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By G. H. Tausch, J. R. Dublin, T. A. Huber

Simplified equipment and techniques have been developed to permit cementing a completion interval in a well and recompleting higher, lower, or at the same depth in such a manner as to: 1. Eliminate the need for a conventional drilling or workover rig. 2. Eliminate mud and other cement contaminants which have long interferred with ideal cementing. 3. Eliminate need for drilling out cement. 4. Provide a more satisfactory recompletion. 5. Provide a more economical recompletion. This technique involves the use of a small-diameter, lightweight, tubing extension which is run on a wireline and set in a landing nipple previously installed in the tubing string. Low squeeze pressure and small cement volumes, with their attendant cost reduction, are successfully used when wells are completed and reworked with salt water or other penetrating fluids. Relatively low-water-loss cement is an integral component of the technique which provides that excess cement be reverse-circulated from the well to leave the casing void of cement when recompleting lower or in the same interval. Substantial cost reductions are realized by using the simplified or low-pressure cementing technique, and the ratio of successful squeeze-cement operations has been increased. Squeeze-cementing or recementing is the act of filling a channel behind casing or filling holes purposely placed in the casing. To obtain a satisfactory squeeze-cement job, it is necessary only to fill the channel or the perforation holes with a cement filter cake and to allow it to harden in that position. In the past, the presence of mud in a well has been considered the chief deterrent to obtaining a good cement bond and satisfactory cement job; however, late developments in squeeze-cementing have made it possible to eliminate cement contamination or interference. Since it is possible to form a cement filter cake with a small pressure differential, squeeze-cementing with high pressures may not be necessary in most cases. The amount of cement needed to fill the annulus about the casing and even to fill part of the casing, if necessary, is generally small in quantity. Use of low squeeze-cementing pressures and small quantities of cement provides the following advantages: 1. Longer effective life of well tubing, casing, and other equipment; and less chance of costly equipment failure due to excessive pressure. 2. Monetary savings effected by elimination of retainers and specal squeeze-cementing tools. 3. Monetary savings effected by use of small quantities of cement and fewer squeeze-cementing operations. 4. Future surface squeeze-cementing equipment may be smaller and more economical to operate and maintain.

Jan 1, 1955

By Stanley C. Herold

A few hates on the occurrence and significance of mud volcanoes in Colombia may be of interest at the present time, owing to the renewed activity in geological exploration of the coastal regions bordering the Caribbean Sea. The best-known volcanoes are found a few miles from the seacoast. One is situated to the south of Puerto Colombia; the second, to the east of Cartagena near the village of Turbaco; and the third, near the village of Puerto Escondido south of the Sinu River. Others are reported in more inaccessible localities. Usually they stand 2 1/2 or 3 ft. (0.762 or 0.914 m.) above the surrounding ground at the crater, though several craters from 10 to 20 ft. -(3.04 to 6.09 m.) "apart will often build up an extensive mound at low gradient. The shallow mound may cover 1/2 or 3/4 acre (0.2 to 0.3 ha.) with an elevation of 12 or 15 ft. (3.65 or 4.57 m.) at the, center. The craters are formed of hardened blue clay; the inside diameters vary from 14 to 24 in. (35.56 to 60.96 cm.). The rim is continuous, except on one side where there is usually a cut 3 or 4 in. deep, thus allowing an overflow. The craters are filled to the' rim-cut with a thick mixture of blue clay mud and water, which is kept in agitation by escaping gas. Fig. 1 shows the bubble in the act of bursting and Fig. 2 the appearance of the surface of the viscous fluid a second or so later. The frequency of the explosions is determined by the weight of the column of fluid in the neck of the volcano, consequently, such explosions are not synchronous in a group of craters. Ordinarily, there arc two or three explosions in about 3 minutes. The supply of gas is small but steady and sufficient pressure must accumulate before the bubble can enter the column of fluid. The water is derived from the surface and enters the scdirnentary strata not far distant from the volcano. During long dry seasons, as the supply of water fails the volcano dries and geyser action ceases. The temperature of the muddy fluid is normal; the gas is dry and inflammable. - No petroleum products come with the gas. On the surface of the fluid, there is sometimes a dark brown streaky scum, which

Jan 1, 1920

By J. T. Brown

AS far as could be ascertained, no one had previously investigated the creep strength of silicon poly-crystals. Literature has appeared showing evidence for plastic deformation in silicon single crystals and whiskers.*1"6 Also the fact that germanium, a material of similar crystal structure to silicon undergoes plastic deformation under stress at temperatures above about 60 pct of its melting temperature, has been known for some time.2"4'7 This investigation was performed for the purpose of determining the strength and ductility of silicon polycrystals under creep conditions that would give fairly long times to rupture. PROCEDURE The silicon specimen blanks were obtained by first placing granulated transitor grade silicon (99.999 + pct pure) in a silica crucible. The crucible was surrounded by a graphite susceptor, and induction heating was used for melting the silicon in a vacuum furnace. Blank specimens were formed by freezing molten silicon onto a polycrystalline seed of silicon in a vacuum furnace. The seed was attached to a motor driven revolving rod. As silicon solidified, this rod was gradually withdrawn from the melt. A shape with a contracted center section was obtained by varying the rate of withdrawal from the melt. Specimens for the creep-rupture tests were ground from these "pulled" blanks. Creep-rupture tests were performed in spring loaded machines under constant load at 1800" and 2000° F. RESULTS AND DISCUSSION A test specimen which was sectioned longitudinally is shown in the photomacrograph in Fig. 1. Very little deformation has taken place in the portion of the specimen shown, however, slip lines from several slip systems within the same grain, and deformation band formation was seen. The elongated appearance of the grains is due to the method of growing the specimens. One of the most interesting aspects of the results obtained from the creep-rupture tests was the high strength and the accompanying large amount of ductility. The data obtained is listed in Table I which shows the stress to rupture in 100 hr at 2000°F is between 8000 and 9000 psi. This indicates that silicon's strength at 2000°F is about equal to that of the best commercial super-alloys. It is important to mention that silicon has less than 1/3 the density of iron-, nickel-, and cobalt-base alloys. The usual type alloys for high-temperature applications

Jan 1, 1960

By C.P. Proctor, J. T. Crawford, J.A. Younkins

Coal-cleaning plants using the launder process generally wash the fine coal (minus ? or minus 5/16-in.) separately in a plant consisting of washing launders or troughs placed one below another and sometimes supplemented by additional washing equipment such as tables and jigs. The coal and its associated impurities enter the feed end of the top launder, with a current of push water. As the material moves along the impurities, being heavier than coal, settle toward the bottom of the launder and are drawn off, with some coal, through "free discharge" boxes to the launder below. These boxes were given their name because their discharge falls freely; that is, it does not discharge into a water seal. Thus the impurities are progressively concentrated in the lower launders until box products are sufficiently free of coal to be discharged to refuse. The overflows of the upper launders go to clean coal while the overflow of the lowest launder, and perhaps that of the one immediately above, is usually recirculated to the plant feed. Thus the bulk of the clean coal is removed rapidly and the impurities are concentrated more slowly. The chief purpose of this paper is to present the cleaning data of such a plant under different operating conditions. OpeRating Equipment The washing units considered here are part of a complete plant cleaning minus 4-in. coal. The primary cleaned product is a high-quality gas and metallurgical coal and another portion of the output may be shipped as a steam coal. The units consist of two parallel Rheolaveur free-discharge units each containing five launders, together with three 7 by 14-ft. Plato tables. The launders are designated by the letters A-B-C-D-E (Fig. I), launder A being the top and longest; E being the bottom and shortest. Launder details are given in Table 1. The launders are equipped with a series of free-discharge Rheolaveur boxes, which are integral parts of the launder (Figs. 2 and 3). Each box with-

Jan 1, 1940

By C. P. Proctor, J. A. Younkins, J. T. Crawford

Coal-cleaning plants using the launder process generally wash the fine coal (minus ? or minus 5/16-in.) separately in a plant consisting of washing launders or troughs placed one below another and sometimes supplemented by additional washing equipment such as tables and jigs. The coal and its associated impurities enter the feed end of the top launder, with a current of push water. As the material moves along the impurities, being heavier than coal, settle toward the bottom of the launder and are drawn off, with some coal, through "free discharge" boxes to the launder below. These boxes were given their name because their discharge falls freely; that is, it does not discharge into a water seal. Thus the impurities are progressively concentrated in the lower launders until box products are sufficiently free of coal to be discharged to refuse. The overflows of the upper launders go to clean coal while the overflow of the lowest launder, and perhaps that of the one immediately above, is usually recirculated to the plant feed. Thus the bulk of the clean coal is removed rapidly and the impurities are concentrated more slowly. The chief purpose of this paper is to present the cleaning data of such a plant under different operating conditions. OpeRating Equipment The washing units considered here are part of a complete plant cleaning minus 4-in. coal. The primary cleaned product is a high-quality gas and metallurgical coal and another portion of the output may be shipped as a steam coal. The units consist of two parallel Rheolaveur free-discharge units each containing five launders, together with three 7 by 14-ft. Plato tables. The launders are designated by the letters A-B-C-D-E (Fig. I), launder A being the top and longest; E being the bottom and shortest. Launder details are given in Table 1. The launders are equipped with a series of free-discharge Rheolaveur boxes, which are integral parts of the launder (Figs. 2 and 3). Each box with-

Jan 1, 1940

By Michael Tenebaum

IN a previous investigation1 the authors studied the effect of pressure on the reduction of iron ores by hydrogen. With hydrogen as a reducing agent, the rate of reduction was increased substantially by increasing the pressure from 1 to 2 atmospheres. The results with hydrogen prompted the present study of the effect of pressure on reduction with carbon monox-ide and with mixtures of carbon monoxide and nitrogen. FEATURES OF REDUCTION PROCESS The gas stream in the lower part of the blast furnace always contains sufficient concentrations of reducing gases to complete reduction provided sufficient time is allowed for the reaction to proceed. Reducing gases react immediately with the iron oxide on the surface of lumps of ore. However, as the unreduced surface recedes from the easily accessible exterior of the lump, the reaction proceeds by virtue of the diffusion of the gases into and out of individual pieces. The rate of diffusion of gases, which undoubtedly plays an important role in the reduction of iron ores, depends on several factors, most impor-tant of which are: (1) molecular weight or density, (2) pressure, (3) tem-perature, (4) concentration gradient. Thus, the rate of reduction of a lump of iron ore at any temperature will depend not only on the specific reaction rate but also upon: (1) available surface of unreduced iron oxide, (2) rate of diffusion of the reducing gas to the reacting surface, (3) rate of effusion of the gaseous products of the reaction from the reacting surface, (4) adsorption of the gases on the reacting surface.

Jan 1, 1939

By C. S. Matthews, W. R. Strickler, M. Prats

To gain an insight into the deviations from normal behavior caused by dip. a mathematical study has been made of single-fluid five-spot floods in dipping reservoirs for flooding techniques likely to be employed in such cases. Streamline patterns and sweep eficiencies are computed for a number of different cases, and the results, where possible, are presented in graphical form. An increase in sweep efficiency can be obtained by moving the central injection well updip, and the opti~num position is found for several cases. The applicnhility of the results is discussed. INTRODUCTION Because of the growing importance of water flooding in California and in other locations where large angles of dip are quite common, it is important to know at least some of the effects of dip on the performance characteristics of water floods in such instances. In the past, only reservoirs having relatively mild dips have been wateflooded. Consequently, little is known today as to the effect of dip on the performance characteristics of a flooding operation from the point of view of field experience; and because of the complexity of the problem, little, if anything, has been done on the problem from the point of view of theory. There are two distinct aspects of the role played by gravity in a flooding operation. The first is that of the preferential segregation of the reservoir fluids at the time when the flood is to commence. The second is the role that it may play in affecting the performance of the reservoir during the course of the flooding operation. In this paper the reservoir is assumed to be filled with only one fluid, so that there is no preferential segregation of reservoir fluids at the commencement of the flood. Moreover, the injected and in-place fluids are assumed to have the same characteristics, so that in effect we consider only a single-fluid problem. Single-fluid results have been used as a guide in the past for predicting and interpreting the behavior of regular five-spot floods in horizontal reservoirs. It is thought that single-fluid results might likewise be used for five-spot patterns in dipping reservoirs as a norm to which the effects of the multifluid problems might he referred.* In confining our attention to the single-fluid case, we therefore do not consider the preferential segregation of injected water in the oil bank, or of the oil bank in the unflooded zone. Instead we consider the deviation from the behavior of a horizontal five-spot which is caused by use of flooding techniques (i.e., the flow potential pattern at injection and production wells) likely to be employed during flooding operations in dipping reservoirs. In other words, we consider effects which are caused by the pattern of injection and production well pressures which we choose to apply. Performance characteristics are given for the five-spot spacing pattern as a function of two parameters; one is the ratio of gravity head to potential difference bctwccn the high updip injection well and the low downdip producer of the same five-spot, denoted by Rg; the second is the orientation of the five-spot pat-

Jan 1, 1956

By G. H., Wigton

THE present milling operations of the Chief Consolidated Mining Co. consist- of flotation of oxidized minerals from siliceous ores of the Tintic Mining district, Utah. As the lead, silver, and gold minerals that give the ores economic value are almost entirely oxidized; their successful flotation has necessitated the solution of many new problems. Laboratory effort resulted in the selection of a, natural float for the oxidized minerals. 'By "natural float," I mean that no reagent was added to produce a sulfide film on the osidized minerals before or while subjecting them to flotation operations. As compared to methods involving sulfide filming, the natural float was selected because it promised successful treatment of a larger variety, of ores without change in quantity or kind of reagents, as well as a better economic balance between metal recovery and concentration ratio. In explanation, I can, state that with sulfide filming, the efficiency of the method decreases rapidly with increase of hydrated, iron osides in the ore, whereas with the natural float the same effect has not been noted. Evidence shows that although sulfidizing can produce greater metal recoveries, it yields a concentrate so much lower in grade that no advantage results.

Jan 1, 1928

Mining Methods GERALD F. SHERMAN, Chairman CHARLES F. JACKSON, Vice-chairman Alluvial Mining CLINTON BERNARD H. R. NORSWORTHY - O. B. PERRY Open-cut Mining Iron MAX H. BARBER J. A. MACKILLICAN Copper MICHAEL CURLEY R. B. TEMPEST Underground Mining Iron C. H. BAXTER TENNEY C. DESOLLAR Copper W. B. DALY R. W. THOMAS

Jan 1, 1936

By Frederic P. Dewey

Having shown1 the difficulty of assaying so-called cyanide bullion and the extreme variations often found in the results, an investigation was undertaken to discover, if possible, the causes of these variations by a series of tests upon the specific action of various metals during cupellation. Zinc.—In order to test the effect of zinc, 48 assays were made in sets of 6, 2 rows of 3. The charge for the middle cupels consisted of 500+ mg. Au, 1,125 mg. Ag, 10 mg. Cu. To the end cupels 50, 75, 100 and 125 mg. Zn were added, and a set of each proportion was cupelled with 4 and 8 grams Pb. The cupels were assayed and showed the following gold contents in milligrams, the figures being arranged as the cupels stood in the muffle: In many instances the zinc does not appear to affect the cupel gold, but various exceptions are apparent, generally in the cupels in the back row. With 100 and 125 mg. Zn, in some cases the Zn burned with its characteristic flame' before it could alloy with the other metals. Also, less fusible oxidized lumps were observed during the cupellation and some cupels showed a scum. In order to lessen the premature burning out of the Zn, an alloy of 2 parts Ag to 1 part Zn was used. A uniform charge of 500+ mg. Au,

Jan 1, 1918

By L. J. Dijkstra

During the past several years an extensive study has been made of the internal friction of iron containing carbon or nitrogen in solid solution.1,2,3,4,5 It has been found that a sharp peak is observed in a plot of the internal friction vs. temperature of measurement. With a frequency of about one cycle per second, this peak occurs at 20°C for N and 36°C for C. The physical origin of this anomalous internal friction was traced by Snoekl to the local tetragonal symmetry of the interstitial positions in body centered cubic (bcc) iron. A change in stress induces a change in the equilibrium distribution of the interstitial atoms among the three types of interstitial positions, the three types corresponding to the three directions along which the tetragonal axis may lie. It is the continual striving of the interstitial atoms to maintain an equilibrium distribution that gives rise to a phase lag between strain and stress during oscillation, and hence, to internal friction. A similar type of internal friction has been observed in the bcc lattice of tantalum containing in interstitial solid solution C, N or 06. The theory of this anomalous internal friction leads to the prediction that its magnitude is strictly proportional to the concentration of either the carbon or the nitrogen in solid solution, provided the concentrations are small. This prediction has been verified3 for the range of solubilities ohtainable in alpha iron. This proportionality provides us with a new tool for the study of nitrogen and carbon in alpha iron. It thus enables one directly to follow the precipitation of either of these solute atoms from solid solution and also directly to measure their solubility as a function of temperature. A preliminary study of precipitation using this method has already been presented by the author.3 The purpose of this paper is to present more extensive observations upon the precipitation of N and C in alpha iron, as well as to present observations upon the solubility of N and C in alpha iron which, at least in the lower tempera- ture range, are believed more accurate than those previously obtained by other methods. The interpretation of the observations upon precipitation involves the use of the appropriate equilibrium diagrams. For ease of future reference in this paper the equilibriunl diagrams for the Fe-N and Fe-C systems are accordingly reproduced as Fig 1 and 2, respective]y. Experimental Procedure The specimens were made of West-inghouse Puron iron and consisted of wires 0.025 in. in diam and about 1 ft long. By a wet hydrogen treatment the specimens were purified of C and N. In

Jan 1, 1950

By M. I. Jacobson, A. S. Yue, A. E. Vidoz, F. W. Crossman

An equation governing the concept of constitutional supercooling under the combined effect of concentration and temperature gradients was used to produce platelike Al-CuAl2 eutectic composites for mechanical properties studies. Compression specimens were prepared from a single-colony Al-CuA12 eutectic composite ingot, 2 in. in diam and 12 in. long. The specirrzens were cut such that the platelets were oriented parallel, 45 deg, and perpendicular to the compression direction. Since the ingot was of eutectic composition, The aluminum-rich matrix could dissolve 5. 7 wt pct Cu in solid solution, and therefore could be strengthened by precipitation hardening. Specimens were tested at room temperature and elevated temperatures in the unidirectionally solidified, solution-treated, and solution-treated plus aged conditions. The results were compared with those for the conventionally cast and extruded specimens. For the controlled material, the highest strengths were obtained with platelets oriented parallel to the compression axis. In the unidirectionally solidified condition, 0.2 pct offset yield strength was 32,000 psi; however, this was increased to 59,000 psi by solution treatment, and further increased to 90,500 psi by solution treatment and aging. The attainment of high compressive strengths in the Al-CuAl2 eutectic composites was interpreted in terms of the buckling of elastic CuAl2 platelets in the plastically deformed a aluminum matrix. SINCE the discovery of high-strength whiskers,' scientists and engineers have made significant progress toward incorporating these whiskers into metallic matrices, forming composites for basic studies and structural application. The general procedure is to produce the whiskers first and then to bind them together with a ductile matrix. The production of whisker-reinforced composites requires tedious handling techniques,, particularly when it is desired to align the whiskers unidirectionally. Furthermore, the interfacial bond between the whisker and the matrix is frequently poor3 so that the resulting composite has strengths lower than expected. These disadvantages are generally true for any metallic composite produced by physically mixing the components. It is possible to eliminate these shortcomings by growing whiskers directly in the matrix material by eutectic solidification.4-8 In eutectic solidification, the matrix phase and a whisker phase are grown approximately simultaneously from a liquid of the same overall composition at the eutectic temperature. If the solidification process is controlled by varying the freezing rate, the temperature gradient, and the impurity content, platelike or filamentlike whiskers are produced parallel to the growth direction. The morphology of the grown-in reinforcement, i.e.. plates or rods, generally depends on the volume fraction9 of the dispersed phase present in the eutectic mixture. Since the unidirectional eutectic solidification is a one-step process, i.e., the liquid-solid transformation process, an excellent interfacial bond between the matrix and whisker is obtained. An additional advantage is that no special handling technique for whiskers is needed. In recent years, many investigators10-13 have studied the effects of growth variables on the micromorpholo-gies of binary eutectic alloys produced by controlled solidification. The study of their mechanical properties was initiated by Kraft and coworkers14-16 who found that the strength of cast A1-CuA12 eutectic alloy can be increased threefold by unidirectional solidification. In the A1-AL3Ni system, a strength of 50,000 lb per sq in, was reported for the unidirectionally solidified eutectic alloy, a value five times higher than for conventionally cast material. Thus, the unidirectionally solidified eutectics can be used as fiber-reinforced composite materials. In this paper, we shall first use an equation17 as a guide for the production of eutectic composites in general and the Al-33 wt pct Cu eutectic in particular. Experimental data supporting the theoretical prediction are given. Second, the compressive properties of the grown A1-33 wt pct Cu eutectic were thoroughly investigated in terms of platelet orientations, thermo-mechanical treatment, and temperature. The experimental data are interpreted in terms of a buckling model of fibers in elastic fiber-plastic matrix metallic composites. EXPERIMENTAL PROCEDURE Crystal Growth. The following experimental procedure was adopted for the production of controlled microstructures in the A1-33 wt pct Cu eutectic alloy. The controlled solidification was accomplished with a movable resistance-wound radiation furnace. Fig. 1 is a schematic drawing of the solidification apparatus. A water-cooled chiller was placed into a degassed high-purity graphite crucible containing the charge. Rubber stoppers wrapped with aluminum foil were used to seal both ends of the quartz tube through which a dried argon atmosphere was passed under a slight positive pressure. At both ends of the quartz tube, radiation shields were used to minimize heat loss. The quartz tube was held in place by two steel clamps and the furnace was drawn vertically by means of a steel cable against the steel truss which permits the furnace to move without touching the tube. The drive mechanism consisted of two pulleys, a counter weight.

Jan 1, 1969

By J. M. Eldridge, P. Balk

Phosphosilicate glass films were formed, by reacting gaseous P2O5 with SiO2, over a large range of temperature (800° to 1200°C) and gas phase composition (nearly two orders of magnitude of effective P2Ospressure). The film compositions generally corresponded with the liquidus curve, delineating the maximum solubility of the tridymite Phase of SiO 2 in phosphosilicate liquid solution at the temperature of film formation. It is shown that the P2O5 concentration of the phosphosilicate liquid film tends to decrease by reaction with the underlying SiO 2 layer until the liquidus curve is reached. The validity of the thermodynamic argument used in this explanation is supported by the results of a determination of the composition of borosili-cute films, prepared by reacting gaseous B2O3 with SiO2 at different temperatures. The kinetics of phosphosilicate film formation were described by a model predicated on a steady-state diffusion of P2O5 through the film. UNDERSTANDING of the processes leading to formation of phosphosilicate and borosilicate glasses is of great importance for producing passivating layers on FET devices. Passivating films with optimum characteristics are preferably formed in a separate step, independent of the doping of the semiconductor.' The results of an investigation carried out to gain improved insight into the mechanism of glass formation are presented in this paper. It would be expected that application of the known Pz05-Si02 and B 2 O 3-SiO2 phase diagrams should be useful in extending understanding of the glass-forming processes. However, the question of the propriety of treating thermally grown SiO2 in these binary oxide systems by the methods of equilibrium thermodynamics must be considered when this application is attempted. Although Sah et a1.' and Allen et al. 3 investigated the kinetics of formation of phosphosilicate glass (PSG), they failed to adequately relate their diffusion models to the occurrence of experimentally observed phases in the PSG/SiO 2/Si system. Horuichi and yamaguchi4 investigated the diffusion of boron through an oxide layer and described their results in terms of a model similar to that of Sah and coworkers. More recently, Kooi 5 and Snow and Deal6 reported the compositions of PSG films formed by depositing P2 O 5 onto SiO2. These compositions apparently coincide with those at the liquidus curve delineating the maximum solubility of crystalline SiO2 in phosphosilicate liquid solutions. These authors did not discuss the thermodynamic implications of their results on the structure of thermally grown SiO2 films. The structure of thermally grown Sio2 films and that of vitreous silica are generally thought to be quite similar. Since the solubility of a substance depends on its structure, it is relevant that the solubility of vitreous silica in water7 is highly reproducible, like the solubility of thermally grown SiOz in phosphosilicate liquid. Furthermore, the vitreous silica-water system appears to be in true thermodynamic equilibrium (viz., the same solubility value can be approached from both supersaturated and under-saturated solutions). Sosman7 suggested that a type of two-dimensional lattice may form at the silica/solution interface, resulting in the observed solubility behavior that is characteristic of a crystalline solid. An alternative explanation may be that vitreous silica has a microcrystalline grain structure. Other investigators have suggested that vitreous silica has essentially the structure of B cristobalite,' or is composed of microcrystals of p tridymite or cristobalite, or a mixture of both. Presumably the grain size would be sufficiently large to minimize any appreciable contribution of the grain boundaries to the solubility of the crystalline matrix. The present investigation was carried out to clarify the significance of the boundaries in the Pa,-SiO, and B2O3-SiO2 Systems in determining PSG and BSG (borosilicate) film compositions. Furthermore, the kinetic data for PSG film formation were extended, using a wider range of formation parameters than were previously reported. One model describing the kinetics of film formation will be presented that is compatible with the thermodynamics of the Pa5-Si02 system. EXPERIMENTAL PROCEDURE Glass Film Preparation. SiO2 films (1000 to 8000A thick) were obtained by oxidation of silicon substrates in dry O2 at 1100°C. PSG and BSG films were prepared by exposing these layers to gaseous oxides obtained by reacting high-purity POC13 and BBr3, respectively, with O2. A double-columned saturator was used to ensure complete saturation of the N 2 carrier

Jan 1, 1969

By D. M. Beeson, G. D. Ortloff

Water-propelled banks of carbon dioxide recovered both high- and low-viscosity crude oil substantially in excess of that recovered by water flood in linear flow model experiments. The increase in oil recovery is explained by oil swelling and viscosity reduction. Additional oil was recovered by solution gas drive at the end of the carbon dioxide floods when the model systems were depres-sured. This study was an investigation of the use of a water-driven carbon dioxide bank to recover crude oil. Techniques involving the injection of carbon dioxide have aroused con-siderable interest in recent years among methods considered for increasing oil recoveries. A number of investigators have studied the process in the laboratory1-' and in the field.7,5 Laboratory studies referenced indicate that carbon dioxide in conjunction with water flooding recovers more oil than does water flooding alone. These re- ports diverge widely, however, in stating magnitude of improvement. We believed that a water-driven carbon dioxide bank would increase recovery of crude oils by two mechanisms: viscosity reduction and oil swelling. Due to reduction in the oil viscosity caused by solution of carbon dioxide, displacement efficiency should be improved. In addition, the residual oil should be highly swollen by the carbon dioxide held in solution. Thus, the final residual oil saturation, in terms of stock-tank oil, would be lower than in the absence of carbon dioxide. To test this hypothesis, experi-

By C. H. North, L. E. Lynd, W. W. Anderson, H. Sigurdson

CONSIDERABLE uncertainty is revealed in the literature regarding the nature of the titanium minerals which make up the bulk of the heavy, opaque fractions of numerous beach sand deposits of the world. An investigation was made, therefore, of beach sand concentrates of North Carolina, Florida, Brazil, and India. Magnetic concentration, X-ray, and microscope data were obtained which show that these concentrates consist essentially of ilmenite and its alteration products. The alteration, brought about by oxidation and leaching of iron values, has resulted in upgrading the ores to a range of 56 to 64 pct TiO2, as compared with 52.7 pct in ilmenite of theoretical composition. Conclusions drawn regarding the nature of the dominant titanium-bearing mineral in beach sand deposits have been based mainly on chemical composition, specific gravity, and petrography. This material has usually been referred to as ilmenite or weathered ilmenite. It has also been referred to as arizonite because in chemical composition it resembles an occurrence in Arizona which was described by Palmer1 in 1909.

Jan 8, 1954

Jan 1, 1952

Prof. H. O. Hofman, Massachusetts Institute of Technology, Boston, Mass. (communication to the Secretary): When Mr. Stetefeldt quotes me as saying that " silver-assays are uniformly made by scorification," he has evidently not understood that I was referring solely to the practice of silver-lead smelting-works. Everybody knows that silver-mills do not employ the scorification-assay for regular work ; and it is equally certain that in very few, if any, silver-lead smelting-works will the crucible-assay be found in use for determining silver. The second part of the quotation, "as it is adapted to all kinds of ores and gives excellent results unless organic matter is present," although, of course, also intended in a restricted sense, might very well be extended to a general one. Mr. Furman, in his Manual of Practical Assaying,* says, on page 123: "We believe that the Colorado practice is preferable, as most ores will yield higher silver-results by scorification." The fact that the scorification-assay is the accepted one in Colorado is strong presumptive evidence for its accuracy, as exactness would nowhere else be more jealously demanded. Mr. Stetefeldt cites Albert Arents- as a supporter of his preference for the crucible-assay, although I had already done so in favor of scorification. Looking up again the reference, I find that I was justified in quoting him, as, while Mr. Arents advocates the crucibleassay for low-grade gold ores, not on account of the greater accuracy of its results, but because it is quicker and less expensive, he condemns it§ for the assay of silver-ores, and prefers the scorifier for rich goldores, and for coppery ores, and in general for ores containing both silver and gold. As I, like Mr. Stetefeldt, have kept no detailed

Jan 1, 1895

By N. Albon, J. F. Miller, R. W. Coutant

The deposition of nickel from nickel carbonyl onto amorphous substrates has been studied, with attention being paid to the specific effects of the physical and chemical nature of the substrate and to the effect of oxygen on the crystal morphology. With substrates having microscratches or etch lines, nu-cleation was observed to occur preferentially at these surface features. Flame polishing of the substrate surfaces was found to remove any regularity in preferred nucleation sites. Nucleation was observed to occur less readily on substrates having relatively low surface energies, e.g., Teflon and carbon, than on materials having relatively high surface energies such as fused silica. At low oxygen concentrations [Ni(CO)4/O2 > 54 x 1031, apparently pure and well-formed nickel crystals were observed to nucleate and grow irrespective of the presence of oxygen. At higher concentrations of oxygen, a secondary growth process, dependent upon oxygen concentration and resulting in a gradual change in crystal morphology, was observed. It is concluded that the influence of oxygen on the nucleation and growth of nickel is determined by the relative kinetics of the various possible reactions, and that under the experimental conditions employed the 0-Ni interaction occurs at some nucleation or prenuclea-tion stage. THE purpose of the research on crystal nucleation in chemical vapor deposition as described in this paper has been twofold: 1) to examine some effects arising from the use of amorphous substrates, and 2) to study the specific effects of oxygen on the nucleation and growth of nickel in a nickel carbonyl-carbon monoxide system. The nickel-nickel carbonyl system was chosen for study for several reasons: 1) nickel films are of potential interest in electronic technology, and 2) the deposition can be carried out at moderate temperatures, thus making possible detailed study of the processes occurring and the use of a variety of substrate materials (including some which melt at relatively low temperatures). Fairly well-characterized chemical kinetics and a broad background of information are available on the py-rolysis reactions and on the mechanisms of Ni-O interactions. NUCLEATION AND GROWTH THEORY The theoretical background for the analysis of nucleation and growth by vapor deposition for a one-component system (physical vapor deposition) and the problems encountered therein have been reviewed by Hirth and pound.' More recently Mande12 has indicated the difficulties of applying such theory to chemical systems. One of the major problems involved is the possible multiplicity of chemical reactions and deposition routes. For example, those reactions which are probably of significance in a discussion of the pyrolytic deposition of nickel from nickel carbonyl under the conditions of the present experimental work are illustrated in Fig. 1. As is true with most cases of chemical deposition, many of the quantitative data necessary for a complete analysis of the system are either not available or not directly measurable. However, with the present system, sufficient data are available for a discussion of nucleation and growth on a qualitative basis. Classically, the rate of nucleation of a monatomic species being deposited from a vapor phase is given by

Jan 1, 1965

By H. W. Kropholler, L. A. Cramer, E. T. Woodburn, J. C. A. Greene

A generalized mathematical structure is proposed whereby internal species mass flows within a flotation network are defined uniquely by a matrix of enhancement factors. An element of the enhancement factor matrix is defined as the ratio of the mass flow of that species leaving a given cell in the concentrate to the species mass flow leaving the same cell in the tailings. To predict the enhancement factors, knowledge of flotation kinetics effects is required. Recently experimental data has become available relating to the performance of industrial flotation circuits which indicate that the discrete or discrete-distributed kinetic schemes are capable of reasonably effective simulations. These simulations show the importance of including froth effects. The prediction of performance of networks from small-scale batch tests on flotation streams shows that the model for the froth phase used in the simulations does not scale-up well and that aeration effects are also difficult to predict. The network analysis should be useful in differential flotation of complex ores and it is disappointing-in this context that little information on the kinetics of activation and depression is available.

Jan 1, 1976

By C. Zener

HE present paper has its origin in an attempt A by the author, extending over the last several years, to understand the influence of the magnetic properties of the constituent atoms upon the various properties of metals and alloys. During this study the author has been impressed by the important role which magnetism plays in the many facets of metallurgy. In writing this paper he has attempted to convey to his colleagues some concept as to the role magnetism will play in the future development of metallurgy. In some of the subjects herein discussed, such as the influence of magnetism upon phase boundaries and upon mechanical properties, only general thermodynamical properties associated with ferromagnetism are introduced. For these subjects, it is not anticipated that any serious differences of opinion will be encountered. A discussion of the other subjects requires the adoption of a quite specific model of the magnetic structure of the metal. This model is discussed under "Magnetic Shells and Their Interactions." The simple model adopted in this paper has been criticized' as being mathematically inconsistent. This criticism has been ably silenced by Dr. W. J. Carr' of this laboratory. The simple model adopted in this paper has been criticized as being inconsistent with observations on magnetic structure using neutron diffraction. This apparent discrepancy has been resolved by Bader3 who has shown that the finite velocity of neutrons prevents neutron beams from detecting the anti-ferromagnetic structure of the type predicted by the simple model adopted in this paper. Magnetic Shells and Their Interactions An electronic shell of an atom is specified by two symbols.' The first symbol is a number and denotes the total quantum number of the shell. The second symbol is a letter and denotes the orbital angular momentum of each electron within the shell. The letters s, p, d, f are used to denote an orbital angular momentum of 0, 1, 2, 3, respectively, in units of h/2a, where h is Planck's constant. As we pass from scandium to nickel in the first transition period, we eraduallv fill the 3d shell. This shell is responsible for ferromagnetism and hence may be called the magnetic shell. The component of the orbital angular momentum along some specified direction must be an integral multiple of h/2~. Thus, for a d electron this component can have any one of the values —2, —1, 0, 1, 2 times h/2a. In addition to its orbital angular momentum, each electron has an intrinsic angular momentum, hereafter called spin, due to a rotation about its own axis. This spin can have either of two components + Yz (h/2a) or — Yz (h/2~) along the specified direction. A fundamental principle of atomic structure, known as Pauli's exclusion principle, is that no two electrons in a given shell may have identical components of orbital angular momentum simultaneous with identical components of spin. The 3d shell thus may have at most ten electrons. Since an intrinsic angular momentum of a charged particle is necessarily associated with a magnetic moment, the spin of an electron may be thought of as referring to either this angular momentum or to the associated magnetic moment. The electron configuration of the ground state of the isolated atoms in the first transition row is reproduced in Table I. The superscript represents the number of electrons in each shell. For the purpose of this paper, the most important principle of atomic structure relates to the manner in which electrons are added to a shell as the atomic number is increased. This principle, commonly known as the principle of highest multiplicity or more simply as Hund's rule, states that within a given shell the maximum number of electrons have spins pointing in the same direction as is consistent with Pauli's exclusion principle. An application of this principle to the d shell is illustrated in Fig. 1, where the spin structure is given for shells containing from 1 to 10 electrons. The physical basis of Hund's rule is the exchange energy discussed first by Heisenberg in 1928. This is a coupling between electrons with parallel spins (spins pointing in the same direction), the coupling

Jan 1, 1956