Search Documents

By J. Chipman

There is no better way of paying tribute to the memory of a scientist than by developing and carrying forward those ideas which he has contributed to science and which are for us the very essence of his immortality. For a lecturer who has not had the great privilege of stdying under Professor Howe or 'ven of knowing him in person, these ideas must be transmitted through the printed word. It is our great good fortune that Professor Howe left to us a rich heritage of publication, not only in his classic monograph on the "Metallography of Steel and Cast Iron" but in a wealth of earlier hooks and papers in the transactions of this Institute arid of other scientific and engineering bodies. An outstanding characteristic of this published record is the great breadth of interest and of vision which it portrays. His was riot a narrow specialization in only the scientific aspects of ferrous metallographg. On the contra1y many of his important contributions had to do with a far broader field of metallurgicial endeavor. He insisted that his students be well grounded in 1 he fundamentals underlying the whole field and not led into the narrow groove of specific applications. Among his first major publications we find papers on copper smelting, extraction of nickel, the efficiency of fans and blowers, thermic curves of blast furnaces, the cost, of coke, and the manufacture of steel. These are the papers of a metalhurgical engineer and it was among engineers that Henry Marion Howe made his early and well-merited reputation. These early engineering contributions display very clearly the strongly sctientific inclination of their author. The classic work on "The Metallurgy of Steel" published in 1890 contains a thorough and critical discussion of all that was known at the time concerning the alloys of iron and of what we would now call the physical metallurgy of steel. In addition it describes steel-making processes in use and some that had become obsolete, and points out in critical fashion the reasons for success and failure. Steel mill design and layout were included as well as some pertinent discussion of refractories. The book is indeed an embodiment of one of Howe's outstanding characteristics—breadth. It is both the science and the engineering of steel production as known in that day. One of Howe's earliest technical papers was entitled "What is Steel?" That was nearly seventy-five years ago when many new processes and new kinds of steel were being developed. The time was ripe for such a question and the answers which Howe was able to give were helpful in understanding the phenomena of heat treatment. Twenty-five years ago Professor Sauveur repeated the question as the title of the first Henry Marion Howe Memorial Lecture. It seemed to him that this question, "What is Steel?," had served as Howe's motto throughout the remainder of his life. Today I shall present for your consideration a question of another sort: "What is Sletallurgy?" Perhaps it is not too much to hope that in the answer we may obtain a clearer and possibly broader view of the nature of our science and our profession. The time is ripe for giving careful consideration to what we mean by metallurgy. If our Metals Branch is to become in fact an American institute of Metallurgical Engineers, it is essential that we understand what is meant by metallurgical engineering. I am convinced that the best interests of the profession have not been served by a narrow interpretation of these terms. We must now place emphasis on the breadth of metallurgy as a science and as an engineering profession. With its usual brevity and wit. Webster's dictionary definesmetallurgy as "the science and art of extracting metals from their ores, refining them and preparing them for use." I shall riot assume that the words "science" and "art" and "metal" are so well understood as to require no defining but others among our contemporaries are better qualified than either your lecturer or the dictionary to present the broad meanings of these terms. When we say that metallurgy is among the oldest of the arts we are not classing it with painting or sculpture or music but rather with the making of tools or weapons or the building of bridges or chariots or cathedrals. In short we are saying that metallurgy is among the oldest of the engineering professions. The question " What is metallurg ? " has been one of rather more than ordinary concern to those of us who have the task of developing a curriculum for the education of students in this field. This development has been going on in a number of universities over a period of some years. but there seems to be as yet no unanimity as to what such a curriculum should contain. I believe there is fairly complete agreement that it must be founded upon sound

Jan 1, 1950

By L. W. Emery

Undergrorlnd combustion operations were initiated in a 60-acre Bartlesville sand "shoe-string" reservoir in Allen Connty, Kans., in 1956. Tests in separate patterns were conducted using various co~nbinations of air and recycle gas to propagate combustion fronts from the injection toward the producing wells. These patterns were made up of 6 injection and 20 prodrrcing wells Gas and liquid prorluctiorz from each pattern was measured on an individual-well basis, and comparisons were made between the three patterns to ascertain the relative effects of injected gas composition on production behavior. Breakthrough of the combustion front at a well was characterized by an increase in water production from the well followed by an increase in bottomhole temperatrrre to approximately 250" F. After burning fronts had broken through at five producing wells, operations were terminated in 1960. From the total project approximately 79,000 bbl of oil were produced during thermal operations at a cumulative produced GOR of 23 Mcf/bbl. No appreciable change in the character of the produced crude was observed. Combustion in the reservoir was maintained with injected gas compositions ranging fronz 6 per cent oxygen in recycle gas to 100 per cent air. lnjectiotz of large quantities of recycle gas resulted in higher producing GOR's from offset wells than were measured from a pattern into ~vhich straight air ~vas injected. The air required to move the combustion front through I acre-ft of reservoir was computed to be 20 MMscf. This valrre was found to be relatively independent of the quantities of recycle gas injected. The recovery efficiency from the swept area was esti~izated to be about 59 per cent. Areas swept were similar in shape to tlzose obtained with a laboratory potentiometric model. Samples of sund taken from behind the burning front by coring indicated almost total oil removal from the sand. Petrographic analysis of the core samples indicated that the sand had been heated to peuk temperature of rlbout 1,200" F. No rignificant difference in peak temperature was forrnd in two areas where compositions of injected gas were quite different. Compression costs for thermal recovery were estimated to be $1,20/bhl of produced oil. INTRODUCTION The use of the "forward combustion" process as an oil recovery method has received a great deal of attention. This method involves ignition of the formation in an injection well, followed by propagation of a combustion front through the reservoir. Combustion is maintained by the injection of an oxygen-containing gas to react with reservoir hydrocarbons. As the flame front progresses through the reservoir, oil and formation water are vaporized, driven forward in the gaseous phase and recondensed in the cooler part of the formation. In turn, the condensed fluids push oil into the producing wellbores. Completed field tests of the process were first reported by Kuhn and Koch,' and by Grant and Szasz.' Results from other tests have since been reported by Walter,3 by Moss, White and McNeil,' and by Gates and Ramey." ach of these tests essentially utilized a single injection well surrounded by four or more producing wells. Sinclair Research, Inc., elected to do field experimental work using a number of test patterns in a single field in order that comparisons between various operating schemes could be made. The site selected and purchased in 1955 for this experimental work was a 60-acre Bartlesville sand reservoir located in Allen County, Kans. Combustion operations were initiated in mid-1956. Between that time and termination of the project in mid-1960, combustion fronts were propagated from injection wells to producers in three separate well patterns, using different mixtures of air and recycle gas. The test was terminated before sweep of the three patterns was complete so that information about the effect of combustion on the swept areas could be obtained by coring. Results from the test in the form of injection and producing well performance have been carefully recorded, and these form the general basis for this paper. DESCRIPTION OF RESERVOIR The reservoir in which the combustion tests were conducted is a Bartlesville sand "shoe-string", typical of a number of small reservoirs in Southeastern Kansas. Average reservoir characteristics are shown in Table 1. Fig. 1 is an isopachous map of the producing sand showing the reservoir to be approximately 400-ft wide and 2,500-ft long. Maximum net productive sand thickness is 21 ft. Fig. 2 shows a typical core analysis obtained by coring with water-base mud. The reservoir has no appreciable dip and is closed on the sides by degradation of sand into shale. The main body of sand is heavily laminated with shale stringers, which are not continuous between wells. The main reservoir is overlain by 30 to 40 ft of laminated low-permeability sand and shale streaks. No information is available on the original properties of

By K. G. Wikle, W. W. Beaver

The factors which control the rate of dissolution of pure gold in cyanide solution were studied both directly and through measurement of solution the current-potential curves for the anodic and cathodic portions of the reaction. The mechanism of dissolution is probably electrochemical the reaction in nature, and the rate is determined by the rate of diffusion of dissolved oxygen or cyanide to the gold surface, depending on their relative concentrations. The significance of the results and the effects of impurities are considered. ALTHOUGH the dissolution of gold in aerated cyanide solutions has been used as an industrial process for treatment of gold ores since the late nineteenth century, the factors which determine the rate of the reaction have never been identified unambiguously. Studies of the rate of dissolution by Maclaurin,1 White,2 Christy,3 Beyers,4 Thompson,6 and others are contradictory in their conclusions; some claiming that diffusion of the reactants to the gold. surface controls the rate, and others that the chemical reaction is inherently slow and related to high activation energy for the reaction. Christy3 and 'Thompson" both suggest that the reaction is electrochemical in nature and that the dissolution of gold proceeds at local anodic regions while the oxygen is reduced at cathodic regions on the gold surface. Although their studies are ingenious and do indicate an electrochemical reaction under the conditions of study, their experiments were of limited nature and failed to identify the rate-controlling process in the system. The importance from an industrial viewpoint of a knowledge of the mechanism and rate-controlling factors in gold dissolution can be illustrated as follows: If the rate is controlled by a slow chemical reaction rather than by diffusion of the reactants, then an increased temperature should have a marked accelerating effect; agitation of the slurry should have no effect on rate: and increased concentration of reactants should cause acceleration of the rate. If the rate is controlled by the diffusion of one or the other of the reactants to the gold surface, then increased agitation should increase the rate; increased temperature will increase the rate, but not as much as for the case of a slow chemical reaction; increased concentration of the reactant which is diffusion limited will increase the rate; and the concentration of other reactants should be without effect on the rate. It may be concluded that for design of a commercial process for gold leaching, the rate-controlling factors of the reaction should be understood so that an intelligent choice of the conditions of agitation, temperature, and reactant concentration may be made. The experiments described here lead to the unambiguous conclusion that in a system of pure gold and a pure aerated cyanide solution the rate of dissolution is controlled either by the rate of diffusion of dissolved oxygen or cyanide to the gold surface, depending on the relative concentrations of each. There is also ample, but not conclusive, evidence that the mechanism of the reaction is identical to that of electrochemical corrosion. The practical significance of these conclusions will be discussed later in the paper. Experimental The experimental method used in this work was to employ an electrolytic cell which performed the overall gold-dissolution reaction, and to study the anodic and cathodic reactions of this cell as to their nature and the rate-controlling factors. Simple experiments on the rate of dissolution and the potential of the dissolving specimen also were performed under conditions of agitation, temperature, and concentration identical to those used in the electrode studies. Analysis of the electrode studies by well established theories of electrochemical corrosion were made, and the results were found to bear a one-to-one relation with actual rate and potential measurements. Electrode Studies: The Anodic Reaction: The gold specimen used for all of the electrode studies and the rate determination consisted of a sheet of 99.99 + pct Au wrapped around a lucite rod and sealed at the edges with plastic cement, thus forming a cylinder of gold of known and constant area (8.0 sq cm). The lucite rod was threaded into a brass spindle which could be rotated at speeds of 100, 300, and 500 rpm. For the electrode studies electrical contact between the gold cylinder and the brass spindle was made by means of a gold strip covered with plastic. The anodic dissolution of gold was studied by immersing the electrode in a solution containing known concentrations of KCN and KAu(CN)2 but free of oxygen, and by passing an anodic current through the gold electrode. The pH of the solution was maintained between 10.5 to 11.0 in these and all other tests by addition of KOH. The pH was measured before and after each test by means of a glass-elec-

Jan 1, 1955

By W. L. McMorris, A. H. Brisse

IN the last several years the coal industry has intensified its effort to solve the growing problem of cleaning and recovering fine mesh coals. On one hand these has been increasing civic pressure for cleaner streams, and on the other hand there has been increasing production of fine mesh coal, resulting directly from adoption of the modern mining methods so essential to the economy of the coal mining industry. Cleaning fine coal with the same precision possible with coarser coals is a difficult task, and for coals finer than 200 mesh it has been impractical. Furthermore, the inclusion of —200 mesh material in the final product markedly increases costs of de-watering and thermal drying, which are necessary steps if coal is to meet market requirements. Consequently these extreme fines have generally been wasted. As a result, problems have been created in many districts because there has not been enough area for adequate settling basins. Wasting of coal in the -200 mesh slimes may account for a loss in washer yield equivalent to 2.0 to 2.5 pct of the raw coal input. With rising mining costs the value of such a loss is constantly increasing and a need for a better solution to the fines problem becomes more pressing every day. From an operating viewpoint, also, continuous removal of extreme fines from the washing plant circuit permits good water clarification practice, improving significantly the overall cleaning efficiency. The obvious desirability of recovering a commercially acceptable coal from washery slimes prompted U. S. Steel Corp. to investigate the merits of the Convertol process developed in Germany." Although this process has been used commercially in Europe for some time, little if any consideration has been given to its possible adoption in the U. S. until very recently. Fundamentals of the Convertol Process: In the Convertol process, droplets of dispersed oil are brought into intimate contact with the solids suspended in the coal slurry to be treated. This contact causes oil to displace the water on the surface of the coal by preferential wetting, or phase inversion, after which the coal particles are allowed to agglomerate in a manner permitting their re- moval from the slurry by centrifugal filtration. The clay and other particles of mineral matter suspended in the slurry do not have the affinity for oil the coal particles have. Consequently the oil treatment is preferential to coal to the extent that more than 95 pct of the oil used reports with the clean coal recovered. Figs. 1 through 3 will clarify the steps involved in the process. Fig. 1 shows the suspended material in the slurry to be treated, which is a thickened product containing 40 to 45 pct solids. Oil is now injected into the slurry under vigorous agitation to produce good oil to coal contact conditions, which result in preferential oiling of the coal particles. These coal particles are then permitted to agglomerate by gentle stirring in a conditioner to form flocs, as shown in Fig. 2. At this point in the process the agglomerated oiled coal can be washed and partially dewatered on a vibrating screen, as shown in Fig. 3. Finally, the washed flocculate can be further dewatered in a high-speed screen basket centrifuge or in a solid bowl centrifuge. Commercial Application of the Convertol Process in Germany: The original Convertol process was developed by Bergwerksverband zur Verwertung von Schutzrechten der Kohlentechnik, G.m.b.H., a German research organization controlled by the Coal Operators Assn. of the Ruhr Valley. The process as reduced to commercial practice in Germany' is shown in Fig. 4. In this process a thickened slurry (40 to 45 pct solids) mixed with a predetermined percentage of oil is fed from a surge tank to the phase inversion mill. After the phase inversion step, the slurry is usually discharged directly to a highspeed screen centrifuge. From 3 to 10 pct oil is used, depending on type of oil, size consist of coal to be recovered, and operating temperature. The top size of fine coal cleaned in Germany by the Convertol process is limited by the size of the openings in the centrifuge screen basket. Any mineral matter coarser than the basket opening, which is generally 60 to 80 mesh, must remain with the oiled coal. If the coal fines have been effectively cleaned down to about 80 mesh, the cleaning performance of the process is practically unaffected by the presence of coarse coal particles. However, since recovery of coal much coarser than 80 mesh is mow economical by conventional methods, it normally becomes more costly to allow substantial percentages of this coarse coal in Convertol process feed. Where the general plant layout does not permit effective cleaning of coal sizes down to 80 mesh or lower. there is some justification for a coarser Con-

Jan 1, 1959

By Donald B. Evans, Robert D. Pehlke

The solubility of nitrogen in liquid Fe-A1 alloys has been measured up to the solubility limit for formation of aluminum nitride using the Sieverts method. The activity coefficient of nitrogen decreases slightly with increasing aluminum content in the range of 0 to 4 wt pct Al. Based on a nitride composition, AlN, the standard free energy of formation of aluminum nitride from fhe elements dissolved in liquid iron has been determined to be: ?F" = -59,250 + 25.55 T in the range from 1600º to 1750ºC. The solubility of nitrogen in liquid iron alloys and the interaction of nitrogen with dissolved alloying elements in liquid iron have been the subject of a number of research investigations.' Most of this work, however, has been reported for concentrations well below those necessary for the formation of the alloy nitride phase. Data in the concentration region near the solubility limit of the alloy nitride, particularly for systems exhibiting stable nitrides, are important in evaluating the denitrifying power of various alloying elements. They are also useful in determining the stability of a given nitride if it is to be used as a refractory to contain liquid iron alloys. In view of the importance of aluminum as a deoxidizing agent in commercial steelmaking and the fact that its nitride, AIN, is a highly stable compound and has merited some consideration as an industrial refractory, the following investigation was undertaken. The use of the Sieverts technique provided a measurement of the equilibrium nitrogen solubility in liquid Fe-A1 alloys as a function of nitrogen gas pressure up to 3.85 wt pct A1 in the temperature range of 1600º to 1750°C. The values obtained by the Sieverts method were checked by means of a quenching method in which liquid iron was equilibrated with an A1N crucible under a known partial pressure of nitrogen gas, and the solubility of A1N in liquid iron determined by chemical analysis. EXPERIMENTAL PROCEDURE The theoretical considerations involved in determining the solubility product of a solid alloy nitride phase in liquid iron by measuring the point of departure of the nitrogen gas solubility from Sieverts law have been discussed by Rao and par lee.' The principal problem is to determine the variation of nitrogen solubility in an alloy as a function of the pressure of nitrogen gas over it with sufficient precision to establish the break point in the curve at the solubility limit of the alloy nitride phase. A fairly large number of data points are required to do this. A second problem is the determination of the composition of the precipitated solid nitride phase. This is necessary in order to define completely the thermodynamic relationships. The Sieverts apparatus used to make the nitrogen solubility measurements in this investigation is of essentially the same design as that described by Pehlke and E1liott.l The charge materials were Ferrovac-E high purity iron supplied by Crucible Steel Co. and 99.99+ pct pure aluminum. Recrystal-lized alumina crucibles were used, and were not attacked by the liquid alloys. The hot volume of the system which was measured for each melt ranged from 46 to 50 standard cu cm and was found to decrease linearly with decreasing pressure and with increasing temperature. The temperature coefficient of the hot volume at 1 atm pressure of argon gas was essentially constant for all experiments at a value of -6 X 10-3 cu cm per "C. The melt temperature was measured with a Leeds and Northrup disappearing filament type optical pyrometer sighted vertically downward on the center of the melt surface. The temperature scale was calibrated against the observed melting point of pure iron taken as 1536°C. The emissivity of all melts was assumed to be that of pure iron, taken as 0.43. The charge weights ranged from 110 to 140 g and the range of aluminum contents covered was from 0 to 3.85 wt pct. Aluminum additions were made as 12 to 15 wt pct A1-Fe master alloys previously prepared in the system under purified argon. The compositions of the master alloys were checked by chemical analysis and found to be in agreement with the charge analyses. Vertical cross sections of the master-alloy ingots were used as charge material for the equilibrations in order to minimize the effect of any segregation which might have occurred during solidification of the master alloys. Determinations of the solubility product of

Jan 1, 1964

By C. Atkinson

A method is described for the numerical solution of the diffusion equation with a composition-dependent diffusion coefficient and applied to the radial growth of a cylinder; the radial growth of a sphere, and the symmetric growth of an ellipsoid. Sample applications of the method are made to the growth of particles of proeutectoid ferrite into austenite. RECENTLY&apos; we described a method for numerical solution of the diffusion equation with a composition-dependent diffusion coefficient for the case of the growth of a planar interface. In this paper we extend this method to describe the radial growth of a cylinder, the radial growth of a sphere, and the symmetric growth of an ellipsoid. In the latter case, limiting values of the axial ratios of the ellipsoid reduces the problem to one of a cylinder, a sphere, or a plane depending on the axial ratio. A check on these limiting values is made in the results section. In all of these cases we consider growth from zero size. A natural consequence of this assumption as applied to the sphere, for example, is that the radius of the sphere is proportional to the square root of the time. This is consistent with the condition that the radius is zero initially, i.e., grows from zero size. It may be argued that it is more realistic to consider particles which grow from a nucleus of finite initial size; even in this case the analysis of this paper is likely to be applicable. This can be seen if a comparison is made of the work of Cable and Evans,2 who consider a sphere of initially finite size growing by diffusion in a matrix with a constant diffusion coefficient, with the results of Scriven3 for growth from zero size. This comparison shows that the rates of growth in each case differ trivially by the time the particle has grown to about five times its initial size." This investigation is a generalization of those of Zener,4 Ham,5 and Horvay and cahn6 to the situation often encountered experimentally, in which the diffusion coefficient varies with concentration. First let us consider each of the cases separately. I) GROWTH OF SPHERICAL PARTICLES FROM ZERO SIZE In this case the differential equation in the matrix depends only on R, the radius in spherical coordinates, and can be written: ? 1 <^\ ^13D . , dt U\dRz + R 3Rj + dR dR [ J where C is the composition, t is the time, and D is the diffusion coefficient which depends on c. The boundary conditions will be: c = c, at the moving interface in the matrix, c = c, at infinity in the matrix (and at t = 0, everywhere in the matrix), c = X, is the composition in the spherical particle. Each of the above compositions is assumed constant. In addition there is the flu condition at the moving interface which can be written: , dR0 ~/3c dt \dR/H =Ra where R,, which is a function of t, is the position of the moving interface. We make the substitution q = RI~ in [I] reducing this equation to: & - m - *ws) »i where we have written D = D,F(c) or simply D,F, and Do = D(c,). Thus F[c(q0)] = 1 where q, = ~,/a is the value of the dimensionless parameter q evaluated at the interface. Multiplying Eq. [2] by dq/dc and integrating, we find: where the lower limit of the integral has been chosen so that dc/dq — 0 as c — c,, thereby satisfying the boundary condition at infinity. We require, then, to solve Eq. [3] subject to the condition c = c, when q = q, (this follows from putting R = R, at the interface) together with the flux condition which can be rewritten in terms of q as: Eqs. [3] and [4] together with the condition c = c, at q = q0 enable us to find 77, and the concentration profile c = c(q). Numerical Method. We treat Eq. [3] in the same way as we did the corresponding equation for the planar interface problem&apos; i.e., by dividing the interval c, to c, into n equal steps so that: cr = ca -rbc [5] where r takes the values 0, 1, ... n and we call no,, q1, ... nn the values of n corresponding to the compositions c,, c,, ... c,.

Jan 1, 1970

By R. E. Ogilvie, N. L. Peterson

Diffi-lsion measurements were conducted at all compositims in the bcc solid solution of the U-Nb system employing incremental couples at composition intemals of 10 at. pct. Diffusion coefficients were determined by the Matano method from concentration gradients obtained with the electron-probe microanalyzer. The activation energy for inter-diffi-lsion as a function of compositim shows three distinct regions: 1) 80 to 100 pct U.6= 30 kcal per mole; 2) 20 to 80 pct U, $ - 70 kcal per mole; 3) Oto 20 pet U, Q = i40 kcal per mole. The frequency factor, fi0 and the activation energy $ were found to be roughly related by the following equation: log Do ^9.7 X IO-5Q -6,6. The Kirkendall marker movement indicates that DU is larger than DNb between 16 and 100 pct U and DNb is larger than DU from 0 to 4 pct U. FOR practical as well as fundamental reasons, the rates of diffusion in alloys are of considerable consequence. Most solid-state reactions are largely dependent upon the diffusion of atoms through the lattice structure and along grain boundaries. The high-temperature strength and reasonable nuclear properties of niobium have prompted its use as a reactor material in contact with uranium fuel. Hence, diffusion data for the U-Nb system are of considerable importance. In the previous diffusion study1 on the U-Nb system using pure element couples, reliable data were obtained only in the range of 0 to 10 at. pct Nb due to the large variance of the diffusion coefficient with composition. Also, a large Kirkendall effect and considerable porosity in the uranium-rich areas of the specimen were reported, which suggests that the true diffusion coefficients are somewhat larger. The purpose of the present study was to obtain reliable diffusion coefficients at all compositions using incremental diffusion couples with intervals of 10 at. pct. In view of the abnormal self-diffusion be- havior of y uranium2-4 and some other bcc transition elements,&apos;-&apos; it was felt that a comparison of the interdiffusion coefficients in the bcc U-Nb system with those of Reynolds et al.9 for the fcc gold-nickel system might shed some light on the diffusion mechanism involved. Both systems have similar phase diagrams, in that complete solid solubility exists above a miscibility gap. EXPERIMENTAL PROCEDURE The uranium used in this investigation was obtained through the courtesy of Argonne National Laboratory. An analysis of this material detected only Si-30, A1-7, C-6, N < 10 and 0-18 ppm. The niobium was electron-beam melted material obtained from Stauffer-Temescal. The gaseous impurities were less than 50 ppm, and the spec troc hemical analysis showed Ta-500 and W-200 ppm. U-Nb alloys were prepared at composition intervals of 10 at. pct by melting the appropriate amounts of the pure elements in an arc furnace. The buttons were inverted and remelted 6 times to assure complete mixing. The buttons were then wrapped in molybdenum foil, canned in Zircaloy-2 or stainless steel, and hot rolled 30 pct reduction in thickness at temperatures between 850" and 1100°C. Alloys with 10, 20, 30, 40, and 90 at. pct Nb rolled quite easily under these conditions, but the 50, 60, 70, and 80 pct alloys remained brittle. After melting and rolling (when possible), the alloys were annealed for 24 hr at a temperature within 100°C of their melting point in a dynamic vacuum of better than 4 x 10-8 mm Hg. These treatments produced alloys which were homogeneous on a 1 p scale within the detectability limits of the electron probe. During fabrication, the alloys picked up as much as 100 ppm Mo and 100 ppm Zr. Other elements checked for but not found were Co, Cr, Fe, Mn, Ni, and Ti. The grain size of the annealed samples ranged from 3 mm for the uranium-rich alloys to 0.3 mm for the niobium-rich alloys. This permitted measurements of the concentration gradients in the diffusion samples without crossing more than one or two grains, thereby eliminating any grain boundary effects. The specimens were bonded by theU&apos;picture frame" technique as reported by Kittel.10 Specimens of composition b)U + (100 - x)Nb were sandwiched between two specimens of composition (x + 10)U + (90 - x)Nb after they were ground flat and parallel

Jan 1, 1963

By J. E. Walstrom

While intensive research continues to promote a more complete understanding of the potential and resistivity measurements that comprise the electric log, it is believed that consideration should also be given to translating these numerous and often widely separated findings into a coordinated and readable body of fundamental facts designed specifically for the petroleum engineer and geologist. Although provision is made through publication for a ready exchange of new theoretical concepts. it is also desirable to provide reviews and appraisals of the more established techniques and methods from the operating standpoint so that an economic and practical application may be realized concurrently with the theoretical progress. With these basic premises as a guide the author reviews the presnt state of electric log interpretation. The paper is directed not so much to the logging or research specialist as to the petroleum engineer and geologist to whom the electric log is only one of the many tools which he employs. Frequently, these persons do not have the time to follow in detail the many specialized contributions that appear and, as a consequence. are not in a position to place these contributions in proper relation to each other, or to the art as a whole. The paper reviews the basic steps in making quantitative determinations from the electric log of the amount of oil or gas present in subsurface formations and also discusses the degree of reliability of these determinations under various conditions. The paper also indicates the trend of future developments in electric logging systems and methods of interpretation. INTRODUCTION The electric log has been used about 20 years as a means for studying the formations penetrated by a well bore. The first half of this period is characterized by the development of suitable logging techniques and equipment. Although progress in this direction is continuing at a satisfactory rate, the last ten years are characterized more by an increasing interest in methods of electric log interpretation. During this period, a large number of fundamental papers have been published, expounding various logging techniques and particular phases of the interpretation problem. Many of these papers represent important contributions, and a few are classic. This paper is an effort to outline as concisely as possible and in simple terms the main course of progress in electric log interpretation. More specifically, it is the purpose of the paper to review the necessary elements and basic steps used in making quantitative determinations of water saturation from the electric log; and to point out the degree of reliability of these determinations under different conditions. It is strongly advised that the operating staffs of the drilling and exploration departments of oil companies cooperate wholeheartedly with both the electric logging service companies and research organizations in the testing and development of new logging systems and interpretation methods. One purpose of the paper is. however, to indicate the degree of caution which must be exercised in placing confidence in new techniques and interpretation methods that have not been thoroughly tested in the field. It is entirely possible to be cooperative in trying new methods and yet reluctant to believe in the results until the methods are firmly established. It is important to define the meaning of quantitative electric log interpretation. In the most general sense, an interpretation of the log has been made when the electrical characteristics of the formations, as portrayed on the log, have been translated into terms describing the formation geometry, rock type, or any other physical characteristics of the formations. The determination that the top of a sand is at a certain depth is an interpretation of the log. Structural determinations made by correlating electric logs from a given area are also interpretations of the logs. The term quantitative interpretation, however, will be used in this paper in the restricted sense to indicate the determination of the water saturation of a formation. This determination defines the fluid content of an oil and gas productive formation only if the porosity is known, and it assumes that the remainder of the pore space contains hydrocarbons. This assumption is believed to be true for most oil and gas productive formations. The quantitative electric log interpretation may he said to be a determination of the fluid content only to the extent which the water saturation, under the conditions given above. defines it. THE BASIC STEPS The fundamental steps in calculating water saturation from the electric log are: 1. Determination of the true resistivity of the formations from the apparent resistivities as recorded on the electric log.

Jan 1, 1952

By D. B. Robinson, C. A. Macrygeorgos, G. W. Govier

Experimental data have been obtained on the volurrletric behavior of ternary mixtures of methane, hydrogen sulfide and carbon dioxide at temperalures of 40°, 100" and 160°F up to pressures of 3,000 psia. The results indicate that the compressibility factors for this system do not agree with compressibility factors for sweet natural gases at the same pseudo-reduced conditions. The deviation increases as the temperature and methane content decrease. Discrepancies of up to 35 per cent were observed. A careful analysis has been made of the existing pUrblished data on compressibility factors for binary systems containing light hydrocnrbons and hydrogen sulfide or carbon dioxide. It has been found that the deviation of actual from predicted compressibility factors for methane-acid gas mixtures is a function of the methane content and the pseudo-critical properties,.v of the mixture. The ratio between actual compressibility factors for methane-acid gas mixtures and compressibility factors for sweet natrlral gases at the same pseudo-reduced conditions has been currelated over a range of pP,, from 0 to at least 7 arid a range of pT, from about 1.15 to at 1east 2 0 with an error not exceeding 3 per cent and over most of the range within I per cent. The validity of the correlation for mixtures containing appreciable hearvier hydrocorbons has not been fully established, but it is shown to be preferable than the use of a corretation based only on hydrocarbons. INTRODUCTION Although a relatively accurate method for predicting compressibility factors of pure materials is provided by charts based on reduced properties and the assumption that the compressibility factor is a unique function of T P and z the determination of the correct values of compressibility factors for gas mixtures is somewhat difficult. Two general methods of dealing with gaseous mixtures have been proposed. The first assumes a direct or modified additivity of certain properties of the mixture in terms of the properties of the individual components. Examples of this method are based on the familiar laws of Dalton and Amagat. The second method averages the constants of an equation of state applicable to the pure components. Both of these methods are of limited value in engineering calculations because the first usually provides reliable answers only over narrow ranges of pressure and temperature and the second is cumbersome to handle. In petroleum engineering practice accurate estimations of the volumetric behavior of natural gases arc frequently required. To fulfill this need, several generalized compressibility charts have been developed.&apos; &apos; Of these, the one prepared by Standing, el al is widely used at present. In the construction of charts of this type a third method for dealing with mixtures has been followed. It is based on correlation of pseudo-critical properties as outlined by Kay and calculated from the critical properties of the individual components in a mixture. Although these charts provide relatively accurate information on the compressibility of dry or wet sweet natural gases, they are less reliable when used for gases containing high concentrations of hydrogen sulfide or carbon dioxide or both. Thus, an experimental program, although time consuming, is the best means now available for the determination of the volumetric behavior of sour or acid gas mixtures. An increased interest in the behavior of these gas mixtures, particularly in connection with some of the fields in Western Canada where the acid gas concentration of the reservoirs may be as high as 55 per cent and where hydrogen sulfide alone may be as high as 36 per cent, provided the incentive for this study. It was the purpose of the investigation to determine the volumetric behavior of selected mixtures of methane, hydrogen sulfide and carbon dioxide over a range of temperature from 40" to 160°F and at pressures up to 3,000 psi. EXPERIMENTAL METHOD The apparatus used in this investigation was basically the same as that described by Lorenzo.&apos;" The amount of each pure component used in preparing the gas mixtures was measured over mercury in a glass-windowed pressure vessel. The pure components were then transferred individually in the desired amounts to a second glass-windowed pressure vessel where the volumetric behavior of the mixture was determined. Volume was varied by mercury injection or withdrawal. The capacity of the cell was about 125 cc. Temperatures in the cells were measured with copper-constantan thermocouples and a Leeds Northrup semi-

By L. R. Raymond, J. L. Hudson

This paper proposes a comparatively short-term (8 to 10 hours) well test for detecting and characterizing well-bore damage and for measuring mean formation permeability. The proposed test is made by injecting fluid at constant pressure, recording injection rate as a function of injection time. After one to four hours of injection, the well is shut in and fall-off of bottom-hole pressure is obtained as a function of shut-in time. Formation permeability is estimated by an iterative technique. First, a value of formation permeability is assumed. Then, a plot of the recorded injection rate as a function of dimensionless time is made, using the assumed pertneability value. From the slope of the injection-rate curve. a new value of formation permeability is calculated. If the new value agrees with the original assumed value, the assumption was the correct formation permeability. If the values do not agree, the process is repeated using the new permeability value in the calculation. Convergence is rapid, and a reliable permeability value results. Pressure fall-off data are used to check the result. Graphs of pressure and injection rate us functions of time given in the paper show that changes in permeability of the formation in the neighborhood of the wellbore are disclosed by this technique. Thus, the short-term test can he used to detect formation damage. Also, a rough measure of the radial extent of damage can be inferred, which is helpful in designing stimulation treatments. The mathematical model used for this work was a single-zone, horizontal reservoir with a damaged zone in which permeability decreased continuously as radial distance to the wellbore decreased. This model is more realistic than the usual two-zone, discontinuous permeability model used in published works; calculations indicate the realistic model is valid. Vertical variations in horizontal permeability were studied with this model, and results indicate that the permeability measured by the short-term test is the mean horizontal permeability for the vertical interval tested. The proposed short-term test thus should be useful in detecting and characterizing formation damage and in measuring formation permeability needed in calculating reservoir transmissibility. INTRODUCTION To plan the most efficient production or injection schedule for a well and to design or evaluate the optimal stimu- lation treatment, it is necessary to know the properties of the reservoir adjacent to the well, particularly the reservoir transmissibility and characteristics of a damaged zone, if one exists. Several techniques for determining reservoir transmissi-bility from well tests have been presented in the literature. 1,2,3,4 All these techniques rely on conducting constant-rate well tests that often are difficult to execute. A constant-pressure well test is generally easier to carry Out. and this paper contains the first available method for the analysis of constant-pressure well tests. Determination of wellbore damage from transient well tests has been the subject of several papers."" From these studies it is apparent that information necessary for determination of the characteristics of a damaged zone is available shortly after the transient well test is initiated. Consequently, it may not be necessary to carry out an extensive well test (for example, a pressure build-up test) if the primary purpose of the test is to detect the existence of wellbore damage. All previous studies of well testing to determine wellbore damage have been based on the two-zone perrneability model. In this model the damaged zone has a permeability k,, extending to a radius r,,, and the formation permeability k obtains from r, to the drainage radius r,.. Consequently, there is a discontinuity in permeability at r = r,,. This discontinuity can be eliminated by assuming a continuous variation in permeability through the damaged zone. The effect of this assumption on transient well tests is discussed in following sections of this paper. In addition, all formations have within them vertical permeability variations associated with lithology changes throughout the zone of interest. This paper also considers the effect of these variations on transient well tests. ANALYSIS OF CONSTANT-PRESSURE WELL TESTS The mathematical analysis associated with the injection of fluid at constant wellbore pressure into a single-zone, horizontal reservoir completely filled with a fluid of small and constant compressibility and constant viscosity is given in Appendix A. In this analysis it is assumed that the well is located at the center of an undamaged, circular drainage area. From this analysis, the formation permeability can be obtained as follows. 1, Estimate a value for the formation permeability k. 2. Prepare a plot of injection rate q vs

Jan 1, 1967

By B. Chalmers

THE practical importance of the phenomena of melting and freezing must have been recognized for a very long time. The difference between ice and water, for example, has had a profound influence on the history of mankind and the evolution of society. The possibility of melting a metal and allowing it to freeze in a mold of chosen shape has been an essential ingredient in our mastery of the art of shaping metals, and therefore in the evolution of the: machine age in which we find ourselves. The importance of melting and freezing, as applied to metals and alloys, has been so great, in fact, that empirical solutions have been found for the multitude of practical problems that have arisen. This approach has been so successful that relatively little attention has been directed to arriving at an understanding of the fundamentals of the processes. But metallurgy has come to a stage at which we may expect that some, at least, of the more complex problems that have not yet been solved (or perhaps even recognized) may be handled more effectively by scientific study, theoretical understanding, and logical experimentation than by trial and error. In this lecture, therefore, I propose to describe in outline what I think really happens when a metal freezes. In doing so I hope to explain many of the phenomena which have been observed, and in particular to account for the structures that are obtained in actual ingots and castings. The basic problem, to which this lecture represents a tentative partial answer, is this: a mass of metal, containing known proportions of various elements, is melted, heated to a given temperature, and then allowed to freeze under specified conditions. What will be the "structure" of the resulting metal? The term structure includes: 1—crystal size, shape, and orientations, 2—distribution of chemical elements, and 3-—shape, including cracks, cavities, pores, etc. The Solid-Liquid Interface We will first consider what takes place if a single crystal of a metal in the form of a rod is heated, not uniformly, but so that one end is hotter than the other. If this heating process is continued long enough, the hotter end will eventually melt; we will suppose that the rod is in a containing vessel so that the molten metal does not run away, Fig. 1. When some of the metal has melted, we have some solid, some liquid, and an interface or surface of contact between them. If the source of heat is now removed, the interface will move so that some of the liquid freezes, and if the supply of heat is suitably adjusted the interface will remain at rest. This very simple arrangement allows us to study the basic processes of melting and freezing, and if we fully understand this simple case, we may be able to account for what takes place under practical conditions where the heat does not all flow in the same direction, and where the heat flow is determined not by a controllable source of heat but by the heat capacity and temperature of metal and mold, and by the heat loss from the mold surface. The solid-liquid interface is evidently the region of the greatest interest to us; on one side of it there is crystalline solid, and on the other, liquid. In the solid, each atom has a well defined position, around which it vibrates as a result of thermal agitation. It only leaves this position in the relatively rare event of a "diffusion jump." The liquid is much less systematically organized. The atoms are about as far from their neighbors as in the solid, but the arrangement is much less systematic and is continuously changing. The solid and the liquid are represented diagrammatically in Fig. 2. The average energy of the atoms in the liquid is greater than in the solid by an amount that corresponds to the latent heat of fusion, i.e., the amount of heat that has to be supplied to convert unit mass of solid into liquid at the same temperature. The Two Processes As has recently been shown by Jackson and Chalmers,3 many of the features of the processes of freezing and melting can be understood if it is assumed that a continuous and rapid interchange of atoms between solid and liquid always takes place at a solid-liquid interface." It is necessary to con- sider two distinct processes, that of melting, in which atoms leave the surface of the solid and become part of the liquid, and the converse process,

Jan 1, 1955

By R. E. Boehler, N. C. Ludwig

At Buffington Station, Gary, Ind., Universal Atlas Cement operates fourteen 8 x 101/2 x 155-ft cement kilns in mill 6 and two 11 x 360-ft kilns in the Harbor plant. The No. 11 and 12 kilns in mill 6 are equipped with Manitowac recuperator sections. This report describes studies in measuring exterior shell temperatures on several of these kilns and the development of a traveling radiation pyrometer with certain novel features. Preliminary Work: At first various temperature-sensing devices were placed on the steel shell: 1) crayons with calibrated melting points, 2) colored paints with temperature-calibrated pigments, 3) aluminum paints with temperature-calibrated binders, and 4) metal-stem dial thermometers. The colored paints and aluminum paints failed to indicate the temperatures correctly. The crayons and thermometers did indicate fairly correct temperatures, but it proved impossible to apply enough of these on the shell to detect all the potential areas where hot spots might develop. Furthermore, considerable labor was required to apply these sensors and read the temperatures. Consequently no further work was done with these devices. Formation of Hot Spots: In the burning or clinker-ing zone of a cement kiln, the thickness of the protective coating and thickness of the brick govern the amount of heat transmitted to the steel kiln shell. Usually the protective coating consists of 4 to 8 in. of fused cement clinker. The formation of a hot spot is usually caused by loss of coating? that is, localized areas of the coating become thin or fall away from the refractory. This is generally caused by excessive temperature in the burning zone over a fairly long period of time. It may also be caused by a sudden thermal change in the burning zone. Variations in raw feed composition and in feed rate require changes in the fuel and air rates, and when these are not appropriately altered, conditions may develop in the kiln that will result in loss of coating. Luminescence on the kiln shell indicates that a hot spot has developed to a point that usually alters the refractory&apos;s thermal conductivity properties. When this thermal weakness zone occurs in the burning zone of the kiln, constant vigilance is required to protect it by maintaining proper coating. Even so, it has been the writers&apos; experience that within a period of several days to about four weeks the hot spot usually recurs with greater severity. This necessitates shutting down the kiln and re-bricking the affected area. One of the prerequisites of a good burnerman is the ability to maintain a protective coating despite the many variables in operation. When he knows that it is getting thin or that an area has dropped off, he reduces the firing rate and kiln speed and brings feed into the affected area in an effort to rebuild the coating. But when powdered fuel is burned, the atmosphere of the kiln may prevent the burnerman&apos;s observing the condition of the coating closely at all times without taking off the fire. It is not considered good practice to do this frequently, as it imposes a thermal shock on the coating and upsets operation of the kiln. To help the burnerman scan the shell of the kiln along the burning zone, therefore, a radiation pyrometer, connected to a potentiometric recorder, was mounted on a slowly moving steel cable. The theory of operation, construction details, and adaptability of the radiation pyrometer are included in an excellent monograph&apos; and also in a textbook.&apos; Shell temperatures of the Atlas Cement kilns were measured with a Brown Instruments Div. low intermediate range Radiamatic unit, of range 200" to 1200°F, and a circular chart Electronik potentio-metric recorder, of range 500" to 1000°F. In Bulletin 59095M the supplier publishes standard calibration data (millivolts vs degrees Fahrenheit) for this radiation pyrometer, These data, however, apply only to flat surfaces having emissivities of unity. Calibration of Radiation Pyrometer for Use on Curved Surfaces: When applied to surface temperature measurements, the radiation pyrometer reading depends on the nature of the surface, the material of which it is composed, and also to some extent on the temperature of the surroundings. Although the present radiation pyrometer is designed to give a calibrated response under ideal (black body) conditions when used commercially, it must be calibrated empirically. The calibration procedure, given below, follows that described by Dike (Ref. 1, pp. 38-39). Calibration tests on plane and curved surfaces showed that the response of the radiation pyrometer was very

Jan 1, 1961

By W. H. Patnode

The effect of suspended solids on the resistivity of slurries is discussed and the relationship between drilling mud resistivity and mud filtrate investigated. It is concluded that it is erroneous to substitute mud resistivity for mud filtrate resistivity in electric log calculations. A recommendation is made that both the bud resistivity and the mud filtrate resistivity be determined when electric logs are run. INTRODUCTION The electric log is influenced not only by the resistvity of the drilling mud in the borehole at the time of logging but also by the resistivity of the drilling mud filtrate. Sherborne and Newtoni investigated the relationship of mud resistivity to mud filtrate resistivity and concluded that, "The resistivity of the mud in most cases closely approximates that of its filtrate," and "In fact, with the exception of Aquagel and its filtrate, the figures for any particular mud and filtrate are almost identical." Present practice is to determine only the drilling mud resistivity and apply this same value to calculations involving the mud filtrate. The purpose of this study is to reexamine the factors governing the relationship between mud resistivity and mud filtrate resistivity. EFFECT OF BOREHO1.E FLUID ON THE ELECTRIC LOG Resistivity Log The resistivity log may be modified by the resistivity of the borehole fluid in two different ways: (1) The apparent resistivity of a for-formation may be different from the true resistivity of the formation because of the flow of some current through the drilling mud in the borehole. Therefore the resistivity of the mud is an important factor. (2) The apparent resistivity may differ from the true resistivity, if a formation is invaded by mud filtrate, because of displacement by the mud filtrate of some of the interstitial fluid in the formation. In this case the resistivity of the mud filtrate rather than the resistivity of the mud is the important factor. Self Potential Log The self potential arises, in part, from electrochemical effects resulting from the interaction of connate waters in porous formations and the fluid in the borehole. Expressed in simple form, E = Klog-p where E is the electrochemical self potential, K is a derived constant, pl is the resistivity of the borehole fluid, and p2 the resistivity of the water in the formation. A theory of the electrochemical component of the self potential in boreholes has been recently set forth by Wyllie.3 In the above equation resistivities have been substituted for activities of the ions in the fluids.&apos; It is therefore apparent that the resistivity of the mud filtrate is more nearly representative of the activities of the ions than is the resistivity of the mud. However, it is possible that in some instances the ionic activities of cations from certain clays may contribute to the total cationic activity of the drilling fluid to such an extent that the mud resistivity is more nearly representative of the activities than the filtrate resistivity. This is particularly the case when the resistivity of the mud is less than the resistivity of the mud filtrate. In addition the apparent self potential may be influenced by the resistivity of the drilling mud because of current flow through the borehole. RESISTIVITY OF SLURRIES Aqueous drilling muds are slurries containing fine-grained solid particles. The solid constituents consist mainly of added clays and weighting materials in addition to solids contributed by the drilled formations. The filtrate is primarily water in which quantities of salts or other chemicals are dissolved. The resistivity of the fiiltrate is a function of the type and quantity of dissolved material whereas the resistivity of the mud is a function of the combined resistivities of the filtrate and the resistivities of the suspended solids. Experiments have been carried out to determine the relationship between the resistivity of solutions and the quantity and type of solid matter insus-pension. Solid materials of high resistivity, as well as solid materials of relatively low resistivity, have been used. The data obtained make possible the evaluation of the probable effect of suspended solids on the resistivity of drilling mud. Procedure Resistivities were determined by means of a conventional conductivity cell with platinized-platinum electrodes. Total resistance between the electrodes was measured by Kohlrausch&apos;s alternating current bridge method using a General Radio Company Type 650-A impedance bridge with telephone. The cell was standardized with potassium chloride solutions of known normalities in order to calibrate the cell so that measured resistances of slurries could be converted to resistivities. Resistivities were determined for mixtures of potassium chloride solution and solid materials by placing a measured quantity of solution in the cell and adding weighed quantities of solid materials in small increments to the solution. The net change in resistance on addition of solid materials was measured. Even distribution of the solid particles was maintained within the cell by a motor-driven glass propeller before measurements were made. Slurries Containing High-Resistivity Solids Powdered silica sand having a maximum diameter of about 60 microns and precipitated chalk of commercial grade were used to make the slurries whose resistivities were measured. Both of these substances have high resistivities, are virtually insoluble, and effectively do not carry current in a slurry. The resistivities of slurries composed of potassium chloride solution and these two solid materials are given in Table 1. The ratio of the resistivity of the solution to the resistivity of the slurries was computed and was found to follow the relationship established by Archie

Jan 1, 1949

By W. H. Patnode

The effect of suspended solids on the resistivity of slurries is discussed and the relationship between drilling mud resistivity and mud filtrate investigated. It is concluded that it is erroneous to substitute mud resistivity for mud filtrate resistivity in electric log calculations. A recommendation is made that both the bud resistivity and the mud filtrate resistivity be determined when electric logs are run. INTRODUCTION The electric log is influenced not only by the resistvity of the drilling mud in the borehole at the time of logging but also by the resistivity of the drilling mud filtrate. Sherborne and Newtoni investigated the relationship of mud resistivity to mud filtrate resistivity and concluded that, "The resistivity of the mud in most cases closely approximates that of its filtrate," and "In fact, with the exception of Aquagel and its filtrate, the figures for any particular mud and filtrate are almost identical." Present practice is to determine only the drilling mud resistivity and apply this same value to calculations involving the mud filtrate. The purpose of this study is to reexamine the factors governing the relationship between mud resistivity and mud filtrate resistivity. EFFECT OF BOREHO1.E FLUID ON THE ELECTRIC LOG Resistivity Log The resistivity log may be modified by the resistivity of the borehole fluid in two different ways: (1) The apparent resistivity of a for-formation may be different from the true resistivity of the formation because of the flow of some current through the drilling mud in the borehole. Therefore the resistivity of the mud is an important factor. (2) The apparent resistivity may differ from the true resistivity, if a formation is invaded by mud filtrate, because of displacement by the mud filtrate of some of the interstitial fluid in the formation. In this case the resistivity of the mud filtrate rather than the resistivity of the mud is the important factor. Self Potential Log The self potential arises, in part, from electrochemical effects resulting from the interaction of connate waters in porous formations and the fluid in the borehole. Expressed in simple form, E = Klog-p where E is the electrochemical self potential, K is a derived constant, pl is the resistivity of the borehole fluid, and p2 the resistivity of the water in the formation. A theory of the electrochemical component of the self potential in boreholes has been recently set forth by Wyllie.3 In the above equation resistivities have been substituted for activities of the ions in the fluids.&apos; It is therefore apparent that the resistivity of the mud filtrate is more nearly representative of the activities of the ions than is the resistivity of the mud. However, it is possible that in some instances the ionic activities of cations from certain clays may contribute to the total cationic activity of the drilling fluid to such an extent that the mud resistivity is more nearly representative of the activities than the filtrate resistivity. This is particularly the case when the resistivity of the mud is less than the resistivity of the mud filtrate. In addition the apparent self potential may be influenced by the resistivity of the drilling mud because of current flow through the borehole. RESISTIVITY OF SLURRIES Aqueous drilling muds are slurries containing fine-grained solid particles. The solid constituents consist mainly of added clays and weighting materials in addition to solids contributed by the drilled formations. The filtrate is primarily water in which quantities of salts or other chemicals are dissolved. The resistivity of the fiiltrate is a function of the type and quantity of dissolved material whereas the resistivity of the mud is a function of the combined resistivities of the filtrate and the resistivities of the suspended solids. Experiments have been carried out to determine the relationship between the resistivity of solutions and the quantity and type of solid matter insus-pension. Solid materials of high resistivity, as well as solid materials of relatively low resistivity, have been used. The data obtained make possible the evaluation of the probable effect of suspended solids on the resistivity of drilling mud. Procedure Resistivities were determined by means of a conventional conductivity cell with platinized-platinum electrodes. Total resistance between the electrodes was measured by Kohlrausch&apos;s alternating current bridge method using a General Radio Company Type 650-A impedance bridge with telephone. The cell was standardized with potassium chloride solutions of known normalities in order to calibrate the cell so that measured resistances of slurries could be converted to resistivities. Resistivities were determined for mixtures of potassium chloride solution and solid materials by placing a measured quantity of solution in the cell and adding weighed quantities of solid materials in small increments to the solution. The net change in resistance on addition of solid materials was measured. Even distribution of the solid particles was maintained within the cell by a motor-driven glass propeller before measurements were made. Slurries Containing High-Resistivity Solids Powdered silica sand having a maximum diameter of about 60 microns and precipitated chalk of commercial grade were used to make the slurries whose resistivities were measured. Both of these substances have high resistivities, are virtually insoluble, and effectively do not carry current in a slurry. The resistivities of slurries composed of potassium chloride solution and these two solid materials are given in Table 1. The ratio of the resistivity of the solution to the resistivity of the slurries was computed and was found to follow the relationship established by Archie

Jan 1, 1949

By George M. Schwartz, Ian L. Reid

THE Soudan mine in the Vermilion district of northeastern Minnesota is the oldest iron mine in the state. It has shipped ore every year since 1884 and still contributes a yearly quota of high grade lump ore. No comprehensive report on the Vermilion iron-bearing district has appeared since Clements&apos; monograph,&apos; but Gruner2 discussed the possible origin of the ores in 1926, 1930, and 1932, and recently Reid and Hustad have added data on mining and geology .3, 4 For many years geologists of the Oliver Iron Mining Div., U. S. Steel Corp., have kept up to date a series of plans and vertical sections of the Soudan mine. In connection with mine operation considerable diamond drilling has been done, and this, together with the mine openings, has permitted a reasonably accurate picture of the structure of the orebodies and wall rocks. It has long been evident to geologists familiar with the mine that the ores were not a result of weathering, a point emphasized by Gruner in 1926 and 1930. As the deeper orebodies were developed it also became clear that replacement had played an important part in their development. In recent years it has been recognized that other iron ores were formed by replacement, as Roberts and Bartly5 have argued strongly for the deposits at Steep Rock Lake. On the basis of these facts G. M. Schwartz suggested to members of the Oliver staff that it would be desirable to study the evidence of replacement, particularly the possible alteration of the wall rock which would be expected if the replacement was a result of hypogene solutions. Rock Formations: The formations directly involved in the iron orebodies of the Soudan mine are few though far from simple. The country rock is largely the Ely greenstone of Keewatin age consisting of a mass of metamorphosed lava flows, tuffs, and intrusives which have been more or less altered by hydrothermal solutions. The predominant rock is chlorite schist. Interbedded with the original flows and tuffs are a series of beds and lenses of jasper to which the name Soudan formation has been applied. In the Vermilion district the term jaspilite has been used for interbanded jasper and hematite. According to modern usage these jasper or jaspilite beds do not comprise a formation separate from the Ely greenstone, inasmuch as the beds of jasper are interbedded with the flows and tuffs of the upper part of the greenstone. It would more nearly accord with modern usage to consider the Soudan beds a member of the upper part of the Ely formation. Because of incomplete rock exposure and exploration the number of interbedded jaspilite beds is unknown. In the mine, however, as many as nine major beds of jasper are known on a cross-section of one limb of the syncline, with an equal number on the other limb. In addition diamond drill cores show beds of greenstone down to half an inch in thickness. The thin beds are probably always tuffs. Structure: Rock structure in the Soudan area is complex, and because there are no recognizable horizons within the greenstone it is extremely difficult to work out the details. Generally speaking, the major regional structure is an anticlinorium, the axis trending east-west, with a westerly pitch. The Soudan mine is related to a synclinal structure on the north limb of the anticline about a mile from the west nose of the folded iron formation. The general structure at the mine is that of a closely folded minor syncline on the major regional anticline. A cross fault has dropped the east side so that the bottom of the syncline has not been reached, whereas to the west it is well shown by the mine openings and diamond drill exploration. Throughout the mine the beds of jasper, and ore-bodies that have replaced the jasper, normally dip northward at angles of 80" or steeper. In detail the jasper beds are extremely folded, probably as a result of deformation while they were still relatively unconsolidated. Orebodies: Ore in the Soudan mine is mainly a hard, dense, bluish hematite. Locally ore has been brecciated and cemented by quartz. The vugs commonly occurring near the borders of orebodies are lined with quartz crystals. They seem to have formed as part of the ore-forming process and are evidence that no folding or compression of the ore has taken place. The orebodies are numerous, varying greatly in size. Many lenses of high grade hematite are too small to be mined. Some of the larger orebodies have been followed vertically for as much as 2500 ft and horizontally up to 1500 ft. The large ore-bodies are extremely irregular in outline in the plane of the beds of jaspilite. In width they are more regular, as they are strictly governed by the width of the jaspilite beds and the greenstone wall rock, which seems to have resisted replacement by hematite. At many places the orebodies replace the jaspilite completely and have a footwall and hanging wall of greenstone. At other places either one or both walls may be jaspilite. Geologists who have studied the orebodies in recent years agree that evidence for the replacement origin of the hematite bodies seems conclusive. AS noted above, many of the orebodies replace jaspilite beds from wall to wall with no evidence whatever of compaction. The replacement origin is also supported by details of the banding which is characteristic of the

Jan 1, 1956

By W. J. Slatosky

W. 0. Philbrook (Cairiegie Institute of Technologyogv—Mr. Slatosky has presented an interesting and constructive paper that represents another step along the way of converting steelmaking from an art to a science. I am confident that his computer will be practical and successful and that with a very few months of experience it will provide a significantly better degree of control than his record of 65 pct of heats within range obtained with the slide-rule calculator . A paper such as this, with a lot of symbols and condensed mathematics, is difficult to comprehend quickly. Since I have had an opportunity to study it carefully, perhaps my evaluation of its validity and accomplishments will save time for others. Mr. Slatosky has correctly used standard principles of stoichiometry and heat balances, which are available to anybody, but he has also brought to them two original contributions: 1) He has developed from operating data some empirical relations for predicting the final FeO content of the slag (at 0.5 pct C end-point) as a function of slag basicity, lance height, and scrap, ore, and scale in the charge. This improves the accuracy of prediction of temperature or scrap requirement compared with assuming an arbitrary, constant FeO content at the end of each heat. There is no assurance yet that exactly the same relations will hold for other furnaces or practices, but similar correlations can be expected. 2) He has combined calculations that are ordinarily carried out laboriously as a number of individual steps into a single, simple linear equation that can readily be fed into a machine. This involved a tremendous amount of painstaking detail work as well as the imagination to see the possibility and work out the steps. While his particular Eqs. [3] and [6] are valid only for the furnace design, charge weight, and blowing time used at Aliquippa Works, only a few numerical values have to be changed to adapt it for other conditions. In order to arrive at a useable solution, Mr. Slatosky had to make some basic assumptions about the process that are similar to those used by others. He neglected variation in some process variables and assumed an arbitrary average value for waste gas analysis and temperature for want of more exact information at the present time. All of these judgments are clearly stated. In addition, some thermody-namic data presently available are not adequate for the job, notably in relation to heats of formation and sensible heat in slag, and some expedient has to be adopted to get around the difficulty. Other people might prefer slightly different judgments about these details and hence obtain somewhat different numerical solutions. This is not of serious importance, however, because the errors accumulate in the "heat loss" term and are largely self-compensating for a constant heat time. Although the extended Eq. l(a) in Appendix I was set up as a rate equation originally, for convenience in using an analogue computer as stated in the paper, the time dependence was removed by later mathematical manipulations and assumptions about the process. The final result is an integration of element and energy balances from initial to final states; this procedure is as legitimate here as in any other form of heat-balance calculation. The formal handling of stoichiometry and thermochemistry appears to be correct, and it is assumed that any arithmetical errors would have come to light in applying the calculations to furnace practice. Mr. Slatosky&apos;s approach is not necessarily unique, in that other people might start with apparently different equations or prefer another form of final equation for another type of computer. However, he has presented an accomplished result that appears to be a theoretically sound and practically useful way of applying scientific principles and rapid computation for better control of steelmaking. His success will undoubtedly encourage himself and others to improve on the mathematical model and its use as better informatioq becomes available. John F. Elliott (Massachusetts Institute of Teck-t2ology)-The last comment by Mr. Richards that a calculator is quite unnecessary for an L-D operation ?-equi??es a rebuttal. The L-D furnace is a very high capacity process which places a premium on close control. When one is making steel at rates between 100 and 200 tons per hr, one cannot afford the luxury of an extra 5 or 10 min at the end of a heat correcting for an error that should never have been made in the first place. Mr. Slatosky&apos;s paper is a very sound application of the simple principles of stoichiometry and the energy balance. It is a satisfactory and valuable start, but only the start of the development of methods of control for this process. An analysis of the process shows that it should be very suitable to control by a computer. This is especially the case when various grades of steel are to be made. In fact, it would seem that the organizations who are planning new and bigger installations of L-D vessels should consider carefully the advantages that would stem from computer control of a vessel with the operator present to do little more

Jan 1, 1962

By K. W. Nelson, John N. Abersold

INDUSTRIAL hygiene has been defined by Patty&apos; as "the science and art of recognizing, evaluating, and controlling potentially harmful factors in the industrial environment." This definition implies thorough study of operations, evaluation of potentially harmful factors through air sampling, micro-analyses and other means and finally, appropriate medical and engineering control wherever indicated. The prevention of industrial health injuries is a vital part of operations of American industry today. Progress and interest in this field has increased steadily for many years, the most rapid progress having been attained, perhaps, during the last three decades. It is significant to note that there are now official agencies in 46 states actively concerned with industrial health problems and that a western field station has been established recently in Salt Lake City by the U. S. Public Health Service to augment its industrial hygiene services directed from headquarters of the National Institute of Health, Bethesda, Md. Many of the larger industries have found it advantageous to establish their own industrial hygiene departments. The American Smelting and Refining Co. is a world-wide organization engaged in the mining, smelting, and refining of lead, copper, zinc, silver, gold, by-product metals, including cadmium, arsenic, and others. In the United States there are 13 smelters and refineries, 11 secondary smelters or foundries, and a number of mines. Approximately 9000 workers are normally employed. It has long been the established company policy to seek out occupational hazards and provide safeguards for employee health. Protective equipment has been supplied to individual workers and exhaust ventilation installations have been in use in some operations for more than 40 years. All of the major units have their own medical departments which provide employees with excellent medical and hospital care. In 1937 full scale industrial hygiene studies were undertaken at the Selby Plant and were extended to most of the other smelters during the next three years. In 1945 the Department of Hygiene was organized with Professor Philip Drinker of Harvard University as Director and with Dr. S. S. Pinto as Medical Director. The department is responsible for coordinating and maintaining a program for the good health of all employees from top management down to the lowest paid day worker. It is essentially a service organization serving all of the United States plants regardless of location or size. Full and part-time physicians employed in all of the company&apos;s American plants and working in close cooperation with the Medical Director are responsible for de- termining the state of health of all the employees and giving treatment when necessary. In general, medical care is confined to accidents or illnesses occurring while the men are on the job. Among the duties of the doctors is the making of careful physical examinations of new employees and routine check-ups of old employees. In addition to medical care a primary responsibility of the department is the prevention of occupational illnesses. In this the main concern is with the working environment in relation to its effect on the worker. Environmental factors may be dusts, fumes, gases, toxic materials, heat, humidity, radiation, or noise. The objectives are: (1) Immediate control of these factors through the education of the worker, through providing the wearing of respirators or other protective devices, and through careful medical examinations and regular analysis of urine specimens; (2) a long range control program which may be accomplished by local exhaust ventilation, wetting of materials, changes in metallurgy, changes in methods of handling, or by use of special devices and special equipment. To accomplish these objectives a fine industrial hygiene laboratory was built in Salt Lake City and equipped to do routine and experimental work. Trained and experienced industrial hygienists obtain the facts by making frequent hygiene surveys. These surveys include tests of the air, studies of all processes, and careful investigation of ventilation, lighting, and general working conditions. Except in emergencies, the air contaminants and often the substances handled by the worker are sent to the laboratory for analysis by chemists and technicians specially trained in industrial hygiene methods. The findings are evaluated in terms of limits recommended by various State and Federal agencies, and in light of all available medical data. The methods used for studying the working environment involve all of the usual chemical and physical procedures employed in industrial hygiene. The Impinger, electric precipitator, thermal pre-cipitator, and filter paper sampler have been used to collect atmospheric dust and fume samples. Of special interest here is the filter paper sampler, shown in Fig. 1, which was developed by Dr. Silver-man at Harvard University. The instrument has been improved and is used very extensively in field studies. A water manometer connected behind an orifice is used to determine the rate of air flow. Calibration is effected by use of a standard gas meter or rotameter. The dust or fume is collected on a filter paper clamped between two rings, as shown in Fig. 2. The filter paper, such as Whatman No. 52, collects both dust and fume with a very high efficiency. The instrument is very convenient and easily transported. The solids collected on the filter paper are analyzed in the laboratory usually by use of a polar-ographic procedure. By this procedure it is possible to measure quantitatively in a single analysis the

Jan 1, 1952

By James R. Stuart

AS the available remaining properties of iron ore reserves on the Mesabi Range are opened up for mining, the various properties located under lake beds are brought nearer an active status. The actual physical problems involved in stripping these properties do not act as a deterrent so much as the legal and political problems that are encountered. When it is proposed to destroy a natural lake that has been used by the public for many years, much local as well as state opposition may be encountered regarding its destruction. Public hearings must be held and some adverse publicity is likely to result. The ownership of the ore under the lake and the rights of the abutting property owners must be settled, and protection from damage caused by a disturbance in surface and subsurface drainage is likely to be demanded by property owners some distance from the proposed mine area. The Embarrass Mine, located near Biwabik, Minn., falls into this classification. A portion of the orebody lies under what was formerly Syracuse Lake, this body of water having been removed in the process of stripping the mine. An additional problem in the case of a meandered body of water is the establishment of a meander line that can be projected downward as mining progresses to form the basis for a satisfactory division between lake bed and upland ore shipments for royalty purposes. Fig. 1 illustrates the complications encountered in maintaining these divisions. A balance point was agreed upon in the center of the lake to make an equable division of lake bed ore to the abutting properties. The entire lake bed has since been adjudged the property of Minnesota. Lake Characteristics Lake bed stripping problems with which this paper is concerned necessarily are limited to a specific type of lake, namely the glacial lakes of the Lake Superior region. One characteristic common to these bodies of water is a deposit of fine black mud or silt on the bottom, frequently underlain by a layer of impervious blue clay. This is also true of the muskeg areas of the region, which present almost identical problems as lakes in stripping. The actual removal of the water and the lake bed material is a routine matter more or less standardized as to equipment, and the period of time required can be estimated easily on the basis of volume and capacity. More important than the foregoing is the execution of preliminary work, and above all, the timing involved. An account could be prepared based entirely on statistical and cost data which would give a very fair picture of the time required and cash outlay needed to effect the removal of a body of water preliminary to stripping the orebody. However, the real interest from the standpoint of the operator and the engineer who carry responsibility for completion of the job lies in the unexpected emergencies and the action of various materials involved in the stripping when the balance has been upset through diversion of water courses and the reduction of the lake level. Runoff and Drainage Lakes are located in natural basins that catch all the rain water and runoff water for a considerable area. Where a lake is involved having an inlet and outlet or a sizeable water course running through it, the drainage area may include a watershed covering many square miles. All available data then must be collected to supply a history extending over as many years for which information can be gathered on the flow of streams, annual rain and snowfall, and most important, the peak flows to be expected. Where the diversion of a stream around the stripping area is a part of the problem, this last factor is of great importance since it controls the cross-section to be selected for the diversion channel and the volume to be removed in its excavation, as well as affecting the hydraulic considerations to be met in the design of the completed channel. Characteristic material in the overburden found at the Embarrass Mine is illustrated in Fig. 2. Well Pumping Pumping from the well holes was started well in advance of the draining of the lake. Fig. 3 shows a gradual lowering of the water table with no noticeable fluctuations during the period in which the lake was being dewatered. Unfortunately, because of tight ground, a maximum flow to the wells was not maintained. This retarded the rate at which the water table was reduced so that in the course of stripping the excavation soon extended below the water table, and the great bulk of the pumping was handled from a system of sumps in the pit itself. Any dewatering program projected by prepumping from wells, a glorified well point system, would have to be started well in advance of the stripping to be of any great advantage. Preliminary drainage of the surface over the mine area is entirely apart from the actual elimination of the lake bed itself. Since the lake is what is called a perched water table because of the impervious character of the lake bottom, the adjoining surface may be dewatered below the surface of the existing lake and the flow will not be affected by the proximity of that body of water. This condition actually has been demonstrated through the establishment of a number of observation holes where a small churn drill was used to put down the holes and a 3-in. pipe was installed for taking water level

Jan 1, 1952

By K. I. Savage, S. C. Sun

This paper describes a process developed to recover coal, clays and pyrite from coal wastes. The process consists of fine grinding followed by coal and pyrite flotation which leaves the clays in the flotation pulp. A bituminous coal refuse containing 10% sulfur and 30% carbonaceous material was treated by this method to yield a coal product containing 4% sulfur, 10% ash; a pyrite product containing 45% sulfur (84% FeS2), 1% carbonaceous material; and a clay product containing 2% sulfur (3.5% FeS2). The coal yield was about 89%. The pyrite yield was about 77%. The process steps may be entirely flotation, or gravity separation (hydrocycloning) may be used to increase the pyrite : coal ratio in the flotation feed. Cost estimates for the process show a profit of $2.28 per ton of low pyrite grade refuse, but these do not include labor, maintenance, overhead and plant depreciation. The development of this process consisted of three parts: (1) exploratory tests, (2) op-timazation tests and (3) confirmatory tests. The objectionable qualities that sulfur imparts to coal have been commented upon from early times, and they have become more objectionable as the uses of coal have grown. In whatever form coal takes — raw, carbonized or gasified —the sulfur content remains objectionable, and therefore its compounds are removed as completely as possible. It has long been known that sulfur occurs in coal in different forms. In 1861, sulfur was said to exist in the state of sulfuric acid in combination with a base; in combination with iron as iron pyrites; as bisulfides of iron; and in combination with the organic elements of coal.&apos; Pyritic sulfur is a term loosely used to cover the sulfur associated with iron in its various forms. The mineralogically recognized forms are pyrite (FeS2), pyrrhotite (Fe 1-x S) and marcasite (FeS2). The particle sizes of pyrites vary widely. Isolated grains of marcasite smaller than 15 microns have been found disseminated through coal.2 Hair-like "veins" of pyrite filling cracks in vitrain have been found. At the other extreme, lumps or nodules of pyrites large enough for removal by hand picking have been encountered. Organic sulfur, unlike pyritic sulfur, does not exist as discrete particles, but is instead intimately associated with the coal structure and thus it is impossible to remove it or reduce its concentration by physical or mechanical means.2 In the preparation of coal for its various markets, the pyrite minerals (pyrites) are separated from the raw coal feed. This separation process concentrates the pyrites in the tailings or other waste products. It would be desirable to recover these pyrites for three reasons: (1) Pyrites are potential sources of sulfur and iron. In 1967, for the fifth consecutive year, Free World consumption of sulfur exceeded production.3 Propelled by the shortage, the domestic price of sulfur has risen from $24 to $38 per long ton (bright). (2) The refuse, when placed in piles, becomes ignited. The pyrites (FeS2) bum, giving off SO,. Thus, the pyrites are a cause of air pollution. (3) Also, the pyrites undergo chemical reaction when exposed to air. The refuse is leached by waters which result in stream pollution due to the water-soluble iron and acidic reaction products. Coal refuse also contains coal minerals and clay minerals. Therefore, any process for recovering the pyrites must successfully separate them from the coal and clay minerals. In the study discussed here, ten different bituminous coal refuse samples were successfully upgraded in pyrite content. These samples represented a wide variety of coal waste materials from Pennsylvania and other states. The variabilities of the sulfur and coal contents are shown in Table I. The extremes are Sample J, a high sulfur-low coal, and Sample B, a low sulfur-high coal. Definitions of some of the symbols or terms used in this report are given below: Mesh size—Tyler standard mesh screen sieves with an opening based on the square root of two. Fe —Indicates iron, as determined by a stannous reduction-dichromatic oxidation method. S—Indicates sulfur, as determined by the ASTM "Eschka" method for sulfur in coal.

Jan 1, 1969

By Mayumi Someno, Kazuhiro Goto, Masahiro Kawakami

The apparent rates of decarburization of liquid alloys of Fe-C, Fe-C-S, Ni-C, and Co-C systems and the rate of oxidation of solid graphite with pure carbon dioxide gas and with gas mixtures of carbon monoxide and carbon dioxide have been measured in the temperature range of 1000° to 1600°C. The cotnposition of carbon dioxide and carbon monoxide gas at the reaction surface has been measured by oxygen concentration cells with the ZrO,-CaO solid electrolyte. 1) The apparent rates of the carbon removal are essentially the same for all the cases of solid graphite, Fe-C, Fe-C-S, Ni-C, and Co-C systems under the same experimental conditions. 2) The apparent rates are independent of the carbon content in the high carbon concentration range but very much affected by the flow rate and the gas composition of the CO-CO2 reactant gas mixture. The ratio of the gas consumed by the reaction to the total quantity of the supplied gas is very large under the present experi~nental conditions. 3) There is a concentration gradient of&apos; carbon dioxide in the vicinity of the reaction surface and the content of CO, becomes extremely small at the reaction surface. 4) A large time fluc-tuation of the gas composition was observed. This jluctuation implies the presence of unstable flow in the gas phase in the vicinity of the reaction surface. THE decarburization of molten steel by an oxidizing gas or by slag may be one of the most important chemical reactions in steelmaking processes. Nevertheless, the kinetics of this heterogeneous chemical reaction do not seem to be well-solved even with the previous studies. Although the conditions for the reaction in steelmaking processes are quite different from those in the laboratory scale, some critical experiments may give information on the mechanism of the decarburization. From the previous work,&apos;-&apos; it is known that the rate of the decarburization is independent of the carbon content in liquid iron with more than about 0.2 wt pct C when the oxidizing gases are supplied to the surface of liquid Fe-C alloys on a laboratory scale. Two rate-controlling steps have been proposed for the decarburization of liquid iron with the high carbon content: one is the surface reaction control proposed by Swisher and Turkdogan;&apos; the other is that the rate is controlled by the gaseous diffusion through the gaseous stagnant layer. proposed by Baker. Warner, and Jenkins.7 and also by .Ito and Sano.2 In the present study, some experiments have been carried out for the evaluation of these rate-controlling steps in the decarburization of liquid iron with high carbon content. The apparent rate of decarburization of liquid iron has been compared with the rates of carbon removal of liquid Ni-C, Co-C, and solid graphite under the same experimental conditions. The composition of carbon dioxide and carbon monoxide gas at the reaction surface has been measured by oxygen concentration cells. I) EXPERIMENTAL PROCEDURE Fig. 1 shows the schematic diagram of the reaction chamber. Solid graphite and liquid metals were contained in an alumina or magnesia crucible of 32 mm ID and 35 mm in height. The samples were heated by high-frequency induction and the temperature was measured by the calibrated optical pyrometer. The temperature was held constant to within 10°C. The re-actant gases were supplied to the surface of the samples through the quartz tube of 8.0 mm ID. The distance from the end of the quartz tube to the surface was 20 mm. The block of high-purity graphite was cut and shaped to the inner profile of the crucible. The height of the shaped graphite was 18 mm, which corresponded to the depth of the liquid iron of 100 g. About 100 g of Fe-C alloy (4.20 to 4.40 pct C), Ni-C alloy (1.84 pct C), Co-C alloy (1.85 pct C), and Fe-C-s alloy (4.35 pct c, 0.5 or 1.0 pct S) were melted in the crucible. The reactant gases were pure CO, and gas mixtures of CO-CO,: the flow rates were controlled by capillary flowmeters with bleeders.

Jan 1, 1970