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By J. R. Hornaday, A. E. Morris, N. A. Parlee, D. C. Carmichael

Rates of absorption and effusion of hydrogen in solid iron were measurede by a Sieverts type of apparatus. With clean a iron these rates are diffusion controlled down to 420°C and are represented by the equation D = 6.70 x e-'100' crn2 sec-I Certain surface impurities can affect these rates at all temper-atuves. Thin oxide films lower, the apparent diffusivity of annealed iron markedly. Cold-worked iron (75 pct) annealed at 430°C has practically the same solubility and diffusivity as anealed iron. THE mechanism of absorption and evolution of hydrogen in solid iron alloys is not fully understood despite the large number of investigations on the subject. While there appear to be many instances of simple solid-state diffusion control of rate, there are many cases where investigators have either concluded that surface reactions are rate controlling or that some "nondiffusible" hydrogen resides in discontinuities. The purposes of this research were 1) to develop a sound method for studying this absorption and evolution behavior, 2) to examine it in pure annealed iron, and 3) to determine the effects of important variables, such as cold work, surface condition, and composition. This paper relates the progress toward these objectives. Much of the present knowledge of the movement of hydrogen through iron alloys comes from permeability studies which involve the measurement of the rate of passage (under steady state conditions) through membranes of the order of 1 mm in thickness. This method is open to question on various grounds. If surface reactions are involved, two different surfaces operating under two different conditions must be considered. The presence of defects in the membrane even of microscopic dimensions may lead to erroneous results. A few people have studied evolution of hydrogen into vacuum, under carefully controlled (unsteady state) conditions, and some of the best diffusivity data come from these sources. Most of these methods measure rates of evolution only and thus do not make a rigorous test for reversibility of behavior. It appeared that an "unsteady state" method that would permit the measurement of both rates of evolution and absorption under controlled temperature, pressure, and other conditions would offer several advantages. Accordingly the modified Sieverts apparatus described below was designed and built. APPARATUS This apparatus is shown in Fig. 1. The sample bulb is detailed in Fig. 2. Hydrogen of 99.5 pct purity and argon of 99.99 pct purity were used. The hydrogen was deoxidized and dried by means of a Deoxo unit followed by a "Dri-erite" tower. The argon was only dried. The gas burette was graduated in tenths of a cubic centimeter, and, with the aid of a travelling magnifier, readings could be estimated to the nearest 0.01 cc. The level of mercury in the burette was adjusted by means of a leveling bulb operated by a fine screw adjustment. An electrical system, consisting of two slightly separated platinum electrodes inserted in one leg of the manometer and a small light bulb was used to obtain rapid accurate adjustment of the pressure. The capillary tubing of the Vycor sample bulb was 3 mm bore as was all tubing back to the gas burette. The samples were discs made from vacuum-melted Ferrovac-E iron of greater than

Jan 1, 1961

By Thomas Wilson

IN a single-crystal cube of iron the arrangement of the atoms is that characteristic of iron at room temperature: the body-centered cubic lattice. X-ray investigation has shown this structure to be characteristic of iron, as it has shown the atomic arrangement of other metals to be characteristic of those metals also. Rarely do substances have more than one characteristic atomic arrangement. Many physical properties of metals are directly connected with their atomic arrangements, so that changes of arrangements produce changes of properties. Only chemical change influences atomic arrangement. If a difference in the physical properties of a metal is caused by a process which involves no chemical change, the cause of the difference in properties must be sought elsewhere than in the atomic arrangement. Frequently this cause can be traced to alteration of crystal orientation. The orientation of a crystal may be defined as the relationship which the crystallographic axes bear to some quantity of reference. A cube of iron appears cubic whether it is regarded from a face, an edge, or a corner. Yet these three positions represent three different orientations of the cube with respect to the observer. It is evident that the orientation of this cube of iron, unlike the atomic arrangement, is not characteristic of iron but is entirely dependent on the previous history of the cube. Most of the processes of metal working, such as wire-drawing, rolling, and bending, change the orientation of the crystals present in the worked metals. These processes usually tend to produce rotation of the crystals into positions approaching a mean. Specimens of metals show-ing this characteristic are said to possess a preferred, orientation. Tensile strength, ductility, and many other properties are influenced by orientation changes; therefore two specimens of the same metal may show different values of these quantities. In metal specimens possessing a narrowly limited preferred orientation, these quantities will vary in magnitude in different directions throughout the specimens. The investigation of the influence of manufacturing operations upon crystal orientation, and hence upon physical properties of metals, is an important

Jan 1, 1929

By Bernhard Blumenthal

A melting process was developed by which high purity electrolytic uranium crystals can be converted into sound ingots without serious contamination. Careful preparation of the crystals, melting in a high vacuum, and directional solidification led to a metal of better than 99.993 wt pct purity. The metallographic examination showed a substantially clean metal with only residual amounts of a second phase which responded to heat treatment. The density of high purity uranium is 19.05 g per cu cm. FOR the study of the fundamental properties of uranium and its alloys, a base metal of high purity is needed, and an investigation was started at Argonne several years ago to examine various methods of preparing high purity uranium. Early success was achieved by the fused salt electrolysis process in preparing high purity metal in crystal form,' and the problem became that of melting the crystals into ingots without contamination. The electrolytic crystals contained a few ppm of heavy metals, less than 15 ppm C, and large quantities of potassium and lithium in the form of trapped fused salt electrolyte. On melting in vacuo in magnesia or urania crucibles, the metal picked up considerable quantities of carbon and some iron, copper, and silicon but lost most of the potassium and lithium. It was not metallographically clean, and much research work was necessary to determine the optimum melting conditions for minimum contamination. This work has resulted in the development of a melting procedure by which sound ingots can be prepared with only a limited contamination by carbon. In the section entitled "Melting of the Electrolytic Metal," the equipment and processes that have been developed for melting the electrolytic crystals are described in detail. The "Metallography" section is devoted to the metallography of high purity uranium, and the section "Density of High Purity Uranium" contains the first property measurement on high purity uranium—a density determination. Melting of the Electrolytic Metal Apparatus—Melting and Vacuum Equipment: Uranium may be melted in either resistance or induction-type electric furnaces. Resistance heating was found to be preferable to induction heating for melting down the electrolytic crystals, for several reasons: Although induction heating permits fast heating, this advantage cannot be utilized when crucibles with limited thermal shock resistance are used. Temperature control of induction-heated melts is poor, and the stirring effect increases the rate of contamination of the melt from the crucible, slag, or the furnace atmosphere; liquation and controlled solidification are difficult to carry out. Because of these objections, resistance heating was chosen. A 10 kw Globar resistance furnace of low heat capacity permitted uniform heating of a uranium charge to its melting point in 45 min. The furnace was insulated with a removable aluminum shield so that, after melting and removal of the shield, the furnace could be quickly cooled to room temperature. The furnace was equipped with an apparatus for directional solidification; see Fig. la. The crucible was suspended in the center of the furnace; and when the melting was complete, the crucible was slowly lowered into the cold end of the furnace tube. Solidification took place upward from the bottom; and when the rate of lowering was small, a sound ingot free from sink holes and shrinkage cavities was produced. To remove the large quantities of gas contained in the electrolytic crystals, melting in a high vacuum is mandatory. While, from the standpoint of contamination, melting in a highly purified argon atmosphere appeared feasible, lithium and potassium removal proved less efficient under such conditions. Also, a vacuum-melted ingot has a cleaner surface than one melted in an inert atmosphere. The vacuum system must be of very high pumping speed and leak tight so that a vacuum of less than 2x10-7 mm Hg is attainable when the system is pumped down cold. The system must have a high pumping speed, so that the pressure maximum which may rise to 1x10-4 mm during heating can be quickly reduced

Jan 1, 1956

By H. O. Hoffman, C. D. Demond

There are two methods of determining the fusibility or refractoriness of fire-clays, the theoretical and the experimental. In the former, conclusions are drawn from the chemical composition; in the latter, from the changes which the clay undergoes when subjeoted to intense heat. It is well to use both methods, beginning with the actual heat-test and explaining the results obtained from this by the help of the chemical analysis. In discussing the subject, however, it is better to reverse this order. I. The Theoretical Method.* Leaving out the hygroscopic and combined waters and any organic matter, as not directly affecting the fire-resisting property, the refractory constituents of fire-clay are alumina and silica, and the fluxing constituents magnesia, lime, soda, potash and ferric oxide. According to Bischof,† alumina is the least fusible component, and silica follows close upon it. If, however, a mixture of the two be heated, it will be found that its melting-point is much lower than that of alumina, as a silicate will then have been formed. The way in which silica affects the refractoriness of alumina has been strikingly presented by Seger 1 in a diagram reproduced in Fig. 1. The abscissæ represent the melting-points of Seger cones Nos. 26 to 36 (see p. 55); the ordinates, the relative amounts of alumina and

Jan 1, 1895

By Robin P. Gardner

Prior work by the author has established that closedform analytic solutions can be obtained for certain steady-state and transient types of operation of open circuit, continuous ball mills. This is possible when the tanks-in-series concept is used with the segregated flow or lumped parameter milling models. Such models should be useful (whenever they apply) in any calculational application since they are efficient and simple to program for digital computation. For example, they might be used within a computer program such as that developed by Herbst et al. for the calculation of model

Jan 1, 1975

By R. T. McLamore

Lack of sufficient native permeability or skin damage caused while drilling wells for in situ leach mining projects may necessitate stimulating injection and production we1ls to increase the leaching rate to economic levels. Such stimulation processes could include acidization, hydraulic fracturing, or explosive fracturing. This paper describes an explosive fracturing process that is being developed primarily to stimulate the production of oil and gas wells, but may be useful in in situ leach mining projects as well. The process utilizes a liquid explosive that has unique safety features. The chemicals that form the explosive are subdivided into two pumpable, non- detonable components. Technology has been developed to pump these two components independently but simultaneously into the well and blend them together downhole to form the explosive. As such, surface facilities and personnel are not exposed to explosive hazards. The explosive formulations utilized in the process have been subjected to numerous safety and characterization tests and been qualified for use in deep wells with temperatures and pressures up to 250°F and 10,000 psi. The explosive composition can be varied to produce an explosive ranging, energetically, from a blasting agent to a high explosive that can be detonated after injection into a borehole, a porous media or into thin naturally occurring fractures within the roc

Jan 1, 1974

By C. F. Gates, H. J. Ramey

Recent literature shows that pronounced increases in oil recovery can result from the use of miscible systems in recovery operations. This literature also points out certain problems associated with maintaining miscibility, e.g., compositional changes resulting from alterations in pressure and temperature or from zone dilution. The purpose of the work described in this paper was to study miscible zones for possible use in waterflooding operations and examine the manner in which these zones break down. The fluid system selected for study was oil—terNary-butyl alcohol—water, which, because of its narrow range of miscibility, is ideally suited for investigation in short, linear systems. The laboratory-observed effects on oil recovery and zone stability of a number of variables are reported. Among the variables investigated were miscible zone size, viscosity ratio, length of travel, and interstitial water saturation. Results obtained with this system show that interstitial water adversely affects recoveries because of premature phase break. Salinity of the water further aggravates Ais situation. This effect, although pronounced for this system, would probably occur in any fluid system containing an alcohol. As expected, viscosity ratio has a decided influence on recovery efficiency and zone stability. The results also show that use of a suficieno zone size, even though the system has poor phase characteristics, yields higher oil recoveries than are obtained from straight water floods. Length-of-travel studies showed a square root relationship between zone growth and path length for favorable viscosity ratios. No such clear-cut dependence was observed under unfavorable viscosity conditions. INTRODUCTION As new oil reserves have become increasingly more difficult and expensive to find and develop, the oil industry has devoted more and more time and money to finding more efficient methods for exploiting known reserves. The increasing number of water floods is one manifestation of this attempt to improve oil recoveries from existing fields. Since considerable quantities of oil are by-passed by the waterflood process, it is only a partial answer to the problem. The search continues. Of late, several proposed processes have received the critical attention of investigators. Among them are gas drives, in situ thermal reactions and miscible displacements. The present paper is concerned with miscible displacements in conjunction with water floods. Recent literature1- reports that, under proper conditions, oil recoveries from LPG floods, propane sweeps, condensing gas drives, etc., approach 100 per cent of the oil in place in the region contacted by the flood. This literature also points out some of the problems associated with these processes, one of the main ones being the maintaining of miscibility. Compositional changes resulting from pressure and temperature variations or from zone dilution give rise to phase breaks and loss of miscibility, the conclusion being that, after loss of miscibility, much of the beneficial influence of the zone is lost.' The results of the subject work show that, if sufficient zone material exists ahead of a phase interface, considerable improvement in oil recovery can be obtained. In order to increase our understanding of the behavior of miscible systems as they degenerate into immiscible processes, a laboratory system having rapid deterioration characteristics was needed. The fluid system oil—ter tiary-butyl alcohol (TBA)—water possesses these properties and was the system investigated. Although these fluids are different from those generally employed in miscible studies, an understanding of their behavior can be applied to other miscible slug processes. However, under conditions where mass transfer maintains a miscible system through multiple contacts, e.g., enriched gas drive or high pressure gas drive, the observed behavior of alcohol zones would not be applicable. The variables of interest were zone size, viscosity ratio, length of travel, initial water saturation, rate and core characteristics. Of these, only the effects of the following on zone breakdown and oil recovery are reported in detail: (1) zone size, (2) path length, and (3) initial water saturation. The effects of viscosity ratio and core characteristics are discussed in conjunction with other variables. Although initial water saturation is not envisioned as important to the phase behavior of hydrocarbon systems, e.g., LPG, it is important in alcohol systems. The properties of the fluids and cores used are given in Table 1. As previously stated, this fluid system was selected because of the limited range of miscibility

By O&apos, R. G. Meara, G. D. Coe

PRIor to the World War most of the barite used in the United States for manufacturing lithopone and barium chemicals was imported. Germany, by virtue of an abundance of high-grade ore and low labor costs, was in a position to dominate the world market. With the cessation of imports and with the war demand for barium chemicals, the barium chemical industry and the mining of barite became well established in the United States. This industry has continued to expand because of the increasing use of lithopone. In 1914 the sales of domestic crude barite was 52,919 tons and in 1934 it was 209,850 tons. Barite deposits of economic importance occur in at least 20 states, but the principal producers in 1934 were Missouri, Georgia, Tennessee, South Carolina, Virginia, California and Arizona. The main mining centers are located near the crude barite markets of the three principal marketing districts—the Pacific Coast, the Midwestern area, and the Eastern area. The Pacific Coast is supplied entirely by California, Nevada, and Arizona. The Midwestern area uses most of the Missouri crude and a small amount from the southern states. The eastern market is the chief competitive area. Practically all of the imported crude is marketed there; also the bulk of the southern crude and ground barite. In addition, this area absorbs a small part of the Missouri crude and 80 per cent of the ground barite. Besides the advantage of low delivered costs and purity of product, the imported barite has commanded a price differential because it is soft rather than hard, like many of the domestic ores. The inherent physical properties of the southern ores remain, but the purity can be controlled to a great extent by beneficiation. Simple washing or gravity concentration has sufficed in the past, but in many cases a more efficient process now becomes imperative to remove impurities not amenable to these methods. Certain deposits now being opened are of lower grade and require more precise milling conditions. In some ores, the kind of impurities has changed as the mining advanced.

Jan 1, 1938

By G. D. Coe, R. G. Meara, O&apos

PRIor to the World War most of the barite used in the United States for manufacturing lithopone and barium chemicals was imported. Germany, by virtue of an abundance of high-grade ore and low labor costs, was in a position to dominate the world market. With the cessation of imports and with the war demand for barium chemicals, the barium chemical industry and the mining of barite became well established in the United States. This industry has continued to expand because of the increasing use of lithopone. In 1914 the sales of domestic crude barite was 52,919 tons and in 1934 it was 209,850 tons. Barite deposits of economic importance occur in at least 20 states, but the principal producers in 1934 were Missouri, Georgia, Tennessee, South Carolina, Virginia, California and Arizona. The main mining centers are located near the crude barite markets of the three principal marketing districts—the Pacific Coast, the Midwestern area, and the Eastern area. The Pacific Coast is supplied entirely by California, Nevada, and Arizona. The Midwestern area uses most of the Missouri crude and a small amount from the southern states. The eastern market is the chief competitive area. Practically all of the imported crude is marketed there; also the bulk of the southern crude and ground barite. In addition, this area absorbs a small part of the Missouri crude and 80 per cent of the ground barite. Besides the advantage of low delivered costs and purity of product, the imported barite has commanded a price differential because it is soft rather than hard, like many of the domestic ores. The inherent physical properties of the southern ores remain, but the purity can be controlled to a great extent by beneficiation. Simple washing or gravity concentration has sufficed in the past, but in many cases a more efficient process now becomes imperative to remove impurities not amenable to these methods. Certain deposits now being opened are of lower grade and require more precise milling conditions. In some ores, the kind of impurities has changed as the mining advanced.

Jan 1, 1938

By J. L. Huitt, B. B. McGlothlin, J. J. Day

Laboratory tests were made with pure minerals and actual reservoir rock samples to study the effects of hydrothermal (steam m hot water) treatments on reservoir rock properties. These tests showed that hydro-thermal treatment of many reservoir rocks can result in significant rock softening. The softening was attributed primarily to the partial destruction of dolomite and kaolinite and the synthesis of montmorillonite in the presence of excess silica. In many cases, the softening was great enough to cause considerable healing of propped fractures; therefore, a serious reduction in welt productivity could result. In other tests it was found that the addition of ammonia to a hydrothermal treating fluid in a concentration as low as 0.013 Ib/lb of water not only could prevent rock softening but could cause rock hardening. The results of X-ray diflraction analyses of rock samples showed that when ammonia was added to the treating fluid, ammonium-mica and analcite were formed instead of montmorillonite. No significant permeability damage was observed in the sandstones that were subjected to the ammonia-hydro-thermal environment; in some sandstones, permeabifity improvements resulted. INTRODUCTION As the use of steam or hot water becomes more prevalent in well stimulation methods. the need for information on the effects of such treatments on reservoir rock properties becomes increasingly apparent. Several works have been published on high-temperature changes in rock properties,',' but these are more applicable to in situ combustion operations than to steam or hot water injection processes. The mineralogical literature contains many publications which report on the changes occurring with various pure minerals in hydrothermal systems. A review of this literature denotes the ease with which entirely new, crystalline mineral phases can be synthesized from other minerals in hydrothermal environments at temperatures, pressures and residence times typical of those encountered in oilfield thermal recovery or stimulation processes. Discussions of many of these experiments are given by Deer et al. Grim,' Roy et al., Zen\ and Hawkins.' One of the most significant of these pure mineral studies is the hydrothermal synthesis work of Levinson and Vian" in which montmorillonite was synthesized from naturally occurring minerals; i.e., kaolinite, quartz and carbonate minerals (particularly dolomite). These reactions occurred at 575F in only 2 days and at 300F in 5 days. These results may be applicable to petroleum reservoir rocks since the minerals studied were those which are commonly found in sandstones. Furthermore, the environmental conditions imposed in the studies were very similar to those involved in thermal stimulation of petroleum reservoirs, e.g., steam or hot water injection. Other studies have suggested that weak rocks could be hardened by "electrochemical induration", a process in which an electric current is applied to a clay-containing rock body. These tests can be regarded as hydrothermal treatments since they were conducted in some instances with aqueous solutions and since clay temperatures during the electrical treatment reached a maximum of about 100C. Although a number of studies of the reaction of pure minerals have been reported, very little has been published on the reactions of petroleum rock-hydrothermal systems. No work has been reported on preventing the more detrimental rock changes in rock softening which might occur during the injection of steam or hot water into reservoirs. The studies described in this paper were conducted to provide such information. EXPERIMENTAL APPROACH The laboratory tests included studies of the effect of hydrothermal treatment on core samples from several different reservoirs. The hydrothermal treatments (simulated steam treatments) were conducted with distilled water at 575F, for the most part, for periods of 2 to 6 days. This temperature level was selected because it represented that temperature which would probably prevail in several cases under consideration for steam injection projects. The core samples, as well as the pure mineral samples, were contained in high-pressure stainless steel, autoclave-type pressure vessels. The effects of the hydrothermal treatments were evaluated by measuring the penetrometer hardness, formation rock embedment strength and permeabilities of the core samples before and after the treatments (Fig. 1)'" In addition, the mineralogical changes in the specimens were studied by X-ray diffraction. Concomitant with the core sample studies, the mineralogical changes were studied in greater detail by conducting hydrothermal synthesis experiments with pure minerals at similar temperature levels and residence times. For the most part, samples of finely-crushed pure dolomite.

By Charles T. Holland, David A. Olsen

Considerable work has resulted in the development of a formula by which the strength of coal pillars for an L to T ratio of up to 12 may be estimated. One of the factors involved in this formula is the coefficient of friction between the coal pillar and the adjacent rock with which it is in contact. This paper presents the results of studies on sandstone, limestone, shale and coal and the coefficient of friction between coal and the other three under wet and dry conditions. With the coefficients of friction thus determined and the use of results obtained earlier by Meikle and Holland, it seems probable that coal pillar strength may be more closely estimated. Several investigators1-3 have found that the com-pressive strength of cubical coal specimens can be correlated by an equation such as

Jan 1, 1969

By F. A. Schaufelberger

Early work on chemical precipitation of metals from metal salt solutions is reviewed. The chemistry and thermodynamics of precipitating copper, nickel, cobalt, and cadmium metals by reaction with hydrogen are discussed. Mechanisms of metal precipitation, nu-cleation, growth, and agglomeration are reviewed, as well as some solubility phenomena of cleation,gases and solids at elevated temperatures. Experimental data presented deal mainly with the reaction of copper sulfate solution with Hz. METAL can be recovered from a leach solution either indirectly by precipitation as a compound that is later reduced or directly by electrolysis, cementation, or chemical reduction, for example, with hydrogen. The widely used electrowinning processes suffer from the inefficiency of converting fuel to low voltage dc and from low current efficiency when complete recovery is attempted. With the batch hydrogen reduction methods outlined here, a unit of fuel converted to hydrogen in modern gas reform plants will make two to three times as much metal as can be obtained with electrolysis. With continuous hydrogen reduction, four to six times as much metal is obtained. Precipitation by reducing a metal salt solution with H, has been known for almost 100 years.' Commercial use of the process, however, awaited the research and development program initiated by Chemical Construction Corp. Within the last few years this program has brought about construction of commercial plants, listed on p. 701. Ideal hydrogen reduction will precipitate a pure metal from a solution obtained by commercial leaching methods at a rapid rate without excessive temperatures and pressures. The metal precipitate will be of desired size and density, less than a percent left in the vessel being deposited on the wetted parts. The present discussion will outline Chemical Construction Corp.'s early development program and will discuss the chemistry and mechanics of reducing copper, nickel, cobalt, and cadmium from solution by H2. Work on selective reduction of nickel from cobalt has been described earlier.2 The article is not concerned with precipitation of copper by disproportionation of cuprous solutions where yield is limited" to 50 pet.* It does not discuss use of gaseous reducing agents other than hydrogen, such as SCV which may lead to contamination with sulfur, or CO," which is considerably more expensive than hydrogen and produces a gaseous reaction product, CO2.† The article does not include use of other nongaseous reducing agents: which are far more expensive than CO. Also, notes on the history, engineering design, and performance of commercial plants have been given elsewhere." It will be shown that a pure metal can be precipitated by reduction with hydrogen from solutions obtained by commercial leaching methods when the solution cohposition is controlled and proper acidity, proper metal ion concentration through controlled complex formation and hydrolysis, and adequate agitation for suspension of metal and for transfer of reducing gas are maintained. Reasonable temperatures and pressures are used which are less excessive than those used by previous workers, although they are maintained at above equilibrium values because of process kinetics.' It has also been found necessary to induce nuclea-tion and to control growth and agglomeration in order to get a powder product of suitable physical properties. Review of the Literature Muller, Schlecht, and Schubardt of I. G. Farbenm claimed a successive reduction of silver, copper, nickel, cobalt, and zinc from ammoniacal solution by applying progressively higher temperatures and hydrogen pressures. Metals produced by this technique were not pure, since no attempt was made to adjust the solution composition between the different reductions. It is doubtful that the zinc product contained any metallic zinc. The major contribution to the literature" was made by the Ipatiews,12 who prepared platinum, iridium, copper, nickel, cobalt, lead, tin, arsenic. antimony, and bismuth at often extreme conditions, up to the critical temperature of water (373"C), at 1500 to 7500 psi, for as long as several days. Even cadmium and zinc were claimed to have been observed in trace quantities precipitated together with basic salts. In the early experiments solutions were not stirred. Extensive formation of oxides and basic salts occurred. probably long before sufficient hydrogen could be supplied in the unstirred liquid to decrease the metal concentration in solution by reduction. The importance of hydrogen pressure was

Jan 1, 1957

Jan 1, 1915

By Arthur L. Bishop

INTRODUCTION Purpose The in-situ leach method for uranium extraction is a relatively new and innovative method of uranium mining. In 1975, the first commercial in-situ facility began operation in south Texas. Since that time numerous other operations have been initiated as either pilot or commercial ventures. Considerable literature has been published that deals primarily with generalities of the process or environmental concerns. Several federal agencies have published documents which do not reflect the true operating or environmental nature of the in-situ leach method of uranium extraction. From an environmental standpoint, this is also evident in the promulgation of rules and regulations. Hence, the purpose of this paper is to present experience with an environmental concern--non- production zone excursions--such that the industry and the regulatory agencies will gain greater insight devoid of preconceived ideas and misconceptions. General Process Description In south Texas, in-situ leach mining is utilized to extract uranium from permeable sandstone ore deposits 61 to 213 meters (200 to 700 feet) below the surface. Uranium is present as an insoluble uranium oxide. In the in-situ or solution mining technique, anoxidizing lixiviant is injected into the formation through injection wells. The solution reacts with the insol uble carbonate complex. This soluble uranium complex is produced at recovery wells, each containing a submersible pump. During production there is a constant sweeping of lixiviant through the formation from the injection wells to the recovery wells. Injection and recovery wells can be arranged in any of a number of geometric patterns dependent upon ore body configuration, aquifer permeability, and operator preference. Submersible pumps in the recovery wells pump the uranium rich pregnant solution to the initial processing facility. Monitor wells surrcsund the pattern area and are screened in appropriate stratigraphic horizons (production and non-production zones) to detect any lixiviant migration that may occur (Fig. 1).

Jan 1, 1980

By R. B. G. Yeo

Pronounced isothermal martensite formation at room temperature was measured dilatometrically in a steel containing 0.01 pct C, 24.9 pct Ni, 0.26 pctAl, 2.58 pct Ti and 0.25 pct Cb. It is shown that martensite will form isothermally if stabilization of the austenite-martensite transformation is eliminated by removal of carbon. The decarburization of two iron-nickel alloys allows isothermal transformation to martensite to occur at temperatures above their athermal Ms temperatures. In an Fe-22.4 pct Ni alloy, at the 0.008 pct C level, the Ms temperature during air cooling is 85°F higher than that during- water quenching-. At the 0.15 pct C level this difference is reduced to only 5°F. The introduction of carbon causes stabilization during air cooling which lowers the Ms temperature virtually to the same level as determined during mate?. quenching. Thus in the 0.15 pct C alloy, the Ms temperature is almost independent of cooling rate. It is suggested that rival theories of martensite formation should be reexamined in alloys of sufficiently low carbon and nitrogen content to eliminate the complication of stabilization. The Ms temperature of a steel containing 0.01 pct C, 24.9 pct Ni, 0.26 pct Al, 1.58 pct Ti and 0.15 pct Cb, solution treated at 1500°F and air cooled as 1/8-in. diam specimens, was found to be 57 °F. 1 However, when held for several hours at room temperature the steel hardened slightly and became appreciably ferromagnetic. Isothermal transformation to martensite was first revealed by Kurdjumov and Maksimova2 in an iron-base alloy containing 0.6 pct C, 6.0 pct Mn and 2 pct Cu. Most of the other studies of isothermal martensite have also been confined to highly alloyed steels which transform at subzero temperatures; for instance, DasGupta and Lement, 3 Cech and Hollomon, 4 Machlin and Cohen,5 Shih, Averbach, and Cohen.6 Averbach and cohen7 noted a rapidly decaying volume increase at room temperature in a steel containing 1 pct C, 1.5 pct Cr and 0.2 pct V. cina8 and Marshall, Perry, and Harpster9 have described the isothermal transformation to martensite at room and subzero temperature in stainless steels. Kurdjumov10 has recently reviewed the subject, noting that the isothermal formation of martensite can be observed only in the temperature range somewhat below Ms or below -50°C. The isothermal formation of martensite may be characterized as follows: 1) It occurs in steels of widely different compositions, the main prerequisite being a low transformation temperature. 2) The transformation occurs by the formation of new plates and not by the growth of old ones. 3) The isothermal transformation is suppresed by stabilization during slow cooling or holding at temperatures near room temperature. However, the factors governing this mode of transformation are still not fully understood. The formation of martensite isothermally suggests an activated process. The early theories of martensite formation did, in fact, utilize classical nucleation concepts. Kurdjumov 11 first proposed the presence of thermally activated nuclei of different sizes and compositions which would grow if they reached critical size during cooling. This treatment was enlarged and developed quantitatively by Fisher, Holloman, and Turnbull12,13 and was later reviewed by the latter two authors.14 Fisher15 associates Ms with a nucleation rate of one per cc per sec. At slightly higher temperatures the nucleation rate is so low that isothermal formation of martensite is not observed in reasonable times. At slightly lower temperatures the nucleation rate is so high that it could not be suppressed by rapid cooling. By judicious use of parameters Fisher 16 was able to obtain good agreement between classical nucleation theory and the incubation times of martensite formation.4 However the application of these principles to martensite formation in iron-nickel alloys15 predicts that an alloy containing about 30 pct (31 at. pet) Ni would not transform. The presence of an Ms temperature at -223° C in an alloy containing 34.1 pct (33 at. pct) Ni led Kaufman and cohen17 to reject the hypothesis of homogeneous nucleation in favor of the reaction path theory originally proposed by Cohen, Machlin and Paranjpe.18 This theory conveniently explains the formation of martensite athermally but becomes labored when dealing with isothermal formation. Kaufman and cohen19 did explain the isothermal activation of embryos by assuming it to be a result of the expansion of their boundary dislocation loops but this treatment predicts an upper temperature limit of isothermal martensite formation.

Jan 1, 1962

By Henry F. Cooper, Lee Burford, John C. Thompson

In the past year or two, considerable effort has been expended to calculate the spherical wave propagation phenomena associated with explosions in a "hard rock" medium (Godfrey, 1969; McKay and Godfrey, 1969; Burford, et al, 1970). This effort was stimulated primarily by the recognition that early calculations predicted peak particle displacements which seriouly disagreed with field data. In most of the calculations mentioned above, rock was modeled as an inelastic continuum (see for example Isenberg, et al, 1970 for some recent results using "classical" elastic-plastic material property models). However, several investigators (Handin, et al, 1967; Cherry, et al, 1967) have shown that the simple classical yield surface models cannot simultaneously account for the observed brittle failures of intact materials under compression, extension and torsion. One approach to more correct modeling of dynamic rock behavior is to make the inelastic model more and more sophisticated. For ex- ample, recent experiments at the University of Utah (Swanson, 1969) have suggested possible modifications to the yield surface model that could better account for the ductile behavior of intact granite sam- ples under various states of stress. The approach followed in this paper proceeds in an entirely different direction. We want the physics which is built into our conception of rock to be as simple as possible while at the same time reproducing the most important features of rock's behavior. Therefore, we abandon the requirement that rock be treated strictly as a continuum. Instead we consider a "discontinuous" model in which one of the most significant characteristics of rock is treated..

Jan 1, 1971

By C. R. Fast

In order to evaluate the ability of a Hydrafrac treatment to effect a sustained increase in well production, data were accumulated on the first 65 wells in 26 fields treated by Stano-lind. Since these data were obtained from such a large number of fields, it is felt that individual well or reservoir characteristics do not affect the overall picture, as might be the case if the study were made in one field or one group of wells in a field. These data are tabulated in Table I and plotted on Figs. 1 and 2. An analysis of Fig. 1 shows that at the end of six months, 75 per cent, or 45, of 60 wells on which data were available showed a sustained production increase. At the end of two years, data were available on 25 wells. Of these, 15 wells, or 60 per cent, showed a sustained production increase. At the end of three years, 55 per cent, or 10, of 18 wells had a production rate greater at that time than before Hydrafrac treatment. The lack of information on additional wells at the end of the third year is primarily a result of the small number of treatments conducted in the early stages of field application

Jan 1, 1952

By A. W. Fahrenwald

The physics and chemistry of the flotation process are not well understood. Many papers dealing with the theory of flotation have been published but most have been narrow in their viewpoint. No theory advanced has done more than explain, more or less satisfactorily, various isolated phenomena. Scientists have done little with the problem, doubtless because they have not seen sufficient of the practical side of the subject to have their interest aroused. Any attempt to explain the mechanism of flotation that considers only contact angles, surface tension, adsorption, the floating of needles, flocculation, or any other single and narrow phase of the question is sure to be disappointing. Flotation is a problem of colloid chemistry and must be studied as such. In a broad general way, flotation is a process involving and operating by virtue of surface reactions. The term "surface reactions" may be open to criticisms. Many chemists give the term "reactions" a definite and restricted meaning and to such the term may connote change in atomic grouping in strict stoichiometric ratios. While Langmuir looks upon adsorption as a reaction, and there is much evidence in support of this view, we may look on adsorption as a physcial process as far as this paper is concerned. The term seems well suited to the work in general. Presumably these reactions are reactions between the same kinds of forces (electrical) and differ only in degree and in the surface manifestations produced. This premise seems logical if we accept the theory that the atoms of dl elements are made up of grains of electricity, having mass and charge, called electrons; and that atoms differ from one another only in the number and arrangement of the electrons about a positive nuclear

Jan 1, 1924

By P. J. Dean

This Paper contains a comprehensive survey of the known electron-hole radiative recombination mechanisms in the family of III-V compounds. Because of space limitations, the luminescence properties of each III- V compound are not reviewed separately and exhaustively. Instead, the different known types of recombination processes are discussed in turn and exemplified with reference to the III- V compound in which they were first recognized, or are best understood. Electron-hole recombinations usually occur predominantly at impurities or lattice defects either introduced de1iberately or inadvertently present, but radiative intrinsic interband electron-hole recombinations, which occur in perfect crystals, have been observed. Recombination processes which involve the participation of impurities or lattice defects ("extrinsic" recombinations) considered include transitions in which a) free carriers recombine with carriers trapped at impurities ("free to bound" transitions) , b) electrons bound at donor impurities recombine with holes trapped at acceptor impurities ("donor-acceptor pair" recombinations), C) excitons bound to charged or neutral donor or acceptor impurities recombine radiatively (both "resonance" and "two-electron" "bound exci-ton" transitions have been observed), d) excitons bound to neutral donor or acceptor impurities recombine non-radiatively (an example of an "Auger" recombination), and e) excitons bound to impurities with the same number of valence electrons as the host atom which they replace ("isoelectronic " traps) recombine radiatively. In addition, Auger recombination processes involving one or more free carriers have been observed. These extrinsic processes all involve impurities which are present as point defects. Some apparently well-authenticated examples of the recombination of excitons bound to complex impurity-lattice defect centers including nearest-neighbor donor-acceptor pairs are also discussed. Identificalions of the transitions involved in stimulated emission from the direct gap III-V compounds are briefly reviewed. Although the examples of these recombination mechanisms are selected from the III-IV compounds ia this review, these processes have quite general relevance in semiconducting crystalline solids; irrdeed most of them have also been identified in the 11- VI compounds and elernental semzconductors. THE development of crystal growth and purification techniques in recent years and concurrent advances in the understanding of physical processes in solids has accelerated the development of a wide variety of solid-state electronic devices of proven utility. These de- vices are generally used for switching or amplifying operations in electrical circuits. Most solid-state circuit elements are very photosensitive. This photo-sensitivity is generally undesirable and the single-crystal chip forming the active portion of the solid-state device is mounted in an opaque container. The photosensitivity is made use of in phototransis-tors and photodiodes, which are among the most sensitive detectors of electromagnetic radiation particularly in the near infrared.' In these devices, light is converted into electrical power. The solid-state lamp utilizes the inverse effect, namely the conversion of electrical power into light. There is an increasing tendency to use single-crystal diodes rather than the earlier electroluminescent cells in which the active material is present as a powder embedded in a suitable dielectric.' The radiation is emitted at a rate far in excess of the thermal equilibrium rate for the frequencies and temperatures involved; i.e., luminescence occurs. The development of practically efficient solid-state lamps is at an early stage compared with solid- state circuit elements or even photodetectors. Considerable progress has been made in recent years, however.3 The present review is devoted to a survey of the radiative recombination processes in the semiconducting compound crystalline solids formed from elements in groups I11 and V in the periodic table. These materials exhibit the full range of known recombination processes in solids. In fact many of these processes were discovered in 111-V semiconductors. Nonradiative recombination processes, which control the lutninescence efficiency, are also discussed. Luminescence is efficiently excited in semiconductors through processes which produce large excess concentrations of free electrons and holes in the energy bands of the crystal. Transitions induced by lattice defects or impurities usually predominate in the recombination process. By contrast, luminescence in the conventional fluorescent lamp is excited by optical absorption at the luminescent impurity center itself (the activator) and/or at a second type of impurity center (the sensitizer). This latter type of photoluminescence process, occurring in doped ionic crystals with wide band gaps, is outside the scope of this review.4 I) ENERGY BAND DESCRIPTION OF ELECTRON STATES IN CRYSTALS The energy band description of the energy states available to an electron in a crystal forms the basis of our understanding of the empirical division of crystalline solids into metals, semiconductors, and insulators in accordance with their electrical and optical properties.' Nonmetallic crystals have a finite energy gap between the highest energy band which is

Jan 1, 1969

By I. Fatt, D. N. Saraf

A method is described for measuring two- and three-phase relative permeabilities in sandstones or sand packs using a nuclear magnetic resonance (NMR) technique to determine fluid saturations. Two- and three-phase relative permeabilities have been determined on Boise sandstone using the NMR technique of saturation measurement. Three-phase relative permeability to water was found to depend only on the water saturation, whereas three-phase permeability to oil depended on both the water and oil saturations. Relative permeability to gas in three-phase flow was found to depend only on the total liquid saturation. INTRODUCTION Three-phase relative permeabilities are extremely useful in calculating field performance for reservoirs being produced by simultaneous water and gas drives. Three-phase relative permeability data are also needed for analyzing solution gas-drive reservoirs which are partially depleted and are being produced by water drive. Some thermal recovery processes involve three-phase flow which require three-phase relative permeability data for predicting reservoir behavior. Unfortunately, three-phase relative permeability measurements have rarely been made. Also, because of the scarcity of three-phase data, it has not been possible to date to relate other measured rock characteristics to the relative permeabilities with a great certainty. Leverett and Lewis,l Reid2 and Snell3 have reported three-phase relative permeability data on unconsolidated sands. Leverett and Lewis used ring electrodes spaced along the length of the sand sample to measure the resistivity of the sample which was assumed to be monotonically related to brine saturation. Gas saturation was determined from pressure-volume measurements. Oil saturation was obtained by material balance on the cell containing the sand sample. This method is involved and time consuming. Another difficulty arises from the fact that the resistivity of the sand is a function not only of saturation of brine but also of the distribution and saturation history of the brine in the pore spaces. Reid2 used a gamma ray absorption technique for measuring liquid saturation. This method has the disadvantage that total liquid saturation rather than oil or brine saturation is all that can be measured and still another method is required to determine the saturations of individual components. snel13 used a neutron bombardment method which also required a separate determination of the individual component saturations. Caudle et al.4 measured three-phase relative permeability on consolidated sandstones using vacuum distillation for determining fluid saturations. Distillation after each reading makes this technique very lengthy and time consuming. Corey et a1. 5 and Naar and Wygal 6 measured three-phase relative permeability on sandstones by the capillary-pressure method. Semipermeable diaphragm assemblies were used at each end of the core specimen to keep the water phase in the core. Gravimetric methods were used to determine fluid saturations. Sarem7 recently reported an unsteady-state method for measuring three-phase relative permeability on sandstones. This method is an extension of Welge's method8 for measuring two-phase relative permeability. Although Sarem's method is simple and comparatively fast, the assumptions involved may oversimplify the problem. Sarem's assumption, that in all rocks relative permeability to each fluid will depend only on the saturation of that fluid, seems to be rather unrealistic. Neglecting capillary effects at the end of the core is also a weak assumption. Donaldson and dean9 measured three-phase relative permeability using a method similar to Sarem's.