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Jan 1, 1919

By R. D. Nelson, F. E. Bowman

Evidence has been found for a (010)a?(111)B[102]a /,11[341]/B crystallographic relationship between the monoclinic a and B phases of plutonium during the a?B transformation. The results of an X-ray diffraction study, where [010] fiber textured a samples were used in the absence of suitable single crystals indicate that the (OIO)a planes become (111)B planes upon transformation under near-equilibrium conditions. The transformation strain along the fiber axis, which was the [010] direction, was measured dila-tomekically; the measured 8.5 pct expansion compares favorably with the 8.44 pct expansion in the in-terplanar spacing represented by the (010)a?(111)B relationship. From plots of the atom positions in each of the related planes, a correspondence was deduced between the [102]a, direction and the [341]B direction. Further analysis of the two lattice structures in the light of this relationship revealed a rotation about the [102] direction of 1 deg 43 min and a slight shearing in this same direction of about 30 min. THIS paper discusses the (B crystal structure of plutonium and the orientation relationship existing between the monoclinic a and B phases during the a?ß transformation. The kinetics of the a?ß and (3 — a transformations have received extensive consideration, and because of the crystallographic complexity of these phases, the question of the mechanisms by which these transformations occur is especially intriguing. Nelson and Shyne1 evaluated the existing experimental evidence and concluded, from the indirect evidence available, that both the ß ? a and a ? ß transformations occur by a martensitic process. Their data reveal the anisotropic nature of these transformations which suggests the existence of specific crystallographic relationships between the parent and product phases. In this paper, we are concerned with the confirmation of the existence of such a relationship resulting from the a ? ß transformation and the derivation of the crystallographic details necessary to specify it. EXPERIMENTAL RESULTS X-ray diffraction and dilatometric data were obtained from samples of a plutonium having a [010] fiber texture. These cylindrical specimens, approximately 1 cm in diam, were prepared by transforming the ß phase to a under the influence of a uniaxially applied compressive load.' The [0l0] direction is parallel to the direction of applied stress; it is also perpendicular to the (010) planes. This correspondence between the plane normal and the direction having the same indices is, in the monoclinic a plutonium structure, restricted solely to this (010)[010] combination. Such a specimen was mounted in an evacuated, elevated temperature specimen holder on an X-ray dif-fractometer so that the diffracting surface was perpendicular to the fiber axis. The a diffraction pattern, Fig. 1, taken at about 115ºC, revealed the predominance of the (020) reflection. This monoclinic, P 21/rn space group yields no (0k0) reflections when k is odd. The temperature was raised slowly to 160°C to effect the complete transformation to the phase; then it was lowered to 120°C so that a diffraction pattern of the ß could be obtained near the a = ß equilibrium temperature for direct comparison with the a at the same temperature. The (3 diffraction pattern, Fig. 2, obtained under these conditions showed a (222) reflection relatively much more intense than in the random pattern. The other reflections appearing with sig-

Jan 1, 1970

By J. H Lightfoot, Stuart E. Buckley

Deep drilling has led to the development of numerous pools which yield products consisting predominantly of natural gas accompanied by high-gravity water-white or slightly straw-colored liquid. Yields of this "condensate" or "distillate," as it is commonly called, vary from traces to over a hundred barrels per million cubic feet of gas. The fact that this liquid exists in the reservoir as an integral part of the gas phase and is formed by condensation attending simultaneous reduction of pressure and temperature after its entry into the well was apparently first recognized about 1932.l The nature of the physical phenomena involved in this condensation was clarified for the petroleum industry in 1933 by a report by Sage, Schaafsma, and Lacey2 of the results of an experimental investigation of the behavior of mixtures of methane and propane. Search of the literature has revealed that the condensation of liquid from gaseous mixtures by isothermal pressure reduction is not a new discovery. Kuenen was led by theoretical considerations to expect such a phenomenon, and in 1892 reported3 the results of experimental verification of his deductions. This was followed by a considerable amount of work on the phase relations of mixtures by Kuenen 4,5,6 and by 0thers,7,8 mostly in European universities. Since 1930 investigators in this country have reported experimental data on the properties and behavior of a number of hydrocarbon systems."' It is now generally known that in the presence of natural gas the solubility in the gas phase of the heavier and normally liquid hydrocarbons increases rapidly with increasing pressure above 500 to 1000 Ib. per sq. in. Thus, at pressures of 2500 Ib. per sq. in. or higher a gas may contain appreciable quantities of hydrocarbons with normal boiling points as high as 6o0°F., which in turn may be condensed from the gas phase by the reduction of their solubility therein attending pressure reduc-tion. The combined effects of pressure and temperature on condensation and vaporiza-tioi of mixtures are most readily visualized by the study of phase diagrams. Since the construction, application, and interpreta-tion of such diagrams have been described fully in readily available literature, 18-20 this paper will not review the theoretical aspects of this subject. While the behavior of gas-distillate sys tems is now clearly understood, at least in a qualitative way, most of the published work deals with the results of laboratory studies of binary systems or of synthetic mixtures of hydrocarbons, and although several systematic investigations of the effects of separator pressure and temperature on the yields of liquid product from gas-distillate wells have been made21,12z it appears that in all cases the limitations have precluded the construction of even approximately complete phase diagrams for naturally occurring systems. There has 2

Jan 1, 1941

By J. H. Lightfoot, Stuart E. Buckley

Deep drilling has led to the development of numerous pools which yield products consisting predominantly of natural gas accompanied by high-gravity water-white or slightly straw-colored liquid. Yields of this "condensate" or "distillate," as it is commonly called, vary from traces to over a hundred barrels per million cubic feet of gas. The fact that this liquid exists in the reservoir as an integral part of the gas phase and is formed by condensation attending simultaneous reduction of pressure and temperature after its entry into the well was apparently first recognized about 1932.l The nature of the physical phenomena involved in this condensation was clarified for the petroleum industry in 1933 by a report by Sage, Schaafsma, and Lacey2 of the results of an experimental investigation of the behavior of mixtures of methane and propane. Search of the literature has revealed that the condensation of liquid from gaseous mixtures by isothermal pressure reduction is not a new discovery. Kuenen was led by theoretical considerations to expect such a phenomenon, and in 1892 reported3 the results of experimental verification of his deductions. This was followed by a considerable amount of work on the phase relations of mixtures by Kuenen 4,5,6 and by 0thers,7,8 mostly in European universities. Since 1930 investigators in this country have reported experimental data on the properties and behavior of a number of hydrocarbon systems."' It is now generally known that in the presence of natural gas the solubility in the gas phase of the heavier and normally liquid hydrocarbons increases rapidly with increasing pressure above 500 to 1000 Ib. per sq. in. Thus, at pressures of 2500 Ib. per sq. in. or higher a gas may contain appreciable quantities of hydrocarbons with normal boiling points as high as 6o0°F., which in turn may be condensed from the gas phase by the reduction of their solubility therein attending pressure reduc-tion. The combined effects of pressure and temperature on condensation and vaporiza-tioi of mixtures are most readily visualized by the study of phase diagrams. Since the construction, application, and interpreta-tion of such diagrams have been described fully in readily available literature, 18-20 this paper will not review the theoretical aspects of this subject. While the behavior of gas-distillate sys tems is now clearly understood, at least in a qualitative way, most of the published work deals with the results of laboratory studies of binary systems or of synthetic mixtures of hydrocarbons, and although several systematic investigations of the effects of separator pressure and temperature on the yields of liquid product from gas-distillate wells have been made21,12z it appears that in all cases the limitations have precluded the construction of even approximately complete phase diagrams for naturally occurring systems. There has 2

Jan 1, 1941

By M. W. Cox, V. F. Hollister

EXPLORATION for metallic mineral deposits is carried on by those special adaptations of methods which the explorer believes will yield most economically or satisfactorily the particular answer sought. In this project the usual methods of geologic observation, recording, and interpretation, when combined with magnetic geophysical methods and geochemical soil sampling, led to disclosures of appreciable zinc mineralization where none was visible in surface exposure. Since 1945 considerable work has been done with geochemical prospecting methods, chiefly in determining the presence and distribution of various elements existing in minor amounts in rocks, soil, vegetation or waters of mineralized areas. Such work, in which the U. S. Geological Survey has taken the lead, finds a ready place in the field repertoire of the exploration geologist as a supplement, not a substitute, for other methods. The Chollet project was carried out in 1951 by the American Smelting & Refining Co. near its Van Stone mine in northern Stevens County, Wash., in the area shown in Fig. 1. The Van Stone mine is located in the Onion Creek drainage of the Selkirk Mountains, midway between the towns of Colville and Northport, Wash., and some twenty airline miles west of the Metaline mining district. Its zinc-lead orebodies, currently yielding about 1000 tpd of ore, occur as bedding replacement deposits in the middle Cambrian Metaline formation near an intrusive granodiorite contact. The target of exploration at the Chollet prospect was a similar geologic environment along the intrusive contact about 5 miles west of the mine. Geographic Setting The Chollet ground covers a north-facing slope at 3000 to 4000-ft elevation. Second-growth jack pine and tamarack with some hemlock and yellow pine make a thick forest cover. A heavy under-forest of alder, willow, and lesser shrubs occupies the draws, see Fig. 2. Grassy slopes appear at higher elevations. The lower slopes are underlain by a thick blanket of glacial till and alluvium so that outcrops are scarce; however, perhaps 50 pct rock exposure prevails at higher elevations. This part of northern Washington annually receives about 25 in. of precipitation, which largely falls as snow in the winter months. Summers are dry with occasional rainy periods. General Geology The Van Stone mine and the Chollet prospect lie along the southern margin of a westerly extending lobe of the Kaniksu batholith, one of the series of granodioritic masses that are intrusive into Cretaceous and older rocks in northern Washington and southern British Columbia. The margin is composed of complexly deformed Paleozoic sediments ranging in age from the lower Cambrian Maitlen phyllite on the east, through middle Cambrian Metaline formation (limestone and dolomite), to Ordovician Ledbetter slate on the west. In general the formations strike N10 to 50E and dip steeply northwestward, although dip reversals and minor folding occur. This general rock distribution is shown on Fig. 3. In this area the Metaline formation, which is the host rock for mineralization, appears to be of about 4000-ft thickness that can be conveniently divided into the same three units defined by Park and Cannon' for the Metaline area. The basal part consists of 1000 ft of interbedded white limestone, argillaceous limestone, and gray silty argillite. The middle part, approximately 1500 ft thick, consists of fine-grained black, gray, and white dolomite. This unit also contains minor interbedded limestone. The upper part is a gray massive limestone about 1500 ft thick that grades upward into slaty limestone and slate capped locally by a thin black jas-peroidal dolomite which is either the uppermost member of the Metaline formation or the basal member of the overlying Ledbetter (Ordovician)

Jan 1, 1956

By F. J. Budin

Steel supports are increasingly used in metal mines for junctions, chambers, and other wide openings and for semi-permanent areas such as haulageways, shaft stations, and pump rooms. Steel lasts longer-especially in wet mines and where foul air is present-and is procurable in different sizes that will carry heavier loads than any timber of equivalent cross section. The chief advantage of steel supports is that less excavation is needed than with timber support of the same strength, so that faster progress can be made. Since there is no possible way to calculate the exact weight on supports, sizes must be chosen by experience. Any adjustment and cutting of steel supports underground would be costly and time-consuming, and it is therefore advisable to cut sets beforehand at the surface workshops. This requires standardization of sets. All these problems have been recognized at Bawdwin Mines, Burma, where mining is difficult, slow, and very expensive. The lead-silver ore is very brittle, with hanging and footwall rock of unconsolidated rhyolite tuff. During the rainy season from May to October water penetrates into the mine, and where soft rock is present disintegration into a loose mass around openings can be expected. For this reason heavy 10x10-in. timber caps break quickly in drifts and crosscuts, and timber rots in a very short time. An average increase of 50 pct in both maintenance work and costs could not be avoided.

Jan 3, 1960

By E. W. Filer, L. S. Darker

ONE of the primary purposes of this investigation was to determine how far blast-furnace metal and slag depart from equilibrium, particularly with respect to sulphur distribution. In studying the equilibrium between blast-furnace metal and slag, there are two approaches that can be used. One method is to use synthetic slags, as was done by Hatch and Chipman;' the other is to equilibrate the metal and slag from the blast furnace by remelting in the laboratory. In the set of experiments here reported, metal and slag tapped simultaneously from the same blast furnace were used for all the runs. The experiments were divided into two groups: 1—a time series at each of three different temperatures to determine the t.ime required for metal and slag to equilibrate in various respects under the experimental conditions of remelting, and 2—an addition series to determine the effect of additions to the slag on the equilibrium between the metal and slag. An atmosphere of carbon monoxide was used to simulate blastfurnace conditions. The furnace used for this investigation was a vertically mounted tubular Globar type with two concentric porcelain tubes inside the heating element. The control couple was located between the two porcelain tubes. The carbon monoxide atmosphere was introduced through a mercury seal at the bottom of the inner tube. On top, a glass head (with ground joint) provided access for samples and a long outlet tube prevented air from sucking back into the furnace. The charge used was iron 6 g, slag 5 g for the time series, or iron 9 g, slag 7 % g for the addition series. This slag-to-metal ratio of 0.83 approximates the average for blast-furnace practice, which commonly ranges from about 0.6 to 1.1. A crucible of AUC graphite containing the above charge was suspended by a molybdenum wire in the head and, after flush, was lowered to the center of the furnace as shown in Fig. 1. The cylindrical crucible was 2 in. long x % in. OD. The furnace was held within &3"C of the desired temperature for all the runs. The temperature was checked after the end of each run by flushing the inner tube with air and placing a platinum-platinum-10 pct rhodium thermocouple in the position previously occupied by the crucible; the temperature of the majority of the runs was much closer than the deviation specified above. The couple was checked against a standard couple which had been calibrated at the gold and palladium points, and against a Bureau of Standards couple. The carbon monoxide atmosphere was prepared by passing COz over granular graphite at about 1200°C. It was purified by bubbling through a 30 pct aqueous solution of potassium hydroxide and passing through ascarite and phosphorus pentoxide. The train and connections were all glass except for a few butt joints where rubber tubing was used for flexibility. The rate of gas flow was 25 to 40 cc per min. As atmospheric pressure prevailed in the furnace, the pressure of carbon monoxide was only slightly higher than the partial pressure thereof in the bosh and hearth zones of a blast furnace—by virtue of the elevated total pressure therein. Simultaneous samples of blast-furnace metal and slag were taken for these remelting experiments. The composition of each is given in the first line of Table I. There is considerable uncertainty as to the significant temperature in a blast furnace at which to compare experimental results. This uncertainty arises not only from lack of temperature measurements in the furnace, but also from lack of knowledge of the zone where the slag-metal reactions occur. (Do they occur principally at the slag-metal interface in the crucible, or as the metal is descending through the slag, or even higher as slag and metal are splashing over the coke?) The known temperatures are those of the metal at cast, which averages about 2600°F, and of the cast or flush slag, which is usually about 100°F hotter. To bridge this uncertainty, remelting temperatures were chosen as 1400°, 1500" (2732°F), and 1600°C. For the time series the duration of remelt was 1, 2, 4, 8, 17, or 66 hr; crucible and contents were quenched in brine. The addition series were quenched by rapidly transferring the crucible and contents from the furnace to a close-fitting copper "mold." Of incidental interest here is the fact that the slag wet the crucible

Jan 1, 1953

R. H. Sweetser.—Mr. Reinartz spoke of slag containing 18 per cent FeO. I think he expressed the iron as oxide. I should like to ask at what point, in iron contents, it is usual practice to quit sending that open-hearth slag to the blast furnace? L. F. Reinartz.—NO problem is involved in disposing of open-hearth slag to our blast furnaces because, on account of the grades of iron and steel made by our company, the iron oxide in the slag is sufficiently high to make it very acceptable to the blast-furnace operator. I have been told that if the total iron oxide in the slag is under 18 to 20 per cent, it is not economical to use such slag in a blast furnace. J. T. Mackenzie,* Birmingham, A1a.—Mr. Reinartz mentioned sulfate in the limestone. I wonder if he did not use the wrong word. We always have assumed that the sulfate sulfur is practically harmless. Most limestone carries some pyrite (sulfide sulfur) which we thought was what gave the sulfur pick-up. L. F. Reinartz.—I have had no experience, personally, in the use of limestone high in sulfates. I have been told, on several occasions, by other open-hearth men, that the sulfates will be reduced and increase the sulfur content of the metal. We have never found any pyrite in our limestone. A. Hayes,† Middletown, Ohio.—I should think that sulfates would be readily reducible to sulfites, and possibly to sulfides at various distances through the slag layer, from the top down to the interface between the bath and the slag, because reducing conditions are certainly sufficiently strong next to the bath in the slag to reduce sulfates to sulfides. A. L. Feild,‡ Baltimore, Md.—What is Mr. Reinartz's theory as to the effect of silica in the slag on the iron oxide content of the metal? L. F. Reinartz.—I have no particular theory as to the effect of silica in the slag on the iron oxide content of the metal. I know from practical experience that it does have an influence on reduction of iron oxide in the metal. We know that if the silicon content of the charge, and, therefore, the silica of the slag is increased, the iron oxide in the slag will be decreased. Based on Dr. Herty's work, we assume that the iron oxide is correspondingly decreased in the metal. C. H. Herty, JR.,§ Bethlehem, Pa.—In the theory of iron oxide control, we have tackled the matter from the physical standpoint, rather than the chemical standpoint or from the slag itself, and we worked on the basis that the change in iron oxide content in a slag—that is, whether the slag increases or decreases in iron oxide—is due to the simple fact that if you put more iron oxide into the slag from the gas than you put oxygen from the slag into the metal, the slag must increase in iron oxide;

Jan 1, 1935

R. H. Sweetser.—Mr. Reinartz spoke of slag containing 18 per cent FeO. I think he expressed the iron as oxide. I should like to ask at what point, in iron contents, it is usual practice to quit sending that open-hearth slag to the blast furnace? L. F. Reinartz.—NO problem is involved in disposing of open-hearth slag to our blast furnaces because, on account of the grades of iron and steel made by our company, the iron oxide in the slag is sufficiently high to make it very acceptable to the blast-furnace operator. I have been told that if the total iron oxide in the slag is under 18 to 20 per cent, it is not economical to use such slag in a blast furnace. J. T. Mackenzie,* Birmingham, A1a.—Mr. Reinartz mentioned sulfate in the limestone. I wonder if he did not use the wrong word. We always have assumed that the sulfate sulfur is practically harmless. Most limestone carries some pyrite (sulfide sulfur) which we thought was what gave the sulfur pick-up. L. F. Reinartz.—I have had no experience, personally, in the use of limestone high in sulfates. I have been told, on several occasions, by other open-hearth men, that the sulfates will be reduced and increase the sulfur content of the metal. We have never found any pyrite in our limestone. A. Hayes,† Middletown, Ohio.—I should think that sulfates would be readily reducible to sulfites, and possibly to sulfides at various distances through the slag layer, from the top down to the interface between the bath and the slag, because reducing conditions are certainly sufficiently strong next to the bath in the slag to reduce sulfates to sulfides. A. L. Feild,‡ Baltimore, Md.—What is Mr. Reinartz's theory as to the effect of silica in the slag on the iron oxide content of the metal? L. F. Reinartz.—I have no particular theory as to the effect of silica in the slag on the iron oxide content of the metal. I know from practical experience that it does have an influence on reduction of iron oxide in the metal. We know that if the silicon content of the charge, and, therefore, the silica of the slag is increased, the iron oxide in the slag will be decreased. Based on Dr. Herty's work, we assume that the iron oxide is correspondingly decreased in the metal. C. H. Herty, JR.,§ Bethlehem, Pa.—In the theory of iron oxide control, we have tackled the matter from the physical standpoint, rather than the chemical standpoint or from the slag itself, and we worked on the basis that the change in iron oxide content in a slag—that is, whether the slag increases or decreases in iron oxide—is due to the simple fact that if you put more iron oxide into the slag from the gas than you put oxygen from the slag into the metal, the slag must increase in iron oxide;

Jan 1, 1935

By GUY B. HUNNER

THOSE magnetite ore bodies comprising the Clifton Mines are situated in the south central part of St. Lawrence County, New York, on the western slope of the Adirondack Mountains. The topography is made up of gently rolling hills densely wooded with second-growth maple, birch, and hemlock. Drainage is north and west to the St. Lawrence River.

Jan 1, 1943

By J. C. Shyne, T. D. Gulden

The steady-state creep behavior, in compression, of indium containing a dispersion of atomized glass particles was studzed over a range of temperature, stress, and composition. The observed behavior was not consistent with a simple model of dislocation climb over dispersed particles. From room temperature to about 100°C the temperature dependence could be described by an activation energy about one and a half times that of self-dijfusion in indium while at higher temperatures a much higher ternperature dependence was observed. THE value of dispersion-hardened and precipitation-hardened alloys has long been recognized. The mechanism of hardening, however, is not completely understood, especially at elevated temperatures where dispersed particles increase creep resistance. Following the suggestion of Schoeck1 that the rate of creep in dispersion-hardened materials is controlled by dislocation climb over second-phase particles, Ansel and weertman2 derived steady-state creep equations for dispersion-hardened materials. Their derivation was based on dislocation climb over non-deformable spherical particles in a metallic matrix. For low stresses they predicted a linear relation between applied stress and steady-state creep rate. For stresses large enough to cause dislocations to pinch off around the precipitate particles, the theoretical creep rate was shown to be proportional to the fourth power of stress. For very high stresses an exponential stress dependence was predicted. In all cases the theoretical creep rate is linearly proportional to the diffusion coefficient. This provided the primary temperature-dependent factor. Subsequently, Ansel and Lenel3 reported some experimental data on SAP, a composite of aluminum and aluminum oxide, that was in good qualitative agreement with the above theories. Their experimental creep rates, however, were four orders of magnitude less than the theory predicts. This was attributed to a low density of active dislocation sources in the material; somehow the dispersed particles inactivated the dislocation sources instead of merely interferring with dislocation motion. Meyers and sherby4 have recently reported on the creep behavior of SAP. Their results were inconsistent with a simple dispersion-strengthening model and led them to conclude that a continuous network of oxide controls the high-temperature mechanical characteristics of SAP. Because of the rather complex mechanical behavior of SAP and the lack of agreement about the morphology of its oxide phase, it appeared desirable to study the creep of a dispersion-strengthened material of controlled morphology. For the present work a dispersion of spherical glass particles imbedded in a matrix of indium was chosen. The microstructure of this material was similar to the idealized uniform dispersion of hard spheres in a deforming matrix assumed by Ansel and Weertman in their theoretical treatment. SPECIMEN PREPARATION For experimental convenience, it was decided to use a low melting-point metal in this investigation. It was necessary that the metal not be oxidized readily up to its melting temperature and that it wet the second-phase particles. It was desired that the material chosen for the dispersed phase be available as a fine powder with closely controlled size and shape. The material chosen to satisfy these requirements consisted of a matrix of indium metal containing a dispersion of atomized particles of a soft soda-lime-silica glass ranging from 5 to 30 µ in diam. The glass particles had a highly regular spherical shape. The composite was made by stirring the glass powder into liquid indium maintained at a temperature just above the melting point of indium, 156°C. The creep specimens were prepared by a hot pressing operation. Five to ten g of the mixture were placed in a steel die and pressed at 125°C for 5 min under a pressure of 30,000 psi. The resulting specimens were cylinders about 3/8 in. in diam and ranged from 0.4 to 0.7 in. high. By following this procedure a uniform dispersion was obtained in the creep specimens. Typical microstructures of specimens containing twenty and forty volume percent glass powder are shown in Figs. 1 and 2. Unfortunately, grain size could not be determined by the metallo-graphic techniques used. CREEP TESTING PROCEDURE Creep tests were performed in compression under constant stress. The specimens were placed in

Jan 1, 1963

By A. M. Rowe

A considerable quantity of experimental hydrocarbon K-factor data has been correlated as a function of component identity, temperature, pressure and convergence pressure. To utilize these correlations effectively, convergence pressure must be determined accurately, particularly for volatile mixtures near their critical states. This paper presents phase diagrams that illustrate physically the meaning of convergence pressure. A new method, referred to hereafter as the "critical composition method", will be outlined for calculating convergence pressure. An example calculation has been included to illustrate how to use this new technique. INTRODUCTION The principle of hydrocarbon phase composition calculations as applied to such diverse problems as optimizing separator performance or predicting fluid compositions at various stages of reservoir depletion is the same. Usually, temperature, pressure and the numbers of moles of the various components of the fluid contained in a given volume are known. Questions answered by the phase calculation are what fraction of the total mass of fluid exists in each of the equilibrium phases, and what are the mole fractions of the various components in the two phases? To answer these questions the Natural Gasoline Supplymen's Assoc. (NGSMA) has correlated a considerable quantity of K-factor data as a function of temperature, pressure, component identity and convergence pressure.l To use these correlations to obtain the best answers possible, one must be able to calculate the convergence pressure. This is particularly true for over-all fluid compositions in the neighborhood of the critical state. STATEMENT OF THEORY Use of convergence pressure as a correlating parameter is based on a postulate similar to the law of corresponding states used in correlating PVT data of hydrocarbon gases. This postulate, which proposes convergence pressure as a correlating parameter, has been stated as follows: "The equilibrium vaporization constant for one component in a complex system is the same as the equilibrium constant at the same temperature and pressure for the same number or kind of components, providing only that the convergence pressures of the two systems are exactly the same at the same temperature and that the components are of the same homologous series".2 This law, as with all laws of physics, cannot be proven theoretically. It can only be justified by experimental data supporting its premises. Arguments have been made that this law violates Gibb's phase rule. For example, consider a four-component system. By Gibb's phase rule, which is thermodynamically rigorous, f = c — P + 2 =4, for a four-component, two-phase system. Thus, four independent intensive variables must be specified to establish completely all the intensive variables of the equilibrium phases. On the other hand, according to convergence pressure theory, only three variables need be specified for any mixture containing four different components. These variables are temperature, pressure and convergence pressure. Thus, the two laws appear to be in conflict. However, the convergence pressure postulate is more restrictive than Gibb's phase rule. It applies only to mixtures of the same homologous series. Hence, these two concepts are not in disagreement. PHASE DIAGRAMS DESCRIBING CONVERGENCE PRESSURE This paper presents phase diagrams grading from the simple two-component system to the more complex four-component system to illustrate convergence pressure. A less abstract definition of convergence pressure will be stated that is

By M. I. Sherman, J. D. H. Strickland

USE of a hydrometallurgical approach to the oxidation of sulfide ores and extraction of metals therefrom may have advantages over the more common smelting techniques when a low grade deposit is difficult to concentrate or the subsequent separation of metals, coexisting in the ore, is laborious by any known smelting operation. For economic reasons, the most promising oxidants are either atmospheric oxygen or electric power. The use of oxygen, or air under pressure, has recently been revised. Pyrrhotite has been converted to iron oxide and elementary sulfur' and a variety of sulfides have been treated by Forward and co-workers.2-4 Generally sulfate is the end form of the sulfur but with galena in an acid medium, elementary sulfur can be formed." For economic reasons chlorine and ferric iron salts are about the only possible alternatives to the atmosphere as oxidizing agents for base metal sulfides. If aqueous solutions of chlorine or ferric iron are employed, the reduction products can be oxidized electrolytically in situ and used again, thus acting as catalysts for electric power as oxidant. The use of ferric salts for this purpose is established hydrometallurgical practicea but, although chlorine gas has been employed in the dry state at an elevated temperature, its use in aqueous solution at or near room temperature has not found favor. The reaction of chlorine water with the soluble sulfide ion has been studied by several workers,7-9 and both sulfate and elemental sulfur are found as end products, the latter being favored by the presence of a low concentration of oxidant relative to that of sulfide in solutions of about pH 9 to 10. Of direct bearing on the work in hand are an early American patent" and a recent Austrian patent." The former advocates stirring powdered ore with an aqueous solution of ferric chloride chlorine oxides and chlorine. In the latter it is claimed that both metal and sulfur can be obtained by electrolysis, in a diaphragm cell, of a metal ore slurry in brine. Details in these patents are scant and no data or explanation is given for the mechanism of the reaction which, in the Austrian work, is attributed to the (unlikely) action of nascent chlorine at the anode surface. No mention is made of possible differences in behaviour between various ores. Apparatus A complication encountered when working with chlorine water is that a serious loss of chlorine occurs by gas partitioning unless an enclosed system is used and any air space in the apparatus is kept very small and constant. Arrangements were made, therefore, to take out samples for analysis without letting air into the system to replace the liquid removed. For convenience in studying a heterogeneous reaction the apparatus was so designed that a reproducible controlled stirring rate could be maintained and the ratio of surface area of ore to volume of solution was approximately constant throughout any experiment. The apparatus used is shown in Fig. 1. The ground ore was placed in the horizontal cylindrical vessel, A, of about 1 liter capacity, heated by a constant temperature circulating bath pumping water through the concentric jacket, B. By adding chro-mate to this water, an ultraviolet radiation filter effectively surrounded the reaction vessel, greatly reducing any possible photochemical decomposition of chlorine solutions. Stirring was effected by glass paddles, C, attached by an axle to a magnet which was rotated by another powerful Alnico magnet, D, outside the glass end, this magnet being itself rotated by an electric motor electronically controlled to constant speed. Speed could be varied from about 150 to 900 rpm and was measured and held to within 1 pct of a given value. The end of the reaction vessel remote from the stirring magnet was closed by another one-ended glass cylinder, E, connected by thin polyethylene bellows, F, clamped by screw clamps and watertight rubber gaskets to the main vessel. Through E, a glass electrode and calomel electrode projected into the solution and a hypodermic syringe pierced a small bung and allowed acid or alkaline to be added to maintain a constant pH. By pushing the fully extended bellows until the two cylinders touched, from 50 to 100 ml of solution could be forced out through a sintered disk into the three-way tap system, G, either to waste (for flushing purposes) or up into a 10 ml burette where the solution could subsequently be measured out for analysis. The ore samples were introduced at H, the tube being stoppered by a thermometer of —1 to +52ºC range, graduated to 0.1°C intervals. To prevent ore from being ground in the end bearings of the stirrer these bearings were pro-

Jan 1, 1958

By D. Moskowitz

IN the course of a general investigation of boride systems, sponsored by the Office of Naval Research, various vanadium boride powders of relatively good purity were prepared which could be used for a determination of the phases present. The X-ray pattern of one of these lots showed, in addition to the known VB1 and VB22 phases, an additional phase, almost certainly of composition V3B4, isomorphous with Cr3B4, Cb3B4, Ta3B4, and Mn3B,. Its pattern fitted in well with the indices worked out by Kiessling for Mr3B4.3 The unit cell for this new compound is orthorhombic, with the dimensions a = 3.030A, b = 13.18A, c = 2.986A7 V=119.2A.' Table I lists the X-ray diffraction data for V.3,.

Jan 1, 1957

By R. G. Ward, A. E. El-Mehairy

A technique was developed to calculate the density of liquid metals from the profile of a weighed levitated drop obtained by emitted light photography and calibration. The density of liquid copper was determined over the temperature range 1370" to 2100°K and expressed with the equation: The molar volumes and thermal coefficients of expansion are calculated. Copper, upon melting, was found to expand 3.34 pct. A knowledge of the density of liquid metals is essential as it is a parameter appearing in most theories of the liquid state. The liquid density is also necessary for the calculation of the commercially important contraction occurring on solidification. Unfortunately good density values are rarely available and the present work was undertaken to establish a new method of density determination free from the limitations of the existing methods. For liquid metals with high melting points, the variation and the limited number of density values reported in the literature have been caused primarily by difficulties in technique, a matter which has been adequately discussed by Urbain.' In all the methods used for measuring the density of the high-melting liquid metals there are sources of error, and corrections have to be made. For example, in the method of balanced columns, the formation of gas bubbles in one or both arms was a great source of error. In the pyknometer3 and immersed-sinker methods, corrections of certain volumes for thermal expansion to the operating temperature exceed 4 pct. In the maximum-bubble method5 a correction for the thermal expansion of the bubble-tube is used (about 1.6 pct); a second correction takes into account the change in the volume of liquid displaced by the bubble-tube (about 3.5 pct). Another method used is based on the shape of a drop of liquid, at rest on an inert refractory plaque, obtained photographically or radiographi-cally. The volume is calculated from the shape, which is sensitive to the surface tension and supporting material, by some intricate empirical relation. The drop contour changes with 90 deg rotation of the support.7 The application of all methods is limited by reaction between liquid metal and the apparatus. The successful stabilization of a mass of liquid metal during levitation melting8 afforded a technique for measuring the density of liquid metals out of contact with solid materials. The technique was developed by using copper as the density of liquid copper has already been studied extensively, thus allowing comparison with the new method. It consists of calculating the volume from the dimensioned profile of the levitated drop obtained by emitted-light photography and careful calibration. The molten egg-shaped drop spins around the magnetic axis of the coil (lined vertically) at a speed which seems to increase with increasing temperature. The method does not involve corrections and the experimental setup allows the use of vacuum or special atmospheres. The maximum operating temperature is limited by excessive evaporation of metal from the droplet. EXPERIMENTAL Levitating System. A stabilizing ring was used in conjunction with a 3-turn levitating coil energized by a 450-kc per sec, 10-kw Toccotron with a high current-low voltage output stabilized to f 1 pet.' APyrex glass tube with a Pyrex Optical flat window inserted through the coil and ring allowed the use of special atmospheres during levitation melting, as shown in Fig. 1. Optical System. Fig. 1 shows the optical arrangement used to photograph the profiles of the drop, parallel and perpendicular to the vertical spinning axis, simultaneously on the same frame of a high-speed 35-mm film. The optical system was adjusted to avoid any distortion of the profiles and to ensure that both profiles are in focus. The length of path from object to objective was about 30 cm, and a magnification factor close to 1 was obtained with the single-lens reflex-camera system. Temperature Measurement and Control. In operation, the specimen temperature was constant to 5 C for a fixed power input to the levitating coil and fixed rate of gas flow through the tube. The temperature was measured by an automatic two-color pyrometer (Coloratio) checked at the melting

Jan 1, 1963

By Leo P. Tarasov

Magnetic torque studies of ferromagnetic single crystals have been carried out in a number of laboratories during the last decade&apos;s2 and some work has been reported on polycrystalline material showing preferred orientation. Goss3 used the method extensively in developing electrical sheet with desirable magnetic properties, but he used it as a control rather than as a means of studying the texture. Bozorth4 made a quantitative correlation of a torque curve he obtained from some cold-rolled iron with the texture as determined from X-rays, but did not extend his studies beyond the one specimen. Other studies, which have been reported from time to time2,5 have also been incomplete in the sense that no effort was made to study a whole series of samples, differing only in degree of cold reduction or in the annealing temperature, in order to ascertain the effect of such treatments on the texture as revealed by torque measurements. It is the purpose of this investigation to make such a study, mainly in order to see how useful the method can be made when used under favorable circumstances and to find what kind of a correlation can be expected between magnetic and X-ray studies of texture. Before proceeding further, it is desirable to say a little about single crystals, so as to make clear the concepts involved in magnetic torque measurements. Magnetic Torque Method It is fairly well known nowadays that single crystals of ferromagnetic substances have directions of easy magnetization and of hard magnetization. In Fig. 1 are reproduced typical magnetization curves for a single crystal of iron, which show that in a < 100 > direction saturation occurs at low fields compared to those required to saturate the same crystal in a <110> or a <111> direction. (The magnetization intensity I is defined by the equation B = H + 4pI.) At fields high enough to

Jan 1, 1939

By Leo P. Tarasov

Magnetic torque studies of ferromagnetic single crystals have been carried out in a number of laboratories during the last decade&apos;s2 and some work has been reported on polycrystalline material showing preferred orientation. Goss3 used the method extensively in developing electrical sheet with desirable magnetic properties, but he used it as a control rather than as a means of studying the texture. Bozorth4 made a quantitative correlation of a torque curve he obtained from some cold-rolled iron with the texture as determined from X-rays, but did not extend his studies beyond the one specimen. Other studies, which have been reported from time to time2,5 have also been incomplete in the sense that no effort was made to study a whole series of samples, differing only in degree of cold reduction or in the annealing temperature, in order to ascertain the effect of such treatments on the texture as revealed by torque measurements. It is the purpose of this investigation to make such a study, mainly in order to see how useful the method can be made when used under favorable circumstances and to find what kind of a correlation can be expected between magnetic and X-ray studies of texture. Before proceeding further, it is desirable to say a little about single crystals, so as to make clear the concepts involved in magnetic torque measurements. Magnetic Torque Method It is fairly well known nowadays that single crystals of ferromagnetic substances have directions of easy magnetization and of hard magnetization. In Fig. 1 are reproduced typical magnetization curves for a single crystal of iron, which show that in a < 100 > direction saturation occurs at low fields compared to those required to saturate the same crystal in a <110> or a <111> direction. (The magnetization intensity I is defined by the equation B = H + 4pI.) At fields high enough to

Jan 1, 1939

By Walter W. Bradley

Barite, or barytes as it is sometimes called, belongs to one of the lesser groups of nonmetallic minerals, of which 15 to 20 varieties are mined in California in amounts varying in value from a few hundred to almost half a million dollars annually. Commercial production of barite in California, according to the records of the State Mining Bureau (now Division of Mines), began in the year 1910 with shipments totaling 860 tons, valued at $5640 f.0.b. rail shipping point. With the exception of the years 1924 and 1925, when no shipments were made, the output has varied, reaching a maximum of 17,993 tons, worth $90,617, in 1927. The 1928 output was 13,406 tons, worth $55,888 f.0.b. rail shipping point, bringing the state total to the end of 1928 to 59,972 tons, valued at $313,930. Consumption of BaRitE in United States Crude barite sold or used by producers in the United States for the year 1927 amounted to 248,219 tons, valued at $1,594,423, according to the U. S. Bureau of Mines.l In addition, there was imported, principally from Germany, a total of 70,274 tons, valued at $253,284. Manufactured products from these tonnages combined were distributed in 1927 (the latest year for which figures are at present available) as follows: ground barite, 57,658 tons; lithopone, 174,083 tons; barium chemicals (including carbonate, 4,960 tons; chloride, 3,541 tons; binoxide and sulfate or blanc Jixe combined, 13,354 tons). Missouri accounts for nearly 50 per cent of the domestic crude barite, followed by Georgia and Tennessee, with lesser amounts from Arizona, California, Nevada, South Carolina, and Virginia. Occurrence and Uses of Babite2 Barite, also called "heavy spar" and "tiff," is theoretically composed of 65.7 per cent of barium oxide (BaO) and 34.3 per cent of sulfur

Jan 1, 1931

By Henry A. Stiff, and Lawrence E. Davis

The authors previously presented a method for predicting the tendency of oil field waters to deposit calcium sulfate. The present paper gives a similar method for calcium carbonate. Methods for predicting calcium carbonate scaling tendencies in fresh waters have been available for some time, but these could not be used for brines. By experimentally deriving the value of the K term in the Langelier equation, a method has been developed which applies to waters of high salt content. A statistical study is included which shows that the experimentally derived values of K are in good agreement with actual conditions. Several applications of the final equation to production practice are given. INTRODUCTION The authors previously presented a method for predicting the formation of calcium sulfate scale in oil field waters.&apos; Although calcium sulfate deposition is important in production operations, the majority of scale problems involve calcium carbonate. The present communication discusses a method by which the formation of this type of scale in oil field waters can be predicted. Calcium carbonate precipitation is caused by a shift toward carbonate in the carbonate-bicarbonate-carbon dioxide equilibrium. When equilibrium shifts in the other direction, the precipitate goes back into solution. Since there is usually considerable delay between the establishment of an equilibrium and the precipitation or solution of calcium carbonate, unstable conditions exist in which a water will precipitate or dissolve calcium carbonate on standing. Tillmans? who did a major part of the early work on carbonate scaling, pointed out that the condition of equilibrium not only indicates the tendency of a water to scale but also is an indication of its corrosive properties. Previously precipitated calcium carbonate combines with iron to form a dense crust which inhibits corrosion. If the water tends to dissolve carbonate, the scale becomes porous, and electrolytic corrosion takes place. Tillmans1 work was extended by several investigators until in 1934 Langeliers developed an equation setting forth the conditions of carbonate equilibrium. By the use of this equation the pH of a water at equilibrium can be calculated. If the actual pH is higher than the calculated pH, the water has a tendency to form scale. If it is lower. the water has a tendency to be corrosive. Langelier&apos;s equation can be expressed in a simple form as follows: SI = pH-pCa-pA lk-K where: SI is the stability index. A positive index indicates scale formation. A negative index indicates corrosion. pH is the pH of the water sample, as actually determined. pCa is the negative logarithm of the calcium concentration. pAlk is the negative logarithm of the total alkalinity. K is a constant, the value of which depends on the total salt concentration and the temperature. This equation has been shown to apply to waters with totaI solid concentrations as high as 4.000 ppm. In fact, control of fresh water treatment by means of this equation has been standard text-book practice for a number of years. Nomographs have been worked out so that the stability index of a fresh water sample can be determined in a matter of minutes. Most oil field waters, however, contain well over 4,000 ppm of salts and for this reason the usual application of Langelier&apos;s equation can not be made. By an empirical method we have extended the application of the Langelier equation to waters of high salt concentration. By the use of this equation the tendency of oil field waters to deposit calcium carbonate can be predicted.

Jan 1, 1952

By N. I. Fisher, J. Shepherd

A rapid method of determining natural fracture trends in collieries has been developed. The method will yield information that is precise enough to permit fracture domain boundaries to be delineated in a coal seam. Instead of a survey of cleat trends in a colliery taking several man-weeks or even man-months, a reconnaissance survey can be carried out in only a few man-days. At each of a sequence of sampling sites along a traverse, five measurements of trend are recorded for each set of fracture directions. A sequential plot of the medians of each fracture set is then made manually underground or by a computer in the mine office. Changes in fracture pattern can be detected easily in colliery development work if a geologist visits advancing faces regularly, and forecasts can be made about the likelihood of forthcoming faults and dykes. A full description of this method is given in Shepherd and Fisher (1981). The concept of mapping fractures rapidly in a colliery is based on using a geological traverse (Compton, 1962), along which observations can be made at chosen, regular intervals. The technique has been widely used for surface mapping across outcrops and in follow-up work in photogeological studies (Hepworth and Kennerley, 1970). In these cases, the geologist surveys the traverse line as mapping proceeds. In a colliery, however, ready-made traverse lines already exist in panels and along main roadways, often in several directions. It is thus possible to traverse a colliery in different directions and record the fracture trends at intervals, generating a reconnaissance fracture map. This can also be done on a continuing basis as mine development takes place. Generally, a sampling traverse should be longer than 0.5 km with sampling sites at relatively close-spaced intervals along the traverse. For example, in room-and-pillar mines pillars are commonly formed on 40-m centers and the sampling sites can then be arranged at 20-m intervals [(Fig. 1)]. The sites might have to be closer together for mines known to have bad mining conditions. The predominant fracture trend is normally the face cleat and the subordinate trend is the butt cleat (McCulloch et al.. 1974). Various changes can occur in the cleat or joint pattern: the face and butt sets may disappear or an entirely new set or sets may appear. Therefore, it is best to record all prominent fracture sets. Sometimes there is only one; in other cases there may be as many as three or more. An odd number of measurements of each fracture set are made (generally five or more) to enable the median value to be determined easily. The median value can be plotted underground using graph paper or a computer plot can be made in the laboratory or mine office [(Fig. 2)]. The sequential linked median (SLIME) plot draws the median trend for each sampling site as a unit line segment. The segments from successive sampling sites can be connected together to form a long chain [(Fig. 2A)]. The needle plot, on the other hand, draws a straight line to represent the traverse and then plots out the median trend for each sampling site [(Fig. 2B)]. The SLIME plot is better for visual display, as it highlights small irregularities and gross changes in trend. However, some work is required to relate the individual segments to their site location along a traverse. In this respect, the needle plot is more convenient because each segment -can be plotted-at a point corresponding to its location. Also, there is precise match-up if needle plots of face and butt cleat are compared. A description and listing of the SLIME program is given by White et al. (1981). An example of the use of this method is given for Wallsend Borehole colliery in New South Wales (Australia) [(Fig. 2)], where domains II and IV are associated with mining hazards. Domain II is coincident with a normal fault of 2.6-m throw, and domain IV with a basic dyke 12 m thick. These hazards were approached driving in a southwesterly direction, and a pronounced change in trend of the cleat to a northwesterly direction occurred at a distance of approximately 45 m from each one. The northwestern joint trend is parallel to that of the dyke and fault, and it occurs at a higher frequency close to these structures. The association of a particular joint set with faults has been found elsewhere (Shepherd and Creasey, 1979). The two minor cleat direction changes within domain V are narrow joint zones that are less than 5 m wide. The fracture trends derived from a SLIME traverse can be verified by collecting larger quantities of data at selected sites, as shown in the balloon density (rose) plots depicted in [Fig. 2C]. We are grateful for the financial support provided by Thiess Bros. Pty. Ltd. and the National Energy Research, Development, and Demonstration Program administered by the Commonwealth Department of National Development and Energy. R.W. Miller Holdings Ltd. and Thiess Bros. Pty. Ltd. are thanked for their permission to publish data from their collieries.

Jan 1, 1982