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By R. Scot Clark

The reactively sputtered silicon dioxide capacitor -was developed for use in the monolithic integrated circuit, thereby requiring the capacitor to be fabricated on an oxidized silicon slice. The silicon dioxide film is formed by reactively sputtering silicon in a 50 pct Ar-50 pct 0, atmosphere and the physical properties are indistinguishable from silica. A practical upper limit of capacitance per unit area of 0.25 pf per sq mil is reached with the capacitors fabricated from the Si0, film. Methods shown to enhance this value are double stacking the thin-film capacitors and addition of aluminum to the silicon cathode during sputtering to form an aluminosilicate dielectric. A major contribution to the field of diffused integrated circuits would be the addition of auxiliary passive devices for replacement of diffused passive devices which are currently being fabricated for many integrated circuits. This accomplishment would increase the flexibility of the diffusion process in order to concentrate more on transistor parameters rather than on fabricating diffused resistors and capacitors. To pursue this technique, a thin-film SiOz capacitor was developed which has _ proven applicable to many integrated circuits. Although the SiOl capacitor has an application, the major deterrent from extending the integrated circuit into many useful areas such as low-frequency linear application is the low dielectric constant of SiO, and the low usable capacitance in an integrated circuit. This paper will cover the sputtering techniques used for forming the SiO, film, the physical and electrical properties of sputtered SiO,, and yield information concerning the application of these capacitors to integrated circuits. REACTIVE SPUTTERING Reactive sputtering is simply the sputtering of a metal or semiconductor in glow discharge in the presence of a reactive gas. The material to be sputtered is seen in Fig. 1 as the cathode of the system and is bombarded with positively charged ions of the ambient gas. In this investigation, the ambient gas is composed of 50 pct Ar and 50 pct O2 at a pressure of approximately 2.5 X l0-' Torr. The ions are accelerated toward the cathode in the cathode dark space by the electric field and upon striking the cathode effect a momentum energy transfer to the surface atoms. The transferred energy is sufficient to dislodge a surface atom or atoms and these particles diffuse through the glow discharge to the collector or anode. Several mechanisms of oxidation in the reaction chamber can be considered during reactive sputtering. 1) The surface of the cathode is oxidized and the oxide is subsequently sputtered. 2) Oxidation and sputtering occur simultaneously. 3) Sputtering of the cathode material is followed

Jan 1, 1965

By C. S. Smith, L. W. Kempf, C. S. Taylor

The thermal conductivity of aluminum alloys is of considerable industrial importance. This is particularly true in such applications as internal-combustion engines where one of the principal reasons for the use of these alloys is their relatively higher thermal conductivity. In spite of this, relatively few data are available on this property of aluminum alloys. The reason is quite apparent to anyone concerned with the experimental determination of coefficients of thermal conductivity. This determination, in theory so simple, is extraordinarily difficult if any high degree of precision is desired. Fortunately, some .knowledge of the relationship between thermal and electrical conductivity has permitted the use of the latter physical property in deducing the relative approximate values of the thermal conductivities of metals. This fundamental relationship, first enunciated by Wiedemann and Franz' as applying to metallic elements and later shown by Lorenz2 to be applicable to alloys within a single metallic system, has been of service in the industrial application of metals. The electrical conductivity of metals is easily determined with a high degree of precision. It is, therefore, quite desirable that the relationship between electrical and thermal characteristics be determined with the greatest possible precision. This paper presents data on the electrical and thermal conductivities of a number of aluminum alloys of industrial importance. Literature on Thermal Conductivity of Aluminum Alloys Masumoto3 determined the electrical and thermal conductivities of 18 aluminum alloys. His results indicated a relatively constant relationship between thermal and electrical conductivity.

Jan 1, 1937

By Philip Schane

THE subject of steel cleanliness has always been a major one in the steel industry and much study and effort have been expended toward improving the cleanliness of steel and meeting the ever increasing demands of customers for steels that will give better performance in service and permit economies in design and efficiency of the final product. Sometimes wee may feel that-these demands are unnecessarily stringent, and probably this is true in some instances. However, the pressure for higher quality has acted as a stimulus toward improving quality and, therefore, has tended to promote progress. In this paper, the whole subject off cleanliness is covered in a general way. In the discussion' on steelmaking practices, remarks have been limited to basic electric- furnace practice in the making of alloy steels.

Jan 1, 1947

By Sir John Cadman

Since my previous review of the Persian fields, presented in 1929,' considerable progress has been made. The main feature of drilling development has been the delimitation of the Haft Kel field and its extensions. Although the limits have not yet been reached, a productive area of about 40 square miles has already been proved and it is now certain that the field will be of the same order of importance as the Masjid-i-Sulaiman field. Production to main pipe line from Haft Kel was begun in November, 1929, and to date about 4,500,000 tons have been produced. Normal production has continued from the Masjid-i-Sulaiman and Naft Khaneh fields. The search for oil in horizons below the main producing limestone is perhaps the most interesting and important exploratory drilling work in progress. Promising results have been obtained in the first well deepened in the Masjid-i-Sulaiman field with this objective, and the exploration of these lower formations is being continued. In this connection an allied program of geochemical research work on the nature of the oils and oil-bearing rocks of different horizons is at, present being undertaken. Masjid-i-Sulaiman Field Since the Haft Kel field was brought into production in 1929, production from Masjid-i-Sulaiman has been reduced in order to equalize to some extent the producing lives of the two fields. The production for the last four years has been as follows: m Approximate Equivalent in TonB Barrels 1929 5,434,071 38,038,497 1930 4,925,869 34,481,083 1931 4,248,086 29,736,602 1932 Approximately 4,500,000 31,500,000

Jan 1, 1933

By R. B. Moore

Page History................................ 708 What is Radioactivity?........................ 710 Disintegration Series.......................... 711 Radium Ore Deposits......................... 713 Metallurgical Treatment........................ 717 Methods of Ore Concentration..................... 722 Future Supply of Ore......................... 723 Uses of Radium............................ 723 Mesothorium as a Substitute for Radium................. 724 Discussion.............................. 725 Probably no other metal excites as much interest, among both scientific men and the general public, as radium. This is due partly to the high cost of radium salts and partly to the peculiar properties of the element. Since radium-bearing ores were discovered in the United States, the interest of American scientific men has been stimulated and, at the present time, more radium is extracted and refined in this country than in all the rest of the world together. HISTORY The property of radioactivity was discovered, partly by accident, by Henri Becquerel, the French physicist, in 1896. He was experimenting with certain fluorescent substances in order to find, if possible, a connection between fluorescence and the recently discovered X-rays. Among other chemicals which possess the property of fluorescence, he was using salts of uranium. His custom was to expose the fluorescent substance to the action of sunlight and then register the effect of possible penetrating radiation on a photographic plate protected from ordinary light. Bec-querel's experiments gave positive results at once, and he at first believed that he had discovered a relation between fluorescence and X-rays. Later he exposed a plate to a uranium salt which had not been previously exposed to sunlight. To his surprise, on developing this plate, he found that he had obtained the same effect as he had previously secured when

Jan 1, 1919

By F. P. Donohue

The observations and data presented in this paper are the result of extensive study of flowing wells, most of which were in the Maracaibo Lake Basin of Venezuela. The Lago Petroleum Corpn. had extensive production in this area, gas-oil ratios were low, and the problem was to determine whether by careful handling of the wells with respect to flowing conditions and by conserving the gas, the oil production of the wells could be maintained by natural flow until it had declined to a rate which could be handled with an ordinary working barrel, thereby avoiding the high cost of gas-lift equipment installation in the lake bed. The problem was complicated by the nature of the wells themselves. Production is from soft, comparatively unconsolidated sands, necessitating screen pipe in all wells. It was not only necessary to keep the wells flowing but to keep them flowing without heading, as the release of pressure upon making a head brought large quantities of sand into the wells, sanding them up or possibly cutting out the screen pipe. In furtherance of the plan of keeping wells flowing as long as possible, each well was equipped with a casinghead and tubinghead recording pressure gage, and an oil and gas separator set. About one-half of the wells were equipped with gas meters. All wells were tubed before bringing into production. Frequently individual gages were taken on each well. A large scale chart was plotted for each well, showing daily oil production, gas production, gas-oil ratio, tubinghead pressure and casinghead pressure. Any deviation from the normal was immediately checked and the condition remedied if possible. Theory of Flowing Wells Based upon considerable study of these records, it is believed that the flow of a well actuated by gas is mainly a problem in velocity, a certain minimum velocity in the flow string being necessary for the gas to carry the oil. If this minimum velocity is not obtained the oil drops back and the well heads or goes dead. The point of minimum velocity is of course at the bottom of the tubing, where the gas is under the highest pressure and therefore occupies the least volume. Some years ago when the success of the gas-lift at Seminole was so pronounced, there was considerable broadcasting of the statement that

Jan 1, 1930

By M. G. F. Söhnlein

IN THE metallurgical treatment of sulfide silver-tin ores mined at Oruro, Potosi, and Chocaya, the most important and difficult step is chloridizing-roasting. The ores are chiefly mined from veins in rhyolite, a detailed description of which can be found in most textbooks on ore deposits. The chief gangue minerals are Pyrite and quartz, and the silver content is derived from tetrahedrite, jamesonite, stibnite, and cylindrite. Most of the tin is present in the form of a rather impure cassiterite, which forms microcrystalline aggregates of varying richness with quartz and pyrite; occasionally, some tin is found as stannite, cylindrite, and other complex sulfantimonates. The silver content of the minerals that compose the ore is approximately as follows: Pyrite, 3 to 5 oz. per ton; jamesonite, 30 to 50 oz. per ton; stibnite, 30 to 150 oz. per ton; cylindrite, 200 to 300 oz. per-Jon; tetrahedrite, 500 to 3000 oz. per ton. Occasionally, some ruby silver ore is found, but it is very rare. In the mines of Oruro, which are the deepest in the sulfide zone, tetrahedrite has nearly disappeared, stibnite, jamesonite, and, in the deepest levels, cylindrite taking its place. At present, there are six mills treating this ore, two at Potosi, two at Chocaya, one at Poopo, and one at Machacamarca. The ore is crushed dry, given a chloridizing roast, leached with water and hyposulfite solution (or with brine) to extract gold, silver and copper, and concentrated for tin with or' without regrinding.

Jan 8, 1920

By D. I. Bardos, Paul A. Beck

The 1100°c isothermal, sections of the V-Fe-Si, V-Co-Si, and V-Ni-Si systems were studied at silicon contents between 0 and 40 at. pct. The single-phase fields in the 30 and 50 at. pct Mn sections of the 1100°C tetrahedron of the V-'Wn-Fe-Si system were also determined. The direction of extension of the elongated O, R, D, and a-Mn Phase fields suggests that the stability of these phases is determined largely by the electron concentration. The peculiar shape of the above ternary a phase fields, as well as of the a phase fields in the V-;Mn-Si and Cr-MTZ-Si systems is accounted for on the assumption that in manganese-(iron-, coball-, nickel-) rich alloys silicon atoms do not exclude d electrons , while in alloys low in the above components they do. This assumption also leads to the expected electronconcentrations for q and ß-Mn phases formed by transition metals with aluminurn. In earlier work it was shown that in ternary alloy systems of transition elements the a a and certain other phases with complex structure, such as the p and R phases,3 form elongated phase fields extending in a direction corresponding to a constant electron concentration. Recently similar behavior was observed in manganese-rich ternary ß-Mn solid solutions with another transition element and with silicon, germanium, or tin,4 confirming earlier indications3 that ß-Mn is also an electron phase. The alloying behavior of silicon in these manganese-rich alloys sug- gested that the four outside electrons of silicon participate in the bonding and that the predominantly d-like bonding electrons are not excluded from the silicon sites. Presumably, some of the normally unoccupied 3d states associated with the silicon atoms are in these alloys lowered to the Fermi level;4 thus silicon behaves as if it, too, were a transition element. The manganese-rich boundary of the a phase in the V-Mn-Si system,4 as well as in the Cr-Mn-Si sys-tem,4,5 extends approximately parallel to the ß-Mn phase boundary, corresponding to the transition ele-mentlike behavior of silicon described above. However, at lower manganese contents (i.e., in the high-vanadium or -chromium region) the a phase field in both ternary systems mentioned extends in a direction roughly perpendicular to that of its manganese-rich boundary, a phenomenon that is apparently inconsistent with the behavior of silicon in the manganese-rich alloys. A similar, although somewhat less pronounced, extension of the a phase occurs also in the high-vanadium (low-iron) region of the V-Fe-Si system at 1175C, but reportedly not in the V-Co-Si or V-Ni-Si systems at the same temperature.5 The present work was undertaken to investigate in more detail the extension of the a phase (as well as of other electron phases that may be present) in the last three systems and to elucidate this phenomenon, which has not been satisfactorily explained previously. EXPERIMENTAL PROCEDURES Most of the alloys were melted in an arc furnace, using a water-cooled copper crucible under helium atmosphere. The transition metals were of better than 99.9 pct purity and the silicon used was 99.98 pct pure. Alloys containing less than 20 pct V were induction-melted in recrystallized alumina crucibles under argon atmosphere.

Jan 1, 1967

By G. J. Saulnier, K. E. Goddard

The US Geological Survey has developed mathematical modeling techniques to assess potential impacts on the hydrologic system resulting from mining of coal and oil shale in northwestern Colorado. Potential impacts of oil shale mining on groundwater hydrology have been simulated using a quasi-three-dimensional, finite-difference model. The model has been used to simulate hypothetical mine dewatering operations at two proposed oil shale mines. Dissolved-solids distribution and solute transport were simulated with a three-dimensional, finite-difference model that was used to evaluate the effects of flooding in hypothetical abandoned mines. The potential impacts of coal and oil shale mining on water-sheds were investigated using a digital watershed model. This deterministic physical-process model predicts responses of the hydrologic system to modifications resulting from mining in basins having snow as the major source of runoff and recharge. Potential impacts of coal development on surface water quality were investigated using a river quality assessment model. The models developed by the US Geological Survey have been useful in defining the potential effects of mining in northwestern Colorado. They are an important first step in analyzing the existing data base and in predicting impacts and new data needs. The models may not be totally applicable on the local scale but are very meaningful on the regional level.

Jan 1, 1983

By G. L. Chierici

Starting from Muskat's theory of water and gas coning, maximum permissible oil production rates without water and/or free-gas production have been determined, in a broad range of reservoir and well parameters, using the potentiometric model technique. The main assumptions made are as follows: (1) the reservoir rock is homogeneeous (either isotropic or anisotropic); (2) the volume of the aquifer underlying the oil zone is very small, so that it does not contribute to reservoir energy; and (3) the gas cap expands at a very low rate, so that it can be assumed to be in quasi-static conditions. The results obtained are presented in the form of diagrams which can be used for solving two types of problems: (1) given the reservoir and fluids characteristics, as well as the position and length of the perforated interval, determine the maximum oil production rate without water and/or free-gas production; and (2) given the reservoir and fluids characteristics only, determine the position and length of the perforated interval which optimize the maximum permissible oil production rate, without water and/or free-gas production. INTRODUCTION In oil reservoirs where the oil-bearing formation is underlain by an aquifer which does not participate in the production mechanism, water-coning is a limiting factor to the flow rates of producing wells. Production rates are usually kept to a value that will prevent the water from entering the wells. The entry of water into a well lowers its productivity by increasing the weigbt of the fluid column; moreover, the separation of water from the effluent, at the surface, may constitute a very difficult problem in cases of heavy viscous oils. A similar situation is encountered in oil reservoirs with a gas cap overlying the oil-saturated zone; here a downward gas cone is induced by the flow of oil towards the producing wells. Production rates must be low enough to prevent the gas from being produced; producing gas from the gas cap would be a waste of energy. Of course, water-coning and gas-coning phenomena can occur at the same time in the same reservoir if the oil-producing formation is both overlain by a gas zone and underlain by a water zone. Due to its relevant practical importance, the mechanism of coning was studied by many people.2,3,5-8 Defining the conditions for getting the maximum water-free and/or gas-free oil production rate is a difficult problem, often encountered under one of the following aspects: 1. Predict the maximum flow rate that can be assigned to a completed well without the simultaneous production of water and/or free-gas. 2. Define the optimum length and position of the interval to be perforated in a well, in order to obtain the maximum water and gas-free production rate. A systematic study of these problems was made by means of the electrical analog technique. The results of this study are presented here, under the form of a set of curves providing solutions for the above stated problems. These curves are valid only for homogeneous forrnations, either isotropic or anisotropic. Should the formation be non-homogeneous (by horizontal or vertical variation of permeability, shale diaphragms, fractures, etc.), a specific potentiometric study would be required for each specific case. Especially when shale diaphragms of some radial extension are present, the critical rates observed are much larger than would be expected from the diagrams. STATEMENT OF THE PROBLEM In the present study the aquifer is supposed to be of such limited volume that it does not contribute to the energy of the reservoir. Moreover, the gas cap is supposed to expand at such a low rate that the potential gradient in the gas cap is negligible. Under static conditions water-oil and gas-oil interfaces (T1 and T2) are both horizontal. When the reservoir production starts, below each well these interfaces take a cone-like shape (Fig. 1) having as an axis the axis of the well. This shape results from the equilibrium between potential gradients in the oil zone and gravitational forces due to density differences between oil and water and between oil and gas. Assuming the oil-bearing formation to be homogeneous and the oil to be incompressible, the analysis of the problem (see Appendix) shows that the oil-water and gas-oil interfaces are stable only if the oil production rate of the well is not higher than the following values.

Jan 1, 1965

By S. Weissmann, P. R. Swann, D. F. Wriedt

The sizes and density of precipitates in an intemally oxidized 0.19 wt pct Al-Ag single crystal have been determined by low-angle X-ray scattering and by transmission electron microscopy . The correlation in particle sizes measured by the two techniques is reasonably good. For an oxidizing temperature of 800°C the particles were found to INTERNAL oxidation of dilute alloys of aluminum in silver produces an oxide which has an excess of oxygen compared to Al2O3.' It is believed that the excess oxygen is an indication of the small sizes of the oxide particles. Depending upon the particular model chosen for the oxide structure, the size of the o-A1 particles can be calculated as a function of the oxygen-to-aluminum ratio. These calculations pre- have diameters in the range 30 to 140A, with a mean size of about 50.4 as observed by electron microscopy. At lower oxidizing temperatures, less than 600°C, no clearly resolved particles are formed, and it is suspected that if A1-0 clusters exist they must be exceedingly small, i.e., 10A or less in diameter. dicto that the particles would vary in size from 15 to 100A. This range of sizes is amenable to detection by both small-angle X-ray scattering and transmission electron microscopy. This paper compares the cluster sizes in such internally oxidized A1-Ag alloys determined by transmission electron microscopy and small-angle X-ray scattering. SPECIMEN PREPARATION Single crystals were prepared from 99.9999 pct Ag, obtained from Cominco Products, and 99.99 pct Al, obtained from Aluminum Co. of America. All melting operations were carried out in graphite molds under flowing purified hydrogen in a horizontal zone refiner. The silver was first degassed,

Jan 1, 1964

By S. F. Emmons

By far the greater number of the members of this Institute are men who are engaged in the strenuous work of the technical part of their profession, and find little time for the abstract scientific work which is less distinctly practical and pecuniarily remunerative. There is, however, a small but increasingly nu, merous class whose members devote themselves to broad geological problems which underlie the systematic development, and whose work, theoretically, ought to precede and form a basis for that of their more practical brethren. These are the so-called mining or economic geologists, who are, for the most part, connected with State or National geological surveys. Prom the character of their work, the life of these men necessarily follows rather different lines from that of most of their colleagues, and is not generally familiar to them. It seems admissible, therefore, that to the life of a prominent member of this class, who died during the past year, having literally sac-rified his life to his work, a more extended notice should be given than the relatively small number of his contributions to the Transactions night seem to justify. George Homans Eldridge, son of Ellery and Sarah (Mathews) Eldridge, was born on Cape Cod at Yarmouth, Mass.; Christmas day, 1854. His boyhood education in the public school at Yarmouth was followed by a six years' course in the Public Latin School at Boston, from which he entered Harvard University in 1872, being graduated with the highest rank in his class in the natural sciences in 1876. During his college course he spent the summers of 1875-6 at Cumberland Gap, Ky.,as volunteer aid to Prof. N. S. Shaler, who was then in charge of the State Geological Survey of Kentucky. This vacation work, undertaken by him rather as a pastime, gave him his first leaning toward geology. Soon

Jan 1, 1907

H. G. KNOX,* Norfolk, Va. (written discussion?).-There is one subject that Mr. Hobart seems to have inadvertently omitted from his very valuable paper, and that is corrosion. The shipbuilder, perhaps more than anyone else, has constantly to guard against it, our chief reliance being paint and galvanizing, where practicable. The corrodibility of a welded. joint is salt water must be determined before deciding whether this type of construction is to supersede riveting. At the present time, this question cannot be answered, although considerable work has been started in an attempt to arrive at a conclusion. The British Admiralty and several British shipbuilders have studied it extensively. Their experiments and conclusions have been very carefully followed and reported in this country by Naval Constructor Goodall of the British Navy. To date, these show that no undue fear need be felt from corrosion. At the Norfolk Navy Yard a series of plates welded with various electrodes were submerged in dilute sulfuric acid, such as is used in cleaning prior to galvanizing. While this test may not be conclusive in any quantitative way, it does show a marked difference in the corrodibility of welds made with different electrodes tinder different conditions. To thaw any conclusions from this accelerated this accelerated test would be, however, ill advised. In riveted joints, the exposed heads and points of the rivets always show the greatest tendency to corrode. This is clue to two reasons: first, as they are raised above the surrounding surface the paint is more susceptible to abrasion; and, second, electrolytic action is set up between rivet and plate. These same reasons lead us to expect a tendency of the welded joint to corrode. Various methods have been suggested for decreasing the probable inherent corrodibility of the weld, in addition to the customary coat of paint. These generally embody the introduction of alloys, principally copper; into the electrode material. Plating the electrode with copper is not effective in that the deposited copper segregates in the weld and actually increases the electrolytic action. As far as is known, no extensive test on the so-called copper-bearing alloy steels, which might be made up into electrodes, has been carried out, but when obtainable, electrodes of this alloy will be subjected to service tests.

Jan 6, 1919

By George W. Maynard

In the biographical notice of Thomas F. Witherbee, published in.Bulletin NO. 32, August, 1909 (p. xxv), it is said that "he is believed to have been the first manager in America to use the chemical laboratory for the purpose of controlling the regular running of the blast-furnace." Since the year is not given, I cannot decide as to Mr. Witherbee's priority; but the statement leads me to contribute a bit of history, showing an early departure from the " rule-of-thumb " blast-furnace work to the employment of a chemist. In the autumn of 1868 the department of mining and metallurgy was established at the Rensselaer Polytechnic Institute. In connection with the assay-department a laboratory was equipped for making general commercial analyses. In January, 1869, Alexander L. Holley, the manager and builder of the Bessemer plant at the Rensselaer Works of John A. Griswold & Co., the first plant erected in the United States under the Bessemer patents, began to send me samples

Jan 1, 1911

By Robert F. Winkle

A detailed breakdown of mining costs, available to management on monthly and year-to-date bases, is mandatory for a controlled and efficient mining operation. A simple lump sum reporting of costs may indicate a profit or loss differential, but it does not allow an effective search for areas of possible cost reduction. Moreover, functional reporting is necessary on a timely basis so as to note trends of increasing costs In specific areas, which in turn allow possible preventive action by management. Definitive cost information helps to eliminate the tendency to overlook areas where cost Improvements can be made. A good cost control system points out salient operational weaknesses by: ( 1 ) allowing comparison of functional costs with similar costs of other mines and (2) pinpointing sudden increases over unit empirical costs within the organization. In general, the cost accounting structure is relatively uniform within large open pit mines, but surprisingly some systems will overlook the need for detailed breakout in comparatively high cost areas. In some other systems, unrelated costs will be lumped together, preventing careful analysis of cost accrual.

Jan 1, 1979

By Arthur H. Wilson

INTRODUCTION The stratified deposits of the coal measures are strongly laminated and exhibit a high degree of anisotropy. The stronger rocks in the sequence possess joints and shear planes, the coal itself has a closely spaced cleat pattern, and the softer rocks are capable of flowage. To calculate the general distribution of stress in such a medium by analytical means based on the theories of elasticity is difficult, and has not yet been satisfactorily achieved. Nevertheless, some estimate is required to aid the design of supporting pillars and permit the correct siting of main roadways. This is important when laying out districts for longwall extraction, particularly if the results of previous experience are not available in the area to be exploited. Although elastic stress analyses, including finite element analysis, may not be very appropriate, the basic equilibrium conditions will apply. These, combined with logical deductions based on observed fact, can be used to give appropriate solutions which experience has shown to be capable of giving acceptable results in the design of pillars associated with longwall workings. Constancy of cover load is one of the fundamental equilibrium conditions. When mining below ground, the cover is not removed, therefore the average vertical load after mining must equal the initial cover load. If mining produces a local decrease in load in any particular area, it must be balanced by an equivalent increase in load nearby. Bending moments in the strata above are capable of compensating for the turning moments which this redistribution of load may produce, and the existence of a "rear abutment", much discussed between 1950 and 1960, is not an essential equilibrium requirement. If the distribution of vertical stress is plotted three-dimensionally, then the load on any small element of area 6S will be o.6S, where o is the average stress. This also represents the volume of the "stress envelope" which lies above 6s. By making the individual areas very small and summing together, it is possible to show that the total load on any particular area can be found by calculating the volume of the stress distribution envelope which lies above it. A similar consideration applies to the stress distribution in a two-dimensional situation. If the stress distribution curve is drawn, then the area below any portion will represent the load per unit depth of section. For example, Figure 1 represents the possible stress distribution across a caved waste and associated ribside. If AW is the load deficiency [ ] These loads must balance, therefore area AW = AS, and if one can be deduced, the other will then be known. Attempts have been made to measure stress distributions in the ribside and in the waste. Stress meters in soft rocks such as the coal measures have not proved very effective. Those based on the measurement of strain have experienced difficulty in strata capable of flowage, high modulus stress meters suffer from cross sensitivity, and overcoming to obtain absolute stress is almost impossible. Load measuring instruments left in the waste have also proved largely ineffective, mainly as a result of the difficulties of protecting the leads in a caving environment. Certain logical deductions, however, can be made about the conditions in the waste. CONDITIONS IN THE WASTE Over the area of the waste the surface trough which develops is remarkably consistent, despite the geological variations which occur from coalfield to coalfield. In Britain, an accuracy of 210% is claimed for subsidence prediction based on width of extraction and depth of cover (National Coal Board, 1975). The subsidence in the USA is more variable (Adamek and Jeran, 1981), particularly with respect to the point of inflexion, but the same general pattern occurs. At the shallower depths the somewhat harder roof strata involved in the caving in the USA may suffer less compaction, giving reduced values of subsidence. Subsidence at intermediate horizons below the surface

Jan 1, 1982

By Forrest V. Williams

The dislocatiorl and stacking-fault structuve of epitaxial GaAs1-,PX lms been examined by chemical etching. The layers were groun in the (100) direction and etch Pils were developed on (111} planes which nad been lapped and polished on the epiLaxia1 layevs. Tile effecL of the jollolcing cariables on the quality of the epilaxial layers has been examined: doping leuel, grouth rate, and composition. High stacking-faullL densilies weve found in the GuAsi_xpx layers. These are not observed in heavily dolled epitaxial layers tzar in layers with low phosphorus compositions. The dislocatiorz density in GuAsi-x px was highest at the sub-stvate- epilaxia1 layer interface. Composilion changes introduced dislocations in the epitaxial layers. ManY semiconductor p-n junction lasers of Group TIT-Group V compounds and their alloys have been reported in the past several years. Laser action at visible wavelengths in GaAsl-x,Px was first reported by Holonyak and Bevacqua. GaAs, a direct transition semiconductor which lases, and Gap, an indirect transition semiconductor which does not lase, form a continuous series of solid solutions.2 Laser junctions can be fabricated in GaAsl-xPx crystals with phosphorus compositions up to about 40 mol pct. In addition to the production of coherent radiation in these crystals, the efficient recombination radiation of p-n junctions in this material has equally important potential in the development of low-power semiconductor lamps. To achieve a high conversion efficiency of electrical to optical energy in p-n junctions in this material, the relation of physical properties of the crystal to luminescence efficiency must be better understood. Although the electrical, optical, and device properties of GaAsl -xPx junction lasers are understandably of considerable interest, the work to date indicates that the more serious problems are the chemical and metallurgical difficulties encountered in the growth of this material.3 In addition to the problems of chemical purity, crystal imperfections, such as dislocations and stacking faults, can be expected to affect both the efficiency of the radiative recombination process and the perfection of the p-n junction.3 The last requirement, i.c., that of the perfection of the p-n junction, is a particularly troublesome one in the fabrication of laser diodes. To obtain good laser diodes, the p-n junction must be flat, which permits the radiation to be reflected from the resonant cavity boundaries. Junction planarity is extremely sensitive to the crystal perfection of the semiconductor material. Also, it is known that at high dislocation densities (-105 per sq cm) it has not been possible to build laser junctions in GaAsl-xPx . Few studies have been reported on the crystal defect structure of GaAsl-,P,. The first serious study seems to be that of Wolfe, Nuese, and Holonyak,3 who examined the dislocation structure of monocrystalline bulk (nonepitaxial) material grown by halogen vapor transport. In this paper are reported some observations on the dislocation and stacking-fault structure of GaAsl_,P, crystals grown by a vapor transport process on substrates of GaAs. EXPERIMENTAL Crystal Growth. The GaAsl-xPx crystals were grown in an open-tube flow system, using two sets of reagents. GaAs, Pr(red), and HC1 were employed in one method. The transport reaction is =950JC GaAs+HC1 = GaCl +1/4As4 +1/2H2 and the deposition reaction is 2GaAs1-xPx +GaCl3 Composition control is obtained by the flow rate of the HC1 and the vapor pressure of the P4, which is maintained in a separately controlled furnace. The second method has been described by Ruehr-wein4 and utilizes gallium, AsH3, PH3, and HC1. The same transport and deposition reactions as above are involved. Composition control is obtained solely by the flow rates of the three gases involved. All of the crystals were grown on chemically polished GaAs substrates oriented on the (100) plane. The thicknesses of the epitaxial layers were typically 100 to 300p. Revealing of Dislocations. Dislocations were re-vealed on both the( 111 ) and { l l l }b faces by chemical etching. The specimen to be examined was mounted at 54.7 deg, lapped on glass with 3-p alumina, polished on cloth with 3-p diamond paste, and, to remove work damage, chemically polished at room temperature for

Jan 1, 1968

By B. H. Sage, W. N. Lacey

The growing background of experimental information concerning the volumetric and phase behavior of binary and ternary hydrocarbon systems is used as the basis for a comparison of these systems with naturally occurring hydrocarbon mixtures under conditions representative of underground petroleum reservoirs. The qualitative and semiquantitative similarities and differences between the two types of systems are considered in reference to the possibilities and limitations of using experimental data on binary and ternary systems for predicting the volumetric and phase behavior of naturally occurring hydrocarbon mixtures of low molecular weight. The possible influence on such phase behavior of water, hydrogen sulphide, nitrogen, and components of relatively high molecular weight is discussed. INTRODUCTION During the past two decades much effort has been devoted to the study of the volumetric and phase behavior of pure paraffin hydrocarbons and of binary and ternary mixtures of these compounds. Many of these studies were carried out with the direct objective of utilizing a knowledge of the detailed characteristics of binary and ternary mixtures of the lighter paraffin hydrocarbons for predicting the behavior of more complex mixtures. The ability to make such predictions with accuracy would be of great value in petroleum production and refining. Although the behavior of the methane-propane system' served at one time as a qualitative illustration of the probable characteristics of the more complex hydrocarbon mixtures found in nature, it' fell far short of requirements for quantitative predictions. The present paper endeavors to indicate the relation of the more recently accumulated information concerning the behavior of binary and ternary hydrocarbons to this problem. In discussing binary and ternary systems as examples pointing toward the behavior of multi-component systems no effort is made to present new methods of predicting the characteristics of natural hydrocarbon mixtures. Preliminary proposals have been made elsewhere for the prediction of volumetric phase equilibrium and thermodynamic data for multicomponent mixtures, utilizing as a basis the behavior of binary and ternary systems. Numerous other proposals have been made. That based upon the concept of a pseudo-critical state" has proved to be of value to the petroleum industry. Concurrently with this study of binary and ternary systems investigations have been made of natural hydrocarbon systems. Of the many publications reporting such experimental information only a few examples will be mentioned. A number of studies of black oil and natural gas have been made and much attention has been directed to extended and detailed investigations of the behavior of fluids in condensate fieldS 16,17,18,19,20. This work has been supplemented by some studies of the separation of bitumen from natural hydrocarbon liquids The over-all behavior of such systems has been used in predicting the volumetric and phase behavior of naturally occurring mixtures This background of experimental and correlated information concerning the behavior of multicomponent hydrocarbon systems also permits a direct comparison of the characteristics of binary and ternary aliphatic systems with those materials produced from underground reservoirs. PRESENTATION OF DATA The primary limitation encountered in using binary and ternary aliphatic hydrocarbon mixtures as examples of the characteristics of the fluids encountered in underground reservoirs lies in the existing lack of knowledge of the quantitative effect upon behavior of the presence of several important constituents, notably hydrocarbons of high molecular weight, water, carbon dioxide, hydrogen sulphide, and nitrogen. The presence of substantial quantities of hydrocarbons of fairly high molecular weight serves to increase the complexity of the phase behavior of natural systems. No simple systems yet studied give adequate guidance in this regard. The influence of such materials of high molecular weight was indicated earlier",?' to an extent which serves to show that definite limitations now exist in the correlation of simple and complex systems. However, significant progress is being made in filling gaps in the information. For example, similarities in the behavior of fluids in condensate fields with that of binary and ternary systems are becoming more systematically evident. A few studies of the behavior of water in paraffin hydrocarbon systems have been made Results of investigations of mixtures of carbon dioxide and the lighter hydrocarbons also are available Limited work has been reported con-

Jan 1, 1949

By W. N. Lacey, B. H. Sage

The growing background of experimental information concerning the volumetric and phase behavior of binary and ternary hydrocarbon systems is used as the basis for a comparison of these systems with naturally occurring hydrocarbon mixtures under conditions representative of underground petroleum reservoirs. The qualitative and semiquantitative similarities and differences between the two types of systems are considered in reference to the possibilities and limitations of using experimental data on binary and ternary systems for predicting the volumetric and phase behavior of naturally occurring hydrocarbon mixtures of low molecular weight. The possible influence on such phase behavior of water, hydrogen sulphide, nitrogen, and components of relatively high molecular weight is discussed. INTRODUCTION During the past two decades much effort has been devoted to the study of the volumetric and phase behavior of pure paraffin hydrocarbons and of binary and ternary mixtures of these compounds. Many of these studies were carried out with the direct objective of utilizing a knowledge of the detailed characteristics of binary and ternary mixtures of the lighter paraffin hydrocarbons for predicting the behavior of more complex mixtures. The ability to make such predictions with accuracy would be of great value in petroleum production and refining. Although the behavior of the methane-propane system' served at one time as a qualitative illustration of the probable characteristics of the more complex hydrocarbon mixtures found in nature, it' fell far short of requirements for quantitative predictions. The present paper endeavors to indicate the relation of the more recently accumulated information concerning the behavior of binary and ternary hydrocarbons to this problem. In discussing binary and ternary systems as examples pointing toward the behavior of multi-component systems no effort is made to present new methods of predicting the characteristics of natural hydrocarbon mixtures. Preliminary proposals have been made elsewhere for the prediction of volumetric phase equilibrium and thermodynamic data for multicomponent mixtures, utilizing as a basis the behavior of binary and ternary systems. Numerous other proposals have been made. That based upon the concept of a pseudo-critical state" has proved to be of value to the petroleum industry. Concurrently with this study of binary and ternary systems investigations have been made of natural hydrocarbon systems. Of the many publications reporting such experimental information only a few examples will be mentioned. A number of studies of black oil and natural gas have been made and much attention has been directed to extended and detailed investigations of the behavior of fluids in condensate fieldS 16,17,18,19,20. This work has been supplemented by some studies of the separation of bitumen from natural hydrocarbon liquids The over-all behavior of such systems has been used in predicting the volumetric and phase behavior of naturally occurring mixtures This background of experimental and correlated information concerning the behavior of multicomponent hydrocarbon systems also permits a direct comparison of the characteristics of binary and ternary aliphatic systems with those materials produced from underground reservoirs. PRESENTATION OF DATA The primary limitation encountered in using binary and ternary aliphatic hydrocarbon mixtures as examples of the characteristics of the fluids encountered in underground reservoirs lies in the existing lack of knowledge of the quantitative effect upon behavior of the presence of several important constituents, notably hydrocarbons of high molecular weight, water, carbon dioxide, hydrogen sulphide, and nitrogen. The presence of substantial quantities of hydrocarbons of fairly high molecular weight serves to increase the complexity of the phase behavior of natural systems. No simple systems yet studied give adequate guidance in this regard. The influence of such materials of high molecular weight was indicated earlier",?' to an extent which serves to show that definite limitations now exist in the correlation of simple and complex systems. However, significant progress is being made in filling gaps in the information. For example, similarities in the behavior of fluids in condensate fields with that of binary and ternary systems are becoming more systematically evident. A few studies of the behavior of water in paraffin hydrocarbon systems have been made Results of investigations of mixtures of carbon dioxide and the lighter hydrocarbons also are available Limited work has been reported con-

Jan 1, 1949

By J. W. Spretnak, V. Kandarpa

Stress -induced ordering of carbon atoms is studied in a series of Fe-Mn-C alloys. A prominent peak is found in the vicinity of 280°C at frequencies of the order of 1.0 cps, with an associated activation energy of 37 kcal per mole. The height of the peak is linearly rekzted to the concentration of carbon in solution. The distortion of octahedral holes by manganese atoms appears to be predominant over carbon-carbon pair interactions. RELAXATION by stress-induced ordering of point defects is expected whenever the introduction of these point defects produces distortions which have a lower symmetry than that of the lattice. Under zero stress, the isolated point defects occupy the crystallographic-ally equivalent positions in the lattice, as these represent states of equal energy. However, if the defect sites are asymmetric, application of an uniaxial stress will split the energy states, and a redistribution of the defects among various states will take place. This is the case of the internal friction peak called the Snoek peak,1 resulting from isolated interstitials in bcc metals. The interstitial sites in this case have tetragonal symmetry. In the case of fcc and hcp lattices, such an effect is not expected from isolated point defects because of the symmetrical nature of the interstitial sites. However, internal friction peaks arising from interstitial diffusion have been reported both in hcp2,3 and fcc4-8 lattices. These peaks are often explained on the basis of stress-induced ordering of interstitial solutes, caused by the deviation of interstitial sites from their cubic symmetry through the presence of nearby defects. In the case of fcc lattices, evidence for interactions of both the substitutional-interstitial4,6,13 and interstitial-interstitial types5'798'14 have been presented by various investigators. The purpose of the present investigation was to study the internal friction peak attributed to the diffusion of interstitial carbon atoms in high purity austenitic manganese steels and to account for the peak in the light of the existing models. MATERIALS The Fe-Mn-C alloys used in the present investigation were made in two different ways, designated as Type I and Type 11. Type I alloys were made from high purity Fe-Mn alloys obtained in the form of 0.04- in.-diam wires from Materials Research Corporation, Orangeburg, N.Y. These alloys were carburized to different levels using gas mixtures of H2 and CH4 at 1000°C. Type I1 alloys were made in this laboratory starting with zone refined iron, spectrographically pure manganese, and spectrographically pure carbon. They were melted in an argon arc melting furnace and drawn into 0.04-in.-diam wires. All the wires were annealed at about 900°C for 3 hr prior to the internal friction experiments. After the measurements of internal friction, the phases in the samples were identified by X-ray diffraction and the carbon determined by the combustion method. EXPERIMENTAL PROCEDURE In the present work, a classical Ke-type pendulum was used. The details of the equipment were described previously by D. T. Peters.9 Dry helium at 40 torr was used in all the experiments. The internal friction, measured as the logarithmic decrement of the torsion amplitude of vibration was determined as a function of temperature, from ambient to about 500°C. The background internal friction was assumed to have the form of the exponential of the inverse temperature and was subtracted from the raw data. The height of the peak was measured at the position of the maximum in the plot of the internal friction versus temperature. The activation energies of the peaks were measured by the peak shift method. The internal friction values for an alloy were obtained as a function of temperature at different frequencies of vibration. The position of the peak changes with frequency, the higher the frequency the higher the peak temperature. The activation energy of the process associated with the peak is obtained using the formula

Jan 1, 1970