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By Charles H. Jacoby

In 1774 a Swedish chemist, C. W. Schule, first recognized manganese as an element. That same year Schule's associate, J. G. Gahn, isolated the element manganese for the first time. In 1856 the Bessemer process of steelmaking gave birth to the economic importance of manganese. Later, in 1882, Robert Hadfield discovered high manganese steels. Although the primary use of manganese is in the ferroalloy industry, two additional important uses for manganese are making chemicals and dry cell batteries. Manganese is also vital to plant and animal life. Various chemical compounds of manganese are used in fertilizers, feeds, glass manufacture, paints, varnishes, and for numerous medicinal and chemical purposes. For the study of industrial minerals and rocks, only the chemical and battery grade material is of concern, but for the sake of comparison, metallurgical aspects are included in this presentation. Although currently the world's largest consumer of manganese, the United States is producing only minor amounts of ore at the present time. This is due primarily to the fact that although huge deposits of manganese occur within our borders, all are of such low grade as to be economically unfeasible to mine. For many years various government agencies and segments of private industry have devoted sizable sums of money and time in an attempt to upgrade ores from the various deposits, and also in an attempt to recover manganese from blast furnace slags. In view of current world prices, and the quantity of high grade material available, there is little likelihood that any of these approaches will be found to be economically feasible in the near future. Geology and Mineralogy Mineralogy There are over one hundred minerals that contain manganese. These minerals vary from those with compositions that are predominantly manganese to those having only minor percentages. [ ] Geology From a geological standpoint most manga¬nese deposits are complex. In general, it can be said that all primary deposits of manganese are carbonates or silicates. The most productive and profitable have been those of sedimentary origin and residual concentrations. Examples of these residual types of deposits are associated with the metamorphosed lodes of Madhya, Pradesh, India, and the lateritic deposits of Orissa and Bihar, India; nodules in the residual clays of the Philippine Islands, U.S. southern Appalachians and Arkansas, Ghana, and Brazil. Sedimentary manganese deposits are best exemplified by the Nikopol district of Russia and the Tchiatouri area of Georgia, USSR. Hydrothermal replacements are characterized by the rhodochrosite deposits of Butte and Phillipsburg, Mont. In general, the hydrothermal type deposit has not resulted in any large tonnages being produced, but may have given

Jan 1, 1975

By J. D. Lindner, Gene E. Roark

Waterflooding operations in the Langston-Kleiner field. Young County, Tex., are described. Widespread application of formation fracturing has been practiced in both producing and injection wells. Field performance data arc cited which indicate than no detrimental effect on sweep efficiencies and that probable benefits in imectivily have resulted from the fracture treatments. I N T R O D U C I O N This paper is a report on a waterflood operation which is being carried out in the Lanpston-Kleiner field located in Young County, Tex. The oil reservoir aflected by this flood operation occurs in a Strawn sand member at an approximate depth of 3.550 ft subsurl'ace. The operators of' the project are Kleiner Estate. Turncr. Fiske. and West who are hereinafter collectively referred to as the Operators. Although the operation is unusual in several respects, the distinctive feature of this flood has been the widespread application of hydraulic formation fracturing treatments as a means to improve productivity and injectivity of the wells. It shall he the purpose of this paper to present basic information regarding the reservoir characteristics. op- craling practices, and waterflood behavior so that conclusions may be drawn concerning the effects which the fracture treatments have had on the performance of this water flood to datc. DEVELOP MENT Development of the 3,550 ft Strawn sand reservoir occurred during 1951 and 1952. The early development occurred on the Langston and Davis leases which arc in the northern region of the Operators' holdings and the wells were drilled on 20-acre proration units according to the field rules. However, studies of the economics of this program. coupled with the decision to proceed with pressure maintenance by water injection. resulted in the adoption of wider spacing in the later stages of development. This variation in spacing is apparent upon inspection of Fig. I upon which only the 3,550-ft Strawn sand producing and injection wells have been located on the Operators' properties. The development to the north of the operators leases is Ihe Garvey Strawn field and that to the south is the Taylor Strawn field. It wits determined that unitization of the leases to he involved in the waterflood program was not feasihle. Consequently. a system of offset injection wells, or lease line injection wells, was adopted from place to place as required to protect correlative rights in the program. This resulted in a dispersed array of injection and producing wells with relatively close proximity of wells along lease line areas and wider spacing toward

Jan 1, 1956

By J. Gordon Parr, D. H. Polonis

High purity alloys of titanium and iron, made by a technique of levitation melting, have been investigated with particular reference to martensite formation and decomposition in the hypoeutectoid range. A preliminary study has been made of the occurrence of the phase corresponding to the structure Ti2Fe. MANY of the previous investigations of Fe-Ti alloys have been made using Kroll sponge as a source of titanium; and the subsequent heat treatments to which alloys have been subjected has, on occasion, led to further contamination. Worrier,',' who suggested a part of the equilibrium diagram for the binary system, and Wallbaum and coworkers,3-5 who worked largely with iron-rich alloys, all used Kroll sponge. Van Thyne, Kessler, and Hansen,6 in their determination of the equilibrium diagram, used iodide titanium for alloys up to 30 pct Fe. Duwez,7 who measured the M. temperature of titanium binary alloys with many solute elements, used iodide titanium in all cases except in his work on Ti-Fe alloys for which he used Kroll sponge. The investigation of the supposed phase Ti2Fe by Rostoker8 nvolved the use of iodide titanium. A section of the constitutional diagram, after Van Thyne et al., is reproduced in Fig. 1. Frequently too much stress is placed on the effect of contaminants in equilibrium and nonequilibrium systems, but there is no doubt that titanium alloys are extremely susceptible to interstitial atoms. Consequently, the main purpose of the work to be described was to determine those features of phase transformations in pure Ti-Fe alloys that were considered of importance in commercial heat treatments. For, although commercial alloys may not be of high purity, the investigation of a system uncomplicated by traces of impurity is a desirable starting point. Another incidental feature, the occurrence of Ti2Fe, was also investigated. The entire study was carried out using powders obtained from alloy ingots, for diffusion reactions are often more rapid in small particles than in bulk specimens. The frequently adopted practice of ascertaining phase constitutions by X-ray analysis of powders, and relating these to the microstructures and mechanical properties of bulk specimens, is considered by the authors to be open to criticism. In the martensite reactions in the Fe-Mn system, for example, it has been shown- hat similar phase distributions in solid and powder may result in different hardness values and appearance under the microscope; and it is possible that similar anomalies might occur in the Ti-Fe system. Consequently, in order to

Jan 1, 1955

By James T. Gow, Oscar E. Harder, Anton de S. Brasunas

This paper deals with the results obtained and the techniques employed in determining: 1. Liquidus and solidus temperatures of the HH and HT type heat-resistant alloys. 2. The relation of true temperatures (thermocouple) to apparent temperatures (optical pyrometer) for the molten HH and HT type alloys. This work was the outgrowth of needing to know something definite about these temperatures in order to study the effect of pouring temperatures, shake-out times, and heat-treatments on the properties of some heat-resistant alloys. The information developed is thought to be of interest to industry for guidance in foundry practices and the industrial heat applications of the alloys. This paper is based upon work that has been done for the Alloy Casting Institute at Battellc Memorial Institute. Liquidus and Solidus Temperatures of HH and HT Type Alloys Experimenta1 Procedures Temperature-time curves were obtained during the cooling and solidification of several HH and HT type alloys. The metal was melted in an Ajax high-frequency, induction furnace and poured into a core-sand mold for cooling. The temperature measurements were obtained by means of a platinum, platinum-rhodium thermocouple contained within a fused silica sheath, which was extended through the side wall of the dry core-sand mold to a point at about the center of the mold cavity, which was 3 in. in diameter by 5 in. deep. The cold junction of the thermocouple was kept in an ice bottle, and the temperature was recorded automatically on a direct-reading potentiometer recorder. Through a switching arrangement, the temperature recorded was checked occasionally with a portable Leeds and North-rup potentiometer indicator. Less than a 5°F. variation in the two instruments was always found. This is within the limit of accuracy of readings. The thermocouple used was checked for accuracy against a standard couple, both before use on this work and after completion of the work, by the instrument laboratory. Temperature-time Cooling Curves Fig. I is an enlarged reproduction of a part of one of the cooling curves over the temperature range of 2600' to 2200°F. for an alloy of the HT type with 0.45 per cent carbon, 16 per cent chromium, and 36 per cent nickel. This is a typically shaped cooling curve as obtained for the alloys. It will be noted that two temperatures "re shown on Fig. I for the liquidus temperature. It is thought likely that the higher temperature, A, at the point at

Jan 1, 1945

By Myron A. Pugacz, Frank S. McKenna, Clarence E. Jackson

The notched-bar impact test has proved worth while in certain applications as a test for control of the quality or the heat-treatment of steel. In view of the serious thought that even so simple a test as the tensile test has evoked during the past years, it is not surprising that the notched-bar impact test should have inspired much experimental work. The correlation of the great number of data has not been successful, although steady progress has been made toward a better understanding of this test. Progress has been made, especially, in the isolation of the effects of the many variables that control the results. The stress system imposed on a specimen with a notch is so complicated and unpredictable that no simple evaluation of the test has been possible. Because of this uncertainty, many engineers hesitate to use the notched-bar impact test, and this attitude may well continue until a better understanding of the effects of the variables in the test are available. Without doubt, any additional data that may be presented should be accompanied by as complete a description of the - details of test as possible, so that it may be added to the general fund of information that is to serve as the basis for the theory of the notched-bar impact test. The many factors that may control the test results have been pointed out repeatedly. The importance of the effect of the type and dimensions of the specimen has been recognized. Most of the work reported by American investigators has been limited to small-size (Charpy) specimens tested as a simple beam; two types of notches (Fig. I) have been commonly used. Considerable data have also been presented by many investigators using a small specimen tested as a cantilever beam; this commonly being called the Izod test. Here, however, a shear component of stress makes the stress system even more complex than that present in the simple beam type of test, hence a critical analysis is difficult. Much work has also been reported by investigators using the tension type of specimen. A second variable that must be controlled is the testing temperature. An indication that the tests were performed at room temperature is not sufficient, since in many steels a variation of a few degrees in the actual testing temperature may be sufficient to give an entirely different range of results. Other factors, such as the composition and condition of the material being tested and the speed of test, should also be considered. Many investigators have contributed data and theoretical discussions on the problems encountered in notched-bar test-

Jan 1, 1944

By Frank S. McKenna, Myron A. Pugacz, Clarence E. Jackson

The notched-bar impact test has proved worth while in certain applications as a test for control of the quality or the heat-treatment of steel. In view of the serious thought that even so simple a test as the tensile test has evoked during the past years, it is not surprising that the notched-bar impact test should have inspired much experimental work. The correlation of the great number of data has not been successful, although steady progress has been made toward a better understanding of this test. Progress has been made, especially, in the isolation of the effects of the many variables that control the results. The stress system imposed on a specimen with a notch is so complicated and unpredictable that no simple evaluation of the test has been possible. Because of this uncertainty, many engineers hesitate to use the notched-bar impact test, and this attitude may well continue until a better understanding of the effects of the variables in the test are available. Without doubt, any additional data that may be presented should be accompanied by as complete a description of the - details of test as possible, so that it may be added to the general fund of information that is to serve as the basis for the theory of the notched-bar impact test. The many factors that may control the test results have been pointed out repeatedly. The importance of the effect of the type and dimensions of the specimen has been recognized. Most of the work reported by American investigators has been limited to small-size (Charpy) specimens tested as a simple beam; two types of notches (Fig. I) have been commonly used. Considerable data have also been presented by many investigators using a small specimen tested as a cantilever beam; this commonly being called the Izod test. Here, however, a shear component of stress makes the stress system even more complex than that present in the simple beam type of test, hence a critical analysis is difficult. Much work has also been reported by investigators using the tension type of specimen. A second variable that must be controlled is the testing temperature. An indication that the tests were performed at room temperature is not sufficient, since in many steels a variation of a few degrees in the actual testing temperature may be sufficient to give an entirely different range of results. Other factors, such as the composition and condition of the material being tested and the speed of test, should also be considered. Many investigators have contributed data and theoretical discussions on the problems encountered in notched-bar test-

Jan 1, 1944

By AIME AIME

PRIZES totaling $450 were awarded at the Annual Meeting luncheon on Monday, Feb. 9, to the winners of the third national student prize paper contest. The undergraduate prizewinners, each of whom received a check for $100, were as follows: Mayo W. Lanning, Lafayette College, for his paper entitled ?Some Aspects of the Mining Methods Employed at the Scrub Oak Mines of the Alan Wood Steel Company,? (entered by the Lehigh Valley Section). Charles F. Parent, Montana School of Mines, for his paper entitled ?Relationships of Manganese Minerals in the Butte District,? (entered by the Montana Section). Harry Czyzewski, University of Illinois, for his paper entitled ?A Metallurgical Study of Cast Irons Used for Glass Molds,? (entered by the Chicago Section).

Jan 1, 1942

By J. S. Crump, H. L. Stone

Laboratory studies have indicated that displacement of oil from a reservoir by means of a condensing gas drive results in extremely high oil recovery, approaching 100 per cent under the most favorable circumstances. A condensing gas drive is defined as a gas drive in which the gas utilized is appreciably soluble in the oil it is displacing. The laboratory studies consisted of a number of gas drive displacement experiments, all using a horizontal, sand-packed, steel tube as the laboratory reservoir. The experimental results indicate that the more soluble a gas is in the oil to he displaced, the more efficient that gar is as a displacing fluid. Experiments were conducted utilizing both a light, volatile crude and a heavy, asphalt crude as the in-place oil. In both cases, oil recovery was appreciably enhanced by solubility of the displacing gas. It is believed that the use of condensing gas drives would result in increased oil recovery from many reservoirs during either primary or secondary phases of production. INTRODUCTION Since the early days of the oil industry there has been an increasing awareness of the problems of oil recovery. During the last few decades particularly a growing recognition of the problems has led to widespread attempts on the part of the industry to increase oil recovery by improved technology. One method which has been used to increase recovery is the maintenance of reservoir pressure by injection of gas. Part of the beneficial effect resulting from this gas injection was to prevent evolution of the gas dissolved in the reservoir oil, since such evolution would cause the oil to shrink and become more viscous, thereby adversely affecting oil recovery. In most instances, the gas injected was predomillantly methane, and so the possibility of oil recovery by retrograde vaporization existed. Laboratory investigations of displacement of reservoir oils by methane, carried out at high pressure, have indicated that considerable additional recovery of light oils could be effected by vaporization, but only at the cost of a severe volumetric shrinkage of the residual oil which would cause a decrease in relative permeability to oil in the reservoir. Consequently, recovery of oil by physical displacement would be impaired. The study suggested, therefore, that recovery of oil might be enhanced by injecting into the reservoir a gas known to be appreciably soluble in the oil at reservoir conditions. Swelling of the oil due to solution of gas should result and yield a consequent increase in the relative permeability to oil. The work described in the following sections was, therefore, undertaken to investigate the possibility of increased recovery by this mechanism. Research similar to that reported in this paper has been conducted by The Atlantic Refining Co.1,2,3 In these studies, Whorton, et al, and Slobod, et al, used methane-rich gas to displace oil from model reservoirs. Solubility of the gas was achieved by keeping the reservoir pressure greater than the saturation pressure of the original oil, and the degree of this solubility was varied by operating at different reservoir pressures. Thus the Atlantic project was primarily a study of the effect of reservoir pressure upon oil recovery by gas drive. The objective of the work reported in this paper was to study the effect of gas composition upon oil recovery while holding the reservoir pressure constant. DESCRIPTION OF EXPERIMENTS The discussion of the preceding section suggests that

Jan 1, 1957

By Reno H. Sales

Since leaving school my efforts have been geared to the task of making geology useful to the mining industry. The responsibility of the economic geologist or mining geologist of today has grown to be more, than that of merely finding a faulted segment of a vein. The very life of our mining industry is at stake. The tremendous progress in every branch of our modern civilization has been made possible through the developments in the use of metals. Many of our great industries, including that amazing field of aircraft production live and thrive only because of metals.

Jan 1, 1942

By Sales, Reno

Since leaving school my efforts have been geared to the task of making geology useful to the mining industry. The responsibility of the economic geologist or mining geologist of today has grown to be more, than that of merely finding a faulted segment of a vein. The very life of our mining industry is at stake. The tremendous progress in every branch of our modern civilization has been made possible through the developments in the use of metals. Many of our great industries, including that amazing field of aircraft production live and thrive only because of metals.

Jan 1, 1942

By Richard F. Link, George S. Koch

Advantages and disadvantages of deflecting (wedging) diamond-drill holes to obtain sampling data are compared with the alternative of drilling additional holes. The discussion is based on a statistical analysis of a large set of deflection data from exploratory boreholes in South African gold mines. Representative cost comparisons show the conditions under which deflections are likely to be desirable.

Jan 1, 1969

By J. A. Hafford, J. K. Kerver, J. G. Richardson, P. M. Blair, J. S. Osoba

This paper presents the results of laboratory measurements of relative permeabilities to oil and gas on small core samples of reservoir rock by five methods, and describes the influences of such factors as boundary effect, hysteresis, and rate upon these measurements. The five methods used were the "Penn State," the "single core dynamic," the "gas drive," the "stationary liquid," and the "Hassler" techniques. In those methods in which the results are subject to error hecause of the boundary effect, the error may be minimized hy the use of high rates of flow. In order to avoid complexities introduced by hysteresis, it is necessary to approach each saturation unidirectionally. Observed deviations of relative permeabilities with rate can be explained as a manifestation of the boundary effect, and disappear as the boundary effect vanishes. The results indicate that all five methods yield essentially the same relative permeabilities to gas. Of the four methods applicable to the determination of relative permeability to oil, three, the Penn State, single core dynamic, and gas drive, gave relative permeabilities to oil which were in close agreement. The Hassler method gave relative permeabilities to oil which were consistently lower than the results obtained by the other methods. INTRODUCTION The relationship between the effective permeability of a reservoir rock to each of the fluids flowing through it and the corresponding fluid saturation is an important characteristic of the reservoir rock. Knowledge of this characteristic is and gas reservoirs and of the ultimate recovery to be expected extremely important in the prediction of the behavior of oil under various operating conditions. These effective permeabilities are usually expressed as the "relative permeability" to a fluid phase, defined as the ratio of the effective permeability to the permeability of the rock to a single phase at 100 per cent saturation. Relative permeability-saturation relations are not the same for all kinds of reservoir rock, but may vary from formation to formation, and within the different portions of a heterogeneous formation. In studying the performance of a specific reservoir, it is necessary, then, that the relative permeability characteristics of the individual portions of the reservoir be measured. These measurements may be made in the laboratory on small core samples from the reservoir. Various techniques have been proposed for the measurement in the laboratory of relative permeability-saturation relations. In varying degree, difficulties attend the use of all of the methods which have been proposed. It is the purpose of this paper to discuss the factors which influence the measurement of relative permeability, the difficulties encountered in several methods, and to present comparative results obtained by the use of various techniques. FACTORS WHICH INFLUENCE THE MEASUREMENT OF RELATIVE PERMEABILITY It is necessary that the relative permeability data measured in the laboratory yield the same relative permeability-saturation relationships that would govern the flow of fluids through the sample if it were to occupy its original position in the reservoir. Since the core sample upon which the laboratory measurements are made is not surrounded by similar core material as it was in the reservoir, an error in measuring the relative permeabilities may arise from the "boundary effect" which results from a discontinuity in capillary properties of the system at the effluent end of the core. Again, the rates of

Jan 1, 1951

By J. K. Kerver, J. S. Osoba, J. G. Richardson, P. M. Blair, J. A. Hafford

This paper presents the results of laboratory measurements of relative permeabilities to oil and gas on small core samples of reservoir rock by five methods, and describes the influences of such factors as boundary effect, hysteresis, and rate upon these measurements. The five methods used were the "Penn State," the "single core dynamic," the "gas drive," the "stationary liquid," and the "Hassler" techniques. In those methods in which the results are subject to error hecause of the boundary effect, the error may be minimized hy the use of high rates of flow. In order to avoid complexities introduced by hysteresis, it is necessary to approach each saturation unidirectionally. Observed deviations of relative permeabilities with rate can be explained as a manifestation of the boundary effect, and disappear as the boundary effect vanishes. The results indicate that all five methods yield essentially the same relative permeabilities to gas. Of the four methods applicable to the determination of relative permeability to oil, three, the Penn State, single core dynamic, and gas drive, gave relative permeabilities to oil which were in close agreement. The Hassler method gave relative permeabilities to oil which were consistently lower than the results obtained by the other methods. INTRODUCTION The relationship between the effective permeability of a reservoir rock to each of the fluids flowing through it and the corresponding fluid saturation is an important characteristic of the reservoir rock. Knowledge of this characteristic is and gas reservoirs and of the ultimate recovery to be expected extremely important in the prediction of the behavior of oil under various operating conditions. These effective permeabilities are usually expressed as the "relative permeability" to a fluid phase, defined as the ratio of the effective permeability to the permeability of the rock to a single phase at 100 per cent saturation. Relative permeability-saturation relations are not the same for all kinds of reservoir rock, but may vary from formation to formation, and within the different portions of a heterogeneous formation. In studying the performance of a specific reservoir, it is necessary, then, that the relative permeability characteristics of the individual portions of the reservoir be measured. These measurements may be made in the laboratory on small core samples from the reservoir. Various techniques have been proposed for the measurement in the laboratory of relative permeability-saturation relations. In varying degree, difficulties attend the use of all of the methods which have been proposed. It is the purpose of this paper to discuss the factors which influence the measurement of relative permeability, the difficulties encountered in several methods, and to present comparative results obtained by the use of various techniques. FACTORS WHICH INFLUENCE THE MEASUREMENT OF RELATIVE PERMEABILITY It is necessary that the relative permeability data measured in the laboratory yield the same relative permeability-saturation relationships that would govern the flow of fluids through the sample if it were to occupy its original position in the reservoir. Since the core sample upon which the laboratory measurements are made is not surrounded by similar core material as it was in the reservoir, an error in measuring the relative permeabilities may arise from the "boundary effect" which results from a discontinuity in capillary properties of the system at the effluent end of the core. Again, the rates of

Jan 1, 1951

By R. E. Holmes, T. W. Leland

The solution to the unsteady-state mass- and heat-transfer equations describing the adsorption of a dilute component from a gas stream flowing through a packed bed is readily applicable to the design of hydrocarbon recovery units. The solution to these equations depends on the assumption of a linear equilibrium equation to relate concentrations on the surface to concentrations in the gas. This assumption is shown to be justifiable for components which are very dilute in the gas stream. This approach permits the prediction of the effects of bed shape and size, cycle time, and gas mass velocity on the recovery of each component. It also allows the time and gas flow rate needed for regeneration to be determined. The equations involve a constant for each component and another constant characterized by the type of adsorbent. These constants must be evaluated from operating data. Values of these constants determined for silica gel are presented. This paper points out the type of experitrrental data needed for a thorough design of hydrocarbon adsorption units. INTRODUCTION The growing importance of adsorption processes to recover hydrocarbons from natural-gas streams has created an urgent need for better methods to design and predict the performance of these processes. Since the original use of solid adsorbents in natural-gas processing was for dehydration, most of the current design methods for hydrocarbon recovery re extensions of those developed earlier for dehydration. These methods are based on an adsorptivity or bed loading factor defined as the amount of a particular component adsorbed per unit weight or per unit volume of the packed bed. The recovery of a given component is then expressed as an empirical function of its adsorptivity on a given adsorbent. In spite of the simplicity and initial utility of these methods, they are not completely satisfactory in that they do not predict the effect of the dimensions of the bed in relation to flow rate and cycle time, and do not predict the distribution of various components along the length of the bed. It is possible, however, to make a considerable improvement in the design of these processes by applying the basic equations of mass and heat transfer applicable to gases containing small concentrations of adsorbing components flowing through granular beds. These equations have been developed and solved by Anzelius,' Furnas,% nd Hougen and Marshall." where G = mass velocity of the inert constituents (assumed to be methane), lb/hr-sq ft, y = weight of an adsorbing component in the gas per unit weight of inert, lb of a given constituent per lb of methane, x = bed length, ft, p, = packed bed density, lb/cu ft, P, = gas density, Ib/cu ft, f = void fraction in the bed, t = time, hours, and w = weight of a given component adsorbed per unit weight of adsorbate free solid, Ib/lb pure adsorbent. The term on the left side of Eq. 1 represents the flow rate per unit bed volume of a component entering less the flow rate per unit bed volume of that component leaving the differential bed length. The terms on the right side represent, respectively, the accumulation rates per unit bed volume on the solid and in the gas phase within the differential bed section. The last term is negligible for this application since pgfv is quite small in comparison with p, and G. The partial differential is determined by the mass-transfer rate between gas and solid in the differential section.

By C. B. Alcock, R. A. Oriani

Some simple models of solutions are described; these include the regular solution, the subregular solution, and the quasichemical model. The assunzption underlying these models, the physical signzficance thereof, and the experimental manifestations are discussed. Examples are presented from the fields of liquid and solid metallic solutions, liquid slags, mattes, liquid and solid ionic solutions, and mixed carbides to show under what conditions and for which systems these solution models are fair descriptions. The deviations of real solutions from the models are of theoretical interest. Some such deviations, both for dilute and for concentrated solutions, arc pointed out and their Physical sigtzzficance discussed. DURING the past half century there has been a gradual accumulation of thermodynamic data for systems of interest to the metallurgist. There remain many gaps in the data, however, and the metallurgist must often face the problem of estimation of thermodynamic quantities where measured values do not exist. One might hope that the experimental progress would be matched by theoretical advances which would make such estimations possible with a high degree of confidence. However, theoretical progress has been disappointingly slow even for the simplest kinds of solutions, and since the multicomponent systems in which the metallurgist is interested are very complex, one cannot expect theory to be of much help to the metallurgist. In this situation, therefore, it seems worthwhile to examine some simple models of solutions from two points of view: firstly, to see if such crude models represent the thermodynamic facts in as many types of solutions as possible sufficiently well for the needs of the metallurgist, and secondly to see what the deviations from such models show to be important for consideration by theorists. BOND ENERGY MODELS OF SOLUTIONS The simple models that we will examine from these points of view may be termed statistical models, in that they are concerned with the thermodynamic consequences of some simple assumptions about the energy of an assembly of atoms, molecules, or ions, and do not inquire into the physical basis of the interaction. The underlying assumption of these models is that the energy of an assembly of molecules (by which we include also atoms or ions) is given by the sum over all interaction energies of molecules taken two at a time; we will discuss only those models in which the pairwise interactions are restricted to those between nearest neighbors. Thus, in a pure substance of bond energy EAA, the internal energy (with respect to some specific reference state) will be expressed as NAA EAA where NAA is the number of nearest-neighbor pairs. A solution of molecules A and B will be characterized by NAA EAA + NBB EBB + NAB EAB where the Eij represent the bond energies of the nearest-neighbor i-j pairs. If one assumes that the EAA and EBB are the same in the pure components as in the solution, and that the coordination numbers in the two pure substances and in the solution are the same, then the energy of the solution with respect to the pure components (i.e., the energy of solution) is a function of the following linear combination of the bond energies: EAB - 1/2(EAA +EBB) = w. The thermodynamically ideal solution is defined as one in which the activity of each component is equal to the mole fraction of that component at all concentrations and all temperatures. It follows that

Jan 1, 1962

By F. W. McQuiston

Idarado Mining Company's mill and surface plant are at the portal of the Treasury tunnel at elevation 10,625 ft, 12 miles south of Ouray, Colo. In 1943 and 1944 this tunnel was extended in a westerly direction to tap the Black Bear vein, and, together with the recently completed 1100-ft inclined Treasury raise, provides access to the Black Bear mine. In 1945 a 250-ton mill was placed in operation to process development ores containing much needed copper, lead and zinc for war requirements, and to serve as a pilot testing unit for larger scale milling operations. In the years 1902 to 1927 some 329,000 tons of ore were produced from mine workings on the Black Bear vein that extended downward from elevation I2,325 ft at the Black Bear tunnel portal to elevation 11,618 ft, the lowest level of the mine. The ores were taken to the Cascade and Smuggler-Union mills near Telluride over two aerial tramways. Gold bullion, a copper-lead concentrate, and a zinc concentrate were produced. Ores The Black Bear is a compound fissure vein that has undergone several stages of mineralization. The first important stage is represented by complex ores of copper. lead and zinc in a quartz gangue. Precious metal content in this stage is low. The galenn is argentiferous and varying amounts of tetrahedrite, freibergite and bornite tend to increase the normal copper content represented in chalcopyrite. The zinc occurs as a true sphalerite with little or no iron. Later re-openings of the fissure took place more or less co-extensively with the successive introduction of (I) abundant quartz gangue containing minor amounts of chalcopyrite, galena and sphalerite; (2) free gold in a fluoritic quartz gangue; and (3) barren, low-grade quartz with minor amounts of pyrite as the only important sulphide. The sulphides show practically no oxidation and little mineralogic inter-growth. Because of the common overlapping of these successive stages of mineralization within a given mining area, considerable dilution of the base-metal content takes place, thus lowering the average mill-head grade. Plant Practice Metallurgical testing was started shortly after the Black Bear vein was encountered on Treasury tunnel level in 1944. Laboratory tests showed good flotability of the minerals in the ore and indicated an economic separation could be made of the copper, lead and zinc minerals into their respective concentrates. The success of the separation is close reagent control to maintain a balance between promotion and depression of the sulphides. To maintain this balance reagent consumption for the three metal separation is considerably higher than in ordinary lead-zinc flotation.

Jan 1, 1949

By Roy R. Weil, John A. Dziubek

This paper discusses the use of computer modeling, data manipulation, and mapping of three multi-seam coal properties in the Appalachian coal basin. Each case history represents a slightly different application of computer usage for estimation of reserves and planning surface mine sequencing. This practical use of computers demonstrates the suitability of data processing for normal evaluation of coal properties.

Jan 1, 1983

By J. M. Tobin, L. H. Cadoff, L. M. Adelsberg

The reaction between liquid zirconium and graphite at temperatures above 2000 °C has been investigated. The reaction products were found to be carbon-saturated zirconium metal and ZrC which formed between the graphite and the metal. Parabolic growth behavior was observed for the ZrC Phase at all temperatures of this investigation. The parabolic growth constant at temperatures between 2000° and 2860°C was measured to be 1.83 exp 84,300/RT) sq cm per sec. The reaclion mechanism was proposed to be the rapid carbon saturation of the liquid metal and the formation of ZrC at the metal-carbide interface with diffusion of carbon through the ZrC, the "rate - determining step" of the reaction. The concentration-independent diffusion coefficient of carbon in ZrC, (DZrC), was expressed as 0.95 exp? 78,700/RT) sq cm per sec. This value mas calculated using the temperature-invariant ZrC phase fields proposed in the literature. The [ZrQiq)] — [ZYQiq) + ZrC] phase boundary over the temperature range 2000° to 2800°C was determined and the ZrC + C eutectic temperature was found to be 2890° ± 50°C. ThE Group IV and VB transition-metal refractory carbides are of interest because of their high melting points, high temperature strength properties, and relative inertness in certain corrosive environments. The present-day understanding of these materials, however, is limited by the general unavailability of accurate and reliable physical and chemical property data. This is due primarily to the difficulties associated with the preparation of suitable, high-density, high-purity carbide samples, and the achievement and control of uniform high-temperature environments. Accurate measurement of temperature is also an important factor limiting the reliability of reported data. The Zr-C reaction was selected for investigation because of the high melting point (>34000C) and favorable nuclear properties of the reaction product, ZrC. The direct reaction method afforded an opportunity to obtain kinetic data on the fully dense carbide. In this paper, layer-growth techniques were used to estimate the diffusivity of carbon in ZrC and to investigate the phase equilibria in the Zr-C system at temperatures above 2000°C. EXPERIMENTAL PROCEDURES AND DATA Crystal bar zirconium (99.9 pct Zr), purchased from the Nuclear Materials and Engineering Corp., and ZTA graphite (99.9+ pct) were used in this study. The analyses of the materials are listed in Table I. A schematic of the high-temperature carburization apparatus is shown in Fig. 1. The sample was a zirconium metal charge in a 1/2 -in.-ID graphite crucible which was capped with a tightly fitting graphite stern. The crucible and stem were designed to closely approximate black-body conditions. The graphite crucible was packed in lampblack (outgassed 1 hr at 2100°C) which provided insulation and thermal stability to the system. The inert atmosphere was maintained by a constant flow of high-purity argon or helium gas. The nozzle-diffuser section on the top flange was sufficient to prevent back-diffusion of air into the system. Chemical analysis of the carburized samples revealed oxygen and nitrogen concentrations of less than 44 and 20 ppm, respectively. The sample was heated by induction with a Westing-house 5 kw-450 kc power source. Temperature was measured with a Milletron two-color pyrometer which was sighted into the crucible by reflection from an overhead front surface mirror. Optical losses due to glass absorption and light reflection at air-glass interfaces were minimized by the employment of the dynamic-gas seal. It was found that no correction was required for the front surface reflector. The pyrometer was calibrated periodically against a U.S. Bureau of Standards tungsten ribbon secondary standard. Temperatures inside the crucible were also calibrated against the Zr-ZrC eutectic (1850°C)1 and the Nb-Nb2C eutectic (2335°C)2,3 temperatures and agreed to within ±10°C of these values. The temperature was controlled by manually adjusting the power input; variations of

Jan 1, 1967

By William Kent

In a paper by Mr. Frank Firmstone, published in vol. iv, of the Transactions of the Institute, on " Comparison of Results from Open-topped and Closed-topped Furnaces," the regularity of the average grade of pig iron procluced by the furnace under different conditions is expressed by means of a curve or diagram. The object of this note is to show that the graphic method, or that of representing variations by plotted curves or diagrams, is capable of a much more extended application to blast-furnace records, making a valuable auxiliary to the " furnace hook," and that by it the practical metallurgist may obtain at a glance information concerning the variations of the furnace during long periods, which could be found in the furnace book only after a tedious search. Plate XII is a graphic record of an anthracite blast furnace for one month. The table on page 554 gives the figures obtained from the furnace book, together with a record of temperature of the atmosphere, barometric pressure, and moisture in the air, which was obtained from a meteorological observatory not far from the furnace. In the records of a furnace, two of the variable qualities are final results, viz., the quantity of pig iron produced, and its grade; all the other variables are antecedent causes which produce the final results. Of these variable callses which contribute to the quantity of product and its grade, some are partially under the control of the furnace manager, others depend upon the state of the atmosphere, and still others are accidental. Of the first class are the character of the materials charged, and their relative proportions, their mechanical conditions, as wetor dry, large or small pieces, etc., the revolutions of the engine, the heat and pressure of blast, and the distribution of the charge. Of the second class are the number of pounds of air blown into the furnace for each stroke of the engine, the amount of moisture in the air, and the condition of the chimney draughts. These vary largely with the season of the year. Of the third class is the leaking of a tuyere or a temporary stoppage. To keep a record of this kind for a whole year, it is only necessary to procure a sheet of common profile or cross section paper, about 38 inches long and 8 or 10 inches wide, with cross lines ruled about 0.1 of an inch apart. The vertical lines, or those in direction of the

Jan 1, 1879

By Edward S. Cook

For several years past, dating particularly from the days of serious "ore-dirt" complications at the Warwick furnace, I have been desirous of providing some safe, quick and easy method of relieving the tuyeres of slag, when the cinder- and iron-notches are chilled through loss of heat in the clucible or when, from dropping or jumping of stock, the molten slag is forcibly driven into the bellyand leg-pipes. Various methods were proposed, but objections of one kind or another always presented themselves, and the subject was postponed to a more convenient season. In the summer of 1887, while running on anthracite alone, 1 found the various expedients in use to be so utterly valueless, that the importance of a practicable tuyere slagging-valve impressed me more forcibly than ever. The holes left in the cast-iron jacket at one side of the bottom of the water-blocks were found to be of no value whatever. The swinging or hinged cap on the elbow of the belly-pipe, while convenient to permit the removal of lag after the belly-pipe was partially or wholly filled, could not be adapted to discharge the slag before solidifying, except at great risk to the men and loss of time just when the constant running of the engine and the keeping of blast on the furnace was of the utmost importance. By removing keys from the caps and holding them in place with props, the slag could be discharged through the tuyeres and belly-pipes, with the engine running, by knocking the props away at a given signal. This method is extremely hazardous to life and limb, and I have always hesitated to make use of it. When the furnace is in such condition as to require the adoption of some method of the kind, the stoppage of the engine, cooling the blast and the contents of the crucible, always aggravates the trouble. When the caps are blown open and the slag is discharged by removal of the props, it is necessary to stop the engine to replace them. An hour or more will elapse before this can be done, as the slag must be partly removed before the tuyeres can be approached by ordinary mortals, and the caps handled and fastened in place again. Any movement of the stock is liable to burn the workman, as he stands, securing the cap in front or at one side of the open belly-pipe.

Jan 1, 1889