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By C. Ernest Birchenall

AS a basis for further progress in several branches of metallurgy, particularly the study of physical properties of solid solutions and the kinetics of solid-solid reactions, a more complete understanding of the structure of solid solutions and the nature of the metallic bond is- necessary. Any investigation contributing to this understanding should be of primary interest to the metallurgist. Since the metallic bond is characteristic of an assemblage of atoms, it can be studied only where this assemblage exists. One of the most promising approaches to this study of the interactions in metals is through the general problem of binary metallic solutions. Although crystal structures of many solid metallic solutions have been determined and solubility limits for many systems are given in phase diagram studies, progress beyond this is irregular. Electromotive force and vapor pressure determinations have provided thermodynamic activity data for small concentration and temperature ranges in the amalgams and a few other systems.' In two systems, however, copper-zinc and iron-carbon, data are available for the calculation of activities over wide ranges of temperature and concentration. This activity data for the brass system is summarized in the preceding paper.= A detailed study of the solubility and distribution of carbon in iron is given by Smith and Darken.3 Their treatment of interaction energies is applicable only to dilute interstitial solutions. The objectives here will be to derive from activity gats given in the previous paper for the brasses and structural considerations as much new and detailed information as possible about the interactions between copper and zinc in metallic solid solution and the effect of these interactions in determining the short range structure of the equilibrium phases; that is, we shall investigate the energy of interaction between pairs of atoms of the same and different kinds, the deviations of the distribution of nearest neighbors from complete randomness, and show that the conclusions found are consistent with the observed behavior of the brass system. The method of treatment is fairly general for substitutional metallic solid solutions and will be applied to other systems. The determination of vapor pressures of the components of alloy systems is being undertaken in this laboratory to supply more data for this purpose. The information obtained from solid solutions may be extended by careful analogy to liquids as long as the metallic type of bonding is preserved. Since it will be necessary to employ the language of thermodynamics, a brief summary defining the terms used extensively in solution theory is given below. Solution Theory4 An ideal solution is one in which the vapor pressure of the constituent molecules

Jan 1, 1947

By Henry Siegmann

HISTORY OF PRODUCTION AND USE In 1899 the consumption of fluorspar in the United States was reported as 16,000 tons. The invention of the open-hearth method of steel manufacture, plus the beginnings of a fluorine chemical industry, pushed consumption of fluorspar to 250,000 tons by 1918. In contrast to these consumption statistics of the past, the most recent statistics available (1972) indicate a total fluorspar usage in the United States of 1.352 million st (Table 15.4D.1). Fluorspar remains the world's cheapest source of fluorine, and its unique properties make the mineral the most desirable fluxing agent for steel refining. The linking of fluorine with carbon in the late 1930s resulted in the production of fluorocarbon, and constant growth in production over the years has formed the backbone of a strong fluorine chemical industry. For example, in 1972 it is estimated that total fluorocarbon production amounted to 2.113 million tons, and that, in this process, over 1.351 million tons of acid-grade fluorspar was consumed. The producers of primary aluminum long have been concerned about the fast dwindling reserves of natural cryolite. They found the solution to their problem by utilizing fluorspar for the manufacture of synthetic cryolite and aluminum fluoride. Nuclear weapons, as well as the growing number of peaceful uses for atomic reactors, constitute a market for uranium hexafluoride. This chemical and chlorine pentafluoride, used as an oxidizer with rocket fuels, are products that are as much a novelty as fluorocarbons were 25 years ago. Judging from past success in the field of fluorine chemistry research, it is safe to assume that the market for these chemicals will grow in the future. Three major industries account for the bulk of the fluorspar consumption: steel refining, fluorine chemical, and primary aluminum production. These industries have had a pattern of fabulous growth in the past, and their future plans point to a continuation of this pattern. It seems logical that the fluorspar usage also should continue its upward trend. Considering the growth of the fluorspar industry since 1899, and the obvious dependence on imports of fluorspar as a raw material, one of the most puzzling aspects of the past has been the apparent lack of coordination between fluorspar production and fluorspar consumption. A few authoritative voices have spoken out concerning the need to expand fluorspar production in order to meet consumption of the future. During World War II, the U.S. Government took positive steps in this direction by authorizing purchases at attractive prices for its "stockpile program." As a consequence, new fluorspar producing facilities were built, not only in

Jan 1, 1976

By Michael B. Bever, Carl F. Floe

The solubility of hydrogen in molten copper-tin alloys is of both practical and theoretical interest. From a practical standpoint, data on the equilibrium solubility as a function of temperature, pressure and alloy composition are valuable for a better understanding of porosity problems in bronze castings. From the theoretical point of view the determination of the hydrogen-copper-tin equilibrium is of interest since it extends the laws governing the solution of gases in metals. This paper presents the results of an investigation of the solubility of hydrogen in representative compositions of the copper-tin system at temperatures ranging from above the liquidus to I300°C. and at pressures from less than 50 mm. of mercury to about atmospheric. Review of Previous Work The solubility of hydrogen in copper was determined by Sieverts and Krumbhaarl in 1910 and by Roentgen and Moeller2 in 1934. Their values are in fair agreement. In 1926 Iwasé3 reported results that were very much higher. The published data on the solubility of hydrogen in tin do not agree. Smithells4 states that no reliable data are available According to Sieverts and Krumbhaar,5 hydrogen is insoluble in tin. Bircumshaw,6 on the other hand, found a definite solubility at 800°C. The latter's experimental procedure did not provide for stirring of the metal and in his opinion he failed to reach equilibrium. Iwasé3 again reported large solubility values. For copper alloys, Sieverts and Krumbhaar5 distinguished between alloying elements that do not markedly affect the solubility of hydrogen, elements that increase the solubility, and elements that reduce it. They named gold, tin, and aluminum as examples of this last group and reported hydrogen solubility data at 1225°C. for the copper-rich side of these alloy systems at atmospheric pressure. Without giving experimental results, they stated that the amount of hydrogen dissolved by liquid copper alloys is proportional to the square root of the pressure as in pure metals. These authors suggested that in a limited way the effect of an alloying element on the solubility of a gas is related to the constitution diagram for the alloy system. Sieverts7 also called attention to the fact that the curve of hydrogen solubility versus composition of copper-tin alloys shows a sharp change of direction at the composition of Cu3Sn and suggested that this compound persists at least to some extent in the molten state. Iwasé3 reported large hydrogen solubility values for several compositions of copper-tin alloys, which appear to be in error.

Jan 1, 1944

By Carl F. Floe, Michael B. Bever

The solubility of hydrogen in molten copper-tin alloys is of both practical and theoretical interest. From a practical standpoint, data on the equilibrium solubility as a function of temperature, pressure and alloy composition are valuable for a better understanding of porosity problems in bronze castings. From the theoretical point of view the determination of the hydrogen-copper-tin equilibrium is of interest since it extends the laws governing the solution of gases in metals. This paper presents the results of an investigation of the solubility of hydrogen in representative compositions of the copper-tin system at temperatures ranging from above the liquidus to I300°C. and at pressures from less than 50 mm. of mercury to about atmospheric. Review of Previous Work The solubility of hydrogen in copper was determined by Sieverts and Krumbhaarl in 1910 and by Roentgen and Moeller2 in 1934. Their values are in fair agreement. In 1926 Iwasé3 reported results that were very much higher. The published data on the solubility of hydrogen in tin do not agree. Smithells4 states that no reliable data are available According to Sieverts and Krumbhaar,5 hydrogen is insoluble in tin. Bircumshaw,6 on the other hand, found a definite solubility at 800°C. The latter's experimental procedure did not provide for stirring of the metal and in his opinion he failed to reach equilibrium. Iwasé3 again reported large solubility values. For copper alloys, Sieverts and Krumbhaar5 distinguished between alloying elements that do not markedly affect the solubility of hydrogen, elements that increase the solubility, and elements that reduce it. They named gold, tin, and aluminum as examples of this last group and reported hydrogen solubility data at 1225°C. for the copper-rich side of these alloy systems at atmospheric pressure. Without giving experimental results, they stated that the amount of hydrogen dissolved by liquid copper alloys is proportional to the square root of the pressure as in pure metals. These authors suggested that in a limited way the effect of an alloying element on the solubility of a gas is related to the constitution diagram for the alloy system. Sieverts7 also called attention to the fact that the curve of hydrogen solubility versus composition of copper-tin alloys shows a sharp change of direction at the composition of Cu3Sn and suggested that this compound persists at least to some extent in the molten state. Iwasé3 reported large hydrogen solubility values for several compositions of copper-tin alloys, which appear to be in error.

Jan 1, 1944

By H. L. Riley, B. W. Gandrud

A froth flotation unit was added to the DeBardeleben Coal Corporation's Empire washer at Empire, Alabama, in the fall Of I94O following an investigation of possible ways and means of recovering coal values from settling-tank overflow or slurry. Officials of the DeBardeleben corporation hoped that some practical and reasonably economical way could be found for recovering fine coal from overflow water, although there had as yet been very little progress along this line in the Alabama coal fields. The Bureau of Mines was asked to cooperate in the project through its Southern Experiment Station, at University, Alabama. This paper presents a brief description of the process and the installation that resulted from the investigation of the overflow water or slurry problem at the Empire mine. The experimental data include' as a Part of this Paper were obtained during the course of the investigation in 1940 Since that time, however, the flotation unit has been running more or less continuously without significant operational changes and is still Performing pretty much in accordance with the data obtained in 1940. Flowsheet at Empire and Type of Coal Treated The Empire mine is developed on the Black Creek bed near the the border of the Warrior field. The coal in this bed is extremely low-ash and although there is an almost complete absence of bone coal and partings, the bed is so thin that, with mechanized mining, a high percentage of rock from roof and floor inevitably gets into the run-of-mine coal. The thickness of the Black Creek bed throughout the part of the Warrior field in which it is mined extensively is rarely over 30 in. and probably would average about 25 in, the coal is of the high-volatile A rank and of excellent quality, but as a result of admixture of roof and floor material, the run-of-mine product usually contains I ; to 20 pct rock by weight. he following is a proximate analysis on an "as-received " basis of a typical seam sample from the Empire mine:' moisture, 3.0 pet; volatile, 34.6 fixed carbon 58.3; ash, 4.1 This sample shelved 15,070 Btu per pound and 0.9 pct sulphur on a moisture-and-ash-free basis. In the Empire preparation plant the lump sizes above 3 in. are removed and hand-picked on a Marcus conveying Screen, the 3 to ? -in. size is removed by vibrating screens and washed in two Montgomery single-cell jigs, and the ?-in. to o slack is cleaned on four diagonal

Jan 1, 1949

By E. G. Leonardon, C. Schlumberger, M. Schlumberger

In the search for practical geological problems amenable to solution by the potential methods, the geophysicist is led to study mathematically various theoretical cases. In these idealistic discussions, the media under consideration are generally supposed to be homogeneous and iso-tropic. The geophysicist, of course, realizes perfectly that these conditions do not occur in their entirety in reality. However, the assumptions made are justified, because very often they are necessary in order to render possible an exhaustive study of a given problem, which otherwise would be too complicated, and would not lend itself to a complete mathematical analysis. Of the above two assumptions, that concerning the homogeneity of a given geological formation is satisfactorily realized except in so far as isotropy is concerned, since this property is not often encountered in practice. As a consequence, it is very desirable for the geophysicist to have quite an extensive knowledge of the properties of anisotropic formations, and of the laws that govern the propagation of electric current therein. With such principles in mind, he will be able to decide whether the conclusions arrived at in simple, isotropic conditions are still correct in more complex cases, or in what way they must be modified or adapted in order to constitute a sound basis for the interpretation of the results obtained in anisotropic media. On the other hand, the fact that in anisotropic formations the mobility of the ions is greater along the strike than perpendicular thereto can be utilized for determining the direction of the dip by induction measurements. We therefore propose to study in three successive chapters the following points: 1. Propagation of the electric current in anisotropic media. 2. Some consequences of the anisotropy of geological formations with reference to the surface electrical measurements, and their interpretation. 3. Determination of the direction of the dip of anisotropic formations by surface induction measurements.

Jan 1, 1934

By Carl F. Floe, John Chipman

THE system molten copper-oxygen-sulphur is of interest from both the practical and theoretical standpoints; practically, because oxygen and sulphur play an important role in the commercial production of copper, and theoretically because it offers a chance to study the reaction between an oxide gas, SO2, and a molten metal. Reactions of this type, such as that between CO or CO2 and molten iron, are important in many metallurgical operations. Again, the determination of any gas-metal equilibrium is of theoretical interest and value insofar as it contributes to the general development of the laws for solution of gases in metals. This problem is being given an increasing amount of attention in modern metallurgy. This paper is the first of a series and presents the results of a determination of the solubility of sulphur dioxide in molten copper at temperatures from 1100° to 1500°C., and pressures from about 20 mm. of mercury to somewhat above atmospheric. REVIEW OF PREVIOUS WORK The solubility of gases in most liquids has been found to obey Henry's law, which states that for a fixed temperature the amount of gas dissolved is directly proportional to the pressure. However this law does not hold for liquid metals. Instead, it appears that for many gases, particularly the simple diatomic ones such as 02, N2 and H2, the amount dissolved in liquid metals is directly proportional to the square root of the pressure. This is known as Sieverts' law. It may be recognized as a special case of Henry's law, which applies when the solute gas is dissociated into atoms or when it reacts with the solvent metal to form solute molecules containing single atoms of the gaseous elements, as, for example: [(MG) l 2M +G2 = 2MG K = Ma X Pa, [I]] which, if the solubility is not too high and the concentration of metal therefore nearly constant, can be simplified to: [MG = Kl Pa,[2]] Following the same reasoning, it would be expected that the solubility of SO2 in copper would be proportional to the cube root of the pressure, the reaction being as follows: [6Cu + SO2 = Cu2S + 2Cu20[3] K _ Cu2S X (Cu20)2 (Cu)6(Pso2)[4]] or, neglecting the change in metal concentration and considering that the concentrations of sulphur and oxygen are both proportional to the volume V of gas absorbed: [8 =KI = Pte, or VSO2= K2 '~/PeO, [S]]

Jan 1, 1941

By Carl F. Floe, Michael B. Bever

TRE solubility of hydrogen in molten copper-tin alloys is of both practical and theoretical interest. From a practical standpoint, data on the equilibrium solubility as a function of temperature, pressure and alloy composition are valuable for a better understanding of porosity problems in bronze castings. From the theoretical point of view the determination of the hydrogen-copper-tin equilibrium is of interest since it extends the laws governing the solution of gases in metals. This paper presents the results of an investigation of the solubility of hydrogen in representative compositions of the copper-tin system at temperatures ranging from above the liquidus to 1300°C. and at pressures from less than 50 mm. of mercury to about atmospheric. REVIEW OF PREVIOUS WORK The solubility of hydrogen in copper was determined by Sieverts and Krumbhaarl in 1910 and by Roentgen and Moeller2 in 1934. Their values are in fair agreement. In 1926 Iwasé3 reported results that were very much higher. The published data on the solubility of hydrogen in tin do not agree. Smithells4 states that no reliable data are available. According to Sieverts and Krumbhaar,5 hydrogen is insoluble in tin. Bircumshaw,6 on the other hand, found a definite solubility at 800°C. The latter's experimental procedure did not provide for stirring of the metal and in his opinion he failed to reach equilibrium. Iwasé3 again reported large solubility values. For copper alloys, Sieverts and Krumbhaar6 distinguished between alloying elements that do not markedly affect the solubility of hydrogen, elements that increase the solubility, and elements that reduce it. They named gold, tin, and aluminum as examples of this last group and reported hydrogen solubility data at 1225°C. for the copper-rich side of these alloy systems at atmospheric pressure. Without giving experimental results, they stated that the amount of hydrogen dissolved by liquid copper alloys is proportional to the square root of the pressure as in pure metals. These authors suggested that in a limited way the effect of an alloying element on the solubility of a gas is related to the constitution diagram for the alloy system. Sieverts7 also called attention to the fact that the curve of hydrogen solubility versus composition of copper-tin alloys shows a sharp change of direction at the composition of Cu3Sn and suggested that this compound persists at least to some extent in the molten state. Iwas3é reported large hydrogen solubility values for several compositions of copper- tin alloys, which appear to be in error.

Jan 1, 1944

By Thomas L. Garwood, F. C. Menk

IT is generally, accepted that no method of coal cleaning except froth flotation is effective in cleaning dust. In the majority of coals mined in the United States the dust sizes contain a high percentage of impurities, hence the removal of the dust from the coarse sizes lowers the impurity content of these sizes. Dedusted coal is desired as a means of providing a better feed to cleaning plants because of increased efficiency in both dry and wet plants. In dry-cleaning plants, a dedusted feed makes for a pervious and uniform bed. With a dusty feed the fines tend to segr6gate in the feed stream and pass en masse over the air separators, causing a lack of uniform aeration and fluidity of the bed necessary to efficient cleaning. In wet-cleaning plants dedusting of the feed often decreases the sludge problem to the point of eliminating the necessity of wasting wash water. It may be advantageous to eliminate sludge-settling equipment in favor of dedusting equipment, to provide the advantages of a dedusted feed to the wet-washing process. Dedusting advantages may include: (1) the removal of fusain, especially advantageous in plants washing coal intended for metallurgical coke; (2) prevention of the gradual build-up of solids in the wash water, with a consequent variation in the washing ability of the system; (3) prevention of the loss of dust to the sludge ponds, providing instead a fuel for local consumption or special markets. DEDUSTING The practice of dedusting, sometimes called aspirating, has presented a problem in disposing of the dust and intermediate small sizes recovered in the process. It has been found that no difficulty is experienced in disposing of the intermediate sizes, since they are free of fine dust and burn freely on grates built for small coal. They handle well, flowing freely from bins and hoppers and into conveyors, and pulverize easily. They have a low angle of repose. In tests made on this size as a feed to coke ovens, the results have been excellent, in that the natural breakdown of .coal in handling and shooting in the mine gives this small-size coal good

Jan 1, 1943

The following is an incomplete list of members and guests who called at Institute headquarters during the period Dec. 10, 1918 to Jan. 10, 1919. P. G. Bandy, Mexico City. Wm. B. McKinley, Yonkers, N. Y. Bennett R. Bates, Berkeley, Cal. Captain C. E. McQuigg, Conn. William T. Bates, Mascot, Tenn. Lt. H. G. Mathews, Cal. Lt. Don C. Billick, Alturas, Cal. Lt. M. S. Mazany, Mich. L. E. Booth, Watertown, Mass. Ralph A. Meyer, Hill City, S. D. J. T. Boyd, Denver, Colo. C. F. Moore, Boston, Mass. J. R. Buchanan, Pasadena, Cal. H. W. Nichols, Chicago, Ill. Ensign G. M. Burke. R. B. Olsen, Mays Landing, N. J. Captain E. H. Clausen. M. L. O'Neale, Gouverneur, N. Y. F. L. Cole, Manila; P. I. F. W. Osborn, New York, N. Y. Joules Cousin. Lt. Fred S. Porter, Alaska. A. Faison Dixon, Washington, D. C. G. M. Richards, Palmerton, Pa. James T. Dixon, London, England. T. C. Roberts, E. Orange, N. J. Everett Drennen, Elkins, W. Va. W. E. Ruder, Schenectady, N. Y. F. Eichelberger, Helena, Mont. Ensign W. A. RuKeyser, Boston. R. B. Eldredge, Colorado Springs, Colo. A. H. Sawyer, Boston, Mass W. F. Ferrier, Ottawa. Lt. D. F. Schindler, New York. Martin Fishback, Benson, Ariz. L. G. Sparks, Greenshurg, Kan. T. E. Fisher, Dover, N. J. W. H. Staver, New York N. Y. D. C. Gilbert, Ft. Wayne, Ind. Douglas B. Sterrett, St. Cyr, Canada. Lt. Lauriston B. Herr, Cuba. Warren D. Thompson. G. S. Holmquist, Washington, D. C. Enrique Touceda, Albany, N. Y. Lt. E. Ross Housholder, Ohio. Mathew van Siclen. Hugh C. Ingle, Santa Rosa, Cal. Flying Cadet Christian Vrang, Cal. Lt. M. W. Kishman, Ariz. L. G. Weeks, Bisbee, Ariz. Hugo E. Koch, Watertown, Mass. C. E. Wheelock, Mogollon, N. M. H. M. LaFollette, LaFollette, Tenn. Major A. E. White, Washington, D. C. Clinton R. Lewis, Dawson, Y. T. Lt. J. L. White, Humboldt, Ariz. The Secretary of the Institute has received with sincere appreciation a Christmas card extending the season's greetings from the officers' mess of the 3d Tunnelling Company, Canadian Engineers, B. E. F., France, and takes this means of reciprocating to these officers and men of the company the best wishes of the members of the Board of Directors. Charles E. Addams has removed from Ray, Ariz., to Phoenix, Ariz., where he is chairman and director of the Arizona State Council of Defense.

Jan 2, 1919

Jan 1, 1933

By L. Adler

The author recently proposed a technique for handling the effect of planes of weakness on failure in geologic material.1 The technique employed an "extended" Mohr's rupture envelope, on which was superimposed a generalized three dimensional stress representation. Subsequently, the method was applied to so-called two-dimensional stress states" which were in reality degenerate three-dimensional ones. Since a two-dimensional stress solution usually refers to a plane stress condition, the terminology was confusing. The distinction between a plane stress state and a degenerate three-dimensional one is shown in Fig. 1. The solution of problems involving a generalized three-dimensional stress state is greatly aided by continual reference to the basic principle that no stress components can act on a plane, oriented as is the weakness plane, which lies outside of the weakness plane's rupture enVelope.2 This is shown in Fig. 2; and if it is also remembered that the radii of the Mohr's Circles give the orientation of such a plane, solutions are easier to follow, and perform. Sample Problem 1: Site Location (generalized three-dimensional case).' Given: 1) Both rupture envelope for the solid and plane of weakness. 2) Existing principal stresses and orientations in space (?12, ?13) obtained from a stress analysis of the proposed structure. Find: Permissible orientations of the weakness plane in order to select a suitable site.

Jan 1, 1963

By Mohamed Mortada

A practical analytical method is developed in this paper which provides the practicing reservoir engineer with a handy method for analyzing oilfield interference problems. The procedure employed entails the principle of superposition of individual eflects. A set of charts has been developed and can be used to evaluate the individual effects. The charts represent non-steady state pressure distribution in an extensive aquifer due to a constant rate of production from an oilfield which can be approximated by circular geometry; they are constructed from solutions to the diffusivity equation considering a circular sink as distinguished from a point sink. The solutions are obtained partially from mathenlatical considerations and partially from analog and digital computations. By virtue of the method of images, the charts can be used also to treat the case of production near a fault. In addition, provisions are made for treating oil fields, which are produced by partial water-drive. Treating an actual field case is deferred to a subyequent writing; however, illustrative example is presented to demonstrate the method of application. The pressure distribution in linear and limited radial aquifers is currently under study. INTRODUCTION With the increasing difficulty of discovering new oil reserves, attention is necessarily focused on the efficient development and production of existing reservoirs. Efficient production depends on the availability of reliable means for predicting the pressure-production behavior of oil fields. The prediction is usually performed by analytical methods or computers. Analytical methods are often limited to systems which can be approximated by simple geometry. However, analytical methods have the distinct advantage of being readily performed without special equipment. Analog and digital computers lend themselves to a variety of problems, but are not always locally available and consequently their use is limited. One particular situation in which analytical techniques are needed involves studies of multiple, water-drive oil fields sharing a common aquifer. Such oil fields are in hydrodynamic communication. Therefore, production from any of the oil fields is accompanied by a pressure decline which is transmitted through the aquifer to the other oil fields and manifested as pressure interference. The rate of propagation of the pressure decline is such that the pressure may be significantly reduced many miles away from a producing pool. An example of pressure interference is found in the Woodbine formation in East Texas. There. a dozen or more pools, including several of major size, draw on the Woodbine formation for water drive. The pressure in the water-bearing portion of the formation has been significantly reduced over an area of several thousand square miles. This reduction of pressure has been such that when the Hawkins pool was discovered in 1940, the pressure in it had already been reduced 280 psi below the initial value in the aquifer. This resulted from prior production from other Woodbine sand pools, including, in particular, the East Texas field some 20 miles to the east of Hawkins.' The above example indicates that the interference effect can be significant and should be taken into con-

Jan 1, 1956

By E. J. Rapperport, J. P. Pemsler

We have made calculations to evaluate the sensitivity of atomic absorption as a technique to measure vapor pressure changes with temperature. Our conclusion, supported by the experimental findings presented in this work, is that the ultimate sensitivity of the technique is well below lo-' Torr. This magnitude of vapor pressure sensitivity makes the method extremely attractive for thermodynamic studies. Atomic absorption techniques have been used previously in this connection by Scatchard and Boyd' and by vidale2 with a much lower sensitivity reported. Scatchard and Boyd's work measured cadmium pressure over Ag-Cd alloys in the range 0.02 to 0.3 Torr, and Vidale estimated that sensitivities of only 10"5 to 10"6 Torr are to be expected. Atomic absorption appears to be particularly well-suited to thermodynamic studies for several reasons: A) It is extremely sensitive; our experiments indicate an ability to measure vapor pressure changes of 10"9 Torr. B) It is highly selective; there is seldom interference among the resonant wavelengths of the various species. C) It may be performed in an absorption cell under static conditions. This alleviates such problems as surface impoverishment of alloys, attainment of equilibrium, and temperature measurement and control. D) Simultaneous, or near-simultaneous, vapor pressure measurements may be made for several elements in a given system. Experimental. The physical basis of the technique is the highly selective absorption of particular wavelengths by specific atomic species. In most atomic absorption work the element of interest is incorporated into a hollow cathode lamp to provide a characteristic spectral source of high intensity. The spectra lines characteristic of the element in the cathode are attenuated by atoms of that element in the radiation path. Radiation from silver or cadmium hollow cathode lamps was directed along a path containing a 10-cm evacuated silica cell. The cell was positioned within a silica windowed furnace and contained silver, cadmium, or an Ag-Cd alloy. As the furnace temperature was elevated, the number of atoms of the absorbing element in the vapor phase within the cell rose, and the resonant radiation was increasingly absorbed. Intensities were measured by passing the radiation through a Techtron Model AA-4 one-half meter grating atomic absorption spectrometer equipped with a photo-multiplier detector. In order to minimize instabilities in the source, the hollow cathodes were allowed to warm up for several hours and were run at only 2 5 to 30 pct of their maximum rated amperage. In addition the attenuated beam was monitored before and after each reading. The attenuation of resonant wavelengths may be related to vapor pressure by the following relationships.

Jan 1, 1969

By Arthur E. Hall

Tax operation of "softening" in lead refining is designed, as the word implies, to separate from the bulk of the lead the elements that tend to make lead hard. These elements, which invariably are present in argentiferous lead, interfere with the desilverization, and must be almost entirely absent in refined desilverized lead. They are mainly copper, antimony, arsenic and tin. The properties utilized in accomplishing this separation are the low solubility of copper or copper sulphide in lead at its freezing-point temperature, and the greater and selective affinity for oxygen of the other elements at temperatures of the order of 700° to 900' C., or, in the prcsence of sufficient, alkali, at a temperature of about 500' C. The major problems of softening lead bullion lie in the necessary subsequent treatment of the by-products of the primary operation, which contain, either chemically or mechanically, lead or reagents that must be isolated for market or re-use. Therefore an important objective of the primary operation must be the highest practicable concentration of these elements in the by-products. Within the past three decades, during which the writer has been engaged in lead refining, the technique of softening lead bullion has had as many variations as there were lead refineries. This was the result of the variation in composition and character of lead bullion recived. The writer has received for refining shipments of lead bullion varying as widely as indicated by the following table: Sb, Per CEnt As. Per Cent Sn, Per Cent Cu. Per Cent Ag. Oz. per Ton 1.00 0.05 nil 0.05 70 0.50 2.50 2.00 0.50 200 3.50 0.50 nil 0.30 350 At times these have been received uniformly and at other times irregularly with a variation from week to week as wide as those shown. Under such conditions, establishment of a universal softening technique presented many problems. Such variations existed because refinery tolls too often were based on a ton of bullion, whatever its composition, and

Jan 1, 1937

By I. Fatt

A recently developed system for measuring electrical resistivity of liquids without use of electrodes offers some interesting possibilities in electric logging technology. The equipment as supplied by the manufacturer is satisfactory for continuous mud logging on a drilling rig or for measuring mud or filtrate resistivity in the laboratory. A simple modification of the commercially available instrument makes it suitable for measuring resistivity of core samples in the laboratory. The continuous measurement of mud resistivity on a drilling rig is a convenient means for detecting mixing of formation water with the drilling mud. Such information is useful to the geologist, the mud engineer and the logging engineer. However, continuous mud resistivity logging by conventional electrode-type resistivity cells is beset with difficulties. The mud, sand and rock chips abrade the electrodes, thereby changing the cell constant and eventually destroying the cell. Also, additives and crude oil in the mud may poison the electrodes by coating them with a nonconductive material. An electrode-type resistivity cell. therefore, may give erroneous readings under certain conditions. Electric logging companies circumvent the electrode poisoning problem by using a four-electrode resistivity cell for measurement of mud resistivity. In this cell, change in electrode area does not change the cell constant. However, the four-electrode cell is difficult to adapt for continuous reading and does not solve completely the problem of electrode abrasion by the sand and cuttings in the mud. The measurement of electric logging parameters on core samples in the laboratory encounters some of the same problems discussed in connection with mud logging. Ideally, the electrical resistivity of a core sample should be measured by placing platinum black electrodes in direct contact with the plane ends of a cylindrical or rectangular sample. Platinum black electrodes however, are much too fragile and easily abraded to be brought in contact with a rock sample. Also, oil or other constituents in the fluid contained in the sample will poison platinum black. In practice, gold-plated brass electrodes, in an AC bridge circuit operating at about 1,000 cps, are used for routine core analysis. For more precise work in research studies, a four-electrode scheme is used.',' Preparation of the samples for the four-electrode method is much too involved for routine core analysis. An apparatus for measuring resistivity of liquids without use of electrodes was described by Guthrie and Boys3 in 1879. They suspended a beaker, containing the electrolyte, by a torsion wire and rotated a set of permanent bar magnets around the vessel. The eddy currents induced in the electrolyte reacted against the rotating magnetic field to develop a torque, which was measured as a deflection of the torsion wire. In 1879 this method could not be made precise or convenient because of the lack of strong permanent magnets. The writer described a very greatly improved apparatus similar to that of Guthrie and Boys, but it was not suitable for continuous measurements or core samples.' Many electrodeless resistivity devices using radio frequency current are described in the literature.5, 6 These generally are suitable only for noting the end-point in a chemical titration. They do not measure resistivity, instead measuring a complex quantity which includes the dielectric constant and the magnetic permeability. The first description of the apparatus to be discussed in this paper was given by Relis.7 Improvements and modifications are described by Fielden,s Gupta and Hills,> and Eichholz and Bettens.10 DESCRIPTION OF APPARATUS The apparatus used in this study is based on the principle that the solution under measurement can form a loop coupling two transformer coils, as shown in Fig. 1. For a fixed AC voltage applied across Coil A, the voltage appearing across Coil B is a function of the resistance of the liquid-filled loop. The details of the voltage generating and measuring circuits are given in Refs. 7, 8, 9 and 10. A block diagram of the equipment is given in Fig. 7. Special features worth mentioning are the operating frequency of 18,000 cps and the automatic temperature compensation which results in the given resistivity readings being automatically correlated to 25°C. The liquid loop supplied by the manufacturer, shown in Figs. 1 and 2, was modified for use in core analysis (Fig. 3). The core sample under test is substituted for a section of the original loop. As shown in Fig. 3, the unit accepts only plastic-mounted cylindrical core specimens. A Hassler-type sleeve easily can be designed for the unit if unmounted cores are to be measured. EXPERIMENTAL PROCEDURE MUD LOGGING A simulated mud line was set up in the laboratory.

By Carl G. Hogberg

During recent months, the acute shortage of steel scrap has necessitated the use of higher percentages of hot metal in the open-hearth charge. With these higher percentages, the sulphur content of hot metal has become an increasingly important factor in the control of the quality of steel. Thus, the blast-furnace operator is faced with a demand not only for more output but for a higher quality of product. More than go per cent of the sulphur charged into the blast furnace is contained in the coke. With the tremendously increased demand, the trend of coke quality has been toward higher sulphur, higher and more variable ash, and poorer physical characteristics. This has been brought about by less selective coal mining, increased production rates in coke plants and resumption of operations of many beehive ovens. In a single month last year, one blast-furnace plant in the Pittsburgh district operated with coke obtained from 52 sources. The effect of variability and quantity of coke ash on blast-furnace operation is well known. The improved results obtained with furnaces operating on coke made from washed coals compared with results on coke made from raw coals is ample proof of the effectiveness of low and uniform ash. Coal-washing plants, however, require a large capital expenditure, and are impractical for most of the large number of small producers, whose operations are confined chiefly to periods of abnormally high demand. Furthermore, not all coals are physically adaptable to washing. Principles 01 Iron Desulphurization in Furnace Although investigations of the blastfurnace process have not clearly revealed the detailed mechanism of iron desulphuri-zation within the furnace, they have been sufficiently extensive to permit a postula tion of the following general principles: 1. Iron, in its travel from furnace top to hearth, continues to pick up sulphur until it has reached tuyere level. The zone of iron desulphurizatioil is relatively narrow, being confined to a vertical distance extending zapproximately from tuyere level to the iron-slag interface in the hearth.' 2. Combustion of coke is confined to spherical zones extending approximately 40 in. from the nose of each tuyere.= Coke ash is released as the coke bums in these combustion areas. 3. With a constant amount of sulphur in the charge, the sulphur content of the metal product is a function of hearth temperature, final slag analysis, slag viscosity, and slag volume. Both hearth temperature and slag analysis affect slag viscosity. For a slag of constant analysis, viscosity always decreases with an increase in temperature;

Jan 1, 1943

By Carl G. Hogberg

During recent months, the acute shortage of steel scrap has necessitated the use of higher percentages of hot metal in the open-hearth charge. With these higher percentages, the sulphur content of hot metal has become an increasingly important factor in the control of the quality of steel. Thus, the blast-furnace operator is faced with a demand not only for more output but for a higher quality of product. More than go per cent of the sulphur charged into the blast furnace is contained in the coke. With the tremendously increased demand, the trend of coke quality has been toward higher sulphur, higher and more variable ash, and poorer physical characteristics. This has been brought about by less selective coal mining, increased production rates in coke plants and resumption of operations of many beehive ovens. In a single month last year, one blast-furnace plant in the Pittsburgh district operated with coke obtained from 52 sources. The effect of variability and quantity of coke ash on blast-furnace operation is well known. The improved results obtained with furnaces operating on coke made from washed coals compared with results on coke made from raw coals is ample proof of the effectiveness of low and uniform ash. Coal-washing plants, however, require a large capital expenditure, and are impractical for most of the large number of small producers, whose operations are confined chiefly to periods of abnormally high demand. Furthermore, not all coals are physically adaptable to washing. Principles 01 Iron Desulphurization in Furnace Although investigations of the blastfurnace process have not clearly revealed the detailed mechanism of iron desulphuri-zation within the furnace, they have been sufficiently extensive to permit a postula tion of the following general principles: 1. Iron, in its travel from furnace top to hearth, continues to pick up sulphur until it has reached tuyere level. The zone of iron desulphurizatioil is relatively narrow, being confined to a vertical distance extending zapproximately from tuyere level to the iron-slag interface in the hearth.' 2. Combustion of coke is confined to spherical zones extending approximately 40 in. from the nose of each tuyere.= Coke ash is released as the coke bums in these combustion areas. 3. With a constant amount of sulphur in the charge, the sulphur content of the metal product is a function of hearth temperature, final slag analysis, slag viscosity, and slag volume. Both hearth temperature and slag analysis affect slag viscosity. For a slag of constant analysis, viscosity always decreases with an increase in temperature;

Jan 1, 1943

By B. Sadtler

The oldest producing district of Park county, and in fact one of the oldest producing gold-districts of the State, is situated on the head-waters of the Platte and tributary streams. Geo-

Jan 1, 1897

By C. C. Koch, M. L. Picklesimer

PHYSICAL metallurgists interested in the alloying behavior and phase transformations in rare-earth metals and alloys require a strain-free polished and etched surface for both metallographic and X-ray examination. However, the rare earths have presented a problem in this respect since they are difficult to polish free from strain and are very reactive to the atmosphere. Their tendency to oxidize readily even at room temperature necessitates careful preparation and rather elaborate protection if their surface is to be examined for any length of time. The "light" lan-thanides (i .e., atomic numbers less than 63), especially lanthanum and cerium, are particularly bad in this regard; they oxidize very rapidly at room temperature. To eliminate the problem of plastic deformation remaining on the surface after mechanical polishing, electropolishingl and chemical polishing techniques2 have been developed. The electropolishing technique requires the specimen to be immersed in an electrolyte at -77°C and thus obviates a metallographic study of, for example, the fcc —double-hexagonal close-packed (dhcp) transformation in cerium which begins at -10°C. The chemical polishing solution has been used only on several of the "heavy" rare-earth metals. However, a convenient method for protecting the polished and etched surfaces from atmospheric corrosion has not been available. Our interest in the superconducting properties of lanthanum, and in the phase transformations in lanthanum and cerium, has led us to develop a technique for the metallographic preparation of lanthanum and cerium which clearly reveals the microstructure and preserves the etched surface for days. The specimens are chemically polished and anodized. The chemical polishing is performed at room temperature, the anodic oxide film provides the required protection from the atmosphere, and colors produced in the film provide a simple positive technique for phase identification. Lanthanum and cerium metal ingots obtained from Johnson Matthey and Co., Ltd., were remelted to suitable shapes and heat-treated to produce various microstructures. The samples were placed in epoxy mounts and, after a small hole was drilled in the back of the mount for electrical contact, were ground on silicon carbide

Jan 1, 1968