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By J. Jones-Parra, R. S. Reytor

The porosities of fractured limestone reservoirs can be divided into two broad types in accordance with their effects on fluid distribution and fluid flow. In the coarse porosity, gravity segregation lakes place freely and the resistance to fluid flow is very small. In the fine porosity there is no segregation and a high resistance to flow, and it has relative permeability characteristics similar to tight sandstones. By analyzing the affect of the two porosities it is concluded that in some cases to recover the maximum amount of oil it is necessary to remove large quantities of gas from the reservoir by producing at high gas-oil ratios. In this manner the fine porosity is drained of its oil and the gas-oil contact drops slowly permitting higher production rates from the oil leg. Since this conclusion is contrary to widely accepted principles of conservation, a mathematical model (Fig. I) was constructed to duplicate the conditions desired. The behavior of the model indicates that under certain conditions it is possible to recover more oil by producing at high gas-oil ratios than by production at low gas-oil ratios, and that the rate of production is affected more by gas shut-offs than by the decrease in pressure (Figs. 2, 3, 4 and 5). INTRODUCTION It has been noted that certain limestone reservoirs behave in such a way as to indicate that there are two distinct types of porous spaces available for fluid storage and fluid flow. Regardless of the nature of these porous spaces the distinguishing characteristic is that in one type of porous space there is definite gravity segregation between the oil and the gas; while in the other, the gas evolved tends to remain distributed equally throughout the reservoir. For the sake of simplicity the porosity in which gravity segregation takes place at a fast enough rate to affect the behavior will be called "coarse po- rosity", while that in which this is not so will be termed "fine porosity". The behavior of a reservoir of this type would be different than that of a sandstone reservoir, especially if most of the oil is in the fine porosity. It has been observed that fluid flow to the wells takes place mostly through the coarse porosity. The large fractures which

By H. Warlimont

In recent investigations of the microstructure and crystallographic features of martensite by electgon microscopy,', '9 thin films (about 50 to l000A in thickness) have been used as specimens. It was found by W. Pitschl ,2 that the lattice relationships between the supefiaturated fcc matrix and the martensite formed in thin films were different from those observed after transformation in bulk material. Corresponding differences are to be expected in nucleation and in reaction kinetics in the formation of martensite in thin films, but have not yet been reported. In the course of the preparation of thin films of iron-base alloys for investigation by electron microscopy it was observed that films of alloys, whose martensite formation temperature (Ms) was below room temperature, formed martensite during the electrochemical thinning process conducted at or above room temperature. The chemical compositions and approximate bulkM,-temperatures of the three materials on which this observation was made are listed in Table I. The alloys were vacuum-melted from high-purity metals. It can be seen that the effect occurred in alloys that contain only sub-stitutional components as well as in alloys that contain carbon as an interstitial solute. The appearance of martensite formed in this manner is illustrated in Fig. 1, which represents a polished film of alloy No. 1 at XI0 magnification. The martensite plates can be recognized by their surface relief effects. In addition, heavily strained (owrinkledo) austenite can be seen near the edges of the film where it is thinnest and transformation stresses or strains can be accommodated by plastic deformation most easily. The nonuniform distribution of transformed regions is probably due to the varying thickness of the film. These observations were common to all materials listed in Table I. Because effects of supercooling or straining can

Jan 1, 1962

By D. W. Fuerstenau

In 1940 Schuhmann1 showed that the size distribution of a comminuted material can be expressed by the following empirical relationship: y = 100 (|f [i] where y is the cumulative percentage of material finer than size x, k is a size modulus, and a is a distribution modulus which is constant for a given material and machine. During the past few years, considerable emphasis has been given to the investigation of the extent of size reduction resulting from the expenditure of mechanical energy in crushing and grinding. Recently Schuhmann' presented a derivation of the energy-size reduction relationship by postulating that comminution in a device such as a ball mill can be considered to be the summation of many single comminution events, each of which yields a size distribution of particles following the Schuhmann size distribution equation. By grinding

Jan 1, 1961

By FRANK COLE

THE territory covered in this discussion includes all the states west of the Mississippi river. Agriculture is expanding each year in this section, but until recent years the application of commercial fertilizers as an aid to crop production was not practised to any great extent. The use of commercial fertilizers has increased somewhat, but is still on a small basis as compared with the tonnages used else- where in the United States. During 1928 these western states used 665,100 tons of all classes of fertilizer as compared 'with 7,933,600 tons used in the whole United States; or this western area, compromising near- ly two-thirds the land area, uses about 5 per cent of the total fertilizer. To show how large a tonnage one state may consume, North Carolina for the year 192s used 1,349,360 tons of commercial fertilizer or about twice the amount used by 22 western states.

Jan 1, 1930

By Walter R. Hibbard, Cyril Stanley Smith

IN 1929 one of the authors1 determined the constitution of copper-silicon-manganese alloys contailling over go per cent copper. Through a combination of circumstances the presence of the copper-silicon kappa phase was overlooked in both binary and ternary systems. In the binary system the omission has already been rectified.2,3 To establish the limits of this phase in the ternary system, the samples that had been heat-treated at the time of the original research have now been re-examined, using more careful technique. Full details of the compositions used and the temperatures and times of heat-treatment are to be found in the earlier paper.2 The etching reagent now used to distinguish the kappa phase had the following composition: hydrogen peroxide (30 vol.), 2o c.c.; water, 25 c.c.; 20 per cent potassium hydroxide solution, 5 c.c.; ammonium hydroxide (0.90 sp. gr.), 50 c.c. 'I'able I lists the newly observed structures. In virtually every case the constituents are the same as those previously recorded, except where kappa is now shown to be present as a result of the improved etching technique. X few other changes will be noted (No. 138 at 450°C., No. 147 at 550°C., Nos. 153 and 149 at 75o°C.). The change from liquid to beta in equilibrium with kappa in No. 137 at 800°C. is based upon newly heat-treated samples. The alloy is very near the solidus at 800°C. and probably there was a slight error in the old heat-treatment temperature. The isothermal phase diagrams shown in Figs. I to 6 were reconstructed on the basis of the new studies. The presence of manganese does not greatly change the composition limits of the kappa phase or cause the K-a + Y change to occur at a markedly different temperature. There is some uncertainty regarding the range of existence of beta, for alloys were not spaced very closely in composition. The proposed diagrams, however, are in accordance with the available experimental data and with the dictates of the phase rule. Theoretically necessary fields with no experimental points are delineated by dotted lines. The alpha boundaries at all temperatures are shown together in Fig. 7. This includes also some additional points on the alpha boundary at 300' and 350°C., which were obtained as a result of electrical-conductivity measurements. Two series of seven alloys with increasing manganese content but with silicon constant at 1.90 + 0.03 per cent or 2.42 ±. 0.05 per cent were cast in ingots of 3-in: diameter. These were hot-rolled, homogenized and drawn to wire, finished at 0.08-in. diameter with a 61 per cent reduction of area following annealing at 700°C. Conductivity determinations were made before and after annealing for 30 days at 300°C. or 21 days at 350°C. Figs. 8 and 9 show the change of conductivity produced by this annealing, plotted against manganese

Jan 1, 1942

By Walter R. Hibbard, Cyril Stanley Smith

IN 1929 one of the authors1 determined the constitution of copper-silicon-manganese alloys contailling over go per cent copper. Through a combination of circumstances the presence of the copper-silicon kappa phase was overlooked in both binary and ternary systems. In the binary system the omission has already been rectified.2,3 To establish the limits of this phase in the ternary system, the samples that had been heat-treated at the time of the original research have now been re-examined, using more careful technique. Full details of the compositions used and the temperatures and times of heat-treatment are to be found in the earlier paper.2 The etching reagent now used to distinguish the kappa phase had the following composition: hydrogen peroxide (30 vol.), 2o c.c.; water, 25 c.c.; 20 per cent potassium hydroxide solution, 5 c.c.; ammonium hydroxide (0.90 sp. gr.), 50 c.c. 'I'able I lists the newly observed structures. In virtually every case the constituents are the same as those previously recorded, except where kappa is now shown to be present as a result of the improved etching technique. X few other changes will be noted (No. 138 at 450°C., No. 147 at 550°C., Nos. 153 and 149 at 75o°C.). The change from liquid to beta in equilibrium with kappa in No. 137 at 800°C. is based upon newly heat-treated samples. The alloy is very near the solidus at 800°C. and probably there was a slight error in the old heat-treatment temperature. The isothermal phase diagrams shown in Figs. I to 6 were reconstructed on the basis of the new studies. The presence of manganese does not greatly change the composition limits of the kappa phase or cause the K-a + Y change to occur at a markedly different temperature. There is some uncertainty regarding the range of existence of beta, for alloys were not spaced very closely in composition. The proposed diagrams, however, are in accordance with the available experimental data and with the dictates of the phase rule. Theoretically necessary fields with no experimental points are delineated by dotted lines. The alpha boundaries at all temperatures are shown together in Fig. 7. This includes also some additional points on the alpha boundary at 300' and 350°C., which were obtained as a result of electrical-conductivity measurements. Two series of seven alloys with increasing manganese content but with silicon constant at 1.90 + 0.03 per cent or 2.42 ±. 0.05 per cent were cast in ingots of 3-in: diameter. These were hot-rolled, homogenized and drawn to wire, finished at 0.08-in. diameter with a 61 per cent reduction of area following annealing at 700°C. Conductivity determinations were made before and after annealing for 30 days at 300°C. or 21 days at 350°C. Figs. 8 and 9 show the change of conductivity produced by this annealing, plotted against manganese

Jan 1, 1942

By Philip B. Bucky

CONTENTS [PACEPACE r. What Is a Rock Burst?2 4. How Can Rock Bursts Be Predicted? . 35 Jack Spalding2Jack Spalding35 A. F. Robertson 2, 5A. F. Robertson35 W. R. Crane 2A. B. Yates and P. J. Shenon. . . . 35 G. S. Rice 2W. R. Crane 35 P. J. Shenon 2G. S. Rice 35 L. C. Graton 2B. F. Tillson 36 2. What Are the Causes of Rock Bursts? 6 5. How Can Rock Bursts Be Controlled?. 36 Jack Spalding6Jack Spalding36 A. B. Yates and P. J. Shenon . 7, 12, 29A. F. Robertson 36 A. F. Robertson 12, 28W. R. Crane37 W. R. Crane 15A. B. Yates and P. J. Shenon. . . . 37 G. S. Rice 15Oscar Weiss38 Oscar Weiss15G. S. Rice37, 42 P. B. Bucky21R. D. Hoffman42, 43 P. H. Bird 21, 26, 28R. D. Hall 42 M. K. Hubbert26R. H. Cromwell42 G. Wheeler 26. J. Shenon 42 B. F. Tillson26, 28P. B. Bucky42, 44 T. T. Read 27B. F. Tillson 42, 44 A. B. Yates 43, 44 3. How Can Rock Bursts Be Prevented? . 30P. H. Bird 43 Jack Spalding. . . . • . • • • • . 306. General Discussion . A. B. Yates and P. J. Shenon. . . . 31Jack Spalding44 A. F. Robertson32R. D. Parker49 W. R. Crane 35C. Baring Horwood 51 G. S. Rice 35P. B. Bucky 52] FOREWORD THIS symposium brings together points of view, experiences and ideas on rock bursts from a goodly portion of the globe. Some conceptions, particularly those regarding the necessity of depth, have been fairly well shattered, as we find that they are present in the water tunnels of New York, on the surface at marble quarries in Vermont, and in the coal mines of the United States, as well as in the deep mines of the South African and Kolar gold fields, and in the nickel, copper and gold mines of Canada. Their occurrence under such a variety of conditions is, therefore, a challenge,

Jan 1, 1942

By F. W. Bowdish

Analysis of data on the equilibrium exchange of sodium ions from salt solutions for calcium ions, from various fractions of an oxidized calcareous iron ore from Lorraine, France, strongly suggests that the calcium may be attached to the solid by only one of its bonds. Nearly equal values were found for the equilibrium expression from data covering concentration ranges of 1000 fold for the salt and 235 fold for the ion-exchangeable calcium. Differences indicated between the exchangeable calcium contents of the slime and the sandy portions of the ore, as well as the equilibrium relationship itself, are of importance in the flotation of the ore. During an experimental program on the flotation of oxidized calcareous iron ores from Lorraine, France, ion-exchangeable calcium was found in the ore. Because this source of calcium ions, if not controlled, could thwart all efforts at flotation, an extensive study was made of the phenomenon. The part of that study reported here was to obtain data on the equilibrium established between ore solids and solutions of sodium chloride, and to analyze the data to try to understand better the physical chemistry of the exchange. The ore contains oolites of goethite and quartz grains embedded in a matrix consisting of calcite and a brown cement believed to be the residue from oxidation of the silicate minerals found in fresh unoxidized ore. When ground, a substantial fraction of the ore becomes a fine slime in which is concentrated more than half of the alumina content of the ore. It is believed that the alumina occurs as unidentified clay minerals with which most of the ion-exchange capacity of the ore is associated. A preliminary experiment on the exchange of ions from the ore for sodium ions from solutions of NaCl showed that calcium was about ten times as abundant as magnesium in the exchange solutions. Thus calcium was the predominant ion in causing difficulties with flotation, and it was the only one for which data was obtained in this study. It is believed that the omission of magnesium ion exchange from consideration does not invalidate the results. It is possible, however, that inclusion of magnesium in the analyses and calculations or its prior elimination from the samples would have improved the consistency of the results. EXPERIMENTAL Data about the equilibrium exchange of sodium from solutions for calcium from the solids were obtained using two different samples of material. The solids

Jan 1, 1963

The Carlin gold deposit is located in northeastern Nevada about thirty-five miles by road from the town of Elko. Following the staking of six square miles 'of ground, a drilling program outlined a fine ore body mineable by open pitting. The resulting mine turned out to be the largest open-pit gold operation in the world, until the Rosario Pueblo Viejo operation was started in 1975. Because of the high profitability forecast at the then $35 gold price, construction of a 2000 stpd mill was commenced on a crash program and was completed for Newmont Mining Corporation by Bechtel Corporation in ten months. Production was started in early 1965. The gold mineralization occurs in marine-type sediments, chiefly silt- stones and limey shales, and the ore characteristics make for a difficult materials-handling problem. At 5% to 6% moisture the ore is dusty during crushing, but even a light rain or snowfall virtually turns the material into a slurry. Crushing this sticky ore below 314 in. (19 mm) in the dry season and 1 in. (25.4 m) during the winter is extremely difficult and leads to problems with conveyors, chutes, and fine ore storage. The initial flowsheet for Carlin's crushing plant used a 5 ft by 22 ft (1.52 m by 6. 7 m) vibrating feeder -grizzly under the 60 -ton dump pocket for feeding the 42 in. by 48 in. (1067 mm by 1220 mm) single toggle jaw crusher and a 5 ½ ft (1.52 m) standard cone crusher in closed circuit with a 6 ft by 12 ft (1.83 m by 3.66 m) vibrating double - deck screen. Because continual packing of fines in the vibrating feeder pan would cause frequent plant shut-downs to remove the fines with jack hammers, the decision was made to replace the vibrating unit with an apron feeder and stationary grizzly ahead of the jaw crusher. A dribble belt was also installed under the apron feeder. This installation has greatly improved the feeding of the pit run ore to the .primary jaw crusher. Mining at Carlin is done by a 5 yd shovel and 7 ½ and 10 yd front-end loaders, and ore transport is by several sizes of trucks from 30 to 75 tons capacity. These pit haulage trucks dump onto stockpiles adjacent to the primary crusher. Ore is then fed to the dump hopper by front- end loaders only when the crushing plant is operating. This extra handling procedure is necessary because plant delays caused by problems with wet ore in the secondary crusher resulted in the ore setting up or packing in the dump pocket. Solidified material in the dump pocket would in turn delay truck haulage. The substitution of an

Jan 1, 1978

By J. Douglas, W. T. Ford, G. E. Henderson, I. F. Roebuck

An implicit numerical method is presented for simulating the differential and algebraic relations governing one-dimensional three-phase flow in porous media. The method is based upon compositional representation of the hydrocarbon system. Variable physical properties and water-oil capillary forces are included in the formulation; however, the effect of gravity is ignored. The effects of changing composition and mass transfer are considered through the use of known phase behavior concepts and correlations. The differential and algebraic equations and the numeric approximations to these equations are presented, and the computing algorithm is discussed in detail. This method is used to simulate a single-phase, two hydrocarbon-component gas displacement laboratory experiment. The method is also applied in simulating a solution gas drive and a gas injection problem using a reservoir oil represented as a nine-component mixture. For comparative purposes, the latter two problems also are examined with a one-dimensional volumetric model. The results of the simulation of the laboratory experiment demonstrate the relevance of this method to problems wherein the effects of mass transfer significantly enter the displacement process. The comparison of the results of the volumetric and compositional methods applied to a reservoir system illustrates not only the advantages and benefits derived from examining the hydrocarbon system composition, but also the necessity of this approach in application to a general reservoir problem. INTRODUCTION The advent of large memory, high-speed digital computers enabled reservoir engineers and mathematicians to pool their knowledge in the development of sophisticated techniques for the prediction of oil and gas reservoir performance. These techniques have progressed from volumetric and trend analysis calculations to the development of "mathematical models", or reservoir simulators. These latter models, in general, utilize finite difference approximations to the rather complex partial differential equations that mathematically describe the physics and thermodynamics of fluid flow in porous media. Many forms of this "model" type are available today, and much of the recent literature has been devoted to either improving known methods or developing new techniques for use in these prediction methods. The more advanced techniques in use at this time consist of the solution of differential and algebraic relations that describe a reservoir geometry in one, two or three dimensions and that incorporate reservoir hydrocarbon and water fluid systems that obey specified physical laws, having properties that might easily be measured in the laboratory. This type of model utilizes formation volume factors and other volumetric data, expressed directly as functions of pressure, to represent the reservoir fluid system. Experience gained with this type of simulator, commonly known as a "beta-factor model", has indicated that the approach has many outstanding defects, most of them due to the assumption that those properties measured in the laboratory completely describe the behavior of the fluid system throughout the life of the project under study. The effects of varying hydrocarbon composition and mass transfer between the phases of this hydrocarbon system must, by definition, be ignored. These defects, which may often be ignored in

Jan 1, 1970

By Thomas R. Mager

An in.t!estigation has been made of the equilibrium conditions at 1200°C in the reaction between hydrogen sulfide gas and sulfur dissolved in Fe-Si alloys From this the equilibrium constant, activity coefficient, and activity of sulfur in solution were calculated. A number of studies of the equilibrium of sulfur with iron and iron alloys have given closely agreeing results from which the activity and free energy of the dissolved sulfur may be found. Sherman, El-vander, and chipman1 discussed the significant researches of dilute solutions of sulfur in liquid iron prior to 1950, and the results of this study indicated that the relationship between the ratio of PH2S/PH2 in the environment and the percentage of sulfur in solution is not a linear one. Morris and williams2 studied the equilibrium conditions in the reaction between hydrogen sulfide gas and sulfur dissolved in liquid iron and Fe-Si alloys, and reported that silicon dissolved in iron has a pronounced effect on the equilibrium conditions. They found that the activity of sulfur in iron is increased by the addition of silicon. At a silicon content of 4 pet the activity coefficient of sulfur was about twice that for sulfur dissolved in pure iron. Sherman and chipman3 investigated the chemical behavior of sulfur in liquid iron at 1600°C through the study of the equilibrium: H2 + S = H2S; K = PH2S/PH2 . 1/as [1] From the known equilibrium constant of the reaction between H2, H2S, and S and the experimental data, the activity of sulfur in the melt was determined. They found that the activity coefficient of sulfur defined as fs = as/%s is increased by silicon and decreased by manganese. Morris4 and Turkdogan5 also reported that manganese decreases the activity coefficient of sulfur in liquid iron and iron-base alloys. A recent technique of sulfur analysis developed by Kriege and wolfe6 of the Westinghouse Research Laboratories permits an accurate sulfur analysis of 0.5 * 0.2 ppm in the range of 0.1 to 3 ppm, whereas in the range of 3 to 50 ppm the accuracy is ±1 ppm. This technique of sulfur analysis was utilized in this experiment. Previous unpublished data reported that sulfur analysis by the combustion technique was not accurate below 20 ppm. EXPERIMENTAL PROCEDURE Five 5-lb ingots of high-purity Fe-Si were prepared. Three of these ingots were prepared without the addition of manganese but with a variation of silicon contents from 2 to 4 pet. The remaining two ingots contained 3 pet Si with the addition of manganese. Ingots were made at each of three silicon levels: 2, 3, and 4 pet. No alloys were made with less than 2 pet Si since below approximately 1.8 pet Si the binary alloy exhibits a to ? transformation. The two additional ingots of 3 pet Si-Fe were made at each of two manganese levels: 0.20 and 0.50 pet. To minimize the effects, if any, of impurities on the activity of sulfur on Si-Fe, the best metals available were used for melting. All ingots were vacuum-melted in magnesium oxide crucibles. After obtaining samples for chemical analyses, the ingots were processed. This consisted of hot rolling and subsequently cold rolling the alloys. Each ingot was hot-rolled at 1000°C, reheating between every pass to minimize grain growth. All heating was done in a protective argon atmosphere. The slabs were hot-rolled to strips 50 mils thick. After hot rolling, all the material was pickled to remove the scale formed on the surface of the strip during hot rolling. The material was then cold-rolled to 12-mil strips. Single strips of the material used in this experiment were hydrogen-annealed at 1200°C for 16 hr in an alumina tube. Chemical analyses of strips M-1, M-3, M-4, M-7, and M-8 are given in Table I. Sulfur, silicon, and manganese analyses were made from the millings from the cold-rolled 12-mil strips. The oxygen analyses were made from slugs of the as-cast material. The hydrogen sulfide used in these experiments was supplied from cylinders containing a mixture of argon and 1 pet hydrogen sulfide. The parts per million of hydrogen sulfide were determined from the analysis of the exit gas of the annealing furnace during each anneal. The flow rate of hydrogen was approximately 1 liter per min in all anneals. The

Jan 1, 1964

By T. Egleston

The materials containing copper which are refined in the United Statrs, are, for the most part, the natiye noppers of Lake Superior. IJntil quite recently but little pig copper Was made for sale, and that came principally from the pure sulphorous ores of New England and the Sonth, and was generally sdd to reSneries not far from the ore filrnaceu. A stnall aiuoiint found its way into the'niarket which was produced either as the by-product of the treatment of gold and silver ores, or as the result of the treatment of impure copper ores; but both these grades, on account of the impurities they contained, were loolced on with stlspicion, and were not sought for. A11 the grtlGis of pig coppcr are sold by the unit of oopper contents, a great redtiction being made in the price when impurities are present. There are at the present time only three works which treat native copper, the two of the Detroit and Lake Superior copper Company, and the works of C:G. Hussey & Co., in Pittsburgh. There are a few works ivhich smelt sulphuroris ores and refine their pig; bo sides these t1le1-e arc a few siuall works where gig copper is refined uuly. Some of these purcIlase blscir copper, refine scrap, or simply refine such grades of ingot copper as are found in the market, but nlostly that from Lake Superior, for the purpose of getting it into swh shapes that can be handled cpmtriercially to advantage, such as in making large plates or high grades of wire fir electrical purposes. A nomher of such works are situated in the Xaugaturk Vatley aud elsewhcre in New England. The recent discoveryof vnlt~sblc ores in Ariarona makm it probable that within a few year8 the refining of capper In the United States will make great develupments. Up to the time of the discovery of the mines on Lake Superior, only a very small quantity of native copper had ever been foond, not sufficient to justify the erection of worlrs fbr its special treatment. It had, besides, never been found in very large maweq so that the discovery of greabblocks of it presented serious difficulties, not oolp in mining it,-I- but in bringing it into a merchantable condit'ion. It seemed a very simple process to melt these large maws,

Jan 1, 1881

Four years of intensive exploration effort by Newmont Mining Corp. came to a climax May 27 in Carlin, Nevada, when local, state and federal officials joined with company officers at a dedication ceremony saluting the start-up of the firm's wholly- owned subsidiary, Carlin Gold Mining Co. Before an invited audience at the plant site, Newmont's President Plato Malozemoff and Nevada's Senator Howard D. Cannon pushed a lever and watched the new melting furnace rotate until a brilliant orange-red stream of molten gold poured forth from its mouth. Two 1200-oz bricks of bullion were poured that day, and they are the first of many that will lift this mine into the number two slot among U.S. gold producers and fourth among all gold mines on the North American continent. Although Newmont Mining first entered the gold mining business in 1929 in Grass Valley, California, the Company had operated no gold producers since the well-known Government directive L208, issued in 1942, closed down U.S. gold mines for the duration of World War 11. Now it is back in the business in a big way-a $10 million mine and plant capable of producing 200,000 oz. per year. All the gold from the Carlin operations is earmarked for the U.S. Mint in San Francisco.

Jan 7, 1965

By A. Moskowitz, L. S. Redmerski

The corrosion resistance of stainless steels can be strongly affected by surface treatments. Changes in corrosion resistance can relate to surface composition, integrity and stability of the passive film, and to surface profile (roughness). Operations producing oxidation at the surface, such as annealing, heat treating, and welding, can result in a chromium-rich scale and a chromium-depleted metal surface. In order to restore full corrosion resistance, chemical or mechanical clean-up techniques must remove not only the oxide, but also a very thin layer of metal. Laboratory and field test studies show that these factors are particularly significant in less highly alloyed steels. Annealing stainless in a reducing atmosphere (bright annealing) avoids chromium depletion, but as-bright-annealed material does not display optimum corrosion resistance in certain environments. Electro passiva-tion can be applied to improve pitting resistance without significantly changing bright surface appearance. Potentiometric studies show that electropassivated material also displays significantly greater resistance to breakdown of passivity in acid solutions. The application of special surface finishes for appearance purposes can affect corrosion resistance. Roughness is a key factor. Samples of related appearance but with different surface profiles can show significant differences in corrosion resistance. Thus nonreflec-tive stainless with a relatively smooth surface produced by a special rolling process is much superior to material chemically etched to a similar low reflectivity. THE corrosion resistance of a stainless steel is affected by other factors in addition to its bulk composition and metallurgical structure. These other factors include those relating to the specific chemical and physical condition of the steel's surface. This paper will consider certain aspects of surface condition in relation to corrosion resistance. In particular, studies will be described on the effects of oxidation encountered in heat treating or welding operations, of passivation after bright annealing, and of different surface finishes. EFFECTS DUE TO OXIDATION When stainless steels are exposed to high temperature in an oxidizing environment, as in annealing or welding, the oxides formed are relatively rich in chromium. As a consequence of oxidation, the metallic layer directly beneath the scale may be low in chromium to some very thin but finite depth.1"8 Such a change in chromium content could lower the corrosion resistance at the surface, whether or not the oxide layer is removed. Studies were performed relating to the effect of oxidation and chromium depletion produced during annealing and welding on the corrosion resistance of stainless steels. The nominal compositions of steels used in this study and others are given in Table I. A) Annealing Studies on 17 pet Cr Steels. 1) Effects of Pickling Treatments. Studies were performed to investigate the corrosion resistance of air annealed type 430 stainless as a function of the amount of electrolytic pickling after annealing. The material used in this study had been air annealed and electrolytically pickled in the mill. All scale had been removed, and yet the material showed unusually poor corrosion resistance. Laboratory electrolytic pickling studies were performed to determine whether additional metal removal from the surface would improve corrosion resistance. Electrolytic pickling was performed in a sulfuric acid bath using various conditions of bath acidity, temperature, time, and current density. The samples were then rated for corrosion resistance in a ferric chloride spot test. For this spot test, a solution was prepared by dissolving 10 g of FeCl3 . 6H2O, 5 g of NaCl, and 2.5 ml of concentrated HC1 in 200 ml of water. An area on a specimen was cleaned and a drop of test solution was placed on the prepared area. After 5 min, the drop was rinsed off and the area wiped dry. The spot was then rated between 1 and 5 by visual comparison with standard spots. The numerical rating of the standard spots can be described as follows: 1—No clouding of surface; 2—very slight clouding of surface; 3—slight clouding of surface; 4—moderate clouding of surface; 5—strong clouding of surface. A rating of 1 or 2 was considered to have passed the test, a rating of 4 or 5 represented failure, and a rating of 3 was considered borderline. The severity of etching in this test has been related to the actual chromium content at the surface.4 Etching (clouding) occurs on type 430 stainless (rating of 4 to 5) when the surface chromium content is 14 pct or less. The effects of current density and retention time when electrolytically repickling this material in 6 pct sulfuric acid are shown in Fig. 1. Increasing the cur-rent density or retention time improved corrosion resistance as measured by the spot test. Similarly, increasing acid concentration of the bath or bath tem-perature was found to improve corrosion resistance. The conditions making for improved spot ratings resulted in increased metal removal, regardless of specific pickling conditions used, Fig. 2.

Jan 1, 1970

By AIME AIME

THE Board of Trustees, made up of three from each of the four societies, conducts the business com- mitted to United Engineering Society by its Founder Societies under its Charter, the Founder's Agreement and the Library Agreement. A draft of a budget of revenue and expenditures for the ensuing calendar year is presented each September to the secretaries of the Founder Societies for the information and comment of their governing bodies. After revision, the budget is adopted, by the incoming Board of Trustees at its meeting in January.

Jan 1, 1929

By A. C. Fieldner

COKE and by-products have prime importance in the war program. The past year was marked by the construction of new and the rehabilitation of old by-product and beehive ovens and by the increase of production from existing plants to practically 100 per cent capacity. W. T. Brown's paper, "Plan to Improve Blast-Furnace Coke," presented at the Fuels Conference in St. Louis, Sept. 30, showed how the blending of low- and high-volatile coal improved the physical properties of coke and that improvement of the quality and uniformity of coke favored an increase of blast-furnace capacity- a vital need in the war program. Others in the industry have likewise increased production of coke or recovery of by- products by various innovations or changes in operation. Recognition of the value of pooling these developments for the benefit of the entire industry led to organization of a survey of coke- oven plants and blast furnaces by the Bureau of Mines in co-operation with the Solid Fuels Co-ordinator with a view to improving metallurgical coke production and recovery of by-products. This survey is being conducted with the help of an advisory committee consisting of representatives of the Bureau of Mines, the Solid Fuels Co-ordinator, the War Production Board, and the blast-furnace, coke-oven, and coal-mining industries.

Jan 1, 1943

By R. G. Fleck, W. R. Webb

Iron ore mining in the Adirondack region of northern New York dates back to the Revolutionary War. It is recorded that Benedict Arnold in his campaigns in the Lake Champlain area during the American Revolution utilized the local ores to produce armament and cannon balls. Through the efforts of early pioneers, the iron mining industry in northern New York gained impetus so that in the 1880's mines in the area accounted for nearly one fourth of the iron ore produced in the United States. Both magnetite and red hematite ores were mined during this period. With the discovery of the Lake Superior ores, the iron ore industry in New York started to decline and remained relatively unimportant until 1938. Modern day methods of mining and beneficiating sufficiently high tonnages of low-grade ores to justify the large expenditures for plant and equipment prompted a resurgence in northern New York mining. During the past several years, the production of iron ore from the Adirondack magnetites has greatly increased, and production which amounted to .6%, of the United States total during the 1918-1928 period (Mining and Metallurgy, November 1943) has been increased to 2.85% of the total in 1948. Today, Republic Steel is mining in the Port Henry-Mineville and Lyon Mountain areas; the

Jan 4, 1950

The Palabora ore consists of two types, a carbonatite containing a low titanium magnetite, and a foskorite containing high titanium magnetite. The latter type also contains substantial quantities of phosphate. These two ore types are separately crushed and are kept separate through copper flotation and magnetic separation, for recovery of magnetite, with the low Ti magnetite being shipped as iron ore. High phosphate tailings are pumped to Foskor, a government-owned phosphate plant nearby. The Palabora plant was originally designed in 1966 for 33, 000 tpd using two 54 in. by 74 in. Allis -Chalmers gyratories; two 7 ft (2. 13 m) standards; four 7 ft shortheads; and six grinding lines, each using one 1,200 hp rod mill and two 1,200 hp ball mills. A fifth short- head and one more grinding line were added later; and with flowsheet improvements, the capacity of the plant was increased to 59, 500 stpd. A further plant expansion involving a third 54 in. primary and two 32 ft by 15 ft (9.75 by 4.6 m) 9,000 hp autogenous mills and another flotation section will bring its capacity to 87,500 stpd in 1977. These two fully autogenous mills are constructed entirely out of doors near the primary crusher, and the ground ore will be pumped a mile to the concentrator by a five-stage pumping system. The Palabora ore is mined with 6, 10, and 12 7d (4.6, 7.6, and 9. 2 cu m) shovels and hauled to the crushers in 110 and 165 st trucks. Sixty-five ton trucks were originally used, but the crusher dump pockets were designed for larger units. Dump pockets, crushers, feeders, and take- away belts are offset in order to keep the two ore types separate. Centerlines of the crushers are only 43 ft (13. 1 m) apart; but, because of their being offset, maintenance room is ample. Initially, more carbonatite ore than foskorite was mined; but as the pit has deepened, this ratio has been reversed. The Palabora ore breaks in the pit with a large amount of oversize boulders; and, with the use of larger trucks, a splitter has been installed on one side of each dump pocket to protect the crusher spider. Smaller trucks dump on the opposite side. To accomodate the splitter, the pocket edge has been raised one meter and moved back one meter. Dust is collected through a special vent shaft between the crushers and the mantle relining area; but even so, two high-pressure water spray headers with nozzles are installed under the edge of the pocket at each dumping position. While only one truck dumps at a time, sprays from all four headers are used to suppress dust. Any leakage of water through the seal around the upper bowl of the crusher is caught by a circular trough under the seal and directed to a sump pump. At this point, there

Jan 1, 1978

By A. L. Holley

THIS process is performed in the Pernot puddling furnace; it removes from 75 to 80 per cent. of the phosphorus, most of the sulphur, and practically all the silicon, from crude iron, in from five to eight minutes. It has been in regular use since March, 1877, and has prod uced over seventeen thousand tons of washed metal for the open-hearth furnace. During two years, nearly all, and lately, all the open-hearth steel produced in these works has been made from about 5 tons of washed pig and 2 tons of scrap per open-hearth furnace heat. There are 12 open-hearth furnaces, of which 4 to 9 are running, according to the state of orders. A large amount of highly phosphoric iron from France and Belgium has been also washed and then puddled for parties who have taken, or are expected to take, licenses. The washing of pig for puddling, however, is not a practice at Krupp's works, because pure pigs are nearly as cheap as impure ones. The author and his assistant, Mr. Laureau, spent, during the last month, three days at Krupp's works, examining this process. They copied out of the office books characteristic analyses and physical tests, some of which are given herewith. They also brought hone many samples of pig, cleaned metal, puddle bar, and steel, which they saw treated. Analyses of some of these samples appear in Table IV. As there are no blast furnaces at Essen, the iron is melted in two Bessemer cupolas with fore-hearths; they melt 12g pounds of iron with 1 pound of coke. The metal is run by a spout from the fore-hearth into an opening at the side of the main door of the washing-furnace. The Washing furnace.-This is a regenerative gas furnace. It has a Pernot revolving-hearth of 12 feet external diameter and 3 feet depth. (See Plate.) The four regenerator chambers have 780 cubic feet capacity, which is about the same as the average regenerator capacity of open-hearth steel furnaces of equal tonnage. The lining is 13 inches thick on the sides and 9 inches on the bottom, thus giving a hearth 9 feet 10 inches by 2 feet 3 inches deep. The lining is composed of lumps of highly refractory ores

Jan 1, 1880

By A. L. Holley

This process is performed in the Pernot puddling furnace; it removes from 75 to 80 pel. cent. of the phosphorus, most of the sulphur, and practically all the silicon, from crude iron, in from five to eight minutes. It has been in regular use since March, 1877, and has produced over seventeen thousand tons of mashed metal for the openhearth furnace. During two years, nearly all, and lately, all the open-hearth steel produced in these works has been made from about 5 tons of washed pig and 2 tons of scrap per open-hearth furnace heat. There arc 12 open-hearth furnaces, of which 4 to 9 are running, according to the state of orders. A large amount of highly phosphoric iron from France and Belgium has been also washed and then puddled for parties who have taken, or are expected to take, licenses. The mashing of pig for puddling, however, is not a practice at Krupp's works, because pore pigs are nearly as cheap as impure ones. The author and his assistant, Mr. Laureau, spent, during the last month, three days at Krupp's works, examining this process. They copied out of the office books characteristic analyses and physical tests, some of which are given berewith. They also brought home many samples of pig, cleaned metal, puddle bar, and steel, which they saw treated. Analyses of some of these samples appear in Table IV. As there are no blast furnaces at Essen, the iron is melted in two Bessemer cupolas with fore-hearths; they melt 124 pounds of iron with 1 pound of coke. The metal is run by a spout from the forehearth into an opening at the side of the main door of the washingfurnace. The The washing-furnace.—This is a regenerative gas furnace. It has a Pernot revolving-hearth of 12 feet external diameter and 3 feet depth. (See Plate.) The four regenerator chambers hare 780 cubic feet capacity, which is about the same as the average regenerator capacity of open-hearth steel furnaces of equal tonnage. The lining is 13 inches thick on the sides and 9 inches on the bottom, thus giving a hearth 9 feet 10 inches by 2 feet 3 inches deep. The lining is composed of lumps of highly refractory ores

Jan 1, 1880