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By N. A. Gokcen

The construction and operation of a simple and accurate vacuum-fusion apparatus are described in detail. Absolute accuracy of the oxygen analysis has been determined by the reduction of oxides weighed to 20.01 mg. The Bureau of Standards steel samples have been analyzed repeatedly, and their inadequacy for the acceptable range of oxygen is presented. The limits of interference of manganese, aluminum, and titanium, and the effects of tin and water-cooling of the furnace tube have been investigated in detail. ANALYSIS by the vacuum-fusion method consists of melting a sample in a degassed graphite crucible under high vacuum and extracting oxygen as carbon monoxide, and nitrogen and hydrogen as gaseous elements. The resulting gas mixture is analyzed for its constituents, from which oxygen, nitrogen, and frequently hydrogen may be determined within 1/2 hr or less. The history and summary of methods1-4 and extensive reviews of literature'.' for the determination of gases in metals have been published in detail. The foundation of the modern vacuum-fusion method of analysis was laid by Jordan and Eckman,11 and Oberhoffer and his associates.1, 10 Diergarten,11, 12 Meyer,13 Thanheiser et al.,14, 15 Ericson and Benedicks,16 Ziegler,17, 18 Sloman,16-23 Thompson et al.,24 and later many others contributed to the improvement, accuracy, and limitations of the method. In some investigations, however, the limitations of the procedure and the errors involved in the analysis require further critical examination and evaluation. In many apparatuses, lunnecessarily complicated and cumbersome features and elaborate precautionary measures do not have conclusive advantages. The purpose of this invest:igation was, therefore, a) to construct a very simple and accurate apparatus, b) to determine the absolute accuracy of results, c) to establish the limits of interference of manganese. aluminum, and titanium, d) to reexamine critically the reduction and recovery of oxygen from oxide powders of various sizes, and e) to evaluate critically the eight steels of the Bureau of Standards."' Apparatus The apparatus used in this investigation is shown in Fig. 1. It has been used for over three years, during which several modifications were made. A brief description of the apparatus is as follows. The transparent silica or Vycor tube, E, is joined to the Pyrex head, B, by mean of a face to face ground joint sealed with mercury. A similarly sealed ball and socket joint would also have been satisfactory. A standard tapered ground joint, successfully used by some investigators, was tried, but in the absence of grease or vacuum cement it was very difficult to disassemble the joint. The graphite crucible, G, 15/16 or l 1/8 in. OD, 2 1/2 or 3 in. high, 1/10 in. wall, shown enlarged in Fig. 3a, is made from the rods containing less than 0.08 pet ash. Two baffles, overlapping sufficiently to prevent spattering, are inserted in two opposite slots cut on a band saw. Two small holes in the baffles permit the temperature measurement of the melt. A second type of crucible, Fig. 2, G, shown enlarged in Fig. 3b, is also satisfactory, though not as convenient as the crucible shown in Fig. 3a. Somewhat similar but more elaborate crucibles with baffles were first tried by Ericson and Benedicks,'" but were abandoned in favor of a crucible with a stopper and a peripheral graphite powder filter. Various versions of their crucible with a stopper have later been used by other analysts, 10-27, 27-30 The crucible is packed directly in E, Figs. 1 and 2, with —35 + 48 graphite powder for shielding and insulation. A minimum layer of 7 mm of powder is necessary for keeping E cool and minimizing the blank. The first use of graphite powder was made by Sloman,10-23 Who found that —200 mesh was the most satisfactory. The author tried various size powders from +20 to —100 mesh and found that a) particles of 28 mesh or larger were not sufficiently insulating and were heated by the induction current, b) the powder finer than 60 mesh packed too much and did not readily permit the escape of gases even when the crucible was heated very slowly; hence, the powder was occasionally blown out of the side in the crucible and in the mercury pump. The optimum size powder is, therefore, 35 to 48 mesh size or 0.4 mm in average diameter. The furnace is designed to eliminate excessive amounts of

Jan 1, 1959

By John R. Don

This paper, under the title of "The Genesis of Auriferous Lodes from a Chemical Point of View, Illustrated by Analyses of Samples Taken from the Chief Auriferous Area of New Zealand, Victoria and Queensland, by John R. Don, D.Sc., M.A., Lecturer on Geology in the University of Otago, N. Z.," was submitted by the author with the frank confession that its length, covering several hundred printed pages of the Transactions of the Institute, would preclude its acceptance for publication in full. But the great value of the original work which it records rendered its rejection on that ground highly undesirable ; and, after correspondence with Dr. Don, it was agreed that the Secretary should condense the paper, subject to the author's approval, omitting what was not essentially connected with the original work reported. In the discharge of this laborious and difficult duty, the Secretary's chief trouble has been his regret to cut out the acute criticisms and admirable theoretical and historical summaries of Dr. Don on the general subject of the science of ore-deposits. It should be added, that the original paper has been returned to the author, with full permission to publish it through any other medium (due mention being made of the first publication by the Institute of portions thereof), and a cordial expression of the hope that the treatise, as a whole, may be thus published, to the advantage of science. The Secretary begs to add, that many of the portions necessarily omitted from this condensed version would constitute, in his judgment, interesting and valuable separate contributions. In attempting to condense this paper, it was necessary at the outset to cut out the tint three chapters, of which the following brief outline is therefore given. Chapter I., introductory in character, indicates the importance of chemical analysis in the investigation of the genesis of ore-deposits, emphasizing the value of Prof. Posepny's Institute paper, and especially of the discussion which it aroused, and stating in general terms the theories of "lateral secretion" and "ascension." Chapter 11. describes the scope of the investigation undertaken by the author, the chief purpose of which was to determine which of the above-named theories was favored by the evidence obtained. This evidence consists chiefly (though not wholly) of analyses of the country-rock taken at various distances from the auriferous "reefs," (a) on deep mine-levels; (b) in the surface or "vadose" region : and also (c) of underlying, neighboring or connected crystallines (granite, gneiss, etc.). In addition to these investigations, there is a separate inquiry into the question of the deposition of gold in marine basins, suggested by the fact that most of the gold in the lodes of Australasia occurs in stratified deposits. Chapter 111. discusses the principles and methods followed by the author in the examination of country-rock for the purpose described. After giving his reasons for believing that careful tests of carefully-chosen samples of country-rock taken at varying distances from the ore-deposit might throw light upon the question

Jan 1, 1898

By Robert M. Keeney, Jay Lonergan

The electric smelting of manganese ore and the production of ferro-manganese did not exist as an industry, in the United States or elsewhere, previous to the outbreak of war in 1914. Ferromanganese had been produced, electrically, during times of high prices by two companies at Niagara Falls and by several European companies, but the production was spasmodic, and none was electrically produced when ferromanganese sold at from $35 to $40 per ton. Thus the electric smelting of manganese ore must be considered as a development caused by the high prices prevailing during the years 1916, 1917 and 1918, and the necessity of smelting domestic ore in order to fill the ferromanganese requirements of the steel industry of the United States, which increased from 189,088 tons in 1914 to 356,356 tons in 1918. The electric furnace is well adapted to smelting domestic ore because it can be located in small units near the source of ore supply. In 1918, the ferromanganese production of the United States was 333,027 tons, of which about 7 per cent., or 23,000 tons, was produced in the electric furnace. The electric furnace not only assisted materially in the development of a domestic-ore supply but made a considerable saving of coke, as it requires about 11/4 tons of bituminous or lignite coal per ton of ferromanganese compared with a blast-furnace consumption of 2.9 tons of coke per ton of ferromanganese. Some of the plants in the United States that smelted manganese orc in the electric furnace during the war and in 1920 are listed in Table 1. From early in 1919 to about February, 1920, little ferromanganese was produced in the electric furnace. During this period the price of ferromanganese (78 to 82 per cent. manganese) was about $100 per ton. During the first half of 1920, several plants resumed operation when the price of ferromanganese (76 to 80 per cent. grade) gradually increased to $200 per ton, delivered.

Jan 1, 1922

By R. J. Blackwell, J. R. Rayne, W. M. Terry

This paper presents results of an experimental investigation of factors that control the efficiency with which oil is displaced from porous media by a miscible fluid. The study was made to elucidate the relevant processes both on microscopic level (within individual or between neighboring pore spaces) and on macroscopic level (within a large sand body). Mixing of miscible fluids on the microscopic level was studied in sand-packed tubes. It was found that molecular diffusion is the dominant dispersion mechanism for reservoir conditions of rate, length and pore sizes. Macroscopic channeling was studied for various mobility ratios in reservoir mode1s scaled to relate viscous, gravitational, and diffusional forces. The formation of channels was due to viscous firzgering, gravity segregation and variations in permeability. With adverse mobility ratios, it was found for reservoirs of realistic widths that diffusion will not be effective in preventing the formation and growth of fingers, even in homogeneous sands. At sufficiently low rates channeling was eliminated by gravity segregation in tilted reservoirs. The dependence of recovery on mobility ratio, length-to-width ratio, flow rate and angle of dip is presented. INTRODUCTION Oil recovery by solvent flooding is finding increasing application in the field. While the process promises high recoveries from the region swept by solvent, under adverse conditions only a small fraction of the reservoir volume may be swept at the time solvent breaks through to the producing well. Further, the high cost of the solvent encourages its use only as a bank whose size must be kept at a minimum. Thus, two important questions arise: (1) what fraction of the reservoir can be swept, practically, by solvent? and (2) what is the minimum size solvent bank that can be used to carry out the displacement? The answers to these questions require knowledge of both macroscopic channeling processes and microscopic mixing processes. The studies described here were carried out to gain this knowledge. Microscopic mechanisms which cause mixing will be discussed first, because an understanding of these mechanisms is necessary for proper interpretation of the experimental work on channeling described later. INVESTIGATION OF MICROSCOPIC DISPLACEMENT PHENOMENA FOR MISCIBLE FLUIDS The questions to be resolved concerning microscopic displacement behavior are: (1) how much mixing occurs between oil and solvent in the direction of flow? and (2) does the solvent completely flush the oil from the pore spaces in the region invaded by solvent? The classic work of Sir Geoffrey Taylor' and its extension by Aris2 have shown that it is possible from theory to describe the amount of mixing in single straight capillaries when solvent displaces a fluid of equal viscosity and equal density. Aris showed that the lengths of the mixing zones, 81, corresponding to the 10 per cent and 90 per cent concentration levels of the solvent can be calculated from the formula, 81 = 3.62 \/Kt, .........(1) where 8l is the length of the mixing zone, cm; t is the time, sec; and K is the effective dispersion coefficient, cm2/sec, given by K/D = 1 + (1/48) (au/D)2......(2) where a is the radius of the capillary, cm; D is the molecular diffusivity, cm2/sec; u is the average velocity

By D. S. Flett, A. W. Fletcher

Equilibrium studies on the extraction of nickel and cobalt with kerosine solutions of naphthenic acid have shown that an exchange extraction reaction occurs at pH 5.5. The nickel/cobalt separation factor is constant at 1.8 for constant total metal molarity and varying nickel/cobalt ratios. The separation factor decreases with increasing total metal molarity in the organic phase beyond 0.2 M and also decreases with increasing temperature. From the equilibrium data, it has been possible to derive a mathematical model for the separation of nickel from cobalt by exchange extraction in multistage systems. Experimental data from a continuously operated multistage mixer/settler apparatus has shown a reasonable correspondence with computer-calculated data. The effective separation of nickel and cobalt in sulfate solution remains a problem in hydrometallurgy and the hope that this would be solved by solvent extraction has not yet been fulfilled. With chloride solutions, advantage may be taken of the ability of cobalt to form anionic complexes with the chloride ion. It can then be readily separated from nickel, which does not form stable chloro complexes, by extraction with a suitable long chain amine. However, in hydro metallurgical operations, sulfate solutions are generally obtained in which no extractable anionic species are present. Thus, the possibility of using cationic extractants must be considered, and in this paper attention is directed to the use of carboxylic acids. The method of separation studied has been termed exchange extraction, which involves replacement of a metal in the organic phase with a more acidic metal in the aqueous phase. Thus, (BR2).+ (Az+)aqt=(AR,).+ (B2+)aq (I) where metal A is more acidic than metal B, R represents the acidic radical derived from the acid RH, and the subscripts e and aq refer to the organic and aqueous phases, respectively. Ashbrook and Ritcey' have used this method for the separation of cobalt from nickel using the sodium salt of di-2 ethyl hexyl phosphoric acid, which preferentially extracts cobalt. Some nickel is coextracted, and this is removed by exchange with cobalt ions in the feed solution by suitable countercurrent operation in a pulsed column. Much work has been carried out by a number of workers in Russia on the general use of exchange extraction for the separation of metal ions using car-boxylic acids. Gindin et aL a have demonstrated that this technique could be applied to the separation of nickel from cobalt using a C--C. carboxylic acid and have applied the technique to the production of high purity cobalt solutions for electrolysis. Further worka was concerned with the development of a process for the separation of nickel from cobalt in a pulsed column. This system permitted the separation of iron and copper from nickel and cobalt in one system. The procedure involved center feeding with acid backwashing at the top and alkali addition lower down the column. Thus the system operated under a pH gradient and the metals were distributed in the column in the order of their basicities. A similar application was studied by Gel'perin et al,4,5 for the removal of copper and iron impurities from a nickel anolyte by means of a C10-C,12 fatty acid fraction. Ginden et al,' and Fletcher and Wilson' have studied the effect of pH on the extraction of a number of metals with carboxylic acids. These studies showed that metals such as iron, copper, lead, zinc, nickel cobalt, and manganese are extracted at pH values close to the pH of hydroxide precipitation. Nickel is extracted at a slightly lower pH than cobalt and thus the nickel/cobalt separation factor has a value not much greater than 1. More basic work on complex identification has been reported by Fletcher and Flett: by Tanaka; and Jay-cock and Jones." These studies have suggested that at low loadings in the organic phase, the nickel and cobalt carboxylates appear to be dimeric and solvated by free carboxylic acid molecules. As the concentration of metal in the organic phase increases, the complex changes and larger polymeric species are formed. In order to permit assessment of the potential of carboxylic acids as extraction reagents for separation of

Jan 1, 1971

By Jay Lonergan, Robert M. Keeney

The electric smelting of manganese ore and the production of ferro-manganese did not exist as an industry, in the United States or elsewhere, previous to the outbreak of war in 1914. Ferromanganese had been produced, electrically, during times of high prices by two companies at Niagara Falls and by several European companies, but the production was spasmodic, and none was electrically produced when ferromanganese sold at from $35 to $40 per ton. Thus the electric smelting of manganese ore must be considered as a development caused by the high prices prevailing during the years 1916, 1917 and 1918, and the necessity of smelting domestic ore in order to fill the ferromanganese requirements of the steel industry of the United States, which increased from 189,088 tons in 1914 to 356,356 tons in 1918. The electric furnace is well adapted to smelting domestic ore because it can be located in small units near the source of ore supply. In 1918, the ferromanganese production of the United States was 333,027 tons, of which about 7 per cent., or 23,000 tons, was produced in the electric furnace. The electric furnace not only assisted materially in the development of a domestic-ore supply but made a considerable saving of coke, as it requires about 11/4 tons of bituminous or lignite coal per ton of ferromanganese compared with a blast-furnace consumption of 2.9 tons of coke per ton of ferromanganese. Some of the plants in the United States that smelted manganese orc in the electric furnace during the war and in 1920 are listed in Table 1. From early in 1919 to about February, 1920, little ferromanganese was produced in the electric furnace. During this period the price of ferromanganese (78 to 82 per cent. manganese) was about $100 per ton. During the first half of 1920, several plants resumed operation when the price of ferromanganese (76 to 80 per cent. grade) gradually increased to $200 per ton, delivered.

Jan 1, 1922

By L. Russell, van Wert

During an investigation in which the solubility relations of the phases in Muntz metal (60 per cent. copper, 40 per cent. zinc) were under study, certain phenomena that had no immediate connection with the main problem were observed, which were thought sufficiently interesting to study further. Because of lack of time, only a preliminary survey was made of two of these; namely, the cleavage structure developed under certain conditions in a 60:40 brass and abnormal grain growth in this alloy. Cleavage Structure in Heat-treated Muntz Metal Carpenter noted many years ago that cold-working a brass of the Muntz metal type, which had been quenched previously from within the beta field, results in a partial breakdown of the supersaturated beta solution and the precipitation of the solute (the alpha solution) in the cleavage planes of the beta grains. This manner of rejection of a solute from a metastable solid solution is not peculiar to this particular alloy, for among others, it occurs in the cold-working of certain austenitic steels; for example, the austenitic nickel steels. In these ferrous alloys, cold deformation produces a partial decornposition of the austenite, with the formation of martensitic "needles" and zigzags in the austenitic poly-hedra. It is interesting to note that while the two solid solutions— austenite and quenched Muntz metal— are metastable and in their mode of decomposition behave quite alike when deformed in the cold, the metastability of each results from a different cause; viz., that of the austenite from the fact that it is a supercooled solution (its solvent. gamma iron, at ordinary temperatures is below its normal stable range whereas the metastability of the quenched Muntz metal is the result of supersaturation. When a 60:40 brass is quenched from above 800" C.—that is, from within the field where the beta phase alone is stable—this solution is retained practically intact and the alloy so cooled is found to consist almost entirely of polyhedra of this solution with only a little alpha present ordinarily at the boundaries of the beta grains—the result of a slight

Jan 1, 1929

By L. D. Mullins, E. B. Elfrink, W. L. Wahl

In the past few years several articles and papers presenting results of solution gas-drive depletion calculations have appeared in the lit-erature. Such calculations are of interest to the oil industry, for investment decisions must often be made before much is known about a reservoir. At other times, an estimate of the possible benefits to be realized from alternate production methods is desirable, and theoretical depletion calculations can serve as a floor or reference level from which to work. In any case, an estimate of ultimate oil recovery based upon engineering data is commonly required. An engineer confronted with the problem of obtaining, for a specific reservoir system, an estimate of ultimate oil recovery by solution gas-drive depletion usually will be forced to perform the calculations himself. This is despite the quantity of data in the literature. Rarely will either experience or the literature provide results from a reservoir system similar in all important respects to the one under consideration, and calculated results are not so plentiful that satisfactory interpolation procedures can be devised. Performing the calculations, however, is a tedious, time-consuming task unless an electronic computer is available, and, in practice, time and manpower are not always available for this purpose. A quick, simple, consistent method was needed for reducing the uncer- tainty in estimated oil recovery from solution gas-drive reservoirs when only minimum information about the reservoir system is available. PROCEDURE Method of Calculation The usual requisite assumptions were made so that the material balance equation could be used to calculate data for the charts. The following assumptions were made: (1) the reservoir is homogeneous and isotropic; (2) oil recovery is due entirely to solution gas drive and neither a gas cap nor a water drive nor gravity drainage is present; (3) the initial reservoir pressure is the bubble-point pressure of the reservoir fluid; (4) initial total liquid saturation is 100 per cent of pore space; (5) interstitial water saturation remains at the initial value as the reservoir pressure declines from the bubble-point pressure to atmospheric pressure; (6) equilibrium gas saturation is 5 per cent of pore space; and (7) oil and gas saturations are uniformly distributed throughout the reservoir at all times. There are no saturation gradients due to a wellbore, nor is the geometry of the reservoir system considered. The material balance equation was written in the form of a differential equation' which was integrated to determine the change in oil saturation for an assigned pressure drop. Formal integration was not possible, so recourse was made to the Runge-Kutta method' of numerical integration. All computations were performed on IBM equipment. Numerical integration yielded the change in oil saturation within the reservoir as the pressure. declined from the bubble-point pressure to atmospheric pressure. The initial oil saturation minus the change in oil saturation yielded the oil saturation at atmospheric pressure. The oil originally in place was obtained by dividing the initial oil saturation by the initial formation volume factor (differential liberation) while the oil in place at atmospheric pressure was obtained by dividing the final oil saturation by the formation volume factor at atmospheric pressure. U1timate oil recovery, expressed as a percentage of the initial oil in place, was obtained by dividing the difference between the oil initially in place and the oil in place at atmospheric pressure by the oil initially in place and multiplying by 100. PVT Data Charts were based upon 135 solutions to the material balance equation. PVT properties of the reservoir fluids were variables in this equation and had to be known as functions of pressure. The required PVT data might have been obtained from either actual reservoir fluid systems or correlated data. However, correlated PVT data were developed and employed in the calculations for the following reasons: (1) it is doubtful that 135 sets of PVT data could have been obtained for the values of variables investigated in this study, and (2) results of recovery calculations from randomly obtained PVT data could not be correlated as well as rssults from selected PVT data. The PVT data used to develop the

By van Wert, L. Russell

During an investigation in which the solubility relations of the phases in Muntz metal (60 per cent. copper, 40 per cent. zinc) were under study, certain phenomena that had no immediate connection with the main problem were observed, which were thought sufficiently interesting to study further. Because of lack of time, only a preliminary survey was made of two of these; namely, the cleavage structure developed under certain conditions in a 60:40 brass and abnormal grain growth in this alloy. Cleavage Structure in Heat-treated Muntz Metal Carpenter noted many years ago that cold-working a brass of the Muntz metal type, which had been quenched previously from within the beta field, results in a partial breakdown of the supersaturated beta solution and the precipitation of the solute (the alpha solution) in the cleavage planes of the beta grains. This manner of rejection of a solute from a metastable solid solution is not peculiar to this particular alloy, for among others, it occurs in the cold-working of certain austenitic steels; for example, the austenitic nickel steels. In these ferrous alloys, cold deformation produces a partial decornposition of the austenite, with the formation of martensitic "needles" and zigzags in the austenitic poly-hedra. It is interesting to note that while the two solid solutions— austenite and quenched Muntz metal— are metastable and in their mode of decomposition behave quite alike when deformed in the cold, the metastability of each results from a different cause; viz., that of the austenite from the fact that it is a supercooled solution (its solvent. gamma iron, at ordinary temperatures is below its normal stable range whereas the metastability of the quenched Muntz metal is the result of supersaturation. When a 60:40 brass is quenched from above 800" C.—that is, from within the field where the beta phase alone is stable—this solution is retained practically intact and the alloy so cooled is found to consist almost entirely of polyhedra of this solution with only a little alpha present ordinarily at the boundaries of the beta grains—the result of a slight

Jan 1, 1929

By M. A. Torcaso, P. Raimondi

To study mass transport in systems simulating oil recovery processes, different porous media were saturated with a mobile (carrier phase) and a stationary phase. Slugs of carrier phase containing a small amount of solute were displaced with pure carrier phase. By analogy to the chromato-graphic processes, the velocity of the solute can be predicted from a knowledge of the partition coefficient and the saturation provided that equilibrium between the two phases exists. Equilibrium was found to exist for different porous media, solutes and rates. The conditions were varied over the range normally encountered in the laboratory and in the field. The longitudinal dispersion of a solute undergoing interphase mass transfer was also investigated. INTRODUCTION The production of hydrocarbons by gas cycling, enriched gas drive and C02 or alcohol displacement involves, among other factors, relative motion between two phases and compounds, hereafter called solute, which are soluble in both phases. The solute is carried forward by the faster flowing phase at a lower velocity than the average velocity of that phase. Retardation of the solute is caused by chromatographic absorption and desorption in the slower flowing phase and by the degree of departure from equilibrium. At equilibrium the concentration of solute in the two phases can be related by the equation* CSw = K Cso ,............(1) where C, and C are the concentration of solute in the aqueous and oleic phases respectively and K is the equilibrium ratio, or partition coefficient. Displacement theories must contain an explicit assumption with regard to equilibrium, i.e., whether the compositions can be related by Eq. 1. The existance of equilibrium depends, in general, on the relative velocity between the phases. Unfortunately, other factors such as gravity segregation and viscous fingering, also depend on velocity. For this reason, whenever effects of rate on displacement were observed,2-4 it was practically impossible to discern what caused them — lack of equilibrium or the factors mentioned above. Equilibrium between phases has been the subject of extensive studies in fields such as extraction or chroma to graphy. It has received only small attention in flow through the type of porous media encountered in oil production.5 For this reason a method was developed which makes it possible to study the movement of a solute as it is affected by rate, type of porous media, partition coefficient and carrier phase, but in the absence of segregation or fingering. The information obtained enables one to determine when the assumption of equilibrium can be made. Briefly, the method consists of (1) saturating the core with a mobile and an immobile phase, (2) injecting a slug made up of the same fluid as the mobile phase and a small concentration of mutually soluble solute, (3) measuring the lag and the peak height of the slug at arrival and (4) correlating these variables with fluid properties such as partition coefficient and mixing constants of the medium. PROPOSED MECHANISM The principles of chromatography are combined with the equation of longitudinal mixing to predict the velocity of a solute slug compared to the bulk velocity and the peak height of a slug.6-9 The equation so obtained is valid under equilibrium conditions only. Therefore, a comparison between experimental and predicted results will give a measure of departure from equilibrium. This work was done with either the oleic or the aqueous phase being immobile. For simplicity, the following development is based on the case where the oleic phase is immobile. However, the treatment is the same in either case.

Jan 1, 1966

C. M. Bishop (Aircraft Div., A. V. Roe Cnnada Ltd., Toronto)—Reference is made to the coherency hardening of ß due to ß' and also to the hardening of ß due to a coherent precipitation of the a phase. What is meant by the term "ß'?" Would not the coherency hardening of ß during cooling be due to precipitation of a sub-microscopic dispersion of a, as is the case during reheating a ß-quenched alloy? I feel that these two phenomena are essentially the same mechanism, i.e., precipitation of a from unstable or supersaturated ß. From the text, it would appear that Tables III and IV are intended to show the effect of the martensite transformation on the properties of Ti-Mn alloys. Referring to Table 111, the ß-quenched alloys would contain a greater proportion of retained ß than would the equilibrated alloy. Could not the increase in properties be attributed to this, along with possible coherency hardening of the ß? In the same way, the structures referred to in Table IV contain ß from which they could derive their hardness. It would appear to be difficult, if not impossible, to assess the role of the martensite transformation from the data contained in these tables. F. C. Holden, H. R. Ogden, and R. I. Jaffee (authors' reply)—In reply to the first question raised by Mr. Bishop, the term "ß"' designates an apparent retained-p structure which is harder than it is after the most rapid cooling from the ß field. It is thought to be the result of a coherent precipitation of a. The mechanism by which hardening takes place is undoubtedly the same as that involved in the early stages of aging of a re-tained-p structure, and we are in agreement with Mr. Bishop on this point. The term "ß'" to designate the anomalously hard retained-ß structure was agreed upon at a symposium in 1953." The authors do not agree that the quantity of retained ß and/or ß' in the ß-quenched specimens of Table III is necessarily greater than that of the 600°C equilibrated specimens. The ß-quenched specimen has a structure which appears to be completely a' formed by the martensite reaction. It is recognized that there could be some retained ß (or ß') between the a plates if the M, temperature is below room temperature. This is unlikely for the 3.4 pct Mn alloy where the M, is known to be at about 640°C. Therefore, the increase in strength cannot be attributed to the presence of a greater quantity of coherency-hardened ß, but, rather, the increase in strength must be attributed to the transformation products formed, e.g., a' (martensiti-cally formed a). Concerning the data in Table IV, we agree that it is difficult to estimate the role of the martensite reaction, since the 6.4 pct Mn alloy was retained ß in the quenched condition.

Jan 1, 1955

By S. W. Poole, J. A. Rosa

The object of this investigation was to determine the distribution of chemical elements within a large, killed alloy-steel ingot, by sulphur printing and quantitative chemical analysis. With regard to segregation in steel ingots, the factors of melting practice, pouring temperatures, mold design, etc., and the mechanics of solidification and its attendant functions, have been the subject of intensive study over a period of years by many investigators. Notable among these is the Sub-committee of the No. 5 Committee of the British Iron and Steel Institute. For an exposition of the many problems awaiting the researcher on the heterogeneity of steel ingots, the methods of attacking these problems, together with some of the answers, the reader is referred to the nine reports and numerous papers of that committee and its membership. Steelmaking Data Melt.—The heat was made in a 70-ton direct arc-type basic electric furnace. Furnace charge consisted of nickel-chromium-molybdenum steel, most of it in the form of heavy mill scrap. All of the scrap was charged cold. The standard double-slag method was employed, the heat being finished under a strong carbide slag. Aluminum was used as the deoxidizing agent. Tapping tempera- ture, as observed with an optical pyrometer, was 3000°F. Detail of Mold and Ingot Size.—Details of the ingot mold and the ingot itself are given in Fig. I. Teeming.—Teeming temperature of the subject ingot as observed with an optical pyrometer was 2830°F. The ingot was top-poured directly through a 1 1/2-in. nozzle and required 7 min., 44 sec. to fill up to the hot top. An additional 2 min., 30 sec. were required to fill the hot top. The ingot was stripped hot and charged with the remainder of the heat into an annealing furnace. There it was given the standard annealing cycle used for these ingots. Subsequent heat-treatments are described elsewhere in this paper. Sectioning and Preparation for Sulphur Printing Because of previous favorable experience in sectioning ingots up to 21 1/2 in. square with an oxyacetylene torch, it was decided to use this method to section the subject ingot. The ingot was preheated to 900°F. for 12 hr. It was then placed on a steel bed in a horizontal position so that the longitudinal axis was level and parallel to the track of the motor-driven torch carrier. Two cuts were made, one 2 in. above the longitudinal axis and the other 2 in. below. The time required to make each cut was approximately 75 min. The cutting operation is shown in Figs. 2 and 3. The 4-in. thick slab was mmediately charged into a furnace standing at 1200F.

Jan 1, 1945

By L. N. Cosner, C. F. Austin, J. K. Pringle

Shock wave attenuation studies with three igneous rocks are reported: a spessartite elastic to low intensity stress waves, a diorite which is anelastic, and a porous scoria. The level of shock passing through a given thickness of rock has been determined by donor-receptor methods using high speed streak cameras. Test results include shock propagation velocities adjacent to the explosive, the dependence of test results upon test geometry, and the variation in shock wave attenuation in these three common igneous rock fabrics. The utilization of explosives in rock mediums involves a series of interrelated phenomena. These are the detonation process within the explosive, the transfer of energy from the explosion products to the surrounding rock medium in the form of sound or shock waves, and the transmission of the resulting waves through the rock medium to create damage in the rock mass. The subject of this paper is the investigation of the close-in phenomena that occur in the intensely shocked rock immediately adjacent to a detonating explosive charge. The specific aspects studied include propagation velocities, free surface velocities, pulse attenuations and the determination of the equations of state for the test rocks employed. In addition, a series of tests was conducted to indicate the dependence of the test results on the charge diameter utilized. The equations of state for rock materials have been investigated by a number of authors. Lombard, ',' Grine and Fowles,3,4 Zharkov, 5 Hughes and McQueen,6 Chabai,7,8 and Bass9 have published equation of state data on rock materials similar in structure or composition to those investigated in the study. Rinehart10 has prepared a voluminous tabulation of the available equation of state data from these publications and in addition has included data on many other rock and earth materials in his compilation. The reader is referred to the extensive tabulations and bibliography of Rinehart for classical studies involving the equations of state of metals and other solids and liquids. The problems of sympathetic detonation between drill holes in hard rock environments has received the attention of various authors as have the problems of explosive rock coupling close-in stress wave attenuation and explosive diameter effects. 11 to 18 In particular, the don or-receptor geometry of this report is very similar to the geometry of adjacent drill holes in rock. Most published pulse velocity and attenuation work in rock has been devoted to velocities at much lower amplitudes than those associated with close-in explosives phenomena and most attenuation studies involve transmission and attenuation across large spans of material. Excellent work in these areas has been published by the U. S. Bureau of Mines and by many individuals and groups engaged in geophysical research. SELECTION OF TEST MATERIALS A series of rock materials was desired for this test program that would be meaningful industrially, and that would also yield comparative results from a research viewpoint. Based on the availability of a series of related petro-fabrics, for which there is an abundance of physical and shock response data, three igneous rocks were selected as the test series. The applicability of shock wave studies in igneous rocks to industrial problems is readily demonstrated. Hardrock tunneling, quarrying and mining take place in igneous rocks throughout the world. From a research point of view, igneous rocks exhibit a wide variety of grain sizes and considerable diversity in composition, yet the common igneous rocks have a general similarity in their constituent mineral structures and in their grain-to-grain bonding mechanisms. The latter is based on the concept of rock formation through magma cooling and crystallization, though the degree of liquefaction in granitic plutonic masses is indeed a moot question. Three specific types of igneous rock were chosen for study. A coarse-grained granitic textured rock was desired that would serve as a representative of the widely abundant intrusive rocks of the world and

Jan 1, 1967

By B. S. Norris, Charles R. Austin

IN a recent paper the authors1 discussed the reactions to tempering of hypereutectoid steels quenched from 1000° C., as revealed by studies on changes in hardness, electrical resistivity, coercive force and metallographic characteristics. The data, which related specifically to tempering temperatures of 550°, 650° and 710° C., for varying periods up to 125 hr., permitted the following important conclusions: 1. The rate of softening of the steels at the temperatures examined differed markedly although the steels were of "similar" general chemical composition. 2. The temperature of maximum softening spread over a range from about 650° C. to the eutectoid inversion. 3. The divergence in behavior was ascribed, at least in part, to a profound difference in tendency to graphitization on annealing at subeutectoid temperatures. 4. The node of spheroidization of the cementite, as revealed by metallographic studies, also varied considerably in the different steels. The purpose of the present investigation is to pursue further the study of the difference in behavior of the steels on tempering over a wider range of temperature. To this end the following features have received particular attention: 1. Comparison of temperatures of maximum softening of the various steels when the quenched samples were tempered for 5 hr. and for 75 hr. followed by furnace cooling and by quenching in water. 2. Determination of the effect of quenching temperature, prior to tempering, on the rate of softening. Quenching temperatures of 1000° and 850° C. were used in the investigations. 3. Examination of the microstructures obtained with the various heat-treatments employed.

Jan 1, 1938

By George H. K. Schenck

The investment analysis methods that are most generally accepted in the mineral industries in the mid-80's are presented along with their advantages and disadvantages. Also covered are current widely-used practices for introducing the uncertain nature of most of the important variables in an investment analysis, which is contrasted to the former dominance of deterministic analysis. Finally, the discussion turns to current practice for handling the two critical areas: cost of capital and inflation. The advice contained is reinforced with data from a survey of current practices in the petroleum industry.

Jan 1, 1985

By Frank D. Hoyt

BY far the most conspicuous of the Pennsylvania slate districts is that extending from the New Jersey line at the Delaware Water Gap westward almost to the Schuylkill River. This covers parts of three counties in east-central Pennsylvania: Northampton, Lehigh, and Berks. The most important development, both in geographic size and product importance, is in Lehigh and Northampton counties. The greater part of the region is underlain by only one formation-the Martinsburg, consisting of slates, clay slates, and sandy shales, all of the Ordovician period. The slate-bearing Martinsburg formation is underlain by Cambro-Ordovician limestones. Immediately overlying the Martinsburg formation is the Tuscarora quartzite of the Silurian period. The Martinsburg formation itself is divided into three distinct divisions, termed simply: the upper, the middle, and the lower members. Commercial slate has been extracted from all of these members, but the formation of greatest importance is the upper member, representing 2600 ft of the total formation thickness of nearly 11,000 ft. The upper member is commonly referred to as the "soft slate" and consists of three facies: 1) beds of blue-gray, very sandy, almost quartzitic slate, in many places, approximately a medium-coarse sand- stone with calcareous cement; 2) blue-gray sericitic slat-the dominant rock type of this member-with occasional chloritic beds; and 3) dark gray or virtually black, highly carbonaceous beds, referred to locally as "ribbons."

Jan 8, 1958

By George E. Aiken

Modern high speed bucket wheel excavators (BWEs) can dig materials which power shovels can't handle without blasting. Yet these machines are not used in any large, open pit ore mines in the United States. American mining has been slow to use the wheel's special capabilities of high production volume at low cost, due perhaps to a traditional familiarity with shovels and draglines and/or the lack of data of BWE operation, design and cost. Of course, shovels and draglines can not be replaced by BWEs in all cases, but under suitable conditions bucket wheels can out-perform other conventional excavators and simultaneously permit significant operating savings. The latter aspect will become increasingly important to American mining men because as more low to medium grade orebodies are found in regions of thick overburden, better and cheaper ways of uncovering them must be developed. Typical of such areas are the thick alluvial fans of the Southwest and the glacial drift areas in northern regions. Much of this material would handle well with a wheel excavator without blasting, although ripping might be necessary in some cases.

Jan 1, 1966

Jan 1, 1898

By Richard Amberg

While the old-time melter was satisfied to bring his metal out in the desired condition, and therefore took care to have the slag liquid enough, the importance of a thorough knowledge of the slag is at present recognized in all up-to-date melting-shops. Formerly slag or cinder was considered a necessary evil, accumulating in some mysterious way wherever a man was striving to produce a clean metal. Nowadays we deliberately aim at a well-defined slag, which varies with the nature of the process and the product. In steel-making we need slag for two main purposes, namely, refining and protecting the metal. To refine metal, essentially oxidizing and reducing processes are required, while to protect the metal we need a reducing or, still better, a neutral atmosphere. Although an absolutely neutral condition between steel, on one side, and the containing vessel and the slag, on the other, is an imaginary conception, the various furnaces in use for the production of liquid steel maybe arranged with respect to the attainment of this ideal in about the following order of merit: converter, open-hearth, crucible, and electric furnace. In dealing with the subject we will find it convenient to avail ourselves of the terms of physical chemistry, which yield a simple conception of the matter and an expedient way of expression. Slag and metal at large are not mixable with each other, and we will therefore call them the two " immiscible phases," though there are certain compounds which dissolve in both phases under conditions to be considered later. Reactions be-

Jan 1, 1913

By H. R. Wuthrich

The Metallgesellschaft AG decided in late 1965 to build an Electrolytic Zinc Plant at Datteln (W. Germany). Lurgi-Chemie was entrusted with the engineering and erection of the entire plant. Ground was broken in February 1967 and the operation was started on August 1st, 1968. The new Electrolytic Zinc Plant was designed to produce a minimum of 100,000 metric tons of special high grade zinc and 200,000 metric tons of sulphuric acid. Concentrates from Meggen (W. Germany) and mainly Timmins (Canada) are roasted in two turbulent layer roasters. The sulfur dioxide containing gases are converted in a "Bayer double catalysis unit" to sulfuric acid. The calcine is leached batch wise, the leach residue separated from the pregnant solution by counter-current thickeners and drum filters. For maintaining the sulfate balance a modified jarosite leach is being used. After a two step purification the neutral solution is mixed with spent electrolyte and cooled in unpacked atmospheric cooling towers. Three electrical circuits are supplying the power to the tankhouse, each rated at 30,000 amperes. With a maximum current density of 750 amperes per square meter and a stripping cycle of 24 hours, an average current efficiency of 90 percent is obtained. Cathodes are melted in one induction furnace and cast into shapes, or alloyed with aluminum and copper for die-cast metal.

Jan 1, 1970