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By J. D. Verhoeven

In the past 15 years a considerable amount of experimental and theoretical work has been done concerning the onset of convection in liquids as a result of interm1 density gradients. This work, which has been doue in many different fields, is reviewed here and extended slightly to give a rrlore quantitative understanding to the probletrz of conzection in liquid metal dlffusion experinletzts. In liquid metal systems the capillary reservoir technique is currently used, almost exclusively, to measure diffusion coefficients. In this technique it is necessary that the liquid be stagnant in order to avoid mixing by means of convection currents. Convective mixing may result from: 1) convection produced as a result of the initial immersion of the capillary; 2) convection produced in the region of the capillary mouth as the result of the stirring frequency used to avoid solute buildup in the reservoir near the capillary mouth; 3) convection produced during solidification as a result of the volume change; and 4) convection produced as a result of local density differences within the liquid in the capillary. The first three types of convection have been discussed elsewhere1-a and are only mentioned for completeness here. This work is concerned only with the fourth type of convection. Local density differences will arise within the liquid as a result of either a temperature gradient or a concentration gradient. It is usually, but not always, recognized by those employing the capillary reservoir technique that the top of the capillary should be kept slightly hotter than the bottom and that the light element should be made to migrate downward in order to avoid convection. In the past 15 years a considerable amount of work, both theoretical and experimental, has been done in a number of different fields which bear on this problem. This work is reviewed here and extended slightly in an effort to give a more quantitative understanding of the convective motion produced in vertical capillaries by local density differences. The Stokes-Navier equations for an incompressible fluid of constant viscosity in a gravitational field may be written as: %L + (v?)v = - ?£ + Wv - g£ [1] where F is the velocity, t the time, P the pressure, p the density, v the kinematic viscosity, g the gravitational acceleration, and k a unit vector in the vertical direction. A successful diffusion experiment requires the liquid to be motionless, and under this condition Eq. [I] becomes: where a is the thermal expansion coefficient [a =-(l/po)(dp/d)], a' is a solute expansion coefficient [a' = -(l/po)(dp/d)], and the solute is taken as that component which makes a' a positive number. Combining with Eq. [3] the following restriction is obtained: Since there is no fixed relation between VT and VC in a binary diffusion experiment, Eq. [5] shows that the condition of fluid motionlessness requires both the temperature gradient and the concentration gradient to be vertically directed. Given this condition of a density gradient in the vertical direction only, it is obvious that, as this vertical density gradient increases from negative to positive values, the motionless liquid will eventually become unstable and convective movement will begin. The classical treatment of this type of instability problem was given by aleih' in 1916 for the case of a thin fluid film of infinite horizontal extent; and a very comprehensive text has recently been written on the subject by handrasekhar.' It is found that convective motion does not begin until a dimensionless number involving the density gradient exceeds a certain critical value. This dimensionless number is generally referred to as the Rayleigh number, R, and it is equal to the product of the Prandtl and Grashof numbers. For the sake of clarity a distinction will be made between two types of free convection produced by internal density gradients. In the first case a density gradient is present in the vertical direction only, and, since the convection begins only after a critical gradient is attained, this case will be called threshold convection. In the second case a horizontal density gradient is present and in this case a finite convection velocity is produced by a finite density gradient so that it will be termed thresholdless convection. Some experimentalists have performed diffusion experiments using capillaries which were placed in a horizontal or inclined position in order to avoid convection. These positions do put the small capillary dimension in the vertical direction and, consequently, they would be less prone to threshold convection than the vertical position. However, if the diffusion process produced a density variation, as it usually does, it would not be theoretically possible to avoid thresh-

Jan 1, 1969

By J. S. Billheimer, B. H. Sage, W. N. Lacey

A restricted ternary system made up of n-pentane, tetralin, and a purified bitumen was investigated at 70, 160, and 220 °F. Most of the experimental observations were at atmospheric pressure or at 200 psi." However, some experimental measurements were carried out at a pressure of approximately 8000 psi. It was found that the purified bitumen was precipitated from its solution or dispersion in tetralin by the addition of n-pentane and that the separation occurred at lower weight fractions of n-pentane at the lower temperatures. The bitumen-tetralin solutions show some colloidal characteristics at temperatures below 160 °F when near compositions at which the bitumen separates as a solid phase. At states remote from the phase boundaries and at temperatures above 160 °F these characteristics become less evident. Under these latter circumstances the mixtures tend to follow the behavior of true solutions, particularly in regard to the approach to heterogeneous equilibrium. An increase in pressure appears to increase the solubility of bitumen in tet-ralin-n-pentane solutions. This effect is more pronounced at temperatures above 160 °F than at lower temperatures. INTRODUCTION Asphaltic phases of plastic or solid nature have appeared in numerous instances during the recovery of petroleum from underground reservoirs. Such depositions occurring underground appear to have caused adverse production histories for particular wells or zones. Because of this field experience, it is desirable to understand the factors which influence the formation or separation of the asphaltic phases from petroleum. The problem is unusually complex because the number of true components involved is very large and the details of the phase behavior encountered are difficult to ascertain experimentally. The literature relating to asphalts, asphaltines, and bitumen is voluminous and widespread.' Only those references which are directly pertinent to the work at hand are cited. The separation of an asphaltic phase, hereinafter called bitumen? from naturally occurring hydrocarbon mixtures has been the subject of several investigations.2'3'4'5'6 It has been found that as many as four phases4 may be produced from a crude oil by the solution of a natural gas and propane at a pressure of 1500 psi and a temperature of 70 °F. The separation of bitumen from such naturally occurring mixtures results in at least one liquid phase which is substantially free of high molecular weight components.³ The influence of the solution of lighter hydrocarbons on the separation of bitumen from a Santa Fe Springs crude oil has been investigated. The results indicate that in the case of the methane-crude oil system, the quantity of plastic or solid phase separated reaches a maximum between 0.14 and 0.19 weight fraction methane and then decreases until negligible at higher weight fractions of methane. Similiar behavior was encountered in the case of mixtures of ethane and crude oil. The decrease in the quantity of the solid phase with an increase in the weight fraction of the lighter component appears to result from the formation of an additional liquid phase6 in which the bitumen is relatively soluble. The formation of this additional phase probably occurs at a weight fraction of methane close to that at which the quantity of separated solid reaches a maximum. A comparison of the deposition of bitumen in the field with the separation of asphalts from lubrication oil has been made' and apparently the phenomena are similar. The phase behavior of bitumen also appears to be comparable to that of coal tar."' The chemical and physical characteristics of asphalts and bitumen have been the subject of extended investigations which have been reviewed in some detail by Katz.¹º The conclusion was reached that the dispersion of bitumen in a number of organic liquids was not entirely colloidal since it was impossible to isolate individual dispersed particles even with the electron microscope. However, the evidence appeared to indicate that at states close to phase boundaries the extent of the dispersion of the phases influenced the equilibrium to a greater extent than is encountered in many simpler systems. From earlier study of field samples it became apparent that the phase behavior of bitumen-hydrocarbon systems was unusually complex. It was difficult to characterize in detail the phase behavior involved in naturally occurring hydrocarbon systems, even after a relatively extended investigation. For this reason, the study of a somewhat simpler system which still behaved in a similar manner became desirable. Three major constituents were necessary as-follows: a bituminous solid, a liquid constituent which was a reasonably good solvent, and a constituent in which bitumen was largely insoluble. A sam-

Jan 1, 1949

By S. J. Sindeband

Prior to discussing the metallurgy of sintered chromium borides, it is pertinent to outline some of the reasoning behind this investigation and the purposes underlying the work. This study was initiated as an aproach to the ubiquitous problem of a material for service at high temperatures under oxidizing atmospheres, and it was undertaken with a view to raising the 1500°F (816°C) ceiling to 2000°F (1093°C) or better. For the reason that no small, but rather a major, lifting of the high temperature working limit was being attempted, it was felt appropriate that a completely new approach be taken to this problem. A summary of the thinking behind this approach was published recently by Schwarzkopf.' In briefest terms, it was postulated that the following requirements could be set up for a material which would have high strength at high temperatures. 1. The individual crystals of the material must exhibit high strength interatomic bonds. This automatically leads to consideration of highly refractory materials, since their high energy requirements for melting are related to the strength of their atom-to-atom bonds. 2. On the polycrystalline basis, high boundary strength, superimposed on the above consideration, would also be a necessity. Since this implies control of boundary conditions, the powder metallurgy approach would hold considerable promise. Such materials actually had been fabricated for a number of years, and the cemented carbide is the best example of these. Here a highly refractory crystal was carefully bonded and resulted in a material of extremely high strength. That this strength was maintained at high temperature is exhibited by the ability of the cemented carbide tool to hold an edge for extended periods of heavy service. Nowick and Machlin2,3 have analytically approached the problem of creep and stress-rupture properties at high temperature and developed procedures whereby these properties can be approximately predicted from the room temperature physical constants of a material. The most important single constant in the provision of high temperature strength and creep resistance is shown to be the Modulus of Rigidity. On this basis, they proposed that a fertile field for investigation would be that of materials similar to cemented carbides, which have Moduli of Rigidity that are among the highest recorded. The cemented carbide, however, does not have good corrosion resistance in oxidizing atmospheres and without protection could not be used in gas turbines and similar pieces of equipment. It would be necessary then to attempt the fabrication of an allied material based upon a hard crystal which had good corrosion resistance as well. It was upon these premises that the subject study was undertaken and at an early stage it was sponsored by the U.S. Navy, Office of Naval Research. Since then, it has been carried on under contract with this agency. Chromium boride provided a logical starting point for such research, since it was relatively hard, exhibited good corrosion resistance, and, in addition, was commercially available, since it had found application in hard-surfacing alloys with iron and nickel. That chromium boride did not provide a material that met the ultimate aim of the study results from factors which are subsequently discussed. This, however, does not detract from the basis on which the study was conceived, nor from the value of reporting the results which follow. Chromium Boride While work on chromium boride proper dates back to Moissan,4 there has been a dearth of literature on borides since 1906. Subsequent to Moissan, principal investigators of chromium boride were Tucker and Moody,5 Wede-kind and Fetzer,6 du Jassoneix,7,8,9 and Andrieux." These investigators were generally limited to studies of methods of producing chromium boride and detennining its properties. Some study, however, was devoted to the chromium-boron system by du Jassoneix,7 who did this chemically and metal-lographically. This system is not amenable to normal methods of analysis by virtue of the refractory nature of the alloys involved, and the difficulties of measurement and control of temperature conditions in their range. Dilatometric apparatus is nonexistent for operation at these temperatures. Du Jassoneix made use of apparent chemical differences between two phases observed under the microscope and reported the existence of two definite compounds, namely: Cr3B2 and CrB. These two compounds, he reported, had quite similar chemical characteristics, but were sufficiently different to enable him to separate them. The easiest method for producing chromium boride is apparently the thermite process, first applied by Wede-

Jan 1, 1950

By M. Schmellenkamp

By comparing two longwall operations, one begun in 1956 and the other in 1960, the author is able to demonstrate the increases in production and performance made possible by longwall mining. These achievements have been brought about by continuous development of longwall mining equipment and associated roof supports. Because of this progress, longwall mining is able to provide, under proper conditions, high production per man-shift, remarkable cost savings, dependable roof control, safe working conditions and truly continuous production. It may seem odd that the title of this paper is not simply "Longwall Mining" but instead "Progress in Longwall Mining." However, the word "Progress" definitely has its place in longwall mining. If it had not been for progress in the development of longwall mining equipment and roof supports, the longwall mining method would not be able to compete in production and performance with modem coal mining machines. The longwall mining method was practiced at the beginning of the century and there were several successful operations in coal fields in Illinois. In those early days of longwall mining, the coal was undercut by hand 2 to 2.5 ft at the bottom of the seam and packwalls were built in the gob to support the roof. The roof eventually subsided and the weight of the subsiding roof was used to ride the face and break the undercut coal. Utilizing natural weight to soften the coal face is still practiced in modern longwall mining; however, the packwalling method has been replaced by the caving method and the roof is now supported by yielding steel roof supports and forepoling steel headers. The purpose of these yielding-type roof supports is to provide a safe working area for the crew along the entire longwall face, to permit continuous mechanical mining across the prop free face, and to provide a strong resistance for the roof by forming an even breaking line at the gob for the roof to cave. Roof supports and associated forepoling headers should be kept as close as possible to the face in order to prevent a caving between face and supports, especially under friable roof. This means that the coal should be extracted in small slices, allowing only a narrow roof area to be exposed and unsupported. The coal planer with its relatively high cutting velocity of 75 ft per min provides such an extraction of coal and has proved its high performance under difficult mining conditions. Since 1951, several longwall faces in southem West Virginia and Pennsylvania which have been equipped with the coal planer and friction-type manual roof supports have been successfully operated. Compared to today's longwall mining, these longwall faces required such a large crew, primarily to handle the roof supports, that the actual high production per shift was charged with too high a labor cost, thereby decreasing the tons per man. Yet, even then the longwall faces outperformed the conventional mining system under the same conditions. In order to demonstrate the progress that has been made in the development of longwall mining, a comparison will be made between a longwall face in Arkansas which was installed in 1956 and a modemized longwall face started in 1960 in southern West Virginia. LONGWALL MINING IN 1956 The 320-ft longwall face was developed in a 32-in. thick coal seam near Greenwood, Ark. The method of mining the 320-ft coal block was the advancing system in which three entries on either side of the face were driven ahead of the advancing longwall face. The face was equipped with a coal planer and a Panzer conveyor; timbering was done with wooden timbers and cribs. The roof supports were set without any pattern. The crew to operate the planer and to handle the roof supports (timbers and cribs) consisted of 15 men per shift. During a period of approximately eight monthsof single shift operating time, the average tonnage produced in this relatively low seam amounted to about 263 tons of clean coal per shift. To show the development in the coal plow from then until now, it should be pointed out that the standard plow was used in this operation. The plow was equipped with rigid bottom bits which could not be adjusted if the plow started to climb, thereby leaving bottom coal to be recovered by pick hammers end causing delays in production. The height of the plow

Jan 1, 1963

By J. U. Messenger

A technique is described whereby the resistance of an emudian to breaking can be quantitatively determined. Produced ailfield emulsions are usually the water-in-oil type and, accordingly, do not conduct an electrical current. However, there is a threshold of A-C voltage pressure above which an emulsion will break and current will flow. The more stable an emulsion, the higher the required voltage. A Fann Emulsion Tester, modified so that low voltages (0 to 10 v) can be accurately measured, is suitable. This technique has application in evaluating the effect of a demuksifier on the stability of an emulsion. Emulsions can, in essence, be titrated with demulsifiers by adding a quuntity of demulsifier, stirring, and measuring the voltage required to cause current to flow. Any synergistic effect of two or more materials added simultaneously can be followed accurately. A demulsifier that significantly lowers the threshold voltage (from 100 to 400 v to 0 to 10 v for the emulsions in this study) is effective and can cause the enlulsion to break. A demulsifier that will bring about this drop in the threshold voltage at low concentration ir very desirable. The technique is also well adapted for rapidly screening demulsifiers. INTRODUCTION Stable emulsions in produced reservoir fluids resulting from certain well stimulation and completion procedures are common problems. The use of suitable demulsifiers can often mitigate these difficulties. At the present time, a rapid and efficient method for selecting satisfactory demulsifiers is not available. It is badly needed. Reliance is now placed primarily on trial-and-error procedures. A new test method has been developed which permits a more rapid and precise selection of demulsifiers. It involves measuring the electrical stability potential of an emulsion before and after a demulsifier has been added. This paper describes this method and shows where it should have application in field emulsion problems. NATURE OF OILFIELD EMULSIONS Two immiscible components must be present for an emuhion to form; we are concerned here with crude oil and water. An emulsifier must be present for tin emulsion to be stable. J Emulsifiers can be substances which are soluble in oil and /or mter and which lower interfacial tension. They can be colloidal solids such as bentonite, carbon, graphite, or asphalt which collect at the interface and are preferentially wet by one of these phases. Unrefined crude oils can contain both types of emulsifiers, A popular theory is that, of the two phases in an emulsion, the dispersed phase will be the one contributing most to the interfacial tension.' Usually this phase contains the least amount of emulsifier. The stability of a water-in-oil emulsion is affected by the fol1owing: l) viscosity; (2) particle or droplet size; (3) interfacial tension between the phases; (4) phase-volume ratios; and (5) the difference in density between the phases. A stable emulsion is usually characterized by high-viscosity, small droplets, low interfacial tensions, small differences in density between its phases, and slow separatian of the phases. It also has low conductivity (high electrical stability potential). Water-in-oil and oil-in-water emulsions"' are both common; however, oil field emulsions are predominantly water-in-oil emulsions. The emulsions which commonly occur during oompletion and stimulation operations contain a combination of several of the following: acids, fracturing fluids (oil, water, acid), and formation water and oil. Produced emulsions usually contain formation water and oil. Emulsions form in oil wells because oil and water are mixed together at a high rate of shear in the presence of a naturally occurring or unavoidably produced emulsifier. During the completion and stimulation of productive zones, and while formation fluids are being produced, oil and water are very often commingled. These mixtures are formed into emulsions by agitation which occurs when the fluids are pumped from the surface into the matrix of the formation or produced through the formation to the surface. Restrictions to flow (such as perforations, pumps, and chokes)".'" increase the level of agitation; tight emulsions are more likely to form under these conditions. Often an emulsified droplet is an emulsion itself.'" Therefore, emulsion-breaking problems can be quite complex. The complexity can be even greater if a third phase (gas) is included. Demulsifiers operate by tending to reverse the form of the emulsion. During this process, droplets of water become bigger, viscosity is lowered, color becomes darker, separation of the phases faster and electrical stability potential approaches zero. Any of these effects could be followed as a means of determining emulsion stability. However, electrical stability potential is the most reproducible and most easily measured parameter for following the stability of a water-in-oil emulsion.

Jan 1, 1966

By S. M. Purdy

Under certain conditions of hot rolling and air cooling from the hot-rolling temperature, bars of a high carbon (0.40 pct C) chrome-nickel austen-itic alloy were found to show magnetism even though no ferrite or martensite could be detected by microscopic or X-yay methods. The appearance of magnetism in such alloys may come from chromium impoverishment of the austenite grains near the precipitated carbide particles. SPORADICALLY, hot-rolled bars of Silchrome 10, an exhaust valve steel, have been found to be magnetic. Because of the analysis of the alloy—0.40 pct C, 18 pct Cr, 8 pct Ni, 3 pct Si —magnetism is unexpected. Preliminary investigation showed neither martensite nor ferrite to be present; only austenite and Cr23C6. Since a literature search was fruitless, a brief study was made of the appearance of magnetism in this alloy. The only basic difference between the two heats is the nitrogen content. Permeability was measured using a Severn magnetic gauge. This instrument consists of a magnet mounted on a counterbalanced arm. A set of calibrated plugs is placed in contact with one pole of the magnet. The specimen is placed close to the other pole of the magnet. If the specimen pulls the magnet away from the plug, it has a permeability greater than that marked on the plug. This technique is swift and reproducible. Previous experience has shown that the permeabilities obtained corresponded to those obtained on a permeater with a field strength of 100 oe. Specimens from both heats were annealed at temperatures between 1700 and 2300°F. One set of specimens was water cooled and another furnace cooled. All the water-quenched specimens were non-magnetic; the furnace cooled ones were magnetic as shown in Table I with no difference being observed between the two heats. Microstructural examination of the specimens showed the expected increase in carbon solubility with increasing temperature. Carbide solution was complete at 2200°F. The specimens heated to 1900°F or below showed some carbide precipitation from the hot-rolled structure. A furnace cooled specimen from a given temperature showed less carbide out of solution than the water-quenched specimen from the next temperature below; e.g., the specimen furnace cooled from 2100°F showed less carbide out of solution than the water-quenched specimen from 2000" F. These studies indicated that the appearance of magnetism was not related to the quantity of carbon in or out of solution and it was related to precipitation at temperatures below 1700" F. A set of samples annealed and water-quenched from 2100° F was aged for 4 hr at temperatures between 1000" and 1600°F; all were non-magnetic. A second set of samples, similarly annealed, was aged 1 to 24 hr at 1200°F with the results shown in Table II. None of the latter set of specimens showed magnetism until they had been aged about 8 hr. Magnetism was quite strong after aging 24 hr. X-ray diffraction studies on several of the magnetic specimens showed that the austenite had a lattice parameter of 3.58A and that the carbide was Cr23C6. Several of these samples were electrolytically digested in 10 pct HCl in ethanol, with a current density of 0.1 amp per sq cm. None of the particles in the residue were magnetic. Accidentally, one cell was run at 1 amp per sq cm; e.g., magnetic particles were found in this residue. After careful separation, the magnetic particles were mounted on a quartz fiber and their diffraction pattern determined using a 5.73-in. Debye-Sherrer camera with CrK radiation. These particles showed a fcc structure with a lattice parameter of 3.57A. Prolonged exposure, up to 16 hr, produced no other lines on the film. The following facts seemed to be established at this time: 1) Austenite was the magnetic phase. 2) Neither ferrite nor martensite could be detected. 3) Magnetization could be produced by aging at 1200°F. One explanation of these data is that the carbide precipitation impoverishes the region immediately around the carbide particle of carbon and chromium and increases the proportion of nickel. All of these serve to increase the Curie temperature of the region around the carbide particle. If the composition change is enough, the Curie temperature will rise above room temperature. If the volume of the affected region is great enough, the magnetism will become detectable. At low aging temperatures, composition changes are great enough but the overall volume of impoverishment is quite small

Jan 1, 1962

By W. N. Lacey, B. H. Sage, J. S. Billheimer

A restricted ternary system made up of n-pentane, tetralin, and a purified bitumen was investigated at 70, 160, and 220 °F. Most of the experimental observations were at atmospheric pressure or at 200 psi." However, some experimental measurements were carried out at a pressure of approximately 8000 psi. It was found that the purified bitumen was precipitated from its solution or dispersion in tetralin by the addition of n-pentane and that the separation occurred at lower weight fractions of n-pentane at the lower temperatures. The bitumen-tetralin solutions show some colloidal characteristics at temperatures below 160 °F when near compositions at which the bitumen separates as a solid phase. At states remote from the phase boundaries and at temperatures above 160 °F these characteristics become less evident. Under these latter circumstances the mixtures tend to follow the behavior of true solutions, particularly in regard to the approach to heterogeneous equilibrium. An increase in pressure appears to increase the solubility of bitumen in tet-ralin-n-pentane solutions. This effect is more pronounced at temperatures above 160 °F than at lower temperatures. INTRODUCTION Asphaltic phases of plastic or solid nature have appeared in numerous instances during the recovery of petroleum from underground reservoirs. Such depositions occurring underground appear to have caused adverse production histories for particular wells or zones. Because of this field experience, it is desirable to understand the factors which influence the formation or separation of the asphaltic phases from petroleum. The problem is unusually complex because the number of true components involved is very large and the details of the phase behavior encountered are difficult to ascertain experimentally. The literature relating to asphalts, asphaltines, and bitumen is voluminous and widespread.' Only those references which are directly pertinent to the work at hand are cited. The separation of an asphaltic phase, hereinafter called bitumen? from naturally occurring hydrocarbon mixtures has been the subject of several investigations.2'3'4'5'6 It has been found that as many as four phases4 may be produced from a crude oil by the solution of a natural gas and propane at a pressure of 1500 psi and a temperature of 70 °F. The separation of bitumen from such naturally occurring mixtures results in at least one liquid phase which is substantially free of high molecular weight components.³ The influence of the solution of lighter hydrocarbons on the separation of bitumen from a Santa Fe Springs crude oil has been investigated. The results indicate that in the case of the methane-crude oil system, the quantity of plastic or solid phase separated reaches a maximum between 0.14 and 0.19 weight fraction methane and then decreases until negligible at higher weight fractions of methane. Similiar behavior was encountered in the case of mixtures of ethane and crude oil. The decrease in the quantity of the solid phase with an increase in the weight fraction of the lighter component appears to result from the formation of an additional liquid phase6 in which the bitumen is relatively soluble. The formation of this additional phase probably occurs at a weight fraction of methane close to that at which the quantity of separated solid reaches a maximum. A comparison of the deposition of bitumen in the field with the separation of asphalts from lubrication oil has been made' and apparently the phenomena are similar. The phase behavior of bitumen also appears to be comparable to that of coal tar."' The chemical and physical characteristics of asphalts and bitumen have been the subject of extended investigations which have been reviewed in some detail by Katz.¹º The conclusion was reached that the dispersion of bitumen in a number of organic liquids was not entirely colloidal since it was impossible to isolate individual dispersed particles even with the electron microscope. However, the evidence appeared to indicate that at states close to phase boundaries the extent of the dispersion of the phases influenced the equilibrium to a greater extent than is encountered in many simpler systems. From earlier study of field samples it became apparent that the phase behavior of bitumen-hydrocarbon systems was unusually complex. It was difficult to characterize in detail the phase behavior involved in naturally occurring hydrocarbon systems, even after a relatively extended investigation. For this reason, the study of a somewhat simpler system which still behaved in a similar manner became desirable. Three major constituents were necessary as-follows: a bituminous solid, a liquid constituent which was a reasonably good solvent, and a constituent in which bitumen was largely insoluble. A sam-

Jan 1, 1949

By R. F. Nielsen, D. E. Menzie

The object of this study was to determine if crude oil could be produced successfully by a process of crude oil vaporization using carbon dioxide repressuring. This process appears to have application to highly fractured formations where the major oil content of the reservoir is contained in the non-fractured porosity with little associated permeability. Crude oil was introduced into the windowed cell and carbon dioxide was charged to the cell at the desired pressure. A vapor space was formed above the oil, and the crude oil-carbon dioxide mixture was allowed to come to equilibrium. The vapor phase was removed and the vaporized oil collected as condensate. Samples of all produced and unproduced fluids were analyzed. Tests were also performed to evaluate the amount of vaporized oil that can he produced by rocking from a high to a lower pressure. The carbon dioxide repressuring process was applied to a sand-filled cell to investigate the performance in a porous medium. A test was performed to evaluate how the condensate recovery changes as the size of the gas cap in contact with the oil changes. INTRODUCTION This study has been directed toward a relatively new process of vaporization of crude oil designed to increase ultimate production of hydrocarbons through the application of carbon dioxide to an oil reservoir. Suggested advantages of carbon dioxide repressuring of a petroleum reservoir are: (1) reduction in viscosity of liquid hydrocarbons due to the solubility of carbon dioxide in crude oil, (2) swelling of the reservoir oil into a larger liquid-oil volume with a resulting increase in production and decrease in residual oil saturation due to an increase in the relative permeability to oil, (3) displacement of more stock-tank oil from the reservoir since the residual liquid is a swelled crude oil, and (4) gasification of some of the hydrocarbons into a carbon dioxide-hydrocarbon vapor mixture. Balanced against these advantages are several detrimental factors which must be evaluated; i.e., high compression costs and corrosion of well equipment and flow lines. Some of the more outstanding contributions to the study of carbon dioxide injection have been reviewed in order to furnish a basis for a continuation of research pertaining to this method. The literature reviewed1-8 has been limited to that dealing with carbon dioxide repressuring processes or with carbon dioxide-crude oil-natural gas phase behavior. Articles relating to carbonated water injection and literature published on the use of low pressure carbon dioxide gas injection in water flooding have not been included in this study. In 1941 Pirson5 suggested the high pressure injection of carbon dioxide into a partially depleted reservoir for the purpose of causing the reservoir oil to vaporize and thus produce the oil as a vapor along with the carbon dioxide gas. By reducing the pressure on this produced mixture of hydrocarbons and carbon dioxide at the surface, it was proposed to separate the hydrocarbons from the carrier gas. He theorized that essentially all the oil in a reservoir could be produced by simply injecting enough carbon dioxide to vaporize the residual oil. This present investigation deals with the vaporization of a crude oil by carbon dioxide, the molecular weight and gravity of the vaporized oil product and the characteristics of the residual oil after several repressuring cycles with carbon dioxide. An attempt is made to evaluate the merits of a vaporization process for the crude oil rather than a flow process where the oil recovery is determined by relative permeability considerations. Such a vaporization of crude oil by carbon dioxide repressuring appears to have possible use in a highly fractured formation where the major oil content of the reservoir is contained in the non-fractured porosity with little permeability. The carbon dioxide flows into the fractures, contacts the crude oil in the matrix and vaporizes part of the crude oil; this vaporized oil is produced and recovered and the carbon dioxide is reinjected again. The specific problem of this study is to attempt to answer this question; Can crude oil be produced successfully (technically, but without economic considerations) from a petroleum reservoir by a process of vaporization of the crude oil by carbon dioxide repressuring? DEFINITION OF TERMS AS APPLIED IN THIS STUDY Carbon Dioxide Contact: One cycle in which carbon dioxide was injected and bled off. Condensate: The hydrocarbon liquid which was condensed out of the mixture of hydrocarbon-carbon dioxide vapor upon reduction of the pressure of the vapor. Hydrocarbons Produced (HCP): All the hydrocarbon!, which were vaporized by the carbon dioxide repressuring process and were removed from the cell during any specific cycle or carbon dioxide contact. Hydrocarbons Unproduced (HCU): All the hydrocarbons which were not vaporized by the carbon dioxide

By A. A. Venghiattis

A rational approach to the selection of the appropriate perforator to use in each specific zone of an oil well is presented. The criteria presently in use for this choice bear little resemblance with actual down-hole condilions. These environmental conditions affect the elastic properties of rocks. One of these elastic properties, acoustic velocity, is suggested as the leading parameter to adopt for the choice of a perforator because, being currently measured in the natural location of the formation, it takes into account all of the effects of compaction, saturation, temperature, etc., which are overlooked in the laboratory. Equations and curves in relation with this suggestion are given to allow the prediction of the depth of perforation of bullets and shaped charges when an acoustic log has been run in the zone to be perforated. INTRODUCTION When an oil company has to decide on the perforator to choose for a completion job, I wonder if it is really understood that, to date, there is no rational way of selecting the right perforator on the basis of what it will do down-hole. This situation stems from the fact that the many varieties of existing perforators, bullets or shaped charges, are promoted on the basis of their performance in the laboratory, but very little is said on how this performance will be affected by subsurface conditions such as the combination of high overburden pressure and high temperature, for example. The purpose of this paper is to show the limitations of the existing ways of evaluating the performance of perforators, to show that performances obtained in laboratories cannot be extended to down-hole conditions because the elastic properties of rocks are affected by these conditions and, finally, to suggest and justify the use of the acoustic velocity of rocks, as the parameter to utilize for the anticipation of the performance of a perforator in true down-hole environment. EVALUATING THE PERFORMANCE OF A PERFORATOR It is natural, of course, to judge the performance of a perforator from the size of the hole it makes in a predetermined target. Considering that the ultimate target for an oilwell perforator is the oil-bearing formation preceded in most cases by a layer of cement and by the wall of a steel casing, the difficulties begin with the choice of an adequate experimental target material. For obvious reasons of convenience, the first choice that came to the mind of perforator designers was mild steel. This is a reasonable choice for the comparison of two perforators in first approximation. Mild steel is commercially available in a rather consistent state and quality, and is comparatively inexpensive. The trouble with mild steel is that it represents a yardstick very much contracted; minute variations in depth of penetration or hole diameter and shape may be significant though difficult to measure. The penetration of projectiles in steel being a function of the Brinell hardness of the steel (Gabeaud, O'Neill, Grun-wood, Poboril, et al), it is often difficult to decide whether to attribute a small difference in penetration to a variation on the target hardness or to an actual variation on the efficiency of the projectile. Another target material which has been widely used for testing the efficiency of bullets or shaped charges in an effort to represent a formation—a mineral target as opposed to an all-steel target—is cement cast in steel containers. This type of target, although offering a larger scale for measuring penetrations, proved so unreliable because of its poor repeatability that it had to be abandoned by most designers. The drawbacks of these target materials, and particularly their complete lack of similarity with an oil-bearing formation, became so evident that a more realistic target arrangement was sought until a tacit agreement was reached between customers and designers of oilwell perforators on a testing target of the type shown on Fig. 1. This became almost a necessity about seven years ago because of the introduction of a new parameter in the evaluation of the efficiency of a perforator, the well flow index (WFI). The WFI is the ratio (under predetermined and constant conditions of ambiance, pressure and temperature) of the permeability to a ceitain grade of kerosene of the target core (usually Berea sandstone) after verforation. to its vermeabilitv before perforation. The value of this index ;or the present state if the perforation technique varies from 0 to 2.5, the good perforators presently available rating somewhere around 2.0 and the poor ones around 0.8, There is no doubt that, to date, the WFI type of test is by far the most significant one for comparing perforators. It is obvious that a demonstration of a perforator

By R. A. Wood, R. I. Jaffee, H. R. Ogden, D. N. Williams

The tensile properties, creep resistance. and thermal stability of highly alloyed Ti-Al-Zr alloys were examined. On the basis of these studies, the Ti-7Al-1ZZr composition was selected for more complete evaluation. The alloy was found to be weldable and free from excessive directionality. In addition, it developed maximum properties without requiring heat treatment other than an annealing operation in the alpha field. The alloy was recommended for scale up and is presently being investigated on a production-level basis. One of the more attractive properties of titanium alloys is their ability to withstand stress at moderately high temperatures, and a considerable amount of effort has been devoted to increasing the maximum service temperature of titanium alloys. This work has suggested that the optimum alloys for high-temperature service will be single-phase a (close-packed hexagonal) alloys containing significant amounts of aluminum. However, the maximum amount of aluminum which can be alloyed with titanium is between 6 and 8 pct,l since at high-aluminum contents an embrittlement reaction occurs in the anticipated service temperature range, 800" to 1100°F. It has been shown that the embrittlement reaction involves decomposition of the high-aluminum a phase to one or more new phases.' Since this reaction does not occur at intermediate or low-aluminum contents, it was felt that intermediate Ti-A1 alloys might be strengthened by a-soluble ternary additions without inducing the embrittlement reaction. The first alloying addition considered was tin, which shows extensive solubility in a titanium and has moderate strengthening tendencies. Unfortunately, it was soon apparent that tin also promoted the embrittlement reaction, and that to obtain a stable alloy, the aluminum content had to be reduced as the tin content was increased. The second alloying addition considered was zirconium, which is similar to tin in its effects on titanium. This element did not contribute to the embrittlement reaction and, in fact, appeared to increase the maximum amount of aluminum which could be alloyed with titanium without inducing instability. This paper describes an investigation of the Ti-A1-Zr a alloy region. Alloys containing from 4 to 12 pct A1 and from 6 to 15 pct Zr were examined. The properties of these alloys are described and the bases for selecting an optimum composition is outlined. This composition, Ti-7A1-12Zr, is presently being scaled up in tonnage quantities, and is being evaluated extensively throughout the industry. In addition to presenting the basis for its selection, this paper presents a description of the properties developed in laboratory material as determined during the alloy investigation. These properties suggest that this alloy can fill an important position in applications requiring light weight, fabrica-bility, weldability, and strength to 1000oF or higher. EXPERIMENTAL PROCEDURES Titanium alloy ingots were prepared by inert electrode arc melting under an argon atmosphere. Alloying elements used were 110 Bhn titanium sponge, high-purity aluminum, and reactor-grade zirconium. Pancake-shaped ingots were prepared weighing approximately 300 g. The composition of the ingots was checked by weight measurements before and after melting. The pancake ingots were forged at 2000°F to approximately half their original thickness to give a flat plate roughly 1/2 in. thick. This plate was then rolled at 1800' to 1600°F to 0.250 in. thick. All of the alloys examined fabricated well. However, alloys containing 15 pct Zr tended to overheat due to exothermic oxidation, and scaling was excessive. As might be anticipated from its effect in decreasing the ß transus, increased zirconium appeared to improve fabricability somewhat, especially during rolling at lower temperatures. Except for a limited study of heat-treatment response, all alloys were examined in the a-annealed condition. Prior to heat treatment the a and ß tran-sus temperatures were determined by metallo-graphic examination of samples quenched after annealing at 50-deg intervals in the transformation region. These data are shown in Fig. 1. Recrystal-lization appeared to occur in about 1 hr in the range 1300º to 1500ºF. Therefore, alloys were annealed for 1 hr at 1550ºF (4 and 5 pct Al), 1600ºF (6 through 7-1/2 pct Al), or 1650°F (8 or more pct Al). This produced an equiaxed a grain structure. In most alloys, a "ghost" structure was visible after the a-annealing treatment, as shown in Fig. 2. This structure apparently resulted from the acicular

Jan 1, 1963

By F. C. Langenberg, J. Chipman

New data on the distribution of silicon between slag and carbon-saturated iron at 1600oand 1700oC are presented which, in combination with previously published data, permit the determination of silica activities over a broad range of compositions in the CaO-Al2O3-SiO2 system. The distribution of silicon between graphite-saturated Fe-Si-C alloys and blast furnace-type slags in equilibrium with CO has been described in previous publications.1"3 In this past work the silica-silicon relation was established at temperatures of 1425" to 1700°C for slags containing up to 20 pct Al2O3. This paper presents the results of additional studies at 1600" and 1700° C which extend the silicon distribution data at these temperatures for CaO-A1203-SiO2 slags over a range from zero pct A12O3 to saturation with A12O3, or CaO.2A12O3. The upper limit of SiO, is set by the occurrence of Sic as a stable phase when the metal contains 23.0 or 23.7 pct Si at 1600" or 1700°C, respectively. The activity of silica over the expanded range is determined directly from the distribution data.3 Recently, 4-7 other investigators have studied the activities of SiO, and CaO, principally in the binary system, using different methods and obtaining somewhat different results. EXPERIMENTAL STUDY The experimental apparatus and procedure have been fully described in previous publications.1, 3 Six new series of experimental heats have been made, four at 1600° and two at 1700°C. Master slags of several fixed CaO/A12O3 ratios were pre-melted in graphite crucibles, and these were used with additions of silica to prepare the initial slag for each experiment. Slag and metal were stirred at 100 rpm and CO was passed through the furnace at 150 cc per min. The initial sample was taken 1 hr after addition of slag at 1600°C or 1/2 hr after addition at 1700°C. The run was normally continued for 8 hr at 1600°C or 7 hr at 1700°C, and the final sample was taken at the end of this period. Changes in Si and SiO2 content indicate the direction of approach to equilibrium, and in a series of runs where the approach is from both sides this permits approximate location of the equilibrium line. Fig. 1 shows the results of such a series of 15 runs at 1600°C for slags of CaO/Al2O3 = 1.50 by weight. Figs. 2 and 3 record other series at 1600°C and Fig. 5 a series at 1700°C with fixed CaO/Al2O3 ratios. The results of the experiments at 162003°C have been reported in part in a preliminary note.3 In the experiments recorded in Figs. 4 and 6, the slags were saturated with A12O3 (or with CaO.2A12O3 within its field of stability) by suspending a pure alumina tube in the melt during the course of the run. The final slag analyses were used to establish the liquidus boundaries8 in the stability fields of CaO.2Al,O3 and of A120,. ACTIVITY OF SILICA The free-energy change in the reaction has been calculated by Fulton and chipman2 from recent and trustworthy data including heats of formation, entropies, and heat capacities. The more recent determination by Olette of the high-temperature enthalpy of liquid silicon is in satisfactory agreement with the values used and therefore requires no revision of the result which is expressed in the equation: SiO, (crist) + 2C (graph) = Si + 2CO(g.) [1] &F° = + 161,500 - 87.4T The standard state for silica is taken as pure cristobalite and that of Si as the pure liquid metal. Since the melts were made under 1 atm of CO and were graphite-saturated, the equilibrium constant for Eq. [I] reduces to K1 = asi /asio2 The value of this constant is 1.77 at 1600°C and 16.2 at 1700°C. Through K1, the activity of silica in the slag is directly related to the activity of silicon in the equilibrium metal.

Jan 1, 1960

By J. G. Richardson, J. W. Graham

The purpose of this paper is to present the results of theoretical and experimental studies of water imbibition. The imbibition processes are involved in recovery of oil from stratified and fractured-matrix formations in natural water drives and water flooding. An understanding of the role of inhibition in implementing the recovery of oil from such formations is deemed essential to proper control of these reservoirs to achieve maximum recovery. The theoretical studies involved development of the differential equations which describe the spontaneous imbibition of water by an oil-saturated rock. The dependence of the rate of water intake by the rock on the permeability, interfacial tension, contact angles, fluid viscosities and fluid saturatiorls is discussed. A few experiments were performed using core samples to determine the effects of core length and presence of a free gas suturation. The role of water imbibition in recovery of oil from a fractured-matrix reservoir by water flooding was investigated by use of a laboratory model. This model was scaled to represent one element of a frac-tured-matrix formation. Water floods were made at various rates with several fracture widths. Interpretations were made of the behavior expected in a system containing many matrix blocks. The presence of a free gas sntu.ration was found to reduce the rate of water imbibition. In the reservoir prototype of the fractured-matrix model, water imbibition rather than direct displacement by water was the dominant mechanism in the recovery of oil at low rates. INTRODUCTION Imbibition may be defined as the spontaneous taking up of a liquid by a porous solid. The spontaneous process of imbibition occurs when the fuid-filled solid is immersed or brought in contact with another fluid which preferentially wets the solid. In the process of wetting and flowing into the solid, the imbibing fluid displaces the non-wetting resident fluid. Common examples of this phenomenon are dry bricks soaking up water and expelling air, a blotter soaking up ink and expelling air and reservoir rock soaking up water and expelling oil. As increasingly better lithological descriptions have been made of the characteristics of petroleum-bearing formations, it has become obvious that imbibition phenomena which were once considered laboratory curiosities are of practical importance. For instance, in reservoirs composed of water-wet sand strata of different permeability in intimate contact, the tendency of water to channel through the more permeable stratum is offset by the tendency for water to imbibe into the tight sand and expel oil into the coarse sand. Also, in fractured-matrix formations the tendency of water to channel through the fractures is offset by water-wet matrix blocks. As some imbibition of the water into the of the largest fields in the world are fractured-matrix reservoirs, it has become increasingly important to understand all the factors involved in the imbibition process. Examples of fractured-matrix reservoirs are the Spraberry field in West Texas which produces from a fractured sandstone', the giant Kirkuk field in Iran', the Dukhan field in Qatar, Persian Gulf2, and the Masjid-I-Sula-main and the Haft-Kel fields in Southwestern Iran, which produce from fissured limestone3. Research into recovery of oil from fractured-matrix formations was stimulated by the rapid decline of oil productivity of wells in the Spraberry formation. One result of this research was the water imbibition process developed by the Atlantic Refining Co.4 Another idea was that much of the Spraberry oil could be recovered by conventional water-flooding procedures5. Subsequently, pilot floods were conducted in this field to test the feasibility of these ideas. It was felt that an understanding of the role played by imbibition processes in displacement of oil from a fractured-matrix reservoir could not be obtained from field data alone because of the many complicating factors and uncertainties involved. Therefore, theoretical and laboratory studies were undertaken to provide this understanding. Study of the equations which describe the linear, countercurrent imbibition process provided an insight into the role of various factors in the process, such as the permeability of rock and inter-facial tension. In addition to the theoretical studies, imbibition experiments were conducted with core samples to determine the effect on the rate of imbibition of such variables as core length and free gas saturation. The principal experimental studies were conducted by water flooding a scaled model of an clement of a frac-tu red-matrix reservoir to evaluate

By G. F. Bolling

STUDIES of grain boundary migration in zone-refined metals have all shown that the rate of migration is greatly reduced by small added solute concentrations. However, it is apparent that a difference exists between boundary migration during normal grain growth and single boundaries migrating in a bicrystal to consume a substructure. To effect the same reduction in velocity in the two cases, much more solute is required for grain growth than for the single boundary experiments. One case is available for direct comparison; both Bolling and winegardl and Aust and utter' added silver and gold to zone-refined lead to study grain growth and single boundary migration, respectively. For comparable reductions in migration rates, about 500 times more solute was required to retard grain growth than to retard the single boundaries. A reason for this difference is suggested here. The rate of grain boundary migration is dependent on solute concentration and must therefore also depend on the solute distribution; i.e., regions of higher solute concentration encountered by a moving boundary must produce greater retardation and thus could determine any observed rate. A dislocation substructure can be the source of a nonuniform solute distribution since it can attract an excess concentration of certain solutes. In fact, it is probable that the solutes which impede grain boundary migration most would segregate most severely to a substructure for the same reasons. Thus a dislocation substructure present in a crystal being consumed could locally magnify the concentration of solute confronting an advancing grain boundary. In the single boundary experiments a low-angle substructure, within single crystals obtained by growth from the melt, was used to provide the driving force to move a grain boundary; in grain growth, no substructure of this magnitude was present. The increased solute concentration at subboundaries should be given approximately by C, = G e c,/kT, where t, is a binding energy and CO the bulk concentration. To account for the difference between the two experiments in the Pb-Ag and Pb-Au cases, C, must be the concentration impeding the single boundary migration, and a value of t, = 0.25 ev is necessary. This is reasonable, even though calculation on a purely elastic basis gives t, = 0.12 ev. because electronic effects must enter for silver and gold in lead. The compound AuPbz forms3 and the metastable compound AgrPb has been reported to nucleate at dislocations prior to the formation of the stable, silver-rich phase.4 Other observations support the hypothesis that a magnified solute concentration impedes the single boundary migration. For example, some crystals were grown by Aust and Rutter at concentrations of ~ 0.1 wt pct Sn and 2 x X at. pct Ag or Au which exhibited a cellular substructure, and in these crystals no boundary migration was observed. It is therefore evident that the higher concentrations at cell boundaries drastically inhibited migration. Inclusions would not have been responsible for this inhibition since according to recent work on cellular segregation,5 no second phase should have occurred in the segregated regions at the cell boundaries for the conditions of growth used, at least in the Pb-Sn system. In the purest lead, only the "special" boundaries observed by Aust and Rutter gave rise to the same activation energy as that obtained in grain growth. It is reasonable to suppose that the structure of special boundaries does not favor segregation at low concentrations and thus solute, or an inhomogeneity in its distribution, would have no effect. Random boundaries, on the other hand, are affected by solute and the substructure would enhance residual concentrations in the zone-refined lead, leading to a higher activation energy. It is clear, even without a detailed theory, that the apparent activation energies and exact solute dependence in the two experiments must be different as long as the non-uniform solute distribution produced by the substructure is important. Recrystallization experiments should also be susceptible to the same kind of local segregation at subboundaries or disloca tion cell walls; a suggestion similar to this has been made by Leslie et al.' Following the arguments presented here, the effects of a given solute concentration would be like those observed by Aust and Rutter if segregation occurred, and like those of grain growth otherwise. This work was partially supported by the Air Force Office of Scientific Research; Contract AF-49(638)-1029.

Jan 1, 1962

By E. A. Gulbransen, K. F. Andrew

In a recent communication14 we have reported on the kinetics of the reactions of zirconium with O2, N2 and H2 as a function of the time, temperature and pressure variables. A systematic study was made and the results correlated with fundamental theories of gas-metal reactions. This paper will present a similar study for titanium. Titanium and zirconium are members of the IV group of the periodic table and possess many similar physical and chemical properties as a result of their similar electronic configuration for the outer electrons. The two metals are relatively inert to both gas and liquid phase corrosion at room temperature. However, at moderate temperatures the metals become active and react readily with the common gases including O2, N2 and H2 which are of interest in this study. A study of the kinetics of these gas-metal reactions is of interest for three reasons: (1) to understand the rate of reaction of titanium and its role in the behavior of high temperature alloys; (2) to understand the practical difficulties of the reduction, refining and working of titanium; and (3) to correlate the data with fundamental theories of gas-metal reactions and crystal structure predictions. Literature Survey Several review papers8 and books4243 exist on the preparation and properties of titanium and its alloys. THE METAL Titanium has, at room temperature, a hexagonal lattice of the zinc type. Hagg19 gives a value of 2.953A for the (a) axis, a value of 4.729 for the (c) axis and a density of 4.427 at 20°C. Burgers and Jacobs6 have observed the transformation of the hexagonal to the body-centered cubic structure at 880°C and have established a value of 3.31 for the cube edge and a density of 4.31. TITANIUM-OXYGEN Carpenter and Reavell6 using a pressure change method have studied the reaction at temperatures of 742° and 1000°C and for a pressure of one-fifth of an atmosphere. The probabilities for reaction are calculated from kinetic theory and they report a value of 10-5 for O2 at 1000°C and 10-6 at 740°C. The titanium-oxygen system has been investigated by Ehrlich.10,11 Five phases are observed. Between (TiO2 and TiO1.90) an alpha-phase, consisting ofarutile lattice, is found. A beta-phase is observed between (TiO1.80 and TiO1.70). A gamma-phase is homogeneous between (TiO1.56 and TiO1.46) and has a structure of the corundum type. The delta-phase exists between TiO1.25 and TiO0.6 and has a sodium chloride structure. From TiO0.42 to Ti the metal structure is observed. The surface oxide films have been studied by Hickman and Gulbransen.20 The rutile structure is observed in the temperature range studied, 300 to 700°C. Three crystalline modifications of TiO2 exist: rutile and anatase which are tetragonal and brookite which has an orthorhombic structure. Anatase is reported36 to exist in two forms: I and II. Anatase II changes to anatase I at 642°C. Anatase I is stable up to 915°C where rutile becomes the stable modification. At 1300°C rutile transforms to brookite which melts at 1900°C. The monoxide, TiO, may be prepared from the dioxide by high temperature reduction with carbon or magnesium. Its melting point is 1750°C. TITANIUM-NITROGEN Carpenter and Reavell6 report that at 1000°C a linear rate law is observed. The probability of reaction is given as 10-8 at 1000°C. Fast12 has studied the solubility of nitrogen and its effect on the mechanical properties of the metal. The crystal structure of TiN has been shown by several workers2'21'44 to follow the sodium chloride structure. However, the calculated density is found to differ from the pycnometric value. This is studied by Brager3,4 in detail. He has suggested that the titanium sites in the lattice are only partially filled at low temperatures. As the temperature of preparation is raised the vacant sites become occupied which expands the lattice and increases the hardness and density. An (a) value of 4.22Å is given for room temperature. TITANIUM-HYDROGEN The solubility and the crystal structures observed in this system have been reviewed in a recent book by Smith.40

Jan 1, 1950

By W. A. Turcotte, A. D. Paananen

Introduction The large reserve of fine grained oxidized iron-formation at the Tilden mine has been the object of research and development efforts to concentrate the iron oxides as far back as 1949. Due to the nonmagnetic nature of the ore and the fine grinding required to liberate the iron oxide minerals, this crude ore was not amenable to concentration by conventional methods. The iron oxides of the Tilden, ore body have a grain size of less than 25 microns and recovery of the finer, well-liberated iron oxides is essential. Conventional methods of desliming employing cyclones or thickeners were not feasible because of the excessive loss of iron oxides in the finer fractions. Development of selective flocculation-desliming was a key to commercialization of the process. Operations started in late 1974 with Algoma Steel Corp. Ltd., J & L Steel Corp., The Steel Company of Canada Ltd., Wheeling-Pittsburgh Steel Corp., Sharon Steel Corp., and The Cleveland-Cliffs Iron Co. as participants. Cleveland-Cliffs operates and manages the operation. Development of the Tilden Flowsheet The geology and ore reserves of the Tilden mine have been detailed in a paper by Villar and Dawe (1975). A joint program was undertaken in 1961 with the US Bureau of Mines in Minneapolis using the flowsheet developed by the Bureau employing the selective flocculation-desliming and calcium activated anionic silica flotation method (Frommer, et al, 1966; Frommer, 1964; Frommer, Wasson, and Veith, 1973). During this time, parallel testing at Cleveland-Cliffs Research Laboratory and Pilot Plant centered on the same type of desliming but was followed by the cationic flotation of silica with amine collectors (Columbo and Jacobs. 1976). The cationic silica flotation system was eventually chosen for its overall efficiency and simplicity. Regardless of the flotation method chosen, the technique of selective flocculation-desliming prior to flotation is the key to the success of the process. The flowsheet is described in detail by Villar and Dawe (1975). [Figure 1] shows a simplified one-line flowsheet of the Tilden concentrator. A total tailings thickener has been added to the original flowsheet and was placed in operation in 1978. The total-tailings thickener overflow reports to the reuse water pond and the underflow is pumped approximately 8 km (5 miles) to a storage basin. A flowsheet of the reuse water system is shown in [Fig. 2]. Selective Flocculation-Desliming Data have been published on the mechanisms and factors affecting selective flocculation in iron oxide-silica systems. The intent of this paper is not to discuss the theoretical aspects of selective flocculation, but rather to present experience gained from the commercial Tilden operation and from bench and pilot plant testing of fine-grained oxidized iron ores. From the bench and pilot plant testing prior to plant startup, certain reagent combinations and rates for the commercial Tilden plant were established. In the experience gained from three years of plant operation at Tilden, some of these reagent dosage rates have required significant adjustments due to changes in reuse water quality and to meet the requirements of varying ore types. Reuse Water The process water quality is a major concern at the Tilden mine and is constantly being monitored for selected chemical and physical characteristics. This monitoring has continued on a regular basis in order to gain a more thorough understanding of the interactions taking place in a dynamic water system and particularly as water quality is influenced by seasonal variations. Control of the reuse water chemistry is essential to the Tilden process both in the selective flocculation-desliming and flotation stages of concentration. With roughly 75% of the reuse water used in grinding-desliming operations, it is readily apparent that the biggest "reagent" in the selective flocculation-desliming process is water. Not enough can be said about the close control that must be exercised on the overall reuse water system. Control of the chemical treatment of the feed to the total tailings thickener is of utmost importance in order to produce a reuse water for the concentrator that is compatible with all stages of the concentrating process. There are many analyses made which aid in judging the quality of the water. Some of these are shown in [Table 1]. Five are particularly important and are monitored daily so that reagent adjustments can be made as required: suspended solids, calcium hardness, pH, dissolved silica concentration and temperature.

Jan 1, 1981

By James K. Hallenburg

INTRODUCTION The delayed fission neutron, or DFN technique for uranium ore body analysis uses the first down-hole method for detecting uranium in place quantitatively. This technique detects the presence of and measures the amount of uranium in the formation. DFN TECHNIQUE DESCRIPTION The DFN technique depends upon inducing a fission reaction in the formation uranium with neutrons, resulting in an anomalous and quantitative return of neutrons from the uranium. Since there are no free, natural neutrons in formation, a good, low noise assessment may be made. There are several methods available for determining uranium quantity in situ. The method used by Century uses an electrical source of neutrons. This is a linear accelerator which bombards a tritium target with high velocity deuterium ions. The resulting reaction emits high energy neutrons which diffuse into the surrounding formation. They lose most of their energy until they come to thermal equilibrium with the formation. Upon encountering a fissile material, such as uranium, these thermal neutrons will react with the material. These reactions produce additional neutrons, the number of which is a function of the number of original neutrons and the amount of fissile material exposed. The particular source used, the linear accelerator, has several distinct advantages over other types of sources: 1. It can be turned off. Thus, it does not constitute a radioactive hazard when it is not in use. 2. It can be gated on in short bursts (6 to 8 microseconds). This results in measurements free of a high background of primary neutrons. 3. The output can be controlled. Thus, the neutron output can be made the same in a number of tools, easily and automatically. There are several interesting reactions which take place during the lifetime of the neutrons around the source. During the slowing down or moderating process the neutron can react with several elements. One of these is oxygen 17. This results in a background level of neutrons in any of the measurements which must be accounted for in any interpretation technique. These elements are usually uninteresting economically. The high energy neutrons will also react with uranium 238. However, the proportions of uranium 235 and 238 are nearly constant. Therefore, this reaction aids detection of uranium mineral and need not be seperated out. Upon reaching thermal energy the neutrons will react with any fissile material, uranium 235, uranium 234, and thorium 232. At present, we do not have good techniques for seperating out the reaction products of uranium 234 and thorium 232. However, uranium 234 is a small (.0055%) percentage of the uranium mineral and thorium 232 is usually not present in sedimentary deposits. When the uranium 235 reacts with thermal neutrons it breaks into two or more fragments and some neutrons. This occurs within a few microseconds after the primary neutrons have moderated and is the prompt reaction. One system uses this; the PFN or prompt fission neutron technique. We don't use this method because the neutron population is low and, therefore, the signal is small and difficult to work with, accurately. Within a few microseconds to several seconds the fission fragments also decay with the emmission of additional neutrons. Now, with a long time period available and a large neutron population we gate off the generator and measure the delayed fission neutrons after a waiting period. These neutrons can be a measure of the amount of uranium present around the probe. Thermal neutrons are detected with the DFN technique instead of capture gamma rays to avoid some of the returns from other elements than uranium. LOGGING TECHNIQUE The exact logging technique will depend, to some extent, upon the purpose of the measurement. However, the general technique is to first run the standard logs. These will include: 1. The gamma ray log for initial evaluation of the mineral body and for determining the position of the borehole within the mineral body, 2. The resistance or resistivity log for determining the formation quality, lithology, and porosity. 3. The S. P. curve for estimating the redox state and shale content, and measuring formation water salinity, 4. The hole deviation for locating the position, depth, and thickness of the mineral (and other formations), and 5. The neutron porosity curve. The neutron porosity curve is most important to the interpretation of the DFN readings. The neutrons from this tool are affected in the same way by bore hole and formation fluids as the DFN neutrons are. Therefore, we can use this curve to determine effect of the oxygen 17 in the water. Of course, this curve can be used to determine formation porosity. It can also be used to calculate formation density.

Jan 1, 1979

By W. Allen

FOR the past six years gravity surveys have been used for underground prospecting in the copper mines at Bisbee, Ariz. The primary purpose of the surveys has been to reduce the diamond drilling and crosscutting necessary for exploration. Since many of the orebodies are small, and geologic control is not always apparent, any information that will direct the drilling and crosscutting is highly desirable. Because of extensive development and exploration work in the copper mines at Bisbee, it has been possible to cover more than 630,000 ft of crosscuts on 30 levels with the gravity surveys. In the process the gravity procedures have been refined to a high degree. Density Contrast: For a gravity survey to be successful, a sufficient density contrast must exist between the geologic feature sought and surrounding host rocks. Most mineralized areas will provide this contrast if fairly massive bodies are present. In the Bisbee area the entire sequence of formations, except for alluvium, appears to have specific gravities ranging from 2.65 to 2.70. These values have been determined by means of a large number of cut samples and diamond drill cores. As a further check, vertical gravity differences have been used where nonmineralized sections are known to occur.' The only known major gravity disturbances result from mineralization that has increased the density and the voids that have decreased density. The voids are caused by mining operations and by underground water movement that has developed several areas of caverns. Equipment: While not absolutely essential, a small rugged gravity meter, such as the Worden meter, is highly desirable. A tall tripod, about the height of a transit tripod, permits instrument set-ups in deep water and in locations where fallen timber and muck piles make it impossible to use a short tripod. An additional advantage of a tall tripod is that it places the meter in the center of the crosscut, reducing the error caused by the crosscut void. Size and weight are important, since the only satisfactory means of operating the meter underground is to carry it by hand. A backpack can be used in rare instances but is usually a hindrance because of the close station spacing. The operator's ability to move through tight clearances will improve survey coverage, as it is then possible to move through raises and caved areas and to pass mine cars and machinery with a minimum of trouble. Station Control: Gravity stations are normally located every 100 ft along the crosscuts, at each intersection, and in the face of all stub crosscuts. In areas of high gravity relief, or where small anomalies might be expected, stations may be located at 25 or 50-ft intervals. When possible, the stations should be offset to avoid effects of raises or other voids. The gravity stations on a level are tied to one or more base stations, which are usually located at the shaft or near the portal of an adit. The base stations may be part of a gravity control net that extends to each level in the mine as well as to the surface. Such a net extending throughout the potential area of the surveys is highly desirable, as it is then possible to compare all gravity stations on a uniform basis. The stations that are part of the base net should be carefully established by multiple readings and, if necessary, by a least squares adjustment of the loops. In some instances where levels do not have a shaft station, or where access may be blocked by caving, it may be necessary to establish secondary bases at the top and bottom of the raises that are between levels. Under fair conditions 70 to 90 gravity stations can be located and run in 6 hr by a two-man crew. The best field procedures depend on conditions. Reduction of Field Data: Most of the time required to produce a final gravity map is consumed in processing the data. Each meter reading must be corrected for a minimum of five factors that affect the gravity value in addition to the density contrast being sought. These factors are 1) instrumental drift, 2) station elevation, 3) topography, 4) latitude, and 5) regional gravity gradient. Mine openings, such as stopes and raises, will affect the value. However, it is seldom practical to make corrections for these voids. Usually a rotation is made on the field note on the station, and any

Jan 1, 1957

By F. E. Werner, B. L. Averbach, Morris Cohen

THAT bainite formed near the M, temperature bears a striking r esemblance to martensite tempered at the same temperature has been shown by the electron microscope.' By means of electron diffraction,' it has been established that carbide and cementite are present in bainite formed at 500°F (260°C); these carbides are also found in martensite tempered at 500°F (260°C).' The investigation reported here is concerned with an X-ray study of the matrix phases in lower bainite and tempered martensite. These phases have turned out to be dissimilar in structure; the matrix of bainite is body-centered-cubic while that of tempered martensite is body-centered-tetragonal. A vacuum-melted Fe-C alloy containing 1.43 pct C was studied. Specimens of 16 in. diam were sealed in evacuated silica tubing and austenitized at 2300°F (1260°C) for 24 hr. One specimen was quenched into a salt bath at 410°+7 °F (210°+4°C), held for 16 hr, and cooled to room temperature. The structure consisted of about 90 to 95 pct bainite, the re: mainder being martensite and retained austenite. A second specimen was quenched from the austen-itizing temperature into iced brine and then into liquid nitrogen. It consisted of about 90 pct martensite and 10 pct retained austenite. The latter specimen was tempered for 10 hr at 410°+2°F (210°+1°C). The specimens were then fractured along prior austenite grain boundaries (grain size about 2 mm diam) by light tapping with a hammer. Single aus-tenite grains, mostly transformed, were etched to about 0.5 mm diam and mounted in a Unicam single crystal goniometer, which allowed both rotation and oscillation of the sample. Lattice parameters were measured by the technique of Kurdjumov and Lyssak. This method takes advantage of the fact that martensite and lower bainite are related to austenite by the Kurdjumov-sachs orientation relationships Thus, the (002) and the (200) (020) reflections can be recorded separately, permitting the c and a parameters to be determined without interference from overlapping reflections. According to these findings, the matrix phase in bainite is body-centered-cubic and, within experimental error, has the same lattice parameter as ferrite (2.866A). On the other hand, martensite, tempered as above, retains some tetragonality, with a c/a ratio of 1.005t0.002. Most workers in the past have assumed that bainite is generated from austenite as a supersaturated phase, but the nature of this product has not been established. The question arises as to whether bainite initially has a tetragonal structure and then tempers to cubic, or if it forms directly as a cubic structure. If it forms with a tetragonal lattice, it might well be expected to temper to the cubic phase at about the same rate as tetragonal martensite. The martensitic specimen used here was given approximately the same tempering exposure, 10 hr at 410°F, as suffered by the greater part of the bainite during the isothermal transformation. About 50 pct bainite was formed in 6 hr at 410°F. On tempering at this temperature, martensite reduces its tetragonality within a few minutes to a value corresponding to 0.30 pct C.' Further decomposition proceeds slowly, and after 10 hr the c/a ratio is still appreciable, i.e., 1.005. Thus, even if the bainite were to form as a tetragonal phase with a tetragonality corresponding to only 0.30 pct C, which might be assumed to coexist with e carbide, it would not be expected to become cubic in this time. It seems very likely, therefore, that bainite forms irom austenite as a body-centered-cubic phase and does not pass through a tetragonal transition. The carbon content of the cubic phase has not been determined, but it could easily be as high as 0.1 pct, within the experimental uncertainty of the lattice-parameter measurements. It has been postulated that retained austenite decomposes on tempering into the same product as martensite tempered at the same temperature. There is now considerable doubt on this point. The isothermal transformation product of both primary and retained austenite at the temperature in question here is bainite," and the present findings show that bainite and tempered martensite do not have the same matrix. Acknowledgments The authors would like to acknowledge the financial support of the Instrumentation Laboratory, Massachusetts Institute of Technology, and the United States Air Force.

Jan 1, 1957

By G. F. Leaming

The paper by R.V. Ramani and R.J. Sweigard is a wonderful description of the labyrinthine web that has been spun about the mining industry by energetic bureaucrats and politicians over the past 50 years. The remedy for the problem, however, is not more of the same, but less. That may be difficult for the industry to achieve, for it is not a technical solution but a political one. And the current fervor for more detailed planning at all levels of government and private enterprise has become deeply ingrained. The authors recommend the provision of more information about mining and mineral resources to "macro" (i.e., government) land use planners. They apparently overlook, however, the already strong tendency on the part of most government land use planners to consider themselves omniscient. Thus, giving them more information about the technical problems of mining will only make them want to get more and more involved in the "micro" (private, site specific) mine development and production plans of the individual mining firm. In fact, this has already happened at all levels of jurisdiction from municipal to federal government. Examples are legion. The most effective way to ameliorate the adverse impacts of government land use planning on existing and potential mining operations is to: (1) introduce greater flexibility in the definition of land use zones by local and state governments; (2) adopt realistic and relevant ambient environmental performance standards in governing relationships between mineral land uses and concurrent or subsequent nonmining land uses; (3) allow greater leeway for economic considerations in land use decisions in contrast to the explicit legalistic approach now in vogue; (4) recognize that all minerals are not the same and that sand and gravel mining should not be treated the same as underground metal mining, coal stripping, oil field production, or in situ leaching; and (5) eliminate the notion that mining operators should be responsible for determining in detail the use of land by subsequent owners of mined land. This last bit of conventional ethic really makes no more sense than requiring the builders of every shopping center or government office complex to provide detailed plans for the use of that land when its use for shopping or government is ended. Did the builder of Ebbetts Field plan for Brooklyn after the Dodgers went to Los Angeles? Should the developer of the Bingham Pit plan for suburban Salt Lake City after the copper mining goes to Chile? The nation's mining industry must address these questions before further bankrupting itself to provide more data to planners and spending thousands of dollars per acre to create land that when reclaimed is worth only a few hundred dollars per acre. ? Reply by R.V. Ramani and R.J. Sweigard We thank Mr. Learning for his valuable contribution. His views on the problems of land use planning and mineral resources are most welcome additions to our paper. As the title indicates, our paper was more concerned with the impacts of land use planning on mineral resource conservation than with the details of the planning process. On the whole, his five recommendations would be helpful for mineral resource conservation. However, we would suggest that the argument he presents for his final recommendation does not address the differences between mining as a land use and commercial or institutional uses. We believe that this difference is the crux of the issue. We share Mr. Learning's desire to ameliorate the adverse impacts of land use planning. Possibly the most detrimental impact is the loss of mineral resources. Any development, whether mineral or community, that does not give proper consideration to other resources can result in permanent loss or sterilization of resources. With proper planning, some of these losses can be avoided. As our paper indicated, one factor that limits the consideration of mineral resources, and ultimately leads to their sterilization, is the generally inadequate levels of resource characterization and understanding of the unique nature of mineral resources and mining operations. The last point raised by Mr. Learning is also important. In terms of reclamation and land use planning in mining districts, we certainly do not advocate spending more than what the results are worth. The main thrust of the paper was to explore the avenues for conserving the mineral resources so that, at some appropriate time, the issue of mining and reclamation can still be addressed. ?

Jan 1, 1986

By Sidney Fischler

Large striation-free single crystals of bismuth have been grown from the melt by rapid freezing. Zone-refined bismuth, together with doping impurities if desired, is placed in a shallow flat-bottomed graphite boat and melted in air with a propane hand torch. The torch is then withdrawn in a manner which causes the melt to freeze direction-ally. Crystallization, which resuires only a few minutes, usually results in the formation of a single crystal even when a seed crystal is not used. Crys -tals of any desired orientation may be grown by using oriented seeds. Undoped crystals grown by this method have residual resistivity ratios greater than 200. THE growth of large single crystals of bismuth by either the Czochralski or horizontal zoning technique is not entirely satisfactory. Specifically, difficulties are encountered in producing single crystals of the required dimensions in all desired orientations, and striations caused by low-angle polysynthetic twins are frequently present in the crystals. In addition, both methods are time-consuming and require special apparatus of some complexity. A simpler method has now been developed for growing large striation-free bismuth single crystals of desired orientation in a short time. Fig. 1 shows a typical setup consisting of a rectangular graphite boat which contains zone-refined bismuth, a 1/8-in.-thick flat quartz plate which covers the entire inner bottom of the boat, and three additional quartz plates about 1/4 in. thick which are used to separate the bismuth from the graphite everywhere except at a small area at the left of the boat. The graphite boat is 1 in. high, and its sides and bottom are about 1/8 in. thick. The quartz plates should be smooth and clean. The graphite boat is heated from the right with a propane torch, as shown in Fig. 1, until the bismuth is completely melted. The melt has the shape of a triangle with a narrow neck at the apex farthest from the torch. The melt is frozen direc-tionally by gradually moving the torch toward the right, away from the boat. The bismuth in contact with the graphite, at the left end of the neck, freezes first. The freezing interface then moves down the neck into the main bulk of material, where it develops a convex shape ideal for the continuation of single-crystal growth. The interface continues to move through the melt until the entire bulk is solid. The entire procedure may be completed, in air, in a matter of minutes. The technique described almost always yields a single crystal whose basal plane is nearly perpendi,cular to the bottom of the graphite boat. In earlier experiments, in which the bottom of the melt was in direct contact with the graphite boat, single crystals were grown with basal planes parallel, perpendicular, or at some intermediate angle to the bottom of the boat. At times the orientation of the bulk of the material differed from the orientation of the material in the narrow neck. In these cases, a nucleation site initiated the growth of a differently oriented crystal, and the thermal conditions favored the new orientation over the initial one. The thermal conditions depend on a number of factors, including the heating technique, the placement, shape, and thickness of the quartz plates, the thickness of the walls and bottom of the graphite boat, and the quantity of bulk bismuth employed. All of these factors, plus the initial orientation and the presence and effectiveness of nucleation sites, will determine the orientation of the final large single-crystal slab. When a crystal of specific orientation is desired, an oriented section of a rapid-freeze crystal is shaped by spark cutting and grinding for use as a seed. To grow a doped crystal, the desired impurity is placed in the graphite boat together with the bismuth chunks and seed. Crystals doped with mercury, cadmium, lead, and selenium have been grown. The rate of freezing is so great that the distribution coefficient of any impurity approximates unity. On a gross scale, therefore, impurities should be more homogeneously distributed in rapid-freeze crystals than in Czochralski or zoned crystals. Because of the possibility of constitutional supercooling, however, it is quite possible that impurities are not homogeneously distributed on a microscopic scale in the rapid-freeze crystals. Generally the single crystal slabs which have been prepared are initially 5 to 7 mm thick. Thicker crystals may be obtained by using one of these slabs as a seed. The slab is placed in a graphite boat resting on a large aluminum block, either air- or

Jan 1, 1964