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By T. P. Chen, F. W. Bowdish

Studies made with a captive bubble apparatus on the sulfidization and collection by amyl xanthate of true chrysocolla specimens have defined the ranges of pH value and sulfide concentration which permit contact between the bubble and the mineral surface. Titanium compounds were the most effective of the materials found to activate the sulfidization of chrysocolla. With titanium activation, the contact angles and the ranges of pH value and sulfide wncentration giving bubble contact were all increased. Chrysocolla ores were concentrated by flotation. Chrysocolla ores occur at many localities in grade and quantity sufficient to make mining and millin feasible, but no satisfactory method of concentratio has been found. Although chrysocolla may be leached with acid, only those ores without acid-consuming gangue may be leached economically. Because of its potential importance, a study of the conditions nece sary for flotation of chrysocolla has been carried ou The literature contains a few references to flotation of chrysocolla. Two methods were developed by the U. S. Bureau of Mines.1,2 The first consisted of a fatty acid soap and a high xanthate as collectors of chrysocolla from a synthetic ore, while the second involved the use of hydrogen sulfide and xanthate. Ludt and DeWitt3 demonstrated the difference in adsorptive powers of chrysocolla and quartz for bas triphenyl methane dyes and suggested the use of butyl, hexyl or octyl-substituted malachite green as collector. Jackel4 emphasized the effects of combin tions of reagents such as Aerofloat 31, pine oil, and Reagents 404 and 425 with sodium sulfide and zinc hydrosulfite as conditioning agents. Although he reported recoveries of 89% from a synthetic ore and 98% from a natural ore containing azurite, malachite, chalcopyrite and chrysocolla, careful application of Jackel's method to chrysocolla from Tyrone, N.M., failed to give a high recovery. MATERIALS AND TECHNIQUE Samples from Inspiration, Ariz., and Tyrone and Magdalena, N. M., were used for experimentation and verified as true chrysocolla by leaching tests, specific gravity tests and X-ray diffraction. Chrysocolla does not dissolve at pH 4, although malachite and azurite do. Chrysocolla is about half as dense as the copper carbonates. X-ray diffraction analyses by the powder camera method confirmed the samples as true chrysocolla. A captive bubble apparatus, which cast an enlarged image of the air bubble and the mineral surface upon a screen, was used to check on the character of the surfaces. The specimens were prepared by grinding a flat surface on a glass plate using fine abrasive; then they were washed and kept in distilled water until they were to be treated with reagents. Before each reagent treatment, the specimen was carefully checked for cleanliness in the captive bubble apparatus. It was assumed that the surface was clean if, after fine grinding and washing of the specimen, the bubble would not stick. Specimens were handled with glass forceps, and precautions were taken to avoid contamination of the mineral surfaces. Contact angle measurements were carefully made several times on each treated specimen to obtain reliable average values. EFFECT OF pH VALUE AND SODIUM SULFIDE CONCENTRATION In each experiment, a specimen with a freshly ground surface was immersed for 10 min in a solution of sodium sulfide, washed and immersed for 15 min in a solution containing 30 mg per 1 of potassium amyl xanthate. The specimen was then washed again in distilled water and tested for contact angle in the captive bubble apparatus while submerged in distilled water. In this series of experiments, the pH of the sulfidizing solution was varied from 3 to 7, and the concentration of sodium sulfide, containing 60% Na2S, was varied from 50 to 650 mg per 1. Many combinations of pH value and sulfide concentration resulted in no contact between the bubble and the surface, but over a limited range of conditions, contact angles varying from 24ºto 52ºwere obtained. The data in Fig. 1 show sulfidization conditions that lead to bubble contact and those that do not. The region of contact is surprisingly small, which may indicate why flotation of chrysocolla involving sulfidization has proven so difficult in practice. Several features of the system are illustrated in Fig. 1. In the region between pH values of 4 and 6 with sodium sulfide concentrations below about 350

Jan 1, 1963

T. L. Joseph (University of Minnesota, Minneapolis, Minn.)—Mr. Killian is to be commended for his inquiry as to why a decrease of 15.3 pct in coke consumption was accompanied by a decrease of only 1.9 pct in the CO/CO, ratio of the top gas. Although I encouraged him in his efforts to find a more significant and meaningful carbon-gas ratio, the method, calculations, and conclusions originated entirely with the author. Whether we agree entirely with the assumptions underlying his corrected ratio, I think we can all agree that a better ratio is needed, and that he deserves credit for recognizing the need and for doing something about it. To be most useful, the CO/CO, ratio for the top gas should reflect the way in which the carbon is gasified in the furnace, particularly the degree of oxidation and the extent of heat release. The effect of CO, from the decomposition of the limestone and the effect of the reaction of CO and water vapor in the upper part of the furnace on the quality of top gas should be isolated from the effect of more basic reactions such as ore reduction and solution loss. The reduction of sufficient iron oxide to produce a ton of pig iron and the accompanying changes in the proportions of the carbon gases can be expressed on a mol basis as follows: 16.5FeA + 16.5CO - 33FeO + 16.5CO, [1] 33FeO + 33.0CO = 33Fe + 33CO. [2] The CO, from eq 1 normally escapes from the furnace because it does not react with coke at the temperature of its release. However, as much as 50 pct of the CO, from eq 2 may react with coke because it is released at temperatures above 1000°C: 16.5CO. + 16.5CO2 = 33CO [3] Thus we see that the gasification of 16.5 mols or about 200 lb of C in solution loss will regenerate as much CO as is required for the last stage of reduction. The pronounced effect of reaction 3 on the final proportions of CO and CO, in the gas stream is obvious. It also follows that reaction 3 materially alters the heat release but it cannot be entirely eliminated in Lake ore practice. A previous study indicates that 100 lb of solution loss may be necessary to maintain the reducing power of the gas. A reduction of 100 lb from the normal level of 200 lb would mean that over 1,-000,000 additional Btu are released in the process. The 100 lb of additional carbon which will be burned at the tuyeres will release 437,000 Btu and the absorption of 583,000 Btu by eq 3 would be prevented. One of the chief objectives of sized ore burdens and more uniform distribution of the gas stream is to minimize solution loss by completing reduction higher in the furnace and in turn to release the maximum amount of heat from the carbon charged. It was odd, indeed, to find that the use of sized ore and sinter in the careful tests reported by Dobscha had changed the CO/CO2 ratio very little. The author has stressed the close correlation between his corrected CO/CO, ratio and production. A correlation of fuel consumption and the CO/CO, might be more logical. Fuel consumption on the prepared ore burden decreased 15.3 pct whereas the corrected CO/CO2 ratio decreased 19.0 pct. Although this agreement between the reduction in fuel and the reduction in corrected CO/CO2 ratio is not as close as the correlation with tonnage, it indicates the corrected ratio is superior to the normal ratio which decreased less than 4 pct. Some adjustment should be made for the reaction: CO + H2O = CO2 + H2 —700Btu [41 because there is evidence to indicate that about one half of the hydrogen is formed in the upper 21 ft of

Jan 1, 1953

By W. T. Cardwell

Physically absurd, triple-valued saturations appear in the straight-forward solution of the Buckley-Leverell equations for the displacement of oil by water or gas. From an engineering viewpoint, the triple value causen no difficulty. It is well known how it may be compensnted in order to obtain physically meaningful, numerical results. From a scientific viewpoint, the question still arises: What did the triple value mean? This paper explains how and why the triple value arose in non-capillary Buckley-Leverett theory. The discussion should serve as a background for the understanding and use of the modern method of characteristics in di.~pkzc(>ment theory. INTRODUCTION Displacement theory was introduced to petroleum technologists in 1 941 by Buckley and Leverett.' Their first equation, which they wrote down without derivation, was equivalent to the following: ?s/?t= - qr/F ?f/?r (1) where S = saturation of displacing fluid (a fraction) r = time q,. = total volumetric velocity of both the displacing phase and the phase being displaced (usually, but not necessarily, assumed to be a constant) F = porosity (a fraction) f - fraction of the total volumetric velocity that is the volumetric velocity of the displacing phase (assumed to he a function of S only x = distance. Buckley and Leverett called Eq. I "a material balance equation". Actually it is derived from both a continuity equation, or material balance equation, and Darcy's law. Buckley and Leverett jumped from their Eq. 1 immediately to their Eq. 2, which was the equivalent of the following: (?x/?t)x = qr/F df/ds = qr/F f'(s) (2) The jump from Eq. 1 to Eq. 2 involves apparently simple mathematics, but in that apparently simple mathematics lies a subtle point that is part of the key to the meaning of the triple value to be discussed here. Eq. 2 may be readily interpreted as saying that a point of constant saturation (on a saturation-vs-dis-tance curve) moves with a constant velocity that is proportional to the total volumetric rate, inversely proportional to the porosity, and is otherwise a function of the saturation itself. So that if one knows the derivativc with respect to saturation of the fractional flow function, f(S), for each saturation, one knows the velocity of each point of the moving saturation-vs-distance curve. The function f(S) can he determined experimentally and its derivative f'(S) can be calculated. It turns out that the experimentally derived f'(S) is not a monotonic function of S, but instead it has a definite maximum and declines away at both high and low saturations. This in turn means, in accordance with Eq. 2, that on a moving saturation-vs-distance curve, ccrtain intermediate saturations will travel faster than the saturations either higher or lower. The result is indicated in Fig. 1. In Fig. 1, the abscissas represent distances along a column of porous medium, which column is assumed to be uniform in cross-section perpendicular to the ab-scissal direction. The ordinates represent fractions of pore space occupied by the displacing phase, which may be either water or gas. It is assumed that the saturation is uniform over all planes perpendicular to the abscissal direction. The saturation is a function only of time and one space variable. Time variation of the saturation is represented by change in shape of a curve such as curve AGJ, which represents the initial saturation-vs-

By G. K. Manning, A. R. Elsea, A. B. Westerman

INTRODUCTION A CONSIDERABLE number of high-temperature alloys, that is, alloys which have load-carrying ability at elevated temperatures, have been developed on an empirical basis. In order to determine why these alloys possess this particular ability, a project was started at Battelle Memorial Institute on the fundamental factors promoting high-temperature strength of alloys. At the time of inception of this study, the cobalt-base alloy, Vitallium, was widely used because of its good high-temperature properties. One phase of this study was to include an investigation of the structures observed in Vitallium after various heat treatments. However, before investigating the structural features of Vitallium, it appeared logical to examine the phase diagrams of the related binary systems in order to develop information as to which phases- might be present in Vitallium. A preliminary survey of the pertinent alloy systems was made, with particular emphasis on the cobalt-chromium system, which is the base for the Vitallium series of alloys. The early work of Lewkonja1 and Guertler2 indicated that cobalt and chromium are completely miscible in the liquid state, and, within a narrow temperature range, in the solid state; that the liquidus shows a minimum; and that the alloys containing 45 to '85 pct chromium undergo a transformation at 1200 to 1250°C. More recently, Wever and Haschimoto,3 Wever and Lange,4 and Matsunaga5 carried out experimental work which led to the diagrams shown in Fig I and 2. Both diagrams are based on thermal analysis, metallographic, magnetic, and dilatation data; in addition, X ray diffraction results were used by Wever and Haschimoto, and electrical resistance measurements by Matsunaga. It is apparent from a comparison of the two diagrams that there was a difference of opinion as to the locations of the boundaries of the various phases, and as to the existence of a phase containing approximately 47 pct chromium. With these exceptions noted, it might be pointed out that the two diagrams are similar, and that, in general, any particular reaction which is shown on both diagrams occurs at a lower temperature on the Matsunaga diagram than on that of Wever-Haschimoto-Lange. Thus, in view of the gaps in the data and the questionable features in the published diagrams, it appeared desirable to start the fundamental study of Vitallium by determining the diagram for the cobalt-chromium system. EXPERIMENTAL WORK For the convenience of the reader, the diagram as determined by the present investigation is presented in Fig g. The liquidus and solidus data for the low-chromium alloys were taken from the work of Wever and Haschimoto,3 while the, melting point for pure chromium is the

Jan 1, 1948

By P. A. Witherspoon, R. W. Donovan, T. D. Mueller

The use of petroleum-barren aquifers for underground storage has become extremely important to the natural-gas industry. A critical problem in assessing the feasibility of a specific aquifer for such use is the permeability determination of the caprock over the proposed storage project. The approach used here is to conduct both static and dynamic field tests on the aquifer being analyzed. Valuable information on the possibility of communication between the storage aquifer and any other aquifers above can be obtained by measuring hydrostatic water levels and water analyses. Significant differences in such data give evidence of the lack of communication between the intended storage reservoir and other horizons. The dynamic approach requires that one well be pumped in the storage aquifer, and changes in fluid levels recorded in both the aquifer and its caprock. The interpretation of the data from such pumping tests involves the solution of nonsteady radial flow in an infinite aquifer and the influence on such flow of a leaky caprock. A finite-difference model has been used to investigate this problem, and the transient behavior has been solved numerically with a digital computer. It has been found that the pressure transients in the storage aquifer are not affected significantly by moderate caprock leakage. The pressure behavior of the caprock is a much better indicator of the degree of leakage, and generalized solutions for this behavior are included. Field data are presented to demonstrate both the static and dynamic approach. If is concluded that appropriate investigation of the groundwater hydrology in an aquifer-type gas-storage project can provide much valuable information for determining the effectiveness of the caprock to hold gas. INTRODUCTION Underground storage of natural gas in the United States has been developing at a rapid rate over the past few years. In 1955, the total gas-storage capacity was about 1.6 trillion cu ft; by 1961, this figure was almost 3.2 trillion cu ft, an increase of 100 per cent in six years.' This trend un- doubtedly will continue because the economics favor the development of gas storage, as opposed to the construction of new pipelines, to meet the inherent cyclic demand for fuel in the metropolitan areas of this country.' About 15 per cent of the current underground gas storage has been developed in petroleum-barren aquifers, i.e., geological domes or anticlines in which no commercial quantities of oil or gas had been produced prior to the storage operations. The necessity for using barren aquifers outside many metropolitan areas of this country has been due to the lack of depleted oil or gas fields that were near enough and large enough to meet the demands of such consuming areas. Pipeline companies have developed aquifer storage along their transmission lines to meet the fluctuating needs of their complex systems. Considerable thought has also been given to the problem of storing gas in a structureless aquifer, both in this country' and in the Soviet Union outside the city of Leningrad.'," Conditions such as these have led to the development of aquifer gas-storage projects in many parts of the U. S. Most of these developments have centered in the Mid-Continent area, and the greatest amount of activity has been concentrated in Illinois.6 Thus, the use of petroleum-barren aquifers for gas-storage purposes has become extremely important to the natural-gas industry. There are three basic problems in developing aquifer-type storage: (1) finding an adequate geologic structure, (2) finding a suitable storage reservoir within the structure and (3) determining the tightness of the caprock over the intended storage zone. The first two problems can be solved by applying conventional methods of exploration geology, but once these problems are solved, the question arises as to why no oil or gas is present in an otherwise favorable setting. Two situations are possible: (1) an adequate source bed was never present, or (2) a source bed was present but the petroleum seeped away because of a leaky caprock. Determining the tightness of the caprock is one of the most critical problems in assessing the feasibility of a specific aquifer for storage purposes. In attacking this problem, one usually takes cores of the caprock and subjects them to a rigorous investigation. Such core data are desirable, but they only detail the matrix properties and cannot be expected to reveal the gross characteristics of the caprock. Several gas-storage projects in the U. S. have had considerable leakage where

By J. E. Powell, F. H. Spedding

WHILE rare earths are reported to be widely distributed in nature and are not really rare," in practice, there are only a few minerals which are sufficiently rich in rare earths to serve as practical sources. Perhaps the best known of these is monazite which is a phosphate mineral containing rare earths and thorium. This mineral occurs as a dense brown sand in gravel beds and is particularly rich in the light rare earths of the cerium subgroup. This mineral is processed commercially for its thorium, cerium, and lanthanum content, and, consequently, furnishes rich concentrates from which neodymium, praseodymium, samarium, europium, and gadolinium may be obtained. Unfortunately, monazite is rather lean in rare earths heavier than gadolinium. A second mineral which is rich in the light rare earths is bastnasite, a fluoro-carbonate. Extensive deposits of this ore have been discovered in the western United States and have received considerable newspaper publicity in recent years. While bastnasite is very rich with respect to cerium, lanthanum, and neodymium, it contains even less heavy rare earths than does monazite. One of the better sources of heavy rare earths of the yttrium subgroup is gadolinite, a black silicate rock from which the rare-earth content can be extracted readily by acid leaching. It is obtained chiefly from Norway at the present time, although there are known deposits in the United States. Other sources of heavy rare earths include fergu-sonite, euxenite, and samarskite which are refractory tantalo-columbate ores. These minerals require caustic fusion or reduction to carbides with carbon before the rare-earth content can be extracted. All of the minerals which are rich in the heavy rare earths contain yttrium as a major constituent. After the rare earths have been extracted as a group from an ore by chemical means, it is generally convenient to precipitate them from acid media with oxalic acid in order to eliminate certain non-rare-earth impurities such as iron, beryllium, etc., which are usually present. The oxalate can then be readily ignited to R2O3. The oxide can be dissolved in acid and is the starting point for subsequent separation into the pure components. Perhaps the principal reason why the rare earths have not been studied as extensively as other elements of the periodic table, whose natural abundances are comparable, is that they are extremely difficult to separate from each other by the usual chemical means. Prior to 1945, the separation of one trivalent rare earth from another was a laborious process. All separations were based on repeated fractionation processes, i.e., fractional precipitation, fractional decomposition, fractional crystallization, etc. These processes were repeated from a few hundred to many thousands of times in order to obtain individual rare-earth salts of reasonable purity. Of course, mention should be made that, in the few cases where a rare earth could be oxidized or reduced to a valence state other than three, more conventional chemical means could be utilized to separate the oxidized or reduced ion from the other normally trivalent rare earths. The ionic states which deserve special mention are CeIV, SmII, Eu11, and Yb11. When it is possible to remove an element of the series efficiently, due to an optional valence state, its immediate neighbors also become easier to isolate. For example, binary mixtures of lanthanum and cerium, and praseodymium and cerium can be obtained by a relatively small number of fractional operations. The tetravalent state of cerium then allows the complete resolution of the binary mixtures by ordinary chemical means. Although the tetravalent state of cerium has been known for a long time, the divalent states of samarium, europium, and ytterbium were not used extensively in separations prior to 1930 because they are relatively unstable in aqueous media.'-" No attempt will be made to give a comprehensive review of the extensive literature dealing with the separation of rare earths. Rather, this paper will be confined to a review of those methods which have been developed at Iowa State College during recent years, and which have proved extraordinarily successful for the isolation of highly pure rare earths in quantity. It was obvious that, if pure rare earths were to become generally available, methods would have to be developed wherein the thousands of fractional operations made necessary by the similarity of rare-earth properties could be performed automatically. The development of chromatographic techniques and ion-exchange resins appeared to offer a mechanism by which this objective could be accomplished. A number of early attempts were made to separate rare earths by these means; for example, Russell and Pearce12 passed a mixture of rare earths through a cation-exchange column and reported

Jan 1, 1955

By R. Simon

The sources of energy dissipation for concentrated loadings on rock are considered in an attempt to account for the experimentally measured magnitude of the work required to break out a unit volume of rock from the free surface of an essentially semi-infinite medium. It is concluded that most of this work probably represents the elastic strain energy developed by the loading in a much larger volume of rock beneath the loaded region than the volume of the rock fragment broken out to the side of the loaded region. This strain energy is largely dissipated in the form of stress waves generated by the high rate of unloading produced by the propagating cracks. The energies associated with the formation of the new surfaces of the cracks and with the stress waves generated directly by the loading process are computed to be negligibly small. Possibilities for improving the utilization of energy to drill rod. subject to the geometrical limitations imposed by down-hole operation, are discussed. It is pointed out that any such possible improvements would probably have to be differential ones, since each rock configuration of more favorabIe loading geometry that can be created down the hole is accompanied by a complementary configuration of less favorable loading geometry. INTRODUCTION Dislodging each cubic inch of rock from the bottom of the hole by the action of a bit requires the expenditure of an amount of energy that varies from approximately 5,000 in.-lb to approximately 100,000 in.-lb, depending on the hardness of the rock, or, more technically, upon its fragmentation strength.1 In this paper we will discuss (I) why the energy expended in drilling is so large, (2) what happens to this energy upon completion of the drilling process, and (3) what are the possibilities for reducing the magnitude of the energy required to drill rock. DETERMINATION OF ROCK DRILLING ENERGY The volume of rock removed per unit time from the bottom of a hole of diameter D is evidently (7/4)D2R, where R is the rate of penetration of the bit. If P is the rate at which work is done by the bit on the rock at the bottom of the hole, the energy required to break out a unit volume of rock is given by: Ev =(4/p) P/D2R............(i) For rotary drilling, of either the rolling-cone or drag-bit varicty, P = 2pLN, where L is the torque resistance to rotation at the bottom of the hole and N is the rate of rotation of the bit. L is essentially the same as the torque measured at the rotary table only when drilling in shallow holes. The energies expended in rotating the drill string against the frictional resistance of the walls of the hole and and against the viscous drag of the drilling fluid are extraneous to the subject under consideration, although these may be much greater in magnitude than E, when drilling in a deep hole. For percussion drilling, P = fE where f is the percussion frequency and E is the work done on the rock per impact. The latter quantity can be both computed and measured for a percussion drilling machine. 2 (Under satisfactory drilling conditions, defined in terms of ranges of numerical values of certain dimensionless parameters, E is only 30 to 50 per cent less than the impact energy of the striker.2) Alternatively, E, may be measured directly by dropping chisels shaped like bit edges, backed by rigid weights, onto the surfaces of laboratory rock samples of effectively semi-infinite extent. Under these circumstances, essentially all of the impact energy is converted to work done on the rock, and the relationships among volume of rock broken out, chisel shape, impact energy and indexing distances can be obtained.3 The values of the energy required to break out a unit volume of rock under favorable circumstances are substantially in agreement for rotary drilling, percussion drilling and drop testing at atmospheric pressure. The energy per unit volume is a quantity of the order of magnitude of roughly twice the com-pressive strength of the rock as measured by a uniaxial loading test. The phrase "order of magnitude" in this paper means from about 1/3 as much to 3 times as much; i.e., the energy per unit volume may range from roughly the same up to several times

By E. F. Poncelet

Forty years ago A. A. Griffith developed a theory explaining why brittle materials displayed such low tensile strengths.' He based his views on two points. First, he found himself compelled to assume that all brittle materials are replete with flaws, cracks, and other defects that act, although quite invisible, as large stress raisers. Second, he applied the "theorem of minimum potential energy," which says that the total potential energy of a system must pass from the unbroken to the broken condition by a process involving a continuous decrease in potential energy. By this means he satisfactorily accounted for the noted low strength of such solids and also for the wide spread obtained in experimental measurement of these strengths. So successful has the theory been that it is favored by some to this day. Unfortunately this theory is of limited use beyond the explanation of these two noted phenomena and it is keenly felt that a better theoretical insight into the physics of the fracturing process is needed as the volume of experimental evidence accumulates. The author proposes in the following to build on the fundamentally sound concepts of Griffith and, with the help of increased theoretical knowledge over that available to Griffith, develop a mechanism for frac-ture which will provide far greater understanding of the experimental evidence accumulated to date than is possible from the original Griffith idea. THE GRlFFlTH THEORY Very little progress indeed can be made without accepting the first postulate of Griffith which supposes all brittle solids to be full of microcracks. It would be difficult indeed to find a better mechanism for the small strength of such brittle materials, in conjunction with the fact that the energy that must be expended for comminution is by no means small. The postulate of the existence of the microcracks permits the breakup of the various bonds a few at a time by concentrating the stress at the tip of the progressing crack, while the total energy expended is the same as if they all had been ruptured simultaneously. The only flaw in the argument is that no reasonable explanation has been proposed to account for the genesis of such cracks. Indeed their very presence is in violation of the Griffith second postulate, the potential energy theorem. This theorem is straightforward for isothermal processes, and, in spite of Griffith, there is some doubt that treating the problem isothermally is legitimate. The surface energy of bodies is a free energy, not a potential energy as stated by Griffith, and the production of new surface free energies is not necessarily an isothermal process. There is ample evidence to the contrary. Generally speaking, if heating a body increases its surface area, then, by virtue of Le Chatelier's principle, any increase of that area by other means will tend to lower its surface temperature. Lord Kelvin calculated the actual cooling that resulted in drawing out a film of liquid.2 R. A. Houston calculated the surface cooling that resulted in stretching a metal wire.3 These calculations were made by applying the Carnot cycle to the process and evaluating the thermodynamics thereof. IRREVERSIBILITY OF THE FRACTURING PROCESS While Griffith was very careful not to say so, the impression gained from studying his papers is that he considered the fracturing process as reversible, that is, a succession of quasi-equilibrium states. There is ample evidence that it is not. The indication that the new surfaces produced by the propagation of a crack are cooler than the original body points to an irreversible heat flow from the interior to the new surfaces to equalize the temperatures. If the process be reversible, any crack accidentally formed should immediately close up as, in the absence of any strain energy, the potential energy would thereby be lowered. The fact that they do not, constitutes a paradox. Such paradoxes are nothing new where certain phenomena that propagate from minuscule nuclei are assumed to be reversible. Such is, for instance, the condensation of a pure saturated vapor that is suddenly chilled by adiabatic expansion. At the beginning the tiny droplets that are formed should be only a few angstroms in size, but the vapor pressure at such droplets is so high that they should evaporate at once. A similar situation arises if a saturated pure solution becomes super-saturated upon cooling; the first tiny crystal nuclei should dissolve as fast as

Jan 1, 1964

By G. K. Manning, A. R. Elsea, C. R. Simcoe

Boron increases the hardenability of hypoeutectoid steels by decreasing the nucleation rate of ferrite and bainite. It is postulated that concentrations of lattice imperfections, such as exist at the grain boundaries, furnish the necessary energy for nucleus formation. Boron, because of its atomic diameter, will concentrate at lattice imperfections where sites of suitable size are present. Boron will decrease the energy of these local areas by occupying these sites. This mechanism accounts for the large increase in hardenability observed with small amounts of boron. The loss of the boron hardenability effect and the boron precipitate formation are explained on the basis of increased concentration of boron at the grain boundaries either with increasing boron content of the material or with increasing temperature. COMMON alloying elements affect both the nucleation and growth rates of the austenite decomposition reactions.' This effect is largely a result of the slow diffusion rates of these elements. Although a small addition of boron markedly increases the hardenability of steel, the diffusion rate of boron, which is of the same order of magnitude as that of carbon, can hardly account for this effect. An addition of boron in the range of 0.001 to 0.003 pct is about as effective as an addition of 0.30 pct Mo, 0.40 pct Cr, or 1.25 pct Ni in increasing the hardenability of a 0.40 pct C steel;' however, increasing the carbon content of the steel decreases the effectiveness of the boron addition."' The difficulty in understanding why so small an addition of boron can replace much larger quantities of the more strategic alloys, together with the erratic behavior sometimes encountered in boron-treated steels, has interfered with their general acceptance by industry. In the belief that an understanding of the mechanism by which boron increases the hardenability of steel should lead to a more general acceptance of boron-treated steels, a research investigation to determine this mechanism was undertaken at Battelle Memorial Institute under sponsorship of Wright Air Development Center. Experimental Work In order to study the effect of boron on the transformation of austenite to ferrite and bainite, a group of steels was made with a basic composition similar to that of the SAE 8600 series. This base composition was chosen because it has sufficient hardenability to permit accurate measurement of the times required for transformation to start at various temperatures. The chemical analyses of the steels used in the first part of this investigation are listed in Table I. These steels were made as 200 lb heats in an induction furnace. The furnace charge was Armco ingot iron with the alloying elements added as ferroalloys. After the alloy additions were made, the heat was deoxidized with 0.125 pct Al. A 100 lb ingot was cast and an addition of 0.003 pct B, as ferroboron, was made to the metal remaining in the furnace. This metal was cast into a second 100 lb ingot. The ingots were forged to 11/4 in. diam bar stock from which end-quench hardenability specimens were obtained. Part of this material was further reduced by hot rolling to lx¼ in. bar stock from which specimens were obtained for isothermal transformation studies. Studies of Nucleation and Growth: End-quench hardenability tests were performed on these steels, using an austenitizing temperature of 1600°F. The hardenability curves, shown in Fig. 1, indicate that boron treatment resulted in considerable increase in hardenability of the steels. Any such change in hardenability must result from a change in the transformation rate of the austenite, and these rate changes can be established readily by isothermal transformation studies. Isothermal transformation studies were conducted on these steels as follows: specimens were austeni-tized at 1600°F for 15 min, transferred to a lead bath operating at a constant subcritical or intercritical temperature, held for various lengths of time, and water quenched. The specimens were sectioned for metallographic examination to determine the amount and the type of transformation products present. In order to determine the effect of boron on the formation rate of ferrite, isothermal transformation tests were made on the 0.20 pct C steel in both the boron-treated and boron-free condition at an intercritical temperature of 1375°F where ferrite is the only decomposition product of this low carbon austenite. The results of these tests are shown in Fig. 2, where the percentage of ferrite formed is plotted as a function of time at temperature. It is apparent that boron markedly decreased the transformation rate of austenite to ferrite at this temperature.

Jan 1, 1956

By C. E. Sims, H. M. Banta, S. L. Hoyt

Over the past few years, metallic arc welding has been extended to steels of the hardenable type. As compared with other methods of fabrication, production has been facilitated, service performance frequently has been improved, and the overall results have been so favorable that engineers and production men have placed great emphasis on this application of welding. The metallurgist and welding engineer, however, have been confronted with new problems, since, for one reason, the harder steels are more apt to crack and special precautions must be taken if sound joints are to be procured. Some of the factors that are pertinent to this problem are metallurgical, and it is an object of this contribution to discuss steel manufacture and processing methods and to show how their control assists in reducing the hazard of cracking. By this time, the problem of cracking— specifically underbead cracking, or "hard cracks," or parent-metal cracks-—is well known, and a large amount of work has been published, both here and abroad, dealing with this subject.' The tests described are made under restraint to facilitate cracking and arc so designed that a semiquantitative, or at least a relative, value of the cracking tendency is obtained. As one would expect, it has been reported that the incidence of cracking increases with the carbon and alloy content of the steel. More specifically, the cracking tendency is said to increase with the hardenability of the steel, though it is now recognized that the situation is not so simple. The phenomenon itself, on the other hand, has been but loosely described, and it is in only broad generalizations that this cracking has been related to steel metallurgy. Thus, while it has been abundantly demonstrated that the hardenable aircraft steel, S.A.E. 4130, must tend to crack when are-welded, the problem still remains of why two lots of the same composition and the same hardenability can vary so greatly in cracking tendency, or what it is about the prior metallurgical history that so strongly affects the results. Further, while the efficacy of preheating and postheating in preventing cracking is recognized and utilized in production, the mechanism by which they function seems not to have been described. These points are thought to be significant in the production of steel for fabrication by metallic arc welding and, hence, of interest to mill and process metallurgists and welding engineers. Consequently, it is another object of this paper to discuss the mechanism of parent-metal cracking, including the influence of the condition of the steel and the control of cracking by manipulation of the time-temperature conditions during and after welding. A new method of rating the cracking tendency is also discussed, and the results of the test are related to steel composition and structure or prior history. The work to be described was the outgrowth of work in 1940-41 at Battelle Memorial Institutc on two projects, one

Jan 1, 1945

Jan 1, 1953

By Persifor Frazer

THERE is always a difficulty in assigning limits to the scope of a science or art, and among the difficulties of that kind besetting practical or stratigraphical geology is that of determining what kinds of natural objects shall be considered as the goals of its search. The term mineral, in its broader sense, includes every solid, liquid, or

Jan 1, 1875

Jan 1, 1953

By Wm. R. Dotson

Forty years ago the atom was split and the Age of Fission dawned. Uranium was the element used in this earth-shaking accomplishment. Thitherto almost unknown to the man in the street, uranium soon became widely and persistently sought. And the quest for this unique material is not likely to diminish during this century. To find is one thing; to own is another. Who owns uranium in the ground? Where no mineral rights in the land have been severed by devise, grant, reservation or lease, the uranium belongs to the fee simple owner of the land. But where there has been a conveyance or reservation of all or part of the "minerals", determining WHAT a substance is has been the traditional way of determining WHO owns it. What, then, is this element called uranium? The 1907 edition of Watts Dictionary of Chemistry calls it "a lustrous, hard, silver-white metal". Of nature's three prime divisions it falls within the embrace of the mineral kingdom - substances neither animal nor vegetable. In its natural state uranium always is combined with other elements or substances in the form of an ore mineral. May we, then, put to rest any doubt or question as to the nature of uranium and classify it for all purposes, including that of ownership, as mineral? Not quite! That self-same logic would find oil and gas primly ensconced in the animal or vegetable kingdom. Technically, oil and gas are not minerals but legally they have been classified as such. Why? The Supreme Court of Tennessee sought the answer in 1897 in the case of Murray v. Allard, 43 S.W. 355. After citing authorities pro and con, and while admitting their origin to be "decomposition of marine or vegetable organises" that court firmly concluded that since they were obtained by a form of mining, oil and gas were minerals. From the above example two elementary truths emerge. First, for purposes of ownership, uranium is and will be whatever the courts say it is. Secondly, the courts historically and currently favor a practical rather than technical test to determine the "mineral" character of a substance. So now we turn to the jurisprudence for enlightenment and definition. EARLY CASES ALLOT URANIUM TO MINERAL OWNERS Two early cases involving the ownership of uranium followed what had been well-settled mineral within the meaning of the conveyances involved, confirming ownership in the mineral owners. In 1956 the U. S. District Court for New Mexico in the case of New Mexico and Arizona Land Company v. Elkins, 137 F. Supp. 767, appeal dism'd 239 F.2d 645 (10th Cir. 1956), found that a 1946 deed reservation of "all oil, gas and minerals underlying or appurtenant to said lands" included uranium and thorium. The court reasoned that uranium and thorium, being minerals within the scientific, geological and practical meaning of the term, would certainly constitute minerals within the purview of the reservation. While agreeing that uranium and thorium were "minerals", defendants argued that at the tine of execution of the conveyance it could not have been the intention of the parties to reserve them because they had no commercial value in the locality and were, in fact, not known to there exist until their later discovery in 1950. The court re¬jected, as a matter of law, this "lack of knowledge" theory citing the Supreme Court of Kentucky holding in Maynard v. McHenry, 113 S.W. 2d 13, that: "The mere fact that a particular mineral has not been discovered in the vicinity of the land conveyed or is unknown at the time the deed is executed rules of construction and held that uranium was a does not alter the rule . . ." that a grant or exception of "mineral" in a deed includes all mineral substances which can be taken from the land unless restrictive language is used indicating that the parties contemplated something less general than all substances legally cognizable as minerals. Further, argued the defendants, the only feasible mining procedure for such substances was open pit or strip mining, which would destroy the value of the land for grazing or agriculture. Finding that the language of the reservation was clear and unambiguous, the court would not permit the admission of extrinsic evidence as to mining procedures required. Elkins is the first uranium case construing the granting clause involved. In 1958 the Texas Court of Civil Appeals at San Antonio, in Cain v. Neuman, 316 S.W. 2d 915, no writ, held that a 1918 lease conveying "all of the oil, gas, coal and other minerals in and under" the land involved covered uranium. The lease provided a royalty of 1/10th on "other minerals." "We find no Texas precedent which discusses uranium," said the court, "but the usual arguments that uranium is not embraced within a lease are that the ejusden generis rule excludes uranium from the meaning of the lease

Jan 1, 1979

By David C. Russell

The Department of the Interior used to be a quiet, noncontroversial, almost boring agency. It, after all is the fifth oldest of the Departments, and as an old line Federal agency it has studiously performed its preservation and resource management functions in a caretaker mode--though some would say more "undertaker" than "caretaker"--locking up the body and soul of America piece-by-piece. Yes, quiet, serene. That is until Jim Watt showed up. And we have all seen that version of Mt. Vesuvius which resulted--only it was the environmentalists who blew their tops. Ronald Reagan chose Jim Watt as Secretary of this fine old agency to prove that one-third of our Nation's land and over a billion acres on the Outer Continental Shelf can work for this Nation. At the foundation of President Reagan's charge to Secretary Watt is a belief in the tenets of the free enterprise system, and in the individual freedoms upon which this country was founded. There are those who don't share this belief in democracy and free enterprise, and those who believe this 205 year experiment called the United States of America will fail. Nikita Krushchev said "we will bury you"--obviously he didn't agree with our system. An Italian sociologist, Franco Ferrorotti, said bureaucratic stagnation will kill capitalism. Certainly we have all felt the ravages of bloated bureaucracies. Perhaps one indicator in the United States is the Federal Register, that daily compilation of Government's largesse. In 1970, 20,000 pages of the Federal Register were published. A decade later, in 1980, that volume had quadrupled to 80,000 pages. The Federal bureaucracy can stagnate from excessive budgets as well. The Interior Department spent $60 million on administering Federal coal leasing in 1981. That's nearly two bits a ton for every ton of coal leased in 1981. You wouldn't stay in business very long if your administrative overhead on inventory was that outrageous. But the pessimism of our critics is apparent from more than red tape and bloated budgets. For decades America has been fasting--consuming too little of America's wealth of minerals, subsisting instead on a diet heavily reliant upon mid-east oil, with little emphasis or concern for inventorying and developing domestic energy and mineral resources. Economics--yes. But short-term, short-sighted economics. Excessively dependent upon foreign imports, of oil, cobalt, chrome and other strategic minerals, the U.S. measures its time before another embargo--or fallen Shah, or Soviet manipulation, or Saudi shift, or, as we witnessed in Egypt, assassination--an untimely loss to mankind and efforts to bring peace to the troubled mid-east. These disruptions, in addition to their tragic human tolls, impair the free world's security. Huge chunks of the United States have been locked away in dozens of single land use categories in the name of conservation, with only the foggiest idea of what resources might be denied the American people-and this at a time of unacceptable levels of energy and strategic mineral imports. More than half and perhaps two-thirds of all Government-owned lands are totally withdrawn from or severely restricted to development under the mining and leasing laws. We must continue to rid Government of the overly zealous restraints which have been keeping us from drawing upon that which can help restore our economy and national security. When we assumed responsibility, the United States was dependent on foreign sources for about 40 percent of its oil. In 1981, our oil import bill was approximately $83 billion--nearly 17 times what it was in 1972. Our reliance on foreign sources for essential minerals is even more disturbing. We must look to other countries--some unfriendly, some unstable--for 22 of 36 strategically critical minerals. Yet the energy resources on federal lands which are owned by the American people could meet our needs for centuries if properly managed. Eighty-five percent of the crude oil yet to be discovered in America is likely to come from public lands, as will 40 percent of the natural gas, 35 percent of the coal, 80 percent of the oil shale, nearly all of the tar sands, and substantial portions of uranium and geothermal energy. Our vast hardrock-mineral wealth includes untapped deposits of essential elements we now import, such as chromium, copper, platinum, and cobalt. The obvious question is, if these abundant resources can help to revitalize our economic strength and to preserve our national security, why aren't we using them to better advantage? To a large extent, the answer can be found in past decisions to restrict public access to the federal estate, thus deferring to us or our successors the tough decisions that flow from Congress' mandate to provide for environmentally responsible development of America's energy and mineral treasures. Here is the legacy this Administration inherited: In January 1981, 7 years after the onset of the Mideast oil embargo: ---Less than 15 percent of federal onshore lands were under lease for oil and gas development; ---No oil and gas leases had been issued in Alaska for 15 years;

Jan 1, 1982

By Katherine Mather

This paper is an attempt to put together petrographic, physical, and chemical data about the large and varied group of rocks generally called limestones. Results of the properties of these rocks on their performance as concrete aggregates are discussed. CRUSHED stone classified as limestone comprises about 70 pct of the crushed concrete aggregate and roadstone produced in this country, and the product has amounted in the recent past to about 97 million tons per year, valued at more than $123,-000,000.' Therefore an evaluation of the properties of rocks classified in these statistics as limestones and an ability to predict their behavior as aggregate in portland cement concrete are matters of considerable economic consequence to producers and consumers of aggregate. This paper is an attempt to put together petrographic, physical, and chemical data about the large and varied group of rocks generally called limestones. It also points out certain results of the properties of these rocks on their performance as concrete aggregates. The problems encountered in efforts to explain the behavior of limestones, dolomites, and related rocks as concrete aggregate lie on the frontiers between the ignorance of the geologists and the ignorance of the engineers. The mineral composition and textures of the rocks have not been adequately explored and described, and the effects of mineral composition and texture on the performance of aggregates have been worked out in only a few cases. There are instances of unsatisfactory performance and some generalizations of those experiences. There are many more examples of satisfactory performance than of unsatisfactory, but there is practically no published information as to why a particular aggregate was satisfactory in a specific use. There are all too few investigations of undeteriorated concrete; more is known about the pathology of concrete than about its normal structure and aspect. As part of the investigation of aggregates, the classification of rocks is not an end in itself, but is a step toward recognition of properties expected to influence the behavior of aggregates in their intended use. Rock of any type may perform well or poorly as concrete aggregate, depending on the physical condition of the rock, its physical and chemical properties as compared to those of the matrix in which it is placed, and the circumstances under which the concrete is exposed. Some classification and descrip- tion of the limestones is necessary to distinguish subgroups whose members will probably behave in similar ways and to evaluate the group as a whole. The group name, limestone, includes and tends to conceal the identity of rocks that have a very great range in chemical and mineralogical composition, structure and texture, conditions of deposition, subsequent history, and suitability for use as concrete aggregate. All the rocks classified as limestones include one or both of the most abundant rock-form-ing carbonate minerals, calcite and dolomite, as major constituents. Carbonate rocks is a more descriptive and more accurate group name than limestone, which has generally been used to include dol-omitic or magnesian limestones and dolomites as well as calcitic limestones. Classification and Description of the Carbonate Rocks The question of names to be applied to the carbonate rocks may appear academic, but it is of practical importance as long as there are specifications for aggregate that result in acceptance or rejection of rocks by name and as long as failure to make distinctions among the carbonate rocks leads to misunderstandings of their properties and of what may be expected of them in performance. Materials included in production statistics as limestone and tested for concrete aggregate as limestone range in fact from calcareous shale and calcareous or dolomitic sandstone and argillaceous limestone and dolomite to calcitic limestone and pure dolomite and to rocks close to calcitic and dolomitic marble. To take a simple example: consider two manufactured coarse aggregates, both dense and unweathered, one composed principally of crystalline calcite and the other of crystalline dolomite, but both known as limestone. If each is used as coarse aggregate in a standardized concrete mixture with the same fine aggregate used in both cases, made into concrete specimens, and tested in accelerated freezing-and-thaw-ing, the test results will probably be quite different, because of the differences in internal bond and thermal properties between the two aggregates. As long as both aggregates are called limestone, the test results cannot be explained, or used except in a very limited way; if the aggregates are distinguished as limestone and dolomite and the consequent differences in texture and thermal properties are recognized, the results are reasonable. Classification of the carbonate rocks used as aggregate should be based on structure and on composi-

Jan 1, 1954

By L. A. Panek

During the past three years, USBM has developed an apparatus and technique for direct measurement of existing pressure and change of pressure in mine rock. This relatively simple and inexpensive monitor is reliable for months after being installed. It is used to determine shift of ground pressure created by different sequences of mining, to ascertain the cause of rock failures, and to evaluate the need for artificial support. The technique has been employed to measure pressures in limestone, greywacke, concrete, diabase, and soft iron ore. When rock is subjected to a load it is deformed. Ordinarily this is observed in a mine as the displacement of one point with respect to another—the deflection of the roof, which may be observed as a convergence between roof and floor; or the extrusion of material from the rib, which may be observed as a decrease of the distance between the rib and the post of a timber set. The effect of excessive pressure may be a rockburst if the rock is strong, or it may be squeezing ground if the rock is soft. Some desirable effects of high stress (high in relation to strength) are the caving of roof in a longwall mining operation, the caving of ore in block caving, and the decrease in mechanical energy required to break down the mineral seam in a retreating pillar-robbing operation. In any case, whether the observable effect of rock load is desirable or undesirable, it is a displacement, and depends on the following four factors: 1) The structure—the size and shape of openings, pillars, and linings, the geologic bedding and jointing. 2) The mechanical properties of the rock—prin-cipally the strength, modulus of elasticity, and flow characteristics. 3) The load or applied stress—primary sources are the weight of superincumbent rock, which increases with depth, and unrelieved tectonic stresses; secondary sources are redistributed pressures caused by other nearby openings, especially large mined out zones (rock pressure depends partly on the rock structure created by mining). 4) Duration of load, related to the length of time the opening is exposed. CONTROL OF ROCK DISPLACEMENT Rock displacement can be controlled by control of these four factors. Consider now the means of exercising such control over these factors. Control of the structural features is obviously possible to a great extent, as such control is exercised largely by choosing the method of mining and the methods of natural and artificial support. Rock properties vary, even within a particular mine, but they are controllable only in the limited sense that control may be exercised by choosing the beds or zones to be mined so that rocks with undesirable properties will not occupy critical positions within the rock structure created by mining. Rock pressure is the most complex of the four factors through which ground control can be achieved because it is invisible, difficult to measure, and poorly understood. Rock pressure is controllable only to the extent that control is exercised on the rock structure created by mining. Considering openings within a particular mine, time of exposure varies, and is readily controllable because it is easily measured and easily understood — the longer an opening stands, the greater the likelihood of failure or excessive convergence. Control is exercised by choice of an appropriate sequence of driving openings of different classes, such as haul-ageways and rooms, which are required to remain well supported for different lengths of time under different conditions. Again, control is exercised through the method of mining. All controllable factors can be controlled by proper design of the mining method. The orientation and relative positions of the mine workings and the sequence of their excavation are likely to be much more important to ground control than is the design of artificial support. This implies that the major decisions in regard to ground control are made, knowingly or not, at the time the mining method is chosen. WHY MEASURE ROCK PRESSURE In addition to restrictions on the several factors, control implies the measurement of these factors in some sense, whether only qualitatively by visual observation, or by actual quantitative determination with a measuring instrument. Rock pressure is the most difficult of these factors to measure, largely because of the interaction between the measuring device and the rock. Nevertheless, the quantitative

Jan 1, 1961

By L. Weyher, H. L. Lovell

This discussion is restricted to a very specific application of the cyclone - its use as a hydro-cyclone in the cleaning of fine coal. It is hoped that the development of the present data will assist in the further elucidation of existing qualitative models, and also in an enhanced application of the hydrocyclone and provide a base for further research. Discussed are the mechanisms of gravity separation in hydro-cyclones, test procedures, experimental observations, and industrial applications from these studies. Within the general area of unit operations, a considerable effort has been expended in theoretical and empirical research associated with cyclone operations. The motivation involves the industrial requirement for devices and techniques to manipulate small particles at low operating costs, a situation required in coal preparation. There are good reasons why the cyclone helps to satisfy this demand, because it combines operational simplicity (no moving parts) with versatility and high throughput capacity per unit area. The cyclone is one of the most widely applied tools in the process technologies. There are areas for potential cyclone application which have been only meagerly explored or not considered at all. This discussion is restricted to a very specific application of the cyclone - its use as a hydrocyclone in the cleaning of fine coal. It represents an initial presentation of a more comprehensive report. Coal preparation can appropriately claim the hydrocyclone since most of its predominant industrial uses have originated in this area and have spread into other applications, including the broad field of ore dressing, the petroleum industry, chemical processing, nuclear engineering and food technology. There is one operational principle common in all cyclones: A fluid is tangentially introduced into a cylindrical or conical container under pressure. A predominantly irrotational flow field1 is established within the cyclone (Fig. 1). The uniqueness of this flow is indicated by the variation in tangential velocity across the cyclone radius, which reaches a maximum a short distance from the center and decays toward the cyclone wall. In contrast, the tangential velocity in a centrifuge increases uniformly toward the wall. Usually two products are discharged from the cyclone. They differ in that one discharge consists predominantly of that portion of the feed fluid which moves along the wall axially away from the feed inlet, while the other consists predominantly of fluid spiralling along the central regions of the cyclone, in an axial direction opposite to that of the wall current. Fig. 2 indicates these discharge points schematically. The latter product may be termed the vortex-product, since it is discharged with the central vortex-current. In the case of conical cyclones, the former product may be referred to as the apex-product. Although the names "over- and underflow" are widely used, many cyclones are operated from extreme angular positions thus the proposed terms are less ambiguous. The cyclone feed fluid can be laden with solid particles or nonmiscible fluid drops. Such a feed component is discharged from the cyclone, after some residence time, into the one or the other product. Yet, the orifice through which a particle will leave the cyclone is dependent upon a number of factors. These factors, in a statistical sense, determine the path of the particle within the cyclone. Thus, different separation phenomena are possible and different process results attainable by the controllable variation of the particle path. It is then, to attain a fuller understanding of this particle path, to which this study is ultimately directed. It is anticipated that the detailed study of the data being developed will allow further elucidation of existing qualitative models. However, the development of a quantitative description of cyclone operation in terms of a mechanism is not currently feasible. The flow conditions in a cyclone are not fully understood even for a pure fluid, without the added complexity of the inclusion of multiple size-density particles. It is hoped that the development of the present data will also assist in an enhanced application of the hydro-cyclone and provide a base for further research. Some practical applications drawn from the data are suggested. Cyclone operations have been classified according

Jan 1, 1967

By W. C. Winegard, J. R. Carruthers, A. Plumtree, L. R. Morris

The unidirectional solidification of dendrites containing central twin planes was studied in A1-Ti alloys. Once nucleated, the twinned dendrites are a Twore ejficient form for solute redistribution and therefore grow in preference to the normal columnar dendvites. Comparison of these twinned dendrites to adjacent colunmar dendrites by means of decanting experinzents and electron-probe rnicvoarmlysis indicates that these special dendrites grow with less undercooling than normal dendrites. These findings are further supported by the effect of forced convection on the dendrite morphologies. COMMERCIAL semicontinuous cast ingots of most aluminum alloys frequently exhibit large grains which appear to be composed of hundreds of parallel, continuous, thin lamellae. This structure has been termed "basaltic",' "fiederkristall", or, commonly, "feathery grain". The lamellae are 'about 100 p thick, several inches long, and each lamella contains a central (111) coherent twin boundary. The feathery grain has been reported to have a (112) direction2 and a (110) direction4 in the twin plane parallel to the casting direction, in contrast with the usual columnar structure where a (100) direction predominates. Aust et uZ.~ proposed that the twin boundaries were growth twins nucleated by stacking faults on the octahedral planes. chalmers6 has suggested that feathery grain may grow by a re-entrant edge mechanism, as proposed by wagner7 for twinned dendritic growth in germanium. Cahn et ~1.~ have concluded that the occurrence of feathery grain is evidence of some form of lateral layer growth rather than the atomically continuous growth normally observed in metals. The postulates by Chalmers and Cahn would seem to be contradicted by the work of Nakao~"' who showed that feathery grain only occurs when growth rates are high and the aluminum contains some solute. Specifically, Nakao found that in order to obtain feathery grain, in small castings solidified unidirec-tionally upward, the rate of growth must be above 2.4 cm per min and a critical solute concentration must be present. Below this solute concentration the grain structure was totally columnar. The critical solute concentration was found to be approximately: 0.04 wt pct Ti, 2 wt pct Cu or Mg, and 8 wt pct Zn. As pointed out by Chalmers it is not obvious why a twin-plane re-entrant edge mechanism would occur in aluminum which is thought to have a diffuse solid-liquid interface. The present experiments were undertaken to determine the growth mechanisms in- volved and to study the solute segregation in more detail. EXPERIMENTAL PROCEDURES Alloys ranging in composition from 0.05 to 0.23 wt pct Ti* were prepared from 99.9 pct pure Ti and 99.993 pct pure Al. Two-hundred-gram samples of A1-Ti binary alloys were solidified unidirectionally and vertically upward from a water-cooled copper base, in a heated insulated mold. The 1-in.-diam, 6-in.-length mold was made of Marinite (manufactured by Johns-Manville Co.). The mold was attached to a 24-in. pivoted arm such that by dropping a weight the mold was rotated 180 deg, throwing the liquid metal from the solid. In this way, the solid-liquid interface was revealed by decanting. A sketch of the decanting mold is shown in Fig. 1. The alloy was poured into the mold at temperatures ranging from 680" to 750°C, partially solidified by water cooling from the base, and decanted after a measured time interval. Growth rates for each metal-pouring temperature were calculated from solidification-time vs length solidified curves. Temperature gradients in the melt were measured using four No. 34 gage thermocouples which protruded into the mold cavity. Grain orientations were determined by X-ray diffraction using Laue back-reflection techniques. Grain substructures were examined metallographically, using polarized light, by applying a thin epitaxial anodic film to polished sections after the method of Hone and pearson." Titanium micro segregation was measured by electron-probe microanalysis using a NORELCO AMR/~ with a mica crystal and proportional-flow counter. Several of the cast samples exhibited feathery and columnar dendrites growing in the same direction and

Jan 1, 1967

By R. Schuhmann

Available thermodynamic data applicable to copper smelting systems are collected and tabulated, and the important gaps are pointed out. A few examples are given of estimations which can be made from the available data. An experimental research program is proposed to supply the thermodynamic data that appear most essential to better quantitative understanding of the chemistry of copper smelting. The proposed program is designed also to shed specific light on the practical problems of slag losses and magnetite behavior. OPPER smelting, from flotation concentrates to V-/ blister copper, is conspicuous among the large scale chemical processes which are conducted with only relatively incomplete knowledge of the physical chemistry involved. For example, no common metallurgy text explains adequately why copper enters the matte phase while iron enters only to the extent that sulphur is left over after satisfying the copper. Explaining this important phenomenon as a manifestation of the greater affinity of sulphur for copper than for iron is unsound because the affinities of copper and iron for sulphur are about the same at smelting temperatures. As will be shown, other affinities are really decisive in the relatively clear-cut separation of copper in the matte. In contrast, thermodynamic studies have contributed much to our understanding of copper refining, zinc oxide reduction, magnesium production, steelmaking, etc. For each of these processes, the important reactions are clearly recognized, and fair to good quantitative values of the free-energy changes and equilibrium constants are available. Such data have proved to be of constantly increasing practical value in process development and improvement. Work in other fields has furnished much thermodynamic data applicable to copper smelting systems. In fact, several promising starts have been made in applying such data to specific smelting problems. Kelleyl made an appraisal of the possibilities of recovering elementary sulphur from low grade matte. His calculations and compilations of thermodynamic data have represented the starting point for much of the work in this field, including the present survey. Huang and Hayward2 nd Aksoy3 used thermodynamic methods in the study of copper losses in reverberatory slags. Peretti4 used thermodynamic data in explaining the chemistry of converting. The recent publications of Darken and Gurry"." and of Darken,' dealing with the iron-oxygen and iron-silicon-oxygen systems, respectively, present equilibrium data that are applicable to copper smelting systems. Also additional data were reported recently on the affinity of sulphur for copper, manganese, and iron8 and on the sulphur pressures of iron-sulphur melts." The survey presented in this paper was made as the basis for planning an experimental program on the thermodynamics of copper smelting. Few researches on the chemistry of copper smelting have been reported in recent years, so that a reappraisal and coordination of old and new data are essential if further work is to take the directions of maximum value. The experimental program is now in progress, and the plan of attack is outlined at the end of this paper. Progressive Oxidation and Desulphurization of Copper-bearing Liquid Phases: The chemical activities of sulphur and oxygen are two of the most important thermodynamic yardsticks to be applied to copper smelting processes. Virtually the entire smelting and refining sequence involves a series of systems characterized by decreasing sulphur activity and increasing oxygen activity. In this section, therefore, an attempt is made to define and explain these activities in terms of equilibrium partial pressures of SO2, s2, and O,. Also, estimates of these quantities are presented, the estimates being based largely on calculations presented in a later section of this paper. The sequence of steps from raw flotation concentrate to fully oxidized copper ready for poling involves progressive and controlled oxidation. Iron is oxidized and enters the slag. Sulphur is oxidized and leaves in the gas. Table I summarizes several important features of this oxidation and desulphurization sequence, starting at the beginning of the matte blow in the converter. The top line gives in order the principal smelting and refining stages up to fully oxidized copper, plus the additional step, not used commercially, of oxidizing all the way to Cu,O. In the second line are shown the principal copper-bearing liquid phases which characterize the process. Through most of the sequence the copper

Jan 1, 1951