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By Edgar Stansfield

WHEN plants decay in a peat bog the woody parts form a brown pasty mass, or peat muck, largely soluble in. alkalis. This brown matter has been termed "ulmin." The same material, but commonly black in color, is found in coal, and there is evidence of the similarity between the material forming the main bulk of the coal and the bulk of the more recently decayed material in peat bogs. The. more recent or low-rank coals, such as lignite, little removed from the peat stage, contain notable percentages of alkali-soluble ulmins, but the percentage decreases with increased, degree of coalification and is negligible in bituminous or higher rank coals. The determination of the alkali-soluble ulmins in any coal gives, therefore, an indication, of its degree of coalification or rank. Coals which contain few or no ulmins soluble in alkalis do contain ulmins which can be rendered soluble by oxidation. The higher the rank of the coal, the more difficult it is to oxidize the insoluble ulmins and make them soluble. High-rank coals can be differentiated by oxidation tests on the, insoluble ulmins; but low-rank coals can be characterized by both their soluble and insoluble ulmins. This paper deals with the determination and significance of the alkali-soluble ulmins, present, as such in- the coal. The chemical nature and composition of ulmins are not discussed.

Jan 1, 1932

By D. U. Deere, F. D. Patton

Introduction A close relationship exists between the geologic investigation and the stability analysis of the slopes of an open pit mine. One significant result of this relationship is that the stability analysis is no better than the assessment of pertinent geologic factors that enter into the analysis. In some slope stability problems the engineering solution becomes obvious once the geologic framework is established. In other cases, establishing the geologic framework is only the first stage in the process of analysis. However, even in these cases the geology should not be neglected once the analysis is made. The geology should be periodically reviewed when new slopes are excavated. This will help ensure that the basic assumptions for the analysis have not changed and will permit changes when new conditions are encountered. In recent years improved methods of stability analysis have been accompanied by advances in laboratory testing techniques and new knowledge of the shear strength of rock discontinuities. At the same time there have been improvements in field geological descriptions. As more experience is gained in analyzing and predicting the stability of rock slopes, the importance of certain geologic factors has become more apparent. Some of these factors were described in a paper given at the Open Pit Mining Symposium in Johannesburg, South Africa in September 1970 (I). This paper includes many of the points covered at that meeting but with additional emphasis on the significance of the major geologic structures. Other papers given at the South African symposium also considered geological and hydrogeological factors in slope stability analysis (2) (3) (4) (5) (6). This paper first describes the approach to a slope stability problem including assessment of the relative roles of field geology studies, laboratory testing, stability analyses, and continued slope monitoring studies. Next, is described a framework which has been found useful for classifying or separating the several types of slope stability problems encountered in open pit mines. The principal geologic factors in slope stability problems in rock are discussed and brief comments are made on how these factors distinguish stability problems in rock slopes from those normally encountered in soil slopes. The over-riding control of major geologic structures, especially faults, in most slope stability problems is emphasized. In this regard the relative importance of statistical studies is contrasted with knowledge of the positions of key structural

Jan 1, 1971

By L. L. Oriard

INTRODUCTION In order to make effective plans for the control of blasting effects, it is necessary to understand a few basic principles relating to the behavior of explosives. For the purposes of discussing this behavior, it is convenient to divide blasting effects into two zones. The first zone is the non-elastic zone in close proximity to the explosive charge where rupturing of the rock occurs. For this zone, our discussion will be oriented towards the factors which affect the rock breakage, and the means of controlling the limits of this breakage. The second zone is that zone more remote from the charge location where elastic vibrations are transmitted through the surrounding medium. In this zone, we are interested in the factors affecting vibration intensity, and the means of controlling the intensity so that no damage is done to structures, utilities, or excavated slopes. It has been easier to gather data in the elastic zone, because the stress levels are lower and time durations are longer. The instrumentation for obtaining data in this zone can be less rugged and less sophisticated. Consequently, more information of ad empirical nature has been gathered. In the non-elastic zone, there has been more dependence on theory, fewer measurements, and more questioning of the validity of the measurements. In spite of these questions, there has been an encouraging advancement in knowledge in recent years, both theoretical and empirical, of the effects that take place close to the source of an explosion. When discussing the problems encountered in rock excavation, we can simplify the terminology by referring to the physical phenomena encountered in the non-elastic zone as a problem in "over-break". The phenomena in the elastic zone could be called "vibration effects". Although there is some interdependence between the two, it is possible to control the rock breakage to neat surfaces and still have very high vibration levels. Similarly, it is possible to control the vibrations to moderate levels and still have a great deal of overbreak. THE ROCK BREAKAGE ZONE First, let us discuss the effects in that zone close to the blast source that we might call the non-elastic zone. This is the zone of cratering, breakage, rupturing, and fracturing. These effects will vary with the site conditions, and a meaningful, specific analysis could

Jan 1, 1972

By ALBERT P. J. BORDEAUX

THIS paper briefly describes the general outline of cyaniding silver-ores in Mexico, with special reference to personal experiments made in the Temascaltepec district. The most important papers on the subject deal with cyaniding gold-silver-ores, the gold predominating in value, so that the treatment is nearly the same as for gold-ores, the losses of silver being considered of little importance. I describe here the treatment of silver-gold-ores containing very little gold, which is more general in Mexico than elsewhere. The cyanide treatment, which was so successfully applied to gold-ores, did not succeed immediately with silver-ores on account of their varying composition. Gold occurs in nature usually in the native state, while silver occurs generally in combination with sulphur (argentite), and various combinations of sulphur, antimony, and arsenic. In former times there was a complete difference in the treatment of gold-ores and silver-ores. Amalgamation, which was successful with gold-ores, was generally inadequate with silver-ores. The usual treatment in Mexico for silver was the patio process, the theory of which was satisfactorily explained only quite recently by Mr. Ortega and others. GENERAL OUTLINE OP THE CYANIDE TREATMENT. The general tendency of the present practice is to slime the silver-ore as much as possible, and in order to obtain a higher efficiency, with less loss of cyanide, and greater speed, the following lines are observed 1. Crushing by stamps with 30- or 40-mesh screens, then crushing by Huntington or Chilean mills, through 60- or 80-mesh screens. 2. Concentration upon vanners.

Jan 1, 1910

By William E. Souder, Eugene R. Palowitch

INTRODUCTION The longwall method of mining coal underground is now a highly developed and accepted mining technology. However, it was only through a long history of successes and failures that this technology now has the potential for reversing the declining trend in underground mining productivity in the United States. From its early beginnings in the United States during the 1800's, several species of longwalls have evolved. The evolutionary record consists of a series of overlapping birth-death eras, with each era giving way to another unique longwall technology. Typically, an era begins when some new longwall technology appears in response to a new technical opportunity or economic need. This new technology is adopted initially by only a few innovators. Later, other imitators get on the bandwagon and the technology diffuses throughout the user population. But evolving technical demands and socio-economic circumstances eventually cause many of the adopters to discontinue its use. This paper chronicles seven eras in the history of the evolution and utilization of longwall technologies in the United States. Some of the important factors that have influenced this history are discussed. Some distinctions are drawn between the operators who were first to adopt longwalls (innovators), and the imitators who followed. Statistics are presented which show that longwall mining is being adopted at an exponentially increasing rate, substantiating the forecast for a significant number of new longwall installations in' the future. Potential barriers to this increased utilization of long- walls are noted.

Jan 1, 1981

By W. Joseph Schlitt

The characteristics of successful heap and dump leach operations are first reviewed in a general sense. Then attention is focussed on solution management as the key operating parameter in leaching. The first part of this study includes a detailed conceptual analysis of fluid flow. This identifies the relationships between the flow parameters and the chemical and physical properties of the rock. Then these relationships are extended to practical systems in order to establish optimum application rates and solution distribution methods for heaps and dumps. The study shows that there is a maximum effective application rate, qmax, that can be used without causing solution short circuiting. This rate is a function of the minimum permeability in the heap or dump. The expression for qmax is qmax (gal/ft2/hr)[~]0.9 k (darcies). Here k is the appropriate permeability coefficient. Using this equation, qmax is found to be on the order of 1 gal/ft2/hr (4 cm/hr) for a typical heap or dump leach operation.

Jan 1, 1984

By Peter M. Anderson

IN recent years many prophets have arisen who hold that gold has outlived its days and that its monetary use is now an anachronism. These prophets include well-known politicians, economists and businessmen. Some of them have called it a joke that metal should be dug up at heavy cost in Africa and elsewhere and shipped to the United States of America only to go underground again at Fort Knox. Others have claimed that all the gold in the world could be sunk in the ocean without anyone being the poorer. The fact that you have invited me to address you on the future of gold may perhaps reflect the fears caused by these various predictions. At present the prophets' taunts show no sign of coming true. The demand for gold is greater than ever before, although stocks held are the largest in history. Nearly all governments have gone to great lengths to suppress any demand that might be made by the public; they have reserved to themselves the right to hold gold and have lost no opportunity of satisfying their own demands. Where the public has been allowed to buy gold, the demand has proved impressively strong. In India the price of gold equals about $82 per fine ounce, having been $90 earlier in the year; in Egypt $65 to $70, after having been $87, and elsewhere it is even higher. In Palestine, for instance, the golden sovereign is traded at about £5, equivalent to $86 per fine ounce, having been nearly £6, equivalent to some $100 per fine ounce, earlier in

Jan 1, 1947

By J. J. Marcus

Mineral industry decision-makers are frequently required to select between competing equipment. Various criteria and methods are currently being used, and this writer would like to suggest a method recently tested on two large power shovels in an open pit mine. An initial examination of both shovel A and shovel B indicated that the latter should give the best overall results. since: 1) It swings 13% faster; 2) it carries a dipper with 23%: greater capacity; 3) purchase price is 8.6% lower; 4) shovel weight is 12.5% greater; 5) it has considerably greater bail pull under most operating conditions; 6) the electric controls are of a more modern design. However, shovel B has half the service life. With these points in mind, shovel A was selected by The Buckingham Method, an operations research technique.

Jan 9, 1965

By Roland Kammel, Takeo Oki

A suspension electrolysis method has been developed which enabled a direct anodic extraction of zinc from zinc sulfide concentrate and simultaneously oxidized sulfide sulfur to elemental sulfur. The investigation was performed in a laboratory-scale electrolytic cell, where the zinc sulfide concentrate particles (chemical composition in weight percent: 61.1% Zn, 2.3% Fe, 30.6% S, 3.4% SiO2 were suspended with or without graphite powder in a dilute sulfuric acid electrolyte. The main parts of the cylindrical electrolytic cell are shown in [Fig. 1]. The cathode (1), a rod of aluminum, is set at the center of the cell. The anode (2), which consists of four plates, is mounted on the inner face of the cell wall. Both PbO2(Pb) and graphite anodes were used. The cathode compartment (3) is separated from

Jan 1, 1976

By Frederick Apgar

(Butte Meeting, August, 1913.) THE valuable results that have followed the application in recent years of microscopic methods of research to problems of ore genesis have been significant, but possibly the recognition of their practical importance is not as general as might be, and while, as a scientific method of investigating ores and rocks, the advantage derived through the use of the microscope is unquestioned, its utility as an aid in solving shining problems arising during actual every-day mine examination and operation may not be fully appreciated. Perhaps the roost logical method of showing some of these practical applications of the microscope will be to consider first the prospect stage of a mining venture, then the uses to which the instrument may be put during the operation of a working and developed mine, and, finally, to discuss some of the problems of a metallurgical nature that ii-my arise during milling and smelting the ore. The valuation of mining property as a preliminary to acquiring ownership or determining the advisability of investing time and money in an enterprise is one of the most important and delicate problems that come before the mining engineer. The many and variable factors that have to be taken into account, as, for example, the geology of the district, availability of supplies, probable mining costs, transportation facilities, and the quality of ore, require a careful balancing of costs against recoverable values.

Jan 6, 1913

By E. J. Roberts, E. B. Fitch

THE mechanism of classification by settling pools is most simply shown in the case of batch sedimentation such as was analyzed by Oden.1 The batch model will be considered, therefore, and it will be shown that the same mechanism applies to continuous operation. Classification in Batch Settling Pools: Consider a beaker or tank of slurry containing particles so dispersed that they can settle independently of one another under the influence of gravity. Originally all particle sizes are uniformly distributed throughout the suspension. All particles start immediately to settle towards the bottom at rates determined by their size, shape, and density—among other factors. Particles reaching the bottom settle out of suspension. After some given time the slurry above the deposited solids is siphoned off or otherwise removed, leaving the deposited solids behind. The deposited solids, together with entrained and any unremoved supernatant slurry, represent the underflow of a classifier. The slurry removed represents the overflow. There is a certain separation, size of particle which during the sedimentation has just time to settle from the top surface of the slurry to the level at which underflow and overflow are parted. All particles with a faster settling rate will have dropped to below this level, no matter where in the beaker they started from originally, and therefore will be absent from the overflow. Particles with a slower settling rate will not reach this level if they started from the top of the slurry, but a portion of them,

Jan 1, 1957

By Richard Moldenke

ONE of the gravest problems of the iron foundry today is the accumulation of sulfur in commercial scrap and its effect on the castings made therewith. The ordinary jobbing castings today show a sulfur content of 0.18 per cent., and occasionally as high as 0.22 per cent. The product of the foundry during the war is undoubtedly .to blame for this rapid increase and conditions will become worse as the millions of tons of gray-iron castings of the war period return to the foundry in the form of commercial scrap. In the ordinary cupola remelting of pig and scrap, at least 0.02 per cent. sulfur is taken up; often double that amount. The high cost and difficulty of obtaining pig iron during the war period compelled the use of considerable scrap in the mixtures; frequently charges containing. 90. per cent. of bought scrap were melted. Naturally the sulfur content of the castings increased. Until the advent of the basic-hearth electric furnace, the only method of holding the sulfur within reasonable limits was to use high percentages of pig in the foundry mixtures. Pig iron seldom contains over 0.05 per cent. sulfur, if well made. With pig iron forming 60 percent. of the .charge and the gates, runners, rejections, and bought scrap the other 40 per cent., the sulfur content of the castings can easily be held down to 0.10 per cent. Pig iron, however, costs more than scrap even when melting loss differences are considered, hence as small a percentage as possible will be used.

Jan 2, 1921

By F. E. Minshall

FoR more than 30 years California has been one of the three leading oil-producing states. Present daily production of crude oil under curtailment, approximately 580,000 bbl., comes from three general areas: Los Angeles Basin, San Joaquin Valley, and the coastal region of Ventura and Santa Barbara Counties. This state produces approximately two-thirds of its oil from eight large fields, and obtains a daily average production of 48 bbl. of oil per producing well, whereas the average for the United States is but 8.15 barrels. During the closing stages of the first half of 1936, discovery of the Section Ten oil field was made, and credit goes solely to geophysical work. It is the first direct important discovery of oil in California that may be credited to geophysics. This discovery may furnish the cue to the means of discovering several fields in California, particularly in the San Joaquin Valley. It is a question, however, whether returns from geophysical work will play as important a part in the future supply of oil in California as have our former types of prospecting. Explobation Methods of prospecting have progressed in the oil industry through invention or improvement in scientific means of locating and defining structure and because of market improvements in drilling equipment. Present methods of prospecting include: 1. A detailed study of geology in an attempt to locate structural and stratigraphic conditions that would be favorable to the accumulation of oil. 2. Geophysical methods involving the use of the seismograph, torsion balance, magnetometer and electrical methods. (There is still much to be learned in California in the application of geophysical methods.) 3. Use of micropaleontology as an aid in correlation,. The principal improvements in drilling equipment are: 1. The Schlumberger dipmeter, which determines the direction of formation dip in an uncased hole.

Jan 1, 1937

By Joseph Pogue

THE, prices of crude petroleum and its derivatives have shown an upward trend from 1915 to 1920, and a downward trend from 1920 to 1923, see Table 1. Over the former period, oil prices were dominated by the rapidly increasing demands and inflation incident to the war and its aftermath, while over the latter period oil prices were influenced at the outset by deflation and then by the conditions of overproduction that have characterized the past three years. The purpose of this paper is to analyze the broader features of the more recent price movements in the petroleum industry and to relate these features to basic economic conditions in the industry. INDEX NUMBERS OF OIL PRICES The analysis and comparison of price movements may be facilitated by converting actual prices into relative prices, or index numbers, with 1913 taken as a base of 100. In this way, the various price groups are expressed as percentages of the 1913 prices and may thus be readily compared with one another or with the average prices of other commodities similarly expressed. Table 1 gives the index numbers representing the average prices of crude petroleum, gasoline, kerosene, fuel oil, lubricating oils, and all commodities. The last named is the index of all commodities as published by the U. S. Bureau of Labor Statistics and .is widely accepted .as the official measure of the general price level. The index numbers of oil prices were calculated by the writer from weekly quotations published in trade journals.

Jan 3, 1924

By Fred C. Bond

AN improved method of measuring the surface area of a comminution product down to any desired particle size has been developed. The method is largely graphical, and requires relatively little calculation. It can be used with materials containing large amounts of clay, or excess fines of any kind. The surface area S is expressed in terms of square meters per100 c.c. of solids. This expression is based upon volume rather than weight, and is considered to be more suitable for crushing and grinding problems, where the machines ordinarily are operated under constant volume conditions. It has the advantage that surface areas of different materials can be compared directly, even though their specific gravities may be unknown. The "specific surface" of a material, or the number of square centimeters of surface area per gram, is equal to 100S divided by the specific gravity. Particle diameters are expressed in microns, K being the diameter of the largest particle present and L the grind limit, or lower size limit of the particles formed directly by grinding. The value of K does not always coincide exactly with the diameters of the largest particles retained on the coarsest testing sieve, since the largest particles formed in crushing and grinding are often slabby, or have other irregular shapes. L has been chosen as 0.700 microns, or number 27.5 in the size number series,1 for reasons to be explained later. S is the total surface area of all particles larger than L microns in diameter. When a homogeneous comminution product is separated into fractions whose diameters bear a constant geometrical relationship [p] to each other, and the log per cent weight retained upon each size and passing the next larger size is plotted against the log diameter, a straight line results, which is called the distribution line, and which has a slope in called the distribution modulus. The distribution line can be extended to any desired limiting size, and the total surface area of all particles larger than that size can be calculated. The equation of the distribution line is w = Cxm [I] where w is the per cent weight retained on each successive sieve; x is the particle diameter; and C is the per cent weight retained on an opening of unit diameter.2 Theoretically, the distribution line can be extended to include infinitely small particles. When it is so extended, and the assumption is made that no fine particles are present other than those accounted for by the equation; the log per cent cumulative weight passing any series of sizes, plotted against the log diameter passed, will result in a straight line lying parallel to and above the plotted distribution line.

Jan 1, 1941

By H. R. Tunnell

Every one connected with a mine knows that it is hard to keep down the costs of moving ore from the place where it is broken to the shaft or portal. Considered broadly, the subject of handling would cover all work done in a mine, but here it has been limited to handling ore in stopes and drifts, through chutes, and on levels. Good ventilation and a strict enforcement of rules for the prevention of dust safeguard the health of the men and lower transportation costs. Handling ORe in Stopes and Drifts The object of all stoping is to mine ore of good grade at low cost. In Butte, most of the ore is mined, from veins dipping from 60° to the horizontal to those which are vertical, by means of square-set, rill, timbered-rill, and back-filling stopes. When blasted, a part of the rock is carried by gravity to the grizzlies over the chutes, the rest is shoveled. Rock, when broken in a stope, may be deflected by inclined floors or slides toward the top of a chute leading to the level below. Ore broken clean enough to ship should be carried, by the force of its fall, into a chute or.as nearly into that chute as the safety of the stope and the men permits. Ore that requires sorting, about 80 per cent. of all ore mined, is caught on a grizzly and the waste picked out. Waste rock broken in a stope is used to fill that stope and should be blasted into the gob with as little handling as possible. About two-thirds of all the ore mined in Butte comes from square-set stopes; this method was used in nearly all cases until 1912, when the rill method of stoping was introduced in the Tramway mine, of the Anaconda Copper Mining Co. The shoveling and timbering costs in square-set stopes are high when compared with the costs in the rill stopes. All the ore cannot be carried to the chute, in falling from place, unless the chutes are very close together or the distance from the back of the stope to the top of the chute is sufficient to slide all the ore broken. The number of chutes is limited by the tendency of the ground to cave; if carried too close together the stope is weakened. Small stopes, or blocks,

Jan 1, 1923

By H. R. Tunnell

Every one connected with a mine knows that it is hard to keep down the costs of moving ore from the place where it is broken to the shaft or portal. Considered broadly, the subject of handling would cover all work done in a mine, but here it has been limited to handling ore in stopes and drifts, through chutes, and on levels. Good ventilation and a strict enforcement of rules for the prevention of dust safeguard the health of the men and lower transportation costs. Handling ORe in Stopes and Drifts The object of all stoping is to mine ore of good grade at low cost. In Butte, most of the ore is mined, from veins dipping from 60° to the horizontal to those which are vertical, by means of square-set, rill, timbered-rill, and back-filling stopes. When blasted, a part of the rock is carried by gravity to the grizzlies over the chutes, the rest is shoveled. Rock, when broken in a stope, may be deflected by inclined floors or slides toward the top of a chute leading to the level below. Ore broken clean enough to ship should be carried, by the force of its fall, into a chute or.as nearly into that chute as the safety of the stope and the men permits. Ore that requires sorting, about 80 per cent. of all ore mined, is caught on a grizzly and the waste picked out. Waste rock broken in a stope is used to fill that stope and should be blasted into the gob with as little handling as possible. About two-thirds of all the ore mined in Butte comes from square-set stopes; this method was used in nearly all cases until 1912, when the rill method of stoping was introduced in the Tramway mine, of the Anaconda Copper Mining Co. The shoveling and timbering costs in square-set stopes are high when compared with the costs in the rill stopes. All the ore cannot be carried to the chute, in falling from place, unless the chutes are very close together or the distance from the back of the stope to the top of the chute is sufficient to slide all the ore broken. The number of chutes is limited by the tendency of the ground to cave; if carried too close together the stope is weakened. Small stopes, or blocks,

Jan 1, 1923

George B. CoRless, Chairman. Superintendent, Gulf Coast Division, Humble Oil & Refining Co., Houston, Texas. W. H. Geis, Associate Chairman. Geologist, Los Angeles, California. Benjamin C. Craft, Secretary-Treasurer. Associate Professor, Petroleum Enginecring, Louisiana State University, Baton Rouge, La. Executire Committee George B. Corless, Chairman. M. Albertson, Production Engineer, Shell Petroleum Corporation, Houston, Texas. D. R. Knowlton, General Production Superintendent, Phillips Petroleum Co., Bartlesville, Oklahoma. R. P. McLaughlin, General Manager, Dominguez Oil Fields Co., Los Angeles, California. Hallan N. Marsh, Production Engineer, General Petroleum Corporation of California, Los Angeles, California. Theron Wasson, Chief Geologist, The Pure Oil Co., Chicago, Illinois. Production Engineering M. L. Haider, Vice-chairman. Petroleum Engineer, Carter Oil Co., Tulsa, Oklahoma. Joseph Chalmers, DeBataafsche Pet. Maatschappij, The Hague, Netherlands. Emile HugUenin, Deputy State Oil and Gas Supervisor, Los Angeles, California. Carl E. Reistle, Jr., Petroleum Engineering Department, Humble Oil & Refining Co., Houston, Texas. Production J. TERry Duce, Vice-chairman. Geologist, The Texas Company, New York, N. Y. Basil B. Zavoico, Associate Vice-chairman. Geologist, The Chase National Bank, New York, N. Y. Engineering Research R. L. Huntington, Vice-chairman. Associate Professor, Petroleum Engineering, University of Oklahoma, Norman, Oklahoma. Economics Sidney A. SwensrUd, Vice-chairman. Assistant to the President, Standard Oil Co. (Ohio), Cleveland, Ohio. Refinery Engineering Walter Miller, Vice-chairman. Vice-president, Continental Oil Co., Ponca City, Oklahoma. 10

Jan 1, 1938

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 J. E. McDonald, J. G. Eberhart

A model is discussed from which the work of adhcslon .tor liquid transition metals on aluminum oxide surfaces can he calculated, A close-packed (00011 oxygen surface on A12O3 is assumed with two different types of surface sites: one type involving metal-oxygen bonds and the other man der Waals into actions. The work of adhesion is thus expressed as the sum of these two bonsding free energies. Calculated works of adhesion for nickel, titanium, chromium, and zirconium on sapphire agree well with the experimentally determined quantities. The model is extentled to the calculation of the work of adhesion and shear stress required to remove a thin metal film from a sapphire substrate and is in good agreement with experimental values. The obsewed dependence of the work of adhesion on the free energy of oxide formation of the metal is shown to also provide an interpretation of the tittle dependence of thin-film adhesion. THIS paper presents a model for the type of bonding which occurs across a metal-A12O3 interface. The model is used to explain the results of two types of experiments in which such an interface exists: 1) the adhesion of thin metal films on Al2O3 substrates and 2) the wetting of A12O3 by liquid metal drops. The adhesion of thin films to various substrates has been the subject of a variety of investigations.'-' Benjamin and weaver3 and Bowie,6 using the scratch test developed by Heavens,10 studied the adhesion of metallic films to glass substrates. Their observations for noble-metal film adhesion agree well with an adhesion model involving a van der Waals type of bonding between the film and the substrate. For films of metals whose free energy of oxide formation. ?F°f, has a negative value. Benjamin and weaver3 and Bowie6 found a time-dependent adhesion with an initial value that can be interpreted in terms of van der Waals interactions but a larger terminal value which was related to ?F°f, Karnow-sky and Estill7 deposited films on sapphire at elevated temperatures and noticed no time dependence of film adhesion but a similar correlation with ?F°f. Because of the kinetic problems associated with thin-film adhesion it is desirable to examine adhesion in an equilibrium system. The wetting behavior of liquid-metal drops on Al2O3 provides such a system. Systems of this metal-ceramic type have been studied extensively.11 Humenik and Kingeryl2 have measured the wetting of A12O3 (and other substrates) by several metals and have pointed out that the wetting ability of these metals increases with increasing values of -?F°f. It is thus seen that thin-film adhesion and metal wetting on A12O3 are both related to the tendency of the metal to react with the surface oxide ions of the Al2O3 substrate and, because of this, both phenomena should be explainable by an appropriate model for the metal-Al2O3 interfacial bonding. In the sections that follow, wetting and adhesion data on A2O3 are reviewed and a model is presented by which these phenomena can be interpreted. ANALYSIS OF WETTING EXPERIMENTS In an equilibrium system involving a liquid-metal drop on a solid Al2O3 substrate, the work of adhesion, WAD, is defined by the Dupre, equation as WAD = ?s + ?L -?sL [1] where ?s and ?L are the surface free energies of the solid substrate and the liquid drop, respectively, and ?sL is the interfacial free energy. The work of adhesion is the work required to separate a unit area of the solid-liquid interface into two surfaces. The work of adhesion is usually determined from a sessile-drop experiment in which yL and the contact angle, ?, are measured. The Young-Dupr6 equation is then used to calculate WAD Wad = ?L (1+ cos ?) [2] The literature of this subject has been examined and Table I shows work of adhesion data for various liquid metals as measured on A12O3 substrates. The standard free energy of oxide formation of the metal at the temperature of the wetting experiment, ?F°f . is also tabulated in kcal per g-atom of oxygen. The data is grouped according to the gaseous atmos-

Jan 1, 1965