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By B. S. Gottfried

A generalized mathematical model is presented, which describes the thermal recovery of oil in linear systems with convective external heat loss. Three-phase fluid flow, conduction-convection heat transfer, chemical reaction between oxygen and oil and aqueous phase change are included, making the model applicable to a variety of thermal recovery processes. The complexity of the model requires that numerical solutions be obtained with a digital computer. The numerical approximations of the partial differential equations are presented and the algorithm is discussed in detail. The analysis is applied to the detailed simulation of a forward-combustion laboratory tube experiment. The results of the simulation exhibit with reasonable accuracy all of the principal thermal and bydrodynamic characteristics observed in the laboratory (i.e., the propagation of a combustion zone, a steam plateau, and oil and water banks). Numerical variations in the parameters appearing in the external heat-loss term, the aqueous phase-change term, and the Arrhenius combustion term are examined, and their effects on the predicted temperature profiles, oil and water production histories, and the air-oil ratio are presented. In spite of an oversimplification in the chemical reaction mechanism and the considerable computer time required to obtain solutions, the model represents a major advance in the ability to simulate the phenomena observed in thermal recovery experiments. INTRODUCTION Thermal oil recovery refers to a class of recovery processes where heat is supplied to a reservoir to provide the necessary expulsive energy. This thermal energy can be supplied externally as steam or hot water, or it can be generated in situ by forward or reverse combustion. In either case, however, thermal recovery processes are charac- terized by the simultaneous flow of two or three fluid phases in a variable - temperature field, accompanied by possible chemical reaction or phase-change effects.2-5, 7- 10, 14,16-18,20-22 Although a physical understanding of the thermal recovery processes is far from complete, it is possible to construct mathematical models which describe approximately all of the principal physical and chemical phenomena. However, attempts to solve such models, even with high-speed computers, involve formidable mathematical difficulties. Consequently, theoretical solutions have been obtained only for idealized cases in which important physical phenomena are neglected. For example, consider the process of forward in situ combustion. All such theories which have been developed consider only certain aspects of the process, such as heat transfer, 2-4,8,9,l6,l8 heat transfer with phase change,10 heat transfer with chemical reaction,7 or the hydrodynamics of three-phase flow.21 A general theory including all of the above phenomena has not been developed to date. This paper presents a unified theory of thermal recovery processes in linear systems. A mathematical model is developed which explicitly includes conduction-convection heat transfer with convective external heat loss, chemical reaction between air and oil, aqueous phase change, and the hydrodynamics of three-phase flow. A system of equations is developed which can be solved numerically on a high-speed digital computer, resulting in predicted temperature, pressure, and saturation histories in space and time. The model allows a more detailed simulation of thermal recovery tube experiments than had previously been possible. THEORETICAL DEVELOPMENT Consider the linear flow of gas, water and oil in a homogeneous porous medium. Assume that the oil will react with gaseous oxygen, and that mass is transferred between the water and gas phase by evaporation or condensation. In the absence of hydrocarbon phase change, intraphase diffusion,

Jan 1, 1966

By A. H. Larson, R. J. McClincy

The activity of Sb,03 in PbO-Sb,03 slags containing less than 50 mol pct Sb,03 was determined by the inert-gas saturation method at 700°C. In this composition range, the activity gf SbzO3 shows a strong negative deviation from ideality. The activity of PbO in these slags was calculated by application of the Gibbs-Duhem iniegration to the Sb203 activity data. The calculated activity of PbO in slags containing more than 63 mol pct PbO was found to deviate in a positive direction from ideality uthile a negative deviation was found for slags containing less PbO. The standard Gibbs free energies of formation of Sb,03 and PbO. Sb203 have been calculated and compared with existing data in the literature. The activity of Sb203 in PbO-Si0,-Sb203 (PbO/SiO, = 2) slags containing less than 25 mol pct Sb,03 was also determined by the inert-gas saturation method at 700°C. In this composition range, the activity of Sbz03 shows a very large negative deviation from ideality. VERY little experimental work has been published in the past to determine equilibrium data in the oxide systems connected with the refining of lead. These data are of value since impurities such as antimony, arsenic, and tin must be removed from lead and recovered for further treatment. Equilibrium studies on antimony and arsenic systems are also of interest for the design of new processes for lead refining and lead dross treatment. Maier and ~incke' first determined the liquidus curves for the PbO-Sb203 system and identified the compound PbO . Sb203. They found the phase diagram for this system to be two simple eutectics located on either side of the congruent melting compound. They also determined a very limited amount of vapor pressure data for Sb406 abbve PbO-Sba3 melts at 697"~. A second phase diagram investigation on this system was reported by Hennig and Kohlmeyer' who confirmed the existence of the compound PbO . Sb203 as well as the form of the diagram. A disagreement was noticed, however, in that their liquidus temperatures over nearly the entire composition range were higher than those reported by Maier and Hincke. Barthel~ and pelze14 redetermined the liquidus curve at the PbO-rich end of the PbO-Sb@, system and agreed very closely with the results of Maier and Hincke. None of the investigators mentioned above reported any mutual solid solubility in the PbO-SbD3 system. Zunkel and Larson5 have determined the phase diagram for the PbO-rich end of the PbO-Sb203 system by slag-metal equilibrium studies in the Pb-PbO-Sb203 system and by thermal analysis studies in the PbO-Sbz03 system. A maximum solid solubility of 5.6 mol pct Sb203 in PbO was observed at the eutectic temperature of 604°C. Their results for the phase diagram agree favorably with those of Maier and Hincke. The vapor pressure of Sb2O3 in the temperature range from 470" to 800°C has been determined by Hincke, using a modification of the transportation meth~d.~ His results for temperatures below the melting point of Sba3 are the only data reported in the published literature. The predominant vapor species has been shown to be Sb,06 by Norman and staley.? Myzenkov and Klushin,8 using the boiling-point method, have determined the pressure of Sb406 above liquid SbD3 in the temperature range from 715" to 1025°C. The agreement between these two studies is not very close. A portion of the discrepancy lies in the fact that Hincke used silica crucibles, which were attacked by the liquid Sbz03 at high temperatures. This fact does not account, however. for the large difference observed at the melting point. ~aier' gives a brief summary of vapor pressure data for Sb,O, above pure liquid Sbz03 which agree quite well with the data of Myzenkov and Klushin at temperatures near the melting point. This paper describes the determination of Sb2O3 activity data in the PbO-Sb203 and Pb0-Si02-Sb203 (PbO/SiOz = 2) systems by the inert-gas saturation method. These activity data are compared with the data calculated by Zunkel and arson. EXPERIMENTAL Materials. The materials used in this investigation were analytical reagent-grade PbO (99.8 pct PbO, 0.14 pct insoluble in CHsCOOH, 0.02 pct not precipitated by HB, 0.1 pct CaO, and 0.08 pct SiOz), Sbf13 (99.6 pct Sb203, 0.004 PC~ C1-, 0.005 PC~ SO;-, 0.15 p~t AS, 0.001 pct Fe, and 0.03 pct other heavy metals such as Pb), and SiOz (chromatographic grade). Apparatus for Vapor Pressure Determinations. The apparatus used in this investigation consisted of a transportation reaction system with two separate gas trains. The argon transporting gas was first mixed with a small amount of hydrogen, metered, and dried by passage through silica gel and anhydrone drying tubes arranged in series. After this preliminary drying, the argon was passed through copper wool at 500°C to convert the residual oxygen to water vapor which was removed by three anhydrone drying tubes. A second stream of argon was metered and dried and then passed around the outside of the alumina reaction tube to flush away the volatile species to pre-

Jan 1, 1970

By R. K. Dann, L. W. Roberts, R. B. Benson

The mechanical properties of 300-series stainless steels were investigated in both high-pressure hydrogen and helium environments at ambient temperatures. An auslenitic steel which is unstable with respect to formation of strain-induced a (bee) and € (hcp) mar-tensile is embrittled when plastically strained in a hydrogen environment. A stable austenitic steel is not embriltled when tested under the same conditions. The presence of hydrogen causes embrittlement at the mar-lensitic structure and a definite change in the general fracture mode from a ductile to a quasicleavage type. The embrittled martensitic facets are surrounded by a more ductile type fracture which suggests that the presence of hydrogen initiates microcracks at the martensitic structure. If a steel is unstable with respecl to fortnation of strain induced martensile, plastic deformation in a hydrogen environment will produce rapid embrittlement of a notched specimen in comparison to an unnotched one. FERRITIC and martensitic steels can be embrittled by hydrogen that has been introduced into the alloys, either by thermal or cathodic charging prior to testing.1-5 However, conflicting reports exist as to whether austenitic steels that are stable or unstable with respect to formation of strain-induced martensite can be embrittled by hydrogen.8-12 A recent investigation has shown that cathodically-charged thin foils of a stable austenitic steel can be embrittled.13 An earlier investigation of a thermally charged 18-10 stainless steel revealed a significant decrease in the ductility only at the lowest test temperature of -78°C, although strain-induced bee martensite was shown to be present in one specimen tested at ambient temperatures.' When martensitic steels are tested in a hydrogen atmosphere, they are embrittled.'4-'7 It has been observed in this Laboratory that 304L steel, which is unstable with respect to formation of strain induced martensite, forms surface cracks when plastically strained in a high-pressure hydrogen environment. Work in progress elsewhere concurrent with this investigation has also established that 304L is embrittled when tested in a high-pressure hydrogen atmosphere." The objective of this investigation was to study the effect of a high-pressure hydrogen environment on the tensile properties of a stainless steel that contained strain-induced martensite (304L) and one that did not (310). EXPERIMENTAL TECHNIQUES Notched and unnotched cylindrical specimens were machined from 304L* and 310 rods that were heat- treated at 1000°C in argon for 1 hr followed by a water quench. The chemical analyses of these steels are given in Table I. The unnotched specimens had a reduced section diameter of 0.184 & 0.001 in., a gage length of 0.7 in., and were threaded with a 0.5-in.-diam. thread on each end. The notched specimens had a reduced section diameter of 0.260 * 0.001 in. and a 0.75-in. gage length, with a 30 pct 60 deg v-notch at the center. The notch had a maximum root radius of 0.002 in. The tensile bars were fractured in a hydrogen or helium atmosphere of 104 psi at ambient temperatures. The system used for mechanically testing the specimens is to be described in detail elsewhere.19 Several specimens of each type were tested in air using an Instron testing machine. The same yield strength and ultimate tensile strength were obtained in 104 psi helium with the above system as with the conventional testing machine. Magnetic analysis was employed to determine that there was a (bee) martensite in plastically deformed 304L and that it was not present in plastically deformed 310. The magnetic technique depended on allowing the material being studied to serve as the core between a primary and secondary coil. Thus, any change in the amount of magnetic material present between the annealed and plastically deformed steels will be indicated by corresponding changes in the induced voltage in the secondary circuit." The ratio of the output signal of a nonmagnetic stainless steel to a completely magnetic maraging steel was 2000 to I. Several unnotched 304L bars tested in hydrogen were analyzed for hydrogen by vacuum fusion analysis. There was an increase in the hydrogen content to approximately 2 ppm for the specimens tested in hydrogen, as compared to less than 1 ppm for the as-received material. Several thin sections cut from notched areas of 304L specimens tested in hydrogen and containing the fracture surface contained approximately 1.5 ppm H. The accuracy of these determinations was estimated to be ± 50 pct.

Jan 1, 1969

By John L. Ham, Robert M. Parke

THE melting point of molybdenum is 2625° ± 50°C. Heretofore the metal has been considered too refractory to be melted in commercial quantities; hence, it has been formed into rod, wire, and sheet by the methods of powder metallurgy, wherein the temperatures do not exceed 90 per cent of the melting temperature. The manipulation of liquid metals at temperatures of about 2000°C. and above presents some difficult problems in heat transfer, in purification, and in container materials. For metals melting at such high temperatures, it is generally regarded as expedient to circumvent the more common melting and casting process by resorting to powder metallurgy. This circumvention is not accomplished without some penalties, the more notable of which are the relatively high cost of the powder metallurgy method and particularly the size limitations of its product. In an effort to overcome the inherent disadvantages of the powder metallurgy method, especially in respect to the limit of size, a project was begun in 1943 at the Climax Molybdenum Co. laboratory to develop a method of melting and casting molybdenum capable of producing larger bodies of molybdenum than were then obtainable. Later, from Feb. 1, 1944, to Aug. 31, 1945, the project was under the supervision of the National Defense Research Committee, Division One. In peacetime, too, there are needs for molybdenum, which make consideration of another process desirable; for example, large parts for heat engines generally, the omnipresent demand for metal of higher quality and lower cost, and the development of molybdenum-base alloys. This paper describes methods for melting and casting molybdenum, with details of the special process needed to make molybdenum castings ductile, and reports some of the properties of what may be regarded as a new, or at least modified, form of the metal. FIRST PROCESS FOR MELTING AND CASTING MOLYBDENUM The maintenance of a temperature greater than 2625°C. in a space large enough to melt several pounds of molybdenum may involve the loss of heat at a very considerable rate. For melting molybdenum, therefore, the source of heat must be of high potential and of fairly high power. Evidently, also, the source of heat must not impair the purity of the product. The electric arc operating in vacuum appeared to meet these requirements and was accordingly the first choice as a source of energy. A number of arc devices for melting molybdenum were examined, and several were tried. In the first experiment, a 20-kw., 60-cycle-per-second alternating-current arc was operated between two horizontal and opposed electrodes of molybdenum. In this arrangement the falling droplets of molybdenum solidified below the arc in an irregular mass. This experiment did not produce a useful casting, but the data obtained indicated that

Jan 1, 1946

By S. Floreen, R. M. Pilliar, H. W. Hayden

The fracture behavior of a 50 pct Cu-50 pct Fe mi-croduplex alloy, laminated composites of copper and iron and an extruded 50-50 Cu-Fe elemental powder composite was studied. Very low ductile-brittle transition temperatures were achieved in all cases, but for different reasons. In the microduplex alloy both the initiation and also the propagation of cleavage fractures appeared retarded by the very small in-terphase distances. In the composites, crack propagation through the sumples was prevented in most cases by delamination fractures perpendicular to the advancing cracks. These delaminations occurred at different regions and by different mechanisms in the various composites. In the extruded powder composite, de-lamination appeared to take place along preexisting flaws. In the crack arrest geometry of the laminated plates, delamination took place by localized shear fractures within the copper near the Fe-Cu interfaces. In this case delamination was enhanced by thicker laminate layers, and by having the resistance to shear failure of the copper sufficiently low compared to the toughness of the iron. BRITTLE fracture in engineering materials has long been a problem, and many different ways of preventing it have been considered. One method that has been of growing interest lately is to prevent crack propagation by the introduction of mechanical discontinuities into the structure. These discontinuities may act in several ways. They may simply act as crack stoppers. They may introduce secondary fractures such as de-laminations that deflect the initial crack into new, less damaging directions. Alternatively, they may subdivide a fairly large bulk sample that would have been loaded in plane strain, for example, into a number of subunits that are individually loaded in plane stress and thus are more resistant to fracture. Other mechanisms, or combinations of mechanisms, are also feasible. A number of methods exist for introducing mechanical discontinuities into a structure. Composites by their nature have discontinuities in structure, and numerous studies have shown that fracture propagation in materials of this type can be radically changed by suitable control of the composite parameters. Of particular significance to the present work are recent investigations of layered composites made by joining high strength steel sheets by various means.'-4 These studies have shown that through proper control of the mechanical properties of the bonds joining the sheets it was possible to introduce delamination fractures that markedly improved the overall toughness of the composites and in some cases completely prevented through-the-thickness fractures. Another technique for introducing structural discontinuities is simply to use a two-phase alloy. It has been recognized for many years that a small amount of a second phase may improve toughness either by homogenizing plastic flow and thus preventing localized stress concentrations that nucleate fracture, or by interacting with an advancing crack. In most of these studies of two-phase materials, the decreases in ductile-brittle transition temperatures produced by the second phase were relatively small. More recently, work on two-phase stainless steels having a very fine grain microduplex structure has shown that the presence of on the order of 40 to 50 pct of a tougher second phase may lower the ductile-brittle transition temperature of the brittle phase by approximately 300°F. 5-7 In these alloys delaminations were seldom observed. The tougher second phase appeared to minimize the ease of both the initiation and the propagation of cleavage fractures. These results show that both the composite approach and the microduplex alloy approach are effective methods of preventing brittle fracture. Therefore, it was of interest to compare the fracture behavior of a microduplex alloy with composites made from the two-phases that were present in the alloy. To simplify this comparison the 50 pct Cu-50 pct Fe system was selected for study. At low temperatures the equilibrium tie line phases in this system are essentially pure ferrite and pure copper. A 50-50 alloy was cast and hot worked to produce a microduplex structure. Two types of composites were studied; laminated structures prepared by roll bonding iron and copper sheets of the tie line compositions, and an extruded powder composite made from high purity elemental powders. The fracture behavior of these materials was then compared. EXPERIMENTAL PROCEDURE Alloy Preparation. The 50-50 Fe-Cu alloy and the components for the roll bonded composites were prepared by vacuum induction melting 30-lb heats using electrolytic grades of iron and copper as charge materials. A carbon boil was used to deoxidize the melts. Small additions of copper and iron were made to the iron and copper heats, respectively, to approximate

Jan 1, 1970

By W. C. Elmore

THE magnetic powder method, long used. for roughly mapping mag-netic fields, has recently been refined 1,2 for investigating the microscopic variations in the surface magnetization of ferromagnetic crystals. Bitter2 first discovered regular powder patterns connected with the crystal structure of such specimens. Several other investigators3 have used Bitter's original technique, with slight modifications, to study the varia-tion of the patterns with variations in the magnetizing field applied parallel to the surface, and their dependence upon the state of strain, of polish and of crystal cut. All of the explanations of these patterns on metallic ferromagnetics have been couched in general terms. In a preliminary report we have described an improvement in the powder technique which led us to the discovery of a new effect throwing con-siderable light on the magnetic secondary structure of alpha iron4 and of nickels single crystals. We now report additional evidence confirming the existence and stability of a magnetic block secondary structure.

Jan 1, 1936

By Albert Sauveur

AT the New York meeting of the Institute, February, 1914, Professor Hopkinson and Sir Robert Hadfield presented an important paper entitled Research with Regard to the Non-Magnetic and Magnetic Conditions of Manganese Steel.1 Any contribution on manganese steel by its discoverer necessarily carries with it much weight and is entitled to serious and close consideration. The momentous discovery of that alloy by Sir Robert Hadfield some 30 years ago was the signal for great activity in the field of alloy steels; and the remarkable results obtained in the last two decades probably constitute the most important modern advance in the metallurgy of steel. The authors of the paper referred to above are unable to reconcile with the allotropic theory the interesting results obtained by them in heat treating manganese steel. When they speak of the allotropic theory, however, I understand that they have more especially in mind the existence of beta iron. It is not my understanding that they question the occurrence of iron in the two allotropic varieties known as gamma and alpha. If I am wrong, I trust they will correct me. A careful consideration of the experimental results reported and discussed by the authors leads me to believe that on the contrary they can be very satisfactorily explained in terms of allotropy and that, in the light of our present knowledge, they cannot be accounted for in any other way. The physical properties of non-magnetic manganese steel described by the authors are those pertaining to iron-carbon alloys in which iron is present in the gamma condition, or, in other words, to austenite. The metal is then characterized by great tenacity and ductility and low elastic limit, while its hardness, mineralogically speaking, is not excessive, but of a special kind termed "tough hardness" by the authors. Even when subjected to the restraining influence of a large amount of manganese and of considerable carbon, however, relatively rapid cooling

Jan 9, 1914

Discussion of the papers of Messrs. Howe and Levy, Burgess, Crowe and Rawdon, and H. M. Howe, presented at the New York Meeting, October, 1913, and printed in Bulletin No. 78, June, 1913, pp. 1075 to 1136. ALFRED STANSFIELD, Montreal, Canada :-In Professor Howe's paper on the position of Ae3, he shows its industrial importance in determining the temperature to which steel should be heated. for "grain refining." Several years ago I carried out a research on the " burning " of steel and found that while hypo-eutectoid steel should be heated to Ae3, hyper-eutectoid steel that has been very much overheated must be reheated to the curve Sa on the carbon-iron diagram, in order to redissolve the pro-eutectoid cementite and thus, to obtain recrystallization and grain-refining. This treatment was necessarily only partly successful, and I should like to ask whether the conditions of heat treatment for refining overheated high-carbon steels have been ascertained. Speaking of the " Persistence of Solidificational Segregation " Professor Howe quotes an experiment made by Mr. Stead in which a bar of 1.2 per cent. carbon steel was immersed in a large mass of molten blast-furnace slag and allowed to cool with it. The steel was heated above the solidus (curve Aa on the carbon-iron diagram), but below the liquidus (curve AB). A drop of eutectic carbon-iron alloy, rich in carbon, had liquated out and hung below the bar. This agrees exactly with my own observations on the burning of steel, but my interpretation differs somewhat from that of Professor Howe. Professor Howe considers that the fusion of a part of the metal (rich in carbon) shows that the solidificational irregularities of composition had persisted through the rolling and heat treatment of the steel, as otherwise no part of the steel would have been sufficiently fusible to melt. It does not appear to me that such an explanation is necessary. A piece of steel represented in temperature and composition by any point within the area ABa will ultimately resolve itself into a solid phase and a liquid phase in equilibrium with each other. It may appear that if the steel were absolutely uniform no fusion could take place, but the smallest nucleus of high-carbon, fusible alloy would ultimately bring about this separation into liquid and solid phases, by diffusion of the carbon from the solid to the liquid areas. A nucleus sufficient for the purpose might be provided by an area of pro-eutectoid cementite which had not become diffused during the

Jan 12, 1913

By W. A. Anderson

IN the pressure die-casting of zinc alloys it is customary to force the molten alloy under high pressure into a permanent steel die by means of a plunger moving in a bushing that has a clearance on the diameter of the order of 0.002 in. Successful operation of the plunger type of machine requires the presence in the zinc alloy of certain percentages of aluminum. Without these aluminum additions, the normal reaction of molten zinc on ferrous materials causes sticking of the plunger and a complete shutdown of the equipment. All of the zinc alloys used for pressure die-casting today contain approximately 4 per cent of aluminum, which is more than sufficient to make plunger operation feasible. The clearance between the plunger and its bushing is an important matter. As the space becomes larger, there is a loss in effective metal pressure. Ordinary gray cast iron served fairly well and is still used in some machines. However, the rate at which the plunger clearance increases with this material is considered by many to be far too great. There is, therefore, a serious interest in finding new materials more capable of retaining the desired clearance during long periods of use. Today many die casters are using special materials for plungers and bushings selected by the somewhat expensive and time-consuming test of actual experience. An analysis of the problem reveals two possible end points of plunger operation: (1) the building up of zinc-alloy plunger-material reaction products in sufficient bulk to cause sticking and (2) rapid solution, wear or erosion, all of which will increase the clearance to an undesirable extent. If neither of these takes place, the plunger will operate for a long time, of course. The authors have developed a laboratory apparatus in which the action of a plunger moving in a bushing immersed in molten zinc alloy could be simulated closely. Such a machine made possible a more rapid and less expensive survey of the available construction materials and an analysis of the specific alloying reactions taking place in the clear-ance area.

Jan 1, 1939

By Frank Alfred Fahrenwald

MetallURgical research has discovered many an alloy possessing properties not combined in any single metal, and progress still consists chiefly in the investigation and utilization of alloys. In the case of iron, the demands of automobiles, high-speed machines and high-duty engines have led to the production of special iron alloys which will meet any reasonable specifications in that field. In like manner, the bronzes, brasses and other alloys of copper have been brought to remarkable perfection, and for nearly every industrial purpose some alloy has been , found more suitable than the pure metal. Less complete success has attended the attempt to find substitutes for gold, platinum, and the other precious metals. Indeed, it is not likeiy that a material can be produced which, will possess all the properties of any one of them; yet it is reasonable to hope that, for any given use, the properties required may be found in some less expensive material. Thus, in incandescent electric lamps, the wire passing through the thick glass neck of the bulb was, until recently, almost universally made of platinum, for the single reason that no other known material, suitable as a conductor, had the same coefficient of expansion as glass. But a comparatively recent investigation of the iron-nickel series1 has shown that alloys of those metals maybe produced, the coefficient of expansion of which can be accurately controlled between that of iron or nickel and zero. Thus, in that particular industry, a substitute for platinum has been found. According to statistical reports, not only considerable quantities of gold and iridium, but also more than one-third of the annual supply of platinum, are used (and, in the nature of the case, irrevocably lost) by dentists. Platinum is thus employed in several forms. As a thin foil, it serves various purposes for which its high melting point, pliability, chemical resistance, and other properties—including the ease with which it may be soldered—are invaluable. But it is most extensively used in

Jan 1, 1916

By J. N. Anderson

Developments in reverberatory furnace practice at Noranda over the period 1928 to 1953 are described. Features of interest are increasing furnace tonnage from 700 to 2000 tons per furnace day, the use of the suspended basic roof, and improvements in furnace fuel ratio. Points of comparison and contrast between Canadian and American furnace practice are given. OPERATIONS at the Noranda smelter have been described in a series of papers published between 1930 and 1945.1-4 In the present paper the development of reverberatory furnace practice over the 25 year period from the beginning of operations up to the present time will be reviewed and current furnace practice will be described in some detail. Particular attention will be given to those features which are characteristic of Canadian practice: first, the use of the suspended basic roof; second, the deliberate driving of furnaces to give tonnages in the range of 1400 to 2000 tons of solid charge per furnace day; and third, the continuous operation of furnaces at high tonnage for many years without any extended shutdown for repairs or rebuilding. Finally, points of comparison and contrast between reverberatory furnace practice in Canada and the United States will be discussed. The Noranda smelter, which started in December 1927, was built for the reduction of ore from the Horne mine where early development had shown a comparatively small tonnage of rich cop-per-gold ore of a grade and character which would require direct smelting. The smelter was designed for a capacity of 1000 tons of ore a day and originally consisted of eight roasters, two reverberatory furnaces, and two converters, together with necessary auxiliaries. The discovery of a large new body of ore in 1928 made it necessary to increase both the size and the scope of the reduction plant. A mill which was ultimately brought to a capacity of 3000 tons a day was built for concentrating low grade ore and in addition the capacity of the smelting plant had to be greatly expanded, so that for the next fifteen years every effort in the smelter was directed toward achieving maximum tonnage. Because the layout and design of the smelter made it impracticable to add a third furnace, it was necessary to increase the tonnage on the two original furnaces by improvements in furnace design and operation, roasting and converting equipment being added as required to meet the demands of increased furnace capacity. The smelter tonnage, which reached a peak in 1941, was curtailed in 1944 when it became necessary to operate on a one-furnace basis because of a reduction in the output of the Horne mine due to a shortage of labor. Two-furnace operation at a moderate tonnage was resumed in 1949. In the early years the smelter tonnage was made up almost entirely of Noranda ores and concentrates. However, since 1937 an increasing tonnage of ores and concentrates from other mines has been treated in the smelter. In recent years, with decreased production from the Horne mine, copper concentrates from several mines in the district, treated on a custom basis, have formed an important part of the smelter tonnage. A review of developments in reverberatory furnace practice at Noranda falls naturally into the following four periods: 1—1928 to 1935, the early years; 2—1935 to 1944, the period of greatest change and development; 3—1944 to 1949, one-furnace op-

Jan 1, 1955

By I. M. Roberts

THE war emergency has affected every phase of industry. The gas and coke-oven companies have sought faithfully to discharge their responsibility in this critical period and have willingly modified their operations where possible to meet the ever increasing demands made upon them. Our company made commitments for blast-furnace coke for war purposes which necessitated a reduction in coking time in order to produce the amount required to. meet the new demands. At the same time there were certain customers of long standing, who had been supplied with foundry and egg-sized coke produced on fairly long coking periods, who also were engaged in war work and whose patronage we desired to retain. Coke produced on short coking rates from the coal mixture we were then using would not have been satisfactory for these customers. The average width of our ovens is 19 ¾ in., which is a little wider than the more modern ovens of the present day. They were originally designed to give somewhat cool tops in order to produce a rich gas. This necessitates carrying the heats a little on the warm side so that the tops will be fully carbonized. A reduction in coking time, as is generally known, is accompanied by a reduction in the average size of the coke produced. This is due to the greater shrinkage that takes place at the higher temperatures required to carbonize the charges in a shorter time. The net result is that the coke is more cross fractured and longitudinally fractured and breaks up into small sizes on handling. The cokes produced from the better coking coals seem to be more susceptible to fracture at high temperatures than those from poorer coking coals. A coal mixture that produces a beautiful foundry-sized coke at 30 to 36 hr. may yield a product at 18 hr. that would be so badly fractured as to be unsatisfactory for foundry practice. COKING CHARACTERISTICS OF COALS Our problem was to find some economical innovation and develop a method that would enable us to reduce the coking time and still produce a coke satisfactory to our foundry trade. However, before discussing the results of our present operations, it might be well to present a few observations on the coking characteristics of coals in general. Most coke-oven operators carbonize a blended mixture of coals. It may consist of a single high-volatile coal with a single low-volatile coal, or of a combination of several high-volatile and low-volatile coals. Medium-volatile coals of the Eagle seam are used for the production of high-grade foundry coke. Medium and high-volatile coals are often blended with one or more low-volatile coals. The possibilities are almost infinite, but the combinations are limited by such factors as cost and facilities for handling multicoal mixtures, and by other practical considerations. Every coal has characteristics that make it blend better with a particular coal or coals in preference to others. This property has

Jan 1, 1944

Discussion of the paper of HENRY M. HONE and ARTHUR G. LEVY, presented at the New York meeting, February, 1915, and printed in Bulletin No. 99, March, 1915, pp. 587 to 600. J. E. STEAD, Middlesbrough, England (communication to the Secretary*).-As I have not personally studied the question of quenched and distorted manganese steels I cannot give any information of my own on the subject. The question as to whether certain indications in strained manganese steel are "slip bands" or "twins" might be settled, I think, by heat tinting-a method I have applied with success to certain meteorites and other alpha irons in which there were undoubted twins. After polishing and very slightly etching with picric acid in alcohol, and then "heat tinting," the colors assumed by the twinned strata and the adjoining metal are different. The reason of this, as I have proved repeatedly, is that different faces of the iron crystals are differently attacked by oxidizing and other reagents, and consequently some of the faces take temper oxidation tints more rapidly than others. This simple method enables one to determine with certainty whether the "twins" are actually, twins and differently oriented from the bed in which they are found. After correspondence with Dr. Howe, I think we both agree that Neumann lines should not be called "lines" but "bands" or "strata," preferably the latter term, as I have found that they are more or less continuous throughout the crystals, and it would be just as improper to call the edges of cementite plate by the term "lines" as to call stratified twins by the same term.

Jan 5, 1915

By David Swan

No mystery shrouds the discovery of chromium. The indefatigable French chemist Vauquelin, in reporting his discovery of this chemical element to 1'Institut National in 1798, concluded his discourse with the statement: "I place before the eyes of the Institute a small quantity of chromium and several of its most re- markable combinations." Working with the so-called "red lead of Siberia, Vauquelin not only prepared numerous chemical compounds of the new metal, but he reduced the oxide to the metallic state. These chemical compounds possessed a variety of remarkably distinctive colors; so, acceding to suggestion, Vauquelin named the new element chrome (chromium), a derivative of the Greek word chroma, meaning color. Siberian "red lead" (crocoite) was not plentiful; however, it was not long before Vauquelin's prediction was realized that the chemical compounds of chromium would become useful in the arts when sources of chromium became more readily available. Although chrome-iron ore (chromite) became obtainable in France, the United States and elsewhere during the early part of the nineteenth century, it is interesting to note that from 1828 to about 1860, Maryland, Pennsylvania, and others of the eastern United States furnished almost the entire chrome-ore requirements of the world. Several countries each in turn have since dominated for certain periods the supply of chromite. In recent years, the largest tonnages have come

Jan 1, 1953

By W. H. Hoffman

At the Glen Summit meeting (Trans., xx., 605) I described in a general way the grinding-machine known as the Sturtevant mill, built by the Sturtevant Mill Co., of Boston, Mass. My first experiments in granulating magnetic. iron-ores with this machine were made five years ago in the northern portion of New York State.

Jan 1, 1893

By B. L. Averbach, M. Cohen, C. H. Shih

The isothermal formation of martensite is studied in Fe-Ni-Mn and Fe-Mn-C alloys under conditions where the athermal transformation is completely avoided, there being no martensite present at the beginning of the isothermal reaction. The initial rate of martensite formation is extremely low under these conditions, but it increases greatly as soon as some martensite is formed. It appears that true initial characteristics of the isothermal reaction can be studied only in samples wherein the formation of martensite on cooling is completely eliminated. THE phenomenon of isothermal martensite formation is well established1 -" but the observations have been made in the presence of varying quantities of athermal martensite. Complete avoidance of athermal martensite and the formation of martensite under pure isothermal conditions have been reported by Kurdjumov and Maksimova2 in an Fe-Ni-Mn alloy (23 pct Ni, 3.4 pct Mn, and the balance Fe) and have been confirmed by recent experiments of Cech and Hollomon in a similar alloy. In each case, the isothermal transformation rate was a maximum at the beginning of the transformation and decreased as the reaction proceeded. These initial transformation rates were used by Fisher7 for the confirmation of calculated nucleation rates based on classical nucleation theory extended to include the effect of elastic strain energy. Cech and Hollomon have admitted, however, that up to 3 pct martensite formed on cooling in their samples and thus was present at the initiation of their isothermal runs. In this paper, experiments on similar alloys are described, except that care was taken to remove the incidental martensite developed at the surface prior to the isothermal reaction. It is shown here that the reaction rate at the beginning of the strictly isothermal reaction is very low. As soon as some detectable amount of martensite is produced, the transformation rate increases rapidly but ultimately decreases as the reaction proceeds. When martensite is allowed to form isothermally in the presence of about 2 pct of prior martensite, the apparent initial reaction rate is a maximum and corresponds to the observations of Kurdjumov and Maksimova and Cech and Hollomon. It is evident that the cooperative nature of the martensitic reaction results in a significant stimulating or autocatalytic effect on the isothermal reaction rate. Experimental Procedure The chemical compositions of the alloys used in this investigation are listed in Table I. The Fe-Ni-Mn alloys A and B were melted in an induction furnace, cast into ingots 2 in. diam by 4 in. long, and forged into % in. diam rods. The manganese steel (alloy C) was melted in an arc furnace and cast into ceramic molds 1/4 in. diam by 5 in. long. The rods were sealed in evacuated Vycor tubes and homogenized at 1175" to 1200°C for 50 hr. The long homogenization resulted in some manganese loss from the surface, producing a thin layer of transformed material. This surface layer was removed by grinding and the specimens were then swaged to 0.050 in. diam wire. Measurements of electrical resistance were made with a Kelvin double bridge to follow the course of the martensitic transformation. A small permanent magnet was also useful in scanning an entire specimen for small localized quantities of martensite. This test is almost as sensitive as the electrical resistance method in detecting the presence of martensite (which is ferromagnetic in these alloys) and it was especially useful in deciding whether a specimen was completely free of martensite. The wire specimens (0.050 in. diam by 2.5 in. long) were sealed in evacuated tubes and austenitized for 5 min at 1150°C. The specimens were quenched into water and, unless otherwise stated, stress-relieved for 1 hr at 650 °C in order to induce greater uniformity in the subsequent martensitic transformation. As dem-

Jan 1, 1956

By W. L. Dennen, V. H. Wilson

THIS paper is a description of the opera¬tion and results of a Humphreys Spiral Silt Cleaning Plant at the Powderly Colliery of The Hudson Coal Co. during the first nine months of operation and follows a pre¬liminary description given at the Anthracite Institute in May, 1947, in a paper titled "Preparation of Anthracite Sift for Boiler Fuel in a Humphreys Spiral Test Plant" by H. H. Otto, V. H. Wilson and W. L. Dennen. This plant is considered a full size operating test plant and, like all new plants, numerous minor changes in the methods of operation have been made from time to time to secure the results desired. Views of the silt preparation plant and of the screening house are given in Fig 1 and 2. This plant consists of 48 spirals in 8 batteries of 6 spirals each, 36 of which were to be operated as primary spirals and the remaining 12 as secondary spirals. A brief description of the plant and its operation follows. The only material cleaned at the plant during 1947 was that carried in the underflow from the Thickener which handles the Breaker waste water. This underflow, amounting to approximately 2000 gpm of water and containing 12.6 pct of solids, is pumped .to vibrating screens where the plus 316-in. material is removed. (Fig 3). This oversize material drops into a pocket from which it is trucked to the run-of-mine

Jan 1, 1948

By W. M. Wojcik, R. F. Kowal

Oxygen and sulfur distributions in commercial, 5-ton ingots of killed, medium carbon steel are described. Oxygen distribution is found to vary with deoxidation practice. Irregular distribution of oxygen within ingots makes necessary special precautions in sampling of rolled products for analysis of oxygen. Oxygen distribution is discussed in terms of recently published solidification concepts which had been successfully applied to simpler cases of segregation. These concepts have been found inadequate to explain observed oxygen distributions. Convective movements of the liquid metal, as determined by tracer elements, are shown to be capable of accounting for the observed distributions of oxygen. IN an effort to explore the origin of surface and subsurface imperfections in pierced steel products, a study of oxygen and sulfur segregation was made on ingots cast in open-top and hot-top molds. The results of our previous investigations1"3 have indicated the importance of the location and amount of oxide inclusions in an ingot. Inclusions close to the surface of the ingot have been found to contribute greatly to the formation of imperfections in the surface of finished products. This study of the effects of deoxidation and casting practice on segregation and the resulting oxygen distribution in ingots was initiated to determine the parameters controlling the location of inclusions in an ingot. Segregation of solute elements during solidification of low-melting binary alloys has been studied in the past.1, 5 Formation and growth of inclusions in iron melts have been studied under specific conditions."- In spite of these and other recent studies,10-12 segregation during solidification of commercial, killed steel ingots is not well understood. Consideration of solidification rates, of segregation during solidification of the chill, dendritic, and central zones, and of material balances for the segregated elements has indicated that a simplified theoretical solidification model is not adequate. However, the observed high oxygen contents in localized volumes of the dendritic zone can be rationalized if additional effects of convection currents in the ingots, precipitation, and rapid growth of new phases are considered. EXPERIMENTAL PROCEDURE Steelmaking and Processing. A group of nine killed. medium carbon steel heats having compositions listed in Table I have been studied. The deoxidation and mold practices used were varied to give a wide range of steel oxygen contents. The amounts of aluminum added to the ladle and the ingot casting practices (hot top and open top) were the main variables. The steel was made by a duplex practice in 160-ton tilting basic open-hearth furnaces. All nine heats were top-cast into 24 by 24 in. big end down, fluted molds, to a height between 60 and 76 in., using both open tops and exothermic hot tops. The deoxidation practice and the tapping and teeming details for each heat and ingot studied are given in Tables II and III, respectively. Hot-top practice is indicated by the letter H following the heat designation. Furnace and ladle temperatures were measured by standard disposable-tip, Pt/10 pet PtRh thermocouples. Teeming-stream temperatures were obtained as described by Samways et al.,13 by immersing a Pt/10 pet PtRh thermocouple, covered by a silica sheath, into the teeming stream under the nozzle. The output of this thermocouple was recorded with Leeds & Northrup Speedomax potentiometer. Calibration of the latter thermocouples was based on the freezing point of a pure iron/oxygen alloy (2795°F). The accumulated errors of measurements were within ±10°F. The thermocouple measurements were supplemented in this investigation by continuous recording of a ratioing, two-color pyrometer (Shawmeter), protected from smoke by a blast of clean air within the sighting tube, and calibrated to read with better than ±10°F accuracy. Following teeming of three heats, P, R, and T, tracer elements were added to the steel in the molds to obtain a record of the progress of solidification. As soon as the teeming stream was shut off, a 0.010-in.-thick steel can containing a mixture of crushed standard ferro-titanium and ferro-vanadium (0.05 pet of each alloy element) was plunged into the middle of the steel pool to a depth of 6 in. In about 30 sec no indication of the can or its contents remained. The surface of the open-top ingots solidified in 20 to 30 sec. A study of liquid metal movement and the precipitation of oxides was facilitated materially by use of the tracer technique as titanium has a low distribution coefficient between solid and liquid steel while vanadium has a high distribution coefficient.

Jan 1, 1965

By Walter B. Lenhart

Introduction and Importance of the Industry Sand, as described in this chapter, is a crude product used for ballast on railroads and highways, and as the fine aggregate in concrete, mortar, plaster and in asphalt paving materials. The sand used in glass, as a molding sand, and as a source of silica is described in Chapter 43. Sand and gravel together constitute the mineral raw materials of largest volume produced from the earth. In 1958, as reported by the U.S. Bureau of Mines,21 680,080,000 tons of sand and gravel (including industrial sand) were produced in the United States. The nearest competitor was crushed rock of which 532,818,000 tons were produced. Coal, both bituminous and anthracite accounted for only 431,616,689 tons in the same year. In dollar value, sand and gravel were exceeded only by cement, crushed rock and fuels. Hence it is a major unit of the mineral-producing industry. As an example, one plant in California operates around the clock at an average rate of 1,500 tons per hour, and at peak intervals has shipped over 4,000 tons per hour, all by trucks. Nevertheless, it is controlled by one man through a panel of push buttons that control the crushing, screening, washing, grading, stock piling, and reclaiming of the products. Because sand and gravel are low-valued commodities, but are used in every construction undertaking in every city, village, farm, dam and highway, they are produced in almost every county in the United States and southern Canada, by thousands of individual operators, very few of whom operate in more than one community. Many operations, particularly those established to supply the needs of major dams that are under construction, or of major segments of new highways, are temporary in nature, and the equipment installed is more or less portable. Because of the bulky nature of sand and gravel, there is very little interstate movement, and almost no exports or imports, except a little movement back and forth across the border of the United States and Canada. First, the material needs definition. Definitions Sand and gravel have been defined as continuously graded unconsolidated materials that appear in the earth's surface as a result of the natural disintegration of rocks. Both normally appear together, but in a wide variety of sizes, types and range of size classification. The American Society for Testing Materials has tentatively revised its definition of "sand" as: granular material passing the 3/8-in. sieve and almost entirely passing the No. 4 (4760-micron) sieve and predominantly retained on the No. 200 (74-micron) sieve, and resulting from natural disintegration and abrasion of rock or processing of completely friable sandstone (ASTM Designation C 58-55T). The Society's tentative revision of its definition of "gravel" is: granular material predominantly retained on the No. 4 (4760-micron) sieve and resulting from natural disintegration and abrasion of rock or processing of weakly bound conglomerate (ASTM 125-55T). Sand and gravel deposits contain materials from the finest silt to the largest boulders. Chemical definition of the two materials is nearly impossible. Sand and gravel always are

Jan 1, 1960

By J. D. Alexander, W. L. Martin, J. N. Dew

This paper presents data obtained using a flood-pot technique to determine the fuel available and the corresponding theoretical air requirements for in situ combustion of crude oils. Since the technique is relatively quick and easy, it is a practical and convenient tool for evaluating reservoirs as fireflood prospects. It is also a research tool which facilitates systematic study of the variables affecting fuel availability and corresponding air requirements. The understanding of these variables is of prime importance to those concerned with the technical and economic development of in situ combustion as an oil-recovery process. The experimental results show conclusively that the fuel available for in situ combustion is not a constant but, rather, varies with crude-oil characteristics, porous-medium type, oil saturation, air flux and time-temperature relationships. Thus, the fuel availability for specified field applications should be determined using actual reservoir crude and core material and the process conditions expected during in situ combustion in the reservoir. INTRODUCTION In situ combustion is a thermal process for recovering crude oil from reservoirs. The thermal energy released during the combustion of a small amount of the oil in place aids in the displacement of the remaining oil. Numerous articles have been published describing the in situ combustion process giving detailed results of laboratory and field experiments.10 In order to engineer an in situ combustion project, a number of important factors must be considered and determined. These factors include: (1) the amount of fuel consumed per unit of reservoir volume swept by the combustion zone, (2) the composition of the fuel consumed, (3) the amount of air required to consume this fuel, (4) the portion of the reservoir swept by the combustion zone, (5) the appropriate air-injection rates and pressures, (6) the amount of oil that will be recovered, (7) the rate of oil production and (8) the operating costs. Nelson and McNiell1 recently have described a procedure which utilizes laboratory combustion-tube data as a basis for the calculation of some of these design factors. Various authors have attempted to describe the in situ combustion process mathematically, and considerable progress has been made. Analytical solutions to the problem of heat transfer from a moving combustion front have been obtained for linear and radial systems."-' All of the published results involve the assumptions that: (1) fuel concentration is constant throughout the reservoir, or that fuel concentration is inversely proportional to the velocity of the front for a given rate of oxygen consumption; and (2) the fuel reacts instantaneously with injected oxygen, while liberating a constant amount of heat per unit weight of fuel at all temperatures. It seems both desirable and reasonable to test the validity of these assumptions experimentally. This paper presents laboratory data which were obtained by means of a "fire flood-pot" method for determining fuel availability and composition, and the corresponding theoretical air requirements for in situ combustion of crude oils under variable conditions. The mechanics of the method are similar to a conventional tube-run experiment.' The important differences involve the size of the reservoir model used and the method for providing the experimental environment. The new method subjects conventionally-sized core samples or unconsolidated sands to a programmed environmental sequence similar to that experienced by a similar volume of rock during the approach and passage of a combustion front in a long tube or in an oil reservoir undergoing in situ combustion. Restored-state samples can also be used. The small samples and relatively simple techniques involved allow an experiment to be set up, run and calculated in about three 8-hour days. This is a considerable improvement over long-combustion-tube techniques which can require several days to run and several more work days to set up and calculate. All the runs presented were run at 40-psig injection pressure. Pressure was not considered as a variable for these experiments, since we previously had found that it had only a small effect on fuel availability up to 600 psig.APPARATUS AND MATERIALS APPARATUS The fire flood-pot apparatus consists of a consolidated