Thus, on both valency and size factor considerations, Mott concludes that the maximum number of bonds&apos; possible in any system was 6, this being the upper limit of the Mott number for miscibility. In considering the alloying behavior of systems with Mott numbers between 1 and 6, Mott plotted the num-

Jan 1, 1970

By D. P. Pope, T. Vreeland

Observations of dislocations in zinc using Berg-Barrett X-ray micrography confirm the validity of a dislocation etch for (1010) surfaces. A technique for measurement of the depth in which dislocations can be imaged in X-ray micrographs is given. This depth on (0001) surfaces of zinc was found to be 2.5 µ using a (1013) reflection and CoKa radiation. BUCHANAN and Reed-Hill (B & RH) have recently questioned the ability of a dislocation etch to reveal all of the basal dislocations which intersect (1010) surfaces in annealed zinc crystals.&apos; This etch was developed by Brandt, Adams, and Vreeland who conducted a number of different experiments to check its ability to reveal dislocations.2,3 B & RH prepared (0001) foil specimens for transmission electron microscopy from annealed crystals and observed dislocation densities of about l08 cm per cu cm in the foils, while the etch indicated densities of the order of l04 cm per cu cm in their annealed crystals. As this etch has been used in a number of studies of dislocations in zinc, it is of considerable importance to reassess its validity in the light of the B & RH results. The X-ray work reported here was undertaken to check the ability of the etch to reveal dislocation intersections on (1070) surfaces of zinc. The X-ray technique was chosen for this check because it could be applied to the as-grown crystals with a relatively small amount of specimen preparation. We believe that the possibility of accidental deformation in preparation of the bulk specimens is considerably less than that for thin foil specimens suitable for transmission electron microscopy. Unfortunately, basal dislocations are not visible on Berg-Barrett topo-graphs of (1010) surfaces, which are the surfaces on which the etch is most effective. Therefore, a one-to-one correspondence between the etch and X-ray observations could not be made. Basal dislocations near (0001) surfaces have been observed by Schultz and Armstrong4 using the Berg-Barrett technique, but they did not report the as-grown dislocation density observed in their crystals. We have applied the X-ray technique in this study to surfaces oriented from 1 to 2 deg of the (0001) to determine the basal dislocation density, and have compared this density with that observed using the etch on a (1070) plane of the same crystal. The X-ray observations permit determination of the depth in which basal dislocations can be observed under the diffracting conditions used. SPECIMEN PREPARATION High purity zinc crystals are very soft, so a good deal of care must be exercised in the preparation of observation surfaces. As-grown crystals approximately 2.5 cm in diam and 20 cm long were acid cut into 1.25 cm cubes. A thin slab was cleaved from an (0001) surface to produce an accurately oriented reference surface on the specimen. Some of the cubes were examined in the as-machined condition while some were annealed in argon at 410°C for 2 hr. Heating and cooling rates were less than 2°C per min. Some of the specimens were scratched on a (0001) surface with a razor blade to produce fresh dislocations. Approximately 2 mm of material was acid lapped from one face of a cube to produce a surface oriented between 1 and 2 deg from the basal plane and parallel to the [1210] direction. A (1070) surface was also acid lapped. The lap used a 1 to 3 pct solution of HN03 in water to saturate a soft cloth which was backed by a stainless steel plate. The cloth was moved over the crystal surface at a rate of 20 cm per sec while a normal force of about 4 g was maintained between the cloth and the specimen. As-lapped surfaces were examined as were surfaces which were chemically and electrolytically polished after lapping. The small angle between a lapped surface and the (0001) plane was measured to 0.1 deg using a Unitron microgoniometer microscope (the cleaved surface was used as a reference in this measurement). The microscope was modified so that the intensity of reflected light could be continuously monitored on a meter. This modification produced nearly a ten-fold increase in the reproduceability of orientation readings. OBSERVATIONS The Unitron Microgoniometer observations indicated that the lapped surfaces had a terraced structure with the terraces quite rounded and spaced about 0.1 mm in the [1010] direction. The maximum change in slope between terraces was 0.25 deg, indicating a terrace height of about 0.1 µ. A Unitron measurement of the average angle between (0001) and a lapped surface was checked by micrometer measurement of the specimen and found to agree within 0.1 deg. The Berg-Barrett micrographs using (1013) reflections and CoKa radiation5 revealed subboundaries, short dislocation segments, spirals, and loops near the surfaces which were oriented from 1 to 2 deg of the (0001). Micrographs of surfaces prepared by lapping appeared very similar to those of the chemically and electrolytically polished surfaces. The loops and spirals were not extinct in (1013) or (0002) reflections, indicating that they have a nonbasal Burgers vector. Extinctions of the short, straight dislocations indicated that they belonged to an (0001)(1210) system. Fig. 1 is an example of a micrograph which shows a subboundary, and dislocation segments which are pre-

Jan 1, 1970

By J. M. Woodall

GuAs crystals which have been grown in quartz boats by the horizontal Bridgman method in the pvesence of Ga20 vapov have beetz found to have carrier and donor distributions which do not correspound to those expected from simple dopant seg-vegation during directional freezing; Instead, the carrier distribution is determined by the heat-trentnzent history of the crystal, while the donor distribution, zohiclz is principally due to silicon, is fixed by the pozuth rate, the geo)tlet.ry of the crystal growth vessel, and tlze initial Ga20 pressure. WHEN semiconducting materials are made into doped crystals by the normal freezing method,&apos; they usually exhibit doping variations along the growth axis. If a) there is no dopant diffusion in the solid, b) the dopant is distributed uniformly in the melt, and c) the distribution coefficient, k, does not vary with composition, then the doping variation along the growth axis is represented by the equation: where C is the doping level in the solid at a point where a fraction g of the original liquid has frozen, and Co is the mean concentration. When the dopant is either a singly ionized shallow donor or shallow acceptor, C also represents the carrier concentration. Even though this equation accurately describes the dcping profiles of a large number of normal freeze systems, there are several special systems for which Eq. [I] does not apply. One such system is the horizontal Bridgman method for preparing oxygen-grown GaAs crystals using quartz vessels. Several workers2"* have shown that GaAs crystals grown by the horizontal Bridglnan method using quartz vessels are generally contaminated with silicon in concentrations in excess of 5 < 10lG atoms per cu cm. This contamination is ascribed to a reaction: occurring at the walls of the crystal-growth vessel which liberates silicon into the melt and Ga2O vapor. It has been shown4 that this reaction, and, hence, the silicon contamination, can be suppressed by the addition of oxygen to the crystal-growth apparatus. It is the purpose of this paper to describe a special apparatus capable of yielding single crystals of GaAs grown in the presence of oxygen and to describe both the kinetics of silicon suppression in this system and the relationship between the carrier concentration profile and the silicon concentration profile. EXPERIMENTAL-CRYSTAL GROWTH A schematic diagram of the apparatus used in the oxygen addition experiments is shown in Fig. 1. The most important features of this apparatus are: a) the use of a sand blasted quartz boat, h) a quartz rod of length 1, with a hole of cross section A, that is placed near the boat to limit the free space volume V, over the melt during the growth, and c) the temperature gradient at and near the solid-liquid interface. Sand blasting the boat is necessary to prevent wetting of the melt. The quartz rod retards the diffusion of the GazO vapor away from the melt to the colder portions of the ampoule. A crystal is prepared by first loading a 5.5-in. boat, which has been cleaned in aqua regia, with 40 g of 99.9999 pct Ga along with 1 to 8 mg of Ga203 powder. GazO3 is a convenient source of oxygen since it reacts with gallium at the melt temperature to form Ga20 vapor, the species which apparently controls the suppression of silicon contamination. The loaded boat, the quartz rod, and the 99.9999 pct As are placed in the ampoule as shown in Fig. 1. Generally, GaAs seeds were not used since most of the unseeded growths resulted in monocrys-tals. The ampoule is evacuated to 10-5 Torr and sealed off. The GaAs melt is synthesized by placing the ampoule into a two-zone horizontal Bridgman furnace. The two zones are separated by several sandwiched layers of -in. Fibre-Fax board drilled with holes slightly larger than the OD of the ampoule. This causes a very large temperature gradient between the two zones, which is necessary for single-crystal growth. The two-zone furnace is mounted on a stand fitted with a roller bearing which allows uniform motion of the furnace in a horizontal direction. A uniform velocity of the stand is achieved by the use of a windlass device which winds up a wire attached to the stand. Movement of the solid-liquid interface is accomplished by fixing the position of the ampoule and moving the stand. Growth rates investigated in this experiment were between 0.4 and 1.2 in. per hr. The composition of the melt is fixed by maintaining an arsenic reservoir at 618°C. The stand is moved away

Jan 1, 1968

By Paul Billingsley, Augustus Locke

The mining districts of the first order&apos; of the western United States (and borders) are those named on Fig. 1. These fall into four groups: (1) in the eastern outliers of the Rocky Mountain system; (2) in the Rocky Mountain system itself; (3) in the Great Basin; and (4) in the Sierras and Coast ranges. Of these four groups, the first three are almost entirely of Tertiary age and are within a belt of compressive folding which we shall call the Rocky Mountain-Great Basin thrust arc. The backbone of this belt is shown by the line BAC. The position of the ore districts in this belt indicates a conformance to linear elements of the continental pattern. These are additional to the peripheral elements emphasized by Butler.2 Nature of the Thrust Arc The thrust arc separates regions of contrasted kinds. To the east of it are flat-lying plateaus interrupted by earlier mountain folds; to the west, sunken basins, in which block-faulted ranges lie like an anchored fleet in a sea of desert wash or lava. The. cross-sections are as shown in Fig. 2. The backbone of the belt is the upward and eastward moving block represented by the Glacier Park, the Wasatch, and the Virgin mountains, successively. The structure represented on these sections is the culmination of events which began far back in geologic time and throughout which a contrast has existed between the regions east and west of the backbone line. Before the Pennsylvanian, as Fig. 3 shows, there was a shallow shelf on the east and a deep marine trough on the west; after

Jan 1, 1935

By Paul Billingsley, Augustus Locke

The mining districts of the first order&apos; of the western United States (and borders) are those named on Fig. 1. These fall into four groups: (1) in the eastern outliers of the Rocky Mountain system; (2) in the Rocky Mountain system itself; (3) in the Great Basin; and (4) in the Sierras and Coast ranges. Of these four groups, the first three are almost entirely of Tertiary age and are within a belt of compressive folding which we shall call the Rocky Mountain-Great Basin thrust arc. The backbone of this belt is shown by the line BAC. The position of the ore districts in this belt indicates a conformance to linear elements of the continental pattern. These are additional to the peripheral elements emphasized by Butler.2 Nature of the Thrust Arc The thrust arc separates regions of contrasted kinds. To the east of it are flat-lying plateaus interrupted by earlier mountain folds; to the west, sunken basins, in which block-faulted ranges lie like an anchored fleet in a sea of desert wash or lava. The. cross-sections are as shown in Fig. 2. The backbone of the belt is the upward and eastward moving block represented by the Glacier Park, the Wasatch, and the Virgin mountains, successively. The structure represented on these sections is the culmination of events which began far back in geologic time and throughout which a contrast has existed between the regions east and west of the backbone line. Before the Pennsylvanian, as Fig. 3 shows, there was a shallow shelf on the east and a deep marine trough on the west; after

Jan 1, 1935

The mining districts of the first order&apos; of the western United States (and borders) are those named on Fig. 1. These fall into four groups: (1) in the eastern outliers of the Rocky Mountain system; (2) in the Rocky Mountain system itself; (3) in the Great Basin; and (4) in the Sierras and Coast ranges. Of these four groups, the first three are almost entirely of Tertiary age and are within a belt of compressive folding which we shall call the Rocky Mountain-Great Basin thrust arc. The backbone of this belt is shown by the line BAC. The position of the ore districts in this belt indicates a conformance to linear elements of the continental pattern. These are additional to the peripheral elements emphasized by Butler.2 Nature of the Thrust Arc The thrust arc separates regions of contrasted kinds. To the east of it are flat-lying plateaus interrupted by earlier mountain folds; to the west, sunken basins, in which block-faulted ranges lie like an anchored fleet in a sea of desert wash or lava. The. cross-sections are as shown in Fig. 2. The backbone of the belt is the upward and eastward moving block represented by the Glacier Park, the Wasatch, and the Virgin mountains, successively. The structure represented on these sections is the culmination of events which began far back in geologic time and throughout which a contrast has existed between the regions east and west of the backbone line. Before the Pennsylvanian, as Fig. 3 shows, there was a shallow shelf on the east and a deep marine trough on the west; after

Jan 1, 1935

By T. A. Rickard

INTRODUCTORY. THE presentation to the Institute, eight years ago, of the paper of Pošepny on " The Genesis of Ore-Deposits " has borne fruit in much fresh: investigation, as is evidenced, for example, by the group of very valuable papers, by distinguished members" of the United States Geological Survey, read at the Washington meeting-discussions of general principles particularly suggestive to those who are engaged in mining. Pošepny, in the discussion of his famous treatise, said that the present writer seemed to look at every new conception in ore-deposition" from the sole standpoint of its immediate usefulness in mining."* Protesting mildly against " sole " and "immediate," I accept the impeachment. It calls for no defence. THE DEVELOPMENT OF RECENT THEORIES. Given the idea of an underground water-circulation as the chief factor in the deposition of ore, the next step in the inquiry as to the genesis of such deposits is, the endeavor to determine which particular part of the general water-circulation is responsible for the results. Around this question have centered the controversies of a generation, and to these controversies we owe the gradual clarification of our ideas upon the processes of ore-formation. It is unnecessary to sketch here their progress from Werner to Le Conte, who combated in 1883 the extreme views of the lateral-seeretionists, and in 1893 opposed the narrow interpretation of the ascensionist-theory. The generally accepted opinions of to-day are a well-deserved tribute to his philosophic discrimination. Thanks to Prof. Van Hise and Mr. Slichter, whose work he utilizes, we have now arrived at a comprehensive conception

Jan 1, 1902

By Augustus Locke, Paul Billingsley

The mining districts of the first order&apos; of the western United States (and borders) are those named on Fig. 1. These fall into four groups: (1) in the eastern outliers of the Rocky Mountain system; (2) in the Rocky Mountain system itself; (3) in the Great Basin; and (4) in the Sierras and Coast ranges. Of these four groups, the first three are almost entirely of Tertiary age and are within a belt of compressive folding which we shall call the Rocky Mountain-Great Basin thrust arc. The backbone of this belt is shown by the line BAC. The position of the ore districts in this belt indicates a conformance to linear elements of the continental pattern. These are additional to the peripheral elements emphasized by Butler.2 Nature of the Thrust Arc The thrust arc separates regions of contrasted kinds. To the east of it are flat-lying plateaus interrupted by earlier mountain folds; to the west, sunken basins, in which block-faulted ranges lie like an anchored fleet in a sea of desert wash or lava. The. cross-sections are as shown in Fig. 2. The backbone of the belt is the upward and eastward moving block represented by the Glacier Park, the Wasatch, and the Virgin mountains, successively. The structure represented on these sections is the culmination of events which began far back in geologic time and throughout which a contrast has existed between the regions east and west of the backbone line. Before the Pennsylvanian, as Fig. 3 shows, there was a shallow shelf on the east and a deep marine trough on the west; after

Jan 1, 1935