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By Tasuku Fuwa, John Chipman, David H. Kirkwood

Fe-C-Si alloys in silica crucibles were held at 1600°C in a controlled atmosphere of CO and Co2 and the approach to equilibrium was obsertsed. Results were not of sufficient precision to establish the activity and interaction coefficients. Observations 012 the equilibrium provided an average value for the standard free-energy change which differed by + 1.1 kcal from the earlier accepted value. The C-SL relation at other temperatures is calculated and shown graphically. IN the refining of steel in an acid-lined furnace, it is well known that, unlike in basic refining, a very significant amount of silicon may remain dissolved in the metal even when the carbon content approaches a final endpoint. Further, it is known that the residual silicon increases with increasing temperature. The quantitative relation between silicon and carbon can be calculated for equilibrium conditions from data already available on the Fe-C-O and the Fe-Si-O systems. Such equilibrium calculations could show us approximately the limitations within which the reaction would be expected to operate in practice. In the oxidation of a bath containing both carbon and silicon it is well known that at low temperatures silicon is preferentially oxidized first. It can be shown by calculation that at high temperatures carbon will be oxidized preferentially. It is the purpose of this paper to record direct observations on the Si-C relation by means of experiments carried out in an atmosphere of carbon monoxide for Fe-C-Si alloys contained in silica crucibles. When such a system is brought into equilibrium, at a fixed temperature, the composition of the liquid metal is governed by the following equations: Both K1 and K2 are known with a fair degree of accuracy, and may be calculated from the tabulated In general the percentage of CO2 is extremely small compared to that of CO and in the experiments to be described the partial pressure of the latter was generally only slightly below 1 atm. EXPERIMENTAL METHOD The induction furnace employed was the same as that described by Rist and chipman' and by Fuwa and chipman.2 It was modified slightly in view of the change from alumina to silica crucibles. The small silica crucible was surrounded by a thin susceptor of molybdenum sheet which in turn rested inside a zirconia crucible. Since the zirconia was subject to breakage, it was supported inside an alumina crucible. The charge consisted of 30 to 35 g of electrolytic iron along with the required amounts of refined silicon and graphite to produce a melt of required composition. Purified carbon monoxide and carbon dioxide were passed into the furnace through carefully calibrated flow meters. Two separate and independent series of experiments were carried out. In Series I (D.H.K.) the melt was held in the furnace at 1600°C for periods of time up to 6 hr. Samples were taken at intervals in silica tubes and were analyzed for carbon and silicon. The results of the last one or two samples taken from each experiment and the direction in which equilibrium appeared to be approached are shown in Table I. In Series II (T.F.) the silica crucibles were of less satisfactory strength and the melts were held at 1600° C for periods of only 2 to 4 hr. In heats number 29 to 45 inclusive, the metal was cooled in the furnace and the ingot itself served as a sample for analysis. In heat 46 and all subsequent heats, samples were withdrawn in silica tubes at the termination of the heat, and these samples were analyzed. The results of all of these experiments in which equilibrium appeared to be approached are listed in Table II.

Jan 1, 1965

By E. C. Tveter, L. A. Roe

The authors present a general outline of the theory and development of heavy-liquid application to mineral processing. Patent literature and processes are reviewed with special emphasis on liquid recovery systems which have been employed or proposed. Advantages and disadvantages of the process are discussed together with the recent developments which have revived interest in this old concentration method. The most important single factor in this resurgence of interest is concluded to be the narrowing gulf between chemical engineering and mineral dressing which has opened the field for new concepts of mineral plant design. A partial summary of patents on heavy liquid separations is included. In spite of the fact that heavy-liquid separation with organic liquids has been used in the laboratory for over 50 years, this process has never graduated to large scale commercial use for any extended period. However, a variation of this process, the sink-float or heavy-media separation process has found wide acceptance and is used to separate minerals from diamonds to gravel. Materials used to increase the specific gravity of the pulps used as heavy media include sand, clay, barite, magnetite, galena, hematite, atomized lead and ferrosilicon. Because of the greater ease of recovery, the magnetic materials, magnetite and ferrosilicon, are the preferred media today. In the U. S. alone, heavy-media iron ore plants with a capacity of over 10 million tons of concentrate per year are in existence. Heavy-media separation involving use of solid, inorganic particles suspended in water rapidly found a wide range of commercial use with the introduction of magnetic media. The minerals engineer is experienced in working with suspensions and quickly learned to develop and control such media at a cost compatible to the type of separation desired. The natural superiority of a heavy liquid with uniform chemical and physical properties has never been questioned since its first use in laboratory mineral separatory procedures. It offers the only method for gravity separation of fine particles of relatively close specific gravity. The most important early attempt to make heavy liquid separations commercial were made by the DuPont Co. which began experimental work on Virginia limonite in 1904. The appended "Partial Summary of Patents" compiled by W.L. O'Connell of The Dow Chemical Co. demonstrates the quantity and sequence of this work. Both inorganic and organic parting liquids were investigated and numerous patents were issued on the use and recovery of these liquids. The work culminated in the heavy liquid plant of the Weston Coal Co. at Shenandoah, Pa. Chemical engineering design of this plant was the responsibility of Francis I. and Hubert I. DuPont. Heavy-liquid separation of coal almost achieved commercial status at this plant which actually processed over 20,000 tons of coal. The liquids used were tetrabromethane, pentachloroethane and trichlo-roethylene, with liquid losses ranging from 8.9 to 12.4 oz per ton of cleaned coal. The reasons for failure of this plant are not clear but probably involved toxicity problems as well as other problems in chemical engineering. Excellent economics were reported. A more recent pilot plant was built in 1954-55 by Norris Goodwin for the Inerto Co. to treat hectorite clay. This plant employed carbon tetrachloride in jigs with liquid recovery by evaporation. Although good separation was achieved, incomplete removal of the CCl, from the clay prevented commercial operation. The only present operations known to the authors employing heavy liquids for gravity separations are limited to the use of calcium chloride in certain coal washers and bromochloromethane in a small batch operation (one ton solids per day) for the separation of beryllium metal particles from slag materials. This is not strictly a minerals beneficiation problem but it has demonstrated the feasibility of such separations. PROBLEMS Critics of early attempts to commercialize heavy-liquid separation of minerals summarize the draw-

Jan 1, 1963

By R. I. Jaffee, C. M. Craighead, G. A. Lenning

Hydrogen forms a beta-stabilized system with titanium, with a beta eutectoid at about 300°C and 44 atomic pct H2. 'The solid solubility of hydrogen in alpha decreases from about 8 to about 0.1 atomic pct from 300°C to room temperature. Hydrogen has little effect on tensile properties, but decreases notch-bar toughness to a large degree. This latter effect appears to be the result of increased notch sensitivity. PRIOR to this investigation, only a small amount of information was available on the effect of hydrogen on the mechanical properties of titanium. The effects of the other interstitially soluble elements, carbon, oxygen, and nitrogen, had received detailed study. Jaffee and Campbell1 indicated that hydrogen up to 1 atomic pct did not affect tensile properties deleteriously. Pitler' indicated that 1 atomic pct H, in titanium reduced the impact strength appreciably, but his alloys contained appreciable amounts of oxygen, and it was difficult to attribute the embrittlement entirely to hydrogen. The high temperature portion of the equilibrium diagram for the Ti-H system was established by McQuillan," and his data generally corresponded with the results of Kirschfeld and Sieverts," Gibb and Kruschwitz," Bevington, Martin, and Mathews," and other investigators. The lower concentration limit of the hydride phase varied considerably among investigators, and Gibb and Kruschwitz9 ad shown that small amounts of contaminants in either titanium or hydrogen caused considerable variation in this lower limit. In view of this pronounced effect of contaminants, the extrapolated value of McQuillan's, about 48 atomic pct at the 325°C eutectoid, appeared the most reasonable. McQuillan's lowest experimental value was 54 atomic pct at a temperature of 450 °C. The density of titanium had been shown to decrease with increasing hydrogen content, but discrepancies were noted among the various investigations. The best values indicated that the density was decreased from 4.56 grams per cc at 0.27 atomic pctl to 3.84 grams per cc at 61.3 atomic pct? This investigation was conducted to determine the effects of hydrogen on a titanium, both in high purity and commercially pure metals, and on high purity a titanium alloys. Material and Fabrication The literature indicated that impurities in either the hydrogen or the titanium must be kept to a minimum. For this reason, the initial studies were made with high purity iodide-refined titanium. The vendor's analysis of the iodide titanium and the hydrogen content of the as-fabricated Y4 in. diameter rods are shown in Table I. Two 1 lb ingots were prepared by arc melting under argon in a water-cooled crucible, using a water,cooled tungsten electrode. This equipment has been described.' As-cast Brine11 hardness numbers of 88 and 58 for these ingots were low enough to insure that the high purity of the metal was maintained during arc melting. The ingots were hot forged to % in. diameter rods at 800°C, cleaned by grit blasting, and then cold swaged to Yz in. diameter rods. The rod was then air annealed at 725 "C, ground to remove scale, and cold swaged to Y4 in. diameter (75 pct reduction in area). The material was then annealed for 1 hr in argon at 800°C to develop an equiaxed a grain size of about 0.05 mm. Micro tensile specimens and microimpact specimens were machined from this rod prior to treatment in the Sieverts-type absorption apparatus. Two lots of commercially pure RC-55 titanium were also used in this investigation to determine the effects of hydrogen and the normal impurities on mechanical properties. The commercially pure RC-55 alloy was obtained in the form of % in. diameter rod. The analysis of this material is also given in Table I. The % in. diameter rods were hot swaged

Jan 1, 1955

By J. F. Held

In a study of the influence of cold rolling on mechani cal properties of steel, it was found that the specific rolling procedure influenced crystallographic orientation. Properties developed by several rolling modes were determined and related to crystallographic orientation. Sanzples were cold-rolled various amounts on a laboratory mill. When palm oil was used as a lubricant, the crystallographic orientation was homogeneous throughout the thickness of the samples. Other samples were rolled without lubrication. Variations in intensity of the recrystallization texture components persisted throughout more than 50 pct of the volume of these samples. When the average plastic strain ratio, which is dependent upon crystallogvaphic orientation, was plotted as a function of percent reduction, a maximum was found at 40 pct in the samples which contained the observed texture variation. No maximum was found for the samples with the homogeneous texture distribution. Other mechanical properties, such as tensile strength and yield strength, were not influenced by the variation in crystallopaphic orientation. MECHANICAL properties of steel sheets depend, in general, upon the structural properties of the steel. For example, the Petch equation describes the relationship between yield strength and grain size. Other properties, such as hardness, vary with chemical composition. The plastic strain ratio, or R value, has been found to be dependent upon crystallographic orientation . In the course of investigating the effect of cold rolling on mechanical properties, it was found that a previously reported relationship between percent cold reduction and R value was not always observed. Published data had shown that the optimum cold reduction for best R values is 70 pct for aluminum killed steel.' However, by altering the rolling conditions, the optimum reduction can be shifted to much lower values, or it can be moved to very high values. This paper describes the rolling conditions that lead to shifting of the optimum cold reduction. The effect of rolling conditions on the various structure parameters and the resulting mechanical properties are evaluated. EXPERIMENTAL PROCEDURE Samples of three low-carbon aluminum killed steels were cold-rolled various amounts on a 9-in.-diam 2-high laboratory mill. Hot-mill thermal practice and steel chemistries are listed in Table I. Steel A was rolled with palm oil lubrication and heavy reductions on each pass; i.e., a total reduction of 75 pct was ac- complished with a maximum of five passes. Steel B was rolled without lubrication, and light reductions were given on each pass. After approximately 75 pct reduction, it was necessary to use a small amount of light oil to achieve any additional reduction in thickness. Following cold reduction, the samples were box-annealed at 1300°F for 10 hr. The heating rate between 800" and 1300°F was 50°F per hr, and the cooling rate following the soak period was 50°F per hr. Tensile specimens were machined from the annealed material and these were used to measure yield strength, tensile strength, and the plastic strain ratio (R value). Recrystallization textures were determined by an inverse pole figure technique.*'3 Integrated intensities of the (110), (002), (112), and (222) reflections were recorded for those planes lying parallel to the sheet surface. Examinations were made on both surfaces of each sample, and also at various levels beneath each surface to approximately 0.010 in. depth by etching techniques. RESULTS R Values. The R values obtained in steels A and B are shown as a function of percent cold reduction in Fig. 1. No optimum cold reduction was observed in steel A, rolled with palm oil lubrication. It is likely, however, that an optimum reduction would have occurred had higher reductions than 88 pct been employed. The optimum reduction in steel B occurred at 40 pct. The behavior in both of these steels is quite

Jan 1, 1968

By H. D. Outmans

The mechanics of filtration are described by a theoretical-empirical nonlinear diffusion equation which, under certain circumstances, may,be linearized and then solved explicitly. For filtration under static conditions linearization leads to a boundary value problem analogous to a heat flow problem with a known explicit solution. The corresponding solution for static filtration is compared with published experimental data. Under dynamic conditions filtration takes place in three successive stages. During each of these the rate of filtration and/or the thickness of the filter cake are different functions of the filtration time. The proposed mechanism explains the observed high resistance of dynamically deposited filter cakes against erosion and also the connection between filtration rate and viscosity of the drilling fluid. Several of the quantities governing dynamic filtration have no counterpart in the static filtration mechanism. The static filtration rate is, therefore, not a reliable measure for the dynamic rate and vice versa. INTRODUCTION Filtration under simulated borehole conditions, i.e.. either from a static suspension or from a suspension flowing parallel to the filter cake (dynamic filtration), has been the subject of several laboratory studies.1-7 This experimental and theoretical work showed that many aspects of the filtration mechanism cannot be explained by an elementary filtration theory based on the assumption that the filter cake is incompressible. For a more satisfactory theory compressibility should be taken into account. This has been done. at least to some extent, in the filtration theory developed for the chemical industry. Surveying the literature (see Ref. 8 for a bibliography) it becomes apparent that, although several properties of filter cakes deposited from many different suspensions have been measured, including compressibility, the filtration equations are essentially empirical in nature. No attempt has been made, for instance, to develop filtration theory along the lines of consolidation theory.12 This theory, upon which a highly successful development in soil mechanics rests, would appear to be an excellent starting point for a filtration theory since the compressibility concept is an essential part of it. As we will use this theory in the following development it is well to state the four assumptions on which it is based: 1. The fluid flow through a compressible porous medium is governed by Darcy's law. 2. The rate of change in fluid content of an element of the porous medium is proportional to the rate of change of solid pressure between the particles. 3. The solid particles are incompressible within the range of pressures considered. 4. The total pressure on a surface normal to the line of flow is equal to the sum of the fluid pressure and the pressure between the particles (solid pressure) at that surface. To calculate the rate of filtration and other quantities of interest it is necessary to know the filter cake compressibility and the permeability as a function of the solid pressure. It has not been possible to calculate these functions from theoretical considerations and they will therefore be introduced in this paper as empirical expressions. Both are determined in a compression cell where the cake is subjected to a mechanical load. Permeability and compressibility are measured after the solid pressure has stabilized, i.e., after the excess fluid pressure has been dissipated and the uniform pressure is transmitted entirely by the solids. The permeability and compressibility thus determined are not the same as during filtration in the borehole, under either static or dynamic conditions, because then, due to frictional drag, the solid pressure and hence also the permeability and compressibility vary along a line normal to the direction of the mean flow and can only be defined locally. DERIVATION OF THE FILTRATION EQUATION FOR COMPRESSIBLE FILTER CAKES As the filter cake in the borehole is thin compared to the radius of the hole the filtration may be considered as linear. Taking the x-axis normal to the wall, with its origin at the formation, we have, according to Darcy's law,

By C. B. Manula, H. Gezik

In planning modem-day mining operations, management needs to pass from the area of subjective decision-making to an area of objective decision-makirlg. Planning procedures currently being practiced by many mine managers depend primarily on common sense and trial-and-error methods which oftentimes never reach optimum solutions. For this reason, an attempt is made to provide an understanding of linear programming to solve production planning problems. More specifically, a linear programming model is proposed to solve the production scheduling problem as it was found to exist in the crushed stone industry. Optimal production scheduling is of prime concern here, since the industry has to cope with seasonal demands for its products. The solution, as determined through the application of the model, provides management not only with an optimal production schedule but also with the following information regarding the improvement of existing facilities: (I) the location of bottlenecks which limit production and profit; (2) the directions in which the company i fixed equipment should be expanded or modified; and (3) the evaluation of unused resources. Future trends in stone production will quite likely parallel those in the construction industry. Continued record expenditures for structures such as dams, highways, and buildings are the reasons for this accelerated growth. Production forecasts for the next decade are predicted to be around one billion tons with an approximate 7% annual increase. The problem of increasing production from 570 million tons in 1966 to 1 billion tons by 1976 offers no small challenge. This situation is further compounded by other problems and economic factors. Population expansion, government regulation, labor agreement, and changes in technology wd cause managers and operators to be confronted by many more complexities than characterize present-day operations. Some of these. problems and economic factors are: (1) In some metropolitan and other urban areas, easily accessible sources of stone are almost depleted. Transportation costs will be a prime concern of the industry. (2) Population growth has forced residential expansion to a point where many quarry operators must conform to urban and suburban regulations. (3) Government regulation in regard to air and water pollution, noise, and reclamation as well as zoning developments necessitate that crushed stone producers keep abreast of changing conditions and requirements. (4) The crushed stone industry operates under pressure of a highly competitive situation. Every company's objective is to retain a favorable marketing position by exercising great attention to production and marketing costs. This is rather difficult, since the crushed stone industry is one segment of modern mining which has to cope with a seasonal demand for its products. Among the problems posed here, the one of exercising great attention to production and marketing costs is of current interest to management. Under seasonal demand conditions, this problem creates further difficulties for managers who need to plan and forecast. STATEMENT OF THE PROBLEM Various methods of Operations Research have been developed to handle a problem whose genesis is explained above. It is very seldom, however, that these quantitative means are used in practice by the mining industry. This paper describes the use of Operations Research methods to solve a production planning problem when demand is seasonal. The seasonal production planning problem is an important one because of the substantial costs associated with changing production, employment, and inventory levels to adjust to seasonal sales patterns. Most companies try to operate within reasonable levels of employment changes and hold inventories within storage capacities. In general, little or no attempts were made to develop minimum cosl schedules or to provide objective means to compare various production policies. When demand varies within a fixed time period, 11:-oduction requirements may be met by following one

Jan 1, 1970

By R. D. Carter

Nurnerical .solutions are presented to some problems of unsteady-state radial flow of gas in which Darcy's law holds. These solutions are intended to aid in explaining the observed behavior of gas wells during drawdown tests. The variation of viscosity and Z-factor with pressure is accounted for in the solutions. Results are presented for three types of problems: (I) unfractured wells producing at a constant rate, (2) fractured wells producing at a constant rate and (3) unfractured wells producing through a critical flow prover. In the critical-pow-prover solutions, a correction of the calculated well-bore pressure to account for non-Darcy flow is made. A good correlation is shown between the solutions to the problem of Type 1 and the corresponding diffusivity-equation solution. Using this correlation, the diffusivity solution may be used to obtain gas-well solutions. The solutions to the problems of Type 2 illustrate the difference in drawdown-curve behavior to be expected between fractured and unfractured gas wells. Methods for estimatting fracture radius and flow capacity are presented and verified from solutions of Type 2. The solutions to the problems of Type 3 illustrate the differences to be expected between critical-flow-prover drawdown tests and constant-rate tests. An equation is presented for correcting critical-flow-prover data to constant-rate conditions. A description of the methods used in obtaining the solulions appears in the Appendix. INTRODUCTION It is necessary for many engineering purposes, such as predicting future deliverability performance, to be able to relate bottom-hole flowing pressure, formation pressure and flow rate for conditions of stabilized flow in gas wells. This information is customarily given as a plot of on logarithmic co-ordinates. It is desirable to be able to predict stabilized performance curves for gas wells based on data obtained from drawdown tests of short duration. Tests of long duration may be wasteful of gas, and low-permeability wells do not stabilize in a short-duration test. Although it is now commonly recognized that non-Darcy flow plays a significant part in gas-well behavior, it is believed that an understanding of transient behavior of systems obeying Darcy's law is still important in the interpretation of short-term test data, and the prediction of stabilized performance curves therefrom. In this connection, an equation for correcting Darcy flow It seems likely that solutions of the type presented herein, combined with the non-Darcy flow correction of the type of Eq. 1 and the usual laminar-flow skin factor, could provide a model which would adequately explain transient gas-well behavior for times after the non-Darcy flow region (which should be confined to a small area surrounding the well) has been established. The solutions presented in this paper are for three types of problems: (1) unfractured wells producing at a constant rate, (2) fractured wells producing at a constant rate and (3) unfractured wells producing through a critical flow prover. In the problems of Types I and 2, no corrections for non-Darcy flow were made in the results presented, since it was reasoned that the constant-rate boundary condition would facilitate such a correction if it was desired later. For the problems of Type 3, however, a condition of varying flow rate required that a non-Darcy flow correction of the type of Eq. 1 be included. This was done. Based on the numerical results presented, a number of approximations and a correlation are presented which may be useful in analyzing gas-well test data. It is assumed that the system can be described as a finite cylindrical gas reservoir produced by a single cylindrical well located at the center of the reservoir. Flow is strictly radial.

By J. J. Taber, W. K. Meyer

Experiments on consolidated sandstones have shown that a variety of conditions are responsible for the wide range of behavior observed when oil and water are displaced simultaneously by a solvent which is miscible with both. The type of displacement is influenced most strongly by the relation between the plait point of the ternary phase diagram and the composition path followed by the system as it achieves mis-cibility. Neglecting viscosity, the displacement becomes less efficient as the distance between the composition path and plait point is increased in either direction so that a very wide spectrum of displacements is possible with different alcohol, oil and brine systems. It is possible by choosing various composition paths as miscibility is achieved to exercise some control over the actual displacement mechanism. Control over the composition path is exercised by adding oil or water in specific amounts to the alcohol prior to its injection into the porous medium. This technique apparently makes it possible to obtain piston-like displacements with systems which are usually characterized by the efficient displacement of only one of the two phases i.e., either oil or water, while the other phase lags behind. However, the simultaneous displacement of oil and water is not as efficient as other miscible displacements at a similar mobility ratio. The evidence indicates that both oil and water "leak" into the alcohol "piston" in compensating amounts. With oils of low viscosities the displacement is inefficient because the low oil saturation in the stabilized bank causes oil to be trapped by water before miscibility is attained. INTRODUCTION The simultaneous displacement of oil and water by solvents such as alcohol has been investigated in the laboratory and in the field. The laboratorv workers investigating all-liquid miscible systems have recognized the great importance that the nature of the traingular phase diagram exerts on the efficiency of the miscible displacement. Gatlin and Slobod pointed out that displacement efficiency will be improved if miscibility can be retained for long periods and that this behavior tends to be followed if the applicable phase diagrams have very low binodal curves. In their unconsolidated sand tests the alcohol was considered an ideal miscible piston displacing both oil and water phases. Later workers have pointed out that an important feature of the phase diagram as far as oil recovery is concerned is the location of the plait point. This is particularly true in the case of consolidated Sandstone.3 Since the original discussion of this effect, the importance of plait-point location has been confirmed and discussed by other author The early workers394 recognized that the position of the plait point could be altered by changing the oil or the alcohol used in an experiment. In addition, recent work has demonstrated that the plait point can be shifted by altering the nature and concentration of dissolved salts in the aqueous phase. However, the entire scope of the relationship between displacement and plait point has not been discussed previously and a technique for changing the composition path as miscibility is achieved in a particular ternary system, i.e., oil, water and solvent, has not been demonstrated. * The importance of oil viscosity on the efficiency of oil displacement by alcohol has not previously been observed, probably because the range of viscosities used in earlier experiments was too restricted. It is the object of this paper to describe the relationships between the ternary phase diagram, fluid properties and the displacement achieved. A technique for controlling the nature of the displacement is also presented. THEORY AND DEFINITIONS PISTON-LIKE THEORY The theory of alcohol flooding has been discussed in some detail.2-4 The concept was advanced that

Jan 1, 1965

By F. Gordon Smith

ALTHOUGH several geological indicators of the critical type are known, including quartz inversions and decomposition of hydrous minerals such as serpentine, there are very few of the general type. Solid solutions are excepted, but the limitations of use are very restricted and interpretations are sometimes ambiguous. General methods for determining temperature and pressure conditions during the crystallization of minerals would have considerable scientific and economic value. It is not the purpose of this paper to discuss the various methods of geological thermometry and barometry, but to present one general method, applicable to all minerals, and to describe what progress has been made in the methods of measurement. The general method, in brief, is a study of the stress conditions in and around various types of foreign inclusions which are trapped in minerals during growth. The method depends upon the fact that any homogeneous gas, liquid, or solid will in general have coefficients of thermal expansion and volume compressibility different from those of any given mineral. Therefore stress must develop in and around all types of inclusions in minerals if the temperature or the pressure, or both, are changed from the conditions which prevailed during the growth of the mineral. The methods of measurement consist of determinations of the temperature-pressure conditions of fit of the inclusions in the host mineral. The types of inclusions in minerals are: I—gas, or liquid plus vapor, when observed at room temperature, due to crystallization under pneumatolytic conditions; 2—liquid, or liquid plus vapor when observed at room temperature, due to crystallization under hydrothermal conditions; 3—glassy solid, or devitrified glass, due to crystallization under magmatic or high temperature metamorphic conditions, in a siliceous liquid; and 4—crystals, due to overgrowth of other minerals crystallizing simultaneously or of other minerals which crystallized previously. A survey of the literature shows that much valuable earlier work on inclusions, especially that car- ried out in England in the last century, has dropped out of current knowledge. The following is a brief summary of the significant contributions to the problem up to the present day. Davy in 1822 asserted that fluid inclusions in minerals consist of an aqueous solution of salts and a gas bubble, the whole being either at lower or higher pressure than atmospheric.' At intervals from 1823 to 1862, Brewster contributed information concerning other types of inclusion consisting of 1—aqueous solution, a much more expansible liquid, and a gas; 2—aqueous solution, salt crystals, and a gas; and 3—the very expansible liquid and a gas. The very expansible liquid fills the gas space between 20" and 30°C. Compression strain effects were seen around inclusions in diamond, topaz, and other minerals.'-" Sorby in 1858 and 1869 further advanced the study begun by Davy, stating that fluid inclusions represent a sample of the mother liquor of crystallization and that the degree of filling of aqueous inclusions at room temperature defines the temperature-pressure relations during formation of the host. The degree of filling may be measured by determining the minimum temperature of filling of the inclusion by the liquid phase. The very expansible liquid in some fluid inclusions is liquid carbon dioxide. The temperature at which salt crystals in fluid inclusions completely dissolve in the fluid is the minimum temperature of formation. Inclusions of glass or devitrified glass indicate crystallization from a melt. Inclusions of crystals in minerals are often centers of strain, which may be seen by optical effects or by radial tension cracks. Sorby realized that an analysis of stress-strain relations about inclusions could be used to provide precise data on the temperature of crystallization, but the matter was never pursued.' , Hartley (1876, 1877),".'" Hawes (1881)," Wright (1881),'V ohnsen (1920),I3 and Holden (1925)"

Jan 1, 1953

By F. Gordon Smith

ALTHOUGH several geological indicators of the critical type are known, including quartz inversions and decomposition of hydrous minerals such as serpentine, there are very few of the general type. Solid solutions are excepted, but the limitations of use are very restricted and interpretations are sometimes ambiguous. General methods for determining temperature and pressure conditions during the crystallization of minerals would have considerable scientific and economic value. It is not the purpose of this paper to discuss the various methods of geological thermometry and barometry, but to present one general method, applicable to all minerals, and to describe what progress has been made in the methods of measurement. The general method, in brief, is a study of the stress conditions in and around various types of foreign inclusions which are trapped in minerals during growth. The method depends upon the fact that any homogeneous gas, liquid, or solid will in general have coefficients of thermal expansion and volume compressibility different from those of any given mineral. Therefore stress must develop in and around all types of inclusions in minerals if the temperature or the pressure, or both, are changed from the conditions which prevailed during the growth of the mineral. The methods of measurement consist of determinations of the temperature-pressure conditions of fit of the inclusions in the host mineral. The types of inclusions in minerals are: I—gas, or liquid plus vapor, when observed at room temperature, due to crystallization under pneumatolytic conditions; 2—liquid, or liquid plus vapor when observed at room temperature, due to crystallization under hydrothermal conditions; 3—glassy solid, or devitrified glass, due to crystallization under magmatic or high temperature metamorphic conditions, in a siliceous liquid; and 4—crystals, due to overgrowth of other minerals crystallizing simultaneously or of other minerals which crystallized previously. A survey of the literature shows that much valuable earlier work on inclusions, especially that car- ried out in England in the last century, has dropped out of current knowledge. The following is a brief summary of the significant contributions to the problem up to the present day. Davy in 1822 asserted that fluid inclusions in minerals consist of an aqueous solution of salts and a gas bubble, the whole being either at lower or higher pressure than atmospheric.' At intervals from 1823 to 1862, Brewster contributed information concerning other types of inclusion consisting of 1—aqueous solution, a much more expansible liquid, and a gas; 2—aqueous solution, salt crystals, and a gas; and 3—the very expansible liquid and a gas. The very expansible liquid fills the gas space between 20" and 30°C. Compression strain effects were seen around inclusions in diamond, topaz, and other minerals.'-" Sorby in 1858 and 1869 further advanced the study begun by Davy, stating that fluid inclusions represent a sample of the mother liquor of crystallization and that the degree of filling of aqueous inclusions at room temperature defines the temperature-pressure relations during formation of the host. The degree of filling may be measured by determining the minimum temperature of filling of the inclusion by the liquid phase. The very expansible liquid in some fluid inclusions is liquid carbon dioxide. The temperature at which salt crystals in fluid inclusions completely dissolve in the fluid is the minimum temperature of formation. Inclusions of glass or devitrified glass indicate crystallization from a melt. Inclusions of crystals in minerals are often centers of strain, which may be seen by optical effects or by radial tension cracks. Sorby realized that an analysis of stress-strain relations about inclusions could be used to provide precise data on the temperature of crystallization, but the matter was never pursued.' , Hartley (1876, 1877),".'" Hawes (1881)," Wright (1881),'V ohnsen (1920),I3 and Holden (1925)"

Jan 1, 1953

By Orville R. Lyons

CENTRIFUGAL force has been utilized for the dewatering of fine coal for over 50 years by means of machines commonly called centrifugal dryers. In any centrifuge the coal and water are subjected to a spinning action which usually inctedtocreases in intensity as the coal progresses through the machine. This spinning action, or the centrifugal force that it induces, tears water away from coal particles and produces a dewatered coal. The effectiveness of the dewatering action for any particular machine is governed by the size-consist of the coal and the centrifugal force imparted to the water on the coal. Four makes of centrifuge are currently being used to dewater fine bituminous coal in the United States. These include the vertical, basket-screen C.M.I. (Centrifugal and Mechanical Industries) Carpenter, Reineveld, and the horizontal solid-bowl Bird. The C.M.I. and Reineveld centrifuges are similar in construction and are variations of the Elmore centrifuge, varying principally in the slope of the basket, operating speed, size of perforations in the basket, and diameter of the basket. The same operating description suffices for both. These centrifuges are made up of two rotating elements, an outside conical screen frame and an inside solid cone which carries spiral pusher blades. The screen frame is supported by a hollow shaft, and the solid cone by a spindle shaft passing through the hollow shaft. Both the screen frame and the solid cone rotate at high speeds; the solid cone, with its scraping flights, rotating somewhat more slowly than the screen. The wet coal enters the machine at the top, falls on the cone, and is thrown against the screen by centrifugal force. The coal slides down the screen until it meets the upper end of the flights, where it is moved slowly along the flights until discharged at the bottom. The elfluent passes through the sieve basket or screen and discharges into a launder. The Carpenter centrifuge consists of a conical rotating element with a vertical axis, built up of three rows of perforated stainless-steel plates or stainless-steel wedge-wire or round-wire sections cut and rolled to conform to the surface of the cone. Wet material is delivered to a conical hopper inside the centrifuge casing and is distributed in a thin, even layer over the inner surface of the cone by a disk mounted on the rotor shaft. Impacting of the coal against the screen and the centrifugal force exerted as the material moves downwards creates a dewatering effect. The moisture is forced through the coal bed and then through the perforated plates of the basket, collecting in a circular trough built into the centrifuge. The effluent is conducted from the trough through the centrifuge casing by outlet pipes. The dewatered coal is discharged over the inside bottom edge of the rotor. The Bird centrifuge consists of a tank or truncated conical shell, which is revolved at the desired speed by means of a drive sheave. A screw conveyor rotates inside the cone or bowl at a slightly lower speed in the same direction of rotation. The feed entrance, in the center of the large end of the truncated cone, is high enough to allow formation of a pool of slurry. Adjustable effluent-discharge ports are located in the large end of the bowl so the level of the liquid can be regulated. The solids are moved forward by the screw conveyor as fast as deposited and carried above the level of the pool for an interval before leaving the bowl. In the past these four makes of centrifuge could be compared only by indirect means. The author published a rough comparison method in 1949' but

Jan 1, 1952

By R. W. Heckel, H. W. Paxton

The growth of grain boundary films and Widmanstiitten plates of proeutectoid cementite in hypereutectoid steels ulas considered quantitatively in three plain carbon steels and one "pure" iron-carbon alloy. Growth was found to take place at a slower rate than would be predicted on the basis of a model invoking rate control by long range diffusion of carbon. The films in the pure alloy grew faster than those in the plain carbon steels. A possible explanation is suggested. In 1904, Nernsst' and Brunner2 postulated that ionic crystals growing in supersaturated aqueous solutions grew at rates determined by diffusion through the solution to the growing crystal interface. The gradient down which the diffusion took place was assumed to be fixed by the supersaturated bulk solution concentration, the concentration dt the crystal surface and some arbitrary distance. The flux of material to the crystal was described as Flux where D is the diffusion coefficient, A the crystal surface area, Ci the bulk solution concentration, Co the saturated solution concentration, and 6 the thickness of the diffusion zone. It is obvious that the expression is an adaptation of F+ick's3 first law of diffusion (steady state). This was the initial formulation of what will be defined here as "diffusion controlled growth," i.e., growth limited by the long range diffusion of a component either to or from the advancing interface assuming both phases at the interface to be in equilibrium. This idea of equilibrium interface concentration implies an infinite reaction rate at the interface. Volmer, Zener,' and 11schner6 have derived expressions for the diffusion controlled growth of spherical precipitates in metallic systems. These analyses agree that the growth in a given direction should be parabolic with time. Brown and Hawkes7 observed that graphite, formed both from the decomposition of cementite and from the decomposition of eutectoid austenite in cast irons, grew according to a parabolic relationship and, therefore, concluded that the laws of diffusion controlled growth, as defined above, were obeyed. They, among others, failed to consider, however, that parabolic growth is a necessary, but not sufficient, condition for diffusion controlled growth. Mehl and Dube"' have pointed out that equilibrium may not be realized because the concentration at the interface cannot change instantaneously from that of the bulk to the saturation value. Furthermore, they propose that an equilibrium solute concentration in the parent phase adjacent to the precipitate would remove the thermodynamic activity gradient across the interface and, thus, stop the growth process. Frisch" has also emphasized the importance of interface concentrations that vary throughout the growth of a new phase. The variation in activity across an interface, as discussed by Onol' and Cahn and Hilliard,12 is of fundamental importance to this question. Ham13 considered the data of Turnbull14 on the growth of barium sulfate in aqueous solutions. He concluded that the data could be analyzed in terms of a radiation-type boundary condition. Flux across interface = K (c, - C,) [21 where C, is the concentration in the solution at the interface, Co the saturated solution concentration, and K the proportionality constant. The edgewise growth of Widmanstlitten plates, frequently referred to as the rate of lengthening, was first considered by Zener.'' Basing a mathematical analysis on steady-state (constant velocity) growth he concluded that where G is the growth rate, D the solute diffusivity, Ci the concentration in the bulk, Co the equilibrium interface concentration, C, the concentration in the precipitate, a a constant, Y the radius of curvature of the edge of the plate, and rC the critical radius, i.e., the radius which would increase the activity of solute at the interface at equilibrium under the influence of capillarity to that of the bulk. Zener1'

Jan 1, 1961

By P. Pietrokowsky

lntermediate phases in the binary metal alloy systems Ti-Zn, Ti-Hg, Zr-Zn, Zr-Cd, and Zr-Hg have been investigated by X-ray powder diffraction methods. Gamma-TiBHg and Zr3Hg have a beta tungsten structure; TiHg and ZrHg are analogous to ordered AuCu (L l0 type); delta-TixHg and ZrHg, are isomorphous with ordered AuCu,, (L l2 type); ZrZnz is face-centered cubic (C 15 type); TiZna crystallizes in a C 14 type structure; and Zrll-, occurs in cubic and tetragonal modifications in which a random distribution of atoms exists. Additional information for the intermediate phase TiZn, is presented. THE physical metallurgy of titanium and zir-conium when alloyed with elements in subgroup 11-B of the periodic table has received comparatively little attention in the literature. Laves and Wallbaum' reported the existence of several intermediate phases in the system Ti-Zn. They identified TiZn as a CsCl (B 2) structure and described TiZn, as an ordered Cu,Au (L 1, type) crystal structure. Gebhardt' investigated very limited zinc-rich regions in the systems Ti-Zn and Zr-Zn. Phase relationships in these partial constitution diagrams were deduced from the results of thermal analysis and metallography, X-ray results being inconclusive. The first zinc-rich intermediate phase in either system was not identified. More recently, Anderson, Boyle, and Ramsey" have had occasion to refer to a partial Ti-Zn phase diagram (unpublished data) covering the region 0 to 10 atomic pct Ti, wherein two intermediate phases corresponding approximately to TiZn,, and TiZn,, were indicated. The metals used in this investigation and typical analyses as determined by the suppliers are given in Table I. The iodide-process zirconium which was used was not hafnium free. Experimental Methods Alloy Preparation: The relative ease with which titanium and zirconium combine with other elements places extensive restrictions on the methods by which alloying can be achieved. The direct current electric arc melting procedure was found to be unsatisfactory for preparing these binary alloys and for this reason solid state diffusion methods were utilized. The iodide process titanium and zirconium rods were filed by hand. Fines were subjected to a magnetic separation and classified as to size as either finer than 200 mesh or coarser than 200 but finer than 80 mesh. Powder mixtures of various binary combinations of titanium and zirconium with zinc and cadmium were compacted in a 12 mm diameter die and then placed in Vycor or quartz vials which were evacuated and sealed. The mercury alloys were prepared in a similar manner; the proper weight of liquid mercury being placed in a vial with minus 200 mesh titanium or zirconium. These ampoules were then heat treated at various temperatures and times depending on the characteristics of the particular alloy system. Upon completion of the heat treatment the ampoules were cooled rapidly and the specimens weighed. The loss in weight varied from 1 to 3 pct (except as noted in the text) and for this reason the calculated compositions were accepted as a fair measure of the actual alloy compositions. X-Ray Dif raction Techniques: Powder diffraction experiments were conducted at room temperature with a 143.2 mm Debye-Scherrer X-ray camera in which the film was placed in the Straumanis arrangement. When copper radiation was used, a nickel filter was employed, and for the cobalt target a filter of iron oxide was used. In both cases, the /i? filter was placed between the X-ray target and the powder specimen which was mounted on a glass fiber. The lack of information based on optical metallography placed reliance on the results obtained from the X-ray experiments for determination of

Jan 1, 1955

By Adam L. Wesner, A. C. Richardson

This paper describes the development of a continuous float-and-sink process to produce coal low enough in ash content to be suitable for production of electrodes. The cleaned coal had a combined iron and silicon content of 0.239 pct. The efficiency of recovery was 84 pct. DURING World War I1 the demand for electrode carbon was greater than could be met by the supply of petroleum coke available for this use. It was believed that coke made from an extremely low-ash coal might be a suitable substitute for petroleum coke. Requirements for electrode carbon to be used for the production of aluminum are that the silicon plus iron content shall be not more than 0.14 pct of the coke. However, during the period when petroleum coke was in short supply, it appeared that relaxations of the specifications might be allowed to permit 0.4 pct iron plus silicon in the coke. For this work, the specifications were that the coal should contain less than 1 pct of ash, and the combined iron and silicon content of the coal should not exceed 0.28 pct. Heavy-liquid separations made on a number of coals showed that if certain size fractions of some coals Were separated at low specific gravities the resulting float products would meet the required specifications. The objective of this work was to develop a continuous, commercially feasible process for producing low-ash coal. After consideration of various processes, the method chosen was a float-and-sink separation using a solution of calcium chloride as the separating medium. Eagle Seam coal was used for the experiments. The —10 +35 mesh fraction was found to be the most promising feed for producing the low-ash content coal. A batch of 30 tons of — --in. coal was screened at 10 and 35 mesh; the yield of —10 +35 mesh was 20 pct of the feed. This fraction comprised the feed for the separation tests. In spite of the fact that this portion was screened a second time at 35 mesh, the coal still contained 16 pct that was finer than 35 mesh. Three-fourths of the undersize was in the —35 +48 mesh range. A representative portion of the —10 +35 mesh fraction was subjected to batch float-and-sink separations to determine the best gravity to be used in the continuous tests to obtain a high recovery of low-ash content coal. The heavy liquid used was a mixture of carbon tetrachloride and benzene which assured complete wetting of all of the particles. As usual in batch separations, adequate time was allowed for each separation so that even the near gravity particles had ample time to separate. The separations were made at increments of 0.01 sp gr from 1.25 to 1.28 and also at 1.32 and 1.59. Each specific-gravity increment was assayed for ash content. From these data it was concluded that 1.27 sp gr was best for the continuous separation of the coal. The products from the batch separation were composited into float 1.27 and sink 1.27 sp-gr fractions; these were assayed for ash, iron, and silicon. Table I shows the results of the batch separations. The composite float 1.27 fraction contained 66.04 pct of the total weight, and had an analysis of 0.79 pct ash, 0.073 pct iron, and 0.112 pct silicon, or 0.185 pct iron and silicon combined. These data are indicative of the results possible if a perfect separation is made at 1.27 sp gr under static conditions. Inasmuch as the method under investigation is a dynamic system these results could not be obtained. It remained to be determined, however, just how close to the theoretical results the actual continuous separation would be.

Jan 1, 1953

By Adam L. Wesner, A. C. Richardson

This paper describes the development of a continuous float-and-sink process to produce coal low enough in ash content to be suitable for production of electrodes. The cleaned coal had a combined iron and silicon content of 0.239 pct. The efficiency of recovery was 84 pct. DURING World War I1 the demand for electrode carbon was greater than could be met by the supply of petroleum coke available for this use. It was believed that coke made from an extremely low-ash coal might be a suitable substitute for petroleum coke. Requirements for electrode carbon to be used for the production of aluminum are that the silicon plus iron content shall be not more than 0.14 pct of the coke. However, during the period when petroleum coke was in short supply, it appeared that relaxations of the specifications might be allowed to permit 0.4 pct iron plus silicon in the coke. For this work, the specifications were that the coal should contain less than 1 pct of ash, and the combined iron and silicon content of the coal should not exceed 0.28 pct. Heavy-liquid separations made on a number of coals showed that if certain size fractions of some coals Were separated at low specific gravities the resulting float products would meet the required specifications. The objective of this work was to develop a continuous, commercially feasible process for producing low-ash coal. After consideration of various processes, the method chosen was a float-and-sink separation using a solution of calcium chloride as the separating medium. Eagle Seam coal was used for the experiments. The —10 +35 mesh fraction was found to be the most promising feed for producing the low-ash content coal. A batch of 30 tons of — --in. coal was screened at 10 and 35 mesh; the yield of —10 +35 mesh was 20 pct of the feed. This fraction comprised the feed for the separation tests. In spite of the fact that this portion was screened a second time at 35 mesh, the coal still contained 16 pct that was finer than 35 mesh. Three-fourths of the undersize was in the —35 +48 mesh range. A representative portion of the —10 +35 mesh fraction was subjected to batch float-and-sink separations to determine the best gravity to be used in the continuous tests to obtain a high recovery of low-ash content coal. The heavy liquid used was a mixture of carbon tetrachloride and benzene which assured complete wetting of all of the particles. As usual in batch separations, adequate time was allowed for each separation so that even the near gravity particles had ample time to separate. The separations were made at increments of 0.01 sp gr from 1.25 to 1.28 and also at 1.32 and 1.59. Each specific-gravity increment was assayed for ash content. From these data it was concluded that 1.27 sp gr was best for the continuous separation of the coal. The products from the batch separation were composited into float 1.27 and sink 1.27 sp-gr fractions; these were assayed for ash, iron, and silicon. Table I shows the results of the batch separations. The composite float 1.27 fraction contained 66.04 pct of the total weight, and had an analysis of 0.79 pct ash, 0.073 pct iron, and 0.112 pct silicon, or 0.185 pct iron and silicon combined. These data are indicative of the results possible if a perfect separation is made at 1.27 sp gr under static conditions. Inasmuch as the method under investigation is a dynamic system these results could not be obtained. It remained to be determined, however, just how close to the theoretical results the actual continuous separation would be.

Jan 1, 1953

By S. T. Wlodek, John Wulff

Dense, adherent, and ductile coatings of chromium can be applied to Molybdenum by selectively freezing out the chromium solute from a supersaturated copper-or tin-rich liquid alloy. The successful exploitation of this technique depends on the control of variables common to any freezing process. Under the most favorable combimtion of supersaturation, nucleation, and mass-transfey, coatings as thick as 0.004 in. can be obtained. In exploratory experiments it was found that a coating of chromium may be applied to molybdenum by immersing the molybdenum body in a supercooled copper-chromium or tin-chromium melt and selectively freezing out the contained chromium onto the molybdenum body. Supercooling of the liquid metal plating bath can be achieved by cooling, or the maintenance of thermal or concentration gradients in the melt. The technique is similar to conventional dip-plating procedures where the sample is immersed in a molten bath of the pure plating medium, except that in these studies, the plating medium consisted of a dilute solution of chromium in liquid tin or copper. The success of this method requires that the base material to be plated be isomorphous with the coating and insoluble in the plating bath. In addition, the plating bath, while having an appreciable solubility for the coating component, must have negligible solid solubility in the solid plate. Such relationships exist in the molybdenum-chromium, chromium-tin, and chromium-copper systems. Liquid tin and copper are satisfactory as the plating solvent, because although chromium is appreciably soluble in both of these liquid metals, solid inter-solubility is almost negligible, and no compound formation occurs. The same relationships exist between molybdenum and copper or tin except that the solubility of molybdenum in liquid tin or copper is insignificant. It is this combination of solubility relationships, as well as the completely isomorphous nature of the molybdenum-chromium system, which allows the formation of a chromium coating on molybdenum by the selective freezing mechanism. Since the main deterrent to the widespread use of molybdenum for high-temperature structural applications is its poor oxidation resistance, the formation of a dense and ductile chromium coating on molybdenum may well be of commercial significance. In addition, the basic principle of coating formation by selective freezing should be applicable to other metallic or even nonmetallic systems. The precipitation of the solute from a liquid metallic solution, for the formation of a protective coating, has not been previously considered in the literature. Frequently, however, a similar phenomenon has been described in the corrosion of metallic heat exchangers by liquid metals1 wherein temperature gradients in the liquid metal heat-transfer medium result in the formation of layers or deposits of metallic residue2 in the cooler portions of the system. Impregnating techniques using liquid baths have been tried as a plating process. Semchyshen and Barr, for instance, have successfully diffused chromium into molybdenum by immersing the molybdenum specimen in a liquid tin-chromium or copper-chromium alloy. This simple holding technique fails to produce a layer of pure chromium and requires prolonged immersion to allow for the diffusion-activated enrichment of the molybdenum. During the course of this investigation, most of the phase relations published for the copper-chromium4 and molybdenum-chromium4 systems, were found reliable. It was necessary, however, to investigate the solubilities of chromium and molybdenum in liquid tin as well as the solubility of molybdenum in liquid copper. These determinations were made by a simpie weight loss technique on materials of the same purity as used in the plating studies. The results of these solubility studies are given in Tables I and I1 and indicate that although the solubility of molybdenum in liquid

Jan 1, 1961

By William L. Langdon

PRELIMINARY COMMENTS Recent years have been difficult for the mining industry, as reported in the most recently published Minerals Yearbook (Volume III), the estimated value of world crude mineral production has been generally declining since an historical peak in 1979 (16).* The costs of mineral extraction have, however, been rising rapidly. Individual project costs are, in general, exceeding the growth rate of mining companies, while operating and technical risks continue to increase (16). Risks resulting from currency flotation and political actions in the host country are also on the increase. Labor difficulties (such as those experienced by Phelps Dodge) and the Reagan Administration's recent rejection of a proposal by the International Trade Commission for higher tariffs and/or quotas on copper imports have also contributed to the mining industry's difficulties. The net result of these factors has been financial difficulties for mining companies with respect to paying for their current financial obligations as well as trouble finding new financing. It may be that one of the main factors in determining the future of the mining industry will be centered upon capital structure, i.e. how its assets are financed. Historical Perspective on Capital Structure In The Mining Industry As discussed by Isreal Borenstein in (4) and Thomas Navin in (7), mining firms typically have used a financial model based upon high financial leverage, i.e. large amounts of debt relative to equity. This has been especially true for American firms developing orebodies discovered overseas. Problems sometimes occurred for those who were forced to commit themselves to completion guarantees in order to obtain bank loans. Mines under these circumstances must be brought into operation regardless of market conditions. Politicians in overseas countries also may use the high profits required by these high risk ventures to argue for nationalization of mines. Coupled with the frequent use of high leverage, mining companies traditionally have paid out a higher percentage of earnings in the form of dividends than manufacturing firms. This is significant, in that such funds paid out in dividends are not available for other uses. Hence, a greater reliance upon debt and/or additional stock issues than would ordinarily be the case for manufacturing firms. Thomas Navin has stated in (7), that the theory behind the high dividend payout was that, "most mining investors thought of themselves as investing in a wasting asset, one that would gradually deplete over time until it ultimately became valueless." Investors, therefore, required a receipt, in the form of dividends, of a percentage of current earnings and a return on original capital. This view of reality, apparently, has not changed in some quarters, even though modern mine management ordinarily replaces depleted mines with new ones. It may be that this practice of high dividend payout coupled with relatively high financial leverage should be reexamined. Current capital structure theory could prove interesting and useful for those concerned with current conditions. Capital structure patterns and related practices in this industry are not, in many cases, congruent with those thought by some to be theoretically optimal. Prelude to Capital Structure Discussion With a few notable exceptions (such as the Guggenheims and Anaconda's chief operating,. officer in 1971) mining companies' chief executives and boards of directors have not been persons with financial backgrounds. This, one could conjecture, might have accounted for the relatively nonsophisticated nature of capital structures of mining companies. In order to appreciate the possibilities with respect to alternative influence on a firm's performance, one must be acquainted with the basics of financial theory. This paper is an attempt to familiarize the reader with (1) capital structure in general, (2) the usual components of this structure, (3) the general theory behind the use of financial leverage, and

Jan 1, 1985

By Nicholas J. Grant, Olaf Troili, John Chipman

IN recent studies of the factors which affect the rate of desulphurization and its equilibrium, it became apparent that certain concurrent reactions were operative which had a significant effect on desulphurization. This is emphasized in the experiments of Hatch and Chipman1 and of Grant, Kalling, and Chipman' by the slow approach to a final state of equilibrium which is in marked contrast to the initial rapid transfer of sulphur from metal to slag. Since the removal of sulphur is of such profound importance in iron and steelmaking, it appeared necessary to investigate the reactions responsible for this behavior. It is now known that the presence of iron oxide in the slag interferes seriously with the principal reaction of blast-furnace desulphurization: CaO (slag) +-S + C - CaS (slag) + CO [l] The interfering reaction is most simply expressed as: CaS (slag) + 0 = CaO (slag) +-S 121 and a small concentration of oxygen (or FeO) is sufficient to hold a considerable amount of sulphur in the metal. It has been shown by Grant, Kalling, and Chipman2 that the addition of MnO to blast-furnace slag slows the removal of sulphur from the metal. This effect overshadows the contribution of MnO to basicity and is ascribed to its oxidizing power. It will be shown in this paper that SiO, also has sufficient oxidizing power to interfere with blastfurnace desulphurization. This is, of course, only one of its several effects. Primarily it is an acid and therefore reduces the concentration of excess lime. But when silicon is reduced to the metal the oxygen to which it was previously bonded becomes in part available for reaction 2. The proof of this statement is found in the following experiments. Experimental Procedure and Results Utilizing the same procedure and apparatus described by Grant, Kalling, and Chipman' five additional heats were made using slags IV and 11, the starting compositions of which were: slag IV—40 CaO, 10 MgO, 35 SiO,, 15 A1,0,; and slag 11—50 CaO, 10 MgO, 25 SiO,, 15 Al3O3. An important difference between these heats and those previously reported was that silicon to the extent of 1 to 4 pct was added to the present heats whereas the starting silicon content was formerly about 0.2 pct. Table I shows the slag and metal analyses for heats 82 to 87, and Table I1 shows the silicon addi- tions made to the charge. These additions are based on 400 g of metal and 400 g of slag. All heats had 1.65 400pct S charged before the cold slagadditions. The temperature was maintained at 1525°C. Rate of SiO, Reduction: Fig. 1 shows the silicon content of the metal in contact with slag IV at 1525°C as a function of time. Heat 70 from the work of Grant, afunctionKalling,of and Chipman is included as the lowest starting silicon. It will be noted that eeven with 4 pct Si in the starting metal, there is an increase in silicon content with time. Heat 84 is apparently approaching silicon equilibrium very slowly. Heats 70 and 82 with very much lower slowly.starting silicon show a more rapid initial rise in startingsilicon content but do not reach equilibrium during a long holding period. Fig. 2 shows 3 different initial silicon contents for Fig.2shows3differentheats 73 (from Grant, Kalling, and Chipman) 86 and 87, in contact with slag II, the most basic slag. Heat 73 is increasing in silicon with time, whereas heat 87 with an initial silicon content of 3.7 pct shows a decrease with time. Heat 86 shows a very close approach to equilibrium. The rate of transfer of silicon from slag to equilibrium.metal is very slow in all of those heats, even those which are initially far from equilibrium. ____

Jan 1, 1952

By C. Gatlin, C. E. Nemir

A common cure of lost circulation is the introduction of granular bridging agents into the mud system. Many materials, such as ground nut shells, are used for this purpose. If the trouble causing void (fracture, fissure, vug, etc.) is not too large, the granular agent forms a "bridge" across or within the opening. Successively smaller particles in the mud stream then accumulate on and/or within this bridge until normal filtration is finally established. The efficiency of many bridging agents has been studied in the laboratory using various slot testers.',' Many investigators have remarked that a granular bridging material should have the proper particle size distribution. With the exception of the broad range specified in the patent of Goins and Nash,3 here is apparently no definition as to what this distribution should be. A bridge may be initiated when several particles of lost circulation material lodge against each other in a fracture or other void. Smaller particles then may bridge the openings between the larger, previously bridged particles. This process continues until the voids become quite small and the problem becomes one of filtration. It would seem logical that an optimum particle size distribution exists, i.e., one containing the proper quantity of properly sized material to fill the successively smaller voids of the bridge. The filtration characteristics of drilling fluids may be subject to a similar analysis. It has been clearly demonstrated by many workers that the filtration behavior of various muds can be altered by particle size control.'.' Slusser, et al, divided filtration into three periods and showed that particle sizes affecting a given period did not necessarily affect other portions of the filtration curve. An analagous problem is the proper sizing of gravel, liner slots and screen sizes in various sand-exclusion problems. Here the situation is reversed in that a proper "void" size, rather than the size of the bridging agent, is sought. The classic work of Coberly 9 forms the quantitative basis for most sand-exclusion processes. It is interesting to note that, in general, Coberly's work has been overlooked by most drilling-mud researchers. Other investigators have made various studies of the effect of particle size distribution .on drilling-mud properties. As a part of their studies, Fancher and Oliphant reported 30-minute filtration loss of a variety of mixtures of particle sizes.'' Gates and Bowie noted an effect of particle size distribution on filtration, as well as on other physical properties.' MAXIMUM DENSITY THEORY A maximum density mixture has been mentioned as the possible solution for both lost circulation and mud filtration problems. Furnas 12 derived mathematically a method for obtaining maximum density of beds of packed solids, having either a given number of component sizes or a continuous gradation of sizes. This work was verified experimentally by Anderegg.13 or mixtures having a continuous grading of sizes, the interval between sizes is taken as successive screen sizes of interval 2 The ratio of the quantity of each size and the next smaller size is given by the equation Fig. I, number of size intervals of ratio 2 taken from Furnas' paper, gives the value of n + 1 for any given values of + and K, where K is the ratio of the diameter of the smallest particles to the diameter of the largest particles. Measurement by weight assumes, of course, constant density for all particle sizes. Choosing the quantity of the smallest particle size as a unit weight, the required weights of the successively larger interials are then r1 r2 r3 . ®1,2,3. Thus, the grading curve of a maximum density mixture represents a geometric pro gression of ratio r.

By Charles Barron McIntosh

BECAUSE of the well known relationship between a low atmospheric pressure and increased amounts of methane in coal mines, attempts have been made to find associations between low pressures and coal mine explosions. An early study by F. Able disclaimed this relationship. He found that half the explosions took place during a rising barometer when methane content in a ventilated mine would be decreasing. A more recent study by C. L. Hosler revealed a close relationship between anthracite mine explosions and low atmospheric pressure. Bituminous coal mine explosions, where coal dust as well as methane can be exploded, were found to be more closely associated with a rising pressure following a low barometer than with the falling or low pressure period. Emphasis on rising pressure periods led the present writer to investigate the effect of the post-frontal or post-cyclonic weather on coal dust. Dust samples of uniform mesh were exposed in an Illinois mine. Analyses of the dust taken before and after the passage of cold fronts and their accompanying low pressure troughs indicated an increase in coal dust moisture prior to a frontal passage and loss of moisture from coal dust following the time of lowest pressure. Thus the warm, moist air (Tropical Maritime)found over the mine during the falling pressure period was cooled in the mine and moisture added to the dust. Cold, dry air (Polar Continental) accompanies' the rising barometer following a frontal passage and the air, being heated in the mine, subtracted moisture from the coal dust. A similar but seasonal phenomenon occurs from summer to winter, the dry dust period in winter being recognized as the more dangerous period. The question arose as to how the short period or daily changes in moisture content of coal dust compared with the seasonal changes. Temperature and humidity statistics were obtained from the surface and mine entry for the months of July andJanuary. The gain and Ioss of mdisture. to the hine were calculated for these two morths as were the gain and loss associated with mT (Tropical Maritime) and cP (Polar Continental),air masses as observed in the investigatiynsl. Temperature and humidity statistics tigatiynsl.taken from [the two air masses represent atimp span of only 34 hr. The redultant changes as presented in the accompanying table verify the supposition that short period changes in coal mine moisture may attain the magnitude of recognized dangerous seasonal changes. Statistics for the mT air and the July air have been placed next each other and those for cP and January air together for easier comparison of the two warm and two cold air units. The last column readily reveals that there is little difference in the amount of moisture being deposited in the mine from the mT air and the July average air. A similar conclusion is reached regarding the loss of moisture from the mine when it is affected by the cP air mass or the average January air. This comparison would be particularly true from late fall through early spring when strongly contrasting air mass changes are a common occurrence. The invasion of cold, dry air following a cold front thus produces a drying period that could well receive more attention as a danger period for coal dust explosions. This drying period would compare with Able's explosion period during a rising barometer. The drying period is also perltinent in Hosler's findings, where it was noted that the average explosion day (for bituminous coal mines) followed the day of lowest atmospheric pressure. Moreover, the author's investigation of some 365 coal mine explosions also indicates that this post-frontal period should receive special attention in connection with mine safety measures. Two comparatively recent major explosions in Illinois (Centralia and West Frapkfort) occurred after the mines had been under the influence of cold-dry air for 25 to 30 hr-following a deep low pressure passage. Dust was the important explosive element in both these explosions.

Jan 1, 1958