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By Donald A. Brobst

The minerals barite (BaSO4) and witherite (BaCO3) are the chief sources of the element barium and its compounds needed for many industrial processes and products. Barite, the principal ore mineral, is found the world over and is abundant and widely distributed throughout the United States.3 Witherite is much less common than barite, though more desirable in many ways as a raw material for the production of barium chemicals. England is the chief producer of witherite. Witherite is not mined in the United States at the present time, but it has been mined with barite from a deposit at El Portal, California. Barite is also called barytes, tiff, cawk, or heavy spar. Ordinarily it is a heavy mineral that crystallizes in the orthorhombic system. It is colorless, white, or gray, and transparent to opaque. In some deposits barite is black, yellow, brown, red, green, or blue because of included impurities. The streak is white and the luster vitreous to resinous or pearly. The specific gravity of pure barite (65.7 pct BaO and 34.3 pct SO3) is calculated to be 4.5, but inclusions and impurities in natural barite may reduce this value considerably. Well-formed crystals are generally tabular and have three cleavages. The barite of many deposits, however, has an uneven fracture and an apparent cleavage caused by separation along planes between successively deposited layers. The hardness is 2.5 to 3.5 on Mohs' scale. Commercially the terms "hard" and "soft" are used to refer to ease of grinding. Barite is relatively insoluble in water and acid, and thus can be used as a chemically inert material. Witherite, the natural carbonate of barium (77.7 pct BaO and 22.3 pct CO2), crystallizes in the orthorhombic system. The fracture is uneven and the luster is vitreous to resinous. The hardness is 3 to 3.5. The specific gravity of the pure mineral is calculated to be 4.29. It is transparent to opaque. The color is ordinarily white, gray, yellow, brown, or green. Geology and Distribution of Deposits Workable deposits of barite are widely distributed throughout the world in many geologic environments in sedimentary, igneous, and metamorphic rocks. Most deposits can be classified into three main types: (1) vein and cavityfilling deposits; (2) bedded deposits; and (3) residual deposits. 1. Vein and cavity-filling deposits are those in which barite and associated minerals occur along faults, gashes, joints, and bedding planes, and in breccia zones and solution channels. They also occur in various collapse and sink structures in limestone. Sharp contacts of the veins and cavity fillings with wall rocks are common. Barite cements fault and collapse breccia by replacement of the matrix or by filling voids. Large-scale replacement of the wall rocks beyond ore-controlling structures is rare. Barite in vein and cavity filling deposits is generally dense, "hard," and white to gray. Associated minerals are fluorite, calcite, ankerite, dolomite, quartz, and many sulfide minerals, especially pyrite, chalcopyrite, galena, and sphalerite. Gold, silver, and rare earth minerals occur with barite in some deposits in the western United States. Barite is also a gangue mineral in metallic ore deposits but production as a byproduct from such deposits will be affected by many economic factors. The host rocks are igneous, sedimentary, and metamorphic rocks of pre-Cambrian to

Jan 1, 1960

By Joseph H. M. Beaty, Gust Bitsianes

Successful blast-furnace operation depends upon securing an optimum balance between a number of important variables. This balance will vary somewhat from furnace to furnace in the same plant and with raw materials available in different plants. It is difficult to isolate the effect of any one variable unless it has a rather pronounced effect upon the efficiency of operation. The physical properties of iron ore and coke are known to affect the process, yet it is difficult to set up any definite yardstick by which these differences can be appraised. In recent years, whenever practicable, operators have taken steps to obtain better control over the absolute size and uniformity of size of the ore and coke. The size and physical character of the stone, however, have received comparatively little attention, emphasis being placed upon chemical composition, fluxing efficiency, and action as a desulphurizing agent. Since the stone occupies only about 10 per cent of the volume of the stock column, its influence upon permeability is less than that of the ore and the coke. The large pieces now used have a tendency to roll to the center and thus increase the permeability of this part of the stock column. Smaller pieces would be more effective in promoting the permeability of denser portions of the stock. The size and physical properties of blastfurnace stone are important also for reasons best understood by considering the results obtained by the crushing and the sizing of iron ore. Crushing ore to about 2 in. at Provo, Utah, and to about I in. in Alabama produced material somewhat less permeable to gases, even though sized. In spite of some sacrifice in permeability, the efficiency of the process was improved by crushing and sizing the ore, as indicated by a substantial saving in fuel and increased output. This saving in fuel is due in large measure to more thorough reduction of ore in the upper part of the furnace and to a corresponding decrease in the amount of carbon consumed prematurely above the tuyeres by the reaction CO2 + C = 2CO - 70,080 B.t.u. [I] The physical properties of stone, its size and rate of calcination are important because they influence the rate at which CO2 is released and the completeness of calcination before reaching a level in the furnace where the temperature does not exceed 1050°C. (1920°F.). Briefly, carbon dioxide from the limestone or from the reduction of ore may cause premature corn bustion of carbon above the tuyeres. Assuming that 1000 Ib. of limestone is used per ton of pig iron, about 435 Ib. of CO2 will be liberated during calcination of a good grade of stone. If all this CO2 from the stone were to oxidize carbon prematurely, about 120 lb, would be consumed above the tuyeres in a heat-absorbing reaction. The amount of carbon thus consumed when a

Jan 1, 1943

By G. P. Gladis, R. H. Atkinson

Palladium has been used for jewelry for many years, particularly in conjunction with gold. This use increased in amount during the war, as palladium and gold were only moderately used for war purposes while demands for platinum and some of the other members of the platinum group were so great that their use in jewelry was prohibited. Palladium hardened with a small percentage of ruthenium has the necessary technical properties and appearance for good jewelry, and it is sufficiently rare to be desirable for luxury items—at least I00 times as rare as gold. Although both visual and spectro-photometric examination demonstrated that the color of Palladium was almost the same as that of platinum, a few jewelers found the surface of palladium, even after some polishing, rather dark in areas that had been repeatedly heated during the soldering necessary to assemble certain types of handmade ornaments. This phenomenon is not to be confused with the thin, bluish oxide film that can be produced by heating in air over the range 400' to 800°C., as that film is easily reduced by dipping in warm 5 per cent formic acid or in warm methanol. It was suspected that the difficulty arose from heating in atmospheres that were alternately oxidizing and reducing, as Wise and Vines1 had found that this opened the grain boundaries of palladium and palladium-silver alloys in the same manner as in pure silver, as reported by Martin and Parker.2 This damage is caused by the reaction between oxygen in solid solution in the metal, acquired when heated under oxidizing conditions, and hydrogen diffusing in from subsequent heating under reducing conditions; the steam cannot diffuse out and therefore builds up sufficient pressure to disrupt the metal near the surface. Copper and various other metals can be damaged similarly, but platinum is nearly immune; therefore the problem was new to the platinum jeweler. Sulphur in the fuel gas also can cause trouble but did not appear to be dominant in the present instance. Metallographic examination of both pure palladium and ruthenium-palladium showed that the usual torch using oxygen and city gas as normally operated did in fact cause the surface and subsurface damage that had been observed, and also disclosed that a reducing flame caused more damage than an oxidizing flame and was very damaging even in the absence of any intentional swing in atmosphere from oxidizing to reducing (Fig. 7); besides the surface damage, there was serious loss of ductility. A full explanation of the mechanism of attack is not evident at the moment, but may be allied to the attack that occurs on heating catalytically active metals in nonequilibrium atmospheres.

Jan 1, 1946

By W. G. Pfann

Under certain conditions, a molten zone can be made to move through a solid by impressing a stationary temperature gradient across the solid. This phenomenon can be utilized in fabricating semiconductive devices, growing single crystals, joining, boring fine holes in solids, measuring diffusivities in liquids, small scale alloying, and purification. Fundamentals and exemplary applications are outlined. ANEW aspect of the travel of a molten zone through a solid is considered in this paper. Whereas, in previously described zone melting techniques,'-' zones were usually caused to move by changing the position or temperature of a heat source, in the present technique a zone is made to move by impressing a temperature gradient across it. For example, a thin layer of molten A1-Si alloy, sandwiched between two silicon slabs having a temperature gradient normal to the layer, will travel through the hotter slab. One feature of temperature gradient zone melting, as this technique will be called here, is that zones of unusually small dimensions can be maintained. This leads to such diverse uses as have been listed in the abstract. In this paper fundamentals of the movement of a molten zone in a temperature gradient, and some practical applications thereof, are outlined. Assumptions The movement of a molten zone through a solid body of solvent substance in which a temperature gradient exists will be discussed. The length of the zone will be its dimension in the direction of motion. The direction of the temperature gradient will be toward the region of higher temperature. To be considered is a binary or higher order solute-solvent system in which the concentration of solute in the molten zone is sufficient to produce a lowering of the freezing temperature of the solvent which is at least of the order of the temperature range impressed on the charge. While we discuss primarily molten zones in a solid matrix, the principles are applicable to solid or vaporous zones in a solid matrix, a requirement being that the diffusivity in the zone be substantially greater than in the matrix. Diffusion of solute into the surrounding solid will be assumed negligible. In general, its presence will not basically alter the conclusions to be drawn. For illustration, a system represented by the partial constitutional diagram of Fig. la will be discussed, in which k, the distribution coefficient defined in the figure, is constant and less than unity. However, the technique is applicable to any solute- solvent system in which one component lowers the melting point of another component. Movement of a Molten Zone in a Temperature Gradient Consider, in the system AB of Fig. 1, where B is designated the solute and A the solvent, the effect of sandwiching a thin layer of solid B between blocks of solid A and placing the whole in a temperature gradient such that the temperature of the layer is above the lowest melting temperature of the system. Surrounded by an excess of A, the layer will dissolve A, becoming molten, and expand in length." As so- lution of A continues, at both interfaces, the mean solute concentration in the zone will move to the right in Fig. la, until at temperature T, the liquid at the cooler interface reaches the liquidus concentration C,. Solution of A thereupon ceases because the liquid T1 is saturated with A. The liquid at the hotter end of the zone, being at temperature T2, is not saturated with A at concentration C1. Hence solution of A continues there and concentration C2 is approached. A concentration gradient therefore is set up in the zone, causing A to diffuse toward the cool end and B toward the hot end. As a result, the liquid at the cool interface becomes supersaturated and a layer of crystalline A containing concentration kc, of B in solid solution freezes. Since a source of A

Jan 1, 1956

By John Griffen

THE modern anthracite breaker or washery uses almost completely a wet method of preparation, which requires, roughly, 1 gal. of water per minute per ton of production per day. The entire anthracite industry uses about 320,000 gal. per min. of water for this purpose or 800,000 tons of water per day. As this water leaves the breakers, it contains fine solids-coal, slate, pyrite, and clay-and is then called silt or slush; as slush is the term most commonly used, it will be employed throughout this paper. The solid content of the slush will be referred to as solids. In the earlier days of anthracite mining, little coal was washed, less crushing was employed, and virgin coal was mined exclusively. As a result, the slush problem was not acute because of the relatively small quantity and the coarseness of the solids. Such slush as was produced could usually be easily impounded and retained or could be discharged into streams without any appreciable pollution being apparent. The character of the fine waste from the breakers, changed materially as its quantity increased until now about 40,000 tons of slush solids are produced daily. Second mining and robbing operations materially increased the quantity of fine solids delivered to the breaker in the mine car. The demand for chestnut, stove and egg sizes, to the exclusion of grate, steamboat, and lump sizes, require finer crushing of the mine-run coal with a consequent increase of fine solids in slush. The use of rice and barley sizes removed a considerable tonnage of coarser solids from the slush but left great quantities of fine solids difficult to retain completely and store and long considered of no possible fuel value. Despite the efforts of the coal operators, the slush solids have found their way into the streams causing, in some cases, serious pollution. The Water Supply Commission of Pennsylvania published, in 1916, a report on Culm in the Streams of the Anthracite Region,1 from which the following is taken: About 40,000,000,000 gal. of water carrying 10,000,000 tons of fine culm are discharged into the water-courses direct, flushed into the mines, or disposed of by various means on the surface. The extent to which the very small sizes of anthracite

Jan 9, 1921

By Robert Linton

Tats paper deals with work that has been carried on for over three years by the management and staff of the North Butte Mining Co. in an effort to standardize mining methods, to eliminate lost motion in the operating organization, and to improve the efficiency of the individual workman. Naturally, much of this work is an adaptation of ideas suggested by other mining operations or by practice in manufacturing and other productive industries. The studies, however, have developed some features that it is believed are new. Both new and adapted features are given in detail. The normal capacity of the North Butte mines is about 2000 tons per. day. Hoisting is done principally through the Granite Mountain shaft, which is 3740 ft. (1140 m.) deep and equipped with an electric hoist capable of hoisting 200 tons per hour from a depth of 4000 ft. (1219 m.). The lowest stoping level is the 3400-ft. The Granite Mountain shaft is connected with the Speculator shaft, about 850 ft. (259 m.) south, and with the Gem, about 1150 ft. (350 m.) east, which are 3000 (914.4 m.) and 2000 ft. (609.6 m.). deep, respectively. These two shafts are equipped with reversible fans for ventilation. The Speculator has a; steam hoist with a capacity of 150 tons per hour from the 3000-ft. level. The Granite Mountain shaft is concrete lined from the 1600-ft. to below the 3000-ft. level and gunited with cement from the 1600-ft. level to the surface. Sections of the Speculator shaft with a total combined length of 500 ft. (152.4 m.) are also concreted. There are approximately 36 miles (58 km.) of drifts and crosscuts in the mine, in which there are 15.2 miles (24.5 km.) of track. At normal capacity, about 75 stoping faces, 20 raises, and 30 sill development faces are working. Stoping is usually by the standard square-set method. Where the size of the oreshoot and character of. the walls permit, the rill (or cut-and-fill) system is employed.

Jan 8, 1920

By H. A. Guess

Introduction. History and Production Statements. Southeast Missouri is the oldest of the large producing districts of the United States. The first recorded production from disseminated ores was in 1869, although for many years prior to that time lead had been milled from shallow pockets, and steady growth in production has been shown ever since, the greatest increases being during the past five years. The production by years for each of the operating companies from 1869 to 1907, inclusive, is given in Table I. In Table 11. is given the production by years from 1908 to 1912, inclusive, for the district as a whole, showing the tonnage of crude ore mined, yield in concentrates, average assay of concentrates; yield in metallic lead both per ton of crude ore and in total; also approximate value of the yearly production. It is interesting to note that the production for the 5-yr. period 1908 to 1912, inclusive, is practically equal to the total previous production, viz., the 39-yr. period 1869 to 1907, the summary being as follows:

Jan 1, 1915

By M. J. Spendlove, H. W. St. Clair

An automatic surface-follower mechanism was used to measure the surface temperature and the rate of evaporation of molten zinc while undergoing distillation at low pressure. At pressures of 50 to 100 microns Hg, the rate of evaporation may be 60 to 80 pct of the theoretical maximum corresponding to the measured temperature. The rate decreases rapidly at pressures above 100 microns Hg, to only 7 pct of the theoretical maximum at 2000 microns Hg. Measured temperature gradients at the surface are in agreement with theoretical gradients calculated from the heat of vaporization, rate of evaporation, and thermal conductivity of molten zinc. THIS paper covers a series of careful measurements of the rate of evaporation of molten zinc at low pressures, undertaken as a part of a general investigation on the separation of metals by distillation.' Preliminary results on the rate of evaporation of zinc were described in a previous publication.' The results of the preliminary study are as follows: 1—The observed rates of evaporation of zinc were as high as 0.60 g per sq cm per min, corresponding to 75 pct of the maximum rate as determined by the temperature of the metal. 2—The evaporation rate was decreased from 0.30 g per sq cm per min at a pressure of 25 microns to only 0.09 g per sq cm per min when the pressure was increased to 5 mm. 3—The temperature of the surface during rapid evaporation may be 35" to 100°C less than the main mass of metal. Observed temperature gradients at the surface are consistent with those calculated from the heat of vaporization and the thermal conductivity of liquid zinc. In the preliminary experiments, the rate of evaporation was determined from the loss in weight of the metal in the crucible during the test. This was compared with the weight of the condensate. Obviously, this method was subject to error because of some uncertainty as to the period of evaporation that should correspond to the loss in weight. Furthermore, this method did not permit taking into account probable variations in the rate of evaporation during the test. A more serious shortcoming was that the temperature at the evaporating surface was not known, so the maximum theoretical rate of evaporation could not be calculated accurately. To improve the precision of rate measurements and to allow accurate measurements of the surface temperature, a refined experimental technique was developed whereby the temperature and position of the surface could be measured accurately. This was done by an automatic surface-follower mechanism that gave a continuous record of the surface temperature and the amount of zinc evaporated. These data permitted an instantaneous determination of the actual rate of evaporation and the surface temperature throughout the test. Pure zinc (99.99 pct Zn) was used in all experiments. Description of Distillation Furnace The details of construction of the distillation furnace are shown in Fig. l. The furnace is enclosed in a large quartz tube open at one end. The open end of the quartz tube is sealed by means of a water-cooled head. The entire enclosure is vacuum tight. The connection between the water-cooled head and the quartz tube is sealed by means of a rubber gasket which fits tightly against the smooth end of the tube. The metal is heated by induced current set up in the molten zinc and the walls of the graphite crucible by means of a water-cooled induction coil outside the quartz tube. High frequency current is passed through the induction coil from a 6 kw mer-

Jan 1, 1952

By C. Scala, F. Bernstein

General expressions are derived relating the streaming potential to the electrochemical potential of a permeable junction separating two electrolytic solutions. By the methods of irreversible thermodynamics, these potentials are related to the flux of mobile species arising from differences in pressure and chemical composition. The flux is conveniently expressed as a transference number, the equivalents of a mobile species transferred through the junction per faraday of electricity. At constant pressure, the flux equation gives the electrochemical potential across the permeable junction. The streaming potential across the junction is obtained by imposing the condition of constant chemical composition. The familiar expression for the borehole SP is shown to be a particular solution of the general flux equation. The derived exprersions were verified in experiments with seven shale samples. Both the theory and experimental data provide additional proof of the presence and magniturle of the streaming potential in shales. INTRODUCTION In the interpretation of electric logs, there has been much concern over the correction to be made to the recorded SP for an electrokinetic or streaming potential originating from the difference in pressure between the mud column and the formation. It was long recognized by M. R. J. Wyllie that such an electrokinetic potential source mas in the mud cake opposite permeable sands.' More recently, M. Gondouin and C. Scala2 showed an additional but opposing electrokinetic source of potential to be in shale beds. Their work was supported by the very extensive and excellent work of Hill and Anderson.3 n the present contribution, the general relationships between the electrochemical potential and the corresponding streaming or electrokinetic potential are examined and clarified. A notable advance towards understanding the relation between the various sources of electrical potential in a borehole has been the application of the now common methods of irreversible thermodynamics to describe the passage of ions and water through charged electrolyte junctions such as in shales.' The advantages of these methods are twofold. Unlike classical thermodynamics, they can be applied to non-equilibrium sys- tems, i.e., systems in which flow takes place, provided the flow processes have reached a steady state. They also permit conventional thermodynamic properties to be related to the steady-state dynamic properties. These methods arc used here specifically to derive expressions relating the potential behavior of shales in terms of ion and water transport. Experimental verification of the expression for the shale streaming potential is given which in turn offers theoretical support to the existence of a streaming potential in shales.' Importantly, the relative contribution of transport parameters to the SP is clarified. The theoretical treatment is essentially that of Lori-mer, Boterenbrood and Hermans3 ut has been extended to derive the general expression for the SP.

By E. A. Gulbransen, W. S. Wysong

THE behavior of tungsten and its surface oxides in oxidizing and reducing atmospheres and in high vacua at elevated temperatures is a question of considerable technical importance. The use of tungsten as a metal or as an important component in alloys in high temperature oxidizing atmospheres has been limited because of the unprotective nature of its oxide film and the volatility of its oxide. This paper will present results of a microbalance study1,2 of the following problems: (I) the oxidation behavior in the temperature range of 25 to 550°C (2) the reduction with pure hydrogen of thin oxide films formed on tungsten, and (3) the volatility of thin oxide films on tungsten. Tungsten is an interesting metal to study for the following reasons: (1) although the oxide to metal volume ratio is greater than one, the oxide is not considered protective, (2) the metal readily oxidizes at temperatures from 300° to 550°C (3) the oxides W02 and WO3 are reduced at temperatures as low as 500°C. by hydrogen, and (4) the oxide W02 is volatile at temperatures from 800 to 1100°C. LITERATURE The oxidation of tungsten in its thin film range has not been studied critically. In the thick film range Dunn3 has made the only systematic study. He found the oxidation rate to obey the parabolic rate law in the temperature range of 700 to 900°C. The temperature variation of the oxidation rate constant was found to follow an exponential law of the Arrhenius type. An inflection was noticed in the temperature plot of the rate law constant at 850 to 900°C. This was attributed to a phase change in the oxides. Scheil4 has studied the oxidation rate at 500 and 700°C over long periods of time and found a linear rate law. This result was interpreted as evidence for the presence of a nonprotective film. Pilling and Bedworth5 analyses of the oxide volume to metal volume ratio would indicate that a compact protective film should form. McAdam and Geil6 have studied the oxidation of tungsten in the thin film range using the interference color method. A parabolic rate law was found. Their curves showed that tungsten oxidizes faster than nickel but more slowly than iron. The lattice structures found in the oxidation of tungsten surfaces have been studied by Hickman and Gulbransen.7 They have reported that W03 is the stable oxide in contact with the metallic substrate up to approximately 600°C while W02 forms first at 700°C. Hägg and Magneli8 have recently reported a study of the lattice structures observed in the tungsten oxides using the X-ray diffraction method. In addition to an a-phase W03 and a d-phase W02, they reported the existence of two new phases. A ß' phase, homogeneous between

Jan 1, 1947

By R. S. Kinasevich, D. D. Crabtree, D. W. Fuerstenau, T. P. Meloy, A. L. Mular

This paper presents details of the concept that size reduction in comminution machines takes place by three mechanisms; namely impact, abrasion, and chipping grinding. Experimental evidence is presented to show that each of these comminution mechanisms produces particles of a characteristic size distribution. The actual product from a comminution device has been postulated to be the result of a composite of these three types of mechanisms. Composite curves are demonstrated for a material following the Gaudin-Schuhmann, Gaudin-Meloy, and Rosin-Rammler size distributions. About forty years ago, Gaudin1 showed that grinding may be considered a combination of impact and attrition. Since that time, major efforts have been devoted to studies, both experimental and theoretical, of impact and compression fracture, while attrition has been almost wholly neglected, at least quantitatively. A significant attempt to distinguish between attrition and impact grinding is the work of Tanaka2 in Japan. By means of an instrumented abrasion grinder and a drop weight device, he determined coefficients relating the increase in surface area of various materials to the energy expended by the two methods of comminution. He showed that physical properties of a material determine its response to attrition and impact grinding. By extending his ideas to ball milling, he concluded that to a large extent the basic comminution process in a ball mill is due to the impact of falling media. Because Tanaka used a mass of particles in his drop weight device, however, he did not obtain pure impact size reduction. The purpose of this paper is to define basic mechanisms of size reduction, to verify that each has a characteristic and meaningful distribution curve, and to show how a combination of these mechanisms results in a size distribution very like that produced by grinding mills. DEFINITION OF COMMINUTION MECHANISMS The product from a grinding device will be considered to be the sum of the contributions resulting from the action of three basic mechanisms of size reduction which operate in a ball and rod mill. These are impact grinding and two forms of attrition, namely abrasion grinding and chipping grinding. Each is defined below. Impact Grinding: If a straight line is obtained when the cumulative weight fraction finer than a given size is plotted on log-log paper as a function of that size, the slope of the line is defined as the distribution modulus. A number of investigators 3,4,5 have shown that impact fracture of single specimens of different composition and shape results in a distribution of daughter particles that exhibit a distribution modulus of unity. This has also been true for materials broken in slow compression. Moreover, under slow compression or impact fracture conditions, theoretical distribution equations6*' which approximate the Gaudin-Schuhmann distribution when the distribution modulus is close to unity agree reasonably well with the experimentally obtained products. If one now considers a comminution process where many impact or compression fracture events are taking place, then any rational summation of the individual events yields, in the finer size range, a Gaudin-Schuhmann distribution whose distribution modulus is also unity. If the size distribution of the product from a mill has a distribution modulus of unity, it is implied that particles are fractured in a manner which results in a comminution event having a distribution like that obtained for the breakage of single specimens. These impact events would occur when a particle is smashed between balls or between a ball and the mill liner. Attrition, on the other hand, is that form of grinding which cannot be called impact grinding, and comprises both abrasion and chipping grinding. Abrasion Grinding: Abrasion is a form of surface wear resulting when particles rub against each other or against balls or the mill liner of a tumbling mill, somewhat like a piece of wood being rubbed over a piece of sandpaper. The surface wears at a more or

Jan 1, 1964

By Marcus A. Grossmann

This paper offers for consideration certain somewhat radical modifications in the iron-carbon diagram, these modifications being the result of the presence of notable amounts of alloying elements. When only small amounts of alloys are present, the standard iron-carbon diagram (Fig. 1) can be used with but insignificant changes; when larger amounts of alloys are present, however, it assumes a distinctly altered appearance. No comment is offered for the present except to call attention to the delta area, A4BM, which represents a region of mixtures of austenite and delta iron, just as area A3SP represents mixtures of austenite and alpha iron. Absence of Carbon We may turn at once to the effect of the presence of alloys. It has been found that in the complete absence of carbon, the gamma change will sometimes disappear entirely when sufficient alloying element is

Jan 1, 1927

By J. L. Tokich, A. R. Troiano

INTRODUCTION SINCE 1921, when Hull' discovered that cobalt can exist in the face-centered cubic and hexagonal close-packed modifications, the transitions that occur in cobalt have been extensively studied. It is generally agreed that on heating the hexagonal lattice changes to the cubic structure at temperatures ranging from 400 to 500°C although considerable doubt exists as to the exact temperature. Data concerning the temperature of the transformation on cooling are much less concordant and their interpretation has not been satisfactory. The study is further complicated by the fact that many investigators have reported the existence of a high temperature allotropic change in the range 850 to 1020°C, at which the cubic lattice reverts to the hexagonal modification. The transition on cooling, which has been reported as occurring at various temperatures from approximately 400 to 100°C, is of particular interest. Troiano and Greninger2 have recently suggested and considered the possibility of allotropic transformations occurring in pure metals by a shear-type, diffusionless (martensite) transformation. The case of cobalt was specifically discussed and certain observations of previous investigators evaluated in terms of this type of transformation. Table 1 briefly outlines the methods and results of previous investigators of the transformation temperatures of cobalt. MATERIALS AND METHODS The major portion of this investigation was performed with cobalt sheet containing a total of 0.2 pct impurities with carbon present to the extent of 0.1 pct. After melting in an induction furnace under an atmosphere of hydrogen, the carbon content analyzed 0.03 pct. Some observations were repeated with hydrogen reduced cobalt compresses analyzing 99.9 pct pure. No significant variations in results were observed employing the as-received sheet, the remelted stock, or the cobalt compresses. Filings for X ray diffraction analysis were sealed in evacuated glass ampoules. Pyrex glass tubing was used for temperatures below 600°C and for higher temperatures clear fused quartz was satisfactory. After appropriate heat treatment at various temperatures, the specimen ampoules were furnace cooled, air cooled or quenched by crushing under distilled water. This allowed a range of cooling velocities from less than one degree C per sec to greater than 1,000°C per sec. X ray diffraction patterns were taken with a Debye camera and filtered characteristic cobalt K-alpha radiation. The proportion of the existing phases was roughly approximated by visual examina-

Jan 1, 1948

By M. F. Hawkes, R. F. Mehl

The rate of isothermal transformation of austenite to pearlite depends upon the rate of nucleation, N, and the rate of growth, G, of pearlite in austenite. Values of N are given in terms of the number of nuclei forming in unit time per unit grain boundary area of unreacted austenite; values of C are given in terms of the linear rate of radial growth. Variations in the isothermal rate with temperature result from variation of N and G with temperature. Depth of hardening of a steel depends fundamentally upon values of N and G; changes in carbon and alloy content effect changes in N and G and thus affect depth of hardening. Quantitative studies are available on N and G for the formation of pearlite in plain carbon eutectoid steels.3 Systematic studies in this field are necessary if the phenomena are to be well enough known to furnish a proper basis for full rationalization and for theory. Accordingly, the studies are continuing, both with respect to the effect of alloying elements upon the values of N and G in the formation of pearlite and to the values of N and G for the formation of ferrite in hypoeutectoid steels. The present paper is the first relating to the effect of alloying elements upon the values of N and G for pearlite. It offers special interest since cobalt is known to have an anomalous effect upon the rate of formation of pearlite, accelerating it, whereas all other elements retard it.4 It will be shown that cobalt increases both N and G for pearlite and that this effect is inherent in the Fe-Co-C system and not dependent upon factors relating to austenite heterogeneity nor upon any recognizable adventitious factor. Inasmuch as the rate of diffusion of carbon in austenite and the interlamellar spacing of pearlite are variables related to G and possibly to N (in a manner not yet certain), measurements of the effect of cobalt upon them are also reported here. In the course of the work, measurements were made on the effect of cobalt upon the marten-site temperature and these are given. COBALT AS AN ALLOYING ELEMENT IN STEEL Properties of Cobalt Cobalt resembles iron more closely than does any other chemical element. Its atomic number is 27, hence it is the element immediately following iron in the periodic system. The two differ in atomic structure only in the fact that cobalt contains seven electrons instead of six in the third, or transition, level of .the third shell. The next shell, which is the

Jan 1, 1948

By Daniel R. Hull

In 1926 Gendersl reviewed the existing theories of this subject and stated his views in support of the gas-pressure theory. Again, in 1937, the subject was thoroughly reviewed by N. B. Vaughan3 and by Phillips and Brick,2 so that no résumé is called for here. The purpose of this paper is to describe certain observations made in the course of mill work, and to point out that they mostly tend to confirm the gas theory of Genders. Vapor Segregation There is, however, one type of inverse segregation that can be accounted for by considering the volatility of one of the constituents of an alloy. The most familiar case is ordinary brass, which is subject to a zinc enrichment of a few tenths of a per cent at the surface of a chill casting. This has been noted in 70-30 brass by Genders, and a typical example of it is given in Table 1, which represents a cylindrical billet 7 in. in diameter by 55 in. long. After lathe-turning 1/32 in. from the surface, the remaining distance to the center was sampled at six equally spaced intervals. the lead, which is essentially the same throughout, will be mentioned later. Consider a brass-mill mold, either round or rectangular in cross section, standing several feet high. It may require a minute or two for pouring. Before it is full, the metal in the lower end has partly solidified and contracted somewhat away from the mold. The initial shell of solidification follows not far behind the top of the column, even if the central portion is liquid for a long way down. There is, then, a space between metal and mold that is filled with zinc vapor. The vapor has no exit, because the liquid at the top of the rising column is not only in contact with the mold but keeps UP a fresh supply of zinc vapor, which has, perhaps, already begun to condense in the lower portion. The cycle is short. Within a minute or two after the mold is full the bar has cooled enough to condense all the zinc. Some of it may condense on the mold; it might be expected that most of it would condense there, but the mold at that time is well coated with a velvety carbon residue from the oil dressing, overlain by fluffy zinc oxide that commenced covering the inside of the mold as soon as pouring began. The clean skin of the freshly cast brass offers a preferred surface for condensation. Reabsorption is quick and inevitable. A simple experiment indicates that a surprisingly large quantity of zinc vapor is trapped in the space between mold and

Jan 1, 1941

By David E. Jones, Dean K. Hunt, C. Y. Chen

INTRODUCTION Of all the numerous geological hazards that threaten the well-being of urban areas in the United States, probably none is so widespread, persistent, and diversified as surface subsidence (HRB-Singer, Inc., 1977). Simply defined, subsidence is the vertical displacement or sinking of the ground surface caused by either natural phenomena or man's activities. The downward movement, however, can be accompanied by horizontal movement, strain, tilt and even by a locally upward movement. Damage to structures and the environment can result from any of these movements. Extracting subsurface materials, fluids and solids, accounts for most man-induced subsidence in the United States. Among all the mining-related subsidences, the collapse of voids created by underground coal mining has been the major cause in inflicting surface damage (Comptroller General of the United States, 1979). Subsidence from coal mining may occur within a few weeks or be delayed for years, depending upon the mineral layer's depth below the surface, the overlying rock strata's characteristics, the extent and methods of mining that were employed, and the time deterioration of pillar and mine structure. Unless underground resources are not mined or control measures are implemented to prevent or minimize damage, some degree of surface subsidence and its accompanied deleterious effects are often inevitable. The ways to control the subsidence and minimize surface damage may include: 1. Precautionary measures built into new structures or surface features. 2. Preventive works applied to existing structures or surface features. 3. Mine design incorporating special underground layouts. 4. Any combination of the above measures. Upon the enactment of Public Law 95-87, the Secretary of the Interior, through the recently created Office of Surface Mining (OSM), was authorized to promulgate rules to regulate mining reclamation including subsidence control. Proposed on September 18, 1978, these rules were finalized, following public comment and hearings, on March 13, 1979, as part of the permanent regulatory program for the regulation of surface mining and reclamation operations which include the surface effects of underground mining. On January 28, 1981, Secretary Watt of the Department of the Interior issued an order to re- quire all agencies to identify with recommendations all regulations which are believed to be excessive, burdensome or counterproductive. Also on February 17, 1981. President Reagan issued Executive Order No. 12291 requiring all Federal agencies to conduct a regulatory review to make a determination that each promulgation of a regulation is clearly within the authority delegated by law and consistent with Congressional intent (Federal Register, 1981). As a result, OSM initiated the regulatory reform to revise the permanent regulatory program. Following a brief discussion of the technical aspects and the effects of subsidence on man and his environment, this paper presents a historical overview of how rules and regulations are used to govern the subsidence related problems. The development of the regulation of subsidence under Public Law 95-87, the Surface Mining Control and Reclamation Act of 1977 (SMCRA or the Act) are also discussed, including the new regulations being developed under the regulatory reform program. SOME TECHNICAL ASPECTS Am EFFECTS OF FINE SUBSIDENCE An extensive historical review of mining subsidence is given by Zwartendyk (1971) and Shadbolt (1978). Comprehensive technical presentations have been given by Henry (1956), King and Whetton (1957), Hall and Orchard (1963). Muller, et al. (1968). Grard (1969), Voight and Pariseau (1970). Kapp and Williams (1972), Cummins and Given (1973), Brauner (1973) , and NCB (1975). A theory of surface subsidence due to underground mining was perhaps first fundamentally stated by a French engineer, Toillez, in 1838, and formulated by a Belgian engineer, Gonot, in 1839 (Goldreich, 1913, cited by Zwartendyk, 1971). Since that time,

Jan 1, 1982

By Leendert de Witte, Fred J. Radd

In many areas caring failures can be directly related to electrical currents observed in the casings. It is the thesis of this paper that the observed casing currents are mainly due to electrochemical potentials of the type in evidence on spontaneous potential curves of electrical logs. The general nature of these potentials are discussed and an equivalent circuit is given for current and potential distributions around open holes. The casing forms a short circuit to these potentials and tends to average the effects of local cells. The case of casing corrosion opposite the Dakota water sands in the salt-mud area of Kansas is discussed anil used us a qualitative, illustration of the relation between SP's and casing currents. A method of quantitative derivation of casing current distribution frorn electric log SP curves, using linear transform theory, is described and results are compared with a measured current profile. The effects of hydrogen over-potentials at the cathodic portions of the pipe are considered and some laboratory data are given in support of conclusions regarding the over-1.01tuge.s. INTRODUCTION To date an appreciable amount of work has been done on the measurement of oil well casing currents and on the correlation of the anodic portions of the current profiles with corrosive casing failures. Speculations on the origin of the casing currents have, however, remained rather vague; and although almost every plausible cause has been mentioned, there is to the writers' knowledge no clear-cut expose' on the details of the causes of the corrosive currents in the literature. A study of current surveys and casing failures in the N.W. Burnett field, Ellis County. Kan.. indicated the probability that concentration cell emf's between the Wellington salt section and the relatively fresh waters in the Dakota sands were a major cause of the corrosion currents. A more general concept evolved upon analysis of the severe corrosive conditions in the Pleistocene sands in the Ventura Avenue and San Miguelito fields in California. In this area no major variations in the salt content of the formation waters occur and yet large casing currents are observed. An explanation is found in the fact that the local spontaneous potentials which are set up due to concentration contrast between the drilling fluid and the connate water are short circuited when casing is set. The very conductive path through the casing increases the magnitude of the currents and has the tendency to average local sources over fairly large intervals. Current will flow between the sections that are predominently shaly and the sections that are mostly sandy. At the places where the current leaves the pipe, corrosive attack will occur. This same phenomenon will be present wherever unprotected pipe is set through sections that show large SP kicks on the electric logs over reasonably thick interval~. GENERAL- NATURE OF THE SPONTANEOUS POTENTIALS When a sequence of sedimentary rocks is penetrated by a drill hole filled with a mud which has a different salt concentration from that in the formation waters, various types of electrochemical potentials are established between the formations and different parts of the mud column. Opposite clean sand sections. a simple liquid-liquid junction potential will be observed; while opposite argillaccous formations, a membrane potential, often referred to as shale potential, will be established. The first quantitative analysis of these emf's in terms of liquid junction and membrane potentials is due to Wyllie.1

Jan 1, 1956

By E. C. W. Perryman

The recovery of X-ray line broadening, hardness, and electrical resistivity from cold worked AI-Mg alloys has been investigated. The results, together with those from density measurements, suggest that magnesium atoms freeze in the excess vacancies formed by cold working, and that this affects the climb of dislocations during the recovery process. PREVIOUS work1, " has shown that while 1 pct Mg increases the activation energy for recrystalliza-tion, it decreases the activation energy for the recovery of mechanical properties and decreases the subgrain size both after cold working and annealing. A similar result has been reported by Varley2 for an A1-2 pct Mg alloy. With plastic deformation at high temperatures, McLean and Farmer' and Rachinger have found that magnesium appears to retard the motion of dislocations and, furthermore, they find little or no effect of magnesium on the size of subgrains formed during high temperature deformation. In view of the apparent contradictions as to the effect of magnesium on subgrain size, the recovery process in Al-Mg alloys has been investigated more thoroughly by studying the annealing out of X-ray line broadening, hardness, and electrical resistivity from alloys cold worked at room temperature. Material Used—The chemical analyses of the alloys are given in Table I. Fabrication—The material used was cold rolled 20 pct at room temperature, the grain size prior to the last cold rolling operation being similar to that used in previous work; i.e., 230. The experimental procedure for annealing, determination of X-rav half-veak breadth. hardness measurement, electEica1 resistivity, and density and metallographic examination was exactly the same as previously described." Variation of X-Ray Half-Peak Breadth with Annealing Time—Isothermal annealing curves at 100°, 200°, and 250°C were obtained for material cold worked 20 pct. The half-peak breadth of the (333) Ka, line directly after cold working is shown as a function of magnesium content in Fig. 1. Only with the 2.87 pct Mg alloy was overlapping of the a, and n.. reflections observed to any appreciable extent. To separate these, Rachinger's method' was used. Typical isothermal annealing curves are shown in Figs. 2 and 3 for 100" and 200°C, respectively. These curves are similar to those obtained previously for super-purity aluminum except that the

Jan 1, 1957

By Eugene N. Cameron

Graphite is the hexagonal form of crystal-line carbon. It is found in nature locally as tabular crystals but occurs mostly as disseminated flakes, foliated, platy, or fibrous masses, or microcrystalline compact to earthy material. Graphite is characterized by its gray to black color, metallic luster, black streak, perfect basal cleavage, softness (H = 1-2) and unctuous feel. It is sectile and flexible and has a specific gravity of 2.1 to 2.3. It is an excellent conductor of heat and electricity and is inert to ordinary chemical reagents. It melts at a temperature of about 3500°C and vaporizes at a temperature of about 4500°C. In the presence of oxygen it oxidizes to CO2 in the temperature range 600° to 700°C, but it is stable at ordinary temperature and markedly resistant to chemical weathering. Although some natural graphite is nearly 100 pct pure carbon, most contains mechanical impurities of various kinds; quartz, biotite, muscovite, pyrite, iron oxides, and feldspars are the most common. Commercial graphite products have a wide range of graphite content, but the better grades contain 80 pct graphite or more. Both natural and manufactured (artificial) graphite are used in industry. Natural graphite products are divided into two broad categories based on grain size. Graphite composed of visible crystals is called "crystalline" graphite, whereas graphite so fine-grained that it is not visibly crystalline is termed "amorphous." The distinction is arbitrary, for all natural graphite is crystalline, and all gradations between the two commercial categories are known. Within the two categories the terminology used in industry is confusing and not entirely consistent. Crystalline graphite comes from two principal types of sources. The first consists of rocks containing disseminated flakes of graphite. This source yields the "flake graphite" of industry. The second comprises vein deposits of graphite, of which those in Ceylon are the most important and furnish the Ceylon graphite of industry. Amorphous graphite comes from any of a variety of sources, including some of those that yield crystalline graphite. Manufactured graphite is made by electric furnace processes, mostly from petroleum coke. Occurrence and Distribution of Graphite Deposits GENERAL Graphite is widely distributed in nature, occurring in igneous, sedimentary, and metamorphic rocks, and even in nickel-iron meteorites. Graphite deposits of economic interest, however, occur mostly in metamorphic terranes. Five principal geologic types of deposits are recognized: 1. Deposits consisting of flake graphite disseminated in metamorphosed siliceous sediments. 2. Deposits consisting of flake graphite disseminated in marbles. 3. Deposits formed by thermal or dynamothermal metamorphism of coal or other highly carbonaceous sediments. 4. Vein deposits of the Ceylon type. 5. Contact metasomatic or hydrothermal deposits in marble. DEPOSITS IN METAMORPHOSED SILICEOUS SEDIMENTS Deposits consisting of flake graphite disseminated in metamorphosed siliceous sedi-

Jan 1, 1960

By C. A. Heiland

The following summary is written for the benefit of the practical operator in the nonmetallic field who wishes to know what geophysics has done and may be expected to do in his line of work. His problem is quite different from that of the geophysicist who has operated with various or all methods and has followed the literature, and who is assumed to be familiar with the geologic possibilities and limitations of each method. This article is not written for the latter, although he may be interested in the four or five hitherto unpublished surveys described. To the operator, on the other hand, geophysics is only secondary. His problem is to determine which geophysical method is best suited to his special needs. If he wanted to know, however, which method could be used to locate a certain material of given physical properties, building stone, for instance, he would have to wade through a tremendous amount of geophysical literature, bibliographies and articles, before he could find what he wanted. Therefore, the purpose of this summary is to present the geological problems first and then to discuss the comparative merits of the geophysical methods that can be, or have been, applied. Choice of Geophysical Methods in Oil, Civil and Mining Engineering In the first two of these fields, the geological problems are not nearly so complex as in the metal and nonmetallic mining fields. The selection of the correct geophysical method in these fields is not nearly so difficult for the operator. For oil prospecting, his problems have been discussed exhaustively by E. DeGolyer.(1) † In civil engineering (foundation and ground-water work), the usefulness of electrical methods has been so well established that there is hardly any choice of other methods at present. The situation may be changed in the future with the perfection of the seismic reflection method for shallow depths. In the mining field the operator and often the geophysicist himself finds difficulty in determining which method is best suited for a given

Jan 1, 1934