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

The vacuum-microbalance method was used to study the oxidation behavior of Zircaloy-2 and -3A over the temperature range of 300 to 850°C and at 0.1 atm pressure. The results fit in well with the authors' earlier studies on zirconium. Tin was found to increase the rate of oxidation and also the temperature at which the metal burns. Both the cubic-rate law and the parabolic-rate law gave imperfect fits to the rate data. Since the parabolic-rate law has been derived from accepted physical principles, this rate law was used to interpret the rate data. A heat of activation of 28,600 cal per mole was calculated. The transition phenomenon previously observed in hot-water and steam-corrosion processes was studied systematically for oxygen atmospheres. Observations on the rate of oxidation, color and properties of the oxide films show that the transition phenomenon was associated with a failure in the adherence of the oxide to the alloy. ZIRCALOY-2 and -3A have found important uses in the field of reactor metals due to their low neutron adsorption, good strength and good resistance to corrosion. One feature of the corrosion reaction in steam or hot water is the sharp transition in the rate of corrosion to a higher value after a certain amount of reaction has occurred. This paper presents a study of the reaction of Zircaloy-2 and -3A with oxygen including a study of the transition phenomenon which has been found to occur also in oxygen atmospheres. A comparison will be made between the oxidation behavior of these alloys and the pure metal. It was hoped that a study of the details of the oxygen reaction would lead to a better understanding of the reactions occurring in hot-water and steam atmospheres. Literature Kinetics-—The reaction of Zircaloy-2 and -3A with hot-water and steam atmospheres has been studied by Thomas.' Goldman and Thomas,' Thomas and Forscher," and Thomas and Kass.' Empirical equations for the kinetics of the reaction have been given by Thomas and Forscher." The change from the initial slow rate of reaction to the final rapid rate of reaction has been termed transition with the post-transition corrosion kinetics following a simple linear equation in time. The corrosion behavior in high-temperature steam was similar in many features to the corrosion in high-temperature water. Goldman and Thomas' and Pray and Peoples' have shown that the addition of tin, while increasing the rate of corrosion, counteracts the deleterious effect of nitrogen. The beneficial effect of iron, nickel and chromium was to improve the adhesion of the oxide to the metal as well as to counteract the deleterious effect of nitrogen. Mallet and Albrecht" have studied the oxidation of two zirconium-tin alloys. The cubic-rate law was found to fit the oxidation data for the 1.5 pct tin alloy while the parabolic-rate law was found to fit the data for the 2.5 pct alloy. Kendall' in a recent paper has studied the oxidation of Zircaloy-2 containing 1.5 pct tin in air atmospheres. Transition Phenomenon—In steam atmospheres Thomas' has observed fora 1.8 pct tin alloy containing small amounts of iron, nickel and chromium that transition to a more rapid rate of corrosion at 400°C

Jan 1, 1959

By T. Sterry Hunt

THE essential principle of this new process, now in operation in Chili and in North Carolina, for the extraction of copper from its ores, is the dissolving of the oxides of copper by a hot solution of protochloride of iron and common salt. In the action which takes place, the protochloride of iron is converted into peroxide, while the oxides of copper are changed into protochloride and dichloride, the latter of which, though insoluble in water, is readily soluble in a hot strong brine. From the solution thus obtained, metallic iron throws down the copper in a metallic state, regenerating the protochloride of iron; which is then ready for the treatment of a fresh portion of oxidized copper ore. In the case of slimy ores, the contact of the bath with the ore is effected by agitation in tubs ; but when the ores are granular, lixiviation in large vats is equally efficient and simpler. The hot solutions, charged with chlorides of copper, are digested in tanks with scrap-iron, or better, are made to flow through covered channels containing the scrap-iron, and in their passage lose the whole of their copper; the reaction at the same time evolving so much heat as to keep up the temperature of the liquid. In order to prevent a certain loss of chlorine, which otherwise takes place from the production of some basic ferric chloride in the reaction between the ferrous chloride and the oxides of copper (both protoxide and dinoxide being generally present in calcined ores), a portion of sulphurous fumes from the roasting is made to pass through the regenerated bath before adding it to fresh ore. This has hitherto been effected by injection, with the aid of a jet of steam.

Jan 1, 1873

By R. F. Mehl, J. T. Ransom

For many years the Metals Research Laboratory of Carnegie Institute of Technology has been concerned with the statistical nature of the engineering properties of steel from an experimental viewpoint, particularly those properties representing ductility.' In the past three years new work has been directed toward evaluating the statistical nature of the endurance properties. It has been shown that both the fracture curve and the endurance limit in fatigue are markedly statistical in nature. The S-N curve (and the endurance limit) of ferrous materials is often determined with specimens which number as few as ten. The common procedure is to test the first specimen at a stress well above the expected endurance hmit. Each succeeding specimen is then tested at a progressively lower stress, until, after five or six tests, a specimen runs ten million or so cycles without failing. Two or three more specimens are then used to find the highest stress at which failure will not occur; the limiting stress determined in this way is called the endurance limit. It has now been found, however, that the variability in the fracture curve and in the endurance limit in heat-treated alloy forging steels is so great that S-N curves must be drawn on the basis of distribution curves which can be appraised only by statistical methods. Two methods have been adopted in this study: (1) straightforward statistical studies of cycles to fracture of a number of specimens at each of a series of stress levels, and (2) a new abbreviated statistical method, known as "staircase testing."2 The latter corisists in testing a series of specimens, one by one, with the test stress for any given specimen automatically

Jan 1, 1950

By E. F. Northrup

THESE brief notes respecting the properties of pure tin that make it useful as a pyrometric substance summarize information gathered by the writer In an extensive experimental investigation on the electrical properties of metals in the molten state. Tin in quantities sufficient for pyrometric purposes may be obtained at relatively low cost and in a state of high purity. The metal melts at 232° C. and, according to determinations made by Greenwood,. 1909, does not begin to boil until a temperature of 2270° C. is reached. The writer can assert, from personal observations carefully made, that tin shows no tendency to boil at a temperature of 1680° C. If Greenwood's observations are correct the temperature interval, 2038° C., in which tin exists as a liquid under atmospheric pressure, exceeds that of any other substance. It has never been observed, as far as the writer is aware, that tin forms any chemical union, as carbide, with carbon at the highest temperatures at which it can exist as a liquid. It is quite certain from the writer's personal observation that tin heated in Acheson graphite to 1680° C. remains chemically uncontaminated. Wires of pure tungsten do not dissolve in molten tin at temperatures at least as high as 1680° C. Tungsten wires or rods may, therefore, be used as electrodes dipping into molten tin when required for measuring the resistance of the molten metal at very high temperatures. When tin is raised to a high temperature in a covered graphite container, the CO atmosphere that exists above its surface has a reducing action, which maintains this surface of mirror brightness. Incidentally, tin maintained molten in a crucible of Acheson graphite makes a most excellent bath into which may be inserted several pyrometers that are to be intercompared at the same temperature.

Jan 8, 1919

By T. Sterry Hunt

THE essential principle of this new process, now in operation in Chili and in North Carolina, for the extraction of copper from its ores, is the dissolving of the oxides of copper by a hot solution of protochloride of iron and common salt. In the action which takes place, the protochloride of iron is converted into peroxide, while the oxides of copper are changed into protochloride and dichloride, the latter of which, though insoluble in water, is readily soluble in a hot strong brine. From the solution thus obtained, metallic iron throws down the copper in a metallic state, regenerating the protochloride of iron; which is then ready for the treatment of a fresh portion of oxidized copper ore. In the case of slimy ores, the contact of the bath with the ore is effected by agitation in tubs; but when the ores are granular, lixiviation in large vats is equally efficient and simpler. The hot solutions, charged with chlorides of copper, are digested in tanks with scrap-iron, or better, are made to flow through covered channels containing the scrap-iron, and in their passage lose the whole of their copper; the reaction at the same time evolving so much heat as to keep up the temperature of the liquid. In order to prevent a certain loss of chlorine, which otherwise takes place from the production of some basic ferric chloride in the reaction between the ferrous chloride and the oxides of copper (both protoxide and dinoxide being generally present in calcined ores), a portion of sulphurous fumes from the roasting is made to pass through the regenerated bath before adding it to fresh ore. This has hitherto been effected by injection, with the aid of a jet of steam.

By N. Standish

By contrast with viscometry and sedimentation, no actual measurements of the applicability of Stokes' law to steelmaking have ever been reported; instead, the proof for and against Stokes' law has been inferred from the frequently observed phenomenon that inclusions collect in the top scum and the bottom of ingots. As such proof is unsatisfactory, continued reference to Stokes' law in steelmaking, even as a model for calculating the terminal velocities of rising inclusions, should be avoided. In fact, all conclusions that have been reached regarding size, density, and viscosity on the flotation of inclusions could be made more rationally without Stokes' law. A worthwhile exception is that of Mitsche1 who in 1934 used Stokes' law to show not only the expected effects of size, density, and viscosity on flotation but also the beneficial effects of i) melting under a slag layer (now Electro Slag Refining); ii) treating melts with synthetic slags (Ref. 2 gives recent applications); iii) bubbling an inert gas through the melt (recent applications in Refs. 3 and 4); and iv) altering the solid/ liquid interface characteristics. At this point, it should again be emphasized that the boundary conditions for which Stokes' law was derived place enormous restrictions on the law but its application, as noted earlier, can yield useful results in some fields under certain conditions and within well-defined limits. When compared with inclusions, which may be solid or liquid, spherical or irregular, dispersed or coagulated, interacting between themselves and the melt, floating in a liquid which is in a state of motion of varying intensity5 and contained in vessels of various shapes and sizes that may change with time as in a solidifying ingot, the conclusion is obvious-Stokes'

Jan 1, 1969

By J. Jolly, R. V. Wheeler

This short note on the probable character of the organic sulfur compounds in coal can do no more than indicate lines of research. We have no new experimental work to describe, nothing comparable in value with the careful studies of American coals by Powell and Parrl and Yancey and Frazer. A study of the manner in which sulfur compounds exist in British coals (and their behavior on heat treatment) is rendered increasingly necessary by the fact that the British reserves of good coking coals of reasonably low sulfur content are fast being depleted. We believe that it is essentially by a study of the modes of formation, occurrence, and decomposition of the various types of inorganic and organic sulfur compounds in coal that it will be possible, with hope of success, to attack the problem of purifying coals, otherwise eminently suitable for coking, from these objectionable ingredients. Sulfur, so far as is at present known, does not normally occur in the free state in the coal conglomerate, but is chiefly distributed, irregularly, in three forms : 1. As primary constituents of the coal conglomerate, organic in nature and probably associated with those molecular complexes that have resulted from the degradation of the proteins of the plant tissues responsible for the formation of the coal mass. These constituents can be classed as "organic sulfur." 2. As metallic sulfides, e.g., iron pyrites. 3. As metallic sulfates, e.g., calcium sulfate and ferrous sulfate. (The occurrence of these compounds varies with the occurrence and degree of degradation of class 2.) It is usually found that sulfur compounds of class 3, the metallic sulfates, are present in coal in small proportions only, amounting to about 1 or 1.5 per cent. of the total sulfur. The compounds in classes 1 and 2 are therefore of more importance. Class 1 alone will receive considera-

Jan 1, 1925

By N. Nakanishi, C. M. Wayman

The effect of small copper additions on the mar-tensitic transformation behavior in Au-47.5 at. pct Cd was studied by measuring electrical resistivity as a function of temperature. The transformation behavior was found to change and transformation start (M,) temperatures for both the ß to ß' and ß to ß' transformations were depressed substantially by the addition of small amounts of copper. Both M, temperatures were lowered approximately 70°C per at. pct Cu. Copper also had the effect of narrowing the transformation hysteresis region (resistivity us temperature), and for the alloy Au-47.5 Cd-1.5 Cu there was little or no hysteresis; in this alloy, the reverse transfmmation upon heating apparently occurs below the thermodynamic equilibrium temperature, To. THE ß phase in the Au-Cd system occurs at the electron/atom ratio 3/2, and is similar to other ß phases in alloys based on copper, silver, or gold. It is of the CsCl type, in which a considerable degree of long-range order persists to the melting temperature.' The phase boundaries of the ß phase are not known precisely below 300° C, but at room tem- perature the phase exists from approximately 46 to 52* at. pct Cd.2 At low temperatures, the ß phase transforms in a diffusionless (martensitic) manner. Alloys having a composition near 47.5 pct Cd transform upon slow cooling to an orthorhombic3 phase, ß', at - 60°C. Alloys having a composition near 49.0 pct Cd, transform at - 30°C into a phase, ß", which has been recently identified as trigonal.4 Alloys having compositions near 48.5 pct Cd will transform into both the 0' and 0" phases over a range of temperatures. The progress of transformations can be observed

Jan 1, 1963

By R. G. Ward

The temperature gradient in the subhearth metal or "salamandern of the iron bhst furnace results in the establishment of gradients in the concentrations of silicon, manganese, carbon, and sulfur. The temperature and compositional variations observed in three blast furnaces are analyzed according to irreversible thermodynamics and the systems appear to be close to the steady state condition. Apparent heats of transport, Q, for silicon, manganese, carbon, and sulfur are found to be respectively -17.5, -5, -2.1, and+22k cal per g mol. In conclusion the significance of thermal diffusion in extraction metallurgy is briefly discussed. INCREASING interest has been shown in recent years in the application of irreversible thermodynamics to metallurgical problems. In particular studies have been made of the transport of matter in thermal gradients1-' and under chemical gradients imposed by a binary solvent However, no detailed example in extraction metallurgy has been reported although gradients are the essence of many extractive processes. The case of the distribution of elements in molten blast furnace iron under a thermal gradient is discussed here. DATA In blast furnace operation the hearth bottom is often extensively destroyed by molten metal, and the metal may penetrate perhaps 10 ft into the furnace foundations forming a "bear" or "salamander". Several hundred tons of molten metal may thus exist beneath the level of the conventional tap hole and remain relatively undisturbed for several years under a thermal gradient. This system is subject to little convective stirring because the temperature decreases from top to bottom, and mechanical stirring due to movements in the stack and to tapping operations is unlikely to penetrate far into the metal. The system may thus be regarded as static

Jan 1, 1963

By A. L. Field

WOOLSEY McA. JOHNSON, Hartford, Conn. (written discussion).¬When ;we regard the number of British thermal units running into the billions that-must be applied to metallurgical slags in the United States, we cannot but conclude that the physical chemistry of-slags is a very important subject when measured in dollars and cents. A further contemplation of the subject shows us that it has been hitherto treated in too purely a practical manner. It is needless to comment at length on the cost of these heat units and on the cost of fluxes to produce these metallurgical slags, for, it amounts to tens of millions of dollars annually. Accordingly, this research is of value to the country. But we must,all balance our results against our efforts. Therefore, while the speaker is unwilling to criticise unduly this meritorious research, lie does criticise it in the interest of the profession for the reason that it seems to him too highly theoretical. The article is much too, scientific to produce results at a minimum cost. Let us explain our meaning. It has been said that there are always two sides to a question. It may be further said that there are always three sides to a question, the two extremes and the middle ground. In any industrial research there are the highly theoretical side, the purely practical side, and the theoretico-practical side. To study a slag and be practical in the studying, there is something needed that represents in the laboratory (or in microcosm) what actually happens macrocosmically in the blast furnace. There is such a thing as the art of metallurgical research occupying the middle ground between theory and practice.

Jan 4, 1917

By N. B. Pilling, R. E. Bedworth

The corrosion of metals is one problem on which time and thought have been expended for many years. In the effort to avert the destructive action of a hostile environment, attention has been directed almost entirely to the conditions under which most metallic structures are called upon to perform, and the extensive and complicated phenomena attending the corrosive action of atmospheric agencies, acting at the ordinary atmospheric temperatures, have been studied, but there is unanimity of opinion regarding many fundamental facts. One neglected phase is the corrosive action of various gases upon metals exposed to temperatures considerably higher than the atmospheric range, and more especially the attack of atmospheric oxygen upon exposed metallic surfaces. That the problem is difficult is connoted by the practical dominance of industrial electric heating by alloys of one type (nickel-chromium). Proprietary interest may account, in part, for the paucity of information available upon even the most general factors determining the behavior of metals and alloys when exposed to such exacting conditions. The present paper gives some conclusions reached as the result of experimental work, extending over several years, on the mechanism and contributory factors of the high-temperature oxidation of a number of simple unalloyed metals; it is free from experimental detail and proof. High-temperature metallic oxidation may be considered as a phase of metallic corrosion. The scheme outlined below, in which corrosive agent and environment are the principal criteria, is one way of analyzing the several groups of corrosion phenomena. Erosion.—Disintegrating or destructive action by physical causes. Corrosion.—Disintegrating or destructive action by chemical causes. Low-temperature Corrosion.—Solid participating phases essentially immobile: (a) Gaseous agent; (b) liquid agent: action electrolytic and action non-electrolytic. High-temperature Corrosion.—Solid participating phases possess diffusive mobility: (a) Liquid agent; (b) gaseous agent: reducing gases, oxidizing gases. (1) Water; (2) miscellaneous elemental and combined oxygen.

Jan 1, 1923

By George Smith

ChillaQoe is situated in latitude 17" S., about 138 miles from the port of Cairns, with which it is now connected by rail. A township has been established on the banks of Chillagoe creek, a perennial stream of irregular volume crossing the field almost at rightrangles, nearly midway between the mining-camps of Calcifer and Mungana, which have been formed at the southeastern and western extremes of the field respectively. This situation was selected because of the water-supply and its proximity to the site most suitable for the erection of reductionworks. By its central position it commands the whole of the mines. The altitude above sea-level is about 1200 ft., whereas that of Calcifer and Mungana is 1400 ft.—a difference sufficient to account for a materially higher temperature at Chillagoe. The surrounding limestone bluffis add by radiation to the heat, and, at the same time, prevent the cool breezes from passing freely through the town; consequently, the temper* ture, which is high throughout the year, and especially so during the summer months, is here ge~ierally very oppressive also. The general trend of the field is southeast and northwest, and its length about 18 miles, with an average width of 5 miles; the approximate area is thus 90 sq. miles. The surrounding mineral-district is, however, much more extensive, and numerous other mines, sprcad over wide areas and producing a variety of minerals, exist in the same or parallel belts of mineralized country, of which Chillagoe proper covers but a very small portion. Immense bluffs of limestone, wollastonite and conglomerate, rising in places to nearly 300 ft., and so~netimes nearly a quarter-mile across, give the field a very picturesque and interesting appearance. The limestone has been classified as Devo-

Jan 1, 1904

By H. F. Bishop, F. A. Brandt, W. S. Pellini

M. S. Fisher and D. R. F. West (Imperial College of Science and Technology, London, England)—It may be of value to compare certain features of the results recorded in this very interesting paper with those of an investigation11 involving determinations of temperature gradients and rates of solidification of steel blocks of 3 in. sq section, cast horizontally in sand molds, some of which contained chills. Castings in plain carbon steels containing up to 0.8 pct C were made and, throughout this range of compositions, both inverse-rate and direct cooling curves, obtained from thermocouples placed within the mold cavity, showed a major arrest, the temperature of which was taken as the "effective liquidus" for the particular steel in question, solidifying under the conditions of the investigation. At the completion of the arrest, the curves showed a comparatively rapid de- crease in temperature. Some of the steels investigated lay within the peritectic region, and a second arrest at 1485°C was detected. In Fig. 15, which shows the effective liquidus temperatures, the limit of the 8 + liquid field has been placed at approximately 0.5 pct C. In inverse-rate curves corresponding to the thermal center of each casting, there was always a discontinuity, viz: an abrupt change of slope, at a temperature about 10 to 20°C below the "liquidus arrest," after which there seemed to be no significant irregularity in the rate of cooling. Curves corresponding to other positions in the casting generally showed some irregularities below the main arrest, probably as a result of heat flow from the solidifying interior. Even the reproducible discontinuity in the curves for the central positions appeared to have no theoretical or practical significance, though it probably corresponded to a stage in the solidification process at which only a relatively small amount of interdendritic liquid remained. Its temperature, rela-

Jan 1, 1953

By R. E. Bedworth, N. B. Pilling

The corrosion of metals is one problem on which time and thought have been expended for many years. In the effort to avert the destructive action of a hostile environment, attention has been directed almost entirely to the conditions under which most metallic structures are called upon to perform, and the extensive and complicated phenomena attending the corrosive action of atmospheric agencies, acting at the ordinary atmospheric temperatures, have been studied, but there is unanimity of opinion regarding many fundamental facts. One neglected phase is the corrosive action of various gases upon metals exposed to temperatures considerably higher than the atmospheric range, and more especially the attack of atmospheric oxygen upon exposed metallic surfaces. That the problem is difficult is connoted by the practical dominance of industrial electric heating by alloys of one type (nickel-chromium). Proprietary interest may account, in part, for the paucity of information available upon even the most general factors determining the behavior of metals and alloys when exposed to such exacting conditions. The present paper gives some conclusions reached as the result of experimental work, extending over several years, on the mechanism and contributory factors of the high-temperature oxidation of a number of simple unalloyed metals; it is free from experimental detail and proof. High-temperature metallic oxidation may be considered as a phase of metallic corrosion. The scheme outlined below, in which corrosive agent and environment are the principal criteria, is one way of analyzing the several groups of corrosion phenomena. Erosion.—Disintegrating or destructive action by physical causes. Corrosion.—Disintegrating or destructive action by chemical causes. Low-temperature Corrosion.—Solid participating phases essentially immobile: (a) Gaseous agent; (b) liquid agent: action electrolytic and action non-electrolytic. High-temperature Corrosion.—Solid participating phases possess diffusive mobility: (a) Liquid agent; (b) gaseous agent: reducing gases, oxidizing gases. (1) Water; (2) miscellaneous elemental and combined oxygen.

Jan 1, 1923

By Lawrence A. Garfield

From the bottom of a shallow fissure the near-naked man-animal hacked out a hand-sized chunk of the red rock-like material which, when beaten between other rocks, could be drawn out to the thinness of a flint edge. Unlike flint, however, it did not shatter when, as the point for a spear or arrow, it went wide of its mark and fell amongst the rocks or tree branches. For this reason and others, the red rock- like material was specially sought and much time was spent in trying to break it from the real-rock in which it grew. Only infrequently was a chunk broken free and in this area many hours had been spent to win but a few fragments. What luck then, to remove so large a piece where before nothing but real-rock dust formed whenever the stone hammer hit. Why did this happen? Did yesterday's food-fire, burning on top the red rock, loosen its hold on the real-rock and cause it to break free when struck with the stone hammer? It is not a matter of recorded history that the first heat assisted extraction of native copper from country rock occurred under the circumstances or in the manner related but it is known that crude mining operations using these techniques were conducted by primitive man. In this way the first mineral production may have been achieved and the original example of rapid excavation unknowingly given to the world. Rapid excavation is not a method of removing rock or ore from an insitu condition nor does the term refer to a type of equipment which is specifically employed in mining and underground construction. It is, rather, the nomenclature currently popular in industry-primarily in underground construction- relating to a comparative rate of performance.

Jan 1, 1971

By Patricia J. Rand, Kailish Narayan

Atlantic Richfield Co. began operating a commercial uranium solution mining project in April 1975, in Live Oak County, Tex., 10 miles southwest of the town of George West. The operation is designed to produce 250,00 lb of U308 per year and is jointly owned by Atlantic Richfield Co., Dalco, and U.S. Steel. The proprietary process employed in this operation consists of injecting an alkaline leaching solution into the ore-bearing formation through a pattern of injection wells. The uranium-bearing solution is then removed through producing wells using submersible pumps in central production wells. The produced solution is pumped through a pipeline to the plant area where the uranium is extracted. The barren solution is refurbished and returned to the pattern area for reinjection. The injection field and plant site are located in the drainage of Spring Creek, a small intermittent stream tributary to the Nueces River. Land use in the area is primarily agricultural cattle ranching and farming---but several producing gas fields are present in the areas as well. A nine month enviromental baseline study was conducted on the property beginning in Feb. 1975. Plants and animals of the Clay West area were identified and representative terrestrial and aquatic communities were analyzed. Physical and chemical parameters of the soils were described and analyzed. The surface and underground waters were analyzed chemically; radionuclides, heavy metals, nutrients, and pesticide concentrations were measured in the creek sediments; bacteriological measurements were made in creek water and sediments; radionuclide and chemical levels in plants and animals, both terrestial and aquatic, were measured. These studies, though not required by existing, state or federal laws, were considered necessary to assess the existing conditions before operations began on site. The in-place leaching technique for uranium mining eliminates the enviromental disturbances associated with open pit or underground mining. No grinding and crushing of ore is needed, nor are large tonnages of waste tailings produced. Surface subsidence is not expected since less than 5 lb of uranium is present per ton of rock and even complete removal of such small amounts should not cause subsidence. Solution mining has fewer environmental problems than conventional mining. Members of the Texas Water Quality Board recognized the differences which exist and have recently formulated new environmental control procedures which apply specifically to solution mining. Some of the solution mining activities which are of particular concern are discussed in the following pages. Process Description The produced uranium-bearing solution is pumped through a pipeline from the pattern area to the plant area. The first pattern area consists of a nest of 125 fluid injection, production, and monitor wells [(Fig. 1)]. Injection wells have 4-in. casings and are spaced 50 ft apart on a square grid. Production wells have a 6-in. casing and are located in the center of each square. A block flow sheet of the plant is given in [Fig. 2]. The produced solution goes through parallel trains, each consisting of a carbon column and an ion exchange column in series. The carbon column removes any sand present in the produced solution and the ion exchange column extracts the uranium. The depleted solution is treated with chemicals and returned to the field for reinjection. The uranium retained in the ion exchange column is removed periodically with a sodium chloride solution. Uranium-bearing solution from the ion exchange column is passed through a charcoal column for removal of impurities and then to a precipitation tank where the uranium is precipitated as yellowcake slurry. The yellowcake slurry is clarified, filtered and dried to produce a granular yellowcake product. Environmental Considerations Sources of waste solutions to storage reservoirs, the backwash reservoir and atmospheric discharges are shown in the block flow sheet [(Fig. 2)]. These waste solutions pose a relatively small problem and are adequately controlled by conventional means. There is one area, however,

Jan 1, 1978

By J. Gurland

The effect of four different second-phase additions on the strength of composite alloys with a common matrix was investigated. The four compositions each consisted of 85 pct by volume of silver with additions of 15 pct of either tungsten, molybdenum, tungsten carbide, or nickel. These particular additives were chosen because of their low mutual solid solubilities with silver at room temperature, the alloys consisting essentially of a dispersion strengthened silver matrix in which the second phase is distributed randomly. Test specimens were prepared by a powder metallurgy procedure consisting of ball milling the mixed powders, compacting, and sintering at 920°C for 1 hr in hydrogen. The constituent powders were of CP quality and of particle size between 2 and 10 ?. The compacts were subsequently hot pressed at 1000 psi and 1400° in an Inconel die, coined at room temperature at 60,000 psi and finally annealed and outgassed in vacuum at 800°F. The microstructures of the alloys are shown in Fig. 1, and the microscopically observed porosity grade was A-2 or better as evaluated by ASTM Recommended Practice B 276-54. The properties of the sintered compacts are listed in Table I, and the load-deformation curves in bending are shown in Fig. 2. The samples, of rectangular cross section, were loaded at the center of 58 in. span, and the reported stress was calculated on the basis of linearly elastic behavior in order to allow the comparison of specimens of slightly different dimensions. It is apparent that the tungsten, molybdenum, and tungsten carbide alloys exhibit very similar deformation curves. The moduli of elasticity were determined from the slopes of the stress-deflection curves at small loads. The measured values agree quite well with those calculated by the strength of materials approximation proposed by Paul1 for the elastic constants of mixtures, the calculated values being 15.0, 15.0, 17.4, and 13.4 million psi, respectively, for the tungsten, molybdenum, tungsten carbide, and nickel combinations with silver. The strength of the Ag-Ni composition is appreciably lower than that of the other three alloys. The discrepancy between the two groups is accounted for by the following characteristics of deformation and failure which were observed microscopically during the tests: A) The deformation of the W, Mo, and WC alloys did not involve the second phase particles to any appreciable extent. Slip and fracture took place in the silver-rich matrix alone, although the fracture path generally skirted the particles by favoring the phase boundaries. The deformation proceeded according to the following sequence: 1) formation of small, discontinuous microcracks in areas of the matrix adjacent to a particle, 2) general slip in the matrix and extension of cracks, 3) failure of specimens by propagation of cracks through matrix. The near coincidence of the 3 load-deflection curves suggests that the nature of the second phase particles does not decisively influence the plastic behavior of composite alloys of this composition as long as the particles do not undergo any considerable deformation themselves. B) A markedly different behavior was exhibited by the Ag-Ni composition where the relatively low flow strength is associated with the low yield strength of the nickel grains. Slip in the nickel grains was first observed at a stress of approximately 10,000 psi, although failure, at a later stage, took place by the propagation of cracks through the matrix. The ductility of this aggregate, in which both components deform plastically, is appreciably greater than that of the elastic-plastic composites. In summary: 1) The measured values of the moduli of elasticity of the composite alloys under discussion are in good agreement with the "strength of materials" approximation proposed by Paul.' 2) The overall plastic behavior of these particle-strengthened alloys is unaffected by the nature of the second phase particles, if the latter remain elastic. This work was supported by the Office of Naval Research. The experimental results are presented

Jan 1, 1962

By A. C. D. Chaklader, Ashok K. Kakar

The basic density equation originally dericed ' to predict the increase in density of a compact of spherical particles with the progressive deformation at the points of contact has been further modified to include the yield strength of the material. This has been done by assuming that the contact areas grow to stable sizes under a fixed stress which is equal to three times the yield strength. The final equation has the form: where Do and D me the initial and final bulk densities of the compact, u is the applied pressure, and Y is the yield strength of the material. This equation was tested with the data obtained on spheres of lead, K-Monel, and sapphire. The calculated yield strength t~alues for lead and sapphire are within the range of values reported in the literature. A few of the earliest hot pressing models proposed to explain the mechanism by Murray, Livey, and williams2 and then by McClelland3 are based on a plastic flow mechanism. However, more recent investigations suggest that the overall densification process is a combination of several mechanisms, such as particle rearrangement, fragmentation, plastic flow, and stress-enhanced diffusional creep. While fragmentation and particle rearrangement are considered to be responsible for the densification in the early stages,"475 it has been concluded that the final stages of hot pressing are controlled by stress-enhanced diffusional creep.516 The manner in which the densification takes place, i.e., by fragmentation, particle rearrangement, plastic flow, or stress-enhanced diffusional creep, would depend upon the type of material, the temperature, and the stress level used during the hot-pressing experiments. Metal compacts can be expected to have a much greater contribution from plastic flow than ceramic oxides. Also, plastic flow would be a significant contributing factor to densification at high temperatures and high stresses. Most of these works, directed towards elucidation of densification mechanism, have dealt with kinetics of the process. The results of most of the authors vary from one another and they have proposed either new empirical or semiempirical equations to fit their data. The densification rate was found to vary with the type of the powder, shape and size of the powder, initial packing density of the compact, and a few other factors such as rate of heating, pressure, and so forth. Beyond the initial stages, the densification process has been considered to be as time-dependent flow, controlled by a diffusional process, e.g., Nabarro-Herring creep. Palm our, Bradley, and johnson' have attempted to use modified creep rate equations to interpret the data of densification under hot-pressing conditions. Beyond the initial stages, however, the densification would be controlled by a process depending upon the temperature, pressure, and size of the powders. It is the authors' belief that such densification cannot be exclusively controlled by a single process and so attempts should be made to study some observable phenomenon like microstructure, yield strength, and so forth. The emphasis of this work has been toward studying the densification problem from a more fundamental point of view. Some of the principal variables, like initial packing density, mode of packing, and size of the powders, have been controlled to a great extent. The total strain produced on pressure application (instantaneous) in such a case can be considered to be due to plastic and elastic deformation. The elastic component of the strain can be determined by decreasing the load to the initial value. The strain remaining then can be correlated with the contact areas produced by deformation and the corresponding applied load. In a previous paper,' the possible deformation behavior of spheres in a compact has been theoretically analyzed and experimentally tested. The change in contact area radius a relative to the particle radius R was related to the bulk density and the bulk strain for simple and systematic modes of packing. Tt was found that a density equation relating the above parameters can be represented by: where D and Do are the bulk densities of the compact at any value of a/R and a/R = 0, respectively. This basic equation should hold for any material as it was derived from geometrical considerations alone. An attempt has been made in this work to include the yield strength in the above density equation, so that a knowledge of the properties of any material can be used in predicting the densification behavior during the hot-pressing process. THEORETICAL CONSIDERATTONS The deformation of two spheres in contact under a static load can be compared to the deformation occurring between a hard spherical indentor and the flat face of a softer metal. Tt has been shown theoretically by both ~encky~ and lshlinskyg and experimentally by ~abor" that, for a material incapable of appreciable work hardening, the mean pressure required to produce plastic yielding (for deformation occurring between flat face and a hemispherical indentor) is approximately equal to three times the elastic limit, Y, of the material (in tension or compression experiments). Tabor has further observed that the same relationship is valid in the case of work-hardening materials, if the elastic limit at the edge of the indenta-

Jan 1, 1969

By R. F. Mehl, C. E. Birchenall

R. E. Hoffman and D. Turnbull—The authors have presented evidence which they have interpreted as indicating that the rate of self diffusion is not intrinsically more rapid at grain boundaries than within the grain. Grain-size effects which apparently exist are attributed rather to impurities concentrated at the grain boundaries. In view of our own experiments and the existing evidence, we believe that the support for this hypothesis is not convincing. We have in progress an investigation in which the rate of self diffusion of silver is being measured over an extended temperature range in both single-crystal and polycrystalline specimens. The results of the single-crystal experiments and some preliminary data on fine-grained polycrystalline specimens have already been reported:' and it is anticipated that a complete report will be published in the near future. The self-diffusion coefficient of large-grained polycrystalline silver (1 grain per sq mm) has previously been measured by Johnson" between 730" and 940°C. The diffusion coefficients which we have measured in single crystals (210 plane normal to diffusion direction) agree within experimental error with values calculated from an extrapolation of Johnson's curve down to temperatures as low as 500 °C. However, it has been demonstrated that the overall self-diffusion rate in fine-grained polycrystalline specimens (initial grain size of 0.003 cm) becomes measurably larger than the overall rate in a single crystal at a temperature of 600°C, and the discrepancy between the two rates becomes greater as the temperature is further decreased. In fact, it has been possible to obtain satisfactory penetration curves for polycrystalline specimens using the sectioning technique at temperatures as low as 400°C. At this temperature, the penetration is 50 to 100 times greater in the polycrystalline specimens than in a single crystal. Fisher" has developed an analysis whereby the ratio of the rate of the unit diffusion process at the grain boundary to the corresponding rate within the grain can be calculated from the penetration curves and an assumption as to the width of a grain boundary. This analysis applied to our data indicates that the unit process at the grain boundary is faster by a factor of 10' at 475°C when the grain boundary width is taken to be 5. The silver used in most of these experiments was obtained from the Handy and Harmon Co. and listed as 99.97 pct pure. Preliminary experiments on 99.999 pct silver from the Jarrel-Asch Co. indicate a grain-size effect of the same order of magnitude as in the less pure silver. Nominally, these purities are as good, at least, as that of the carbonyl iron used by the authors, but of course if an impurity effect does exist its magnitude might be very dependent upon the nature of both major and minor constituents. The authors have cited the work of other investigators who have found no grain-size effects. Neither Steigman, Shockley and Nix" nor Maier and Nelson8 were able to correlate self-diffusion coefficients of copper with grain size. However, all their measurements were performed at or above 750°C; and on the basis of our work with silver, no grain-size effect would be expected at temperatures above about 0.7 of the absolute melting temperature unless the grain size were exceedingly small. Likewise, in the investigation of the self diffusion of lead by Seith and Keil,14 the lowest temperature at which the diffusion coefficient was measured in polycrystalline specimens was 207°C, which is still sufficiently high so that the lack of a grain-size effect is not surprising. Finally, in those experiments on iron from which they concluded that there was no grain size effect, Drs. Birchenall and Mehl seem to have no information as to the actual grain sizes immediately prior to and following the diffusion anneal. Without this information, we believe that their own experiments offer little support for their hypothesis. F. S. Buffington, I. D. Bakalar, and M. Cohen—The results given in this paper agree in order of magnitude with those tentatively reported by us.27 However, significant differences exist in the two sets of data, and it may be well to make an explicit comparison. The diffusion studies at M.I.T. were conducted on somewhat higher purity iron (99.98 pct Fe) than the grades used by the authors, but this is undoubtedly not the answer. Fig. 4 shows the diffusion results of both laboratories for the gamma phase, omitting the authors' data on the commercial steels, while fig. 5 presents a similar comparison for the alpha phase. The divergence is much more marked in the latter case than in the former. In connection with the M.I.T. determinations, all of the runs in the gamma range and those above 800 °C in the alpha range were conducted with specimens having a relatively thick (0.002 cm) electrodeposit of radioactive iron. This practice minimizes any possible error due to extraneous diffusion that may occur during the heating to and cooling from the operating temperature. An exact solution of Fick's law for these boundary conditions was used in calculating the diffusion coefficients. At a later time, three runs were made below 800°C, using very thin electrodeposits similar to those of the authors, and the points fell considerably below the values expected from the extrapolation of the results based on the specimens with the thick deposits (compare dash-dot line in fig. 5). However, in the runs with the thin deposits, deviations of 100 pct were found between the individual specimens, whereas the maximum deviation with the thick deposits was less than 25 pct. Accordingly, it is not known at the moment whether the M.I.T. points below 800 °C should be given as much weight as those above 800°C. If this were done, the frequency factor would be of the order of 400 cm2 per sec, which is quite high. In other metals, the frequency factor for self diffusion lies between about 0.1 and 10 cm2 per sec. As the points below

Jan 1, 1951

By Arvid E. Anderson, Frank K. Cameron

The weathering of copper-bearing ores with the formation of a water soluble salt and the recovery of the metal by leaching and evaporation precipitation, are processes long known, which have at various times been utilized with more or less commercial success. It is commonly assumed that the technical principles involved are quite simple and their application to a particular case easy. If these assumptions were true, we should anticipate a long list of uniformly successful leaching operations, which is not the case, and one would be justified only in calling attention to either unique or peculiar features of any particular enterprise; whereas, in studying the problems of the recovery of copper from the old workings of the Ohio Copper Co. in the light of available descriptions of other leaching projects, we have not found the assistance hoped for to guide us to the best realization of our own opportunities. It appears desirable, therefore, to call attention to these guiding principles, together with a description of the facts of accomplishment. Justification lies in the fact that the leaching and precipitation of copper at the Ohio Copper Co. mine in Bingham Canyon, Utah, is successful. This success is measured by an average monthly production of 600,000 Ib. of copper at an average operating cost, to date, of 3.85 cents per pound at the company's workings, or 6.32 cents per pound after paying shipping and smelter charges on the finished copper. A total of 17,076,099 Ib. of copper had been shipped to the smelter from the beginning of operations, August, 1922, to April 1, 1925. Probably these results can be bettered with further study and realization of the factors involved and the devising of methods of meeting them. It is now an assured fact that the enterprise will have a relatively long and continuously profitable life and that its reserves will not, nor cannot, be suddenly and permanently depleted. It is particularly noteworthy that the financing of this enterprise has been entirely from its earnings. The few hundred dollars necessary for the first experiments and production were obtained by the sale of used, and no longer needed, equipment from a mill belonging to the company; and all funds since required throughout the growth and development of the enterprise, from a few troughs with a production of 2000

Jan 1, 1926