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By Robert Mehl

IT has been shown that quenched iron of high purity exhibits a Widmanstätten figure much resembling martensite in appearance.1 This figure exhibits a maximum of four directions of the surface traces that characterize it, suggesting that a Fe forms from y Fe in plates parallel to the {111}, octahedral, planes in the y lattice. Because of this, and also because of the general similarity to the structural appearance of martensite and to the Widmanstätten figure obtaining in slowly cooled hypoeutectoid steels it has been suggested2 that the orientation relation-ships obtaining between the y and a phases in pure iron are identical with those demonstrated in martensite3 and in slowly cooled hypoeutectoid steels,4 and indeed that the crystallographic mechanism of formation of a Fe from y Fe is the basic mechanism determining the orientation relation-ships found in both martensite and in slowly cooled hypoeutectoid steels. This paper will present experimental evidence in support of this view.

Jan 1, 1934

EDMUND NEWTON, Minneapolis, Minn. (communication to the Secretary?).-In discussing the question of the deoxidation of steel and material suitable for performing this function at the end of the heat, it would seem logical also to include the question of prevention of oxidation in the steel or the formation of iron oxide, FeO. I refer to the use of manganese in the basic open-hearth and basic Bessemer processes. The advantages of high manganese in pig iron for these processes have evidently been clearly understood in Germany for a number of years, although little has been written in regard to the exact manner in which the benefits are obtained. In this country, while we make no steel by the basic Bessemer process, our basic open-hearth process is becoming more and more important. Until 10 years ago, in this country, manganese in the pig iron for this process was considered of little value and by many writers it was spoken of as a disadvantage. During the past 10 years, however, in certain parts of the United States, higher contents of manganese in basic pig have been used with considerable success, although there is apparently nothing in our technical literature to show the reasons for this trend. A German book, "The Basic Open-Hearth Steel Process" by Carl Dichmann does, however, offer an explanation. Dichmann says that if the charge for either of the above-mentioned processes contains 3 per cent. of manganese or above, satisfactory steel.

Jan 6, 1917

By C. S. Matthews, H. C. Lefkovits

The purposes of this study are (a) to determine the accuracy of a previously proposed method for calclrlating average reservoir pressure and (b) to find a method for estimating the shape of the drainage area of each well in a bounded reservoir. Both numerical and experimental methods are used to determine the pressure distribution and the location of drainage bounrlaries in idealized reservoirs at steady state. A number of photographs are included which show flowlines and drainage areas in reservoir models of various shapes. Results from these studies are then compared with those from the previously proposed method for calculating average reservoir pressure.' It is concluded that the previously proposed method is sufficiently accurate for most reservoir engineering purposes. In addition, some simple methods are given for estimation of .shapes of drainage boundaries. INTRODUCTION A method for the determination of the average Pressure in a bounded reservoir was previously developed by Matthews, Brons, and Hazebroek,1 and presented at the Petroleum Branch Fall Meeting in 1953.† In aP- plying this method, the reservoir was first divided into drainage volumes; second, the average pressure in each drainage volume was calculated; and third, these drainage volume pressures were averaged volumetrically to give the average pressure in the reservoir. It was shown that each well's individual drainage volume, at steady state, is proportional to the well's production rate; however. the question of how to estimate accurately the shape of these drainage volumes could not be answered. Furthermore, in calculating the average pressure for each drainage area, the actual drainage areas, which are in general quite asymmetric in shape, are replaced with one of the symmetric prototypes given in T.P. 3876. A question may then be raised as to how accurately the symmetrical figures depict the pressure behavior of the actual unsymmetrical drainage areas. The study reported on in the present paper was made in an attempt to shed light on the above questions. METHODS It was shown in T.P. 3876 that after a period of steady rate of withdrawal the rate of pressure decline becomes constant at every point in a bounded reservoir containing a single-phase fluid whose compressibility is small and constant and whose viscosity is con-

Jan 1, 1956

By J. R. Cain

In every process for making steel there are one or more stages where the metal is exposed to gas of one kind or another. Thus, in the open-hearth furnace, the carbon dioxide and water vapor in the products of combustion are oxidizing toward the ferrous and manganous oxides in the slag, tending to convert these to higher oxides; the higher oxides then , oxidize the steel, so that indirectly the products of combustion are oxidizing toward the steel. In the Bessemer process, there is direct contact of air and steel; also, the water vapor in the air blown into the converter is continually decomposed by the molten steel, yielding hydrogen and ferrous oxide, both of which are in part taken up by the metal. In the electric-furnace processes, there is always more or less air in contact with the slag covering the metal, and this air and the gaseous reaction products from it are dissolved in the slag to some extent and thus transmitted in part to the steel. In the crucible processes, there is always entrapped air in the charges and the crucibles are more or less permeable to the gaseous products of combustion from the furnace. In all the processes of manufacture, the molten metal is exposed to air while tapping into ladles and ingot molds and has an opportunity to saturate itself with air or with gaseous or solid products generated by chemical reactions between air and steel. Sievertsl has shown that molten metals requirc but a few seconds to saturate themselves with a surrounding gas. No one familiar with the operations at a steel plant needs to be reminded of the important role that gases play at all stages. The familiar "boil" of open-hearth furnaces, due to evolution of carbon monoxide when iron ore is added to the molten steel; the spectacular operation of the Bessemer converter brought about entirely by a gaseous reagent; the almost magic effect of small quantities of silicon, manganese, or aluminum added to the molten metal in ladle or furnace in quickly preventing bubbling and evolution of gases; the unwelcome phenomena of blowholes in ingots that have not been properly manufactured—these

Jan 1, 1920

By Y. C. Liu, R. H. Richman

From rolling textures of polycrystalline AgCl determined as a function of temperature, changes in the amounts of the individual textural components are correlated with temperature-dependent changes in glide geometry. The preferred orientations are influenced by the slip behavior as follows: 1) pencil glide, characterized by (110) slip directions and a greater participation in the deformation the higher the temperature, leads to a(012) fiber texture; 2) low-temperature deformation, primarily on (110) (110) systems, generates the {237}-(11, 9, 7) component; and 3) slip on {111}(110), comprising a significant portion of the room-temperature deformation, generates the {135}(211) and {110}(112) components. Typical re crystallization textures are also presented and briefly discussed. SPECIFIC relations between flow mechanisms in crystals and the individual orientations or components in deformation textures are necessary for a thorough understanding of the origin of such textures. Within each ordinary class of crystal struc- tures there is insufficient variety in the observed preferred orientations to permit direct and unambiguous correlation between flow mechanism and texture. A second approach to this problem is the correlation of textural changes with some known variation in glide geometry within one substance,1 In this paper, the latter approach is applied directly to a material in which there are distinct changes in the character of glide with changes in temperature. Silver chloride, although a nonmetal, is reported to exhibit slip,2,3 fiber textures,4 and rolling textures5,6 crystallographically similar to those of the well-studied fcc metals;7,8 in addition, there is a marked temperature sensitivity of the glide planes upon which flow occurs.3 Previous investigations of textures in AgCl unfortunately did not employ methods sufficiently sensitive to define possibly important minor components in the texture, nor did they utilize the temperature dependence of the glide systems. Thus, in order to clarify the effects of changes in slip mechanism, this paper reports a survey, using semiquantitative methods, of preferred orientations in rolled AgC1. Inasmuch as the influence of prior deformation texture upon preferred orientations after annealing is also of interest, some representative annealing textures are presented.

Jan 1, 1965

By H. W. Johnson

DURING part of the year 1932, conditions at the plant of the Inland Steel Co. made possible the collection of data on two of the variables of blast-furnace operation, between which we observed an interesting correlation. The variation in percentage of coke ash in the coke seemed to be reflected in the variations in percentage of silicon and sulfur present in the iron. This subject is of particular interest during this period of low production because of its effect on quality and cost of pig iron. The consumers of pig iron are now more exacting in their requirements. Formerly 0.050 per cent sulfur was considered satisfactory; now many foundries and steel plants insist on iron under 0.030 per cent sulfur and expect it to average 0.025 per cent sulfur. To attempt to produce iron so low in sulfur and still have reasonably good furnace operation means that everything possible must be done to minimize all variations. This subject is also directly connected with the cost of producing iron. A blast furnace operates most economically and efficiently in rather narrow limits and so any variable that has range enough to disturb regular operation must be moderated. The importance of regularity is accepted and the methods followed to eliminate variations in materials such as coke and iron ore are recognized as indispensable. Uniformity of Ore and Variations in Coke Ash The delivering of uniform cargoes of well mixed ore to the blast furnace involves much handling and expense, but it is accepted that the trouble and expenditure are justified. After the ore reaches the dock, further mixing is assured by spreading ore in thin layers, preventing segregation by keeping piles level, variations in digging, and the use of several bins for one ore. And finally, the fact that the furnace burden generally contains three or more ores, together with several miscellaneous materials, eliminates the possibility of ill effects due to variations in any one. Thus, much effort is made to insure a uniform ore. But a variation in the percentage of silicon in ore is less detrimental than a variation in the percentage of ash in coke. The former affects

Jan 1, 1933

By E. W. Edson, F. W. Hertal

In some fields the problem of mud fluid is simple and easy of solution. But in the Ventura Avenue field the acquisition and disposal of good drilling mud is not the least of the problems that confront the operator. In fact, mud fluid in the Ventura Avenue field is a very important factor in the drilling of the wells. It is quite probable that many of the factors affecting mud in this field will not be found in most of the fields with which the reader is familiar. However, in the fields where the mud fluid causes no apparent problem it is probable that some of the points brought out in this paper could be used to economic advantage. In fields where caving and squeezing formations and high gas pressures are present, as in the Ventura Avenue field, it is believed that application of methods outlined will be of great assistance in drilling wells. On account of the sandy nature of the formation and the lack of suitable shale bodies in the strata drilled through in the Ventura Avenue field, the wells make practically no mud during drilling. It is necessary therefore to supply drilling mud to the wells that will carry the drill cuttings to the surface, and also will " wall up" the drill hole and prevent the sandy formations from caving. Mixing and Handling Mud Fluid The clay used to make the mud fluid is obtained from a shale stratum in the upper Pico (Plioccne) formation found about a mile on either side of the field. Since high gas pressures and caving formations were first encountered in the Ventura Avenue field and mud fluid was needed to combat them, the mixing of this mud fluid has gone through a process of evolution. First, the clay was mined and hauled to the derrick, where it was shoveled into the well and left for the churning action of the bit to mix into a mud in the hole. The next move was the construction of a mixer to mix the clay to a mud fluid which was pumped into the well. These mixing

Jan 1, 1930

By J. William Fehnel

The health hazard due to the inhalation of certain dusts in the mining industry has been recognized, but was not subject to state or federal inquiry in the United States until about 1916. Reports on miners' phthisis and associated effect of dust inhalation were published as early as 1903 in South Africa and in 1906 in Australia. A report was made by Lanzal in January 1917 of a study of 433 cases of miners' consumption among zinc miners in southwestern Missouri. In a preliminary report issued in 1915 Lanza and Higgins2 concluded that, while there were general causes, such as housing and working conditions, that tended to produce a high incidence of tuberculosis, the flint dust constituted an unusual element of danger, to which it was reasonable to attribute the unusual prevalence of tuberculosis. Later a clinic established under the joint sponsorship of the United States Bureau of Mines, the mine owners, and the Metropolitan Life Insurance Co. carried on an extensive study covering a period of five years. The results of this study have borne out the conclusions reached in the earlier surveys. The early surveys in this country indicated the necessity of determining the extent of the dust pollution of air associated with the various mining operations. The first determinations were reported on the weight basis, undoubtedly to make comparisons with work previously done in Australia. Later studies of dust in industry led to the development of more refined methods of sampling and enumeration on the basis of count in place of weight, so that by 1919 Knowles3 reported 53 methods.

Jan 1, 1937

By J. G. Thompson

OXYGEN, nitrogen and hydrogen are present in practically all metals in one or more of the following forms: (1) molecular gas in blowholes or blisters, (2) combined in nonmetallic inclusions such as nitrides, oxides or silicates, and (3) in solid solution in the metal. Gaseous elements, in some of these forms, are encountered in practically all metals and alloys but possibly have received most publicity in connection with iron and steel. In fact, the entire steel industry depends upon the control of the oxygen content during the refining process, as well as in the finished material, and it was only after the adoption of the use of efficient deoxidizers such as manganese that the production of good steel with a low carbon content became possible. In normally clean, sound steel the amount of hydrogen is negligible and the amounts of oxygen and nitrogen vary from a few thousandths to a few hundredths per cent. However, many of the effects attributed(27,31,40.41,53,54,55,56,62) ? to the presence of these elements are important and at first glance appear to be out of proportion to the amounts of impurities involved. The presence of oxygen is believed to affect the solubility of carbon in austenite and ferrite and thereby to affect the structure of the iron or steel. Such properties as strength, hardness, ductility, elastic limit, impact resistance, magnetic permeability, tendency toward caustic embrittlement, irregularity in carburization, the cutting life of tools, certain corrosion phenomena, the presence of flakes, seams, bands, ghost lines and hair cracks, and the tendency to age-harden, all have been attributed to the presence of oxygen.

Jan 1, 1932

By Tasuku Fuwa, John Chipman, David H. Kirkwood

Fe-C-Si alloys in silica crucibles were held at 1600°C in a controlled atmosphere of CO and Co2 and the approach to equilibrium was obsertsed. Results were not of sufficient precision to establish the activity and interaction coefficients. Observations 012 the equilibrium provided an average value for the standard free-energy change which differed by + 1.1 kcal from the earlier accepted value. The C-SL relation at other temperatures is calculated and shown graphically. IN the refining of steel in an acid-lined furnace, it is well known that, unlike in basic refining, a very significant amount of silicon may remain dissolved in the metal even when the carbon content approaches a final endpoint. Further, it is known that the residual silicon increases with increasing temperature. The quantitative relation between silicon and carbon can be calculated for equilibrium conditions from data already available on the Fe-C-O and the Fe-Si-O systems. Such equilibrium calculations could show us approximately the limitations within which the reaction would be expected to operate in practice. In the oxidation of a bath containing both carbon and silicon it is well known that at low temperatures silicon is preferentially oxidized first. It can be shown by calculation that at high temperatures carbon will be oxidized preferentially. It is the purpose of this paper to record direct observations on the Si-C relation by means of experiments carried out in an atmosphere of carbon monoxide for Fe-C-Si alloys contained in silica crucibles. When such a system is brought into equilibrium, at a fixed temperature, the composition of the liquid metal is governed by the following equations: Both K1 and K2 are known with a fair degree of accuracy, and may be calculated from the tabulated In general the percentage of CO2 is extremely small compared to that of CO and in the experiments to be described the partial pressure of the latter was generally only slightly below 1 atm. EXPERIMENTAL METHOD The induction furnace employed was the same as that described by Rist and chipman' and by Fuwa and chipman.2 It was modified slightly in view of the change from alumina to silica crucibles. The small silica crucible was surrounded by a thin susceptor of molybdenum sheet which in turn rested inside a zirconia crucible. Since the zirconia was subject to breakage, it was supported inside an alumina crucible. The charge consisted of 30 to 35 g of electrolytic iron along with the required amounts of refined silicon and graphite to produce a melt of required composition. Purified carbon monoxide and carbon dioxide were passed into the furnace through carefully calibrated flow meters. Two separate and independent series of experiments were carried out. In Series I (D.H.K.) the melt was held in the furnace at 1600°C for periods of time up to 6 hr. Samples were taken at intervals in silica tubes and were analyzed for carbon and silicon. The results of the last one or two samples taken from each experiment and the direction in which equilibrium appeared to be approached are shown in Table I. In Series II (T.F.) the silica crucibles were of less satisfactory strength and the melts were held at 1600° C for periods of only 2 to 4 hr. In heats number 29 to 45 inclusive, the metal was cooled in the furnace and the ingot itself served as a sample for analysis. In heat 46 and all subsequent heats, samples were withdrawn in silica tubes at the termination of the heat, and these samples were analyzed. The results of all of these experiments in which equilibrium appeared to be approached are listed in Table II.

Jan 1, 1965

By E. A. Peretti

BEFORE embarking on a detailed investigation of the system indium-antimony-bismuth, experiments were carried out to determine the existence of quasi-binary sections. The bordering binary systems are known1 and show the occurrence of three intermetallic binary species corresponding closely to InSb, InBi and In2Bi. Attention was focused on the low-indium end of the ternary diagram where the possible quasi-binary sections, excluding ternary compound formation, would involve the pairs: InSb-Bi, InBi-Sb and InSb-InBi. The latter pair revealed itself as a true quasi-binary, so it was investigated fully by thermal analysis, x-ray and microscopic examinations. All compositions were made by proper combination of three elements involved. The indium had a guaranteed purity of 99.97 pet; the antimony contained 99.99 pet Sb, and the bismuth had a purity of 99.99 pet. Alloys were made by melting together antimony, bismuth and indium in evacuated, sealed pyrex-glass tubes at a temperature of 600°C with vigorous agitation. The melts, weighing about 80 grams, were allowed to freeze in the sealed tubes and finally were transferred to glass tubes for the taking of cooling and heating curves. A protective atmosphere of helium was used, and the melts were stirred mechanically while cooling at rates of from 0.5 to 3°C per min. Temperatures were measured with a calibrated chromel-alumel thermocouple and were recorded graphically on a Minneapolis-Honeywell extended-range recorder working in conjunction with a Leeds and Northrup type K-2 potentiometer. Conventional polishing techniques gave satisfactory results in preparing specimens for microscopic examination. Etching was carried out with Vilella's reagent or aqueous mixtures of chromic oxide with either nitric acid or sulfuric acid plus dichromate. Conclusions deduced from the thermal analysis and microscopic examinations were confirmed by X-ray photograms using Co-K alpha radiation. The phase diagram is shown in Fig. 1. The liqui-dus consists of an uninterrupted line running from the freezing point of InSb (525°C) to a eutectic point experimentally indistinguishable from the freezing point of InBi (110°C). X-ray patterns of the InSb show a slight expansion of the lattice with the addition of InBi, and microscopic work indicated the solid solubility of InBi in InSb to be less than 0.5 pet at room temperature. Acknowledgment We wish to thank the Indium Corporation of America for the loan of the indium used in this investigation. References 1 E. A. Peretti and S. C. Carapella, Jr.: Trans. ASM., 1949, vol. 41, P. 947. T. S. Liu and E. A. Peretti: Trans. ASM, 1952, vol. 44, p. 539. Metals Reference Book, vol. 1, 2nd ed., AIME, p. 345.

Jan 1, 1959

By P. G. Winchell, M. Cohen, J. Woodilla

The kinetics of stabilization have been studied with respect to the isothermal component of the martensitic reaction in ivon-nickel alloys. Although the carbun (or nit-vogen) content may be very low in these alloys, it plays an important vole in the stabilization phenomenon. In fact, if these interstitial elements are removed by moist-hydrogen treatment, no evidence of stabilization is found. In the pvesence of 0.007 wt pct C, the activation energy for the stabilization process is comparable to that -for the diffusion of carbon (or nitrogen) in ferrite) rather than in austenitc. This suggests that the interstitial diffiision controlling the stabilization occurs within the martensitic embryos rather than in the matrix of the parent phase. The kinetics furthev indicate that the interstitial atoms tend to diffuse -from the embryos toward the suvroundings, thereby immobilizing the interface. This appears to be the origin of the stabilizing effect -found in these alloys. PHILIBERT' has shown recently that interstitial elements play an important role in the stabilization of martensitic transformations in iron-base alloys. However, determination of the temperature dependence for this stabilization process has produced values (- 11,000 cal per mol) that cannot be readily identified with the activation energy for diffusion of carbon (or nitrogen) in either ferrite or austenite. In the present work, the isothermal mode of the martensitic reaction was employed to derive the activation energy for stabilization, and this was found to agree fairly well with that for diffusion of carbon (or nitrogen) in ferrite. An iron-nickel alloy with 30.8 wt pct Ni and 0.007 wt pct C was used in these experiments, the specimens being in the form of rods 0.074 in. in diam and 2 1/2 in. long. The specimens were sealed in evacuated vycor tubes and austenitized at 1100°C for 1/2 hr prior to quenching in water. A second series of specimens was decarburized (and denitrogenized) prior to the above austenitizing treatment by annealing in moist hydrogen for 182 hr at 1215°C. In order to achieve a "standard" condition in the austenitic state, all the specimens were transformed to martensite by cooling to - 195°C before the final austenitizing. Both the 0.007 pct C and the decarburized series then had an Mi temperature of about - 30°C. The isothermal martensitic transformation was carried out at a reference temperature of -88"C, and was traced by means of electrical resistance measurements. Each resistance value was normalized by dividing by the resistance of the austenitic specimen at O°C, thus giving a resist- ance ratio R. The rate of decrease of the resistance ratio (-dR/dt) provided a measure of the transformation rate. It was found that a plot of R vs log t at the reference temperature resulted in a slightly curved line which could be closely approximated by two straight lines intersecting at a time of 10 min, as shown in Fig. 1. If G = dR/dlogt is the linear slope of either straight segment, the rate of transformation at any given time is: The ratio of G for 1 less than 10 min to that for t greater than 10 min was 1.19 for the 0.007 pct C series and 1.24 for the decarburized series. These ratios made it possible to compute the transformation rate at any time greater than 10 min, knowing the transformation kinetics prior to 10 min. The stabilization treatment was introduced by up-quenching from the reference temperature, usually after 10 min of isothermal transformation: to one of four stabilizing temperatures between 0" and 22"C. After holding for various times, the specimens were down-quenched to the reference temperature for additional isothermal transformation. In this way, it was possible to compare the transformation rate (- dR/dt), immediately after stabilization with the transformation rate (- dR/dt)U in the unstabilized condition. The degree of stabilization was defined as: Ordinarily, Gs and Gu would be measured after the same time of prim isothermal transformation.

Jan 1, 1960

By P. G. Winchell, A. J. Heckler

An experimentally simple method for determining the effect of alloying elements on the activity of carbon is validated in Fe-Ni-C austenite. The technique consists of the equilibration of carbon between specimens of different nickel contents within a sealed silica capsule. The attainment of carbon equilibrium within each capsule is evidenced by: 1) in each capsule specimens of the same nickel content attained the same final carbon content regardless of their initial carbon contents, 2) in every capsule the final carbon content was reached for most nickel contents by carburizing and by decarburizing. The activity of carbon attained within each capsule was calculated from the carbon content of a binary Fe-C alloy placed within the capsule, and from the activity coefficient of carbon in the Fe-C system as found by Smith for CO/CO2/C equilibrium. The activity of carbon in Fe-Ni-C austenite determined by this method at 1000°C agrees with prior work by Smith, who used mother method. The measurements are extended to 800°and 1200°C. The activity coefficient of carbon 7c, in Fe-Ni-C austenite is given by: where xC is the ratio of carbon to metal atoms and XNi is the ratio of nickel to metal atoms and where the standard state is chosen such that yC = 1 as xc approaches zero in Fe-C alloys. This equation appears to be valid for xni < 0.3, and 1073° < T<1473°K. ThE activity of carbon in Fe-C austenite has been measured by smithL at 800°, 1000°, and 1200°C. Smith has also studied the effect of nickel on the activity A. J, HECKLER and P. G. WINCHELL are Graduate Student and Associate Professor of Metallurgical Engineering, respectively, School of Metallurgical Engineering, Purdue University, Lafayette, Ind. This paper is based on a thesis submitted ty,to Purdue University, in partial fulfillment of the requirements for the degree of M.S. in Metallurgical Engineering which A. J. HECKLER received from Purdue in January 1962. Manuscript submitted August 13, 1962. IMD of carbon in austenite at 1000°C. In both these studies the activity of carbon was fixed by a flowing CO-C02* *Gas mixtures of hydrogen and methane were also used in Ref. 1 but these results are not incorporated in Ref. 2 or in the present study. gas mixture. In the present work, Smith&apos;s results for Fe-Ni-C austenite are confirmed and extended to 800" and 1200°C by a different experimental technique. EXPERIMENTAL PROCEDURE In essence the experimental technique consisted of enclosing specimens of various nickel contents in an initially evacuated silica capsule and annealing the capsule until carbon equilibrium was attained among the enclosed specimens. The carbon activity obtained within the capsule was determined from the final carbon content of the binary Fe-C alloy included in each capsule and the results of smith.&apos; In order to evaluate this method the absence of nickel transfer between specimens must be established and the attainment of carbon equilibrium between samples must be assured. The absence of nickel transfer was demonstrated in the case of an originally pure iron sample which was annealed at 1200°C in a capsule with a 27.3 at. pct Ni alloy. The final nickel content of the iron specimen was less than 0.1 at. pct, a change which has a negligible effect on carbon activity. The attainment of carbon equilibrium was demonstrated within every capsule and in over half the results by achieving the same final carbon content in a sample which carburized during equilibration and in a sample of the same nickel content which decarburized during equilibration. The base Fe-Ni alloys were vacuum melted from Ferrovac E or electrolytic iron and Mond or electrolytic nickel. The samples were rolled and/or swaged and their carbon content adjusted to the desired pre-equilibration level either by methane-hydrogen carburization or by direct carbon transfer from a graphite source in a sealed silica capsule. As mentioned previously, high-carbon and low-carbon samples were prepared for most nickel levels in each capsule. The specimens were cleaned and

Jan 1, 1963

By R. V. Riley

IN the metallographic examination of the alloys of iron and silicon, several investigators1-&apos; have reported on the occurrence of an unusual type of etched structure, particularly in the alloys of higher silicon content. This, the so-called "barley shell" structure, has been observed with iron-silicon alloys over a wide range of silicon content, and under certain circumstances it can be seen upon the micro-sections of pure iron. The barley shell structure may be demonstrated most easily with iron-silicon alloys in the range 8 to 20 pct Si after etching in a hydrofluoric acid base etchant. Two etchants which produce the structure are: Corson&apos;s reagent, which is 2 parts hydrofluoric acid, 1 part nitric acid, and 2 parts glycerol; and picric acid reagent, which is 1 part hydrofluoric acid and 1 part saturated solution of picric acid in alcohol. Both when freshly prepared and used for etching commercial silicon-iron alloys containing 14 to 16 pct Si, invariably produce the barley shell structure shown in Fig. la. It is now well known that the barley shell structure is a pseudomorph and the true structure of an alloy of this composition consists of a single phase of silico-ferrite together with graphite as shown in Fig. lb. Lower silicon alloys and even pure electrolytic iron may also be etched in the above reagents to give the barley shell provided the etchant has been either: 1—Stored in contact with glass or silica, or 2—used previously for etching an iron containing silicon. Pure iron etched in perfectly pure hydrofluoric acid base etchants free from silicon contamination gives a normal structure free from the barley shells. Therefore, although the hydrofluoric acid in the reagent primarily is responsible for the barley shells, silicon, or its compounds, also must be present, either in the etching reagent or in the specimen. It was of considerable interest to the author to read the paper by Wachtell,? in which the barley shell etch was deliberately used for the identification of the boundaries of high and low silicon areas in diffusion experiments made upon laminate bars of compacted and sintered pure iron and ferrosili-con powders. This method of utilizing the barley shell etch is novel and in the hands of the investigator gave a useful differentiation between the high and low silicon areas in those specimens. For the reasons already given, however, the technique is not to be regarded as of universal application. Misleading results might be obtained, for example, if two or more specimens were etched in the same etchant. Fresh pure reagents only must be used each time. Provided this is done and the investigators are well aware of the limitations of the method, then the barley shell pseudomorph can be made of limited use in distinguishing between higher and lower silicon areas in a microspecimen of a ferrous material. The greatest of care must be exercised in the interpretation of the results which may be regarded as qualitative only and may, in fact, not be specific to silicon alloys.

Jan 1, 1952

By Hsun Hu

NOT much data are available in the literature on textures in cross-rolled metal sheets. Among the body-centered-cubic metals, a few investigators have studied the preferred orientations developed in cross-rolled and in subsequently annealed molybdenum specimens.1-4 Semchyshen and Timmons5 onstructed complete pole figures for the cross-rolled and subsequently annealed arc-cast molybdenum. They used the conventional photographic method. Similar data on cross-rolled iron are still lacking. In view of the fundamental importance of iron as a basic metal for magnetic alloys and many industrial steels, the present investigation was undertaken in an attempt to understand more about its properties. The material selected for the present work was of high purity, and the textures were determined by the Geiger counter spectrometer technique, which permits the construction of quantitative pole figures. Experimental Procedure The material used for this investigation was NRC (National Research Corp.) high-purity, gas-free iron. The total gas content (N2 + O2 + H2) given was less than 0.026 pct, and the carbon content, less than 0.005 pct. Spectrographic analysis of a 2 in. cast ingot showed the percentage of metallic impurities as 0.0004 pct Cu, 0.0002 pct Mg, 0.001 pct Mn, 0.01 pct Ni, and 0.006 pct Si. A 1 in. thick slice was cut off from the 2 in. cast ingot. It was hot-forged at 850 °C to destroy most of the cast structure. Surface scale was removed by milling the forged piece to a size 2 in. long, 1½ in. wide, and ¾ in. thick. After normalizing at 915 °C for 15 min, the piece was alternately cold-rolled 40 pct and annealed at 750°C in hydrogen to a final thickness of 0.165 in., with a resulting uniform grain size of 0.1 mm.

Jan 1, 1958

By H. A. Bedworth, W. H. Bassett

The amount of oxygen present in refined copper bears an important relation to the effects of various impurities on physical properties of copper, as well as the effects of reducing gases at higher temperatures. It seems fitting at this time, when the effects of reducing gases on copper are being discussed, to describe methods that have proved satisfactory for the determination of oxygen and sulfur, and to present some results obtained by investigation of these methods in the authors&apos; laboratory. The procedure for the determination of sulfur is closely interrelated with that for oxygen and has, therefore, been included. It was first proposed by Hampe1 that oxides in copper could be accurately determined by the loss in weight sustained by finely divided copper when reduced at red heat in pure hydrogen, or by the weight of water produced. Hampe&apos;s method was later modified by Archbutt,2 who established the accuracy of the method and demonstrated that equally accurate results were obtained by noting the loss in weight or by weighing the water formed. The determination of oxygen by heating in carbon monoxide has been proposed by West.3 In our hands this method has given slightly lower results than obtained by heating in hydrogen. Heath4 found that the loss in weight after heating in hydrogen did not represent the true oxygen as cuprous oxide but included also gases derived by the metal from the fuel and refining in the furnace, and any trace of mechanically held moisture. He found, further, that the copper after ignition retained hydrogen equivalent to about 0.01 per cent. Heath proposed to determine the amount of occluded gases by preliminary ignition for 20 min. in pure carbon dioxide—and to correct the error caused by absorbed hydrogen by subsequent ignition and cooling in carbon dioxide, finally replacing this gas with air.

Jan 1, 1926

By G. R. Mansfield

THE third year of Government exploration f or potash by the U. S. Geological Survey and-the U. S. Bureau of Mines under the authorization of the act approved June 25, 1926 (Public 424-69th Cong.) is drawing to a close. The results thus far obtained are thought to be sufficiently interesting and satisfactory to justify the presentation of a brief preliminary account of the work. REVIEW OF EARLIER EXPLORATION The general geologic similarity of the Permian basin of Texas and New Mexico to the potash field of Germany had long ago suggested the possibility of the presence of potash salts somewhere in that basin, but petroleum exploration was then making little headway there and the necessary data could not be obtained. The discovery by Udden in 1912 of potash in brine from the Spur well in Dickens County, Texas, was the first direct evidence of its presence. In 1915-17 the U. S. Geological Survey drilled a test well with standard tools at Cliff side near Amarillo, but failed to find potash. Nevertheless, an observer has been kept in the field, at first in cooperation with the Texas Bureau of Economic Geology but since 1922 by the Survey alone, to `secure data and samples from oil and gas tests. Since the discovery of oil in Reagan County in 1923 exploration by drilling has been rapidly extended to many parts of western Texas and southeastern New Mexico. The identification of the potash-bearing mineral polyhalite was first announced by the Geological Survey in June, 1921, the material having come from cuttings from the Bryant well in Midland County and the Burns well in Dawson County, Texas. Successive discoveries and announcements of similar purport aroused widespread interest in potash exploration, which culminated in the action by Congress already noted.

Jan 1, 1929

By K. A. Johnson, H. F. Yancey

Physical properties have been used for a long time in characterizing different kinds of coal, and such physical properties as friability and slacking have been included along with chemical properties in grouping coals according to the widely used system of classification adopted by the U. S. Geological Survey. Nevertheless, the usefulness of physical properties for classifying the different ranks or kinds of coal has been limited because it has not been possible to express these properties in definite form as numerical values. Because of the present wide interest in the formulation and adoption of a satisfactory system of coal classification, the Northwest Experiment Station of the U. S. Bureau of Mines, in cooperation with the College of Mines of the University of Washington, has recently completed a study of the physical and chemical properties of approximately 100 different coals ranging in rank from lignite to anthracite. Purpose and Scope For this investigation samples were collected in approximately 45 mines and prospects in Washington and 23 mines in other states. The following studies, in addition to proximate and ultimate analyses, were made of the samples: Determination of (1) friability, (2) slacking or weathering characteristics, (3) yield of products by low-temperature carbonization in a laboratory retort, and (4) agglutinating value. Most of the coals examined were subjected to each of the tests enumerated, but with coal of some ranks this was unnecessary in some instances, and in others it was not feasible to do the work involved. A report which includes the analyses of the coals and the details of the methods of examination used in the investigation is being published by the Bureau of Mines.&apos; It is the purpose of the present report to show the results of the friability, slacking, low-temperature and agglu-

Jan 1, 1932

By H. S. Wang, Y. P. Gupta

Diffusion of zinc and germanium in liquid silver is measured in the temperature range 975" to 1400°C by use of the capillary-reservoir technique. The ex-perinzental results are discussed in terms of the fluctuation and the "hole" theories of liquid diffusion, assunzing the solute as a point charge equal to the difference in the valences of the solute and solvent atoms. The additional coulombic interaction term due to the excess solute charge is evaluated in terms of the Thomas-Fenni approximation. The theoretical and experimental results agree with both the fluctuation and "hole" theories of liquid diffusion. No perceptible effect on solute diffusion in liquid silver of the size difference between the solute and solvent atoms/ions is apparent. DIFFUSION in liquid silver of electropositive solutes indium, tin, antimony, and homovalent gold has been previously reported by Leak and Swalin1 and Gupta,&apos; respectively. These solutes have nearly the same atomic size but differ principally from one another in excess valence (+2, +3, +4, respectively). The observed differences in the temperature dependence and the rate of solute diffusion were explained in terms of an added coulombic interaction between the solute and the solvent atoms. In the case of diffusion of gold in liquid silver, the data were found to be consistent with an effective valence for gold of -0.85, as proposed by Le Claire.3 Recently, Wang and Gupta4 have reported a study of diffusion of ruthenium, iron, and cobalt in liquid silver. The results of diffusion of these solutes and their temperature dependence were found consistent with the hole theories and the fluctuation theories of liquid diffusion, if ruthenium, iron, and cobalt were diffusing in liquid silver with relative valences -2, -1.3, and -0.5, respectively, instead of -3, -3, and -2 as suggested by the relative position of these elements in the Periodic Table of Elements. Furthermore, the predicted valences for these solutes were observed to be consistent with the sparsely available information on the magnetic properties of some of the dilute alloys of copper and silver with these solutes. In theoretical calculations of solute diffusivity, the solute was assumed as a point excess charge equal to the difference in the valences of the solute and solvent atoms. Both the assumption of a point excess solute charge and the use of the Thomas-Fermi approximation to calculate the potential of a solute charge are less precise for the case of electronegative solutes. Therefore, it was not possible to infer from the data on ruthenium, iron, and cobalt an effect, if any, on solute diffusion of the relative differences in either the Period or the size of the solute and solvent atoms or the solute atoms themselves. A study of the diffusion of Period 4 elements, specifically zinc and germanium was, therefore, undertaken since zinc and germanium, respectively, have relative valences of +1 and +3 in liquid silver and the data obtained on diffusion of these solutes could be compared with the available data on diffusion of Period 5 electropositive solutes, indium, tin, and antimony in liquid silver. From such a comparison, it was hoped to learn something about the effect, if any, of the ion size or the structure of the ion core on impurity diffusion in liquid silver. EXPERIMENT The diffusion of tracer zinc and germanium in liquid silver was studied by the capillary reservoir technique, modified adequately for use at high temperatures. In principle, capillaries containing liquid silver

Jan 1, 1970

By Kun Li, Alex Simkovich

The rate of dissolution of alumina in carbon-saturated liquid iron has been studied experimentally in a system where alumina was in the form of a cylindrical rod immersed in an iron bath contained in a graphite crucible. Data obtained consisted of the concentrations of aluminum in the melt as a function of time. In the case of static experiments, the data are shown to agree with theoretical prdictions based on the diffusion of aluminum.. The rate of dissolution was greatly increased by the rotation of the alumina rod. It is concluded that the diffusion of aluminum from the alumina/metal interface is the rate-controlling step. In the past, thermodynamic investigations of systems encountered in ferrous process metallurgy have received widespread attention. More recently, considerable work has been devoted to the study of kinetics associated with these systems in an effort to determine their rate controlling mechanisms. The alumina-iron system is of great importance in ferrous metallurgy. Yet information concerning kinetics of reaction in this system is seriously limited. The present study was made in order to establish the rate-controlling step for dissolution of solid alumina in liquid iron. LITERATURE REVIEW A number of papers concerning dissolution of solid metals in liquid metals have been reported in the literat~re. Generally, for these simple systems, dissolution is controlled by mass transfer of the dissolving species. Complex systems involving dissolution of solid metal carbides and oxides in liquid metals and slags have been studied to a much lesser extent. Skolnick5,6 reported on the reaction between liquid cobalt and poly-crystalline cylinders of tungsten carbide, in which the cylinders were dissolved while being rotated about their longitudinal axes at various speeds and temperatures. As a result of unexpected preferential grain boundary attack by the liquid cobalt, large errors in the measured dissolution rates occurred because of loss of tungsten carbide grains to the liquid cobalt. Nevertheless, it was possible to establish that the liquid Co-W carbide reaction was not controlled by mass transfer. In a similar approach, cooper7 was able to show that artificial sapphire rods, (alumina single crystals) dissolving in lime-alumina-silica slags obeyed a mechanism of mass transfer control. Here, again, the rods were rotated at various speeds and temperatures, and the process was followed as a function of these variables. Forster and Knacke8 took a practical approach to reaction between slags and refractories. By blowing argon through refractory cylinders of silica, silli-manite, or dolomite and directing the gas to rise along the slag-refractory interface, it was possible to increase the rate of mass transfer. Although the method was admittedly crude, it nevertheless permitted an evaluation of the relative stabilities of refractories with respect to slag attack. Data were interpreted on the basis of mass transfer control. EXPERIMENTAL TECHNIQUE Apparatus. An illustration of the apparatus used in this study is shown in Fig. 1. The furnace consisted of a Morganite recrystallized alumina tube wound with a molybdenum coil. A secondary molybdenum heater was mounted around the upper half of the primary coil to aid in controlling the thermal gradient within the furnace. The primary heater tube was 3 in. in ID and 30 in. long. A reducing mixture of 95 pct N and 5 pct H was maintained around the heating elements. Thermal insulation was provided by alumina powder. The chamber within the primary combustion tube contained a boron nitride block near the top to assist in controlling the thermal gradient to the furnace and also to provide a bearing surface for the rotating graphite shaft. The outside diameter of the graphite shaft was $ in. A separate threaded graphite specimen holder was screwed into the end of the shaft. The holder contained a tapered hole drilled into the end to guide the oxide specimens as they were pressed into it for mounting. Additional guidance for the rotating graphite shaft was furnished by a water-cooled bronze bushing attached to the top of the furnace. A steel clamp was fastened to the upper end of the graphite shaft and rested on a thrust bearing; the shaft and clamp were driven by a dc motor through a set of gears. Two O-rings located immediately above the bronze bushing maintained a gas-tight seal about the graphite shaft. The lower half of the alumina tube housed the crucible and charge, which were placed on a 3/4-in. diam movable alumina support tube. With this arrangement, charges could be inserted into or removed from the furnace while the hot zone was maintained at or above 1000°C. To control the temperature of the furnace, the thermocouple was mounted inside the support tube and in contact with the crucible bottom. Stray electric fields in the furnace were of sufficient intensity to cause erratic indications by the thermocouple. By enclosing the thermocouple protection tube in a molybdenum sheath and grounding this shield, the problem was eliminated. Output of the thermocouple went to an automatic continuous balance controller. Procedure. A typical run was as follows. First, electrolytic iron was premelted in graphite crucibles and cast into graphite molds with the same configura-

Jan 1, 1970