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By Arthur C. Simmons

The area that produces Pennsylvania grade, which includes New York, Pennsylvania, West Virginia and a part of Ohio, increased its production in 1942 about 1,580,000 bbl. over that attained in 1941. Such an increase is substantial for this area, and measured in terms of increased output of lubricants, for which the crude is particularly suitable, it represents a needed arid worth-while addition to the lubricant resources of the United States. The year 1942 was a difficult operating period for most of the petroleum-producing areas in the United States, but the Appalachian region, owing principally to its location, type of operations, and crude value, suffered less from war influences than other areas. The state of Pennsylvania produced 17,823,870 bbl. of crude oil, which is approximately 63 per cent of the total production of Pennsylvania grade in the entire area. Production Bradford Field The Bradford field, which produces almost wholly by water-flooding methods, increased its production nearly 4000 bbl. per day over 1941 despite a very slight reduction in total number of wells completed. Well completions in the Bradford field (in both New York and Pennsylvania) includc both producing oil wells and water-intake wells. About half of the well completions are producing oil wells and the remaining half are water-intake or injection wells. About 10 per cent of the total well completions of the Bradford field were in Cattaraugus County, New York. No segregation of well completions is available, so that precise statistics cannot be given for New York and Pennsylvania.

Jan 1, 1943

By Arthur C. Simmons

The area that produces Pennsylvania grade, which includes New York, Pennsylvania, West Virginia and a part of Ohio, increased its production in 1942 about 1,580,000 bbl. over that attained in 1941. Such an increase is substantial for this area, and measured in terms of increased output of lubricants, for which the crude is particularly suitable, it represents a needed arid worth-while addition to the lubricant resources of the United States. The year 1942 was a difficult operating period for most of the petroleum-producing areas in the United States, but the Appalachian region, owing principally to its location, type of operations, and crude value, suffered less from war influences than other areas. The state of Pennsylvania produced 17,823,870 bbl. of crude oil, which is approximately 63 per cent of the total production of Pennsylvania grade in the entire area. Production Bradford Field The Bradford field, which produces almost wholly by water-flooding methods, increased its production nearly 4000 bbl. per day over 1941 despite a very slight reduction in total number of wells completed. Well completions in the Bradford field (in both New York and Pennsylvania) includc both producing oil wells and water-intake wells. About half of the well completions are producing oil wells and the remaining half are water-intake or injection wells. About 10 per cent of the total well completions of the Bradford field were in Cattaraugus County, New York. No segregation of well completions is available, so that precise statistics cannot be given for New York and Pennsylvania.

Jan 1, 1943

PRESIDENT BENJAMIN B. THAYER, NEW YORK, N. Y. PAST PRESIDENTS JAMES F. KEMP, NEW YORK, N. Y. CHARLES F. RAND, NEW YORK, N. Y. FIRST VICE-PRESIDENT SIDNEY J. JENNINGS, NEW YORK, N. Y. TREASURER GEORGE C. STONE, NEW YORK, N. Y.

Jan 1, 1917

PRESIDENTS L. D. RICKETTS, NEW YORK, N. Y. PAST PRESIDENTS BENJAMIN B. THAYER, NEW YORK, N. Y. WILLIAM L. SAUNDERS, NEW YORK, N. Y FIRST VICE-PRESIDENT SIDNEY J. JENNINGS, NEW YORK, N. Y. TREASURER GEORGE C. STONE, NEW YORK, N. Y.

Jan 1, 1917

By J. H. Johnson, H. J. Schock

The cases of no auxiliary ventilation and ventilation with tubing were mathematically modeled, using a turbulent dispersion model. The Scooptram® used to load is modeled as a variable-speed, variable-strength source of pollutants moving in and out of the dead-ended drift. Model predictions are compared to experimental measurements. A parametric analysis was performed to determine If a relationship existed between C02 and NO levels. It was concluded from this analysis that when modeling a load-haul-dump cycle, it is necessary to use a model that can predict changes in source strength as well as source location. Carbon dioxide was used as a tracer to calibrate the model since, knowing the fuel flow rate, it is possible to calculate C02 production. The model was then verified after this calibration process using additional experimental results. With the calibrated model, it is possible to predict pollutant concentrations at any location in the heading using an engine map and the previously calculated flow field.

Jan 1, 1984

By Leslie W. Austen

ROTARY kiln operators will agree that some of the most severe conditions a refractory must stand occur in the hot zone of a kiln burning Portland cement, dead burn dolomite, magnesite, peri-clase, and similar materials. Frequently the operator is faced with factors beyond his control which drastically shorten the life of refractories. Shutdown due to mechanical failure can be serious if the period is of sufficiently long duration to cause the dropping of coating or the loosening of the lining. A change in slurry can affect the coating and cause ring buildup. A change in type of fuel and its effect upon the flame can cause a shift in location of the hottest zone. Weekend shutdowns or any other interruption can cause the operator trouble and may damage the refractories, since stopping and starting a rotary kiln is certainly more difficult than stopping and starting a motor. Some operators have tried to set an estimate of damage for each shutdown in equivalent days of running time. Conditions affecting the refractory may be roughly grouped in four classes: chemical attack, mechanical stress, thermal shock, and abrasion. Chemical Attack: The drive to obtain maximum production through a kiln demands maximum operating temperatures, temperatures which are limited more by the ringing up or melting of the clinker. This can cause interface temperatures at the junction of coating and refractory which require the use of a basic kiln block to withstand the chemical attack. Chemical changes take place within the refractory itself, especially in chemically bonded or unburned kiln blocks. These changes cause the formation of the ceramic or burned bond. Migrating liquids or fluxes from the kiln charge have an effect within the refractory and lead to mineral or glass formation. The alkalies, sodium and potassium, migrate into the refractory as silicates, chlorides, sulphates or other salts. They may move under capillary action or may be caused to move by volatilization with condensation in the cooler portion. Mechanical Stress: Concentrated stress may be caused by several factors or combinations thereof. I—The rings of refractories must be kept tight and rigid within the kiln, and this alone demands considerable force to hold the blocks in place. So that the force will not be concentrated, the blocks should fit the circle as perfectly as possible, with the faces in contact overall. 2—As the kiln is heated, thermal expansion takes place at the hot end of the kiln block. Since this disturbs the plane face it too can cause a concentrated stress at the two ends of the block, and shearing stress can be set up within the brick itself because of the difference in expansion between the two ends. 3—If a lining becomes loose and moves in the shell very severe stress can be set up, and as the kiln rotates this load changes and gives the effect of repeated loading. Permanent expansion of the refractory can also cause severe loading. 4—Not least important, flexing of the kiln is frequently the cause of concentrated stresses. Thermal Shock: Thermal shock, the result of heating and cooling too rapidly, occurs on starting and stopping or when a large patch of coating drops, exposing the bricks. Again, its destructive effect is often the result of phase change, liquid to solid or the reverse; dense refractories loaded with glass-forming impurities are particularly susceptible. Thermal shock is a. problem with refractories set in the wall or roof of a stationary furnace, and becomes even more serious in a rotary kiln, the tendency to spa11 being magnified with movement and concentration of stress. Uniform rate of feed and loading insures both better coating and a more uniform stress. Abrasion: If the refractories do not take a coating, abrasion can become a most destructive factor. Movement of the lining in shell or movement of loose blocks causes abrasion, which is also most destructive if the refractories do not take a coating. An analysis of the problem of basic lining for the hot zone reveals, therefore, a number of desirable characteristics: high refractoriness, basic chemical reaction, resistance to spalling, good strength at all stages, ability to take coating, true sizing, volume stability, and abrasion resistance. Increased demand

Jan 1, 1953

By Leslie W. Austen

ROTARY kiln operators will agree that some of the most severe conditions a refractory must stand occur in the hot zone of a kiln burning Portland cement, dead burn dolomite, magnesite, peri-clase, and similar materials. Frequently the operator is faced with factors beyond his control which drastically shorten the life of refractories. Shutdown due to mechanical failure can be serious if the period is of sufficiently long duration to cause the dropping of coating or the loosening of the lining. A change in slurry can affect the coating and cause ring buildup. A change in type of fuel and its effect upon the flame can cause a shift in location of the hottest zone. Weekend shutdowns or any other interruption can cause the operator trouble and may damage the refractories, since stopping and starting a rotary kiln is certainly more difficult than stopping and starting a motor. Some operators have tried to set an estimate of damage for each shutdown in equivalent days of running time. Conditions affecting the refractory may be roughly grouped in four classes: chemical attack, mechanical stress, thermal shock, and abrasion. Chemical Attack: The drive to obtain maximum production through a kiln demands maximum operating temperatures, temperatures which are limited more by the ringing up or melting of the clinker. This can cause interface temperatures at the junction of coating and refractory which require the use of a basic kiln block to withstand the chemical attack. Chemical changes take place within the refractory itself, especially in chemically bonded or unburned kiln blocks. These changes cause the formation of the ceramic or burned bond. Migrating liquids or fluxes from the kiln charge have an effect within the refractory and lead to mineral or glass formation. The alkalies, sodium and potassium, migrate into the refractory as silicates, chlorides, sulphates or other salts. They may move under capillary action or may be caused to move by volatilization with condensation in the cooler portion. Mechanical Stress: Concentrated stress may be caused by several factors or combinations thereof. I—The rings of refractories must be kept tight and rigid within the kiln, and this alone demands considerable force to hold the blocks in place. So that the force will not be concentrated, the blocks should fit the circle as perfectly as possible, with the faces in contact overall. 2—As the kiln is heated, thermal expansion takes place at the hot end of the kiln block. Since this disturbs the plane face it too can cause a concentrated stress at the two ends of the block, and shearing stress can be set up within the brick itself because of the difference in expansion between the two ends. 3—If a lining becomes loose and moves in the shell very severe stress can be set up, and as the kiln rotates this load changes and gives the effect of repeated loading. Permanent expansion of the refractory can also cause severe loading. 4—Not least important, flexing of the kiln is frequently the cause of concentrated stresses. Thermal Shock: Thermal shock, the result of heating and cooling too rapidly, occurs on starting and stopping or when a large patch of coating drops, exposing the bricks. Again, its destructive effect is often the result of phase change, liquid to solid or the reverse; dense refractories loaded with glass-forming impurities are particularly susceptible. Thermal shock is a. problem with refractories set in the wall or roof of a stationary furnace, and becomes even more serious in a rotary kiln, the tendency to spa11 being magnified with movement and concentration of stress. Uniform rate of feed and loading insures both better coating and a more uniform stress. Abrasion: If the refractories do not take a coating, abrasion can become a most destructive factor. Movement of the lining in shell or movement of loose blocks causes abrasion, which is also most destructive if the refractories do not take a coating. An analysis of the problem of basic lining for the hot zone reveals, therefore, a number of desirable characteristics: high refractoriness, basic chemical reaction, resistance to spalling, good strength at all stages, ability to take coating, true sizing, volume stability, and abrasion resistance. Increased demand

Jan 1, 1953

By Joseph Zwierzycki

By an extension of drilling activities in 1938, the Polish oil industry succeeded not only in maintaining production but even in increasing it slightly. This increase, however, was from present oil reserves and not due to the discovery of any new fields. Most of the new wells were drilled in the Jaslo district, particularly in the Lipinki-Libuszal oil field, because of the shallow depth of the producing sands. At the Boryslaw field the 12,332 meters drilled could not compensate for the steady drop in production. A drilling campaign similar to that of the previous year in the Stanislawow district resulted in a slight decline of production. A number of the new wells have been subsidized by the Fund for the Advancement of Drilling2 in Poland. As the present sums at the disposal of this fund are insufficient for a great exploration program, they are chiefly used for the maintenance of the actual production. New wells on known folds, but more than 1000 m. outside the present productive areas, are entitled to a subsidy. Applications for wildcats outside the known productive areas have not been received in 1938. Even when the Polish oil industry was prosperous, wildcatting was not frequent and in their present impoverished condition the oil companies are no longer able to bear such financial burdens. The only way to start a large-scale drilling campaign on the still existing promising areas seems to depend on the granting of new substantial subsidies from the Treasury. Such measures are being considered by the Polish Government. It has been suggested that a fund for wildcatting might be raised by a small increase in the price of benzine. An advance of one grosz per liter of benzine would raise, on present home consumption of 108,000 kilogram-tons, about 1.3 million zloty, an advance of 5 grosze more than 6 million zloty.3 This small increase in price would hardly be felt by the motor-car owners, as it would mean an extra expense of 80 to 400 zloty in a year.

Jan 1, 1939

By Joseph Zwierzycki

By an extension of drilling activities in 1938, the Polish oil industry succeeded not only in maintaining production but even in increasing it slightly. This increase, however, was from present oil reserves and not due to the discovery of any new fields. Most of the new wells were drilled in the Jaslo district, particularly in the Lipinki-Libuszal oil field, because of the shallow depth of the producing sands. At the Boryslaw field the 12,332 meters drilled could not compensate for the steady drop in production. A drilling campaign similar to that of the previous year in the Stanislawow district resulted in a slight decline of production. A number of the new wells have been subsidized by the Fund for the Advancement of Drilling2 in Poland. As the present sums at the disposal of this fund are insufficient for a great exploration program, they are chiefly used for the maintenance of the actual production. New wells on known folds, but more than 1000 m. outside the present productive areas, are entitled to a subsidy. Applications for wildcats outside the known productive areas have not been received in 1938. Even when the Polish oil industry was prosperous, wildcatting was not frequent and in their present impoverished condition the oil companies are no longer able to bear such financial burdens. The only way to start a large-scale drilling campaign on the still existing promising areas seems to depend on the granting of new substantial subsidies from the Treasury. Such measures are being considered by the Polish Government. It has been suggested that a fund for wildcatting might be raised by a small increase in the price of benzine. An advance of one grosz per liter of benzine would raise, on present home consumption of 108,000 kilogram-tons, about 1.3 million zloty, an advance of 5 grosze more than 6 million zloty.3 This small increase in price would hardly be felt by the motor-car owners, as it would mean an extra expense of 80 to 400 zloty in a year.

Jan 1, 1939

By V. C. Smith

Reliable and detailed statistical data available for Kentucky, Ohio and West Virginia are the most meager and unsatisfactory of any of the producing states. Detailed histories and statistics are available for only a few pools. The antiquity of these pools, loose nomenclature, particularly where several names are applied to the same pool or various parts of the pool or a new namsed when the pool was rediscovered, made the collection of accurat historical and statistical data almost impossible. So many of the data reported are unreliable that a breakdown by pools or even by counties, until more accurate information is available, would lead to gross errors. Rather than perpetuate inaccuracies, we have endeavored to go to original sources wherever possible, sift these and provide data that may serve as an incentive and basis for future work. The necessity for accurate information is thoroughly recognized by the operators, particularly because of the effect of recent government regulations and request? for data in connection with the preparation of the various codes a pending legislation. Producers, both major operating companies and individuals, . freely given their time and assistance in the compilation of these data. Valuable information was obtained from tax records, rate cases, statistics published by the oil and gas publications and the Bureau of Mines. So many individuals cooperated in the preparation of these data that individual credit cannot be given. Undoubtedly many errors will be found. Some of the data are open to controversy, and many have been omitted in the hope that new information of a more reliable character may become available. Other omissions are due to an inability to contact the proper individuals, many of whom are no longer connected with this industry. Pennsylvania grade crude sold in 1933 for the lowest price since 1895. Gas production could not find sufficient new markets to fill the void left by industrial stagnation. In the gas industry, where the market price is fixed by contract, uncertainty persisted because of impending legislative action affecting both taxes and utility rates. As a result of these factors and a lack of new money, drilling was restricted to a new low. The lifting of proration toward the end of the year in the Pennsylvania

Jan 1, 1934

By T. S. Fuller

The work of D. J. McAdam, Jr.1,2 at the U. S. Naval Engineering Experiment Station, Annapolis, Md., on what has been called by him "corrosion-fatigue" has focussed the attention of the engineering profession in general, and of those interested especially in the study of corrosion in particular, on the importance of making tests which will indicate as nearly as possible what can be expected from a given material in service. Pitting is unquestionably the chief agent operating so tremendously to reduce fatigue limits, but in the light of previous work3, 4, 5, 6, 7, 8 it is fair to assume that absorbed hydrogen resulting from the action of the corroding medium upon steel may, under certain conditions, have a perceptible influence. The experiments described in this paper deal more precisely with stressless corrosion, or "prior-corrosion fatigue,"9 and have been carried out to test such an assumption, to segregate, if possible, the effect of pitting from that of absorbed hydrogen, and although very preliminary in nature they indicate results which are striking.

Jan 1, 1929

By T. S. Fuller

The work of D. J. McAdam, Jr.1,2 at the U. S. Naval Engineering Experiment Station, Annapolis, Md., on what has been called by him "corrosion-fatigue" has focussed the attention of the engineering profession in general, and of those interested especially in the study of corrosion in particular, on the importance of making tests which will indicate as nearly as possible what can be expected from a given material in service. Pitting is unquestionably the chief agent operating so tremendously to reduce fatigue limits, but in the light of previous work3, 4, 5, 6, 7, 8 it is fair to assume that absorbed hydrogen resulting from the action of the corroding medium upon steel may, under certain conditions, have a perceptible influence. The experiments described in this paper deal more precisely with stressless corrosion, or "prior-corrosion fatigue,"9 and have been carried out to test such an assumption, to segregate, if possible, the effect of pitting from that of absorbed hydrogen, and although very preliminary in nature they indicate results which are striking.

Jan 1, 1929

By Edward Richardson

As DEVELOPED up to the end of the Great War, an airplane was essentially a mechanism of wood and fabric, joined and held together by metal fittings and, fastening. The engine and accessories, wire for wheel spokes and other tension members, and the occasional use of metal for interplane struts and the shafts of surface controls required some metal, but essentially it was a. wood and fabric structure. Attempts had been made to use metal for other purposes, such as struts in the drag-trussing of wing panels and for short interplane struts, and Junkers had produced an airplane of iron in 1915. By 1917 he was using steel tubes and duralu-min sheets, securing noteworthy advantages aerodynamically and from the standpoint of weigh PRINCIPLES OF AIRPLANE CONSTRUCTION The loaded weight of airplanes ranges from 500 lb. for the light plane of which we heard so much a short time ago, to about 40,000 lb. The great majority of planes range from 2000 to 10,000 lb. Of this weight from 15. to 30 per cent. is for the dividend-earning load. This percentage is so low that every per cent. saved on the rest of the weight increases the pay load from 3 to 6 per cent. The economic value of every pound that can be saved in designing or constructing a plane is sufficiently great to warrant spending money on refined methods of structural analysis, materials of superior strength properties for a given weight, methods of manufacture which may make possible the use of refinements in structural design, and the like, to an extent unknown heretofore.

Jan 1, 1928

By N. F. Dyson, T. R. Scott

The iilzfluence of catalytic agents on the oxidation of ZnS has been studied under pressure leaching conditions, using a chemically prepared sample of ZnS which was substantially unreactive on heating at 113°C with dilute sulfuric acid and 250 psi oxygen. Nurnerous prospective catalysts were added at the ratio of 0.024 mole per mole ZnS in the above reaction but pvonounced catalytic activity was confined to copper, bismuth, rutheniuwl, molybdenum, and iron in order of. decreasing effectiveness. In the absence of acid, where sulfate was the sole product of oxidation, catalysis was exhibited by copper and ruthenium only. Parameters affecting the oxidation rate were catalyst concentration, temperature, time, oxygen pressure, and a7riount of acid, the first two being most important. The main product of oxidation in the acid reaction was sulfur, with trinor amounts of sulfate. An electrochemical (galvanic) mechanism has been suggested for the sulfuv-forming reaction, whereby the relatively inert ZnS is "activated" by incorporation of catalyst ions in the lattice and the same catalysts subsequently accelerate the reduction of dissolved oxygen at cathodic sites on the ZnS surface. Insufficient data was obtained to Provide a detailed mechanism for sulfate fornzation, which is favored at low acidities and probably proceeds th'rough intermediate transient species not identified in the preseni work. THE oxidation of zinc sulfide at elevated temperatures and pressures takes place according to the following simplified reactions: ZnS + io2 + H2SO4 — ZnSO4 + SG + HsO [i] ZnS + 20,-ZSO [21 In dilute acid both reactions occur but Reaction [I] is usually predominant, whereas in the absence of acid only Reaction [2] can be observed. Both proceed very slowly with chemically pure zinc sulfide but can be greatly accelerated by the addition of suitable catalysts, as suggested by jorling' in 1954. Nevertheless, an initial success in the pressure leaching of zinc concentrates was achieved by Forward and veltman2 without any deliberate addition of catalytic agents and it was only later that the catalytic role of iron, present in concentrates both as (ZnFe)S and as impurities, was recognized and eventually patented.3 It is now apparent that another catalyst, uiz., copper, may have also played a part in the successful extraction of zinc, since copper sulfate is almost universally used as an activator in the flotation of sphalerite and can be adsorbed on the mineral surface in sufficient amount The importance of catalysis in oxidation-reduction reactions such as those cited above has been emphasized by various writers and Halpern4 sums up the situation when he writes that "there is good reason to believe that such ions (e.g., Cu) may exert an important catalytic influence on the various homogeneous and heterogeneous reactions which occur during leaching, particularly of sulfides, thus affecting not only the leaching rates but also the nature of the final products." Nevertheless relatively little work has appeared on this topic, one of the main reasons being that sufficiently pure samples of sulfide minerals are difficult to prepare or obtain. When it is realized that 1 part Cu in 2000 parts of ZnS is sufficient to exert a pronounced catalytic effect, the magnitude of the purity problem is evident. An incentive to undertake the present work was that an adequate supply of "pure" zinc sulfide became available. When preliminary tests established that the material, despite its large surface area, was substantially unreactive under pressure leaching conditions, the inference was made that it was sufficiently free from catalytic impurities to be suitable for studies in which known amounts of potential catalytic agents could be added. The first objective in the following work was to identify those ions or compounds which accelerate the reaction rate and, for practical reasons, to determine the effects of parameters such as amgunt of catalyst, temperature, time, acid concentration, and oxygen pressure. The second and ultimately the more important objective was to make use of the experimental results to further our knowledge of the reaction mechanisms occurring under pressure leaching conditions. The fact that catalysts can dramatically increase the reaction rate suggests that physical factors such as absorption of gaseous oxygen, transport of reactants and products, and so forth, are not of major importance under the experimental conditions employed and an opportunity is thereby provided to concentrate on the heterogeneous reaction on the surface of the sulfide particles. As will appear in the sequel, the first of these objectives has been achieved in a semiquantitative fashion but a great deal still remains to be clarified in the field of reaction mechanisms. EXPERIMENTAL a) Materials. The white zinc sulfide used was a chemically prepared "Laboratory Reagent" material (B.D.H.) and X-ray diffraction tests showed it to contain both sphalerite and wurtzite. The specific surface area, measured by argon absorption at 77"K, varied between 3.9 and 4.6 sq m per g. Analysis gave 65.0 pct Zn (67.1 pct theory) and 31.9 pct S (32.9 pct theory). Other metallic sulfides (CdS, FeS, and so forth) used in the experiments were also chemical preparations of "Laboratory Reagent" grade. Samples of mar ma-

Jan 1, 1969

By J. E. Tobey, David R. Mitchell, J. H. Kerrick

DETAILED knowledge of purchase specifications established by coal consumers is essential to the successful design and operation of a coal-preparation plant. ANTHRACITE Specifications should be considered by both the consumer and the producer as guide posts outlining a certain path for both to follow. Plants differ, therefore specifications must differ to meet the varied requirements. Specifications are not of themselves a "cure all" or an assurance of complete satisfaction in fuel utilization. Specifications should not be regarded as a license to engage in an orgy of buying any and all coals that may happen to fall within their limits. This would lead to the-indiscriminate mixing of coals which may vary in their burning characteristics. Different coals of equal grade tend to be individualistic in their burning characteristics. Rather, specifications should be used to help simplify coal selection, to reduce the actual number of coals used over a given period; in other words, to have a stabilizing influence on coal or customer turnover. In the final analysis, the use of too many coals per year in a plant is costly to both the consumer and the producer. Too many sources usually result in higher operating and maintenance costs for the consumer and higher sales costs for the producer. Finally, the statement included in the report accompanying the comprehensive Coal Selection Charts prepared by the Coal Committee of the National Association of Purchasing Agents, and released in 1938, is significant. This Committee worked diligently for a period of 15 years seeking to find a scientific and reliable method for selecting coals. The two following paragraphs are quoted from its report: More important is the fact that no ready-made classification or set of specifications can possibly replace the judgment and resourcefulness of an experienced combustion engineer, or fuel technologist, nor the usual need for full scale plant tests under the exact conditions of use before a final decision is made . . .

Jan 1, 1943

By Max Mason

IN 1923 a Western mining company was experimenting with the device of an inventor designed to locate buried ores by radio. Because the progress was slow and the results were confusing, the company began to doubt the usefulness of the method and invited me to review the whole question of the application of physics to ore detection. I was fortunate in securing the cooperation of several physicists who had worked with me during the war on the problem of submarine detection. This group has been increased and has been studying the problem of physical exploration for ores since that time. It was evident that the problem is a big one, with many angles of approach. Its general features may be set down, in rough outline, as follows: The soils, rocks and ores hidden beneath the surface differ, one from another in many respects. These differences may be made to furnish a clew for the physicists working from the surface. To bring these differences into action the physicist creates some kind of an effect, which penetrates into the ground and is distorted and, reflected when it meets boundaries between different sorts of underground structure. In other words, he sends a message down, and the rocks and ore send back signals in, reply. In picturing this process, we should not regard the ground as dense and impenetrable. The kind of messages used pass through the earth about as readily as a sound wave travels the air. If, then, the fundamental procedure is to shout down questions in the hope that an orebody will hear and answer back to us, it is clear that a large part of the expert's study must relate to the kind of questions best suited to the temperament and intelligence of orebodies. It will be easier for the ore to, reply to some of our questions than to others, and it is for us to find the right questions. In certain cases, we are-spared the necessity of using a messenger, because nature has already provided one. For example, we already have a terrestrial magnetic field which auto-matically and continually conveys messages from underneath. We also have available the earth's gravitational field which furnishes us

Jan 1, 1927

By Robert K. Waits

The resistivity, temperature coefficient of resistance, stability at 200°C, and structure of annealed Si-Cr films have been studied as a function of film cowposition. Colorimetric analyses of the films indicated 20 to 60 wt pct Cr over the resistivity range of 1 to 10-4 ohm-cm. Resistors were delinealed by photolithographic etching, contacted with aluminum, and mounted in TO-5 packages. The average temperature coefjicient of resistance, a, between 50" and 150°C is related empirically to the film resistivity, p, by a (ppm per °C) = -2900 - 1140 log p (ohm-cm). Near a resistivity of 3.5 x 10-3 ohm-ctn (30 at. pct Cr) , the temperature coefficient changes from positive to negative. The temperature at which the resistance maximum occurs increases with decreasing resistivity. The conduction mechanism between —196" and +360 C appears to have two components—an activated conduction dominating a1 lord chromium content and higher temperatures and a linearly temperature-dependent conduction dominating at high chromium content and low temperatures. Electron diffraction patterns showed the films to consist of Cr3Si and amorphous silicon. Resistors thicker than 150A typically drifted less than 0.6 pct after 5000 hr stor-age at 200°C. Resistors as thin as approxinzately 80°A that had a silicon overlayer showed similar stability. Such films had sheet resistivities of 10 kilohm per square and temperature coefficients near —600 ppm per "c. THIN-FILM resistors having sheet resistivities greater than 1 kilohm per square are required in many integrated circuit applications. A process for producing such resistors should be compatible with present circuit fabrication and packaging, including exposure to maximum temperatures of 300° to 570°C during contact alloying, die-attach, and ceramic package sealing. In addition, the resistors should have a low temperature coefficient of resistance and change less than 1 pct during storage at temperatures up to 200°C for 1000 hr or longer. Reports of work beginning in 1949 at Battelle Memorial Institute indicated that, among other materials, the silicides of chromium, Cr-Co, molybdenum, tantalum, and tungsten were worthy of further study as high-stability resistive films. Later work on Si-Cr films vacuum-deposited by flash evaporation from a tungsten boat1 led to the conclusion that Si-Cr had "excellent properties for development into high- stability ... resistive elements". More recently, Si-Cr films have been vacuum-deposited from a tantalum boat,2 from a BeO-coated tantalum boat,3 by flash evaporation from an electron-beam-heated tungsten Source,4 and by triode sputtering.5 This paper describes a study of Si-Cr films vacuum-deposited by electron-beam heating of Si-Cr alloys. Resistivity, temperature coefficient of resistance, stability at 200°C, and structure were studied as a function of film composition. EXPERIMENTAL PROCEDURE Film Deposition. Si-Cr sources were prepared by vacuum-melting pressed pellets of mixtures of powdered chromium (99.9 pct, -100 mesh, Lunex Co., Pleasant Valley, Iowa) and silicon (99.99 pct, -325 mesh, United Mineral and Chemical Co., New York). A permanent-magnet focused electron-beam gun having a water-cooled copper crucible was used to heat the pellet until complete melting occurred. The mixture was then kept molten for an additional 5 min. The alloy thus formed was used as the source material for Si-Cr film depositions using the same electron-beam gun. Pieces of semiconductor-grade silicon ingots were used as sources for silicon depositions. The films were deposited within a standard vacuum evaporator having an 18-in.-diam Pyrex bell jar, a liquid-nitrogen-cooled trap, and a Consolidated Vacuum Corp. 6-in. diffusion pump containing Dow Corning DC-705 pump fluid. The substrates were thermally oxidized* silicon wafers 2 to 2.5 cm in diam. The

Jan 1, 1969

By Larry Kaufman

A useful method for estimating the entropy of NaCl type compounds has been developed by combining the Debye theory of specific heat with the Lindemann formula. This method pemnits calculation of the entropy from a knowledge of the atomic weight, atomic volume, and melting point of the compound. Comparison of the calculated and observed entropies of 35 NaCl type compounds over a wide temperature range yields good agreement thus establishing the usefulness of the method. Application of the method to other crystal types is also discussed. KUBASCHEWSKI~ has suggested a useful method of estimating the enthalpy of formation of inter-metallic compounds from a knowledge of the crystal structure, lattice parameter, and heats of sublimation of the component elements. This method is quite valuable in predicting the tendency for compound formation in a given system and is of particular value in considering systems for which no experimental data are available. In order to supplement the enthalpy calculation afforded by Kubschewski's method, it would be of value to be able to estimate the entropy of compounds so that the entropy and free energy of formation could be evaluated. Although a considerable body of such data determined by calorimetric and equilibration techniques exists at present, the difficulty of making such measurements (particularly at high temperatures) and the ever increasing number of new compounds which are of interest make the desirability of such a computational method clear. This paper deals with a method for calculating the entropy of a compound from a knowledge of the atomic weight, atomic volume, and melting point. Since these data are generally easier to determine and therefore more readily available than thermo-dynamic data, they should provide an additional tool in estimating the stability and reactivity of compounds at high temperatures. I) THE ENTROPY OF PURE METALS As a first approximation, the specific heat of a pure metal can be represented by a sum of terms where C,($/tI is the vibrational specific heat calculated on the basis of the Debye theory, lo4 TC, (0/T) is an approximation to the Cp - C, correction. T is the electronic specific heat, and Cp (p) is the magnetic specific heat. Although the Debye theory does not provide a complete description of the vibrational specific heat, i.e., the Debye temperature 0 is not a constant, it does provide a good approximation when used properly. Blackman6'7 has written several reviews on this subject discussing the different values of 0 determined by various methods (specific heat, X-rays, elastic constants, electrical resistivity, and so forth), as well as the observed temperature dependence of 0 with T. In the present case the 0 in Eq. [I] naturally refers to the specific heat 0. The variation of Debye 0 (as determined from specific heat measurements) with temperature is observed to exhibit its most radical behavior at very low temperatures. At higher temperatures the 8 values are observed to become more nearly constant. Blackman6'7 has presented the variation of 0 with temperature for several metals. His tabulation is reproduced in Table I. Reference to Table I shows that above a certain temperature level, 0 remains fairly constant. The value of 0 which is most useful in computing the specific heat, and hence the entropy, is the value of 0 in the range 0/6 « T « 0. In 1910, Lindemann' suggested a relation for estimating Debye 0 values. According to this formula, where V is the atomic volume, T is the melting point in 'K, M is the atomic weight, and CL is a constant. Mott and Jones9 present this formula and state that there is at present no satisfactory theoretical explanation, but that it does have an empirical basis. By using the valuesof 0 in Table I along with known1' values of M, T, and the molar volume VM, where the Lindemann constant can be evaluated. This

Jan 1, 1962

By M. A. Dayananda, R. E. Grace

Vapor-solid diffusion couples were employed in a study of ternary diffusion in the single-phase copper-rich corner of the Cu-Zn-Mn system Interdiffusion coefficients were measured at three different compositions corresponding to the intersections of diffusion paths determined at 850°C. Intrinsic diffusion coefficients were determined at two compositions by the Philibert-Guy method. New relations between the various intrinsic diffusion coefficients are also presented. MOST of the investigations of ternary diffusion have been made with "sandwich" couples formed by welding together two homogeneous solid solutions with or without markers placed at the interface. With such couples Kirkaldy and his coworkers1,2 have determined interdiffusion coefficients which describe ternary diffusion in the substitutional alloy systems, Cu-Mn-A1 and Zn-Cu-Al. Guy and Leroy3 have reported intrinsic diffusion coefficients for Co-Ni-Cr alloys as a function of composition using the analysis of Philibert and Guy.4 The use of semi-infinite diffusion couples, for example, vapor-solid couples, where the diffusing species are supplied from a vapor source in contact with a diffusion disk, has so far been confined to studies of binary diffusion. Balluffi et a1.5,6 have successfully determined the interdiffusion as well as the intrinsic diffusion coefficients in several binary metallic systems employing vapor-solid couples with markers initially placed at the vapor-solid interface. They have also discussed the general advantages and limitations of such couples. Vapor-solid diffusion couples can successfully be employed in ternary diffusion studies. The importance of such couples in ternary diffusion lies in the fact that inert markers lie close to the vapor-solid interface, and the composition of the marker plane is virtually known before experimentation begins. Another minor advantage is that the method of Philibert and Guy4 may be used with three alloys instead of four. Lastly, the diffusion paths need not be S-shaped, as pointed out by Meijering7 for "sandwich" couples. The Cu-Zn-Mn system is convenient for ternary diffusion studies because of the large single-phase field in the copper-rich corner. The vapor pressure of zinc above such alloys is known, and X-ray measurements indicate that the molar volume is nearly constant over a wide range of compositions.8,9 It is the purpose of this paper a) to extend the analysis of Balluffi and seigle5 to permit an evaluation of interdiffusion coefficients in ternary vapor-solid couples, b) to use the method of Philibert and Guy to determine intrinsic diffusion coefficients with such couples, and c) to present experimental data on both interdiffusion and intrinsic diffusion coefficients for the Cu-Zn-Mn system at 850°C. INTERDIFFUSION IN TERNARY VAPOR-SOLID COUPLES The analysis of Balluffi and seigle5 is extended in this section to a vapor-solid couple where two solutes diffuse from a vapor source into a ternary solid solution. To take into account the expansion of the diffusion disk caused by the absorption of mass from the vapor phase, the total fluxes are expressed on the basis of a coordinate system that moves with the velocity of the vapor-solid interface; thus. where D3ij are the intrinsic diffusion coefficients,4 v(x, t) is the local Kirkendall velocity of mass flow, and F(t) is the negative velocity of the vapor-solid interface (x = 0). Both these velocities are based on a fixed coordinate system far removed from the diffusion zone. Using the continuity relations and Darken's method1' for a ternary system in which components 1 and 2 diffuse from the vapor phase into a solid of negligible vapor pressure, one obtains

Jan 1, 1965

By Junius D. Edwards

WHEN Charles Martin Hall invented the electrolytic process for the production of aluminum, one basic requirement was a supply of pure alumina. Now, more than 50 years later, the same requirement still holds, and there are no technical straws in the wind to indicate that this situation is likely to change. Long ago, Aluminum Company of America took a number of steps to see that this country should not face shortages of alumina and aluminum in time of emergency. As one step to this end, the Company developed and used a supply of bauxite in South America in order to conserve dwindling Arkansas reserves. Another, and more a program than a step, was to investigate every type of process that might bear the possibility of utilizing the low-grade ores of aluminum that are more plentiful than bauxite. It is a long story, but the investigation included electric-furnace processes, acid extraction processes and alkaline extraction processes, with or without preliminary furnace and sinter treatments. Some of the processes developed were operated in commercial production. This work has been continuous since the first World War. The turn of the wheel came sooner than was expected when, in 1942, bauxite shipments through the Caribbean became uncertain and hazardous through the operation of submarines. The tremendous requirements of aluminum for the war effort were consuming high-grade bauxite at an alarming rate and a national search for substitutes began. High-grade bauxites, for technical and economic reasons, have been defined as those containing about 7 per cent or less of silica. While bauxite of this grade was limited in amount in the United States, there was in sight a substantially greater volume of low-grade, high-silica bauxite not amenable to economic treatment by the Bayer process, but richer in alumina than the clays or other available low-grade ores. It was at this point, and after several years of intensive research on this particular phase of the problem, that Aluminum Research Laboratories brought to completion the invention of one of its research staff, which made practical the utilization of large reserves of low-grade bauxite in America. BAYER PROCESS The Bayer process has been almost universally used for the 'production of alumina from bauxite. This process, in outline, comprises the digestion of finely ground bauxite in a solution of caustic soda (NaOH) under pressure and at an elevated temperature. Alumina in the bauxite goes into solution as sodium aluminate and the impurities-oxides of iron, titanium and silicon-remain undissolved. The undissolved residue, known as "red mud," from its color, is separated and run to waste. Aluminum hydrate (A1202.3H20) is precipitated from the solution of sodium aluminate, and the liquor containing the caustic soda and some alumina is returned to the process for digesting more bauxite. The aluminum hydrate, after washing, is calcined at a high temperature to produce

Jan 1, 1945