Search Documents

By Edward Sampson

Despite the many industrial uses, the world market for silver as a commodity is far from free, being dominated by the U.S. Government both through acts of Congress and by policy of the Treasury Department. This discussion will consider aspects of supply, demand, and price with a view to the future. Changes in Sources of Supply: The world's peak production of silver, 278 million oz, was in 1937. In the 1850's world production was about 30 million oz, having risen from a yearly average of 11 million oz for the first half of the century. From 1860 to 1940 there was a steady rise, broken only by World War I and the depression of the early 1930's.

Jan 7, 1960

By Robert H. Richards

VERY little has been published recently on this subject in the mining journals or proceedings of societies. The attention of experts has been diverted perhaps by the demands for pan amalgamation of refractory ores. Yet free milling ores occur in many localities, and it may be interesting to have on record some data as to details of running a small test-mill, especially as details of results do not seem to be accessible to students and investigators. Küstel, in 1863, under battery amalgamation, dismisses the subject by stating that "amalgamation on copper-plated platforms, troughs, and other copper fixings" is " very imperfect, and mostly abandoned." J. Arthur Phillips says, in 1867, under placer mining : A well-amalgamated copper plate is considered as effective for

Jan 1, 1880

By J. R. Kyte, R. L. Dalton, V. O. Naumann, R. L. Ridings, R. W. Greene

This paper presents a one-dimensional numerical method for calculating dissolved-gas-drive behavior for a single well or a linear reservoir. Pressure and saturation distributions can be calculated, including the effects of capillary and gravity forces. The analysis has been programmed for solution on the IBM 7090 digital computer. A comparison of experimental and calculated behavior for two linear models demonstrates that the method is suitable for calculating dissolved-gas-drive behavior under reservoir conditions of flow. Dissolved-gas-drive tests were run, at different production rates and with oils of different viscosities, on short (6.ft) and long (173ft) flow models. For tests approximating reservoir pressure gradients and flow rates, there was excellent agreement between experimental and calculated results. A series of calculations of well behavior for thin, horizontal, homogeneous, dissolved-gas-drive reservoirs shows that ultimate recovery is independent of production rate or well spacing in such cases. These calculations also show that Muskat's method and similar material-balance analyses are not applicable under some conditions particularly for high pressure drawdowns. INTRODUCTION The problem of calculating dissolved-gas-drive reservoir performance has received a great deal of attention throughout the oil-producing indusfry for many years. Really significant advances, however, have been made only in recent years. The rapid evolution of high-speed computing equipment and techniques has opened up new approaches to the problem and led to realistic, quantitative analyses free of many of the assumptions and limitations of earlier methods. The one-dimensional numerical method described in this paper includes the effects of both gravity and capillary forces. A number of test calculations, based on different rates, spacings, and rock and fluid properties, have shown that the method is adequate for systems that can be reasonably represented by a one-dimensional model (linear or radial) and in which fluid segregation perpendicular to the direction of flow is not important. Along with the development of mathematical methods, an experimental program was conducted and the data were used to test the validity of the theoretical basis of the mathematical method. Linear models were used and all experiments were run using 1,000-psig bubble-point oils. The use of long, high-pressure models enabled us to more closely approach reservoir gradients and flow rates. MATHEMATICAL FORMULATION DIFFERENTIAL EQUATIONS The differential equations describing dissolved-gas-drive behavior in one dimension dare summarized here. They include Darcy's law for flow of oil and gas (Eqs. 1 and 2) and the equations for conservation of mass for oil and gas (Eqs. 3 and 4). The oil and gas pressures are related by capillary pressure (Eq. 51.

By Edward D. Peters

IT frequently occurs in the establishment of reduction works, in an entirely new and untried mining district, that the metallurgist in charge finds considerable difficulty in determining the process best adapted to the ores which he receives for treatment. At the first glance it would seem easy enough to decide what style of furnace is best adapted for beneficiating any one class of minerals. If the ore possessed a quartzose gangue and was comparatively free from base metals, while salt could be obtained at a reasonable price, one would naturally resort to a chloridizing roasting, and pan or barrel amalgamation for the extraction of its silver contents. If galena or carbonate of lead was the prevailing mineral, and charcoal could be obtained at moderate figures, the blast-furnace would beneficiate the ores most advantageously. But if, as is usually the case in Colorado, the ores consisted of an intimate mixture of galena, zinc-blende, copper-pyrites, and noble silver minerals, associated with an overwhelming mass of siliceous heavy spar, or limestone gangue, the common reverberatory furnace can be used to the greatest advantage; and, although the product is only a copper matte, I do not hesitate to affirm that it can be treated, and the silver, gold, and copper produced at nearly the same price for which silver and lead can be separated. In Germany, blast-furnaces are frequently used for this same purpose, both for argentiferous and non-argentiferous copper ores ; but any one who will take the trouble to examine the statistics of smelting at Fahlun, the Oberharz, and other Continental works of this description, will see that the expenses are far too great, and the production much too small to think of employing this method in our mining districts, where only the softest and most miserable kind of charcoal is obtainable. I propose in this paper to give an accurate account of the expenses incurred at the Mount Lincoln Smelting Works in treating the same kind of ore, and producing the same end-product in both blast and reverberatory furnaces. I have taken for comparison a favorable campaign of the blast-furnace, and a good average month's running of the reverberatory. In the blast-furnace estimate I have included the calcining and concentration of the matte produced during that campaign, as I always, when possible, concentrated the regulus made

Jan 1, 1874

By T. S. Lundy, R. E. Pawel

Effects of short-circuiting paths on observed diffusion behavior in real crystalline systems are considered. It is concluded that experimentally measured diffusion coefficients may vary widely from values associated with true lattice diffusion to those appropriate for short-circuiting paths alone depending upon the conditions of the experiment and the sensitivity and completeness of the data. IN 1961 Harrison1 classified experimentally observed diffusion behavior in systems involving both lattice and dislocation-enhanced atomic transport into three categories. His types A and C were limiting cases where the measured diffusion coefficients using the usual serial sectioning techniques were representative of lattice diffusion (with only slight effects of dislocations) and dislocation-network diffusion (with only slight effects from lattice diffusion), respectively. In both cases A and C for a sectioning experiment in which the diffusion couple has the semi-infinite geometry and unidirectional diffusion takes place from a plane source located at the origin of the coordinate system, he pointed out that Gaussian penetration behavior should be observed. For case A the lattice coefficient should be slightly enhanced by dislocation contributions, and the model of Hart2 can be used to predict the amount of this enhancement. For case C the observed coefficient should be that for the dislocation network and have little or nothing to do with lattice diffusion. Hart's model in its general form is still applicable, but the apparent diffusion coefficient for this case is virtually independent of dislocation density. Harrison's case B is that for which non-negligible contributions exist for transport by both mechanisms and "the concentration distribution does not approximate to any simple form." With the possible exception of very low temperatures where diffusion distances approach atomic dimensions, any real diffusion specimen will in general show non-Gaussian behavior provided the data are complete enough to uncover it. Thus, a "complete" set of data for any real system cannot be expected to be totally amenable to treatment by a simple mathematical model which does not take into account the relative distribution of transport by the various modes or submodes. For a particular sensitivity of specimen analysis and at a given temperature of annealing if the concentration profile could be observed as a function of time, "the behavior will initially be type C, and will develop into type B. and ultimately type A".1 Thus, it appears that the type of diffusion behavior which is experimentally observed in a given system depends very much upon the particular experimental conditions and the particular tools available to obtain the data. Interpreted in this fashion, Harrison's classification refers not to the diffusion behavior as a whole but to the relative sensitivity of the method of examination and completeness of the data. In the present paper we will: 1) assume that the measured penetration behavior follows the same general classification as that proposed by Harrison; 2) give, for diffusion in tungsten, examples of the range of diffusion coefficients that it is possible to obtain in a single experiment; and 3) speculate that some arguments which consider the possibility of short-circuiting effects being responsible for "anomalous" diffusion in several bcc metals may have been discarded prematurely.3 Both monocrystalline and polycrystalline tungsten were used in this work. The former was obtained as triple-pass, electron-beam zone-refined 6.0-mm-diam rod from Materials Research Corp.. Orange-burg. N.Y. The latter was swaged, high-purity bar stock which was annealed for 2 hr at 2200°C and 10-9 torr to yield an average grain diameter of about 25 /i. The tracer Nb95 was received in oxalate solution from the Isotopes Division, Oak Ridge National Laboratory. Experimental procedures of specimen preparation, isothermal diffusion annealing, serial sectioning by anodizing-and-stripping, and y counting of the individual sections to determine the tracer penetration profile after a given diffusion anneal have been described elsewhere.4 However, it should be noted that the anodizing-stripping sectioning technique has the particular advantage for this research of permitting sectioning to be accomplished over a wide range of

Jan 1, 1970

By Persifor Frazer

For various reasons I have not specified the locality where the research indicated in the following pages was undertaken. It will suffice to say that it was on the grounds of a villa once remote from, but now completely surrounded by, its neighboring city, and in close proximity to an industrial establishment of great extent and importance manufacturing many kinds of steel articles and employing upwards of thirty chimney-stacks for power and process work. The problem was to discover the cause or causes of the mortality to trees and plants on the place, and to trace these causes to their origin. Before undertaking this experimental work, the bibliography accompanying this paper was compiled and studied. It appears from an examination of the careful scientific work performed by the ablest French, German, and English chemists during the last 25 years that they are unanimous in assigning the principal—in fact, the overwhelmingly predominant— cause of the destruction of vegetation to sulphur oxides, resulting either from direct oxidation of sulphur in oil of vitriol works, etc., or from the oxidation of the sulphur from the minerals associated with commercial coal. Schroder and Schertel showed in 1884 that the sulphates deposited upon the leaves are not injurious to the plants; and Freytag proved that free sulphuric acid could not be found

Jan 1, 1908

The passing of Benjamin Bowden Lawrence in January, 1921, was a distinct loss to the engineering profession. Mr. Lawrence had a genius for reviving abandoned mines and developing them into substantial producers. A notable example of his work in this line was the Dives-Pelican near Georgetown, Colo. While on an exploring expedition in 1888, he examined this old mine and was convinced that bonanza ore still existed there. He located the owners of the property, and induced them to place sufficient capital at his disposal to enable him to re-open and explore this mine. So confident was he of the outcome that he undertook this work on a profit-sharing basis without salary. Within eighteen months the old Dives-Pelican was operating profitably, and for the following ten years it paid very substantial dividends. The late Theodore N. Vail was one of the owners of this old mine, and many years later, at a dinner given to Mr. Lawrence by the Alumni of Columbia University, Mr. Vail told the story of the resuscitation of the Dives-Pelican by Mr. Lawrence, and declared that the dividends he himself had received provided a large part of the funds that made possible the realization of his dream of establishing the long-distance telephone in this country. The E1 Cobre mines at Santiago de Cuba also owed their renewed life to Mr. Lawrence. Under his management, these mines produced and shipped several million pounds of copper per year. He was for several years consulting engineer for the Kerr Lake and other silver mines in the Cobalt region; the Kerr Lake became famous as a silver producer. Mr. Lawrence spent more than twenty years of his life in the mining camps of the West. He was but twenty-one years of age, and only a few months out of college, when he was appointed manager of the great Chautauqua Lode (a silver mine) located on Glacier Mountain near Montezuma, Colo. Here, isolated in the mountains for several months each year by ice and snow, he worked for five years to make these mines Pay. He possessed unusual breadth of vision and human understanding; he had ''personality plus," and when he opened an office in New York City as consulting engineer he quickly rose to an enviable position in his profession. Young engineers worked with enthusiasm under his guidance. He carefully selected his men, discussed fully with them the plans and policies to be pursued, then left them free to accomplish results in their own way. This attitude developed individuality and resourceful-

Jan 1, 1922

The passing of Benjamin Bowden Lawrence in January, 1921, was a distinct loss to the engineering profession. Mr. Lawrence had a genius for reviving abandoned mines and developing them into substantial producers. A notable example of his work in this line was the Dives-Pelican near Georgetown, Colo. While on an exploring expedition in 1888, he examined this old mine and was convinced that bonanza ore still existed there. He located the owners of the property, and induced them to place sufficient capital at his disposal to enable him to re-open and explore this mine. So confident was he of the outcome that he undertook this work on a profit-sharing basis without salary. Within eighteen months the old Dives-Pelican was operating profitably, and for the following ten years it paid very substantial dividends. The late Theodore N. Vail was one of the owners of this old mine, and many years later, at a dinner given to Mr. Lawrence by the Alumni of Columbia University, Mr. Vail told the story of the resuscitation of the Dives-Pelican by Mr. Lawrence, and declared that the dividends he himself had received provided a large part of the funds that made possible the realization of his dream of establishing the long-distance telephone in this country. The E1 Cobre mines at Santiago de Cuba also owed their renewed life to Mr. Lawrence. Under his management, these mines produced and shipped several million pounds of copper per year. He was for several years consulting engineer for the Kerr Lake and other silver mines in the Cobalt region; the Kerr Lake became famous as a silver producer. Mr. Lawrence spent more than twenty years of his life in the mining camps of the West. He was but twenty-one years of age, and only a few months out of college, when he was appointed manager of the great Chautauqua Lode (a silver mine) located on Glacier Mountain near Montezuma, Colo. Here, isolated in the mountains for several months each year by ice and snow, he worked for five years to make these mines Pay. He possessed unusual breadth of vision and human understanding; he had ''personality plus," and when he opened an office in New York City as consulting engineer he quickly rose to an enviable position in his profession. Young engineers worked with enthusiasm under his guidance. He carefully selected his men, discussed fully with them the plans and policies to be pursued, then left them free to accomplish results in their own way. This attitude developed individuality and resourceful-

Jan 1, 1922

By H. C. Johnson, J. K. Elliott

One of the primary requirements for successful operation of an enriched gas-drive project is to control the composition of injection gas. This can become a serious and difficult problem, particularly in cases where the enrichment material is being furnished from a number of field -produced gas streams. It is possible to effect control of the injection gas composition through frequent or continuous sampling; however, this can be extremely costly and, in many cases, impractical due to laboratory requirements of time. Another alternative would be to provide a calculation technique which would be flexible and sufficiently accurate to predict composition of the liquid and gas streams of interest at any point in the system. The purpose of this paper is to discuss a technique that was used successfully on an operating enriched gas-drive project for developing information which could be used for controlling composition of the injected gas. FIELD OPERATIONS The particular field (hereafter called Example field) in the example operation being discussed is composed of four oil reservoirs (A. B, C and E) and one gas condensate reservoir (D). Casinghead gas from the oil reservoirs and gas from the gas condensate reservoir are gathered through a field gathering system as shown in Fig. I for injection into Reservoir C. The gas mixture which is recovered from the five reservoirs for injection purposes is composed of gases liberated in 19 individual separators, each operating at a separate temperature and pressure. PROPOSED CALCULATION TECHNIQUE It is well known that vapor-liquid equilibrium calculations in general use throughout the petroleum industry can be used to predict reliably the phase behavior of hydrocarbon mixtures, particularly at pressures less than 1,000 psig. It is then a simple matter to account for the material on a ComPonent basis by m''ing flash and material balance calculations at each separation point in a hydrocarbon system. Accordingly, it was proposed to use vapor-liquid equilibrium and material balance cal- culations with a medium-sized electronic digital computer as a basis for developing a control procedure for use in controlling injection gas composition in the enriched gas-drive project. Although the approach is a simple one, the numerous vapor-liquid equilibrium calculations involved make the problem laborious; in this particular case, it would have been impractical to make sutficiently complete analysis without the aid of digital computing equipment. SAMPLING AND VERIFICATION OF CALCULATION PROCEDURE To obtain representative gas and liquid stream samples and to provide a quantitative measure of overall system Performance for comDarative purpLses, a thorough test of the field and plant system was conducted in the summer of 1957. Oil production at each battery was sta-

By R. L. Templin

The increasing use of aluminum and its alloys in commercial fields tias demanded a better understanding of their machining properties. This fact is exemplified by problems that have arisen in the automotive and airplane industries, but many in other fields might be cited. As pure alunlinum and its alloys in their various commercial conditions show appreciable differences in their machining properties, it is not surprising that quite divergent solutions have been offered for the machining problems encountered. However, if the fundamental requirements of the most suitable cutting tools for these metals are understood, these machining problems lend themselves more readily to satisfactory solutions. Since the machining of free cutting brass and mild steel is understood by most persons accustomed to working these metals, it may serve our purpose better to first make a general comparison of the tools more commonly used in machining these metals with the tools most suitable for machining aluminum, then proceed to a more specific discussion of the individual tools. Comparison oF Cutting Tools Cutting tools commonly used for machining free cutting brass usually have little, if any, top and side rake; they are ground on a medium to coarse abrasive wheel and used without any cutting compound or with a cutting compound that has a paraffin base. Those ordinarily used for steel have some top and side rake, are usually ground on a medium to fine abrasive wheel, and are often used with soluble-oil cutting compounds. The proper tools for aluminum and its alloys should have appreciably more side and top rake than the tools for cutting steel; should have very keen edges obtained by grinding with fine or very fine abrasive wheels supplemented in many cases by hand stoning with an oil-stone; and should be used with suitable cutting compounds whenever possible. In many cases, tools suitable for machining aluminum and its alloys are not appreciably different from tools commonly used for cutting hardwoods. The front clearance of a tool most suitable for machining aluminum and its alloys should be about 6°, the top rake from 30" to 50°, making the total angle of the cutting edge of the tool from 35' to 55". A side

Aamot, Olav Crone, Research Engr., Guggenheim Bros. Labs., 3,771 10th Ave., New York, N. Y. '29 Abbott, Clarence E., V.P., Charge of Raw Materials, Tenn. Coal, Iron & R. R. Co., 1242 Brown-Marx Bldg., Birmingham, Ala. '04 Abbott, Louis Benjamin, Chief Engr., Consolidation Coal Co., Watson Bldg., Fairmont, W. Va. '15 Abeel, George H., Jr., Cons. Min. Engr 128/ S. Canon Dr., Beverly Hills, Calif. '18 Abel, Raymond L., Asst. Prof., Dept. of Pet. Refin., Univ. of Pittsburgh Pittsburgh, Pa. '28 Abel, Walter D., Cons. Engr 364 S. Cloverdale Ave., Los Angeles, Calif. '32 Abele, Louis T 1457 Euclid Ave., Zanesville, Ohio. '31 Abell, Leo M Sullivan Concentrator, Chapman Camp, B. C., Canada. '31 Abort, Robert H., Asst. Met., Research Lab., U. S. Steel Corp., Lincoln Highway, Kearny, N. J. '19 Abraham, W. E. V., East India United Service Club, 16 St. James' Sq., London, S. W. 1, England. '28 Abstain, Henry T., Engr. & Mgr., Profile-Tamarack Mines Co Yellow Pine, Idaho. '27 Acker, E. O'C., Met 128 East Washington Late, Germantown, Philadelphia, Pa. '86 Ackermat, D. E., Research Met., International Nickel Co., Inc. Bayonne, N. J. '35 Acres, T. H., Geol. Dept., Valuation & Pet. Engrg., Richfield Oil Co., 555 S. Flower St., Los Angeles, Calif. '29

Jan 1, 1934

By T. S. Spice, H. L. Lovell, R. W. Utley

With the increased demand for lightweight aggregate, such materials have been manufactured from slags, clays, slates and, to a minor extent, the refuse of coal preparation processes. The latter source is attractive due to current interest in eliminating air pollution and improving the unsightly appearance of refuse piles as well as potential economic advantages, if a satisfactory product can be manufactured. A study has been made relating the composition of coal refuse, expressed as washability data, and the properties of a resulting aggregate. Three different refuse samples (bituminous and anthracite) were separated at gravities ranging from 1.4 to 2.96. Their chemical composition was determined. Aggregates were prepared in the laboratory from these fractions before and after ashing, at temperatures between 1250' and 1350°C. The specific gravity, expansion and compressive strength of the products were measured. The response of the refuse to bloat is related to the chemical composition of the ash to yield a glass of desirable viscosity and to the presence of a material which will form a gas in the appropriate temperature range. Carbonaceous material within the particle is a negative factor since after the glassy phase forms, oxygen cannot enter the mass thus inhibiting bloating. Precombustion of the refuse is also detrimental since it removes substances of gas-forming capability. The fraction sinking at 2.60 yielded an aggregate which had the lowest specific gravity, greatest expansion and greatest compressive strength. The purpose of this study was to seek and evaluate possible relationships between the composition of coal refuse, as expressed by washability data and factors affecting the production of a lightweight aggregate from refuse by bloating. The study was related to an intense program in the Department of Mineral Preparation at the Pennsyl- vania State University to study the possible elimination of air pollution from coal refuse fires by producing a low-carbon secondary refuse. Another phase of this program is considering possible uses of such a secondary refuse. Thus one study was to determine if a lightweight aggregate could be produced from this new refuse material and what effect the nature of refuse beneficiation would have upon the characteristics of a commercial aggregate product. It was hoped that these studies would assist in the design of a process and in establishing the optimum specific gravities at which refuse separation could be made in respect to the production of a low grade fuel from the float product and a raw material for lightweight aggregate from the sink product. The combination of producing a saleable low grade fuel and a lightweight aggregate, while at the same time minimizing disposal costs and air pollution contributions would be attractive to the coal mining industry. MECHANISM OF BLOATING Austin, Nunes and Sullivan,1 Ehlers,3 Everhart, 4 Riley7 and others, have stated that bloating is an expansion process in which two essential conditions exist simultaneously. These are: the development of a glassy phase over a relatively wide temperature range (the viscosity of this glassy phase plays a major role in the retention of the evolved gases) and the evolution of gases (SO2, SO3, CO2 and O2) from mineral decomposition in sufficient quantities at appropriate temperatures to form a cellular structure in the mass. Unless these two "type" reactions take place at the same time or in overlapping ranges of time and temperature, cellulation will not occur. In this event, the gas will escape or the melt will be too fluid to retain it; or if retained, the cells may be too large or the walls too thin for good strength in the product. The stages that occur when clays and shales are heated in an oxidizing atmosphere may be summarized as follows: 1) Drying and removal of free water to 200°C. 2) Absorbed water dehydration period (200 to 480°C). 3) Chemically-combined water dehydration period (480 to 700°C).

Jan 1, 1965

By Robert B. McCormick

WORLD WAR II has developed a use for the nonmetal mineral quartz crystal that was unknown in World War I. During the interim period of peace, experimental work in the radio field with the piezoelectric properties of quartz crystal resulted in the almost universal adoption of quartz-crystal radio oscillator plates to control frequency in radio broadcasting, police, commercial and amateur communications equipment. Telephone resonators and filters made from quartz crystal also were developed, which vastly improved the frequency control of long distance telephone circuits. EXPANSION OF THE INDUSTRY The sudden war demands of the armed services for radio equipment using quartz crystal for frequency control led to an unprecedented expansion of the manufacturing industry. It is estimated that the 1940 peacetime volume amounted to approximately $1,500,000, while today a vast new quartz-crystal industry supplies more than $150,000,000 worth of quartz oscillator plates to the Army and Navy each year. This demand has caused an enormous expansion not only of American manufacturing facilities but also of Brazilian mining output, virtually our only source of raw quartz crystal. Actual figures of imports and consumption cannot be cited, for security reasons, but certain comparisons have been made, which indicate the transformation of quartz crystal from a minor to a major nonmetal. Lends has shown that the value of quartz-crystal exports from Brazil is now about equal to that of phosphate rock produced domestically in 1941 and actually exceeds the combined value of crude feldspar, gypsum and fluorspar production in the United States in the same year. This great expansion under wartime pressure was not accomplished without some anxious moments, but all the demands of industry have been met and the Government has been able also to accumulate a substantial stock pile of material against future contingencies. INSPECTION AND GRADING OF QUARTZ CRYSTAL The swift growth of the quartz-oscillator industry necessitated the simultaneous evolution of methods and criteria for inspecting and grading quartz crystal. It has been found that, generally speaking, it is economically feasible to cut only crystals that are at least 30 per cent by volume free from major defects such as optical and electrical twinning, cracks and fractures. Blue needles, bubbles, "chuva" and other minor imperfections can be tolerated in the usable portion unless present in great excess. The present marketing system in use in both Brazil and the United States, as far as quality is concerned, depends solely on the "usability" of a crystal, which is defined in the Brazilian-American agreement2

Jan 1, 1945

By I. S. Servi, N. W. Marr

TIN markedly increases the softening temperature of pure copper with only a moderate effect on conductivity. Smart and smith' indicated a substantial increase in softening temperature upon addition of different levels of tin up to 0.05 pct in oxygen-free copper. However, after finding no effect of tin in copper containing about 0.025 pct O, they concluded that "the presence of oxygen completely nullifies these changes in properties by precipitation of SnO2.'' Since preliminary tests on Cu-Sn-0 alloys indicated that this conclusion is not valid outside the extremely limited tin range investigated by Smart and Smith, research was primarily directed toward the partition of tin between the copper-base matrix and the oxide phases. Experimental. Material was prepared by sealing an 80 to 100-g charge consisting of oxygen-free copper, tin, and copper oxide into a y-in.-ID quartz capsule which was evacuated and back-filled with tank-grade argon to 3 atm. The sealed vials were heated to 1125ºC, kept at temperature for 30 min, occasionally agitated, and then allowed to air-cool outside the furnace ("as-cast"). The castings were cold-swaged to 0.370 in., annealed 1 hr at 600°C ("as-annealed"), and cold-swaged 16.5 pct ("as-swaged"). Cross sectional wafers were annealed for 1 hr at various temperatures and Rockwell F hardness measured. The "softening temperature" was defined as the interpolated temperature at which the hardness was 50 Rockwell F. Electrical resistance was measured by an ac poten-tiometric method on 0.040-in.-diam wires after a 1 hr anneal at 600°C. Relative accuracy was of the order of 1 pct. Chemical analyses for tin were performed by two methods, identified as "Acid flux" and "HN03 dissolution". The first consisted of fusing the sample with potassium pyrosulfate and leaching the resulting melt with 10 pct sulfuric acid. The spectrophotometric procedure which followed is described in Ref. 2. Oxygen analyses were performed by the vacuum-fusion method with a bath temperature of 1650°C. Tin content of oxides and copper phases was measured with the X-ray microprobe, using a calibration curve based on a series of oxygen-free Cu-Sn alloys. Results. In Fig. 1, the nominal tin composition for alloys containing nominally 400 ppm O was plotted vs the analyzed or the computed tin content—the latter derived from one of the following: 1) "acid flux" chemical analysis; 2) "HN03 dissolution" chemical analysis; 3) X-ray microprobe analysis of the copper matrix; 4) equivalent tin content, based on the measured increase in electrical resistivity (an increase in resistivity of 1.6 microhm-cm is approximately equivalent to 1 wt pct of sn1,3). It is evident from Fig. 1 that the results of the acid flux analysis are consistent with the nominal composition while the HNO3 dissolution method generally yields lower values, consistent with those obtained from electrical resistivity measurements and somewhat higher than those obtained by microprobe analysis. Microprobe and resistivity values are affected only by the tin in solid solution; hence the HN03 method

Jan 1, 1970

By Robert B. McCormick

World War II has developed a use for the nonmetal mineral quartz crystal that was unknown in World War I. During the interim period of peace, experimental work in the radio field with the piezoelectric properties of quartz crystal resulted in the almost universal adoption of quartz-crystal radio oscillator plates to control frequency in radio broadcasting, police, commercial and amateur communications equipment. Telephone resonators and filters made from quartz crystal also were developed, which vastly improved the frequency control of long distance telephone circuits. Expansion of the Industry The sudden war demands of the armed services for radio equipment using quartz crystal for frequency control led to an unprecedented expansion of the manufacturing industry. It is estimated that the 1940 peacetime volume amounted to approximately $1,500,000, while today a vast new quartz-crystal industry supplies more than $150,000,000 worth of quartz oscillator plates to the Army and Navy each year. This demand has caused an enormous expansion not only of American manufacturing facilities but also of Brazilian mining output, virtually our only source of raw quartz crystal. Actual figures of imports and consumption cannot be cited, for security reasons, but certain comparisons have been made, which indicate the transformation of quartz crystal from a minor to a major nonmetal. Lundl has shown that the value of quartz-crystal exports from Brazil is now about equal to that of phosphate rock produced domestically in 1941 and actually exceeds the combined value of crude feldspar, gypsum and fluorspar production in the United States in the same year. This great expansion under wartime pressure was not accomplished without some anxious moments, but all the demands of industry have been met and the Government has been able also to accumulate a substantial stock pile of material against future contingencies. Inspection and Grading of Quartz Crystal The swift growth of the quartz-oscillator industry necessitated the simultaneous evolution of methods and criteria for inspecting and grading quartz crystal. It has been found that, generally speaking, it is economically feasible to cut only crystals that are at least 30 per cent by volume free from major defects such as optical and electrical twinning, cracks and fractures. Blue needles, bubbles, "chuva" and other minor imperfections can be tolerated in the usable portion unless present in great excess. The present marketing system in use in both Brazil and the United States, as far as quality is concerned, depends solely on the "usability" of a crystal, which is defined in the Brazilian-American agreement2

Jan 1, 1948

By Robert B. McCormick

World War II has developed a use for the nonmetal mineral quartz crystal that was unknown in World War I. During the interim period of peace, experimental work in the radio field with the piezoelectric properties of quartz crystal resulted in the almost universal adoption of quartz-crystal radio oscillator plates to control frequency in radio broadcasting, police, commercial and amateur communications equipment. Telephone resonators and filters made from quartz crystal also were developed, which vastly improved the frequency control of long distance telephone circuits. Expansion of the Industry The sudden war demands of the armed services for radio equipment using quartz crystal for frequency control led to an unprecedented expansion of the manufacturing industry. It is estimated that the 1940 peacetime volume amounted to approximately $1,500,000, while today a vast new quartz-crystal industry supplies more than $150,000,000 worth of quartz oscillator plates to the Army and Navy each year. This demand has caused an enormous expansion not only of American manufacturing facilities but also of Brazilian mining output, virtually our only source of raw quartz crystal. Actual figures of imports and consumption cannot be cited, for security reasons, but certain comparisons have been made, which indicate the transformation of quartz crystal from a minor to a major nonmetal. Lundl has shown that the value of quartz-crystal exports from Brazil is now about equal to that of phosphate rock produced domestically in 1941 and actually exceeds the combined value of crude feldspar, gypsum and fluorspar production in the United States in the same year. This great expansion under wartime pressure was not accomplished without some anxious moments, but all the demands of industry have been met and the Government has been able also to accumulate a substantial stock pile of material against future contingencies. Inspection and Grading of Quartz Crystal The swift growth of the quartz-oscillator industry necessitated the simultaneous evolution of methods and criteria for inspecting and grading quartz crystal. It has been found that, generally speaking, it is economically feasible to cut only crystals that are at least 30 per cent by volume free from major defects such as optical and electrical twinning, cracks and fractures. Blue needles, bubbles, "chuva" and other minor imperfections can be tolerated in the usable portion unless present in great excess. The present marketing system in use in both Brazil and the United States, as far as quality is concerned, depends solely on the "usability" of a crystal, which is defined in the Brazilian-American agreement2

Jan 1, 1948

By Raymond B. Ladoo

TIIe milling of talc, as is the case with many non-metallic minerals, until recently, has not received adequate technical consideration, for the talc industry has become of importance only within the last decade. At first, talc was used only in the massive form, for foot warmers, griddles, and so on, and milling methods were unnecessary. As the demand for ground talc increased, producers adopted the machinery used in the milling of flour; in fact, many talc mills were rebuilt flour mills. Improvement has been slow, but today several types of grinding and separating machinery are in use; many of them, however, are still inadequate and inefficient. To determine the best methods of milling talc, it is necessary to understand the essential properties a talc must possess to fit it for a particular use. For toilet purposes, whiteness, freedom from lime and grit, fineness of grain, and good "slip" are essential. As a paper filler or coating, the talc must be white, uniform, and fine grained, have a good slip, and be free from grit and iron; freedom from lime is a disputed point. Fibrous talc is supposed to be superior to massive on account of the interlocking of grains in the paper, thus increasing its strength; this point, though, is in doubt. In general, talc for the paper industry need not be of as high quality or as fine grained as that used for toilet purposes. Talc is usually bought by sample, for which reason it is difficult to state the essential properties for use in paint, rubber, roofing, and so on. The adoption of standard screen tests and standard grades by producers is necessary before an accurate basis for manufacturing or selling standards can be established. Off-color talcs might be utilized, as in Germany and Austria, by the establishment of standard grades of colored talcs. The machinery to be used depends on whether the talc is fibrous, foliated, or massive; hard or soft; of uniform or variable grade; pure or impure. In some cases, it is possible to change the mining practice or to utilize different sections of the deposit in order to vary some of these factors, but in many cases these factors are fixed, so the milling must be designed to suit the conditions.

Jan 1, 1922

By R. Schuhmann, G. W. Powell

The concept of local equilibrium is examined and, in particular, the applicability of the concept to two-phase binary diffusion couples is discussed. It is concluded that, if binary solid solutions are treated thermodynamically as ternary solutions, vacancies being the third component, then recent experimental observations of nonequilibrium interface compositions (i.e., compositions different from the phase diagram values) are consistent with a state of complete dynamic equilibrium at the interface. CLASSICAL approaches to diffusion and to other irreversible processes often utilize a postulate of "local equilibrium". That is, one assumes even in the presence of gradients, fluxes, and time changes of properties, a) that the Second Law can be formulated locally, and b) that thermodynamic equations of state among intensive properties are identical with those for equilibrium phases. A direct consequence of this assumption, for example, is that one would calculate the total entropy of a nonequilibrium phase simply by integrating the entropy density (eu per unit volume) over the volume of the phase, assuming that entropy density is the same function of energy and particle density as for equilibrium phases. In the study of diffusion and of diffusion-controlled phase transformations, metallurgists take this concept of local equilibrium for granted and utilize it automatically. In fact, experimental evidence of all kinds is overwhelming that "local equilibrium" is a valid limiting law, approached more and more closely as gradients and rates of change approach zero. On the other hand, we have neither experimental nor statistical thermodynamic proof that this principle of "local equilibrium" should remain rigorously valid at high gradients and for rapid processes. Theoretically, in fact, one would expect deviations because interactions between adjacent volume increments of material affect the evaluation of entropy. Also one observes experimentally structural and small energetic differences between equilibrium and nonequilibrium phases. The purpose of this paper is to present a thermodynamic framework for the study and correlation of deviations from strict local equilibrium in isothermal diffusion and related processes. This procedure, in effect, preserves the principle of local equilibrium by thermodynamically assigning the deviations from static equilibrium properties to a defect component. Although this theory is entirely phenomenological, the possibility does exist of correlating the theory with experimental observations of defects under favorable circumstances. The most immediate application appears to be to the equilibria at the interfaces in two-phase binary diffusion couples. A recent pertinent work by Eifert et al.1 has shown that the concentrations of aluminum in the a(fcc) and B(bcc) phases at the 0-8 interface in Cu:Cu-12.5 wt pct A1 diffusion couples are greater than those given by the phase diagram. It is postulated by these authors that the supersaturation of the o phase at the interface provides the driving force for the a-to-B lattice transformation; the excess free energy of the a phase, ?Gaxs, arising from the greater-than-equilibrium aluminum concentration is about 3 cal per g-atom. On the basis of the schematic free energy-composition diagram shown in Fig. 1, Eifert et al. concluded that the thermodynamic situation at the interface is one of the partial equilibrium; that is, = for the more mobile aluminum whereas will be reexamined in the latter part of this paper. THERMODYNAMIC PROPERTIES OF DEFECTS A rigorous analysis of the thermodynamics of defects requires an added degree of freedom in the Phase Rule sense, because the standard formulations of solution thermodynamics (partial molal properties of components, free energy minimization, equality of chemical potentials, and so forth) involve the implicit

Jan 1, 1970

• In 1949 the United States imported 7,400,000 tons of iron ore; Chile, Sweden and Canada, in that order of importance, supplied over 80 pct of this amount. U. S. imports have increased from 3 pct of the total supply in 1940 to 8 pct in 1949. • Mica has been successfully synthesized by scientists of the National Bureau of Standards. quartz, magnesite and bauxite, plus a fluorosilicate compound to act as a crystallizing agent, are heated to 2500°F in a platinum-lined crucible and as the furnace cools mica crystals grow. The key to parallel growth to make sheets is in precision control of temperature. • Inland Steel Co. of Chicago has taken an option to lease from Steep Rock Iron Mines, Ltd., of Canada -- a large undeveloped acreage in the vicinity of Steed Rock Lake, Ontario -- for the purpose of exploring and developing a new iron ore mine. The exploration program is expected to begin at an early date. •A 20-yr test conducted by the U. S. Bureau of Mines with the cooperation of Cleveland-Cliffs indicated that chemically treated timbers last from 2 to 3-1/2 times as long as untreated ones set in the same passageway. Of the three reagents used, zinc chloride gave the best result -- 13.3 yr as compared to 3.8 yr for untreated timber. •Senator Pat McCarran charged that President Truman used a "shotgun approach" to the taxation problem when he accused the mining industry of enjoying excessive depletion exemptions when actually mining taxes should be lowered. He introduced to the Senate a report of the National Advisory Council -recommending a decrease * The country's first graduate program of research and instruction in conservation of natural resources will begin at Yale in September. The Conservation Foundation is supplying $20,000 a year to finance the program. •Felix E. Wormser urged that adequate tariff protection should be provided to offset effects of devaluation on the domestic mining industry in an address before the Colorado Mining Association. He advocates tariffs rather than subsidy legislation, such as S. 2105, for the protection of the lead-zinc miners because the latter would promote inefficiency and "impair our priceless free market." •"It may be startling to realize that for the world's white population the per capita requirements for minerals have multiplied 30 times in 30 yr, or that more minerals have been mined in the last 40 yr than in all prior history." -- Evan Just, in "Mineral Depletion and Metal Supply." •The National City Bank in its monthly letter states that both management and the unions concede that there are too many miners trying to make a living out of the industry for its present market. •On Feb. 3 it was reported that 6000 Anaconda employes in Chile quit jobs in sympathy with striking telephone and electric workers. The government has ordered them back to work on penalty of discharge. It appears that the walkout will not be prolonged in view of the government stand.

Jan 3, 1950

By E. T. Turkdogan, L. J. Martonik, R. J. Fruehan

Electrochemical measuretnents of the solid oxide electrolyte galvanic cells CY-Cr2O3 I ZrO2 (CaO) 1 O (in Fe alloy) CY-Cr2O3 I Tho2 (Y2O3)I O en Fe alloy) have been made at 1600°C (2912°F) in order to test the Performance of such cells at liquid steel temperatures. The oxygen pvobe (cell) consists of a disk of ZrO2 (CaO) or Tho2 (Y2O3) electrolyte fused at one end of a silica tube filled with a mixture of Cr-Cr2O3 which is the reference electrode. Upon immersion in liquid steel, the electromotive force readings achieve a steady value within a few seconds, and remain steady for 30 win or more. The perforwzance of the probes has been tested using Fe-O, Fe-Si-O, Fe-Cr-O, Fe-V-O, and Fe-Al-O alloys; the oxygen contents of liquid steel derived from the measured electromotive forces are in satisfactory agreement with those determined by arulysis. Use of the probe in the deoxi-datiorz of steel, in laboratory experiments, is discussed. The results indicate that there is insignificant electronic conductivity in ZrO2(CuO) at oxygen activities down to those corresponding to 10 ppm in steel. At lower oxygen activities, probes tipped with ThOn (Y2O3) disks perform satisfactorily at oxygen activities down to 1 ppm O or less. THE key to the control of deoxidation of steel is a sensing device to measure rapidly the concentration of oxygen in liquid steel in the furnace, ladle or tun-dish at any desired stage of deoxidation. The analysis of the cast steel by the neutron-activation or vacuum-fusion method gives total oxygen as oxide and silicate inclusions. This analysis is important for guidance to steel cleanliness; however, such a postmortem is of little value in the control of deoxidation of liquid steel. At the General Meeting of the American Iron and Steel Institute in New York, 1968, Turkdogan and Fruehan' presented a paper on the preliminary results of the work done in this laboratory on rapid determination of oxygen in steel by an oxygen probe. Details of the work done in this laboratory leading to the development of a galvanic cell for the determination of oxygen in liquid steel, and the results of the tests made are given in this paper. It was through Wagner's contributions, since the early Thirties, to the physical chemistry of semiconductors in general that it ultimately became possible to construct galvanic cells for application at high temperatures. In 1957, Kiukkola and wagner2 successfully demonstrated the use of several solid electrolytes in measuring the free energies of several chemical reactions, in particular, the use of lime-stabilized zir-conia in high-temperature oxidation reactions. Starting 7 years later, a number of papers appeared in the technical literature3-' demonstrating possible applicability of galvanic cells for the determination of oxygen in liquid steel. In the earliest work, Japanese investigators3j4 experimented with various types of reference electrodes, e.g., graphite-saturated liquid iron at 1 atm CO or Ni-NiO mixtures; the results obtained, though promising, were not of sufficient accuracy. Except for the work of Baker and West,6 all other investigators5,7,8 showed that ZrO2(CaO) electrolyte could be used for this purpose. The main part of the galvanic cell used by Fischer and ~ckermann' and by schwerdtfeger7 (the latter work was done in this laboratory), consisted of a ZrO2(CaO) tube, -1 cm ID, closed at one end, with a platinum contact wire fixed mechanically inside the closed end. The tube was flushed with a gas of known oxygen partial pressure, e.g., air, CO-CO2 or H2-CO2 mixtures; gas along with the platinum lead wire served as the reference electrode. The oxygen contents derived from measured electromotive forces agreed reasonably well with the oxygen contents determined by vacuum-fusion analysis. It is evident from recent investigations that the electromotive force technique using a solid oxide electrolyte is fundamentally well suited for the determination of oxygen in liquid steel. However, it is equally clear that the cell arrangement of the type as commonly used is in need of considerable improvement, as it exhibits several shortcomings for industrial and even laboratory use. 1) Because of its size, the zirconia tube, though stabilized, has a poor resistance to thermal shock. 2) Fine pores and microcracks, which are invariably present in zirconia tubes, are detrimental to the satisfactory operation of the cell, particularly when gas reference electrodes are used. 3) Air or carbon dioxide reference electrodes give rise to high electromotive force readings; as a result, the determination of oxygen in steel becomes less accurate. For higher accuracy, the oxygen partial pressure of the reference electrode should be in the range similar to that of oxygen in steel. 4) Even in laboratory experiments, difficulties are experienced when flushing the tube with gases and maintaining the proper gas flow rate. Fischer and Ackermann,' who used air as the reference electrode, reported that when the flow rate was too low, furnace gases would leak into the electrolyte tube, therefore lowering the oxygen potential and measured electromotive force. The required flow rate in order to avoid leakage depended on the tightness of the electrolyte tube which varied with different tubes, thus making it difficult to predict in advance the required flow rate. However, if the flow rate is too high the inside wall of the electrolyte tube would be cooler than the wall

Jan 1, 1970