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By J. H. Henderson, R. J. Wygal, J. Naar

Experimental work is reported which shows that consolidated rocks and unconsolidated porous media exhibit different imbibition flow behavior. At a given saturation the imbibition nonwetting permeabilities for a rock are smaller than the drainage permeabilities. The contrary happens for unconsolidated aggregates — imbibition nonwetting permeabilities are larger than drainage ones. A similar difference is observed for the wetting phase. Imbibition permeabilities are larger than drainage ones for a consolidated rock but smaller than drainage permeabilities for an unconsolidated medium. The results of these differences are examined for two cases. 1. Flooding Efficiency — Craig's1 scheme for the computation of production history of a five-spot water flood is shown to agree extremely well with experimental results obtained when using a system packed with glass spheres if imbibition relative permeability curves are used. 2. Alcohol-Slug Displacement — Published theory 2 on oil displacement by alcohol slugs has been questioned despite the apparent agreement between predicted and observed results. The present work suggests that, if imbibition relative permeability curves characteristic of the unconsolidated media used in the early experiments had been available to make the predictions, the inadequacy of the theory would have been immediately evident. The experimental work shows that poorly consolidated formations tend to behave like unconsolidated media. Finally, it is shown that the difference in imbibition behavior is directly related to pore-size distribution and cementation. PART 1 — THE FLOW BEHAVIOR OF UNCONSOLIDATED AGGREGATES Experiments on scaled models of field reservoirs are useful for studying new displacement processes which are incompletely understood. Even when a mathematical description is possible, the solution might be difficult and complex. An answer obtained from a scaled model is extremely valuable in such cases. A great amount of work$-5 therefore, has been devoted to the derivation of scaling laws. Similarity groups have been defined which assume (1) that the relative Permeability curves of the prototype and the model are the same whether the displacement is an imbibition or a drainage process and (2) that there is a linear relationship between the capillary pressure of the model and the prototype. For practical reasons (simplicity in the preparation of models, duration of the experiments, etc.), the porous media of laboratory models are usually unconsolidated packs of sand or glass particles. Hence, unless the capillary and flow characteristics of unconsolidated and consolidated systems are identical, the model data are applicable only to unconsolidated formations. The usefulness of scaled-model studies may then be seriouslyrestricted since most oil-bearing sands are consolidated. Perkins and Collins6 suggested the use of model and prototype curves normalized with respect to both relative permeability and saturation to improve compliance with scaling criteria. Even this technique does not give a satisfactory model-prototype match. This paper reports an observation of two-phase flow in unconsolidated sands which shows that, for most displacements, "scaling" in the strict sense of the word is not even qualitatively feasible with a sand model. It provides, however, a firm foundation for testing a theory by matching it with observed performance of laboratory-size models. EXPERIMENTAL AS a part of a basic study of packed aggregates, the relative permeability of glass-spheres and sand-grain packs was measured with capillary control. The fluids were oil and air' The spheres were packed in plastic cylinders 1-in. in diameter;

By Robert S. Young

During the last quarter-century, exploration for metallic deposits in Maine has been sporadic with peaks generally coinciding with periods of high metal prices. Known cases of regional or semi-regional evaluations are few; most efforts have been local and usually intensive. On the basis of broad geologic groups, the State has been divided into five fundamental environments: ( 1) coastal metamorphic belt; (2) southern volcanic belt; (3) Silurian slate belt; ( 4) northern volcanic belt; and ( 5) Devonian slate belt. Although not restricted to these areas, exploration in recent years has been concentrated in the northern and southern volcanic belts. Notable examples of recent exploration activity, directed to sulfide minerals, include: ( 1) the Knox County nickel-copper-bearing ultramafic rocks; (2) the Harborside (Cape Rosier) copper-zinc deposit; (3) the Second Pond (Black Hawk) zinc-copper-lead-silver deposit; ( 4) the Big Hill-Barrett lead-zincsilver- copper-gold zones; (5) the Parmachenee copper-zinc belt; ( 6) the Moxie Lake nickeliferous peridotite; and (7) the Attean quartzmonzonite molybdenum-copper occurrences. The Second Pond and Harborside prospects appear to be close to production. Systematic investigations for non-metallic deposits appear to have been aimed principally toward limestone, asbestos, diatomaceous earth, and spodumene-bearing pegmatites. Advances in prospecting methods, high metal prices, a favorable business outlook, increasing cooperation from large landholders, and some discoveries support the probability of increased exploration activity in Maine during the coming decade.

Jan 1, 1968

By E. N. Cameron, H. M. Bannerman

During the years 1942-1934, about 125 New England deposits were mined for sheet and punch mica, and many others were briefly prospected. During this period the Geological Survey, United States Department of the Interior, carried on detailcd studies of the deposits and the pegmatite bodies that contain them. The primary purpose of the studies was to provide geological information that would contribute toward efficient mine development and operation. The studies were aimed directly at practical production problems. Detailed maps showing the structure of the deposits were prepared, and geological findings were closely correlated with data on specific yields and costs of mining and processing. The result is information that permits a reasonably accurate appraisal of the mica deposits of New England and the mining industry that they support. At a time when the future of the industry is in doubt, it seems desirable to submit this appraisal for consideration. Domestic mica deposits supply only a small fraction of the country's needs in normal times? for only the richest domestic deposits can compete with the low-cost mines of India and Brazil. However, the possibility that this country may be cut off from its supplies in time of war gives domestic deposits an importance much greater than their peacetime production would imply. New England supplied about 22 per cent of domestic output in 1943 and 1944, the peak years of wartime production. Its actual contribution to the war effort was greater, for the proportion of sheet mica of high quality in the New England product is higher than the average for domestic mica. The data analyzed below were collected for the Geological Survey by D. M. Larra-bee, A. H. McNair, J. J. Page, V. E. Shai-nin, G. W. Stewart, and the co-authors of this paper. The cooperation of officials of Colonial Mica Corporation and of mine operators and owners in furnishing information is gratefully acknowledged. D. M. Larrabee, A. H. McNair, and V. E. Shainin have made various suggestions based on critical reading of the manuscript. Analysis oF Warrtime Operations In considering the data presented in this report, it must be remembered that the scale of mica operations is very small compared with that of many other mining industries. The typical New England mica mine of 1943 and 1944 was worked by a crew of five or six men. Equipment was varied but on the whole extremely simple. The first stage of operation at a deposit was normally opencut mining. Drilling was done mostly with jackhammers powered by portable compressors driven by gasoline engines. Muck was shoveled by hand into buckets with a capacity of 45 to 35 ton and commonly hoisted by derrick to a dump adjacent to the cut. As operations were carried to greater depth, and the tram sition to underground mining was made, these methods were modified to a degree depending largely on the attitude of the deposit mined. At steeply dipping deposits,

Jan 1, 1948

By H. M. Bannerman, E. N. Cameron

During the years 1942-1934, about 125 New England deposits were mined for sheet and punch mica, and many others were briefly prospected. During this period the Geological Survey, United States Department of the Interior, carried on detailcd studies of the deposits and the pegmatite bodies that contain them. The primary purpose of the studies was to provide geological information that would contribute toward efficient mine development and operation. The studies were aimed directly at practical production problems. Detailed maps showing the structure of the deposits were prepared, and geological findings were closely correlated with data on specific yields and costs of mining and processing. The result is information that permits a reasonably accurate appraisal of the mica deposits of New England and the mining industry that they support. At a time when the future of the industry is in doubt, it seems desirable to submit this appraisal for consideration. Domestic mica deposits supply only a small fraction of the country's needs in normal times? for only the richest domestic deposits can compete with the low-cost mines of India and Brazil. However, the possibility that this country may be cut off from its supplies in time of war gives domestic deposits an importance much greater than their peacetime production would imply. New England supplied about 22 per cent of domestic output in 1943 and 1944, the peak years of wartime production. Its actual contribution to the war effort was greater, for the proportion of sheet mica of high quality in the New England product is higher than the average for domestic mica. The data analyzed below were collected for the Geological Survey by D. M. Larra-bee, A. H. McNair, J. J. Page, V. E. Shai-nin, G. W. Stewart, and the co-authors of this paper. The cooperation of officials of Colonial Mica Corporation and of mine operators and owners in furnishing information is gratefully acknowledged. D. M. Larrabee, A. H. McNair, and V. E. Shainin have made various suggestions based on critical reading of the manuscript. Analysis oF Warrtime Operations In considering the data presented in this report, it must be remembered that the scale of mica operations is very small compared with that of many other mining industries. The typical New England mica mine of 1943 and 1944 was worked by a crew of five or six men. Equipment was varied but on the whole extremely simple. The first stage of operation at a deposit was normally opencut mining. Drilling was done mostly with jackhammers powered by portable compressors driven by gasoline engines. Muck was shoveled by hand into buckets with a capacity of 45 to 35 ton and commonly hoisted by derrick to a dump adjacent to the cut. As operations were carried to greater depth, and the tram sition to underground mining was made, these methods were modified to a degree depending largely on the attitude of the deposit mined. At steeply dipping deposits,

Jan 1, 1948

By John Suman

DURING the past few years the taking of cores in drilling with rotary equipment has been perfected to a remarkable degree in the Gulf Coast fields of Texas and Louisiana. Taking of cores is becoming quite a common thing, especially in the newer fields, and drillers are becoming expert in this work. The writer has seen cores 5 to 8 ft. long taken with great ease in wells as deep as 4500 ft. Coring is doing much to remove the prejudice which so many petroleum engineers seem to have against .the use of rotary drilling equipment for exploratory work. Some operators .are now claiming that when used with a reasonable amount of coring the rotary system is even more satis-factory than cable tools for exploring in certain territory. A case has recently been pointed out in the South Electra field of North Texas, where producing oil sands, passed over by cable-tool drillers, are being brought in with rotary equipment. It seems that in this particular territory the sands are rather thin. Cable-tool drilling was carried on for the most part in a wet hole and the red mud encountered in drilling caved into the hole very badly, so that the cuttings showed mostly red mud and the driller, thinking that the sand did not amount to anything, carried his water string through the sand. The later .operators, drilling into the sand with rotary equipment and coring it, found that it was well worth testing.

Jan 10, 1922

By S. L. Couling, D. J-P. Adenis

i2) twinning in poly crystalline magnesium does not usually occur homogeneously but is concentrated in localized regions or bands inclined at about 45 deg to the stress axis. These bands of twinning are in many ways similar to the Luders bands seen in mild steel alzd Al-Mg alloys. Within a hand the percentage of the volume twinned may approach 100 with no twinning outside the band. Bands are not produced in specimens of grain size a3 x 10-= in. or in samples deformed at temperatures 300°F. Annealing of heavily twinned regions leads to re crystallization textures markedly different from those found in the starting material. The exact preferred orientation appears to depend on the starting grain size, the amount of compres-sive strain and the manner in which it is introduced. MAGNESIUM, with its hexagonal crystal structure, deforms plastically at room temperature by a variety of deformation mechanisms, one of the most important of which is (1012) twinning. In single crystals such twinning occurs on compression parallel to the basal plane or tension perpendicular to it. In wrought polycrystalline magnesium, such as rolled sheet, the preferred orientation is such that almost all the grains have their basal planes nearly parallel to the sheet surface. Therefore, if sheet material is deformed by cold rolling or by tension in the plane of the sheet, deformation of the grains by (1012) twinning is not favored. On the other hand, twins form readily on compression parallel to the plane of the sheet as in a compression test, on the compression side of a bent sample, or at the outer rim of a drawn cup. The first part of this paper deals with the morphology of (1012) twinning in polycrystalline magnesium. Some aspects of this subject were covered by Barrett and ~aller.' Of direct bearing on the work to be reported here are the comments of Jetter' in discussion to Ref. 1. He shows that Mg + 1.5 pct Mn alloy sheet when bent about a transverse axis develops a pattern of transverse bands on the surface of compression. A longitudinal section through the sheet shows that the bands are wedge-shaped and inclined to the rolling direction. The bands were identified as "outcrops of regions in which deformation is localized as the result of the reorientation brought about by (1012) twinning". The second part of the paper treats the recrys-tallization texture of the specimens twinned by compression. Magnesium deformed and then annealed generally recrystallizes with no change in orientation.1'3'4 This statement is true provided that the amount of (1012) twinning occurring during deformation is small. In an isolated observation, Anse15 has shown that, when deformation produces much (1072) twinning, annealing causes new maxima to appear in the pole figure. The second part of the paper elaborates on this point. I) MATERIALS AND PROCEDURES All of the experimental work to be reported was done using the commercial sheet and plate alloy AZ31B (nominal composition: 3 pct Al, 1 pct Zn, 0.4 pct Mn, balance magnesium). This alloy is available commercially in two tempers, -0 (fully annealed) and -H24 (partially annealed), and specimens of both tempers were used in various experiments. The average grain. diameter (AGD) for -0 temper 0.125-in. sheet is about 0.5 x 10- in.; where material of larger grain size was desired, anneals at elevated temperature were used to grow the grains. compression tests were made on a screw-driven "hard" machine. The specimens were clamped in a

Jan 1, 1964

By Bernard MacDonald

The writing of this paper was prompted by the discussion by H. M. Chance of the paper written by Thomas M. Chance,l and by the remarks of the editor in which he stated that while the matter contained in discussion did not refer to the original paper it " was presented as of interest to the operators of cyanide and other lixiviation processes dealing with fluid mixtures of varying specific gravity." For some years past the principle enunciated in the discussion referred to has been known to the writer and demonstrated by him to be an efficient and economical way of separating water or solution from solids in the cyanidation, lixiviation or acid leaching of ore pulps. In utilizing this principle in commercial practice he has invented a method whereby not only the separation of solution from solids may be effected in any given tank, but also the counter migration of the solids and solution may be effected continuously through a series of tanks in which the hydro-metallurgical treatment of ore pulps is being carried on. In effect this method is analogous to the counter-current system, but is different physically in that it is carried on throughout a series of tanks on practically the same level, continuously and automatically, by hydrostatic pressure and gravity-flow, without the aid of intervening pumps or elevators, at the same time that agitation is being carried on in the same tanks. In the Parral system, agitation is effected in tanks by a number of air lifts of comparatively small diameter through which the pulp is continuously transferred from the bottom of the tank and spouted horizontally on top of the charge. The spouting force of the several streams thus discharged maintains a rotary flow in the pulp charge which extends from top to bottom of the tank. This continuous transfer of pulp and the spiral flow from top to bottom of the tank maintains the pulp constituents in uniform proportions and meets the requirements of efficient treatment in a most economical manner. The quantity of compressed air required is very small, as the pulp is not lifted but simply transferred from the bottom to the top of the tank charge under hydrostatic balance. Fig. 1 gives a bird's-eye view of two adjoining tanks in any series equipped with the apparatus for producing the separation of

Jan 1, 1919

By William Hurst, A. F. van Everdingen

For several years the authors have felt the need for a source from which reservoir engineers could obtain fundamental theory and data on the flow of fluids through permeable media in the unsteady state. The data on the unsteady state flow are composed of solutions of the equation Two sets of solutions of this equation are developed, namely. for "the constant terminal pressure case" and "the constant terminal rate case." In the constant terminal pressure case the pressure at the terminal boundary is lowered by unity at zero time, kept constant thereafter, and the cumulative amount of fluid flowing across the boundary is computed, as a function of the time. In the constant terminal rate case a unit rate of production is made to flow across the terminal boundary (from time zero onward) and the ensuing pressure drop is computed as a function of the time. Considerable effort has been made to compile complete tables from which curves can be constructed for the constant terminal pressure and constant terminal rate cases, both for finite and infinite reservoirs. These curves can be employed to reproduce the effect of any pressure or rate history encountered in practice. Most of the information is obtained by the help of the Laplace transformations, which proved to be extremely helpful for analyzing the problems encountered in fluid flow. The application of this method simplifies the more tedious mathematical analyses employed in the past. With the help of Laplace transformations some original developments were obtained (and presented) which could not have been easily foreseen by the earlier methods. INTRODUCTION This paper represents a compilation of the work done over the past few years on the flow of fluid in porous media. It concerns itself primarily with the transient conditions prevailing in oil reservoirs during the time they are produced. The study is limited to conditions where the flow of fluid obeys the diffusivity equation. Multiple-phase fluid flow has not been considered. A previous publication by Hurst' shows that when the pressure history of a reservoir is known, this information can be used to calculate the water influx, an essential term in the material balance equation. An example is offered in the literature by Old² in the study of the Jones Sand, Schuler Field, Arkansas. The present paper contains extensive tabulated data (from which work curves can be constructed), which data are derived by a more rigorous treatment of the subject matter than available in an earlier publication.' The application of this information will enable those concerned with the analysis of the behavior of a reservoir to obtain quantitatively correct expressions for the amount of water that has flowed into the reservoirs, thereby satisfying all the terms that appear in the material balance equation. This work is likewise applicable to the flow of fluid to a well whenever the flow conditions are such that the diffusivity equation is obeyed. DIFFUSITY EQUATION The most commonly encountered flow system is radial flow toward the well bore or field. The volume of fluid which flows per unit of time through each unit area of sand is expressed by Darcy's equation as where K is the permeability, the viscosity and aP/ar the pressure gradient at the radial distance r. A material balance on a concentric element AB, expresses the net fluid traversing the surfaces A and B, which must equal the fluid lost from within the element. Thus, if the density of the fluid is expressed by p, then the weight of fluid per unit time and per unit sand thickness, flowing past Surface A, the surface nearest the well bore, is given as The weight of fluid flowing past Surface B, an infinitesimal distance 6r, removed from Surface A, is expressed as

Jan 1, 1949

By A. F. van Everdingen, William Hurst

For several years the authors have felt the need for a source from which reservoir engineers could obtain fundamental theory and data on the flow of fluids through permeable media in the unsteady state. The data on the unsteady state flow are composed of solutions of the equation Two sets of solutions of this equation are developed, namely. for "the constant terminal pressure case" and "the constant terminal rate case." In the constant terminal pressure case the pressure at the terminal boundary is lowered by unity at zero time, kept constant thereafter, and the cumulative amount of fluid flowing across the boundary is computed, as a function of the time. In the constant terminal rate case a unit rate of production is made to flow across the terminal boundary (from time zero onward) and the ensuing pressure drop is computed as a function of the time. Considerable effort has been made to compile complete tables from which curves can be constructed for the constant terminal pressure and constant terminal rate cases, both for finite and infinite reservoirs. These curves can be employed to reproduce the effect of any pressure or rate history encountered in practice. Most of the information is obtained by the help of the Laplace transformations, which proved to be extremely helpful for analyzing the problems encountered in fluid flow. The application of this method simplifies the more tedious mathematical analyses employed in the past. With the help of Laplace transformations some original developments were obtained (and presented) which could not have been easily foreseen by the earlier methods. INTRODUCTION This paper represents a compilation of the work done over the past few years on the flow of fluid in porous media. It concerns itself primarily with the transient conditions prevailing in oil reservoirs during the time they are produced. The study is limited to conditions where the flow of fluid obeys the diffusivity equation. Multiple-phase fluid flow has not been considered. A previous publication by Hurst' shows that when the pressure history of a reservoir is known, this information can be used to calculate the water influx, an essential term in the material balance equation. An example is offered in the literature by Old² in the study of the Jones Sand, Schuler Field, Arkansas. The present paper contains extensive tabulated data (from which work curves can be constructed), which data are derived by a more rigorous treatment of the subject matter than available in an earlier publication.' The application of this information will enable those concerned with the analysis of the behavior of a reservoir to obtain quantitatively correct expressions for the amount of water that has flowed into the reservoirs, thereby satisfying all the terms that appear in the material balance equation. This work is likewise applicable to the flow of fluid to a well whenever the flow conditions are such that the diffusivity equation is obeyed. DIFFUSITY EQUATION The most commonly encountered flow system is radial flow toward the well bore or field. The volume of fluid which flows per unit of time through each unit area of sand is expressed by Darcy's equation as where K is the permeability, the viscosity and aP/ar the pressure gradient at the radial distance r. A material balance on a concentric element AB, expresses the net fluid traversing the surfaces A and B, which must equal the fluid lost from within the element. Thus, if the density of the fluid is expressed by p, then the weight of fluid per unit time and per unit sand thickness, flowing past Surface A, the surface nearest the well bore, is given as The weight of fluid flowing past Surface B, an infinitesimal distance 6r, removed from Surface A, is expressed as

Jan 1, 1949

By I. Fatt

The chromalographic effect refers to the separation of constituents in a moving fluid phase which occurs when the phase is passed over a stationary phase, either solid or liquid, or large areal extent. In performing chemical analyses, the large surface contact areal is provided in the case of gas-solid chromatography by-passing the gas over a porous solid and for gas-liquid chronla tog rap hy by-passing the gas over a porous solid which has been coated with a nonvolatile liquid. The porous medium is usually placed in a cylindrical tube, although it may be a relatively flat sheet as in paper chroma-tography. According to one theory,' the separation results from the difference in time spent by various components in the stationary phahe. A gaseous component which is conlpletely insoluble in the stationary phase, or is not adsorbed on the solid, proceeds unimpeded through the column. The versatility and power of the various types of chromatogruphy for the analysis of complex mixtures are evident from their widespread use in performing chemical analyses and from the large number of symposia, books, and papers devoted to the subject in recent years. Associated developments are the application of chromatography to the determination of heats of solution, heats of adsorption, solubilities orK-values, etc. Gas-liquicl chromatography analyses may be characterized by the manner in which the samples are introduced and displaced from the column'. The three techniques used are known as (1) frontal analysis, (3) displacement analysis, and (3) elution analysis. The frontal analysis is performed by displacing an inert gas from the column by a continuous stream of the sample. As indicated in Fig. l(A), all but the first fraction leaving the column represent mixtures rather than pure components. The displacement analysis is conducted by filling the column with a sample, then displacing it with a more strongly adsorbed or absorbed vapor. The resulting chro-matogram is illustrated by Fig. 1(B). Finally, in the elution analysis a small sample of the mixture to be analyzed is introduced as a "plug" into a Rowing stream of carrier gas to give an elution-type chromato-gram. Fig. l(C). The three techniques may be used to provide models to which Row patterns in other physical situations may be compared. PURPOSE OF THE INVESTIGATION The purpose of this investigation was to determine whether natural reservoir rocks, when coated with crude oil, provided sufficient surface areas to give rise to a chromato-graphic separation of light hydrocarbon constituents. The tests were conducted with the light hydrocar-bons in the gaseous state. SANDS TESTED Two sands of widely different permeabilities have been studied: (1) Ventura core (16 md), and (2) Torpedo sandstone core (578 md).Table 1 gives a description of the cores that were tested. With the exception of one frontal-type flow arrangement which was performed on Core 3, the tests were of theelution-type in which a methane-propane mixture was eluted through the core by means of helium. The Ventura core, when impregnated with a weathered crude from the same field, became so impermeable to gas flow that it was necessary to conduct the tests on the granulated cores (Cores 2 and 3).

By J. R. Szedon, T. L. Chu, G. A. Gruber

Amorphous adherent filnzs of silicon dioxide have been deposited on silicon substrates by the oxidation of silane at temperatures ranging from 650 to 1050C. Various diluents (argon, nitrogen, hydrogen) were used to suppress the formation of SiO2 in the gas phase. Deposition rates of the oxide were determined over the temperature range in question as functions of' re-actant flow rates. Etch rate studies were used for a cursory comparison of structural properties of deposited and thermally grown oxides. From electrical evaluation of metal-insulator-silicon capacitors it was determined that the interface charge density of deposited films is similar go that of dry-oxygen-grown films in the 850° to 1050 C temperature range. Deposited films exhibit several ionic instability effects which differ in detail from those reported for thermal oxides. Stable passivating films of silicon nitride over deposited oxides appear to be practical for use in silicon planar device fabrication. Such films can be prepared under temperature conditions which have less effect on substrate impurity distributions than in the case of grown oxides. AMORPHOUS silicon dioxide (silica) is compatible with silicon in electrical properties and is the most widely used dielectric in silicon devices at present. Silica films can be prepared by the oxidation of silicon or deposited on silicon or other substrate surfaces by chemical reactions or vacuum techniques. The ability of thermally grown silicon dioxide films to passivate silicon surfaces forms one of the practical bases of the planar device technology. Properly produced and treated films of grown SiO 2 can have low densities of interface charge (-1 X 10" charges per sq cm) and can be stable as regards fast migrating ionic sgecies. 1 To maintain these properties, even with an otherwise hermetically sealed ambient, the Sia layers must be at least l000 A thick. Such thicknesses require oxidation in dry oxygen for periods of 7.8 hr at 900°C or 2 hr at 1000°C. Although oxidation in steam or wet oxygen can reduce these times to 17 and 5 min, the resulting oxides must be annealed to produce acceptable levels of interface charge., Oxidation or annealing involving moderate to high temperatures for extended periods of time can be undesirable. Under some conditions, there can be changes in the distribution of impurities within the underlying substrate. A chemical deposition technique using gaseous am-bients is particularly attractive and flexible for preparing oxide films. With a wide range of deposition rates available, films can be produced under condi- tions of time and temperature less detrimental to impurity distributions in the silicon than in the case of thermal oxidation. The pyrolysis of alkoxysilanes, the hydrolysis of silicon halides, and various modifications of these reactions are most commonly used for the deposition of silica films.3 Silica films obtained in this manner are likely to be contaminated by the by-products of the reaction, organic impurities, or hydrogen halides. The use of the oxidation of silane for the deposition process has been reported recently.4 The deposition of silica films on single-crystal silicon substrates by the oxidation of silane in a gas flow system has been studied in this work. The deposition variables studied were the crystallographic orientation of the substrate surface, the substrate temperature, and the nature of the diluent gas. The electrical charge behavior of Si-SiO2-A1 structures prepared under various conditions was investigated by capacitance-voltage (C-V) measurements of metal-insulator-semiconductor (MIS) capacitors. The experimental approaches and results are discussed in this paper. 1) DEPOSITION OF SILICA FILMS The overall reaction for the oxidation of silane is: The equilibrium constants of this reaction in the temperature range 500° to 1500°K, calculated from the JANAF thermochemical data,= are shown in Fig. 1. In addition to the large equilibrium constants, the oxidation of silane is also kinetically feasible at room temperature and above. However, the strong reactivity of silane toward oxygen tends to promote the nucleation of silica in the gas phase through homogeneous reactions, and the deposition of this silica on the substrate would yield nonadherent material. The formation of silica in the gas phase can be reduced by using low partial pressures of the reactants. Argon, hydrogen, and nitrogen were used as diluents in this work. 1.1) Experimental. The deposition of silica films by the oxidation of silane was carried out in a gas flow system using an apparatus shown schematically in Fig. 2. Appropriate flow meters and valves were used to control the flow of various reactants, i.e., argon, hydrogen, nitrogen, oxygen, and silane. Semiconductor-grade silane, argon of 99.999 pct minimum purity, oxygen of 99.95 pct minimum purity, and nitrogen of 99.997 pct minimum purity, all purchased from the Matheson Co., were used without further purification. In several instances, a silicon nitride film was deposited over the silica film. This was achieved by the nitridation of silane with ammonia using anhydrous ammonia of better than 99.99 pct purity supplied by the Matheson CO.' The reactant mixture of the desired composition was passed through a Millipore filter into a horizontal water-cooled fused silica tube of 55 mm

Jan 1, 1969

By James Gardner

IN 1923, Oklahoma took second place as an oil-producing state; whereas in 1922 it was the leader. California surpassed it, in 1923, by nearly 100,000,000 bbl. In 1923, Oklahoma produced, according to statistics of The Oil & Gas Journal, 165,013,685 bbl., or an increase of approximately 10 per cent. over the preceding year; the increase in California was approximately 90 per cent. The number of wells drilled in Oklahoma and the results of the two years are contrasted in the following table from data published in a preliminary bulletin by the U. S. Geological Survey. 1922 1923 Oil wells 4,149,68%. 3,515, 60% Gas wells 571, 9 %u 587, 11% Dry holes 1,428,23% 1,731,29% Total wells 6,148 5,833 The initial production from wells drilled in Oklahoma in 1923, according to The Oil & Gas Journal, was the largest in the history of the state, being 1,277,936 bbl. It has been 32 years since oil development began in the state, last year being the largest in the amount of production. The production of the past year would have been considerably greater were it not for the shutdown order in the Burbank field and curtailment of production in the Hewitt and Tonkawa pools.

Jan 3, 1924

Reno, Nevada. J A Fulton, Director For publications of either the Mackay School of Mines or the State Bureau of Mines, address the School of Mines at the given address. Except where the contrary is indicated in the following list, available publications are sent free From the Mackay School of Mines. Bulletin 1, The identification of Nevada's common minerals, 50 cents; 3, Notes on the ore deposits of Cave Valley mining district, Lincoln County, 4, A preliminary survey of the Scossa mining district, Pershing County, 5, Ore deposits of the Gold Circle mining district, Elko County, 6, Bedded deposits of manganese oxides near Las Vegas, 7, Spruce Mountain district, Elko County, and Cherry Creek (Egan Canyon) district, White Pine County From the State Bureau of Mines: Bulletin 1, Mineral resources of southern Nevada One volume: Mining districts and mineral resources of Nevada, by F C. Lincoln (1923), $1.50.

Jan 1, 1933

By Lyall Zickrick

Experiments of previous investigations have indicated that calcium-copper alloy, when used as a deoxidizer for molten copper, results in a sound copper casting of good physical and electrical properties. Braden-berg and Wiensl have obtained successful results in casting sound copper using calcium for deoxidizing. Masing2 has obtained deoxidized copper of high density and high conductivity by use of calcium. Pratt,3 in 1907, patented the use of calcium for the deoxidation and degasification of copper. Schumacher, Ellis and Eckel,l in 1929, conducted a series of experiments on deoxidizing copper with calcium. They concluded that so long as there is only a small percentage of residual calcium the mechanical and electrical properties of the copper deoxidized are not impaired, and the deoxidation is thorough. For this investigation, a copper-calcium alloy high in calcium and 10 variously deoxidized copper ingots were prepared. The investigation concerns itself with the casting properties and structure of these variously deoxidized ingots, their working and annealing characteristics, and the resulting physical and electrical properties of the worked materials. Preparation of Special Copper-calcium Alloy and Experimental Ingots For use as a deoxidizing agent, an alloy of copper and calcium with fairly high calcium content was prepared, by melting pure electrolytic copper in a graphite crucible in an ordinary gas-fired pot furnace. The molten copper was kept well covered with calcium chloride slag. Small chunks of calcium were wrapped in thin copper sheet, placed on the end of a graphite rod and plunged down into the molten copper and thoroughly stirred. Upon completion of the calcium additions the crucible content was poured out into a cake about one inch thick. Analysis of this alloy gave 4.4 per cent calcium. The alloy was brittle and easily broken into small chunks. Some calcium was lost during the addition, owing to

Jan 1, 1933

By M. H. Pilkuhn, H. Rupprecht

p layers on n-type substrates of GaAs were prepared by difhsion of zinc into these substrates. Experimental details about the diffusion technique will be presented. It will be shown that inhomogeneity in the substrate doping level and crystal shucture defects cause nonplanarity in the junction plane. These nonplanarities give rise to high threshold current densities. From incremental sheet-conductivity measurements the zinc profile is derived. Data about surface concentration and gradient of the zinc concentration at the junction are presented. Finally, some results of laser diodes, which were made of wafers with extremely planar diffusion fronts, are discussed. ThE investigations reported here are part of a program concerned with the materials aspect in the fabrication of GaAs laser diodes. This includes studies of the influence of crystal defects introduced both during the growth of the crystal and as a consequence of subsequent diffusion. Compared with the progress made in the investigation of structure defects, for instance by X-ray microscopy in materials like silicon, no similar results are known so far for the case of GaAs. The further progress in laser diodes will depend very much upon our knowledge of these structure defects and subsequently upon our ability to avoid them. Laser diodes of GaAs had been made mostly by diffusing an acceptor impurity, normally zinc, into an n-type substrate. This procedure was found more convenient than the inverse one for various technical reasons. We will follow this line and restrict ourselves to zinc diffusion only in this paper. DIFFUSION TECHNIQUES AND EXPERIMENTAL DETAIL In order to set a refgrence for our experiments, we used a standard procedure for the diffusion runs. The diffusions were carried out in a sealed quartz tube for 2-1/2 hr at 850°C. One milligram zinc arsenide (ZnAsz) per cu cm of the tube volume served as zinc source. Under these conditions the junction depth was between 25 and 30 p. It is assumed, according to the investigations of the zinc arsenide system by V. Lyons and V. ilvestri,' that ZnAs2 dissociates completely at 850°C into ZnsAsz and Asg. Since there is a condensed phase of ZnsAs2 in the tube at 850°C, the partial pressure of zinc is controlled by the pressure of the arsenic formed by the dissociation of ZnAs2. Due to the fact that the zinc partial pressure resulting from the dissociation of ZnsAsz is only a weak function of the partial pressure of arsenic, the amount of the initial ZnAs2 is not very critical. Experimentally, we found that the junction depth, as well as the surface concentration, was practically the same, if the ingots of ZnAs2 varied between 0.2 and 5.0 mg per cu cm. The wafers were oriented with the main faces in (100). Surface damage due to cutting and lapping was removed by a chemical-etch treatment in a rotating beaker (etch solution: HzSOr, H202, and HzO in a ratio 3:l:l). The GaAs substrate material was n type and doped with tellurium, selenium, silicon, or germanium. It was grown by means of horizontal or Czochralski techniques. After the diffusion process, junction depth and planarity were checked either by grooving with a

Jan 1, 1964

By Paul B. Crawford, Melvin B. Burton

A procedure is given which describes how the gelatin model may be-used to study the effect of mobility ratio on areas swept before and after breakthrough in fluid injection programs. Differences in mobility ratio are achieved through the proper selection of electrolytes for the invading and displaced fluids. The progress of the front is followed visually and photographed or traced onto plates (it desirrd positions before and after breakthrough. Example applications to standard flooding pattrrrls, vertically and horizontally fractured reservoirs and the in-situ combustion recovery process ore presentrtl. INTRODUCTION In water flooding, gas cycling and other fluid injection programs, the sweep efficiencies and swept areas after breakthrough are known to depend on the mobility ratio. Previous investigators have described the application of the X-ray technique, stepwise use of the poten-tiometric model and numerical procedures for studying these problems.1,3,4,6 Others have described the application of the electrolytic and gelatin models for studying sweep efficiencies at a mobility ratio near one.2,5,7,8,9 It is a purpose of this paper to describe a procedure for using the gelatin model to study swept areas at mobility ratios other than one. PROCEDURE The technique developed for gelatin model studies is composed of four phases: the construction of the model, the selection and preparation of electrolytes, the running procedure, and the recording of the swept areas. Each phase is discussed independently in order that the over-all procedure will not be confused. Construction of the Model Since some of the advantages of the gelatin model are its economy, and speed, it is desirable to have as small a model as is possihle without creating error through the inability to follow visually the progress of the colored front. For this work, it was found that a distance of 4 to 6 cm between salt bridges is convenient to use. Since the size is relatively small, it follows that the gelatin layer must be thin. For this study, 1/8 in. was used as the gelatin thickness in each case. The model was constructed on a flat 1/2-in. plastic (Lucite) base with boundaries constructed from 1/8-in. plastic strips. The well pattern to be studied was outlined with the 1/8-in. plastic strips on the base with narrow apertures (- - 2 mm) in the boundary to represent the wells. Behind each well opening, a rectangular area of some 8 to 12 sq cm was outlined by additional plastic strips. The plastic strips were fastened to the base by any suitable non-conducting cement so that the boundary system was liquid tight. The electrodes were constructed from sheet copper in a fashion that would allow easy removal. In this work, it was found that by simply forming a large U-shaped clip from a strip of the copper that would slip over the boundary was satisfactory and easily removed. The electrodes should be as wide as one of the sides of the rectangular area behind the well opening. If a fractured pattern is studied, fractures inside the well pattern may be represented by strips of copper of the desired shape mounted in some easily removable fashion. The reason that apertures (or salt bridges) were used for wells instead of metallic electrodes is that the plating of the electroactive ion at the cathode and the introduction of an electroactive ion at the anode has a detrimental effect on the swept area outline if these operations \rere permitted to be carried on within the well pattern itself. The anode may be used within the well pattern

Jan 1, 1957

By R. G. Aspden

Crystals with an (001) [loo] initial orientation of an iron-base alloy containing 3 pct Si were cold rolled with and without the use of constraints. A major difference in the rolling and annealing textures was observed between crystals rolled with and without constraints. These data show that the contribution of constraints at grain boundaries in a poly crystalline sheet should be considered in applying textural data on single crystals to grains in an aggregate. SILICON-iron alloys with a cube texture have been recently developed and their magnetic characteristics reported.1-4 Of interest in the development of this texture were the textural changes of single crystals accompanying rolling and annealing and the influence of constraints at grain boundaries in an aggregate on the behavior of individual grains. The present study was primarily concerned with the effect of constraints during rolling on the textures of 3 pct Si-Fe crystals initially (001)[100]. Barrett and Levenson5 were among the first to observe an influence of constraints at grain boundaries on the textural changes of individual grains during deformation. They tested Taylor's6 theory of plastic deformation of face-centered-cubic metals in which deformation textures were predicted. About one-third of the grains in poly crystalline aluminum did not rotate as predicted. Grains of the same initial orientation were observed to rotate in different directions under the influence of applied stress and anisotropic flow of neighboring grains. Recently, the various inhomogeneities of flow of crystals in an aggregate have been studied7'8 and reviewed.9-11 Barrett and Levenson" rolled (001) [loo] iron single crystals inserted in close-fitting holes in copper to limit lateral flow and to simulate rolling of grains in an aggregate. Deformation bands were formed after a 90 pct reduction in thickness, and the cold-rolling texture contained two components described by rotating the (001)[100] about 35 deg in both directions around the normal of the rolling plane. No annealing textures were reported. Chen and Maddin13 rolled molybdenum single crystals initially (001) [loo]. The crystals were mounted between two hardened silicon-iron plates and 96 pct reduced in thickness by rolling at a low rate of reduction, about 0.0001 in. per pass. The deformation texture had the mean orientation of (001) [loo], and the azimuthal spread included orientations described by rotating (001) [loo] about 35 deg in both directions about the pole of the rolling plane. The presence of deformation bands were not reported by Chen and Maddin or detected in subsequent work of Ujiiye and Maddin.14 The ideal orientation of the annealing texture was (001) [loo]. Recently, Walter and Hibbard 15 reported on the textures of 3 pct Si-Fe alloy crystals initially near (001) [loo]. Each crystal was in an aggregate cut from a columnar ingot. After 66 pct reduction by rolling, the texture consisted of two symmetrical components which had the orientations described by rotating (001) [loo] about 30 deg in both directions about the pole of the rolling plane. Annealing texture was near (001) [loo]. In the above work, the textures of body-centered-cubic crystals were studied after rolling under the influence of constraints. The deformation textures varied from (001) [loo] to near the (001) [110] type and appeared sensitive to the manner in which the crystals were rolled. No textural data were available on the effect of rolling (001) [loo] crystals with and without constraints. The purpose of the present work was to evaluate the influence of constraints during rolling on the textures of 3 pct Si-Fe crystals initially (001) [loo]. Rolling and annealing textures were studied for a) crystals rolled with no constraints at different rates of reduction, and b) crystals rolled with constraints imposed by neighboring grains and by plates between which a crystal was "sandwiched". PROCEDURES AND EXPERIMENTAL TECHNIQUES Data are presented on four crystals which are representative of several crystals studied. The orientation of each crystal prior to rolling was (001) [loo] as determined by the Laue X-ray back-reflection method," i.e., each crystal had an (001) within 3 deg of the rolling plane and [100] within 3 deg of the rolling direction. These crystals were obtained from two iron-base alloys containing 3 pct Si by weight which were prepared by vacuum melting electrolytic iron and a commercial grade of silicon. Crystals 1, 2, and S-1 were cut from a large single crystal grown from the melt of one alloy by the Bridgman technique17 in an apparatus described by

Jan 1, 1960

By THOMAS J. CLIFFORD

IN 1926, finer grinding began to be a feature of the milling practice of the Southeast Missouri lead district. Nothing since the adoption of flotation has caused greater changes and greater improvement in results. The trend toward finer grinding, with the consequent discarding of tailing at finer sizes, and consequent lower assays in lead, continued to progress until 1931, when the abnormally low price of lead brought a halt: that is, the better metallurgical results obtained would not offset the increased costs due to higher power and necessary maintenance. Since 1931 a slight tendency toward the discard of coarser tailing has taken place. , In 1926, larger rod mills i.12 ft. 1 in. by 6 ft. 6 in.) than any previously used in the district were installed in cue plant, and a new primary crushing plant, of greater capacity was built. This combination demonstrated immediately the better metallurgical results obtainable by finer grinding and all the mills now running have adopted the practice.

Jan 1, 1934

By John L. Boardman, C. W. Goodale

The motives behind the organization of the Bureau of Safety were twofold. First, there was the policy of the company toward its employees, which was one of fairness and consideration for their welfare and which entails the prevention of injuries; second, in order to prevent injuries, a study of their causes was essential, and this study could be made only by a thorough systematic classification of accidents, which required a special department to form and carry out the plans. The Bureau of Safety was organized to begin operation Jan. 1, 1914, hut practically all of the first year was spent in collecting data, making plans, etc. This department is semi-independent of others and reports directly to the president and general manager. It consists of the president of the company and the managers of the following departments: Mines, Washoe Reduction Works, Great Falls Reduction Works, Coal department, lumber department, B. A. & P. railway; and the chairman of the Bureau of Safety. Working under this group is the General Safety Committee consisting of the manager of mines, as chairman, the general superintendent, two assistant general superintendents, and the heads of the following departments: mechanical, geological, purchasing, sampling works, and framing plant; and also the safety engineer. Operating under the General Safety Committee are the group safety committees, consisting of the Anaconda group of mines, Boston & Montana group of mines, zinc group of mines, Washoe reduction works at Anaconda, B. & M. reduction works at Great Falls, coal department, lumber department and the R. A. & P. railway. Each of these group safety committces was in charge of the superintendent or manager of the group represented and the committee consisted of the foremen of the mine's or works that the committee served, as well as the safety engineer. These foremen and superintendents had met regularly for the purpose

Jan 1, 1923

By John L. Boardman, C. W. Goodale

The motives behind the organization of the Bureau of Safety were twofold. First, there was the policy of the company toward its employees, which was one of fairness and consideration for their welfare and which entails the prevention of injuries; second, in order to prevent injuries, a study of their causes was essential, and this study could be made only by a thorough systematic classification of accidents, which required a special department to form and carry out the plans. The Bureau of Safety was organized to begin operation Jan. 1, 1914, hut practically all of the first year was spent in collecting data, making plans, etc. This department is semi-independent of others and reports directly to the president and general manager. It consists of the president of the company and the managers of the following departments: Mines, Washoe Reduction Works, Great Falls Reduction Works, Coal department, lumber department, B. A. & P. railway; and the chairman of the Bureau of Safety. Working under this group is the General Safety Committee consisting of the manager of mines, as chairman, the general superintendent, two assistant general superintendents, and the heads of the following departments: mechanical, geological, purchasing, sampling works, and framing plant; and also the safety engineer. Operating under the General Safety Committee are the group safety committees, consisting of the Anaconda group of mines, Boston & Montana group of mines, zinc group of mines, Washoe reduction works at Anaconda, B. & M. reduction works at Great Falls, coal department, lumber department and the R. A. & P. railway. Each of these group safety committces was in charge of the superintendent or manager of the group represented and the committee consisted of the foremen of the mine's or works that the committee served, as well as the safety engineer. These foremen and superintendents had met regularly for the purpose

Jan 1, 1923