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By C. B. Alcock, R. G. Hudson

Sulfur pressure measurements above FeS in equilibrium with iron have been carried out by the Knudsen orifice method. A comparison is made of the weight loss of the cell per unit time obtained in the above experiments, that calculated from Richardson and Alcock's measurements of the S2 pressure above FeS in equilibrium with iron, and the dissociation constant for diatomic sulfur from spectroscopic and thermal data. EXTENSIVE equilibrium measurements have been made to determine the sulfur potentials of a great many systems of metallurgical interest.' In order to confirm their reliability, to supply data which may be of use in further thermodynamic calculations, and to establish the reliability of the Knudsen orifice in obtaining accurate thermodynamic values at high temperatures, the present investigation on the pressure of the gaseous species above FeS in equilibrium with iron has been carried out. The Knudsen orifice method has been used for these pressure measurements. Experimental The apparatus and general technique for this investigation are the same as that reported for the determination of the vapor pressure of silver.' To reduce the residual gas pressure in the evacuated chamber, a titanium getter, maintained at run temperature, was introducbed. Several types of Knudsen cells were used—platinum, zircon, and fused silica. The orifice in the zircon cell was fashioned with a small diamond wheel. The same precautions were used in this investigation as were employed in the work on Mo2S2.3 The FeS-Fe mixture was prepared by heating a sample of pure FeS,, supplied by K. K. Kelley of the Bureau of Mines, with excess iron powder, cp grade, obtained from the Fisher Scientific Co. These two substances were heated in a closed Armco iron crucible at 960°C, held in a vacuum of less than 10" mm Hg for 24 hr. The mass was then removed from the cell and ground in an agate mortar. In this form it was charged to the various Knudsen cells. Heating the Knudsen cell for an additional two days was sufficient to obtain constant rates of weight loss of the cell. The data obtained in this investigation are recorded in Table I. To establish whether or not a sulfide of iron is volatile at these temperatures, 0.7646 g of the FeS-Fe mixture, described above and containing 69.2 pet Fe, was placed in the zircon Knudsen cell. Run Nos. 103 to 109 were performed on it. After the completion of these runs, the total amount of iron left in the cell was obtained by chemical analysis. It contained 0.537 g Fe, compared to 0.529 g in the original charge. Thus, there was an apparent gain in iron of 1.5 pet. This is attributed to unknown experimental error, and the conclusion is that no sulfide of iron is volatile. The vapor pressure of pure iron4 is about one thousandth that of the sulfur pressure' at these temperatures. The vapor pressure of iron inside the Knudsen cell will be almost exactly that of pure iron, since in the iron-rich phase the percentage of sulfur is of the order of 0.025 pet.At this low percentage of sulfur Henry's law is probably obeyed by the sulfur. Thus, the iron will obey Raoult's law. In any event, the vapor pressure of iron will be lower than that of pure iron and, since the vapor pressure of pure iron is negligible compared to the pressure of sulfur, the weight loss of the cell due to the vaporization of iron should be negligible. Since neither iron nor FeS is volatile to an appreciable extent, the total weight loss of the cell must be due to the vaporization of sulfur. Discussion and Calculations On the assumption that S, is the only gaseous species present in appreciable quantity, its pressure

Jan 1, 1957

By H. L. Overton, J. B. Lipson

The concept of sodium single-ion equivalent activity as developed by Gondouin, Tixier and Simard,' was used to determine the filtrate resistivity-activity relationships for 150 laboratory and 49 field drilling muds. With the exception of the native and phosphate high-resistivity muds and the calcium-treated muds, the filtrate resistivity-activity relationships were found to be within 20 per cent of that for pure sodium-chloride solutions. Gondouin, et al,* previously suggested a method of treating the high-resistivity muds in quantitative electrical log analysis. A new treatment is presented which uses the P-alkalinity of the filtrate as a correlating parameter in handling the calcium-treated muds in quantitative electrical log analysis. INTRODUCTION Gondouin, Tixier, and Simard in 1957 introduced new interpretive procedures for analyzing the self-potential curve of electric logging. They re-emphasized the previous work of the Schlumberger brothers, Wyllie and others, and re-defined the activity concept in terms of a number which they termed the effective resistivity. Their procedures are particuarly effective when the connate-water resistivities are less than 0.08 ohm-m or greater than 0.3 ohm-m. For gyp muds where the calcium content is known, a procedure was presented which allows calculation of the connate-water resistivity with improved accuracy. These procedures assume that one of the fluids in the system is a pure sodium-chloride solution, but they are not limited by the assumptions. For the fresh and saline connate waters, for instance, it is assumed that the drilling mud filtrate is a pure sodium-chloride solution. For the gyp mud interpretive procedure, it is assumed that the connate water is a pure sodium-chloride solution. Brown,' on the other hand, has suggested that it would be extremely fortuitous if drilling mud filtrates could all be treated electrochemically as sodium-chloride solutions, and he cites some examples where discrepancies exist. A study has been made of the deviations of sodium single-ion equivalent activities, an of drilling mud filtrates from that of pure sodium-chloride solutions. Drilling fluids in common use on the Texas and Louisiana Gulf Coast and laboratory-controlled muds were investigated. Using a cell patterned after Gondouin, et al, (Fig. I), the equivalent activities were measured. It should be remembered here that the activity measured is merely an index which uses numbers that represent the sodium single-ion equivalent activity a,., of the mud filtrate. The membrane potential developed across the cell was determined with a null-type potentiometer. The resistivities of the solutions were measured by the four-electrode method. The resistivity system was calibrated by using saturated KC1 solution as a standard. Chemical properties of the drilling fluids studied were measured with standard API-approved equipment for the particular property in question. For the activity measurements, two shale discs were chosen to serve as cationic membranes. These two discs were both 1 1/4 in. in diameter and, respectively, 1/4 and 1/8 in. in thickness. The membrane potential, Em, was determined using the shale discs as cationic selective membranes separating two standard sodium-chloride solutions of known mean activity. Then by comparing the constant Km in the following equation, with the theoretical value of — 59 mv at 75OF, the perfection of the membrane was determined. The variation of Km for the two membranes used in this experimental work, as well as one of the many unsuitable membranes, is shown in Fig. 2. The measurement of the activity of mud filtrate involves the balancing of its combined individual activities against a standard solution of known mean activity. At the point where there exists zero potential across the membrane cell, the activity effects may be assumed equal for all practical purposes. The mechanics of making a null reading of this sort requires having a large number of different mean activity solutions. A more practical method involves

By J. H. Scaff, H. C. Theurer, E. E. Schumacher

The microwave region of the radio spectrum was effectively utilized in radar designs during the recent war and it has become of increasing interest in the field of communications. Work in this field has led to an important use for silicon—that of the point contact rectifiers†1 in the frequency converter of microwave (radar or radio) receivers—and has stimulated considerable interest in the electrical properties and preparation of silicon and its alloys. Silicon is an electronic semiconductor. Its conductivity at room temperature results principally from the presence of certain impurities. While for metals an increase in impurity content increases the resistivity, for semiconductors such as silicon the opposite occurs and, in general, the addition of impurities lowers the resistivity. Silicon materials may be classified into one of two groups depending upon the manner in which the impurities contribute to electrical properties. These have been termed for convenience p-type or n-type. P-type silicon develops a very large positive thermal emf against metals, has a Hall coefficient of positive sign and a low resistance direction in point contact rectification with the silicon positive with respect to the point. N-type silicon, on the other hand, develops a negative thermal emf against metals, has a Hall coefficient of negative sign and a low resistance direction in rectification with the silicon negative with respect to the point. Impurities which produce n-type silicon are called donors inasmuch as these elements contribute to electrical conductivity by donating electrons to an unfilled energy band in the silicon. On the other hand, elements which produce p-type silicon are known as acceptors as these impurities contribute to the electrical conductivity by accepting electrons from a filled energy band permitting what is known as conductivity by "holes" in which the sign of the carriers appears to be positive. A general treatment of the mechanism of conduction in semiconductors from the viewpoint of modern band theory has been given recently by Pearson,2 by Becker, Green and Pearson,3 and by Torrey and Whitmer.4 In this investigation boron and aluminum have been found to be acceptors, and phosphorus, arsenic, and antimony to be donors in silicon. Data on the effect of boron and phosphorus on the electrical properties, when present singly and in combination, have been acquired. These data are discussed in the present paper. Raw Materials Used and Methods for Adding Seeond Constituents Silicon from two sources was used in this work and these will be referred to as A and B respectively. Silicon A is a material of high purity supplied by the Electro Metallurgical Co. It is prepared by chemical purification of "commercial" silicon obtained from the arc furnace reduction of SiO2. It contains 99.8 pct silicon, minimum, with small amounts of calcium, iron, aluminum, boron, and phosphorus as the principal impurities. This material was extensively employed in these studies as well as in the commercial preparation of rectifier materials. Silicon B is a material of high purity from the du-Pont Co. It is prepared by a pyrolytic reduction of Sicl4 and is free of analytically detectable amounts of boron and phosphorus. Its use permitted study of the effect of boron and phosphorus individually on the properties. This material contains, however, spec-troscopic traees of a number of metals, some of which affect electrical and rectification properties. Typical analyses for the two grades of silicon are given in Table 1. To make controlled additions of boron to the charge it was necessary to employ a low boron content master alloy since the quantity of boron to be added was usually only a few thousandths of one percent. The alloy containing nominally one percent boron was prepared by melting chemically pure boron with silicon A using the melting techniques for 320 g silicon

Jan 1, 1950

By Blake M. Caldwell, Harrold D. Owen

The continued use of permanent-type, we11 completion Iras pointed LIP the need for more powerful through-tubing perforating equipment. A new expendable shaped charge perforator has been developed in which the charges are run through the tubing in a vertical position and then opened out to a horizontal position when at the desired shooting zone. The performance of this new tool is comparable to that of conventional casing type perforators. This paper describes the new tool and its applications. Performance data in targets rind under various actual well conditions are presented. INTRODUCTION The general acceptance and increasing use of pernianent-type well completion by the oil industry has indicated the need for through-tubing perforating equipment with performance comparable to that of conventional casing type perforators.'.' To achieve the performance desired, a new, expendable, shaped charge perforator has been developed with adequate power for effectively perforating both 51/2-in. and 7-in. casing below tubing. This has been accomplished without resulting severe damage to the casing and can he obtained under extremes of pressure and temperature. The design of this new tool is a radical departure from previous concepts of tubing guns since it was felt that the two major limitations imposed by previous designs severely handicapped performance. The first of these limitations was the restriction imposed upon the length of the charges by the necessary small inside diameter of the carrier. This resulted from the necessity for compromises in designing a hermetically sealed gun small enough to allow free passage through 2-in. tubing, yet with sufficient wall thickness to withstand some minimum pressure. In an effort to overcome this limitation, the charges were in some cases placed at an angle with the axis of the well with resulting loss in effective depth of penetration. The second limitation concerned the extreme distance of the charges from the casing when the gun was fired. An example of the latter situation is demonstrated by the fact that a conventional 13/4-in. tubing gun centralized in 51/2-in., 17-lb casing has a clearance of more than 1-9/16-in. on all sides. This means that a considerable portion of the force from each charge must be expended in penetrating this 1-9/16-in. of well fluid before it even reaches the casing. With the gun centered in 7-in., 23-lb casing, the amount of fluid penetration required of each jet is in excess of 21/4-in. In a situation where the 13/4-in. gun is touching one side of the 51/2-in., 17-lb casing, the jets from the charges on the opposite side have more than 3%-in. of fluid to penetrate. A similar situation in 7-in., 23-lb casing necessitates the penetration of more than 4-9/16-in. of fluid. The penetrating effect of the charges is severely impaired in passing through so much fluid. Under such conditions, there is usually insufficient force left to penetrate the casing. Previous studies have shown the decided disadvantage of having to shoot through such an excessive quantity of well fluid.'.' The problem. then, was how to position large powerful charges close to the casing prior to firing and still manage free passage through 2-in, tubing. The solution appeared to be in some method of folding sealed charge units in an open type, expendable. 13/4-in. carrier for travel through the tubing, and unfolding them upon their arrival at the shooting zone in the casing. It was desired to control the mechanism electrically from the surface through the regular shooting cable, making the release of the charges independent of the physical characteristics of the well, yet with a provision to prevent the gun from firing until the

Jan 1, 1955

By D. R. Wieland, H. T. Kennedy

The object of the work reported here was to determine the content of elemental sulfur in gaseous methane, carbon dioxide, hydrogen sulfide, and in mixtures of these gases, at pressures and temperatwes encountered in natural gas reservoirs. Sulfur content at equilibrium is reported for pure methane, carbon dioxide, hydrogen sulfide, and on three binary mixtures of each of the three pairs of gases at pressures of 1,000, 2,000, 3,000, 4,000, 5,000 and 6,000 psia and at temperatures of 150°, 200° and 250°F. In addition, the sulfur content of three ternary mixtures at the same temperatures and pressures are reported. The results indicate that the sulfur content is higher in the gases at higher temperatures and pressures. The content is highest in hydrogen sulfide, intermediate in carbon dioxide and lowest in methane. INTRODUCTION At ordinary pressures and temperatures, the concentration of a nonvolatile material, such as sulfur in a gas at equilibrium, is a function of the vapor pressure of the material and is independent of the nature of the gas. As the pressure and temperature increase, the gas assumes some of the properties of liquids, including the power to dissolve other liquids and solids, to an extent dependent on the nature of both the gas and the material dissolved. At equilibrium, the content of sulfur in the several gases considered here may thus be considered as solubilities which are fixed for a given composition of gas, temperature and pressure. The study of the solubility of elemental sulfur in gases is of interest because sulfur is sometimes present in reservoirs producing natural gas and must be present in the vapor phase. Upon reduction of pressure and temperature, the sulfur precipitates from solution in the reservoir and in the tubing and fittings. Due to the fact that the greatest pressure drop in the reservoir is around the wellbore, the volume of sulfur precipitated will be greatest in this locality and can cause a substantial reduction in the permeability of the formation in this area. As the natural gas flows up the tubing string, the pressure and temperature are further decreased, causing further sulfur precipitation. If the volume of free sulfur is large and remedial measures are not taken, complete plugging of the tubing can occur. Knowledge of the content of sulfur as a function of composition, temperature and pressure will enable the operator to determine what changes in pressure and/or temperature are necessary to keep the sulfur in solution. If the sulfur solubility is large and can be controlled, the operator may desire to produce the well at a high wellhead pressure and temperature and reclaim the sulfur at the surface. The high solubility of sulfur in hydrogen sulfide (5.6 per cent by weight at 5,000 psi and 200°F) suggests the feasibility of recovering sulfur by injecting this gas into sulfur-bearing reservoirs and expanding the produced gas to precipitate out the sulfur. The present project was designed to measure the solubility of sulfur in carbon dioxide, methane, hydrogen sulfide and mixtures of these three gases at various temperatures and pressures. These gases were the major constituents of the gas well where plugging by sulfur was encountered. A study of the published literature shows no data on the solubility of sulfur in any gas, although Hannay and Hogarth,' in 1880 reported that it was soluble in carbon disdlide above the critical temperature of carbon disulfide. EQUIPMENT AND PROCEDURE Fig. 1 shows the layout of equipment employed to bring gases to equilibrium with sulfur and to isolate the quantity of sulfur contained in a known volume of gas. Pure gases were measured in the charging bomb at known temperatures and pressures and displaced into the reservoir bomb to make up the desired mixtures. When equilibrium was achieved

By R. Schuhmann, E. J. Michal

Experimental measurements are reported for the oxygen pressures of iron-silicate slags in equilibrium with solid silica. CO2-CO mixtures were bubbled through the slags in silica crucibles to find equilibrium values of p co2/p co over the entire composition range of silica-saturated slags at 1250°, 1300°, and 1350°C. From the data, the activity vs. composition relationships were calculated for O, FeO, and Fe. SLAGS composed primarily of silica and iron oxides have particular practical importance in copper smelting,' in acid steelmaking, and in accounting for the service behavior of silica refractories. These slags all contain both ferrous and ferric iron, so that, strictly speaking, they are ternary or three-component liquid solutions. For convenience, the components may be taken as the three oxides, FeO, Fe2O3, and SiO2. The constitution of the FeO-Fe,O,-SiO, system at slagmaking temperatures has been studied in a recent investigation described in a separate paper.' This work showed the compositional ranges of iron-silicate melts at temperatures up to 1450°C and also the temperature-composition relationships for melts in equilibrium with various solid phases, including iron, wüstite, magnetite, and silica. Broadly speaking, the compositions of iron-silicate melts at a given temperature should be thought of as varying over a two-dimensional field. In the first place, the silica/total iron oxide relationship varies from maximum silica for silica-saturated melts to minimum silica for wüstite-saturated melts or, at higher temperatures, to zero silica for straight iron oxide melts. In copper smelting, for example, the converter slags approach the low silica limits while the reverberatory-furnace slags have intermediate silica contents, perhaps approaching silica saturation in some circumstances. Liquids formed in the pores of silica refractories presumably are close to silica saturation. The second type of composition variation is in the ferric/ferrous relationship, which depends on how oxidizing or how reducing the process conditions are. Relatively reducing slags, such as acid-steelmaking slags, are lower in ferric oxide and ap- proach saturation with metallic iron. Oxidized slags, such as copper-smelting slags, contain larger percentages of ferric oxides and approach or reach saturation with magnetite. Since these two kinds of compositional variations are closely related to two general properties of interest for all metallurgical slags, basicity, and oxidizing power, it is hoped that the thermodynamic study of iron-silicate slags eventually will throw further light on the significance and nature of these long-recognized but as yet poorly understood slag properties. Measurements of oxygen activity as a function of slag composition, using CO-CO2 gas mixture to fix oxygen activities, afford an experimentally convenient approach to the study of the thermodynamic properties of iron-silicate slags. In a preceding investigation,³ his approach was used in a systematic study of iron-silicate slags in equilibrium with solid iron. The present paper gives the results of a similar study of the iron-silicate slags in equilibrium with solid silica. The experimental work consisted in the determination of CO2: CO ratios in gas mixtures at equilibrium in the system: gas: liquid slag: silica Determinations were made at temperatures from 1250° to 1350°C for slags ranging in composition from iron saturation to magnetite saturation. Also, equilibrium CO,: CO ratios and slag compositions were determined for the univariant systems: gas: liquid slag: silica: iron gas: liquid slag: silica: magnetite Experimental Methods The experimental procedure was essentially the same as that used in the previous study of iron-silicate slags saturated with solid iron," but in order to work with the silica-saturated slags an all-silica crucible assembly was used. A liquid slag was prepared from pure prefused stock materials and brought to equilibrium with the silica crucible at the desired temperature. Then a mixture of CO2 and CO was continuously bubbled through the melt

Jan 1, 1953

By J. B. Agan, R. J. Fernandes

This paper utilizes the layered-system approach, modified to include areal sweep efficiency, to determine the miscible-slug size required and to predict the perfort7zance of a miscible-slug process in a highly stratified reservoir having a permeability variation of 0.76. The slug size in each layer was determined from theoretical calculations and laboratory data which showed that, to maintain miscibility in the reservoir, the slug size had to be 8.2 per cent of the floodable hydrocarbon pore volume. Economic considerations, however, such as the value of the miscible product injected, the cost of injection and the cost of reprocessing the miscible product, limited the amount of miscible product which could be injected into the lower-permeability layers. This resulted in subjecting only 60 per cent of the reservoir to a slug size sufficient to maintain miscibility. Utilizing the relationship of producing gas-oil ratio and areal sweep efficiency as a function of pore volume injected (as obtained from data published by Dyes, Caudle and Erickson2), the theoretical performance was determined. This prediction is compared with actual performance to date. Actual performance reflects an increasing percentage of tniscible product in the produced fluid to a particular level, which remains static for a short period and then increases again to a higher level. This performance suggests that the reservoir has performed as a layered system. It is concluded that the layered-system approach can be used to predict performance in a highly stratified reservoir and that economic consideration is a limiting factor in determining the amount of the reservoir which can be miscibly swept. INTRODUCTION The Paloma zone in the Paloma oil field, Kern County, Calif., is comprised of several sand members separated by siltstone, shale and/or cherty sections. Rapid facies changes within the zone indicate that the sediments were deposited in a "near shore" environment. As a result, the Paloma sands have a high permeability variation, and the Paloma zone is comprised of several sand reservoirs. Since one of the sand reservoirs containing crude oil was not receiving the benefits of gas injection, consideration was given to recompleting certain wells to isolate the sand in order to perform a miscible-phase injection project and, thereby, to increase its ultimate oil recovery. Before proceeding with the project, a review of the literature was made to determine the miscible-slug size that would be required to maintain miscibility throughout the displacement process. Although the review showed that considerable information was available for homogeneous systems, insufficient information was available to determine slug-size requirements and to predict performances for a highly stratified reservoir. This paper has been prepared to describe the method used to determine the miscible-slug-size requirement and to predict the performance of the miscible-phase injection project initiated in the Paloma oil field. Although the Paloma project has only been in operation since Aug., 1958, sufficient production history has been obtained so that a comparison can be made with the predicted performance. DESCRIPTION OF RESERVOIR The reservoir in which the miscible-phase project was initiated in the Paloma field is shown on Figs. 1 and 2. Reservoir properties are as follows: average sand thickness, 43 ft; porosity, 19.1 per cent; water saturation, 47.2 per cent: oil viscosity, 0.328 cp; reservoir temperature, 250°F; reservoir pressure, 3,500 psi: gas saturation, 21.2 per cent at time of miscible product injection; and total net hydrocarbon pore volume, 19,993,000 reservoir bbl. LIMITATIONS The method described herein utilizes a layer-system approach, where injection into and production from each layer is assumed to be proportional to the layer's fractional capacity. The effects of increased fluid mobility on injection and production rates, in layers which have had breakthrough, are not reflected in this method. There has been considerable controversy over the slug size necessary to maintain miscibility throughout the displacement process. In this method, the slug-size

By C. L. Meyers, A. V. Levy, G. Y. Onoda, R. J. Kotfila

This paper presents the hypothesis that solid-solution hardening of regions in the order of tens of angstroms thick along grain boundaries is the most important mechanism controlling the ductile -brittle transition behavior of poly crystalline bcc refractory metals. Further, a physical model is developed and a general equation is derived to describe the dependence of the solute concentration at grain boundaries on temperature, nominal impurity concentration, thermal treatments, vain size, and prior plastic deformation. Analytical curves of the solute concentration at grain boundaries us temperature, calculated by means of the derived equation, are found to have the same general form as curves of ductility us temperature plotted from experimental data. Senziquantitative relationships between the transition temperature and metallurgical variables can he determined by using the physical model. The room-temperature brittleness of the poly-crystalline refractory metals (tungsten, molybdenum, and chromium) is a result of their high ductile-brittle transition temperatures. Recently studies on single crystals have revealed that, when sufficiently pure, these crystals have much lower transition temperatures than polycrystalline specimens of similar purity.'-3 For example, the transition temperature (measured by reduction in area in tensile tests) for very high-purity tungsten crystals has been reported to be as low as -50°F whereas polycrystalline specimens of similar purity had a transition temperature near 400" ~.' These results suggest that the ductile-brittle transition behavior of these polycrystalline metals can be attributed principally to the influence of grain boundaries on plastic flow and fracture. This paper contains a discussion of the manner in which grain boundaries influence the ductility of the poly-.crystalline bcc refractory metals and proposes that the segregation of impurities to grain boundaries is the most important mechanism for controlling the ductile-brittle transition behavior of these metals. Further, this paper contains an analysis of the effect of the compositional and structural variables on the grain boundary-ductility relationship, and introduces a semiquantitative model that can provide a foundation for more theoretical treatment to describe the influence of these variables on ductile-brittle transition behavior. PHYSICAL MODEL FOR PREDICTING DUCTILE-BRITTLE TRANSITION BEHAVIOR Grain Boundary Segregation of Impurities. Based on their own observations and on theoretical grounds, numerous investigators have suggested that impurities segregate to the grain boundaries. Such segregation would be expected because regions exist where both large and small foreign atoms fit with less strain than within the undistorted crystal structure. Therefore, the concentration of impurities should be higher at boundaries than within the grain body. TO estimate the degree (i.e., the ratio of grain boundary to nominal bulk concentration) to which an interstitial solute tends to segregate at boundaries within a solvent metal, the solubility rather than the size misfit could be used as a guide because solubility expresses the joint effect of both elastic and electronic factors.5 The solubilities of interstitial elements such as carbon, hydrogen, nitrogen, and oxygen are low in the group V-A metals and very low in the group VI-A metals.6 These low solubilities suggest that segregation to grain boundaries should occur for each of these solutes in both refractory metal groups. The difference between the ductility of single-crystal and polycrystalline bcc refractory metals can be described in terms of two distinct effects.4 The first of these is the general observation that grain boundaries hinder slip within grains and slip transfer between grains, and the second is that deformation is more complex in each grain of a polycrystalline specimen than it is in a single crystal. Mc Lean has pointed out, furthermore, that strong slip-hindrance effects at grain boundaries should occur in metals having strong segregation of impurities to grain boundaries. Therefore, the effect of grain boundaries on the hindrance of slip is expected to be the dominating influence on the ductile-brittle transition behavior of these polycrystalline refractory metals. cahn5 has suggested that temperature and solute mobility should influence solute equilibrium segregation at grain boundaries, and Fig. 1 illustrates

Jan 1, 1965

By Klaus Schwerdtfeger

The rate of formation of silicon monoxide from silica spheres has been measured at 1500°C in H2, H2-H2O, H2-He, H2-Ar, and CO-CO2 gas mixtures. Indications are that in the hydrogen-containing gases the reaction rate is mainly determined by convective diffz~sion. In the CO-CO2 mixtures the rate approches a constant value which is independent of sphere diometer (and gas velocity). This suggests that a surface reaction becomes rate controlling in CO-CO2 gas. WHENEVER silica is exposed at elevated temperature to a strongly reducing atmosphere there occurs, inevitably, a volatilization of silica by the formation of gaseous silicon monoxide. Because of the importance of this reaction in metallurgical processes and laboratory experiments, its kinetics were studied in the present work. EXPERIMENTAL The spheres made of vitreous silica were suspended by a molybdenum wire in the hot zone of a gas-tight high-purity recrystallized alumina furnace tube of 3.1 cm internal diam and 100 cm length. Molybdenum wire resistance heating was used. A purified H2, H2-H2O, H2-He, H2-Ar, or CO-CO2 gas mixture was passed through the tube, from top to bottom. The amount of silicon monoxide formed was determined by weighing the silica balls before and after the experiments. The silica balls were made from commercially available translucent fused quartz glass. In experiments with hydrogen-containing gases the silica stayed vitreous during the experiment, whereas in experiments with CO-CO2 mixtures, which were performed over longer times, the balls were always crystallized to cristobalite (as determined by X-ray examination) at the surface. Constant-pressure head capillary flowmeters were used to control the composition of H2-He, H2-Ar, and CO-CO2 gas mixtures. The oxygen and water vapor were removed from the gases containing hydrogen by passage through columns containing platinized asbestos (450°C) and an-hydrone. The CO was purified from O2 and CO2 by passing it through activated copper (200°C) and through ascarite. The H2-H2O gas mixtures were prepared by passing purified Hz through a mixture of oxalic acid dihydrate and anhydrous oxalic acid held at a constant temperature in a water bath. The equilibrium water vapor pressures of oxalic acid dihydrate-anhydrous oxalic acid mixtures were taken from the available data.1 The furnace system was checked for sufficient gas tightness at regular intervals. As an additional check, the H2O and CO2 contents were measured in the exit gas and were found to agree closely with the metered contents when H2-H2O or CO-CO2 mixtures were used. When purified H2 was used, H2O pressures found in the exit gas were always below 0.1 mm Hg. These contents originate either from an incomplete reoxidation of silicon monoxide in the cold part of the furnace or from small leaks which cannot be avoided. If the latter is the case, such small uncontrolled H2O contents decrease the partial pressure of SiO in equilibrium with SiO2 by less than about 7 pct, which is considered small in comparison to other experimental uncertainties. The temperature of the furnace was controlled automatically in the usual manner. The reported temperature was measured with a Pl-Pt/l0pct Rh thermocouple and was accurate to ± 5°C. TRANSPORT-CONTROL LED RATE OF REDUCTION The gaseous convective diffusion from the surface of a sphere can be predicted from the semiempirical relationship obtained by Ranz and Marshall2 in a study of the evaporation of water and benzene drops in air. The following equation applies:

Jan 1, 1967

By J. Weertman

It is shown that conditions suitable for the conversion of straight dislocations into helices are common in crystals hardened either through long-range dislocation interaction or by jog formation on dislocation lines. For dislocations other than screw dislocations or dislocations nearly screw in orientation, helices can be formed with the aid of core difhsion at temperatures low relative to the melting point of the material. It is assumed that, once formed, helices will degenerate into dislocation tangles. THE dislocation tangle is one major dislocation arrangement observed by the transmission electron microscope which had not been predicted previously from dislocation theory. Since first being observed, the tangle itself has become important in applied dislocation theory. The Cambridge school (P. Hirsch) bases part of its theory of work hardening upon this phenomenon.' In spite of the fact that the tangle obviously is a structure of prime importance to a cold-worked crystal, until recently relatively little attention has been paid to the question of exactly why or how tangles arise. It was generally assumed at first that cross slip and perhaps jog formation will lead to tangles. However Wilsdorf and schmitz2 concluded that cross slip cannot markedly contribute to the tangles. The Wilsdorfs and Maddin3'* have proposed that tangles arise by means of prismatic dislocation loops and superjogs which are produced by a precipitation of point defects. Dislocations with superjogs or which have joined with prismatic loops are themselves dislocation sources and they can produce new dislocations, a process they call "mushrooming", which then tangle with each other. There is no question that the Wilsdorfs et al. mechanism as well as the cross slip one can pro- duce tangles. However these may not be the only paths leading to tangle formation. In this paper we wish to consider another way tangles can form. Our work will be based on the theory of dislocation screw We wish to show that whenever a crystal is cold-worked there always is present a "driving force" leading to helix formation and thus to tangle formation. We do not expect to observe well-developed, regular helices in cold-worked metals. Rather we would expect that after a helix is formed random interactions with nearby dislocations will cause a well-developed helical dislocation to go over into an irregular form. A dislocation tangle is, of course, a grouping of dislocations with irregular forms. Therefore we feel that, in accounting for the formation of dislocation tangles, it is sufficient to show that many dislocations in a cold-worked crystal will take on helical form. The crucial step is helix formation. In order to have a straight dislocation assume a helical form, diffusion of vacancies, or interstitials, must occur. Our discussion of tangle formation therefore will be limited to crystals which have been deformed at temperatures ranging from about one fifth to half their absolute melting point. In this tem per a ture range appreciable core diffusion is possible. (There is no problem in explaining tangle formation at temperatures greater than half the melting point. At such temperatures dislocation climb through a bulk diffusion of point defects gives an extra degree of freedom to dislocation motion. This extra freedom of motion makes tangle formation easy.) At temperatures much below one fifth the absolute melting temperature diffusion processes are sufficiently slow that helix formation does not occur. Of course helix or tangle formation could occur in material deformed at very low tempera-tures which was subsequently warmed in order to make the thin specimen necessary for electron-microscope examination. Since within the temperature range of approximately one fifth to half the melting temperature the diffusion of point defects in the core of the dislocation is rapid, we can reasonably assume that within

Jan 1, 1963

By I. M. Bernstein

The steady-state creep behaviov of zirconium and zivcaloy-2 was examined in the temperature vatlge 520° to 620°C A1 low stresses the creep rates were cimracterized by a linear stress dependence; at highev stresses the stress dependence was much more pronounced. Temnperature-cycling tests yielded values for the aclivation enevgy for creep. Various tlzeories were examined in the ligltt of- the experimental re-sults and it mas concluded that the low-stress creep behavior is the result of the stress-direcled diffusion of vacancies along gain boundaries. It has been observed,"&apos; usually under conditions of high temperature and low stress, that creep deformation can occur for which the steady-state creep rate is linearly dependent on the applied stress. For magnesium and certain magnesium alloys, Harris and ones&apos; and ones&apos; have argued that this type of creep occurs by mass transfer as a result of the stress-induced generation and migration of vacancies, along a gradient defined by the stress direction. Jones&apos; demonstrated that the rate-controlling diffusion path is sensitive to grain size and temperature, and that by suitable control of these variables creep could occur by vacancy diffusion either predominately along grain boundaries or through the lattice. Recently, Jones3 suggested from an examination of limited high-stress data for zircaloy-2, composition in Table I, that significant diffusion creep could occur at low stresses, at least between 375" and 500°C, controlled by grain boundary vacancy diffusion. This process could have an important implication in assessing the role of zirconium alloys as a structural or cladding material in certain classes of nuclear reactors, since it predicts creep deformation far in excess of any estimates based on extrapolating slip creep data from higher stress levels. If the diffusion creep process occurs it should be possible to describe the total steady-state creep rate of zirconium and its alloys as the sum of two terms, Eq. [I]; the first term relates to a slip creep process important at high stresses and which is manifested by a much more pronounced dependence of creep rate on stress4 than diffusion creep and the second to a process controlled by mass transfer,5&apos;6 dominant at low stresses: where A and BI are parameters which can depend on structure, Ql and Q2 are the activation energies for the particular creep process occurring, and n describes the sensitivity of the creep rate on stress. It is the purpose of this paper to present some direct experimental evidence in support of this view. It is recognized that other analytical approaches have been proposed to explain data of this kind and these will also be discussed. 1) EXPERIMENTAL PROCEDURE Flat creep specimens (gage length 1 by 0.25 by 0.02 in. approx) were prepared from cold-rolled, argon-remelted, crystal bar zirconium and cold-rolled commercial-grade zircaloy-2, the analyses of which are given in Table I. The specimens were annealed at a pressure of < 10-5 Torr at temperatures from 625" to 675°C for 2 hr and slow-cooled. This treatment produced stable grains of average size (defined here by the average linear intercept) of for zirconium and -4xin. (-10 p) for zircaloy-2. The specimens were tested in a dead load tensile creep rig. The stress was maintained constant by adjusting the applied load after approximately each 1 pct of strain. The specimen temperature was controlled to better than +1°C. This system had a small thermal lag, so that rapid temperature changes were possible. To minimize corrosion, the specimens were tested in high-purity (99.95 pct) argon, further dried,

Jan 1, 1968

By M. A. El-Aouar

Drilling muds are complex colloidal systems. In an effort to analyze the physical properties that affect their performance at high temperature, an investigation was made of the hydrothermal stability of the monoionic hydrogen, calcium and magnesium forms of montmorillonite and attapulgite. Samples were heated to 400°1F in a simple autoclave and analyzed for cation exchange capacity, c-axis X-ray diffraction spacing and pH factor us sodium hydroxide titration dependence. Out of the six monoionic clay minerals tested, calcium montmorillonite and magnesium attapulgite showed the least base exchange capacities and were relatively unaffected to heat. It is concluded that, of the six clays studied, these two clays were the most suitable forms for use in drilling fluids. INTRODUCTION The drilling of deep wells is dependent upon the drilling mud, and problems frequently arise concerning the effect of mud temperature and prolonged heating. Drilling muds are complex colloidal systems. In an effort to analyze their behavior in deep, hot boreholes, it was thought desirable in this investigation to study suspension of pure, monoionic montmorillonite and attapulgite clays before and after hydrothermal heating. Chemically, clays are hydrated aluminum silicates, such as montmorillonites and attapulgites. The structure of montmorillonite is composed of units made up of two silica tetrahedral sheets with a central alumina octahedral sheet. Attapulgite consists of double silica chains running parallel to the c-axis with the chains linked together at their longitudinal edges. The apexes of the tetrahedrons in successive chains point in opposite direc-tions.4,7,10 One of the most important characteristics of clay minerals is their property of sorbing certain anions and cations and retaining them in exchangeable state. The property of exchange capacity is measured in terms of milliequivalents (meq) per 100 gm of clay. The cation-exchange capacities are taken at pH 7 from titration curves which show the relation between pH and milliequivalents of added NaoH.9,11 The following are causes of cation exchange: (1) broken bonds around the edges of the silica alumina units would give rise to unsatisfied charges, which would be balanced by adsorbed cations; (2) substitution within the lattice structure of trivalent aluminum for quadrivalent silicon in the tetrahedral sheet and of ions of lower valence; and (3) the hydrogen of exposed hydroxyls may be replaced by a cation which would be exchangeable. The primary techniques employed to study the effects of hydrothermal treatment were titration curves and X-ray diffraction analyses. Titration curves were useful in characterizing the nature of the clay mineral surface and the stability of the various samples to attack by acid or alkali before and after hydrothermal treatment. X-ray diffraction analyses were used to determine changes in the nature and crystal structure of the minerals present and to determine the cations in exchange positions on the montmorillonite samples. EXPERMENTAL PROCEDURE PREPARATION OF SAMPLES Selected samples of Wyoming bentonite and attapulgite clay from mines along the Georgia and Florida border were purified by centrifugation to remove all particles larger than 2 microns. In preparing magnesium attapulgite, first a 1.00-normal solution of magnesium acetate was prepared. The pH of the solution was adjusted to 7.0 by adding magnesium oxide. One hundred grams of attapulgite clay were mixed in a blender for 30 minutes with the magnesium acetate solution. The attapulgite solution was left overnight, and then filtered in a Buchner funnel. The suspension was leached with further quantity of magnesium acetate solution and then washed with distilled water for 20 days, after which the filtrate was free from magnesium ions. The concentration of magnesium attapulgite in the clay slurry was adjusted and determined quantita-

By F. F. Poland

The purpose of this paper is to describe the recent applications and improvements made in the process and equipment for the recovery of metallic zinc from secondary metals by means of high temperature electric resistor furnace distillation. The process and high temperature furnace, as developed by Revere Copper and Brass Incorporated, Research and Development Department, was described in a previous paper. † Since the publication of that paper the process and equipment have been licensed to others. Consequently its field of application has been expanded, particularly for the treatment of scrap brass, galvanizers dross and scrap zinc. Other applications are being considered, particularly the melting of metallic titanium and special alloys requiring a controlled atmosphere. Consideration is also being given to modification in design that would allow the melting of copper cathodes for the production of oxygen-free and electrolytic tough pitch copper shapes without the necessity of blowing and poling. In the design of a furnace for melting copper cathodes it is intended that the fundamental principle of charging the solid material into a large pool of molten metal through a double door charging vestibule as shown in Fig 3 of the previous paper, † would be adhered to and, in addition, either dehydrated and desulphurized producer gas or commercial nitrogen, that is, approximately 96 pct nitrogen, 2 pct hydrogen 2 pct CO, also dehydrated, would be used to provide a protective atmosphere for the resistors and to flush out more soluble gases from the molten copper. The operation of a small unit producing approximately 1000 lb of copper per hr has shown that the commercial nitrogen will allow the production of tough pitch electrolytic copper when the metal is transferred from the meltdown unit contemplated to a special type induction unit where the oxygen absorption and temperature can be controlled. Standard practice in treating low grade scrap brass has been to oxidize the zinc by blowing air through the molten metal. This operation results in the recovery of approximately two-thirds or less of the zinc content of the brass in the form of an impure zinc oxide having only a fraction of the value of the zinc in metallic form. The balance of the zinc is lost to slag, fume and drosses. Fig 1 shows the revised flow sheet of the process for the treatment of scrap brass. For this application and as shown on the flow sheet a low frequency induction furnace has been substituted for the Wilkins-Poland type as a melting unit. This type of furnace has been found the most suitable for the purpose as will be shown by the following discussion. Serap Brass The melting of refinery scrap brass preparatory to distillation presents a melting problem quite different from the usual melting of brass mill scrap for recasting because refinery scrap is a heterogeneous mixture of alloys each having different melting and boiling points, and coated with a variety of corrosion products and foreign materials. In addition, brass and copper plated pieces of sheet iron, stainless steel, ceramic materials, and others are present that do not melt except at temperatures above the boiling point of the liquid bath. In the previous paper it is noted that difficulty was encountered in the melting of refinery grade scrap brass without excessive loss of zinc by volatilization and that 5 to 10 pct razorite flux was used to alleviate this condition. While this flux was successful in preventing the excessive loss of zinc by volatilization it interposed a low heat conductivity layer between the source of heat and liquid charge and resulted in lowering the melting rate of the furnace. This same problem presents itself in all types of furnaces in which the metal is heated by radiation and conduction from above the charge. It has been found in melting this type material that the melting rate per hour or per square foot of hearth area

Jan 1, 1950

By A. D. Mutch

IT has long been known that there are wide variations in the thermo-electric potential of pyrite. In the last few years a study of this variation and other properties of pyrite was carried out at the University of Toronto by F. G. Smith on specimens of pyrite from many localities.1-3 As a result of these studies the pyrite geothermometer was developed by Professor Smith. The calibration of the pyrite geothermometer is based on the assumption that "crystals of any one electronically conducting mineral species deposited at a high temperature have a more positive thermo-electric potential than crystals deposited at a low temperature, and the thermo-electric potential varies continuously between any given limits of the temperature of deposition." The cause of the variation was postulated to be crystal discontinuities, such as lineage boundaries. As yet this postulated relationship has not been established as fact. On theoretical grounds it is indicated that the thermo-electric potential of pyrite or any other partial conductor is dependent upon a number of factors as well as the temperature of formation. For this and other reasons there is ground for doubt as to the validity of the relationship postulated above. To date a large number of readings have been made with the pyrite geothermometer which have been recorded in terms of the calibration of the instrument in degrees centigrade. So far most of the pyrite tested by this technique has been in association with gold ore. The values for the temperature of formation obtained in these tests appear to be reasonable and, in relation to geological problems, to vary in the right sense. Determinations on some specimens not in association with gold ore have given readings that appear to be much too high, taking into account the probable maximum temperature of the host rock. To sum up, although many determinations made with the. pyrite geothermometer appear to give reasonable values for the temperature of formation of the pyrite, there are at the same time other readings which seem anomalous. On the basis of an examination of available results of work with the pyrite geothermometer, two problems must be considered: 1-the validity of the calibration of the pyrite geothermometer; and 2-the nature of the distribution of the thermo-electric potentials of pyrite in relation to the specific problems that have been examined. In this paper the academic problem relating to the validity of the calibration of the pyrite geothermometer will not be discussed. Instead, the variations of thermo-electric potential of pyrite in association with gold veins will be discussed with regard to specific examinations. The first of these two examinations deals with the distribution of thermo-electric potentials of pyrite in association with a gold vein and was carried out in the McIntyre Porcupine Mine, Schumacher, Ont., in the summer of 1949 as part of a study with this technique. The second problem deals with variations of thermo-electric potential of pyrite in gold ore specimens from all over the world. The specimens used in this study were part of the private collection of Frank Ebbutt, geologist for Howe Sound Exploration Co. Results of Detailed and Reconnaissance Studies In discussion of the results of determinations made in these two studies the values of thermo-electric potential in millivolts will be used. It will be noted that in some of the diagrams the determinations are recorded in terms of pyrite geothermometer temperatures. Fig. 1 is a calibration chart relating, pyrite geothermometer temperatures and thermo-electric potentials. A full discussion of the technique is given in the original paper by F. G. Smith.&apos; Briefly, the determinations are made by placing two stainless steel probes, one hot and the other cold, against the surface of the pyrite crystal being tested. The thermo-electric potential that is developed is read with a null-point potentiometer that is calibrated in what

Jan 1, 1952

INTRODUCTION The meaning of cash flow has already been defined as after-tax earnings available for use by the corporation or business. It is therefore apparent that a significant part of mineral economic evaluation is concerned with correct and accurate computation of taxable income under existing tax laws, and the proper treatment of tax allowances and deductions. The various methods of depreciation, depletion, and amortization are all means whereby the investor can earn back or recover, before taxes are imposed, the investments made for purposes of doing business or for the production of income. Each of these three types of tax deduction are applied to different investment items such as property, equipment, buildings, research, etc. The cost of buildings, equipment, machinery, and transportation equipment are representative of capitalized business costs that must be recovered by depreciation over the life of the asset. The property investment costs of acquiring natural resources such as minerals, oil and gas, and standing timber are examples of investment costs that may be recovered by depletion. Several other capitalized business costs, such as research expenses and trademark expenses, may be recovered by amortization. The term "capitalized" means that the in- vestment cost is not deducted as an operating expense in the year that it is incurred, but is spread out over a period of years through depreciation, depletion, or amortization deductions according to lawful schedules. Of course, any capitalized cost can only be deducted once. The other costs of doing business which are not capitalized, such as labor and operating costs, are said to be "expensed," i.e., they are written off for tax purposes in the year they occur. DEPRECIATION Depreciation, according to US tax law, is a deduction from taxable income permitted as a "reasonable allowance for the exhaustion, wear and tear of property out of its use or employment in a business." The original cost of the property is the usual basis for determining depreciation. Since depreciation write-off is applied over the useful life of the asset, the first step is to determine the estimated useful life or its allowable depreciable life. These two lives may or may not be the same. No average life is applicable to all types of depreciable assets under different conditions or in different types of business. It is the taxpayer&apos;s responsibility to determine the useful life of the asset according to his own operating conditions and experience, within the guidelines set by the US Internal Revenue Service (IRS). The Class Life Depreciation Range (ADR) System permits the taxpayer to choose from a range of depreciable lives at 20% below or above the present guideline life. The second step required in calculating depreciation is to determine an estimated salvage value for the asset. The salvage value is an estimate, made at the time of acquisition, of the amount of money which can be realized by the sale of the asset at the end of its useful life. The four depreciation methods most widely used in the US are: (1) the straight-line method, (2) the declining balance method (double declining balance), (3) sum of the years - digits method, and (4) units of production method. Straight-Line Depreciation Method The straight-line depreciation method is the simplest for calculating depreciation. The depreciation for each year is determined by subtracting the estimated salvage value from the first cost of the asset and dividing the result by the years of life. The method gives equal annual deduction over the depreciable life. Salvage value equal to or less than 10% of the first cost may be ignored. [first cost - salvage Straight line = years of life ] Declining Balance Depreciation Method Declining balance depreciation, or double declining balance (DDB) as most frequently applied, is used for accelerating depreciation in the early years of the asset and is the fastest depreciation method allowed by the US Internal Revenue Service. The declining balance

Jan 1, 1980

By R. W. Heckel, H. W. Paxton

The growth of grain boundary films and Widmanstiitten plates of proeutectoid cementite in hypereutectoid steels ulas considered quantitatively in three plain carbon steels and one "pure" iron-carbon alloy. Growth was found to take place at a slower rate than would be predicted on the basis of a model invoking rate control by long range diffusion of carbon. The films in the pure alloy grew faster than those in the plain carbon steels. A possible explanation is suggested. In 1904, Nernsst&apos; and Brunner2 postulated that ionic crystals growing in supersaturated aqueous solutions grew at rates determined by diffusion through the solution to the growing crystal interface. The gradient down which the diffusion took place was assumed to be fixed by the supersaturated bulk solution concentration, the concentration dt the crystal surface and some arbitrary distance. The flux of material to the crystal was described as Flux where D is the diffusion coefficient, A the crystal surface area, Ci the bulk solution concentration, Co the saturated solution concentration, and 6 the thickness of the diffusion zone. It is obvious that the expression is an adaptation of F+ick&apos;s3 first law of diffusion (steady state). This was the initial formulation of what will be defined here as "diffusion controlled growth," i.e., growth limited by the long range diffusion of a component either to or from the advancing interface assuming both phases at the interface to be in equilibrium. This idea of equilibrium interface concentration implies an infinite reaction rate at the interface. Volmer, Zener,&apos; and 11schner6 have derived expressions for the diffusion controlled growth of spherical precipitates in metallic systems. These analyses agree that the growth in a given direction should be parabolic with time. Brown and Hawkes7 observed that graphite, formed both from the decomposition of cementite and from the decomposition of eutectoid austenite in cast irons, grew according to a parabolic relationship and, therefore, concluded that the laws of diffusion controlled growth, as defined above, were obeyed. They, among others, failed to consider, however, that parabolic growth is a necessary, but not sufficient, condition for diffusion controlled growth. Mehl and Dube"&apos; have pointed out that equilibrium may not be realized because the concentration at the interface cannot change instantaneously from that of the bulk to the saturation value. Furthermore, they propose that an equilibrium solute concentration in the parent phase adjacent to the precipitate would remove the thermodynamic activity gradient across the interface and, thus, stop the growth process. Frisch" has also emphasized the importance of interface concentrations that vary throughout the growth of a new phase. The variation in activity across an interface, as discussed by Onol&apos; and Cahn and Hilliard,12 is of fundamental importance to this question. Ham13 considered the data of Turnbull14 on the growth of barium sulfate in aqueous solutions. He concluded that the data could be analyzed in terms of a radiation-type boundary condition. Flux across interface = K (c, - C,) [21 where C, is the concentration in the solution at the interface, Co the saturated solution concentration, and K the proportionality constant. The edgewise growth of Widmanstlitten plates, frequently referred to as the rate of lengthening, was first considered by Zener.&apos;&apos; Basing a mathematical analysis on steady-state (constant velocity) growth he concluded that where G is the growth rate, D the solute diffusivity, Ci the concentration in the bulk, Co the equilibrium interface concentration, C, the concentration in the precipitate, a a constant, Y the radius of curvature of the edge of the plate, and rC the critical radius, i.e., the radius which would increase the activity of solute at the interface at equilibrium under the influence of capillarity to that of the bulk. Zener1&apos;

Jan 1, 1961

By E. B. Burwell, R. H. Nesbitt

Designed by army engineers, the NX borehole camera provides the most economical method of subsurface exploration so far devised. Continuous cylindrical color photographs now reveal minor flaws in foundation bedrock not always disclosed by borehole samples. A unique projector transforms the photographs into true-to-scale images of three dimensions. ANEW milestone in the progress of photography and subsurface exploration was reached when the Chief of Army Engineers announced the development of the NX borehole camera. In obtaining continuous undistorted cylindrical color pictures of dry or water-filled borings the device surpasses all other cameras designed for photographing interior surfaces of pipes, wells, and conduits. The usefulness of the camera and the unique projector that comes with it are at once apparent. To the geological, mining, and civil engineer alike it signifies the end of guesswork with respect to underground conditions that have eluded identification by conventional core-drilling methods. To the medical profession it may well signal new progress in photo optics which could result in cylindrical color photographs supplementing the X-ray and existing photographic methods used in exploratory surgery. The pilot model of the camera has more than paid for itself as a result of its success in bringing to the surface at two dams information previously obtainable only by costly drilling of mansized boreholes for subsurface on-the-spot examination. Such bores cost as much as $200 per lineal foot as against $10 per ft for the conventional 3-in. or NX exploratory core borings from which the present invention derives its name. The NX camera can now photograph completely the interior surface of these borings. Research and development for the first camera and projection equipment were conducted by Engineering Research Associates, Division of Remington Rand, Inc., under the technical supervision of the Geology and Geophysics Branch, Office of the Chief of Army Engineers in Washington, in accordance with plans and specifications furnished by this branch. Subsequent modifications of the camera-lowering device, transporting equipment, and special field tools were made in the Corps of Engineers&apos; Ohio River Division Laboratories in Cincinnati. The background of this development is interesting. Among the more difficult foundation problems involved in construction of concrete dams are those resulting from bedrock imperfections that escape disclosure by conventional exploration methods. Often these imperfections are of sufficient magnitude to introduce costly changes, especially when their presence is discovered only after foundation excavation is well in progress. Bedrock flaws most frequently camouflaged may be ruptures resulting from the enormous stresses to which rocks have been subjected, or they may be planes or zones of weakness related to chemical alteration and underground erosion. Obviously, detailed information on their location, dimensions, and structure is important, as these factors can affect the stability of a dam and the security of life and property downstream. Their discovery and appraisal entail extensive subsurface exploration. At present the most economical exploratory tool available to geologists and engineers is the small-diameter diamond core drill by means of which cores of the foundation bedrock are recovered for examination and testing. All too often, however, these samples fail to disclose minor foundation flaws that may be of major importance before a structure is completed. As a result, the small-diameter drillings are supplemented generally by more reliable but much more costly shafts, tunnels, or large-diameter calyx drill holes that permit the investigator to examine the foundation rocks in place. It was to reduce the number and cost of these expensive and time-consuming investigations, as well as to obtain more complete information on rock structure from the smaller borings, that the NX borehole camera was developed. That it has been eminently satisfactory in accomplishing that purpose is demonstrated by its success most recently at the Folsom dam, under construction on the American River, 23

Jan 1, 1955

By M. T. Simnad, R. F. Mehl, L. Yang

Techniques for studying marker movement in K-Rb interdiffusion have been worked out. The results indicate that Rb diffuses faster than K and that the ring mechanism of diffusion cannot be the dominant one operating in this case or probably in cases involving other alkali metals, despite their low ion core repulsive energies. SEVERAL theoretical attempts have been made in the past decade to elucidate the mechanism of diffusion in body-centered-cubic metals. No general agreement, however, has been reached by different authors. Zener,1 and later LeClaire,2 on the basis of a correlation between the entropy of activation for self-diffusion and the temperature dependence of the elastic constants, predicted that a ring mechanism should operate in the diffusion of body-cen-tered-cubic metals. Paneth3 calculated the activation energies of various ring, vacancy, and interstitial mechanisms for the self-diffusion in alkali metals and concluded that the most likely one was based on the linear motion of "crowdions," which is in fact a different form of interstitial diffusion. Fumi,1 however, showed that the experimental values of the activation energies for self-diffusion in the alkali metals could be better accounted for if the diffusion process in these metals was assumed to follow a vacancy mechanism. The same conclusion was reached by Kojima5 for the self-diffusion in lithium. Experimental evidences published during the past few years seem to exclude the ring mechanism as the predominating one in the diffusion of body-centered-cubic metals. For instance, maker movement has been observed in ß-brass, first in this laboratory" and later by Resnick and Baluffi.5 Shewmon and Bechtoldh also found marker movement in the body-centered-cubic system Ti-Mo and showed that the argument which led Zener and LeClair to favor a ring mechanism was not incompatible with a vacancy mechanism. In spite of this, it seemed to the authors that further experimental tests should be made by studying the Kirkendall effect in body-centered-cubic systems that characteristically have small ion core repulsion, such as the alkali-metal systems. Since the ion core repulsion term constitutes the main part of the activation energy needed for the rotation of a ring, such a test should be the most critical of all. The system K-Rb was chosen for experimental study because these metals form a continuous series of solid solutions. Experimental Investigation Owing to the extremely active nature of these two metals, a brass dry box (18 x 11 x 10 in.) was built for making the diffusion couple. It had a big lucite window on top, two side ports through which neo-prene-rubber gloves were inserted, and another side port covered with an optically flat-glass window for microscopic examination of the sample. Inside the box there were a circulating fan driven with a rotating horse-shoe magnet located outside the box, a heater used to generate potassium vapor for getter-ing the box, and a cold trap for keeping the inside of the box cool. Chemically pure grade K and Rb were triple distilled before they were transferred in vacuum into cylindrical steel molds kept in pyrex-glass ampules, Fig. 1. The latter together with the tools needed for making the diffusion couple were put into the dry box. After the box was flushed with purified argon and gettered with potassium vapor, generated from a heated steel crucible inside the box, the glass ampules were broken and the mound on the top of the alkali-metal ingot was cut off with a razor blade to yield a flat surface. To make the diffusion couple, one K ingot and one Rb ingot were pushed out of the molds together with their steel supports by screwing a metal plunger into the bottom of each mold. They were then laid on a brass cradle inside the assembling carriage (shown separately in Fig. 2) with the flat faces opposite to each

Jan 1, 1959

By P. A. Beck, Hsun Hu

It has been known for many years that in cold drawn polycrystalline aluminum the recrystallization texture is practically identical with the deformation texture.l,2,3 V. Goeler and Sachs4 stated that in cold rolled polycrystalline aluminum, too, the deformation texture is retained upon recrystallization. This behavior was interpreted by Dehlinger9 as an indication that each recrystallized grain inherits the orientation of the matrix in which it grew. However, Burgers and Basart showed6 that in deformed aluminum single crystals the orientation of the recrystallized grains strongly deviates from that of the matrix. Barrett demonstrated8 that even in deformed polycrystalline aggregates the local orientation within each deformed grain changes on recrystallization. No explanation has as yet been offered of how the aggregate texture can be retained, while the local texture is everywhere changing. According to Burgers and Louwerse6 the orientation change on recrystallization in compressed and rolled aluminum single crystals corresponds to a rotation around [112] axes lying in the active slip planes and perpendicular to active slip directions. This orientation change was rationalized by them on the assumption that the orientation of the recrystallized grains is determined by the orientation of the available nuclei, and that these nuclei are small fragments of the deformed crystal, rotated in the deformation process. Barrett pointed out,? however, that these assumptions were by no means proven, and that the total volume of material necessary for the nuclei is so small, that it must be available in any orien- tation whatever. It is, therefore, unlikely that an "oriented nucleation" theory could satisfactorily explain the orientation changes in recrystallization of a deformed crystal. Furthermore, in contradiction to Burgers and LOU-werse&apos;s conclusions, Barrett&apos;s results for the orientation change could be best expressed in terms of rotations around. [Ill] axes. Thus agreement is lacking not only in the interpretations but apparently even in the experimental results contributed by the various investigators. The orientation relationships on coarsening* in a highly oriented polycrystalline matrix were first investigated by Burgers and Basart.5 They produced a fine grained highly oriented matrix by the recrystallization of a compressed or rolled single crystal of aluminum, and studied the orientation relationships in three successive generations of crystals: the "deformation texture" in the single crystal, the recrystallization texture, and the coarsening texture. Burgers24 showed that the preferred orientation of each successive generation was almost always widely different from that of the preceding one, but that the coarse grains often approximately reverted to the orientation of their grandparent, the deformed single crystal. This observation, and the idea that the orientation of the coarse grains is determined by that of the available "nuclei," led to the concept that the coarse grains are nucleated by the remnants of the deformation texture.12,15 On the other hand, Bowles and Boas16 found, in a carefully conducted experiment, that in recrystallized fine grained copper of cube texture coarse grains grow in orientations which can be derived from the orientation of the recrystallized matrix by rotation around a [lll].] direction: the coarsening texture here does not appear to be related in any simple manner to the original rolling texture from which the cube texture had been obtained by recrystallization. It may be assumed that in a recrystallized material, even with a strong texture, there always are present some grains of practically any orientation. These may serve as "nuclei" for the coarse grains, provided that the conditions are favorable for their growth. The existence of a coarsening texture may be considered as an indication that grains with certain relative orientations with respect to the preferred orientation of their neighbors can grow much faster than others. This "oriented growth" theory was briefly suggested by van Arkel, as early as 1936,13 and it was mentioned by Burgers." Recently, C. G. Dunn produced direct

Jan 1, 1950

By C. B. Scotty, E. F. Egan

INTRODUCTION The neutron-garnma log has been used for stratigraphic correlation by the oil industry for a number of years. In the past few years, the quantitative application of the log to provide information with respect to porosity has received considerable attention. The basic concept of quantitative interpretation has been pointed out in the literature.1 It shall be the purpose of this paper to develop by empirical means a method whereby the relationship of porosity to neu. tron-gamma deflection may be predicted for various bore hole diameters. This relationship is applicable to the present commercially available neutron-gamma log run in open hole. Data available at present are insufficient to establish similar correlations for cased holes. Through the development of such a correlation, the importance of the various factors which influence the log become evident. NEUTRON-GAMMA CURVE The logging tool conisists of a source of neutrons and a means of detecting and measuring gamma rays, the detector being shielded from the direct emission from the source. The gamma rays reaching the detector have three sources of origin: (1) the natural gamma radiation emitted by the formations, (211 induced gamma radiation resulting from neutron bombardment. (3) gamma rays emitted by the source and scattered by the formation. It has been found that a neutron derived porosity correlation is best for shale-free formations. Under this condition the natural gamma ray radiation is quite low, and therefore, will be neglected in this work. The induced gamma ray radiation resulting from neutron bombardment is predominantly a function of the hydrogen atom concentration of the substance penetrated. Due to the geometry of the presently used system, the neutron-gamma curve indicates low radioactivity opposite high hydrogen concentration and high radioactivity opposite low hydrogen concentration (Figs. 1 and 2). Having a curve which measures hydrogen atom concentration, it follows that if the matrix of the formation penetrated consists only of atoms other than hydrogen, and if the fluid filling the pores is either oil or water, the curve should be an indication of porosity (both oil and water have practically the same number of hydrogen atoms per unit volume&apos;). The above criteria for a porosity (Correlation are fulfilled in clean sandztones and limestones in which the pore volume is completely filled with liquids (oil or water), but not in formations containing either free gas or shale or both. Free gas. even under pressure, contains considerably less hydrogen per unit volume than oil and water; therefore, a variation in response on the curve would be expected. Camp- bell and Winter,&apos; indicate that this difference in hydrogen concentration is sufficient to distinguish between sands containing water or oil and those containing dry gas. Shale is a mineral that contains hydrogen in its molecular structure in addition to the hydrogen which is present in the water of hydration. Thus, in formations containing variable amounts of shale, the hydrogen concentration indicated by the curve is not a direct indication of porosity. Bush and Mardock&apos; have indicated that a correction may be made by use of the gamma ray curve to provide a porosity correlation. Since the induced gamma rays are predominaiitly a function of hydrogen concentration, it would be anticipated that the fluid filled bore hole would materially influence the logs. It has been pointed out that the neutron-gamma curve response decreases with increase in hydrogen concentration, therefore, the response due to the induced gamma ray component decreases with increase in fluid filled hore hole diameter. The scattered gamma ray component of the log increases with increase in bore hole diameter. Although there is an

Jan 1, 1952