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INCREASING realization that pouring and ingot-mold practices involve many factors of fundamental importance to ingot quality and general steel-mill operations has caused these phases of steelmaking to become major concerns of operators and metallurgists engaged in control of quality and costs. Methods of pouring steel from the ladle into the ingot molds have some direct effects on ingot quality. The mold itself governs solidification and dimensions of the ingot and in so doing exerts some very tangible influences not only on ingot quality but also on product yields and general steel-mill processing. In addition, practices are employed' in the handling of molds during daily open-hearth operations that are important to quality and production costs. Therefore, pouring and mold practices must be considered highly specialized and important steps in steel-mill operations. MOLD DESIGN Mold design is difficult to discuss in a precise manner because it varies greatly throughout the industry, both in theoretical concepts and practical application, and few well developed data are available. Most ingot molds are designed to meet conditions peculiar to a given plant wherein quality standards are dictated by end-use requirements, which may differ considerably, even for the same grade of steel. The mold designer must also consider the equipment available to process ingots and the product obtained from them. Such equipment, used for stripping, heating, blooming and finishing operations, is seldom, if ever, exactly the same in any two steel plants. Thus, pronounced contrasts in mold designs can be expected to continue, even among plants making strictly comparable types of product, particularly because some producers are just beginning to realize the benefits possible from specialized designs. Certain fundamentals are used in mold design but even these

Jan 1, 1951

INCREASING realization that pouring and ingot-mold practices involve many factors of fundamental importance to ingot quality and general steel-mill operations has caused these phases of steelmaking to become major concerns of operators and metallurgists engaged in control of quality and costs. Methods of pouring steel from the ladle into the ingot molds have some direct effects on ingot quality. The mold itself governs solidification and dimensions of the ingot and in so doing exerts some very tangible influences not only on ingot quality but also on product yields and general steel-mill processing. In addition, practices are employed in the handling of molds during daily open-hearth operations that are important to quality and production costs. Therefore, pouring and mold practices must be considered highly specialized and important steps in steel-mill operations. MOLD DESIGN Mold design is difficult to discuss in a precise manner because it varies greatly throughout the industry, both in theoretical concepts and practical application, and few well developed data are available. Most ingot molds are designed to meet conditions peculiar to a given plant wherein quality standards are dictated by end-use requirements, which may differ considerably even for the same grade of steel. The mold designer must also consider the equipment available to process ingots and the product obtained from them. Such equipment, used for stripping, heating, blooming and finishing operations, is seldom, if ever, exactly the same in any two steel plants. Thus, pronounced contrasts in mold designs can be expected to continue, even among plants making strictly comparable types of product, particularly because some producers are just beginning to realize the benefits possible from specialized designs. Certain fundamentals are used in mold design but even these

Jan 1, 1964

By B. C. Burgess

IN the first edition of this volume,44 feldspar was introduced as "the I commonest mineral of the crystalline rocks," usually in small grains associated with other minerals and commercially produced only from pegrnatites. Now other crystalline rocks, such as alaskites and granites, have become present or potential sources of feldspar. In addition, feldspar has encountered very vigorous competition from such substitutes as nepheline syenite and aplite. COMPOSITION AND PROPERTIES The feldspars form a group of which the principal species are orthoclase, microcline, albite, and anorthite. These are aluminum silicates of potassium, sodium and calcium. There are also a barium feldspar, celsian, and barium orthoclase feldspar, hyalophane, rarely found and of no commercial importance. None of the minerals in the feldspar group are found pure or nearly pure. The potash feldspars, orthoclase and microcline, nearly always contain some albite (soda microcline, an- orthoclase); the soda feldspars usually contain some anorthite (lime feldspar). There is a series of soda-lime feldspars known as plagioclase in which the albite and anorthite molecules replace each other in varying proportions from albite through oligoclase, andesine, labradorite, and bytownite to anorthite. Theoretical chemical composition of the principal feldspars is given in Table 1. The Whiteware Division of the American Ceramic Society sub- mitted a list of definitions of ceramic terms, in April 1947, for use in technical literature. For feldspar it gives: "A group of igneous minerals consisting chiefly of the aluminum silicates of potash, soda and lime, in which one base generally predominates." Commercial feldspars are intergrowths of at least two species of feldspar, which occur associated with one or more accessory minerals such as quartz, muscovite, biotite, garnet and tourmaline as well as with small but varying proportions of the decomposition product, kaolinite. An intergrowth of quartz and feldspar frequently contains

Jan 1, 1949

THE solid nonmetallic inclusions present to some extent in all commercial steels have been variously designated. In early references they were usually called slag inclusions, and this terminology is still retained to some extent. On the premise that all nonmetallic matter produced in a metallurgical process is slag, this can be justified. We have come to think of slag, how- ever, in a more restricted sense, and calling these particles slag inclusions is further objectionable because it fosters the erroneous concept that they are actually incorporated portions of furnace slag. Rarely is this true. The term sonims (coined from solid nonmetallic impurities) was proposed many years ago but never came into common use. In general, the term non- metallic inclusions seems to be satisfactory and adequate. NATURE AND CONSTITUTION OF NONMETALLIC INCLUSIONS From the standpoint of origin, inclusions fall naturally into two classes: (1) those occurring as a result of reactions taking place in the body of molten or solidifying metal and (2) those resulting from mechanical incorporation of refractories or other materials with which molten steel comes in contact. The former are by far the more numerous and have been called indigenous, natural, or native inclusions. The latter are by their very nature sporadic in occurrence and have been called exogenous, accidental, adventitious, or foreign inclusions. They are often referred to as the "slag-stringer" type, though here also the material is not likely to be furnace slag. Substances Found in Inclusions. Nonmetallic inclusions are composed principally of oxides and sulfides but carbides and nitrides sometimes play an important role. In the case of indigenous inclusions the reactions by which these particles are precipitated from molten or solidifying steel may be caused by: (1) oxidation such as may occur during refining or during tapping and teeming, (2) deoxidation by added alloys, (3) change

Jan 1, 1951

THE solid nonmetallic inclusions present to some extent in all commercial steels have been variously designated. In early references they were usually called slag inclusions, and this terminology is still retained to some extent. On the premise that all nonmetallic matter produced in a metallurgical process is slag, this can be justified. We have come to think of slag, however, in a more restricted sense, and calling these particles slag inclusions is further objectionable because it fosters the erroneous concept that they are actually incorporated portions of furnace slag. Rarely is this true. The term sonims (coined from solid nonmetallic impurities) was proposed many years ago but never came into common use. In general, the term non-metallic inclusions seems to be satisfactory and adequate. NATURE AND CONS1lTUTION OF NONMETALLIC INCLUSIONS From the standpoint of origin, inclusions fall naturally into two classes: (1) those occurring as a result of reactions taking place in the body of molten or solidifying metal and (2) those resulting from mechanical incorporation of refractories or other materials with which molten steel comes in contact. The former are by far the more numerous and have been called indigenous, natural, or native inclusions. The latter are by their very nature sporadic in occurrence and have been called exogenous, accidental, adventitious, or foreign inclusions. They are often referred to as the "slag-stringer" type, though here also the material is not likely to be furnace slag. Substances Found in Inclusions. Nonmetallic inclusions are composed principally of oxides and sulfides but carbides and nitrides sometimes play an important role. In the case of indigenous inclusions the reactions by which these particles are precipitated from molten or solidifying steel may be caused by: (1) oxidation such as may occur during refining or during tapping and teeming, (2) deoxidation by added alloys, (3) change

Jan 1, 1964

By H. E. Brauer

PART I INTRODUCTION Among the zinc base alloys used for casting in metal moulds, particularly die casting, those alloys containing aluminum usually together with copper, are probably the most widely used. The reason lies in their desirable mechanical properties and the fluidity and absence of hot shortness which facilitate casting. Objection to the use of these alloys may bee raised on account of the rather frequent instances of failure of a type variously described as disintegration, exfoliation and intercrystalline corrosion. In all cases which have come to our knowledge where the conditions of service were known, failure has occurred upon exposure to moisture and heat varying from a hot moist atmosphere to high pressure steam. Moreover, the alloys described in all such cases contain impurities or alloying metals which the present authors have found to have enormous accelerating effects on intercrystalline oxidation in zinc-aluminum alloys. Thus Williams1 experimented with an alloy containing a large percentage of tin exposed in Cuba. Bauer2 reports failure of a boiler plug containing over 1 per cent. of impurities, doubtless lead for the most part, and Rawdon's3 examinations were made on an alloy containing 0.4 per cent. lead also exposed to the Tropics. No thorough investigation of the nature and cause of this type of failure has been made heretofore, so far as the authors are aware, although Rawdon correctly classified it as internal oxidation. We have, therefore, carried out this investigation in order to determine the exact nature of this phenomenon and the effect of other metals present as impurities or intentional additions in accelerating or-retarding it. In the appendix we include a considerable amount of data which may be valuable in selecting an alloy combining good physical properties with high resistance to oxidation.

Jan 8, 1922

By R. K. Ham, M. L. Wayman

TD-Nickel has been broken in tension and in fatigue at voom temperature. Rod specimens failed in tension by necking, with axial cracks attributed to voids elongated in the extrusion direction. Fatigue specimens failed in shear. Thin-film electron microscopy showed that the subgrain structure of TD-Nickel was very stable, and that particle-matrix detachment was very difficult, in tension and fatigue. TD-Nickel softened slightly during fatigue but had a high fatigue ratio (0.5at 10' cycles). Fractography suggested that Stage I fatigue crack propagation is greatly extended in TD-Nickel. Td-NICKEL* is a dispersion of 2 pct by volume of thoria (ThO2) in nickel, produced by powder-metallurgical methods including compaction, sintering, and extrusion. The spherical thoria particles, which may have a mean diameter of a few hundred angstroms, are dispersed with a mean planar spacing of a few thousand angstroms. By a combination of cold working and annealing, a subgrain or cell structure of dislocations intimately associated with the dispersion can be produced.' This gives the material useful tensile properties which are extremely resistant to exposure to high temperatures.'-= At the same time, the material shows considerable ductility.3'4 At the beginning of the present work, it was considered of great interest to investigate the mechanical stability of TD-Nickel under conditions of fatigue. On the one hand, materials which derive strength from a cold-worked structure are unstable in that they are susceptible to fatigue softening: in addition, the presence of discontinuities such as the particle-matrix interfaces might be expected to assist in the initiation and propagation of fatigue cracks, in that they may provide local concentrations of internal stress and sites for the initiation of voids." On the other hand, the substantial ductility of TD-Nickel suggests that if it obeys Coffin's relation8 (or the more refined form proposed by Manson9) it should have good fatigue resistance. The initial purpose of this investigation was to assess the importance of these factors. Also, relatively little fundamental work has been done on the mechanism of fatigue in dispersion-strengthened materials. Work on overaged A1-4 pct CU10-12 revealed a very large Bauschinger effect indicative of internal stresses at the particles, and very great fatigue hardening1' presumably due to the multiple slip stimulated by these internal stresses, followed by softening which was initially due to softening in the matrix, but later might have arisen from cracking at the particle-matrix interfaces. The study of overaged Al-4 pct Cu could not settle this latter point by the electron microscopy of thin films, since the dispersion is too coarse. A previous study of the fatigue of internally oxidized copper13 was complicated by inter granular failure, attributed to oxide particles at grain bouhdaries; internal oxidation of single crystals, however, improved their fatigue properties.'3 Investigations of SAP (sintered aluminum powder) are complicated by the complex particle shapes, and the possibility of continuous internal oxide films.14 It was hoped to avoid these difficulties with TD-Nickel, which had the further advantages that it was commercially available and suitable for study by the thin-film technique. 1) MATERIALS AND EXPERIMENTAL PROCEDURE TD-Nickel was purchased from the Driver-Harris Co. as 3/9-in.-diam rod which had been extruded, swaged, and "stress-relieved" (normally at 1010°C for 1 hr). Continuous-radius fatigue specimens with a minimum diameter of -0.1 in. were ground to shape and electropolished in 40 pct phosphoric, 35 pct sul-furic, 25 pct water at 25oC, with a stainless-steel cathode, at -6 v. Fatigue tests were carried out at room temperature with a Sonntag SF-1-U machine operating in push-pull at 1800 cycles per min, and in an Instron TT-C-L modified for reversed stressing at 26 cycles per min as described elsewhere.10 Round tensile specimens were ground with 0.85-in. gage lengths of 0.135 in, diam, electropolished, and tested in a Tinius Olsen hydraulic machine. The surfaces of fatigue specimens were examined with a Reichert metallograph. Discs for electron microscopy with a Siemens Elmiskop I were spark-cut 0.01 in. thick with a modified Servomet 11 employing a tool of moving molybdenum wire, cleaned in 50 pct acetic, 30 pct nitric, 10 pct phosphoric, and 10pctsul-furic at 85oC, and thinned by the window method in the electropolishing solution at -20°C and -6 v. Two-stage replicas (parlodion, then Pt-50 pct C self-shadowed at 40 deg) were taken from fatigue fracture surfaces for electron microscopy. Plane sections parallel to the specimen axis and containing the direction of fatigue crack propagation were polished, etched with Carapella's reagent, and examined optically. Transmission Laue X-ray photographs of as-received material electropolished to a point were used to determine preferred orientation. 2) RESULTS 2.1) The Structure of As-Received Material. Grains -1 µ diam and elongated 20 to 30 u in the direction of the rod axis were observed, With' elongated "intergran-ular" voids (-4 p diam and -90 µ long and identified as such using longitudinal and transverse sections and

Jan 1, 1968

By J. Waldman, M. B. Bever, A. K. Jena

The heats of formation at 273°K of 6 silver-rich Ag-Cd solid solutions and the heat of formation at 78°K of one solid solution have been measured by tin solution calorimetry. The heats of formation are analyzed in terms of the quasichemical theory. If the enthalpy diffel-ence between a hypothetical fcc form and the hcp form of cadmium is taken into account, this analysis does not lead to the conclusion put forth in the literature that electronic effects make significant contributions to the heats of formation of silver-rich Ag-Cd solid solutions. The temperature dependence of the heats of formation is appreciable and negative near 78ºK, but decreases gradually to nearly zero abore 400°K. The relative partial enthalpies per grarn -atom of silver at 541°K and cadmium at 532" and 541°K in tin have also been determined. THE composition range of the silver-rich Ag-Cd solid solutions stable at room temperature extends to about 40 at. pct Cd. Heats of formation of these solid solutions at 308" and 723°K have been measured by solution calorimetry.1,2 Heats of formation for an average temperature of 800°K have also been calculated from vapor pressures.2,3 The heats of formation deviate from the values predicted by the quasichemical theory above about 30 at. pct Cd. This deviation has been attributed to electronic effects at the Brillouin zone boundaries.2 The heats of formation of Ag-Cd alloys are essentially the same at 308", 723", and 800°K; consequently the temperature dependence of the heat of formation d?H/dT = ?Cp is vanishingly small, although from the exothermic heats of formation a negative value would have been expected. In the investigation reported here the heats of formation at 273°K of 6 silver-rich Ag-Cd solid solutions and the heat of formation at 78°K of 1 solid solution have been measured by tin solution calorimetry. The results are analyzed in terms of the quasichemical theory and the dependence of the heats of formation on temperature is discussed. The relative partial enthalpies per gram-atom of silver in tin at 541" and cadmium in tin at 532" and 541°K were obtained in the course of this investigation. The values of the temperature dependence of the relative partial enthalpies per gram-atom of silver in tin derived from the data reported by various investigators2,4-9 are contradictory. The literature contains only a value for 517°K of the relative partial enthalpy per gram-atom of solid cadmium in tin.2 EXPERIMENTAL PROCEDURES Samples of Ag-Cd solid solutions were prepared by melting weighed amounts of silver (99.99 pct pure) and cadmium (99.95 pct pure) in graphite crucibles under a flux of molten potassium chloride.10 The solidified ingots were sealed in evacuated Vycor tubes and annealed at 775°K for 10 days. The ingots were swaged and drawn into wires. The wires, sealed in evacuated Pyrex tubes, were held at 725°K for 5 hr and cooled to 365°K at an average rate of 2.5ºK per hr, followed by furnace cooling to room temperature. Chemical analysis of samples taken from different parts of each ingot gave no indication of segregation. Metallographic examination showed the samples to be homogeneous. Samples of the solid solutions or of the component elements were added to tin-rich baths in a calorimeter." At the start of a run the bath consisted of pure tin. Silver was used in the form of wire of 0.01-in. diam as supplied and cadmium in the form of lumps. Gold (99.999 pct pure) was added with the samples in order to reduce the endothermic heat effect of additions of Ag-Cd solid solutions. Samples of only one composition were added in a run and the ratio of the weight of alloy to that of gold was the same in all additions of a given run. In each run several calibrating additions of tin were made from 273°K. The heat contents of tin were calculated from the following equation, which is based on published data:12 (HTºK- H279º) = 6.70 T - 72,300/T + 20 cal/gram-atom; 505°K < T < 650°K The heat effect of each addition was plotted against the average of the sum of the atom fractions of solutes in the solution before and after that addition. The total concentration of solutes at the end of a run was less than 2 at. pct. In this range the heat effect was a linear function of the atom fraction of the solutes. The heat effect at infinite dilution and the composition dependence of the heat effect were obtained from the plots. RESULTS AND DISCUSSION Evaluation of Data. The linear dependence on composition of the heat effects of additions suggests that in the dilute range the enthalpy interaction coefficients other than the first-order coefficients of silver, cadmium, and gold are negligible, as shown in a concurrent publication.13 The heat effects at infinite dilution and the values of the composition dependence of the heat effects are listed in Table I.

Jan 1, 1970

By Sven Fornander

L. F. Reinartz (Armco Steel Corp., Middletown, Ohio) —I would like to know, in the practical application of the Kalling process, what kind of a lining was used, how thick was the lining, and how much metal was treated at one time? S. Fornander (author&apos;s reply)—The rotary furnace is lined with a course of fireclay bricks 6 in. thick. This course is backed by 5 in. of insulation. The furnace has a capacity of about 15 tons. Mr. Reinartz—How was the ladle preheated? Mr. Fornander—As pointed out in the paper, the furnace was heated by a gas flame in the beginning of the experiments. During these first tests, however, the desulphurization was inconsistent. We think that this was due to the fact that iron droplets sticking to the furnace walls were oxidized by the gas flame. Now, the furnace is operated without preheating of any kind, and the results are much better. T. L. Joseph (University of Minnesota, Minneapolis, Minn.)—I might add one comment. This furnace was heated with a flame and for a time they had a little difficulty due to some residual metal in the rotating drum that would oxidize in between treatments and they found therefore, that it was very essential to drain the drum completely of metal so that they would not build up any ferrous oxide between treatments and they eliminated some of their erratic heats by maintaining those more reducing conditions. It was interesting to watch this operation. As soon as the drum started to rotate there was considerable flame, at least, at the time I saw it, that came out around the flanges, indicating there was quite a little pressure on the inside of the drum. W. 0. Philbrook (Carnegie Institute of Technology, Pittsburgh)—Is the reaction slag in the Kalling process liquid or solid, and how is it separated from the metal? Mr. Fornander—In the process there is no slag in the usual sense of the word. The lime powder does not melt during the treatment. After the treatment the lime is still in the form of a fine powder. It is separated from the metal by means of a piece of wood of suitable size placed within the furnace before it is emptied. D. C. Hilty (Union Carbide & Carbon Research Laboratories, Niagara Falls, N. Y.)—Dr. Chipman has given us some of his ideas in connection with a specific effect of silicon and silica on sulphur elimination and how silicon might interfere with desulphuriz- ing in the blast furnace. I wonder if he would like to elaborate on the possibility of a similar effect of silicon in the Kalling process? J. Chipman (Massachusetts Institute of Technology, Cambridge, Mass.)—Silicon does not interfere with the Kalling process. Anything that has strong reducing action is good for desulphurization. In these tests where the temperature was low compared to blast furnace temperatures, the silicon that is in the metal is a better reducing agent than the carbon. At high temperatures, carbon is the better. It is not the silicon in the metal that interferes with desulphurization, it is the silica in the slag. Mr. Joseph—I might add that the metal that was tapped from the drum after desulphurization was really at quite a low temperature. It was not measured, but I think it was well under 1300 °C, probably 1200" or a little above that. That was one of the difficulties, and I think there is no question about the fact that the Kalling process—in that it affects desulphurization between powdered lime, solid and liquid iron— is a reaction definitely between the solid lime and the liquid iron. E. Spire (Canadian Liquid Air, Montreal, Canada) — This Kalling process seems very interesting to us and after all it is only a mixing action that is taking place between the iron and the slag. We have attempted to do the same thing in another way. We have placed at the bottom of the ladle a porous plug through which we injected an inert gas. It can be nitrogen or argon. This plug is placed at the bottom of the conventional ladle and gas injected through the plug. That has appeared in our patent. To define this new type of treatment, I use the word gasometallurgy. I do not know if you like it, but it is a way of defining methods of treating metal using gases. What we do is exactly what is done in the exchange process in another way. We have a porous plug at the bottom with a high lime slag on top of the metal. Using this method, we have very good agitation of metal and slag, and with a small flow of gas, we can achieve a very strong agitation. For instance, in the 500 lb ladle, we use only 5 liters of gas a minute. We have an agitation compared to very rapidly boiling water in a pail. Moreover, the agitation can be controlled to create any amount of mixing desired. In a few minutes, with this method, the sulphur dropped from 0.58 to 0.11. These results have been improved since, and we have obtained results like 0.08

Jan 1, 1952

By A. Simkovich, R. W. Lindsay

The possibility of using sodium sulfide slags to remove copper from ferrous alloys has been investigated by Jordan1 and by Langenberg.2, 3 In these studies, such slags were determined to be capable of removing copper and sulfur from the melt. The present work represents additional effort to clarify the effects of temperature on copper removal. The experiments were performed in a 17-lb induction furnace. Graphite crucibles contained the melts and kept the baths saturated with carbon. Temperatures were measured with a calibrated optical pyrometer and were controlled by manipulation of power input to the furnace. Estimated accuracy of temperatures in this investigation is ± 10°C (18°F) for measurements prior to slag additions, and + 20°C (36°F) after slag formation. The procedure consisted of melting 800 g of electrolytic iron. During this step, powdered graphite covered the exposed iron surface. After a predetermined temperature was reached, copper shot was added. A sample of the molten alloy for chemical analysis was then aspirated into a silica sheath. Next, a slag-forming mixture of sodium sulfite and graphite was added instantaneously to the melt. The sodium sulfite amounted to one-tenth the charge weight of iron; sufficient graphite was added to combine with oxygen in the sodium sulfite, assuming formation of carbon monoxide and reduction of the sulfite to sulfide. Subsequent to the slag addition, the molten alloy was sampled periodically, with the exception of heat A in which no intervening samples were taken between the slag addition and the end of the run. The iron was poured into a graphite mold, and the ingots sectioned and drilled for samples. Results of selected heats are presented in Table I. Analyses of samples drawn from the iron prior to slag addition are listed under zero time. Two samples from heat D were reported with copper contents greater than the initial concentration in the bath. Owing to the gradual but complete disappearance of slag during this heat, it is believed copper momentarily became more concentrated in the upper portion of the bath while reverting from the slag. This is the region from which samples were drawn. It should be noted that analysis of the ingot was equal to the copper content at the time of slag addition. The terminal temperatures of heats D and E, and the initial sulfur content of heat A are also to be noted. Because of the large temperature drop which occurred when slag was formed in heat D, power input to the furnace was increased in heat E after the slag addition, causing a higher terminal temperature. In heat A, the initial sulfur concentration was relatively high as compared to heats B through E owing to contamination by some slag remaining in the crucible from a previous heat. It is evident from Table I that copper was removed at the onset of slag formation. Roughly 30 pct of the copper was taken into the slag, with the exception of heat D, which had approximately 50 pct removed. For a comparatively short time of slag-metal contact, it appears that no gain is to be made in copper removal through use of high or low temperatures. If the slag initially formed remains in contact with the iron for an extended period, temperature has a marked effect upon copper removal, as can be seen by studying results for the two extremes in temperature. At about 1425°C, the copper level remained relatively constant after the initial removal by the slag. However, in the region of 1670°C, a definite reversion of copper occurred. Reversion was incomplete in heat D, and complete in heat E. The final temperatures of heats D and E differed by about 75°C. This temperature difference is thought to be the reason for only partial copper reversion in heat D. It is believed the effects of temperature noted above are related to the evolution of a white fume, which appeared in every run except heat A. (In the case of heat A, the fume was practically indiscernible.) After each slag addition, a yellow flame formed for about 5 sec. When the flame subsided, a white fume appeared. Upon contact with surrounding cooler surfaces, this fume deposited as a white solid. In the experiments made at 1425°C, evolution of fume continued unchanged to the end of the runs. However, heats D and E exhibited a different behavior. A very noticeable decrease in fume evolution from heat D was observed. Furthermore, this heat had much less slag remaining than did runs A through C when the experiments were terminated. No slag remained at the end of heat E; evolution of fume from this heat ceased prior to pouring. Spec-trographic analysis of the white deposit indicated sodium to be the major metallic element, with the maximum concentration of iron and copper as 0.1 and 0.01 pct, respectively. It is supposed the white fume observed in these experiments is principally sodium oxide (Na2O), formed by oxidation of sodium in the slag and subsequent sublimation. (Sodium oxide is a white to gray substance in the solid state; at 1275oC, it sublimes.4) According to this mechanism, elevated temperatures would accelerate removal of sodium from the slag, sulfur pickup by the

Jan 1, 1961

By Ottar Dragge, C. Danielsson, Bo Kalling

DISCUSSION, T. L. Joseph presiding L. F. Reinartz (Armco Steel Corp., Middletown, Ohio) —I would like to know, in the practical application of the Kalling process, what kind of a lining was used, how thick was the lining, and how much metal was treated at one time? S. Fornander (author&apos;s reply)—The rotary furnace is lined with a course of fireclay bricks 6 in. thick. This course is backed by 5 in. of insulation. The furnace has a capacity of about 15 tons. Mr. Reinartz—How was the ladle preheated? Mr. Fornander—As pointed out in the paper, the furnace was heated by a gas flame in the beginning of the experiments. During these first tests, however, the desulphurization was inconsistent. We think that this was due to the fact that iron droplets sticking to the furnace walls were oxidized by the gas flame. Now, the furnace is operated without preheating of any kind, and the results are much better. T. L. Joseph (University of Minnesota, Minneapolis, Minn.)—I might add one comment. This furnace was heated with a flame and for a time they had a little difficulty due to some residual metal in the rotating drum that would oxidize in between treatments and they found therefore, that it was very essential to drain the drum completely of metal so that they would not build up any ferrous oxide between treatments and they eliminated some of their erratic heats by maintaining those more reducing conditions. It was interesting to watch this operation. As soon as the drum started to rotate there was considerable flame, at least, at the time I saw it, that came out around the flanges, indicating there was quite a little pressure on the inside of the drum. W. 0. Philbrook (Carnegie Institute of Technology, Pittsburgh)—Is the reaction slag in the Kalling process liquid or solid, and how is it separated from the metal? Mr. Fornander—In the process there is no slag in the usual sense of the word. The lime powder does not melt during the treatment. After the treatment the lime is still in the form of a fine powder. It is separated from the metal by means of a piece of wood of suitable size placed within the furnace before it is emptied. D. C. Hilty (Union Carbide & Carbon Research Laboratories, Niagara Falls, N. Y.)—Dr. Chipman has given us some of his ideas in connection with a specific effect of silicon and silica on sulphur elimination and how silicon might interfere with desulphuriz- ing in the blast furnace. I wonder if he would like to elaborate on the possibility of a similar effect of silicon in the Kalling process? J. Chipman (Massachusetts Institute of Technology, Cambridge, Mass.)—Silicon does not interfere with the Kalling process. Anything that has strong reducing action is good for desulphurization. In these tests where the temperature was low compared to blast furnace temperatures, the silicon that is in the metal is a better reducing agent than the carbon. At high temperatures, carbon is the better. It is not the silicon in the metal that interferes with desulphurization, it is the silica in the slag. Mr. Joseph—I might add that the metal that was tapped from the drum after desulphurization was really at quite a low temperature. It was not measured, but I think it was well under 1300 °C, probably 1200" or a little above that. That was one of the difficulties, and I think there is no question about the fact that the Kalling process—in that it affects desulphurization between powdered lime, solid and liquid iron— is a reaction definitely between the solid lime and the liquid iron. E. Spire (Canadian Liquid Air, Montreal, Canada) — This Kalling process seems very interesting to us and after all it is only a mixing action that is taking place between the iron and the slag. We have attempted to do the same thing in another way. We have placed at the bottom of the ladle a porous plug through which we injected an inert gas. It can be nitrogen or argon. This plug is placed at the bottom of the conventional ladle and gas injected through the plug. That has appeared in our patent. To define this new type of treatment, I use the word gasometallurgy. I do not know if you like it, but it is a way of defining methods of treating metal using gases. What we do is exactly what is done in the exchange process in another way. We have a porous plug at the bottom with a high lime slag on top of the metal. Using this method, we have very good agitation of metal and slag, and with a small flow of gas, we can achieve a very strong agitation. For instance, in the 500 lb ladle, we use only 5 liters of gas a minute. We have an agitation compared to very rapidly boiling water in a pail. Moreover, the agitation can be controlled to create any amount of mixing desired. In a few minutes, with this method, the sulphur dropped from 0.58 to 0.11. These results have been improved since, and we have obtained results like 0.08

Jan 1, 1952

By W. H. Patnode

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

Jan 1, 1949

By W. Weissberger, Frankiewicz, L. Pommier

Introduction In the U.S., about one-quarter of the fuel oil and natural gas consumption is associated with power production in utility and industrial boilers and process heat needs in industrial furnaces. Coal has been an attractive candidate for replacing these premium fuels because of its low cost, but there are penalties associated with the solid fuel form. In many cases pulverized coal in unacceptable as a premium fuel replacement because of the extensive cost of retrofitting an existing boiler designed to burn oil or gas. In the cases of synthetic fuels from coal, research and development still have a long way to go and costs are very high. Another option, which appears very attractive, is the use of solid coal in a liquid fuel form - coal slurry fuels. Occidental Research Corp. has been developing coal slurry fuels in conjunction with Island Creek Coal (ICC), a wholly-owned subsidiary. Both coal-oil mixtures and coalwater mixtures are under development. ICC is a large eastern coal producer, engaged in the production and marketing of bituminous coal, both utility steam and high quality metallurgical coals. There are a number of incentives for potential users of coal slurry fuels and in particular for coal-water mixtures (CWMs). First, CWM represents an assured supply of fuel at a price predictable into future years. Second, CWM is available in the near term; there are no substantial advances in technology needed to provide coal slurry fuels commercially. Third, there is minimal new equipment required to accommodate CWM in the end-user&apos;s facility. Fourth, CWM is nearly as convenient to handle, store, and combust as is fuel oil. Several variants of CWM technology could be developed for different end-users in the future. One concept is to formulate slurry at the mine mouth in association with an integrated beneficiation process. This slurry fuel may be delivered to the end-user by any number of known conveyances such as barge, tank truck, and rail. Slurry fuel would then be stored on-site and used on demand in utility boilers, industrial boilers, and potentially for process heat needs or residential and commercial heating. An alternative approach is to formulate a low viscosity pre-slurry at the mine mouth and to pipeline it for a considerable distance, finishing up slurry formulation near the end-user&apos;s plant. Finally, at the other extreme of manufacturing alternatives, washed coal would be shipped to a CWM manufacturing plant just outside the end-user&apos;s gate. Depending on fuel specifications and locations of the mine and end-user facility, any of these alternatives may make economic sense. They are all achievable in the near term using existing technology or variants thereof. The Coal-Water Mixture CWMs contain a nominal 70 wt. % coal ground somewhat finer than the standard pulverized ("utility grind") coal grind suspended in water; a complex chemical additive system gives the desired CWM properties, making the suspension pumpable and preventing sedimentation and hardening over time. Figure 1 shows the difference between a sample of pulverized coal containing 30 wt. % moisture and a CWM of identical coal/water ratio. The coal sample behaves like sticky coal, while the CWM flows readily. The combustion energy of a CWM is 96-97% of that associated with the coal present, due to the penalty for vaporizing water in the CWM. Potentially any coal can be incorporated in the CWM, depending on the combustion performance required and the allowable cost. CWMs are usually formulated using high quality steam coals containing around 6% ash, 34% volatile matter, 0.8% sulfur, 1500°C (2730°F) initial deformation temperatures, and energy content of 25 GJ/t (21.5 million Btu per st). Additional beneficiation to the 3% ash level can be accomplished in an integrated process. There are a number of minimum requirements which a satisfactory CWM must meet: pumpability, stability, combustibility, and affordability. In addition, a CWM should be: resistant to extended shear, generally applicable to a wide variety of coals, forgiving/flexible, and compatible with the least expensive processing. It was found that a complex chemical additive package and control of particle size distribution are necessary to achieve these attributes simultaneously, while maximizing coal content in the slurry fuel. Formulation of Coal-Water Mixtures A major consideration in the manufacture, transportation, and utilization of a slurry fuel is its pumpability, or effective viscosity. Most CWM formulations are nonNewtonian, i.e., viscosity depends on the rate and/or duration of shear applied. Viscosities reported in this paper were obtained using a Brookfield viscometer fitted with a T-spindel and rotated at 30 rev/min, thus they are apparent viscosities measured at a shear rate of approximately 10 sec-1. The instrument does reproducibly generate a shear field if spindle size and rotation rate are held fixed. By observing the apparent viscosities of several slurries at fixed conditions it is possible to obtain a relative measure of their viscosities for comparison purposes. A true shear stress-shear rate relationship at the shear rates at which the CWM will be subjected in industry may be obtained using the Haake type and a capillary viscometer. These viscometers are used for specific applications. However, for comparison purposes, apparent viscosities are reported.

Jan 1, 1985

By W. H. Patnode

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

Jan 1, 1949

By J. R. Szedon, T. L. Chu, G. A. Gruber

Amorphous adherent filnzs of silicon dioxide have been deposited on silicon substrates by the oxidation of silane at temperatures ranging from 650 to 1050C. Various diluents (argon, nitrogen, hydrogen) were used to suppress the formation of SiO2 in the gas phase. Deposition rates of the oxide were determined over the temperature range in question as functions of&apos; re-actant flow rates. Etch rate studies were used for a cursory comparison of structural properties of deposited and thermally grown oxides. From electrical evaluation of metal-insulator-silicon capacitors it was determined that the interface charge density of deposited films is similar go that of dry-oxygen-grown films in the 850° to 1050 C temperature range. Deposited films exhibit several ionic instability effects which differ in detail from those reported for thermal oxides. Stable passivating films of silicon nitride over deposited oxides appear to be practical for use in silicon planar device fabrication. Such films can be prepared under temperature conditions which have less effect on substrate impurity distributions than in the case of grown oxides. AMORPHOUS silicon dioxide (silica) is compatible with silicon in electrical properties and is the most widely used dielectric in silicon devices at present. Silica films can be prepared by the oxidation of silicon or deposited on silicon or other substrate surfaces by chemical reactions or vacuum techniques. The ability of thermally grown silicon dioxide films to passivate silicon surfaces forms one of the practical bases of the planar device technology. Properly produced and treated films of grown SiO 2 can have low densities of interface charge (-1 X 10" charges per sq cm) and can be stable as regards fast migrating ionic sgecies. 1 To maintain these properties, even with an otherwise hermetically sealed ambient, the Sia layers must be at least l000 A thick. Such thicknesses require oxidation in dry oxygen for periods of 7.8 hr at 900°C or 2 hr at 1000°C. Although oxidation in steam or wet oxygen can reduce these times to 17 and 5 min, the resulting oxides must be annealed to produce acceptable levels of interface charge., Oxidation or annealing involving moderate to high temperatures for extended periods of time can be undesirable. Under some conditions, there can be changes in the distribution of impurities within the underlying substrate. A chemical deposition technique using gaseous am-bients is particularly attractive and flexible for preparing oxide films. With a wide range of deposition rates available, films can be produced under condi- tions of time and temperature less detrimental to impurity distributions in the silicon than in the case of thermal oxidation. The pyrolysis of alkoxysilanes, the hydrolysis of silicon halides, and various modifications of these reactions are most commonly used for the deposition of silica films.3 Silica films obtained in this manner are likely to be contaminated by the by-products of the reaction, organic impurities, or hydrogen halides. The use of the oxidation of silane for the deposition process has been reported recently.4 The deposition of silica films on single-crystal silicon substrates by the oxidation of silane in a gas flow system has been studied in this work. The deposition variables studied were the crystallographic orientation of the substrate surface, the substrate temperature, and the nature of the diluent gas. The electrical charge behavior of Si-SiO2-A1 structures prepared under various conditions was investigated by capacitance-voltage (C-V) measurements of metal-insulator-semiconductor (MIS) capacitors. The experimental approaches and results are discussed in this paper. 1) DEPOSITION OF SILICA FILMS The overall reaction for the oxidation of silane is: The equilibrium constants of this reaction in the temperature range 500° to 1500°K, calculated from the JANAF thermochemical data,= are shown in Fig. 1. In addition to the large equilibrium constants, the oxidation of silane is also kinetically feasible at room temperature and above. However, the strong reactivity of silane toward oxygen tends to promote the nucleation of silica in the gas phase through homogeneous reactions, and the deposition of this silica on the substrate would yield nonadherent material. The formation of silica in the gas phase can be reduced by using low partial pressures of the reactants. Argon, hydrogen, and nitrogen were used as diluents in this work. 1.1) Experimental. The deposition of silica films by the oxidation of silane was carried out in a gas flow system using an apparatus shown schematically in Fig. 2. Appropriate flow meters and valves were used to control the flow of various reactants, i.e., argon, hydrogen, nitrogen, oxygen, and silane. Semiconductor-grade silane, argon of 99.999 pct minimum purity, oxygen of 99.95 pct minimum purity, and nitrogen of 99.997 pct minimum purity, all purchased from the Matheson Co., were used without further purification. In several instances, a silicon nitride film was deposited over the silica film. This was achieved by the nitridation of silane with ammonia using anhydrous ammonia of better than 99.99 pct purity supplied by the Matheson CO.&apos; The reactant mixture of the desired composition was passed through a Millipore filter into a horizontal water-cooled fused silica tube of 55 mm

Jan 1, 1969

By P. K. Strangway, H. U. Ross

Briquets consisting of pure artificial magnetite, pure artificial hematite, and mixtures of the two were reduced by hydrogen in a loss-in-weight furnace at temperatures in the range 500° to 1000° . The rate of reduction of the pure hematite briquets increased continuously with increased temperature. In contrast, the pure nmgnetite briquets exhibited a pronounced rate ninimutn at about 700°C. Metallographic studies of partially reduced briquets rerlealed that, at this temperature, the he.matite samples reduced in a topo-chemical manner while the magnetite ones reduced uniformly throughout, and after partial reduction their cross sections contained a mixture of iron and unreacted wustite grains. No iron shells could be detected on the surfices of any of these uwstite grains. X-ray diffraction investigations indicated that these grains had a rzinimum lattice parameter when they had been formed at the rate rninimum temperature. Also, it was found that an activation energy of 41,000 cal per mole zoas required for reduction when only these wustite grains were present. Thus, it is suggested that the overall reduction rate of the rnagnetile su?nples at temperatures in the range influenced by the rate nzinirnum phenomenon was limited by the rate qf iron ion diffusion in the unreacted wustite grains. THE rate minimum phenomenon, which has often been observed when reducing iron oxides at a temperature of about 700°C, is one of the most interesting, yet unresolved, problems in the field of reduction kinetics. Basic principles of chemical kinetics and &apos;In some instance, a second rate minimum has been observed at about 900°C. Since most investigators are in agreement that this minimum is directly related to the transformation from a to y iron (which takes place at 911°C) and since it was not encountered during the present reduction tests, it will not be referred to in this vaver. fundamental laws of diffusion all agree that, as the temperature is increased, the rate of reduction should also increase. However, with certain ores, it has been found that their reduction rate actually decreases with an increase in temperature up to some value X where a minimum reduction rate is reached. With further temperature increases beyond X the rate becomes more rapid again. Temperature X is usually referred to as the "rate minimum temperature", while the overall type of behavior constitutes the "rate minimum phenomenon". This phenomenon has been reported by numerous investigators. They have found rate minima during the reduction of both artifiial&apos; and natural374 magnetites and artificia15j6 and natural5" hematites. Rate minima have been observed when reducing high-purity material2 or low-grade ores,3&apos;4 when studying particles in the micronsize range5 or relatively large agglomerates,g10 and during reduction with either hydrogen7 or carbon monoxide.11"2 Previously, this phenomenon has been attributed to many factors; these include sintering and recrystallization of the iron formed during reduction374 changes in microporosity of the ore upon redction,"" formation of dense iron shells around retained wustite grains,11716 and chem-isorption,17 to name only a few. However, most investigators who have reported a rate minimum merely speculated as to what seemed to influence it and they did not examine the fundamental causes. Consequently, the present experimental study was initiated in order to evaluate the basic factors which could be associated with this phenomenon. MATERIALS AND METHODS The experimental techniques, followed during this investigation, are similar to those which have been described previously.18 The chemically pure magnetic powder was prepared by partially reducing Fisher reagent-grade hematite with a gaseous mixture of carbon monoxide and carbon dioxide in a rotating-drum furnace. Three-quarter-inch diam cylindrical briquets which weighed about 12 g were formed from this magnetite powder and pure hematite powder. All of the briquets were sintered while they were slowly raised through the 1200°C hot zone of a vertical tube furnace. An argon stream was continually flushed through this furnace in order to prevent oxidation of the magnetite briquets, while in the case of the pure hematite briquets sintering was carried out in air. The sintered hematite briquets had a density of 5.06 g per cu cm while the density of the sintered magnetite briquets was 4.27 g per cu cm. The sintered briquets were reduced by purified hydrogen in a loss-in-weight furnace at temperatures in the range 500" to 1000°C. In all instances, the critical reducing gas velocity was exceeded and, in order to ensure that the results were reproducible, duplicate briquets of each type were reduced under each set of experimental conditions. A continuous record of the weight loss during reduction was obtained with the aid of a Statham transducer. The present experimental setup was capable of detecting a change in weight as small as 10 mg. Since a weight loss of over 2 g usually occurred during each reduction test, an accuracy of better than 0.5 pct of the total weight loss could be achieved. RESULTS AND DISCUSSION Reducibility Tests. In the first set of experiments, pure hematite and pure magnetite briquets were used.

Jan 1, 1969

By W. F. Chiao

With the application of dislocation damping theory an attempt was made to determine whether the generation and extension of dislocations is inherently more difficult in a brittle steel than in a ductile steel. A ductile steel was compared with a brittle stee1 by simultaneously measuring the ultrasonic attenuation and velocity during tensile test, and the density of free dislocations and their mean loop length were then calculated as a function of strain. The results showed that in the ductile steel there was always a large generation of dislocations and great extension of loop length occurring at some stage within the early plastic region. In contrast, the brittle steel showed very little or no such sudden changes in dislocation dynamic states after the onset of plastic deformation. Furthermore, a strong temperature dependence of dislocation dynamic states was also observed in the ductile steel and a hypothesis was suggested that a thermally activated process of dislocation rearrangement could occur at higher deformation temperatures. The activation energy of dislocation rearrangement at room temperature was estimated as about 2030 cal per mole.C. DUCTILITY is an indispensible property in the application of engineering materials, especially steel. During the past two decades the theoretical and experimental approach to the understanding of flow and fracture of metals has been constantly undergoing changes and progress." while the fracture behavior of metals can be influenced by many factors such as chemical Composition,3 second-phase particle mor-phology,4 and dislocation arrangement,5 it is now a general belief that the fundamental understanding of the ductile-brittle fracture phenomena of solid materials must stem from the study of dislocation dv-namics developed under stress conditions.6,7 Most of the traditional ductility tests, such as Charpy impact test, slow bend test, and tensile fracture test, cannot by themselves reveal directly the mechanisms of ductile to brittle transition of materials. In the experimental investigation of tensile ductility it would be ideal to be able to study directly the dynamics of dis-locations in a bulk specimen during the process of deformation. Since the ultrasonic pulse technique is the only satisfactory method for studying dislocations and the fine details of deformation characteristics in metals in the course of a tensile test, it would appear that a comparative study of ultrasonic attenuation changes during tensile tests of metallic materials exhibiting different ductility might be very informative. So far no work comparable to this study has appeared in the literature. Recent progress in both theory and experiment has indicated the feasibility of studying the dislocation mechanisms of ductility behaviors by ultrasonic measurements during tensile test. Granato and Lucke8 have developed a quantitative theory that enables the calculation of dislocation density and their average loop length from the measurements of ultrasonic attenuation and velocity, and several investigators, including Chiao and Gordon,9&apos;10 have shown that simultaneous ultrasonic measurements can be successfully made during a tensile test. Furthermore, many investigators11-13 have repeatedly proposed in the past several decades that deformation and fracture are mutually self-exclusive, and that the ability or inability of a material to deform plastically, i.e., to generate dislocations, is a major factor in determining whether the material will be ductile or brittle. Thus, in the present work an attempt was made to determine whether the generation and extension of dislocations is inherently more difficult in a brittle steel than in a ductile steel. This article is principally concerned with the study of the relation between the propagation of ultrasonic waves and tensile deformation in a steel series which displays quite different toughness at room tempera-turk. changes in attenuation and velocity of ultrasonic waves have been measured as a function of strain during the deformation process. The results have been interpreted in terms of the vibrating string model for dislocation damping as developed by Granato and Lucke, and it has been found that some of the more subtle predications of the model are in good agreement with the experiments. This would be especially meaningful because most of the previous experiments in testfying the model were carried out with single crystals of high-purity materials and little work has been done with polycrystalline steel alloys. EXPERIMENTAL PROCEDURES AND RESULTS Specimen Materials. The tensile specimens used throughout this experiment were of two compositions selected from a series of Fe-Mo-0.77 pct Mn-0.22 pct C steels prepared for a ductile-brittle fracture transition study. One steel contains 0.21 pct Mo and the other 1.03 pct Mo. These two compositions were chosen for the present study because they possess quite different toughness properties at room temperature. The 0.21 pct Mo steel is quite ductile while the 1.03 pct Mo steel is rather brittle, as measured by the standard Charpy impact test. The alloys had been prepared by vacuum induction melting and chill casting in steel molds. The ingots were hammer-forged into 1/2-in.-sq bars from which tensile specimen blanks were cut. These blanks were first normalized under argon atmosphere at 1700°F and then reaus-tenitized and isothermally transformed at 1050°F to a bainitic microstructure. The chemical compositions, heat treatments, hardness measurements, and Charpy transition temperatures of the two steels are listed in Table I.

Jan 1, 1970

By M. A. Selim, W. H. Somerton

Thermal expansions and heats of reaction of three typical sandstones were measured in the temperature range of 25°to 1,000°C. The significance of these data in subsurface heat-transfer calculations is discussed. Linear thermal expansions were measured both parallel and perpendicular to the bedding planes. Volume expansions are reported as the perpendicular expansion plus two times the parallel expansion. Expansion behavior of the sandstones was found to be controlled by the expansion characteristics of the quartz content. Differential expansion of the quartz grains and other minerals included in the sandstones caused permanent deformation of the heated samples after they were cooled to room temperature. Structural damage resulting from heating is probably an important cause of the reduction of thermal conductivity of heated samples. Measurements of heats of reaction were based on the known heat required for a- quartz inversion. Thermal reactions, which probably include deby-droxylation of clay minerals and decomposition of carbonate minerals contained within the samples, were found to require more than one-fourth of the amount of heat necessary to raise the temperature of the rock alone. In shales and limestones, the reaction heat could be substantially greater than that required from specific heat considerations alone. INTRODUCTION In earlier work, l-3 methods of measuring thermal properties were developed and thermal data for several sedimentary-rock types were reported. Data included thermal conductivity, specific heat and thermal diffusivity. In addition, calculations of heat transfer in subsurface formations may require data on the thermal-expansion characteristics of rock and the heats of reaction of mineral constituents. Thermal expansion of rocks is relatively small in magnitucle and, from the standpoint of change in bulk density, has only minor effects on heat-transfer cliaracteristics. Thermal-expansion behavior, however, may have significant effects on the structure of rocks. Differential expansion of different minerals and along different crystal-lographic axes may result in structural damage which could effectively reduce the thermal conductivity of the rock. Many mineral constituents of sedimentary rocks undergo phase or related changes when heated to sufficiently high temperatures. Although some of these reactions (such as the a-ß quartz inversion) are reversible and the heat absorbed is returned to the system upon cooling, many of the major reactions are irreversible. Through certain temperature ranges, the additional heat energy required to complete the reactions may be nearly as great as that necessary to raise the temperature of the rock in the absence of thermal reactions. If the heat requirements for these reactions are not considered, serious errors in heat-transfer calculations may result. Thermal-tzxpansion and thermal-reaction data have been obtained for three typical sandstones. Methods of measurement and results obtained are reported and discussed in the following. THERMAL EXPANSION OF SANDSTONES The linear expansions of three outcrop sandstones (Bandera, Berea and Boise) have been measured in the temptbratue range of 25° to 1,000° C. Expansion measurements were made in the directions parallel and perpendicular to the bedding. The differential expansion apparatus used is that described by Mitoff and Pask.4 The test sample is heated in an electric furnace with a temperature rise of 6°C/minute. The lengthening of the samples upon heating is compared with the small and known expansion of a fused silica rod. The change in length is transmitted to an X-Y recorder by means of a Statham transducer. A maximum error of ± 1.5 per cent has been obtained with this apparatus

By Frank M. Brooks

Endeavoring to meet the requirements of more oil created by the war effort, the oil industry of Kansas in 1944 maintained a level of exploratory and development work well above the average of previous years. During the year, 1866 test wells were drilled, of which 838 were completed as new oil wells, 89 as new gas wells and 939 as dry holes. These figures compare with 895 new oil wells, 32 new gas wells and 834 dry holes for a total of 1761 tests in 1943. Thus, there was a marked decrease in the number of new oil wells, and an increase in the new gas wells and dry holes. The total daily initial potential of production discovered by the successful wells amounted to 494,689 bbl. of oil as compared with 736,297 bbl. in 1943. The increase in unsuccessful tests and decrease in the daily initial potential of production has caused considerable comment and speculation among the oil operators of the state. This tends to confirm the fact that each year it is becoming harder to find the remaining oil fields. The total number of wildcats drilled in Kansas was 651 in 1944, including the so-called "extension wildcats" (more than 1/2 to I mile from known production). Of this number, 410 are classified as "rank wildcats," being more than one mile from production. The total of 651 compares with the total of 577 for 1943, showing an increase in wildcat drilling of 74 test wells: Of these tests, 81 were successful in finding new oil fields or substafitially extending known areas of production, and 20 either found new gas pools or extended old ones. The ratio of dry holes to producing wells among the "rank" wildcats was approximately 10 to I (372 dry and 38 successful). This compares with a ratio of 10 to I in 1943, 11 to I in 1942, and 6 to I in 1941. A compilation of the results obtained by 34 active companies, including all of the major companies, reveals that their efforts accounted for 286 rank wildcat wells, of which-37 found oil or gas, making a dry-hole percentage of 87. Approximately 55 per cent of all, tests (pool and wildcat) were failures. Thc Kansas Nomenclature Committee of the Kansas Geological Society named and classified 43 new oil fields and 8 new gas fields during the year. The discovery wells of the new oil fields had a total initial potential of 18,358 bbl. for a per well average or&apos; 427 bbl. The average initial potential per well in 1942 and 1943 was 894 and 419 bbl., respectively. With nearly all wells producing at their economic capacity, the total production for Kansas during 1944 totaled 101,896,704 bbl., which compares with total runs of 107,709,679 bbl. in 1943. Production of natural gas during 1944 reached a new high record of 135 billion cubic feet. This compares with 122 billion cubic feet for 1943, and 98 1/2 billion cubic feet for 1942. The large Hugoton field of Southwestern Kansas accounted for about half of the total gas produced. Highlights OF the Year Although 51 new fields were found in the state during 1944, it is apparent that the

Jan 1, 1945

By Castle. J. E., J. L. Gillson

In this chapter there is a wide difference in the meaning of some words used for rock and mineral names as defined by scientists and tabulated in the "Glossary of Geology and Related Sciences," published in 1957 by the American Geological Institute, and the meaning as used by the commercial producers of feldspar. It is necessary, therefore, to define these terms giving both the "scientific" and the "practical" definitions. There is no ambiguity about the name feldspar itself. This is a general term for a group of related minerals which are silicates of aluminum, combined with sodium, potassium and calcium. The feldspars are the most abundant minerals of the igneous rocks, and since these rocks make up the largest proportion of the earth&apos;s crust by volume (although not of the actual surface area of the continental land masses) the feldspars are the most abundant minerals of all. The igneous rocks themselves are classified on the basis of the variety of the feldspar present. The potash feldspars, which are called orthoclase and microcline, are the dominant minerals of the granites and syenites, and of their fine grained equivalents, the rhyolites and trachites. The plagioclase feldspars form an isomorphic series, of which the sodic endmember is called albite, and the lime endmember, anorthite. The members near the sodic end, albite, oligoclase and andesine are the characteristic feldspars of the granodiorites and diorites, and of their fine grained equivalents, the dacites, and andesites. These feldspars-orthoclase, microcline, albite oligoclase and andesine-are the feldspars used commercially. Labradorite, a member of the plagioclase group, in which the lime exceeds the soda in the chemical composition, is the common feldspar of the gabbros, anorthosites, norites, basalts and other so-called "basic" rocks. Although some attempts have been made to use labradorite as a commercial feldspar, none is now used except as an ornamental stone. The mineral anorthite is very rare. Since the feldspar in most of the common igneous rocks is relatively fine grained, and mixed intimately with other minerals, from which it can be separated cleanly only with difficulty, most masses of the common rocks cannot be used as sources for the feldspar contained in them. It is only the rarer types of rocks in which the feldspar is very coarse-grained, or ones containing very little of the iron-bearing minerals which are objectionable impurities in commercial feldspar, that are quarried to yield an acceptable product. The most widespread type of such a rock from which commercial feldspar can be produced, is that called "pegmatite." These rocks are dikes and bodies of irregular shape and of a size measured in feet or yards in most cases, rather than in miles. They are more commonly associated with granites, rather than with other coarse-grained igneous rocks. Many of them contain crystals of various minerals, including the feldspars, that are much larger than are found in the host rock, the granite, and in many there are large masses of feldspar that are sufficiently free from iron-bearing silicates so that products acceptable to the ceramic industry can be produced, in some cases simply by hand sorting. Most of this feldspar in pegmatites, however, does contain intergrown quartz up to 25 pct. Pegmatites are so important, not only as commercial sources of feldspar, but also of other minerals which are produced com-

Jan 1, 1960