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By H. F. Winham

THE history, development, subsurface geology, production, economics and estimated reserves are discussed in this paper. The Magnolia structure is an anticline with a known maximum structural relief at 372 ft., and the areal extent of the producing acreage is 4494 acres. Production is obtained from the Smackover oölitic lime and 116 successful wells have been drilled. The field, which was developed on 4o-acre spacing, has been under strict control. It is believed to be producing with a strong water drive. To date it has produced more than eighteen million barrels and the estimate of ultimate recovery is 220 million barrels. EARLY HISTORY The Magnolia field is in Columbia County, Arkansas, T. 17 S., R. 19 and 20 W. Various geologists had long been interested in this general area, and as early as 1921, John F. Magale was able to define a surface structure. The first wildcat, one of the first in Columbia County, was drilled in 1923 by Mid-States Oil Co., in sec. 10, T. 17 S., R. 20 W. This well was about 1 ½ miles northwest of the Kerlyn Oil Company's discovery well and was based on surface geological work done by jewel and Dobie. Subsequently, several shallow wells that were not carried below the Upper Cretaceous beds were drilled in the immediate area of the discovery well, but none of them contained any commercial showings of oil or gas. In the latter part of 1935, Elam and Magale (or Southwood) Garrett No. I was located in sec. 13, T. 17 S., R. 20 W., ¾ mile east of the discovery well. It was drilled to a total depth of 4018 ft. in the lowermost Glen Rose beds but failed to obtain any showings of oil or gas. Interest had been stimulated in this general area, however, by the discovery of several oil fields, mainly Glen Rose oil production in the Rodessa field in Louisiana in 1935, Smackover lime production in Snow Hill in May 1936, production from the Cotton Valley formation in Schuler in 1037, and Smackover lime production from the Buckner field in November 1937. With this background and subsequent seismic work, which was carried on partly because the old shallow wells drilled in the township had shown evidence of closure in the Upper Cretaceous beds, the discovery well, Kerlyn Oil Company's Barnett No. I, sec. 14, T. 17 S., R. 20 W., was originally projected to a total depth of 6300 ft., to test the equivalents of the Morgan sands of the Cotton Valley series, then producing at Schuler. The well was carried to a total depth of 6325 ft. and tested the objective beds without finding commercial production. In the meantime, however, one well had found production in the Jones sand and another in the Smackover lime at Schuler. Kerlyn immediately made arrangements to deepen the Barnett well to the Smackover lime. The top of the Smackover lime was encountered at 7618 ft. and the well was cored and drilled to a depth of 7740 ft.

Jan 1, 1942

By D. Harrington

During the past few years, there has been a trend toward the use of rock-dusting, rather than relying on humidifying, or the use of water, to limit or prevent explosions in the coal mines of the United States. This is partly because British coal mines have adopted rock-dusting and, at least in a sense, have condemned the use of water. Moreover, during the past few years, particularly in the latter part of 1922 and in 1923 and 1924, several explosions with heavy loss of life occurred in coal mines of the United States that were known to have more or less extended sprinkling, or humidifying, systems. The sentiment created by these disasters quickly caused a distrust of explosion-prevention methods requiring use of water and simultaneously caused more or less of a stampede into rock-dusting. Much of the wholesale condemnation of watering methods was without adequate knowledge, or at least without adequate consideration, of local conditions in each case, and rock-dusting was adopted largely without sufficient knowledge of how to rock dust safely or correctly. However, mines that had been using watering methods and had suffered these recent serious disasters (notably Dolomite, Dawson, and Castle Gate) instead of abandoning the use of water when operations were resumed after the disaster, greatly extended their watering systems. At the same time they took other precautions as to electricity, ventilation, blasting, etc., and supplemented the watering system with rock-dusting where the latter was likely to be the more effective. The trend toward rock-dusting during the past year or two (succeeding the recent mine disasters) is very similar to the rapid movement toward watering, or humidifying, methods, about 1910 to 1912, after a series of disastrous mine explosions. The Phelps-Dodge Corpn., which operates a large property at Daw-son, N. M., after an explosion in its No. 1 mine in February, 1923, decided that it is dangerous to have all its "explosion-prevention eggs in one basket" and so adopted what may now be termed the Western coalmine explosion-prevention system, in which both rock-dusting and watering are used, supplemented by other up-to-date mining methods and practices; such as exclusive use of modern electric safety lamps, with magnetically locked flame safety lamps for testing purposes; use of

Jan 1, 1925

By Leslie W. Austen

ROTARY kiln operators will agree that some of the most severe conditions a refractory must stand occur in the hot zone of a kiln burning Portland cement, dead burn dolomite, magnesite, peri-clase, and similar materials. Frequently the operator is faced with factors beyond his control which drastically shorten the life of refractories. Shutdown due to mechanical failure can be serious if the period is of sufficiently long duration to cause the dropping of coating or the loosening of the lining. A change in slurry can affect the coating and cause ring buildup. A change in type of fuel and its effect upon the flame can cause a shift in location of the hottest zone. Weekend shutdowns or any other interruption can cause the operator trouble and may damage the refractories, since stopping and starting a rotary kiln is certainly more difficult than stopping and starting a motor. Some operators have tried to set an estimate of damage for each shutdown in equivalent days of running time. Conditions affecting the refractory may be roughly grouped in four classes: chemical attack, mechanical stress, thermal shock, and abrasion. Chemical Attack: The drive to obtain maximum production through a kiln demands maximum operating temperatures, temperatures which are limited more by the ringing up or melting of the clinker. This can cause interface temperatures at the junction of coating and refractory which require the use of a basic kiln block to withstand the chemical attack. Chemical changes take place within the refractory itself, especially in chemically bonded or unburned kiln blocks. These changes cause the formation of the ceramic or burned bond. Migrating liquids or fluxes from the kiln charge have an effect within the refractory and lead to mineral or glass formation. The alkalies, sodium and potassium, migrate into the refractory as silicates, chlorides, sulphates or other salts. They may move under capillary action or may be caused to move by volatilization with condensation in the cooler portion. Mechanical Stress: Concentrated stress may be caused by several factors or combinations thereof. I—The rings of refractories must be kept tight and rigid within the kiln, and this alone demands considerable force to hold the blocks in place. So that the force will not be concentrated, the blocks should fit the circle as perfectly as possible, with the faces in contact overall. 2—As the kiln is heated, thermal expansion takes place at the hot end of the kiln block. Since this disturbs the plane face it too can cause a concentrated stress at the two ends of the block, and shearing stress can be set up within the brick itself because of the difference in expansion between the two ends. 3—If a lining becomes loose and moves in the shell very severe stress can be set up, and as the kiln rotates this load changes and gives the effect of repeated loading. Permanent expansion of the refractory can also cause severe loading. 4—Not least important, flexing of the kiln is frequently the cause of concentrated stresses. Thermal Shock: Thermal shock, the result of heating and cooling too rapidly, occurs on starting and stopping or when a large patch of coating drops, exposing the bricks. Again, its destructive effect is often the result of phase change, liquid to solid or the reverse; dense refractories loaded with glass-forming impurities are particularly susceptible. Thermal shock is a. problem with refractories set in the wall or roof of a stationary furnace, and becomes even more serious in a rotary kiln, the tendency to spa11 being magnified with movement and concentration of stress. Uniform rate of feed and loading insures both better coating and a more uniform stress. Abrasion: If the refractories do not take a coating, abrasion can become a most destructive factor. Movement of the lining in shell or movement of loose blocks causes abrasion, which is also most destructive if the refractories do not take a coating. An analysis of the problem of basic lining for the hot zone reveals, therefore, a number of desirable characteristics: high refractoriness, basic chemical reaction, resistance to spalling, good strength at all stages, ability to take coating, true sizing, volume stability, and abrasion resistance. Increased demand

Jan 1, 1953

By Leslie W. Austen

ROTARY kiln operators will agree that some of the most severe conditions a refractory must stand occur in the hot zone of a kiln burning Portland cement, dead burn dolomite, magnesite, peri-clase, and similar materials. Frequently the operator is faced with factors beyond his control which drastically shorten the life of refractories. Shutdown due to mechanical failure can be serious if the period is of sufficiently long duration to cause the dropping of coating or the loosening of the lining. A change in slurry can affect the coating and cause ring buildup. A change in type of fuel and its effect upon the flame can cause a shift in location of the hottest zone. Weekend shutdowns or any other interruption can cause the operator trouble and may damage the refractories, since stopping and starting a rotary kiln is certainly more difficult than stopping and starting a motor. Some operators have tried to set an estimate of damage for each shutdown in equivalent days of running time. Conditions affecting the refractory may be roughly grouped in four classes: chemical attack, mechanical stress, thermal shock, and abrasion. Chemical Attack: The drive to obtain maximum production through a kiln demands maximum operating temperatures, temperatures which are limited more by the ringing up or melting of the clinker. This can cause interface temperatures at the junction of coating and refractory which require the use of a basic kiln block to withstand the chemical attack. Chemical changes take place within the refractory itself, especially in chemically bonded or unburned kiln blocks. These changes cause the formation of the ceramic or burned bond. Migrating liquids or fluxes from the kiln charge have an effect within the refractory and lead to mineral or glass formation. The alkalies, sodium and potassium, migrate into the refractory as silicates, chlorides, sulphates or other salts. They may move under capillary action or may be caused to move by volatilization with condensation in the cooler portion. Mechanical Stress: Concentrated stress may be caused by several factors or combinations thereof. I—The rings of refractories must be kept tight and rigid within the kiln, and this alone demands considerable force to hold the blocks in place. So that the force will not be concentrated, the blocks should fit the circle as perfectly as possible, with the faces in contact overall. 2—As the kiln is heated, thermal expansion takes place at the hot end of the kiln block. Since this disturbs the plane face it too can cause a concentrated stress at the two ends of the block, and shearing stress can be set up within the brick itself because of the difference in expansion between the two ends. 3—If a lining becomes loose and moves in the shell very severe stress can be set up, and as the kiln rotates this load changes and gives the effect of repeated loading. Permanent expansion of the refractory can also cause severe loading. 4—Not least important, flexing of the kiln is frequently the cause of concentrated stresses. Thermal Shock: Thermal shock, the result of heating and cooling too rapidly, occurs on starting and stopping or when a large patch of coating drops, exposing the bricks. Again, its destructive effect is often the result of phase change, liquid to solid or the reverse; dense refractories loaded with glass-forming impurities are particularly susceptible. Thermal shock is a. problem with refractories set in the wall or roof of a stationary furnace, and becomes even more serious in a rotary kiln, the tendency to spa11 being magnified with movement and concentration of stress. Uniform rate of feed and loading insures both better coating and a more uniform stress. Abrasion: If the refractories do not take a coating, abrasion can become a most destructive factor. Movement of the lining in shell or movement of loose blocks causes abrasion, which is also most destructive if the refractories do not take a coating. An analysis of the problem of basic lining for the hot zone reveals, therefore, a number of desirable characteristics: high refractoriness, basic chemical reaction, resistance to spalling, good strength at all stages, ability to take coating, true sizing, volume stability, and abrasion resistance. Increased demand

Jan 1, 1953

By S. R. Goodman, Hsun Hu, R. S. Cline

The quenching technique has been used to study phase relations in the composition area 2FeO.SiO2-FeO-SiO2-MnO.Si02-ZMnO.SiO2 of the system iron oxide-manganese oxide-silica under strongly reducing conditions such as exist in a gas mixture consisting of equul parts of carbon dioxide and hydrogen. Liquidus and solidus temperatures of most mixtures in the composition area studied are in the range of 1173° to 1345°C. EQUILIBRIUM relations existing among the oxides of iron, manganese, and silicon are of particular interest in two areas of steelmaking: slags and ingot inclusions. Mixtures of these oxides represent about 90 pct of the slag in the acid steelmaking process, and so dominate the chemistry of the whole refining process. These constituents also play an important role in the early slags existing at the time of the "lime boil" in the basic open hearth process. If these slags are liquid, they "wet" the lumps of lime rising from the bottom of the bath, and react with them. A liquid slag rich in CaO is then formed at the very beginning of the refining. Because the temperature is still low, all conditions for a good dephosphoriza-tion are fulfilled at this stage of the operation. Metal deoxidized with ferromanganese or silico-manganese is likely to contain, as inclusions, phases made up from among the oxides of iron, manganese, and silicon. A knowledge of stability relations existing among the phases present in this system, therefore, enables one to predict the hardness of the inclusions encountered. Moreover, because the shape of the inclusions in steel has a profound influence on the physical properties of the metal, it is important to establish whether or not the oxidic material is present as liquid or crystalline phases during heating and rolling of the steel (-1150 to 1350°C). A knowledge of melting relations in synthetic mixtures of iron oxide, manganese oxide, and silica will give a clue to these problems. Methods for determining such relations and the results obtained are described iln this paper. I) PREVIOUS WORK A number cf previous studies have dealt with the three "binary"* systems bounding the system iron oxide-mangar,.ese oxide-silica. The system iron oxide-silica was studied by Bowen and shairerl in 1932. Their data were obtained by equilibration of mixtures in contact with metallic iron. Phase relations for the system iron oxide-silica ill atmospheres of different oxygen pressures car1 be derived from data on the system FeO-Fe2O3-SiO2 as determined by Muan.2 The diagram shown iri Fig. l is a section of this system in an atmosphere of CO2 and H2 in ratio 1:l. The system manganese oxide-silica has also been the subject of several investigations. Most of the early studies suffered from a lack of proper control of the atmosphere under which the equilibrations were carried mt. Phase diagrams for the system at two well defined levels of oxygen pressures have been determined recently. Glasser3 determined stability relations in an atmosphere consisting of carbon dioxide and hydrogen in ratio 5:1, diagram Fig. 2, and Muan4 studied phase relations in the system in air.

Jan 1, 1962

By N. L. Carwile, G. W. Geil

A metallographic study was made of deformation twinning (Neumann lamellae) in ingot iron slowly deformed in tension at —196O and —150°C. The results showed that twinning is initiated mainly during the initial stages of plastic deformation. However, the breadth of the twins generally increases with increase in strain up to fracture of the specimen. HE results of an investigation of the effect of low I temperatures on the flow, fracture, strain hardening, and strain aging characteristics, and the true stress-strain relationship for specimens of ingot iron deformed in tension were reported recently.1,2 In that study specimens of ingot iron, in different initial conditions, were slowly deformed in tension at various temperatures between —196" and +100°C. A phenomenon observed, but only briefly reported, was the formation of deformation twins (Neumann lamellae) in the specimens deformed at the lower temperatures. Preliminary metallographic examination of these specimens indicated that there was apparently some correlation between the deformation twinning and the strain of the specimen and that this factor merited further investigation. Some recent investigations have indicated a direct association of Neumann lamellae and the fracture of the metal. Bruckner".' * postulated that the twinning immediately precedes the fracture and the latter is initiated by the stopping of the propagation of twins, either at subgrain boundaries or at other structural features. Tipper and Sullivan5 postulated that Neumann lamellae are initiated by the shock or a shock wave set up at fracture in the still highly stressed unbroken metal, and that a high rate of deformation is a necessary condition for their formation. An extensive metallographic examination, therefore, was made of many of the specimens used in the study of ingot iron at this Bureau and of additional specimens deformed to selected strains under various conditions. The present paper summarizes the effects of deformation under these conditions upon the breadth and scope of the deformation twins. Other features of twinning will be discussed in another paper. Material and Testing Procedure All of the specimens were prepared from one lot of ingot iron, as hot-rolled, of chemical composition other than iron as follows: C, 0.02 pct; Mn, 0.02; P, 0.005; S, 0.018; Si, 0.002; Cu, 0.10; 0, 0.058; and N, 0.002. Cylindrical tensile specimens with a 2 in. gage length were used. The reduced section was slightly tapered from each end; the diameter (0.438 in.) at the midsection of the gage length was about 0.003 in. less than at the ends. The specimens were finished to the final dimensions by grinding and polishing in the axial direction. The ends of the specimens were machined with 3/4 in. x 10 threads and the shoulder fillets were machined to a radius of 0.75 in. The specimens were extended slowly in tension (deformation rate less than 0.5 pct reduction in area per minute) while immersed in an appropriate cryogenic liquid maintained at the desired temperature. The minimum diameter of the specimen was measured during the test by means of a specially designed reduction of area gage accurate to 0.0001 in." A detailed description of the testing equipment and the method of maintaining the desired temperature is given in a previous paper.' Each specimen, after deformation to a specified strain at a selected temperature, was sectioned longitudinally and examined metallographically. The preparation of specimens for metallographic examination was carried out in the usual manner by mechanical polishing and etching. Results and Discussion Deformation twins in specimens of ingot iron extended slowly in tension at —196" and —150°C are shown by the representative micrographs of Figs. 1

Jan 1, 1954

By N. C. J. Ros

The paper deals with pressure gradients occurring in flowing and gas-lift wells, a knowledge of which can be applied to the determination of optimum flow-string dimensions and to the design of gas-lift installations. The study is based on a pressure-balance equation for the pressure gradient. It appears that a pressure-gradient correlation of general validity must essentially consist of two parts-—one part being a correlation for liquid hold-up and the other part being one for wall friction. Dimensional analysis indicates that both liquid hold-up and wall friction are related to nine dimensionless groups. It is shown that in the field of interest only four groups are really important. On the basis of these four groups a restricted experimental program could be selected that nevertheless covered practically all conditions encountered in oil wells. This experimental program has been carried out in a laboratory installation. Three essentially different flow regimes were found. The pressure gradients in these regious are presented in the form of a set of correlations. Comparison of these correlations with a few available oilfield data showed excellent agreement. INTRODUCTION Prediction of the pressure drop in the flow string of a well is a widely known problem in oilfield practice. Accurate data on the pressure gradient of a simultaneous flow of gas and liquid in a vertical pipe are especially useful for the determination of optimum flow-string dimensions. It is well known that with moderate gas and liquid flows such a vertical string acts as a "negative restriction". The pressure drop decreases (1) when the throughput through a given pipe increases, and (2) when at a given throughput the cross-sectional area is decreased. The reason is that, with increasing velocities, the flow becomes more agitated so that the gas slips relatively more slowly through the liquid. With the resulting increase in gas content in the string, the static head decreases. When the area becomes very small, however, the high velocities entail great wall friction, which causes an increase in pressure drop. For a given flow, therefore, minimal pressure drop is obtained by using a certain cross section. This means that, in principle, each well can be provided with an optimum flow string for minimum pressure drop and, hence, maximum possible production rate. The procedure for the selection of the optimum string has been discussed by Gilbert.' A necessary tool in the procedure, however, is accurate knowledge of the pressure gradient to be expected for various values of the governing variables. Another application of pressure-gradient data lies in the field of gas-lift practice: they provide a means of determining the optimum gas-injection rate, optimum injection pressure and optimum injection depth. Much work has already been done in the study of the pressure gradient of vertical gas-liquid flow. Poett-mann and Carpenter2 presented a pressure-gradient correlation based on measurements in wells. This correlation has been found to provide accurate predictions in high-pressure wells and in high-production wells for flow through both tubing and annuli.2-5 However, when their method is checked on low pressure-low production wells or on wells with viscous crudes, serious discrepancies are found. As we shall see in the next section, this is due to the fact that their correlation factor, representing all irreversible energy losses, is given as a function of only one correlation group. Some important variables, such as gas-liquid ratio and liquid viscosity, are not incorporated in this group so that their specific effects are not accounted for. To study also the mechanism of vertical gas-liquid flow outside the ranges covered by the Poettmann-Carpenter publication and extensions, a laboratory investigation has been carried out. This study is founded on a pressure-gradient equation that is based on a pressure balance. To reduce the number of test runs required, a dimensional analysis has been carried out, followed by a selection of relevant dimensionless groups. These groups guided a subsequent experimental study, and with their aid the experimental program could be minimized while still covering the majority of the situations encountered in oilfield practice. In this paper the choice of a formula for the pressure gradient is discussed first. This is followed by a brief description of the experimental setup. Subsequently, the dimensional analysis is discussed and the relevant dimensionless groups are selected, resulting in the experimental program required. The general relationships of pressure gradient and liquid hold-up are then described; various flow patterns and a certain flow instability (so-called "heading") are discussed and a set of correlations is presented which shows a good agreement with the measurements and a few available field

By Richard G. Warren, Michael M. Minor, Gayle J. Thomas

INTRODUCTION Los Alamos Scientific Laboratory (LASL) initiated its effort in the Hydrogeochemical and Stream Sediment Reconnaissance (HSSR), a part of the Department of Energy (DOE) National Uranium Resource Evaluation (NURE) program, in late 1975. Since that time, LASL has completed sampling of the Rocky Mountain states of New Mexico, Colorado, Wyoming, and Montana at a density of about one water or waterborne sediment sample per 10 km2 and has sampled about 85% of Alaska at a density of at least one per 25 km2. Analytical results for these samples are reported by National Topographic Map Series (NTMS) quadrangle. All collection and analytical procedures have been standardized from the outset (Sharp, 1977; Sharp and Aamodt, 1978). Until early 1979, only uranium results were reported for these samples; thereafter, results include analyses for at least 42 additional elements in the sediment samples. Each LASL HSSR report also includes a discussion of the relationship of these analytical data to known or possible uranium resources; more recently, these data have been re- examined for their relationship to resources for other metals (Beyth et al., 1980; 1980a). Analytical results for LASL HSSR sediment samples are both comprehensive, including 43 elements, and precise, allowing close inter-comparison of data between quadrangles. A recent HSSR study shows that elemental concentrations in sediment samples from the Dixon Entrance quadrangle in Alaska are insensitive to the choice of sieve size fraction and do not vary significantly between stream locations a few meters apart, except for extremely high elemental concentrations (Warren, et al., 1980). Elements that are particularly reproducible include thorium, hafnium, and the .ram earth elements. Fortunately, sensitivities for these elements, which are often associated with uranium, are excellent by the nondestructive analytical technique of neutron activation analysis that LASL employs. Wet chemical techniques may not always give reliable results for these elements in sediment samples due to the difficulty of dissolving the resistate mineral phases that normally contain these elements. LASL has recently open-filed results for a large number of NTK3 quadrangles; to date analyses have been reported for about 605 of the quadrangles within the states of the Rocky Mountain region. As a result, uranium analyses am now complete for all sediment samples collected from the state of Wyoming. We have chosen to sumnarize the analytical results for Wyoming and portions of adjoining states hereafter termed "the ~ Wyoming regionn (Fig. 1 ) ; nearly 24 000 uranium analyses and nearly 17 000 analyses for 42 additional elements are available for sediment samples collected from this area. The DOE open-file report numbers are shown in Fig. 1 for reports open filed before September 1, 1980. The Wyoming region provides an ideal area for an examination of regional geochemical patterns ex- hibited by sediment samples. It is endowed with a variety of exposed geologic units and with widely distributed uranium districts associated with host units of several ages. However, discussion will focus on rock units of Eocene and Precambrian ages because they are widely exposed and host the majority of the uranium resources within the region (Fig. 2). Miocene units are also widespread and host mineralization in the Brown's Park Formation (Fig. 2). Epigenetic uranium mineralization occurs in sand- stones of lower Eocene age such as the Wasatch, Battle Springs, and Wind River Formations whereas vein type mineralization occurs in Precambrian crystalline rocks. Precambrian rocks within the region consist of a variety of granitic and meta- morphic rocks with l .4-2.8 billion year ages, except within the Uinta Arch, where they consist of a sequence of very low grade metamorphosed or unmetamorphosed 1.0 billion year old sedimentary rocks. Precambrian rocks have served as sources for much of the clastic material comprising the lower Eocene units, and may also have provided the source for the uranium in mineralized Eocene or Miocene sandstones (Stuckless, 1979). The remainder of this paper describes the relationship of elemental concentrations in HSSR sediment samples to exposures of Eocene and Precambrian rocks. The results are used primarily to determine where these Precambrian rocks might provide the most suitable uranium source areas and to infer the direction of transport toward adjacent depositional basins during the Eocene.

Jan 1, 1980

By R. Schuhmann, J. Th. Overbeek, P. L. De Bruyn

THE technique of concentrating valuable minerals from lean ores by flotation depends upon the creation of a finite contact angle at the three-phase contact, mineral-water-air. If the mineral is completely wetted by the water phase, contact angle zero, there is no tendency for air bubbles to attach themselves to the mineral. However, when the contact angle is finite, the surface free energy of the system, water-air bubble-mineral particle, can be diminished by contact between the bubble and the particle, and if not too heavy the mineral will be levitated in the froth. With a few exceptions, all clean minerals are completely wetted by pure water. Thus the art of flotation consists in adding substances to the water to make a finite contact angle with the mineral to be floated, but to leave the other minerals with a zero contact angle. The contact angle concept and experimental measurements of contact angles have played important roles in flotation research for several decades.'-" Nevertheless, there remain unanswered some basic questions as to the scientific significance of the contact angle and the nature of the processes by which flotation reagents affect contact angles. The contact angle is a complex quantity because the properties of three different phases, or rather of three different interfaces, control its magnitude. Considering the interfaces close to the region of ternary contact to be plane, the relation among the contact angle and the three binary interfacial tensions is easily derived. The condition for equilibrium among the three surface tensions, Fig. 1, or the requirement of minimum total surface free energy leads to Young's equation, Eq. I: ysa — ysl = yLA cos 0 [1] According to this equation, the contact angle has one well-defined value. Actually it is found in many experiments that the value of the contact angle depends on whether the air is replacing liquid over the solid (receding angle) or the liquid is replacing air (advancing angle). The receding angle is always the smaller of the two.4 Two explanations have been offered for this experimental fact. According to some investigators,5-8 roughness of the surface causes apparent contact angles that are different for the receding and the advancing cases although the actual local contact angle may be completely determined by Eq. 1. The other explanation involves the hypothesis that the solid-air interface after the liquid has just receded is different from the same interface when no liquid has previously covered it.1,4 Adsorption of constituents of the air or liquid might play a role here. In this discussion the difference between advancing and receding contact angle will be neglected and plane surfaces where Eq. 1 describes the situation will be considered. But there is still a fundamental obstacle to the application of Young's equation. The surface tension of the liquid (rla) can easily be determined, but the two surface tensions of the solid (rsa and ySL) cannot be measured directly. Eq. 1, however, is not without value. By contact angle measurements it is possible to establish how ysl — ysl varies with the addition of solutes to the liquid phase. Also, Eq. 1 affords a convenient starting point for calculating net forces and energy changes involved in the process of bubble-particle attachment.1,2 . If for the moment surface tension of the liquid (yLa) is considered a constant, an increase in ysa — ysL, will tend to decrease the contact angle. A decrease in ySA — ysl, corresponds to an increase of the contact angle. In cases where ySA — ySL > yLa the contact angle is zero; it will only reach finite values when ysa — ysa has been decreased below YLA. Thus on the basis of Young's equation and contact angle measurements alone, it can be learned how flotation reagents affect the difference Ysa — ysl, but no conclusions can be drawn as to the effects of reagents on the individual surface tensions ysa, and ysL, not even as to signs or directions of the surface tension changes resulting from reagent additions. A quantitative relationship between the surface tension or interfacial tension and the adsorption occurring at a surface or an interface is given by the Gibbs equation, which for constant temperature and pressure reads dy = — 2 T, du, [2] where dy is the infinitesimal change in surface tension accompanying a change in chemical potential

Jan 1, 1955

By G. Borelius

ABOUT the turn of the century, Gibbs' thermo-dynamic theory of heterogeneous equilibrium, on the one hand, and the experimental methods of thermal and microscopic analysis, on the other, gave to the physical metallurgist his first scientific tool, the equilibrium diagram. The classical equilibrium diagram of a binary alloy system shows the boundaries between ranges of homogeneous and heterogeneous equilibrium in their dependence of concentration and temperature. A homogeneous solid sohtion which on cooling passes such a boundary is assumed to precipitate, forming a mixture of two phases with different concentrations. The equilibriunl diagram and the equilibrium theory, however, give no information about the time scheme of the process or the intermediate states passed during precipitation. For this reason it satisfies neither the practical need of the metallurgist nor the curiosity of the physicist. As a matter of fact, in the heat treatment of alloys for technical use the objective very seldom is the equilibrium state. Thus good mechanical properties of construction material are connected, for the most part, with some intermediate state. As these intermediate states are thermodynamically unstable, there is, from a theoretical point of view, always to be expected a decay of the good properties with time; and it is a matter also of practical interest to know whether this natural life time of a material is of the order of, say, ten or thousands of years. Thus, for many reasons, there is a current demand to complete our knowledge of equilibrium through knowledge of the kinetics of the precipitation phenomena. From the point of view of the physicist, the most interesting question in this case is whether there are any general laws governing the kinetics. According to a generally accepted view, precipitation is ruled by two more or less independent phenomena, the formation of nuclei of a new phase and the growth of these nuclei. It is also commonly accepted that there is a tendency for the velocity of growth to increase with increasing temperature because of the increasing mobility of the atoms. There is also a tendency for the velocity of growth to decrease in the neighborhood of the two-phase boundaries. So far, however, very little is known quantitatively about this fundamental phenomenon in the case of solid metallic systems. In our laboratory attention has been directed especially toward the nucleation phenomena, and a series of measurements have been carried out with the guidance of a work- ing hypothesis (based on experiences from previous work on order-disorder transformations in alloys) about the influence on the nucleation of thermo-dynamic potential barriers. However, before discussing the experiments, the theoretical ideas will be considered. In a binary solid solution the arrangement of atoms on the lattice points approaches with increasing temperature a state of full randomness, as illustrated by the ball model of Fig. 1, that might represent a [111] plane of a face-centered alloy with 30 pct "black" and 70 pct "white" atoms. In reality the atoms are changing places continually with their neighbors so that the picture should rightly have been a moving one. On account of this thermal motion the concentration of black atoms within a certain group of, say, a hundred or a thousand lattice points fluctuates with time around the bulk concentration of 30 pct in a manner governed by statistical laws. With decreasing temperature two independent changes in this state grow more and more important. First, the mobility of the atoms decreases, and second, the forces between the atoms will have an increased influence on the fluctuations. In alloys with a tendency for precipitation, which are the concern of this lecture, the distribution function of concentration fluctuations will broaden, so that the relative probability of great local variations from the bulk concentration increases. Fig. 2 gives an example of such a fluctuation. When the alloy is supercooled below the solubility limit into the range of two-phase equilibrium, the fluctuations will now and then at some point give rise to a state that resembles the equilibrium state and thus will form a stable nucleus that is capable of growing by diffusion processes. In discussions with colleagues and in the literature, I have often encountered the idea that three or four atoms of the dissolved metal could form a nucleus of the new phase. A look at the ball model might be enough to indicate that this cannot be true. If it were true, there should be nothing but nuclei, whereas we know from experiment that nucleation must be a rather rare occurrence. In fact we have, as will be mentioned later, certain reasons to believe that the nuclei are formed by fluctuations containing some hundreds of atoms, which should be the order of the number of black balls in the fluctuating group of the figure, if it were extended into three dimensions. As a working hypothesis we have assumed that the fluctuations producing nuclei, though large and rare, still are ruled by the distribution laws of fluctuations of the supercooled solid solution in its initial state. Thus the probability of nucleation will be connected to the thermodynamic properties of the solid

Jan 1, 1952

Jan 1, 1923

By R. H. Terhune

THE enormous production of pig-iron, together with the many difficult and interesting problems with which its manufacture is fraught, has secured to this industry the exclusive attention of scientists with reference to the chemistry of iron, while some of the minor departments of its metallurgy have suffered neglect. Particularly is

Jan 1, 1873

Jan 1, 1923

By SME

A regular feature of the December issue is the abstracts of graduate theses in the mineral industry field presented during the preceding year. The following abstracts were submitted for this second article in the series.

Jan 1, 1976

By Will Mitchell, T. G. Kirkland, C. L. Sollenberger

The beneficiation of a scheelite ore by flotation was investigated with emphasis on determining optimum conditions for obtaining maximum grade and recovery in the rougher concentrates. Variables such as pH, time, temperature, and pulp density during conditioning were plotted against the grade and recovery of the rougher concentrates. Several gangue regulators were tried, and several methods of cleaning rougher concentrates are described.

Jan 1, 1951

Jan 1, 1942

Jan 1, 1942

By Allan Gibb

The ores of copper are usually associated with minerals containing arsenic, antimony and bismuth. Whatever the means adopted for extracting the copper, these metals are usually found, to a greater or less extent, in the product. There is, however, usually some elimination in the various metallurgical operations to which the ores are subjected, and some attempt is made here to determine the degree to which this elimination is effected.

Jan 1, 1903

Discussion of the paper of E. S. Moore, presented at the Colorado meeting, Sep-tember, 1918, and printed in Bulletin No. 135, March, 1918, p. 687. W. F. SMEETH, * Bangalore, Mysore, India (written discussion ? )-Before dealing with the air blasts, I would like to clear up a geological point. The author states that the matrix of the conglomerate resembles a hornblende schist. This is a, misapprehension. The conglomerate

Jan 10, 1918

By D. J. Crouse, W. D. Arnold

The potential behavior of radionuclides released in an underground nuclear detonation to fracture copper ore for subsequent in-situ leaching and copper recovery was studied with regard to contamination of the copper product and hazards to operating personnel. The laboratory test results indicate that only small fractions of the radioactive fission products would be dissolved on leaching the ore. Tritium (as tritiated water) would be the dominant radionuclide in the circulating leach liquor, assuming use of a fusion explosive. The test results showed solvent extraction to have important advantages over cementation for recovering copper from the leach liquors. While the radioactivity of the copper metal product produced by either method should be extremely low, the solvent extraction process provides a more effective separation of copper from the radioactive contaminants and entails fewer radiation protection problems. For these reasons it is the preferred process.

Jan 1, 1976