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By F. E. Harris

It has been said that carbon is "ubiquitous" with reference to iron alloys. Certainly at temperatures where carbon and iron form the solid solution, austenite, it may be readily added to, or removed from, steel surfaces. Differences in concentration potential are the sole requirements for carbon flow. To measure the rate of carbon flow, a proportionality factor, D, is arbitrarily expressed in units of (length)2 X (time)-'. If the term used for carbon concentration is weight Pet C, as is customary, then a factor must be found, changing this term to One of weight Per unit volume when the diffusion coeficient, D, is used in flow formulae. The determination of D values for carbon is complicated since D varies with the concentration itself. The Matano method has often been employed for systems involving a variant D. This method expresses all evaluation of unsteady flow whereby D is given a relationship with the numerical value of C-x slopes. The author contends that this solution is incorrect, except when D is invariant. The primary purpose of this paper is to support this contention. Here diffusion is controlled under two conditions of flow. The first part deals with the steady state; the second part considers unsteady flow under definite restrictions. Beginning with the fundamental concept, the development is continued until equations for C-x curves are obtained. The solution is then subjected to experimental data. It is realized that a great amount of reliable data is required for a rigorous proof. KO such research is claimed. Instead an attempt is made to set forth the physical significance of the diffusion mechanism, and particularly to express the factors which influence the flow of carbon in austenite. Of equal significance is the implication that gaseous media may be employed with reasonable accuracy in making these determinations. The Steady State Diffusion of Carbon in Au~tenite The fundamental experiment defining diffusion in solid metals may be readily performed for carbon in gamma iron.' For this experiment a thin plate of medium carbon steel is chosen. The surfaces of this plate may be taken as two parallel planes which may be considered infinite for points well in the Center of the planes. These two planes are held at different concentrations of carbon at a constant temperature. This temperature, 1700°F for example, is one where the single phase: carbon in solution with gamma iron, exists. When these conditions are held for a sufficient time the concentration of carbon of the different points of the solid ment down towards its steady state value. At points well removed from the ends, the concentration will remain the Same along planes parallel to the surfaces of the plate.

Jan 1, 1948

By Glenn C. South, Charles C. Russell

A primary factor in the selection of coals for making coke at high temperatures is the amount of pressure the coal will exert upon the oven walls when carbonized in modem by-product ovens.l-3 This factor has become increasingly important in recent years because of demands for increased throughput and higher coke yields. As a result of the increasing necessity for assessing coals in regard to their carbonization pressures, more and more research work is being directed toward developing labora-tory-scale tests for predicting carbonization pressures and for showing how blends of coking coals may be modified to eliminate pressures liable to damage coke-oven walls. The specific reasons have never been defined as to why some blends of coking coals develop dangerous carbonization pressures and others do not, therefore specific procedures to eliminate dangerous pressures could not be prescribed. It is true that the major processes occurring during carbonization have been described by many writers,4 and there is a general agreement on the ideas of the changes that occur as coal is transformed into coke. However, there is little evidence relating the processes occurring during carbonization to the pressure developed and the available evidence is very incomplete and often contradictory. This deficiency arises in part from the fact that the fundamental causes of pressure development have not been defined, at least from experimental data, and in turn this is the result of the lack of satisfactory testing equipment for studying the problem. Operating experience has shown several ways of reducing or eliminating dangerous pressures,5 but probably none of these ways is applicable to all blends of coking coals, and such empirical methods often lead to production of inferior coke. They are trial-and-error methods, not designed to remedy specific causes of pressure development. The number of laboratory-scale testing devices designed to estimate the carbonization pressures that result when coals are carbonized in commercial ovens is probably well over a hundred.6 Few of these instruments have remained in use for any length of time, either because the predictions were not sufficiently accurate or, more often, because too many exceptions were found. Often testing devices are operated without any attempt at duplication of conditions in commercial ovens and erroneous and contradictory results are frequently obtained. Therefore, it has seemed desirable to study the properties of coal itself and to determine any relationships between the properties of the coal and the carbonization pressures developed. Relationship between Properties of Coal and Carbonization Pressure Attempts to determine relationships between various properties of coal and carbonization pressures, for the most parti have been indirect because no satisfactory and reliable laboratory testing device has

Jan 1, 1944

By K. A. Gschneidner, O. D. McMasters

DgIel-ential thermal, nretallographic, and X-ray paramzetric methods were used to establish the Yb-Pb phase dingram. The terminal solid solubilities in the system are less than 0.2 at. pct. Lead additions lower the 792°C transformation tewzperature of pure ytterbiun~ at 787°C by means of an inverted peritectic veaction. Ytterbium additions raise the 327oC melting point of lead to 329°C by means of a perilectic reaction. Three intermetallic compounds Yb2Pb, YbPb, and YbPb, melt congruerttly at 1246", 1116o, and 740°C. respectively. YbsPb3 forms by a peritectic reacliorz at 1250°C. YbzPb crystallizes in the PbCh (C23) type structure and the orthorhombic latliceo constants are a, = 7.478. bo = 5.225, aud C0 = 9.549A. YbsPbs crystallizes in the hfnsSi3 (D8a) type structure. The hexa~nal lattice constants for this phase are a, = 9.325 and co = 6.92d. YbPbl crystallizes in the cubic AuCU3 (Ll2) type structure with a: = 4.8628 + 0.0008A. YbPb is diwrorphic with the structure change occurring al 507°C upon healing. The crystal structures of the two forttzs were not determined. Eulectic reactions occur at 5.1 at. pct Pb and 769oC, 41.5 at. pct Pb and 1086oC, and G8.0 at. pct Ph and 717°C: RELIABLE information concerning the alloying behavior of most of the rare-earth metals is scarce. A systematic study of the rare earth-lead alloy systems now in progress is an effort to supply such information. Determination of the phase diagram of the Yb-Pb alloys is the first step of this study. Variations in the valence of normally divalent ytterbium may be studied by comparing the characteristics of the Yb-Pb alloys to those of the trivalent rare earth-lead and of the divalent alkaline-earth-lead systems. Of particular interest are the melting temperatures of the intermetal-lic compounds since these are known to be high relative to the melting points of the constituent metals. Crys-tallographic and magnetic susceptibility data for the rare earth-lead alloys are to be included in the comparative study. Results from this and subsequent investigations should provide a better understanding of alloy formation. EXPERIMENTAL PROCEDURE Materials. The major impurities in the ytterbium and lead used in this investigation are listed in Table I. The lead was obtained from Cominco Products, Inc., and was specified to be 99.99 pct pure. The ytterbium was prepared in this laboratory by the lanthanum reduction of the oxide followed by a distillation of the ytterbium. Alloy Preparation. The alloys were prepared by

Jan 1, 1968

By M. H. Loveman

THE orebody described below has been rediscovered and developed within the last 3 years. It has, however, been known and worked by the Chinese for hundreds of years. When assay values and size are considered, it contains what is probably one of the largest single bodies of zinc and lead sulphides yet found. The tonnages developed at other places, as at Broken Hill, are much greater but the average zinc and lead sulphide contents are considerably lower than at Bawdwin. Bawdwin is situated in the semi-independent State of Tawng Peng, one of the numerous units which make up the Northern Shan States. These States are under British rule and are generally considered as a portion of Burma. They are governed as a separate administrative unit, however, under the Lieutenant Governor of Burma. Each State is under its own chief, or Sawbwa, who has considerable power over his own subjects. Bawdwin is approximately in latitude N 23°6', longitude E 97°20', about 50 miles south of the nearest point on the Chinese border and 450 miles north of Rangoon (Fig. 1). The period at which mining was first begun at Bawdwin is unknown. The most reliable records have been obtained by deciphering local Chinese inscriptions and from these it is concluded that the work dates back to at least the beginning of the 15th century. The first undoubted reference to the mines by a European is by Symes in 1795. Crawford in 1827 estimated the output of silver from the mines at $600,000 annually. At about the middle of the 19th century the rebellion of the Chinese Mohammedans in the neighboring Chinese province of Yunnan so weakened the power of the Chinese that the incursions of hostile tribes (Kachins) made work extremely dangerous. The mines were finally abandoned by the Chinese about 1868. The closing down of the mines was probably not entirely due to outside causes but may have been influenced somewhat by the increasing difficulty of handling the water, as the workings gradually descended below the water level of the district. Several attempts were made by the Burmese kings, Mindon Min and Thebaw, to resume operations, but because of a

Jan 12, 1916

By M. H. Loveman

The orebody described below has been rediscovered and developed within the last 3 years. It has, however, been known and worked by the Chinese for hundreds of years. When assay values and size are considered, it contains what is probably one of the largest single bodies of zinc and lead sulphides yet found. The tonnages developed at other places, as at Broken Hill, are much greater but the average zinc and lead sulphide contents are considerably lower than at Bawdwin. Bawdwin is situated in the semi-independent State of Tawng Peng, one of the numerous units which make up the Northern Shan States. These States are under British rule and are generally considered as a portion of Burma. They are governed as a separate administrative unit, however, under the Lieutenant Governor of Burma. Each State is under its own chief, or Sawbwa, who has considerable power over his own subjects. Bawdwin is approximately in latitude N 23°6', longitude E 97°201, about 50 miles south of the nearest point on the Chinese border and 450 miles north of Rangoon (Fig. 1). The period at which mining was first begun at Bawdwin is unknown. The most reliable records have been obtained by deciphering local Chinese inscriptions and from these it is concluded that the work dates back to at least the beginning of the 15th century. The first undoubted reference to the mines by a European is by Syrnes in 1795. Crawford in 1827 estimated the output of silver from the mines at $600,000 anually. At about the middle of the 19th century the rebellion of the Chinese Mohammedans in the neighboring Chinese province of Yunnan so weakened the power of the Chinese that the incursions of hostile tribes (Kachins) made work extremely dangerous. The mines were finally abandoned by the Chinese about 1868. The . closing down of the mines was probably not entirely due to outside causes but may have been influenced somewhat by the increasing difficulty of handling the water, as the workings gradually descended below the water level of the district. Several attempts were made by the Burmese kings, Mindon Min and Thebaw, to resume operations, but because of a

Jan 1, 1917

By H. R. Thresh, A. F. Crawley

THIS paper reports the results of viscosity measurements on cadmium and indium undertaken as part of a continuing program of liquid metals research at the Mines Branch, Department of Energy, Mines and Resources, Ottawa, Canada. For several years this work has continued with support from the Canadian Zinc and Lead Research Committee and the International Lead and Zinc Research Organization. In the literature, existing viscosity data for cadmium are conflicting and for indium are scarce. To achieve reliable viscosity values, further work was deemed desirable. Viscosities were measured using an absolute technique applied to an oscillating closed right cylinder of liquid metal. The apparatus, constructed in this laboratory, and the techniques involved in its use have been described in an earlier paper.' In calculating viscosity coefficients from the experimental data. Roscoe's2 mathematical analysis was used. Because accurate viscosity determinations are dependent on accurate density data, and since the available data in the literature are conflicting, the densities of liquid cadmium and indium were also determined in this laboratory by a pycnometric technique. This increased the control exercised over all the variables contributing to the accuracy of viscosity measurements. For both density and viscosity determinations, cadmium and indium of 99.999 pct purity were used. These materials were obtained from Cominco Ltd. In order to suppress excessive evaporation losses and help prevent oxidation, a technique developed in measuring the viscosity of zinc' was used for cadmium. This involved maintaining an atmosphere of purified hydrogen in the viscosimeter during the rela- tively long periods while the experimental temperature was changed and stabilized between individual determinations of the logarithmic decrement. Then, immediately prior to a decrement measurement. the viscosimeter was rapidly evacuated to a pressure of about 2 X 10-6 torr. On the other hand. with indium. no difficulties arise from vaporization or oxidation. In this case. therefore. the apparatus was held under a constant vacuum of about 2 x 10-6 torr. When all sources of random and systematic error have been evaluated, the technique is considered to yield data accurate within 10.5 pct. The viscosity of cadmium was measured to a maximum temperature of 451.8°C and that of indium to 346.5°C. These temperatures are. respectively. 130° and 190°C above the melting points. Two separate runs were made on indium. The results are given in Table I and, when plotted. yield the smooth curves evident in Figs. 1 and 2. Values of A and C to fit the well-known Andrade1 equation were determined by a regression analysis. The equation is: where n = coefficient of viscosity. i = specific volume. T = temperature in °K Despite its empirical nature. Andrade's equation has been shown by many workers to describe accurately the temperature dependence of viscosity. During the current research program, this equation has been found to fit the data precisely for all the metals and alloys that have been studied.5,6 The A and C' values for cadmium and indium are given in Table 11. Comparing the magnitude of the present data with those of previous workers,7-10 as has been done in Fig. 1, it is evident that the results of Fisher and Phillips10 deviate markedly from the rest. With the exception of one point from Gering and Sauerwald,7 all other data agree within ±2.5 pct. However, the agreement between the present results and the work of Menz and sauerwald9 is especially good over the entire experimental temperature range. Such agreement may be expected since Menz and Sauerwald's

Jan 1, 1970

By Harvey T. Kennedy, Charles R. Olson

In many investigations of the performance of petroleum reservoirs the assumption is made that the liquid, if below its bubble-point pressure, is at all times in equilibrium with gas. On the other hand, observations by numerous investigators have indicated that gas-liquid systems including hydrocarbon systems, may exhibit supersaturation to the extent of many hundred psi in the laboratory. Up to the present, there has been no reliable data on which ti judge the actual extent of supersaturation under conditions approaching those existing in petroleum reservoirs. The work reported here deals with observations and measurements on mixtures of methane and kerosene in the presence of silica and calcite crystals. Bubbles were observed to form on crystal-hydrocarbon surfaces in preference to the glass-hydrocarbon interface or to the body of the liquid. Statistically, it was found that the number of bubbles formed per second per square centimeter of crystal surface was a function of the supersaturation only. and the function was evaluated graphically. Supersaturations were observed up to 770 psi, under which condition bubbles formed quickly and with considerable violence. With decreasing degrees of supersaturation, the frequency of bubble formation became less, until at 30 psi supersaturation and lower, no bubbles were observed to form, even though the observation at 30 psi was continued for 138 hours. It was found that silica and calcite crystals had identical effects, within experimental error, in accelerating the formation of bubbles, and that small amounts of water and crude oil had no effect on the results. It is shown that the maximum supersaturation that can exist in a reservoir may be calculated from the data presented and from the area of the rock surface. It is also shown that the number of bubbles formed in the reservoir, in order of magni- tude, may be calculated for any rate of pressure decline imposed on the reservoir by production. The bearing of the number and distribution of bubbles on reservoir performance is discussed. INTRODUCTION A liquid system is supersaturated with gas when the amount of gas dissolved exceeds that corresponding to equilibrium at the existing pressure and temperature. The degree of super-saturation may be conveniently expressed as the difference between the bubble-point of the mixture and the prevailing pressure. Thus, if a mixture having a bubble-point of 1,000 psi at a given temperature exists in single liquid phase at 700 psi at the same temperature. it is supersaturated to the extent of 300 psi. There are many examples of high supersaturations, mostly in aqueous solutions, reported in the literature. Thus, Kenrick, Wismer and Wyatt1 showed that water may be saturated with oxygen, nitrogen or carbon dioxide at 100 atmospheres, and the pressure reduced to one atmosphere without producing bubbles immediately. When liquids are in a state of tension, they may be considered as supersaturated at least to the extent of the tension. The tensile strength of water has been reported as 30 atmospheres by Meyer,1 60 atmospheres bv Budgett. 30 to 50 atmospheres by Temperley and Chambers,4,5 200 atmospheres by Dixon6. and 223 atmospheres by Briggs.7 Vincent8,9 determined the tensile strength of a mineral oil as 45 psi. Gardescu1 maintained pressures for short times in a model reservoir at 115 psi below the bubble-point. It should be noted that the high supersaturations observed were obtained on systems carefully purified to remove particles or surfaces which might promote the formation of bubble; These "nuclei" were considered as contaminants which interfered with the determination of a property of the liquid. In

Jan 1, 1952

By Paul A. Beck, M. N. Parthasarathi

By determining the (220) pole figure for OFHC copper rolled to 96 pct R. .A., the occurrence of four texture components of the type (135) [211] was confirmed. It was found that the total volume fraction of material close to the four symmetrical orientations of this type is larger than the volume fraction of the other components put together. THE rolling texture of copper was described by early investigators1'" as a mixture of components of the (110)[l12] and (112) [11l] types. Other studies, still using the qualitative photographic method of texture determination arrived, instead, at orientations of the type (135) [533] or (135) [211] for copper3'4 and at the closely related "Z-texture" for a fee nickel-iron alloy.5 The prevalence of this type of orientation, near (123) [412], in the rolling texture of aluminum and of copper was later confirmed by means of quantitative diffractometer methods.' However, in a recent paper7 Jones and Fell stated that the (110) [112] and (112) [111] double texture was in better agreement with the measurements of Young's modulus for cold-rolled copper.' These authors also expressed their belief that the "roll texture" can be determined by means of two photographic quasi-fiber texture patterns taken with sheet specimens rotated around the rolling direction and the transverse direction, respectively. Jones and Fell found7 that the results obtained from such patterns for cold-rolled nickel did not agree with any of the orientations mentioned above, but they suggested that the observed diffraction spots may have been brought about by the overlapping of reflections due to the (110) [112] and (112) [11l] double texture components. Jones and Fell concluded that the (123) 14121 type orientation is inconsistent with their patterns. They also stated, without offering any supporting evidence, that this orientation is inconsistent with the (220) pole figure. "Ideal orientations" are often used for a very rough description of the principal orientations encountered in a texture, It is, however, well to remember the fact that, no matter how "accurate", these ideal orientations are only schematic representatives of a continuous distribution9, which often (as in the case of rolled copper) includes extensive orientation spreads. The attempt by Jones and Fell7 to use elastic modulus data in deciding between various ideal orientations in the rolling texture of copper neglects this fact. The inadequacy of two-dimensional "axis density figures" in describing orientation distributions in sheet textures was previously discussed.9 It was also pointed out9 that there is no reliable evidence to prove that orientation distributions derived by the "quasi-fiber method" from rotated sheet specimens are fully equivalent to the corresponding information obtainable from quantitative pole figures. The view that a sheet texture could be adequately determined by means of two photographic quasi-fiber texture patterns is obviously erroneous9. The question as to the consistency with the (220) pole figure of ideal orientations derived from the (111) and (200) pole figures is, on the other hand, certainly very relevant. Since no quantitative (220) pole figure for cold-rolled copper appears to be available in the literature, the following work was undertaken. EXPERIMENTAL METHOD An extruded rod of OFHC copper, 1 in. in diam, was given alternate rolling (30 to 35 pct R.A.) and

Jan 1, 1962

By D. O. Wyble

Five water-driver fields, for which pressure predictions had been made within a few years after discovery, were re-studied when four to five years of additional pressure and production data became available. It was fortnd that forecasts of the pressure in water-dri~fe reservoirs may be subject to considerable unccrtainty. Predictions car be erroneous when there is insufficient presswe history to define the cllaracteristics of the aquifer, and when there are errors in the pressure, production or geologic data. INTRODUCTION The efficient operation of an oil or gas reservoir requires that the important characteristics of the reservoir be determined soon after its discovery. It is especially desirable to evaluate the pressure-production relationship quickly, for this relationship provides a basis for deducing the type of production mechanism that is operative, and for making pressure predictions. The pressure predictions, in turn, provide a basis for calculating efficient rates of production, determining whether water or gas should be injected, etc. The importance of pressure prediction is such that forecasts should be made as accurate as possible, and the limits of error well defined. Historically, pressure forecasts for some fields have proved very accurate, while for others the forecasts were so erroneous that they resulted in the adoption of wrong, or at best, unnecessary production practices. Pressure predictions made for water-drive fields are especially subject to error. Accurate forecasting for these fields requires that much be known not only about the reservoir proper but about the adjacent water-filled rock as well. The water-containing rock, or aquifer, may extend for many miles, and often there is only meager data regarding its thickness, permeability and porosity. Much of the information must be inferred from the previous pressure behavior of the reservoir. A brief pressure history may provide little information about the characteristics of the aquifer. Hence, pressure predictions made early in the life of water-drive fields can be incorrect. The work described in this paper was done to determine the degree of reliability which can be expected of pressure predictions made within a few years after water-drive fields are discovered. Five fields, for which the original pressure predictions had been based on less than seven years' history, were re-examined with the aid of four to five years of additional pressure data. Where the predictions were inaccurate, the reasons for failure were ascertained. The studies were accomplished by use of the electric reservoir analyzer.' The analyzer was first adjusted to repeat the original pressure-production match using the same values for the various parameters as were used in the original study. Then, the actual production rates experienced during the time elapsed since the initial study were set into the analyzer, and the pressure behavior indicated by the machine for this period was compared with that which actually OCcurred. Where the pressure profile traced out by the analyzer deviated from the observed field behavior, the analyzer was readjusted to obtain a better over-all match. The old and the new solutions were compared to determine the reasons for any differences. COMPARISON OF PREDICTED RESERVOIR PRESSURE BEHAVIOR WITH ACTUAL PERFORMANCE Field A The original pressure-production match is entirely adequate as evidenced by the pressure match of the field's history subsequent to Jan., 1952 (see Fig. 1)'.

By E. F. Sumner, C. K. Eilerts

A partial differential equation was developed and programmed to compute the cumulation and flow of the liquid phase of a gas-condensate fluid. It was found that such cumulation near the wellbore may attain saturations permitting liquid flow within periods of the order of 1 day. The radius at which this saturation obtains advances toward the external reservoir boundary with continued recovery, although it may move only 2 to 5 percent of that distance during the productive life of the well. This relatively high saturation can cause a serious dimunition in delivery capacity. The pressure dilferential required for flow of gas through a formation with such saturation may be as much as three times greater than the corresponding differential in a formation where saturation is less than 2 percent. Because of the radial geometry, total reservoir pressure differential required for flow with a zone of relatively high liquid saturation about the well was indicated to be two to three times greater than without the saturation. INTRODUCTION A computing program developed by the authors 1 to integrate the partial differential equation for transient radial flow of gas-condensate fluids required a prevalued function, W(Po) = kD(p0)/M(p0)z0(Po).......(1) related to cumulation of condensate in pores of the reservoir as pressure declines. Methods were available for relating mobility to saturation, saturation to liquid-vapor volume ratio, liquid-vapor volume ratio to pressure and, hence, mobility to pressure to obtain W(pD). However, certain assumptions had to be made in advance of program execution concerning movement of the liquid phase and change in radial distribution of liquid saturation as recovery progressed. Because reservoir fluid mobility and related pressure gradients are markedly dependent on liquid saturation, it was desirable to eliminate the necessity for these assumptions and in this respect improve the reliability of a result obtained by integration. Experimental research was begun to determine the relationship of variables that control the reservoir flow of low liquid-vapor ratio fluids. With the porous medium partly saturated, permeability to a two-phase flowing fluid could not be measured because the viscosity was unknown. Viscosity could not be measured without knowing permeability of the liquid-containing medium; but mobility, the ratio of permeability to viscosity, was measurable. This property, and liquid-vapor volume ratio of the flowing phases, have values determined by nature of the fluid and porous medium and, in addition, were found to be pressure, velocity and saturation dependent. A program developed by Kniazeff and Naville 2 for computing multicom-ponent, two-phase flow used polynomials to represent saturation dependence of permeabilities for gas and for liquid phases, and an effluent viscosity constant under reservoir conditions. The authors developed a program based on a partial differential equation of similar mass balance origin but designed to represent distribution of an unlimited number of components between gas and liquid phases utilizing the experimental information available as to variable dependence. Attention was given to liquid-vapor volume ratio of the flowing phases, a property which is essential as a liquid saturation boundary condition. A program for computing implicitly saturation increase at uniform intervals along the drainage radius was combined with an existing program for calculating pressures, and the two were used alternately in an iterative solution for both saturations and pressures. The function W(pD) needed for calculating pressures was replaced by the ratio of mobility to compressibility factor. BASIC EQUATIONS The partial differential equation for calculating

By W. O. Philbrook

An engineering analysis indicates that the coke rate in present blast-furnace practice is set not by chemical or thermal needs but to give adequate charge permeability for economical driving rates. An equation showing interrelations among pressure drop, gas flow, and charge characteristics has been derived. Flooding conditions and the location of the fusion zone are discussed. Maximum ore size is probably limited by chemical re-ducibility rather than by heat transfer. THE intention of this paper is to show that the ].imitations on the production rate and coke requirement of the iron blast furnace are not primarily chemical or thermal in nature but are related to characteristics of the burden and operation that govern gas flow, heat transfer, and stock movement. A semiquantitative analysis will be developed in terms of standard engineering principles to give a useful picture of the relative importance of physical and mechanical factors in contrast with the chemical features of the process that are more commonly emphasized. Most of the details of calculation have been omitted in the interest of brevity and to avoid submerging the rnain points in a sea of arithmetic. Numerical values have been arrived at by objective methods from reported operating data or by reasonable estimates of material properties where exact data are lacking and then tested to see how well they fit practice, rather than by working backward to find what assumptions are needed to give the desired answers. The analysis is oversimplified in many ways because exact engineering relations have not yet been studied for bed distributions as complex as are known to exist in the blast-furnace stock column. One objective of this paper is to show that the blast furnace, in spite of its complexity, can be at- tacked by engineering methods in the hope that this viewpoint will stimulate the kind of research needed for a more exact treatment. The basic ideas and many of the conclusions presented are qualitatively well known. A careful literature survey to credit the source of all observations not original to the author would indeed be voluminous, and such has not been attempted. T. L. Joseph's Howe Memorial Lecture' gives an excellent background of what is known about the internal workings of a blast furnace. Other important reference works or sources of specific information will be noted. It is hoped that the present paper will contribute something new, in method of attack and interpretation, that will aid in a clearer understanding of how to operate the blast furnace to best advantage. Factors Limiting Production and Coke Rates The rate of combustion of coke in a blast furnace, as in any fuel bed, is exactly proportional to the rate at which air is supplied. It is axiomatic, then, that the production rate of a furnace is limited by the rate at which it will take wind, i.e., burn coke, and the amount of coke that must be burned at the tuyeres to make a ton of iron of suitable composition. These two possible limiting factors will be considered briefly in the order mentioned. One common restriction on wind rate is flue-dust production. Since the volume of top gas is nearly proportional to the blast volume (by a factor of about 1.35 on a dry basis), an increased wind rate causes a correspondingly increased linear velocity of top gas in the throat of the furnace. The higher

Jan 1, 1955

By Cyril Wells, Robert F. Mehl

The practical importance of a knowledge of the rates of diffusion of carbon and of alloying elements in steel has often been pointed out.l,13 This importance lies chiefly, though by no means only, in the study of carbufizing and in the study of reactions involved in the eutectoid inversion in steel. The present paper is one of a series in which the rates of diffusion of carbon and of alloying elements in ?-Fe and their mutual effects are measured with precision. The present paper reports the results of measurements of diffusion coefficients D of manganese in ?-Fe over wide ranges of temperature, and concentration, and of the effect of carbon and impurities and of grain size upon these diffusion coefficients.‡ Data on the rate of diffusion of manganese in ?-Fe have been reported by Fry2 and by Paschke and Hauttmann.3 Claussen4 calculated the diffusion coefficient D from Fry's data as 3 X 10-10 sq, cm. per set. at 960º, which will be shown to be incorrect by many orders of magnitude. Paschke and Hauttmann gave a rough value of 9.6 x 10-8 Sq. cm. per set. at 14000. Neither of these workers considered the variation of D with concentration and with temperature, and neither studied the effect of carbon. Method and Materials Method.—The method employed is identical with that used earlier.5 Owing to the volatility of manganese and the consequent loss of manganese from the outer surfaces of the welded diffusion bars, these surfaces were discarded. The diffusion anneals were performed in argon, except One (test 18) in which hydrogen was employed for purposes noted below. The temperatures reported are accurate to about 3" and constant within 1°C; the diffusion times are reported to the nearest half hour. The specimens were furnace-coo1ed after the diffusion ation, at about 2° per min. Layers, usually 0.004 in. thick, parallel to the welded interface, were machined from the specimens after the diffusion anneal and analyzed for manganese to 0.I Per cent Mn; the distances of these layers from the interface was measured to ±0.0002 in. The concentration-penetration curves obtained were analyzed by both the Grube and the Matano solutions.8 The D values calculated by these two methods do not differ appreci000. The Grube solution was used except in tests in which the effect of concentration upon D was greater than so per cent; in such cases the Matano method, which explicitly provides for the variation of D with concentration,' is the more reliable. In general, the number of layers machined from the zones of variable composition were large enough to permit the use of the average layer composition as that of the center of the layer. In 3 of the 3' tests, however, this is not justified, and the D values

Jan 1, 1941

By Cyril Wells, Robert F. Mehl

The practical importance of a knowledge of the rates of diffusion of carbon and of alloying elements in steel has often been pointed out.l,13 This importance lies chiefly, though by no means only, in the study of carbufizing and in the study of reactions involved in the eutectoid inversion in steel. The present paper is one of a series in which the rates of diffusion of carbon and of alloying elements in ?-Fe and their mutual effects are measured with precision. The present paper reports the results of measurements of diffusion coefficients D of manganese in ?-Fe over wide ranges of temperature, and concentration, and of the effect of carbon and impurities and of grain size upon these diffusion coefficients.‡ Data on the rate of diffusion of manganese in ?-Fe have been reported by Fry2 and by Paschke and Hauttmann.3 Claussen4 calculated the diffusion coefficient D from Fry's data as 3 X 10-10 sq, cm. per set. at 960º, which will be shown to be incorrect by many orders of magnitude. Paschke and Hauttmann gave a rough value of 9.6 x 10-8 Sq. cm. per set. at 14000. Neither of these workers considered the variation of D with concentration and with temperature, and neither studied the effect of carbon. Method and Materials Method.—The method employed is identical with that used earlier.5 Owing to the volatility of manganese and the consequent loss of manganese from the outer surfaces of the welded diffusion bars, these surfaces were discarded. The diffusion anneals were performed in argon, except One (test 18) in which hydrogen was employed for purposes noted below. The temperatures reported are accurate to about 3" and constant within 1°C; the diffusion times are reported to the nearest half hour. The specimens were furnace-coo1ed after the diffusion ation, at about 2° per min. Layers, usually 0.004 in. thick, parallel to the welded interface, were machined from the specimens after the diffusion anneal and analyzed for manganese to 0.I Per cent Mn; the distances of these layers from the interface was measured to ±0.0002 in. The concentration-penetration curves obtained were analyzed by both the Grube and the Matano solutions.8 The D values calculated by these two methods do not differ appreci000. The Grube solution was used except in tests in which the effect of concentration upon D was greater than so per cent; in such cases the Matano method, which explicitly provides for the variation of D with concentration,' is the more reliable. In general, the number of layers machined from the zones of variable composition were large enough to permit the use of the average layer composition as that of the center of the layer. In 3 of the 3' tests, however, this is not justified, and the D values

Jan 1, 1941

By H. Hooykaas

A few years ago Marsal published a method of predicting oil recovery as a function of time for an edge-water-drive reservoir with several rows of wells.' The method is based solely on oil- and water-production data obtained during a short period for the first row of wells and the gross productions (past and future) of all wells. This paper presents a streamlined version of the original publication and experimental evidence showing the reliability of this version. For this purpose scaled experirnents were performed in a large model (750 X 500 X 23 cm, 24.4 ft X 16.2 ft X 8.9 in.) in which edge-water-drive reservoirs with three rows of production wells were simulated. From the results of the experiments it is concluded that the method gives a fairly accurate prediction of the future production behavior of the reservoir and enables us to select the most profitable production plan. Results obtained with the method were always slightly conservative. INTRODUCTION The calculation method developed by Marsal aims at forecasting future reservoir behavior.' It can be applied to floods in which a number of down-dip wells are rapidly going to water. Essentially it is a method for predicting the future behavior of the up-structure wells on the basis of the observed behavior of the down-structure wells. As such, the method is especially useful for predicting behavior of edge-water drives toward several rows of wells. The requirement to be met for justifying the approach is identity of production mechanism in all regions of the reservoir. The attraction of the method then lies in the fact that it applies even when we have no complete description of the prevailing production mechanism. The original publication was in the German language and for this reason, perhaps, did not attract widespread attention. In our opinion it deserves to do so because it does offer in a simple way results which are in fair agreement with observed data. The aim of the present paper is to bring the method to the attention of a wider audience. The method in its most simplified form is reviewed and experimental data in support of it are presented. PRINCIPLES To show Marsal's principle. we will first write the continuity equation for very simple conditions, linear flow (in the positive x-direction) in an incompressible porous body [cross-section A(x), porosity +(x)], saturated with incompressible fluids (oil saturation S). When the oil in this formation is displaced by water, injected at x = 0 (inlet face), we get where q(t) is the total gross displacement rate and f the fractional oil flow. The equation can be solved if we make the assumptions: (1 ) that the fractional oil flow (f) is a univalent function of saturation (S); and (2) that the function is the same throughout the porous medium. Then: f = f(S) Solving this equation with the method of characteristics, we obtain

Jan 1, 1966

By Leon W. Dupuy

INTRODUCTION A BRIEF elemental discussion of the fundamental factors involved in diamond drilling often fills a need, particularly when a mine operator is contemplating for the first time an exploratory drilling campaign. Mr. James A. Barr, of the Mining Methods Committee of the Institute, has suggested that many engineers must undertake a drilling program of one kind or another and, in the case of diamond drilling, sometimes even are at a loss as to how to start correspondence. The Bureau of Mines has acquired much experience in managing exploratory diamond-drilling activities. Its activities in diamond drilling included exploring for potash in Texas, Utah and New Mexico 1-4 during the 1920's. The Strategic Minerals Exploration program was started in 1939 and was materially expanded during the war to include critical and essential minerals. At the peak of its war-time activity more than 200 engineers were employed, a majority of whom supervised diamond drilling. Many of them had little experience with such work prior to their employment with the Bureau, and it was necessary to instruct them in their duties. The purpose of this paper, therefore, is to present the fundamentals of exploratory diamond drilling from the viewpoint of management in such a way that they will serve as a basis on which those beginning exploratory diamond drilling may build an experience and acquire ability to direct exploration as they gain that experience. SELECTION OF METHOD OF DRILLING Selection of the method of drilling is governed by the type of material to be penetrated and by the type of sample needed to determine the quality and importance of a deposit. Types of drills that might be used for a given job include diamond drills, churn drills, hand auger drills, power auger drills, bucket drills, and rotary drills (sometimes called "seismograph rigs"). Each type has a specific field in which it is most useful. While the Bureau of Mines utilized all the types of drilling mentioned, diamond drilling was used on a majority of its exploratory projects. FACTORS GOVERNING SELECTION OF DIAMOND DRILLING The prime consideration in selecting a method of drilling is first to determine what results are desired and then to choose a method that will furnish reliable data in the ground to be penetrated. Use of diamond drills permits recovery of a core as well as sludge at a comparatively low cost. The core provides an excellent means of studying the formation being drilled and furnishes much information that would be difficult to obtain otherwise. Diamond drills will recover a satis-

Jan 1, 1947

By J. F. Butler

Boron nitride, BN, has been identified in boron low-carbon steels by means of light microscopy, electron microscopy and diffraction, and chemical analysis. This boron nitride is responsible for strain aging suppression in these steels through the removal of nitrogen from solution; however, small oxidizing potentials which result in deboronization In the austenitic temperature range also result in boron nitride decomposition and the subsequent occurrence of nitrogen strain aging. THE addition of boron to low-carbon steels is an effective means of eliminating the detrimental effects of strain aging;',' however, the mechanism by which boron suppresses strain aging has not been established. In studying the effect of heat treatment on the strain aging of boron low-carbon steels, Butler3 found that no detectable nitrogen was present in the ferrite solid solution after various heat treatments even though the total nitrogen analyses of the steels were 0.003 pct N. Apparently the function of boron in suppressing strain aging is the removal of nitrogen from solution to form a relatively stable second phase. A clue to the identity of this phase was found by Speight4 who extracted from an aluminum-killed boron steel an acid insoluble residue which contained boron and nitrogen in proportions corresponding to the compound, BN. Shyne and Morgan5 found that the addition of nitrogen to a hardenable boron steel lowered its hardenability in a manner which suggest-d the presence of nucleating particles (presumably BN) even at high austenitizing temperatures. Although this indirect evidence for the presence of boron nitride in boron steels has been found, the compound was not identified metallographically as a separate phase in these steels. Because boron has an affinity for oxygen comparable to that of silicon,5 boron steels must be thoroughly killed with aluminum in order to prevent the reaction of boron with oxygen.7 The affinity of boron for oxygen also is demonstrated through the ease of deboronization of a boron steel in an oxidizing atmosphere. Digges, Irish, and Carwile8 found that a mixture of wet natural gas and air caused both deboronixation and decarburization of a boron steel at 1900°F. The boron content rose at the surface of the steel due to the formation of boron oxide. Shyne and Morgan9 encountered deboronization at much lower oxygen potentials; loss of boron occurred in steels treated at 1750o F under argon purified to 0.0014 pct 0, even though decarburization did not occur. Boron oxide, B2O3, is much more stable than the nitride, BN, as is indicated by the standard free energies of formation at 980oC: -235 kcal per mol of B2O3 (liquid) and -28 kcal per mol of BN (crystal). It is evident that the oxygen potential must be kept low in the presence of BN in order to prevent its decomposition and the subsequent formation of B2O3' The purpose of the work described in this paper was to identify the nitride phase responsible for the removal of nitrogen from solution and to study its stability under oxidizing conditions. IDENTIFICATION OF BN In order to identify the phase containing boron and nitrogen, several alloys high in boron and nitrogen were made up in a small vacuum furnace. In alloys 3 and 4, Table I, electrolytic iron was used as a charge material. Boron additions were made in the form of 18 pct B ferro-boron after the iron was molten. In the case of alloy 3, the charge was solidified at this point; for alloy 4, nitrogen at 1 atm pressure was admitted over the melt before it was

Jan 1, 1962

By H. H. Kellogg

Available high-fernperatzwe equilibrium measurements and other thermochernical data have been critically reciewed for sulfation reactions of the type: Recommended values for log K and ?Fo as junctions of temperature are given for thirty-six suck reactions involving twenty-six different metals. Methods of calculation and choice between conflict-ing data are discussed. SELECTIVE sulfation now enjoys a considerable renaissance as a metallurgical unit process due, in large part, to the available of the fluid-bed re- actor—a device capable of the close control of temperature and gas composition necessary for a successful sulfation process. An additional need, however, if sulfation chemistry is to be approached in a scientific manner, is a reliable body of data on the equilibrium and kinetics of sulfation reactions in simple and complex systems. This paper offers a critical review and compilation of equilibrium data on pure sulfates (simple systems). The last such review, by K. K. Kelley in 1935:30 has proven itself most useful, but the existence of many new data makes necessary a re-evaluation of the available information. METHODS OF CALCULATION For a simple sulfation reaction such as MS04(c) = MO(c) + SO3 [1] there are two approaches one may take toward establishing the value of ?Fo or K as a function of

Jan 1, 1964

By C. G. Fink, G. L. Putnam

The dissolution of gold by cyanide solutions was studied by determining the time required for the solvents to dissolve gold leaf. Minute traces, even 0.5 ppm, of sulphide ion retard the dissolution of gold, and this behavior cannot be accounted for by the presently accepted hypotheses involving oxygen-depletion or thiocyanate formation. On the other hand, traces of the salts of lead, bismuth, mercury, and thallium considerably accelerate the dissolution. The beneficial effect of lead is dependent upon the pH and cyanide ion concentration of the solution. ALTHOUGH cyanide solvents are used very ex-x*. tensively for the recovery of gold from ores and concentrates, the normal rate of solution of the precious metal as determined by Barsky, Swainson, and Hedley,1 and others2 is less than about 3 mg per sq cm of exposed gold surface per hour, corresponding to a corrosion depth of approximately 1.5 microns (0.00006 in.) per hr. Although the slow rate may be increased to some extent in certain cases, as, for example, when the the gold is partially imbedded in iron pyrites,3 the leaching operation is generally the most time-consuming step of the cyanide process. Frequently it is necessary for the leaching solvents to remain in contact with the ores for 50 to 200 hr in order to dissolve all of the gold particles.' Not only does the slow solution rate cause some increase in the capital costs, but the cyanide consumption also may be increased because of vaporization of hydrocyanic acid and secondary reactions with minerals such as malachite (CuCO3 • Cu(OH)2), and pyrrhotite, which often are associated with gold. It is not surprising that numerous attempts have been made to accelerate the dissolution of gold in cyanide solutions. Experimental Gold Leaf Test: The gold leaf test was apparently originated by M. Faraday, who, by means of it, discovered that dilute cyanide solutions would dissolve gold readily in the presence of oxygen. The usefulness and reliability of the test have been discussed elsewhere.5,6 Essentially, the method consists of determining the time required for 5-ml portions of cyanide solvents to dissolve squares of 23 carat gold leaf, 0.5 cm on edge, when shaken in 10-ml test tubes with the solvents. The weight of gold leaf per test was 0.051 mg as determined by the direct weighing of a leaf 8.6x8.6 cm (weight = 15 mg) and measuring the area of the test sample (0.25 sq cm). Gold leaf is of remarkably uniform thickness.6 Since gold leaf, like native gold, contains small amounts of copper and silver, the results are comparable with those one might expect in cyaniding gold ores. As six or more tests can be made simul- taneously, the relative efficiencies of the solvents can be evaluated readily. All dilute solutions of lead, bismuth, thallium and mercury salts were prepared by the ordinary dilution method used by chemists. Our C.P. sodium cyanide and buffering reagents had no detectable amounts of either sulphide ion or heavy metals. Soluble Sulphides in the Cyanide Process: The action of soluble sulphides is of interest in the study of the dissolution of gold in cyanide solutions. That gold ores which contain compounds of arsenic and antimony often are not amenable to direct cyanide treatment is well known, and it said that arsenic and antimony are "cyanicides."7 It is commonly believed that part of the sulphur content of such ores is soluble in alkaline solutions to give sulphide ion, which reacts with the free cyanide content of the leaching solutions to form inert thio-cyanates or reacts with the dissolved oxygen to form sulphites or sulphates.8 A purpose of this paper is to demonstrate that sulphide ion may behave in a manner that cannot be explained by either the oxygen-depletion or thiocyanate formation theories and to prove directly that concentrations of sulphide ion which cannot be detected even by colorimetric methods may retard the dissolution of gold.

Jan 1, 1951

By C. G. Fink, G. L. Putnam

The dissolution of gold by cyanide solutions was studied by determining the time required for the solvents to dissolve gold leaf. Minute traces, even 0.5 ppm, of sulphide ion retard the dissolution of gold, and this behavior cannot be accounted for by the presently accepted hypotheses involving oxygen-depletion or thiocyanate formation. On the other hand, traces of the salts of lead, bismuth, mercury, and thallium considerably accelerate the dissolution. The beneficial effect of lead is dependent upon the pH and cyanide ion concentration of the solution. ALTHOUGH cyanide solvents are used very ex-x*. tensively for the recovery of gold from ores and concentrates, the normal rate of solution of the precious metal as determined by Barsky, Swainson, and Hedley,1 and others2 is less than about 3 mg per sq cm of exposed gold surface per hour, corresponding to a corrosion depth of approximately 1.5 microns (0.00006 in.) per hr. Although the slow rate may be increased to some extent in certain cases, as, for example, when the the gold is partially imbedded in iron pyrites,3 the leaching operation is generally the most time-consuming step of the cyanide process. Frequently it is necessary for the leaching solvents to remain in contact with the ores for 50 to 200 hr in order to dissolve all of the gold particles.' Not only does the slow solution rate cause some increase in the capital costs, but the cyanide consumption also may be increased because of vaporization of hydrocyanic acid and secondary reactions with minerals such as malachite (CuCO3 • Cu(OH)2), and pyrrhotite, which often are associated with gold. It is not surprising that numerous attempts have been made to accelerate the dissolution of gold in cyanide solutions. Experimental Gold Leaf Test: The gold leaf test was apparently originated by M. Faraday, who, by means of it, discovered that dilute cyanide solutions would dissolve gold readily in the presence of oxygen. The usefulness and reliability of the test have been discussed elsewhere.5,6 Essentially, the method consists of determining the time required for 5-ml portions of cyanide solvents to dissolve squares of 23 carat gold leaf, 0.5 cm on edge, when shaken in 10-ml test tubes with the solvents. The weight of gold leaf per test was 0.051 mg as determined by the direct weighing of a leaf 8.6x8.6 cm (weight = 15 mg) and measuring the area of the test sample (0.25 sq cm). Gold leaf is of remarkably uniform thickness.6 Since gold leaf, like native gold, contains small amounts of copper and silver, the results are comparable with those one might expect in cyaniding gold ores. As six or more tests can be made simul- taneously, the relative efficiencies of the solvents can be evaluated readily. All dilute solutions of lead, bismuth, thallium and mercury salts were prepared by the ordinary dilution method used by chemists. Our C.P. sodium cyanide and buffering reagents had no detectable amounts of either sulphide ion or heavy metals. Soluble Sulphides in the Cyanide Process: The action of soluble sulphides is of interest in the study of the dissolution of gold in cyanide solutions. That gold ores which contain compounds of arsenic and antimony often are not amenable to direct cyanide treatment is well known, and it said that arsenic and antimony are "cyanicides."7 It is commonly believed that part of the sulphur content of such ores is soluble in alkaline solutions to give sulphide ion, which reacts with the free cyanide content of the leaching solutions to form inert thio-cyanates or reacts with the dissolved oxygen to form sulphites or sulphates.8 A purpose of this paper is to demonstrate that sulphide ion may behave in a manner that cannot be explained by either the oxygen-depletion or thiocyanate formation theories and to prove directly that concentrations of sulphide ion which cannot be detected even by colorimetric methods may retard the dissolution of gold.

Jan 1, 1951

By A. J. WADHAMS

THE relative importance of things is a fascinating subject for thought. As we look about us we realize the Creator of all things has provided the metals for our use, each in the quantity needed-iron in vast quantities gold in small quantities. Had gold been given us in the quantities of iron, the mechanical age mould Eave been very different. You may find some pleasure in running over in your mind this question of the quantity available of an element and man's need of it in the scheme of things. Nickel in this sense is a middle group element. It was not essential to man's early development. Its usefulness dates back only about one hundred years. The quantity available to man has increased as his needs in- creased. On two occasions more nickel became available than was needed and on both of these occasions the ex- cess was soon absorbed by new and useful developments.

Jan 1, 1929