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By C. R. Whitney, G. N. Maniar, D. R. Muzyka

Previous results have shown that Pyromet 860, an Fe-Ni-base heat-resistant alloy, is stable at temperatures as high as 1500°F for aging times as long as 100 hr. This Paper describes the results of long-time creep-rupture testing at 1050" to 1400°F at various stress levels. Times as long as 37,660 hr were employed. The effects of time, temperature, and stress on the precipitates and their morphologies were studied by optical and electron microscopy, X-ray and electron diffraction, and microprobe techniques. phase, containing cobalt, nickel, and molybdenum, was detected after extended exposures from 1200" to 1400°F and careful study was performed to describe the kinetics of its formation in this alloy. µ phase formation apparently has little effect on the elevated-tem-perature properties of Pyromet 860. For times as long as 500 hr at 1300°F and below, with µ phase present, m significant effects on ambient temperature properties were noted. For longer times at 1300°F and after 1400°F exposure, the effects of u phase on ambient temperature tensile strength properties are not clear due to y' effects and grain boundary reactions. Electron-vacancy, N,, numbers were calculated using different methods described in literature and correlated with the present findings. In the selection of alloys for use in gas turbine applications, structural stability ranks as a primary criterion. High-temperature strength and cost are also of major concern. With these factors in mind, Pyromet 860 alloy, an Fe-Ni-base superalloy was designed. This alloy combines the cost advantages of Fe-Ni-base alloys such as A-286, 901, and V-57 with improved strength and structural stability'1,2 and no tendency to form the embrittling cellular 77 phase. A previous study3 reported on the stability of Pyro-met 860 at temperatures from 1375" to 157 5°F and times up to 100 hr. That study showed that the y' precipitates increased in size and separation and decreased in number with an increase in time or aging temperature. No deleterious phases were found to occur. In the present work, samples from four production heats were subjected to long-time creep-rupture testing at 1050" to 1400°F at various stress levels. Various heat treatments were used on the starting samples and tests were run up to 37,660 hr. The effects of time, temperature, and stress on the precipitates and their morphologies were studied by optical and electron microscopy, X-ray and electron diffrac- tion, and microprobe techniques. Electron vacancy numbers, Nv , calculations were made by TRW.4 Experimental results are correlated with the Nv data used to predict occurrence of intermetallic phases such as a phase. EXPERIMENTAL PROCEDURE Mechanical Tests. Material for the present study came from four production size heats of Pyromet 860 alloy, weighing from about 3000 to about 10,000 lb. All of these heats were made by vacuum induction melting plus consumable electrode vacuum remelting. The nominal analysis for this alloy is compared with the actual analysis of the four heats in Table I. Sections of these heats were forged to 9/16-in. round bar,3/4-in. square bar, 3-in. round bar, 4-in. square bar, and a gas turbine blade forging about 16 in, long, about 6 in. wide, and weighing about 20 lb. In general, all forging of this alloy is done from a 2050°F furnace temperature. Longitudinal test blanks were cut from the centers of the smaller bars, from mid-radius positions for the 3- and 4-in. bars, and from the air foil of the gas turbine blade and heat-treated according to the procedures outlined in Table 11. Heat treatment A is the "standard treatment" recommended for this alloy for best all-around strength and ductility. Heat treatment B is a modification of treatment A for improved tensile strength at moderate temperatures. The treatment coded C was designed for treating large sections according to a procedure previously described.' Heat treatment D was developed to yield optimum stress relaxation characteristics at 1050°F for a steam turbine bolting application. After heat treatment, the test blanks were machined either to plain bar creep specimens with a gage diameter of 0.252 in., to combination smooth-notched stress-rupture bars with a plain bar diameter of 0.178 in. and a concentration factor of Kt 3.8' at the notched section, or to notch-only specimens. All specimens conformed to ASTM requirements. Metallography. Most of the creep-rupture tests were continued to failure. A few bars were fractured as smooth or notch tensiles after creep-rupture exposures. After fracturing, ordinary metallographic sections were made primarily in gage areas adjacent to fractures to represent a "high-stress" region and through specimen threads to represent a "low-stress" region. All metallographic sections were made in a longitudinal direction with respect to the test specimen axes. For optical microscopy, the samples were etched in glyceregia (15 ml HC1, 5 ml HNO,, 10 ml glycerol). For XRD analysis, the phases were extracted electrolytically in two media: 20 pct &Po4 in H20 for selective extraction of y' and 10 pct HC1 in methanol for carbides and other phases.

Jan 1, 1970

By Stanley D. Michaelson, Norman Weisis

The purpose of beneficiation is to increase the economic value of an ore by elimination of waste rock or by separation of minerals that require separate reduction, without destroying the physical and chemical identity of the minerals. Flotation has replaced older methods of beneficiation to a very great ex- tent, nearly entirely in the case of the copper, lead, and zinc minerals and less completely in the case of such other minerals as iron, coal, and titanium. Flotation is also used to recover barite, fluorspar, feldspar, cement rock, spodumene, vermiculite, silica, beryl, and potash in the nonmetallic field, and cobalt, vanadium, germanium, antimony, mercury, molybdenum, manganese, nickel, gold and silver, cadmium, and bismuth for metals. The rapid growth of flotation to pre-eminence cannot be attributed to its low cost, because gravity, magnetic, and electrical methods may in some cases cost only half as much. But for ores containing finely disseminated minerals, these other methods are successful only in exceptional cases, for example the magnetic taconites or titanium-bearing sands. For low grade ores with coarse texture or spotty mineralization the advantages of low-cost gravity methods and highly efficient flotation are often combined, as in the beneficiation of coal and some ores of lead and zinc, phosphate, tungsten, and manganese. When an ore is responsive to either flotation or non-flotation concentration, or to combinations of the two, the choice depends upon cost of the process only when dealing with ores of low value; in other cases it is dictated by either the process efficiency or the product specification. Generally speaking, flotatio.1 is so efficient as compared with other methods of concentration that process cost is rarely an important factor in its selection. It is said, "The metal in the mill tailing has already been mined." Once the mining cost has been paid it doesn't increase total costs very much to do a thorough job of milling. With the exception of the few types of ores that are not amenable to flotation, the chief reason for preferring electrical and gravity methods to flotation may lie in the specification of the product. Flotation demands fine grinding, and specifications may not permit this with many nonmetallic ores or coal. Another reason is the size of investment-where capital is hard to obtain or the life of the property is short, the justification for a flotation plant may not exist, and one must be content to skim off the cream. y not exist, and one must be content to skim off the cream. Gravity processes often cost less than flotation because a large part of the waste rockcan be rejected without costly grinding, no chemicals are required,

Jan 1, 1962

By K. A. Natarajan, I. Iwasaki

Platinum electrodes are not inert as often thought to be. The reactivity of platinum electrodes can explain their erratic behavior in many electrochemical measurements of metallurgical interest, e.g, in flotation systems, streaming potential measurements, contact-angle measurements, and in leaching systems. The anomalous behavior of platinum electrodes in redox potential measurements in aqueous systems was studied through Eh and pH measure ments in water-oxygen, iron-water-oxygen, and manganese-water-oxygen systems. Stability relations between Fe++ and Fe (OH), and between Fe (OH), and Fe (OH), were studied to judge the correspondence between experimental and theoretical equilibrium lines. The practicality of redox potential measurements in estimating ferric-ferrous ratios in aqueous systems was investigated along with their suitability as indicators in leaching operations, e.g., the removal of iron by aeration from manganese leach solutions. Platinum electrodes have often been used in the measurement of dissolved oxygen concentrations and of redox potentials (Eh) in a variety of fields, e.g., analytical chemistry,' corrosion," geology and mineralogy,,'' biology,"' sewage treatment,' * hydrometallurgy,"I" and flotation."la The effectiveness of Eh-pH diagrams, first reported by Pourbaix' in 1949, has contributed much towards the theoretical understanding of numerous problems encountered in the metallurgical industry. Not many references are available in the literature, however, wherein attempts have been made to confirm Eh-pH diagrams from experimental measurements. One reason might be that, in spite of the apparent simplicity of the electrochemical technique, the direct measurement of Eh involves complex practical problems.' Factors such as the purity of the solution, the type of electrodes used, the history of the indicator electrode, and the type of atmosphere (namely, oxidizing, reducing, or inert) do have effects on the measured Eh values. The influence of mixed potentials cannot be underestimated. The poisoning of platinum electrodes by organic and inorganic impurities present in the solution may lead to erratic results. Platinum, commonly thought to be an inert electrode material, is not really so, as attested by a number of previous investigators who advised caution concerning the anomalous behavior of platinum electrodes in various electrochemical measurements.'" In the present article, a few pertinent experiments related to Eh-pH measurements in systems of interest in the metallurgical and water pollution fields are described in an attempt to correlate such information with what is already known, especially in the electrochemical literature. Iron-water and manganese-water systems were selected with a view of studying the correspondence between experimentally observed and theoretically established equilibrium lines. The work included an investigation of the behavior of platinum electrodes with respect to pretreatment and adsorption characteristics, the measurement of dissolved oxygen concentrations and their relation to Eh, the determination of the electrode potential of the ferric-ferrous couple at different pH, and the measurement of oxidation potentials in iron-manganese leaching systems. Experimental Procedure A rotating platinum electrode was used in many of the measurements to study the effect of rotation on measured Eh values. The electrode made by the Pine Instrument Co. consisted of a stainless steel rod with a platinum disk soldered to the end. It was covered with a Teflon insulation along the sides, so that only the circular tip of the electrode was exposed to the solution. Prior to its use, the platinum surface was brightened on a metallurgical polishing wheel with alumina as an abrasive, unless specified otherwise. The electrode was rotated with a Sargent cone-drive motor at 350 rpm. The contact of the electrode with the external circuit was made by filling a notch at the top of the stainless steel shaft with mercury and by dipping a copper wire into the mercury pool. The performance of the rotating platinum electrode was compared with the performances of a Beckman platinum button electrode and a platinum wire electrode. All the potentials were measured with respect to a saturated calomel electrode. A saturated KC1-agar bridge was used to minimize the liquid junction potential. A Beckman Zeromatic pH meter together with a Beck-man electrode switch was used to measure both the Eh and pH. A double-walled, all-Pyrex jar with a capacity of about 1 liter and themostated by circulating water of constant temperature was used for a reaction cell. Four equally spaced ports in the cover provided access for a glass electrode, a salt bridge connecting the saturated calomel electrode, a dispersion tube for bubbling gases into the cell solution, inlet and outlet tubes for passing the desired gases over the solution, and a graduated burette for introducing reagents from outside. The rotating platinum electrode was inserted through an opening in the top-center of the cover, and a positive gas pressure was maintained inside the cell to prevent air from entering into the cell compartment. A magnetic stirrer was used to mix the solution inside. For the determination of dissolved oxygen in the test solutions, the polarographic techniquex was used.

Jan 1, 1971

By R. J. Borg, C. E. Birchenall

Vapor pressures of eight compositions of Mg-Cd have been determined by the Knudsen effusion technique. Measurements are made at several temperatures for each alloy and the results interpolated to a common temperature for the calculation of the activities. It is not possible to obtain values for the partial molar enthalpies because of the narrow temperature range spanned by the measurements. The results show less precision than those obtained for pure Cd which are also reborted. These alloys are extremely susceptible to corrosion which provides a possible explanation for the lack of precision. Nevertheless, the values of the activity are in good agreement with the results of electromotive force measurements previously reported for the Mg-Cd system. MAGNESIUM and cadmium are mutually soluble in all proportions in the solid state and form a single phase which has the hexagonal close-packed structure. X-ray investigations of this system1,2 have revealed a rapid variation in the relative dimensions of the unit cell occurring at approximately 50 at. pct. The rate of change of the c/a ratio with composition increases markedly for alloys containing more than 50 at. pct Cd. The purpose of this investigation was to determine the activity of Cd in the neighborhood of 50 at. pct and to discover whether or not the thermo-dynamic properties undergo a similar rapid change. The activities are calculated from vapor pressure data obtained by the Knudsen effusion method. Unfortunately the precision of the data from which the thermodynamic values are calculated is insufficient to establish unequivocally a departure from the normal trend. The results are reported primarily because they substantiate the only previously reported activity measurements3 and because they include values for pure Cd which in contrast to those of the alloys show excellent precision. The Cd-Mg system is known to contain several ordered phases. However, this investigation was made at temperatures considerably above the transition temperatures, and the alloys may be regarded as nearly random solid solutions. EXPERIMENTAL Apparatus—The effusion cells are machined from solid tantalum rod. The lids consist of threaded, flanged rings of tantalum onto which are welded shallow cups of 4 mil molybdenum foil. The orifice, which is located at its center, is made by grinding off a small dimple produced with a sharpened punch. Such an orifice has been mounted in plastic, sectioned, and the thickness of the orifice edge measured in a microscope. The maximum thickness is 0.00016 in., and the Clausing factor is consequently equated to unity. The area of the orifice is determined by tracing its projection on the screen of the metallograph at a known magnification and measuring the area of the tracing with a planimeter. Excellent temperature control is achieved with a 4 by 18-in. alundum core, gradient-wound, furnace

Jan 1, 1960

By J. F. Havard

Gypsum is a useful industrial mineral found abundantly on the earth's crust. It is inexpensive to mine and process, and its calcined products have a wide range of readily controllable properties such as strength, density and setting time. It has proven to be such a useful material indeed, that ten American companies, operating some 57 calcining plants in 25 states in 1958, produced or imported in that year a total of 13,649,000 tons of the crude mineral valued at $39,361,000, which they then converted into manufactured products with a value of $329,070,000. Gypsum (CaSO4.2H2O) is calcium sulfate with two molecules of combined water, which are responsible for most of its useful properties. It is closely associated in most deposits with anhydrite (CaSO4), which contains no combined water and has limited commercial value in the United States. Man has long recognized the useful qualities of gypsum. It was utilized by the Egyptians in the construction of the pyramids and, later, by the Romans for important structures. Many of the ancient peoples prized gypsum for artistic and ornamental purposes, carving statuary from alabaster and making casts with plaster. The tabular variety, selenite, was used for windows, and the light transmitted through these windows reminded people of light from the moon (selene), hence the name selenite. The use of gypsum continued through the Middle Ages and into modem times. Benjamin Franklin was a famed exponent of gypsum because he applied ground gypsum to clover fields in the form of large letters which later read, in the more luxuriant growth, "land plaster used here." Gypsum is still used as an effective conditioner for some soils, but in recent decades, particularly in North America and Europe, it has become much more important as a major material for the building industry. Description Gypsum and anhydrite are closely associated minerals. Gypsum is found in a number of forms: massive rock gypsum, alabaster, selenite, satin spar, and gypsite. Anhydrite is found as massive rock or as smaller bodies or isolated crystals included in gypsum. Massive Rock Gypsum comprises most of the commercial gypsum and occurs as a sedimentary rock, interbedded in most places with shale, limestone or dolomite. This rock is soft and crystalline. Its color is white or shades of gray, pink, yellow, brown or other colors. Alabaster is a pure, compact and fine-grained variety suitable for use in sculpture or turning into artistic forms; it may be white or selected for attractive coloration. Selenite is gypsum crystallized in flat, transparent, flexible foliated plates, found in clays or in surface vugs in gypsum. Satin Spar is a fine silky fibrous variety with the axes of the crystalline fibers perpendicular to the vein or joint in which it has formed. Gypsite is an earthy mixture of gypsum with clay and sand in secondary formations; it is sometimes useful as a soil conditioner and has been used in making base-coat plasters. Pure gypsum contains 20.9 pct combined water, 46.6 pct sulfur trioxide (SO3) and 32.5 pct lime (CaO). Standard specifications (American Society for Testing Materials Designation C 22-50) read that minimum purity for material to be called gypsum is 70 pct CaSO4.2H20. Most of the commercial gypsum is 85 to 95 pct pure as produced. Impurities in

Jan 1, 1960

By E. T. Turkdogan, P. Grieveson

Experimental results are presented for the rate of solution of nitrogen in a iron in the temperature range 750° to 873°C and in 6 iron in the temperature range 1410° to 1470°C. It is shown that the rate controlling process is diffusion of nitrogen into the iron. The diffusiting of nitrogen in a and 6 iron is derived from the results, and the temperature dependence of the diffusivity is represented by the equation D = 7.8 x e- 18,900/RT sq cm per sec. The solubility of nitrogen in a and 6 iron, in equilibrium with 1 atm pressure of nitrogen, has been measured. Using these results and other available data, it is found that the variation of the logarithm of nitrogen solubility with the reciprocal of absolute temperature is nonlinear. In an Appendix, some results of Darken and Smith are presented for the rate of solution of nitrogen in iron using ammonia + hyidrogen mixtures. These data also support the view that diffudsion of nitrogen in iron is the rate-controlling process when ammonia + hydrogen mixtures are used. A considerable effort has been made to obtain data on the solubility1-5 and diffusivity of nitrogen in a iron6-l2 because an understanding of the effect of nitrogen on the properties of steel must be based on an accurate knowledge of the properties of nitrogen in pure iron. However, no information is available concerning the kinetics of solution of nitrogen in a and 6 iron. Recently the authors13 have investigated the rate-controlling mechanism operating in the kinetics of solution of nitrogen in y iron. This study was directed to determine the rate-controlling processes for similar reactions with a and 6 iron as well as to establish values for the solubility of nitrogen in equilibrium with nitrogen gas in a and a iron. EXPERIMENTAL The procedure used in experiments to determine the rate of solution in cylindrical iron rods was the same as that described in a previous communication.13 Ferrovac E grade iron used in all experiments contained the following impurities in weight percent: C, 0.005; Mn, 0.001; P, 0.002; S, 0.006; Si, 0.006; Ni, 0.025; Cr, 0.002; V, 0.004; W, 0.02; Mo, 0.01; Cu, 0.001; Co, 0.01; 0, 0.007. After cleaning the surface, the iron rods were treated in an atmosphere of purified hydrogen for 17 hr before the reacting gas was introduced for known experimental times. After quenching, the samples were sectioned radially and analyzed for nitrogen. In addition to experiments using rods, iron foils were used in the measurements of solution rates of nitrogen in a iron. The foils of two different thicknesses were prepared by cold rolling Ferrovac E grade iron cylindrical rod to 0.051 and 0.152 cm. Foil samples were used in a rectangular form 5 cm long and 1.25 cm wide. The specimens were thoroughly cleaned of surface oxide with fine emery cloth and degreased with carbon tetrachloride immediately before entry into the furnace. The experimental procedure was the same as that used in the study with rods. At the completion of an experiment, the foil samples of the nitrogenized iron were analyzed for nitrogen after discarding 0.3 cm from the perimeter of the specimen. Iron foils were nitrogenized and denitrogenized in the a and 6 range with a gas mixture of 95 pct N and 5 pct H for times varying from 5 min to 2 hr. Results obtained for the average composition of nitrogen in iron for these experiments are presented in Fig. 1. Prior to the denitrogenization experiments, the samples were saturated with nitrogen at 1000°C and 0.67 atm N, giving a uniform nitrogen concentration of 0.0204 pct. According to the known a-y phase boundary in the Fe-N system,14 this composition lies within the ferrite region at temperatures 750" to 850°C. Use of this initial nitrogen content insured that reaction occurred between the gas and a single solid phase, a iron. Examples of the results for the mean concentrations of nitrogen in cylindrical iron rods, 0.356 cm radius for both the a and 6 ranges are given in Fig. 2. Typical examples of the results obtained for the radial distributions of nitrogen in rods are presented in Fig. 3. It appears that the results for radial distributions can be extrapolated to constant surface compositions which agree with the equi-

Jan 1, 1964

By S. D. Strauss

The marketing of nonferrous metals and of the ores and concentrates from which these metals are recovered is a fascinating trade, international in character, sensitive to every change in the economic tide, and complex in its organization. Each individual metal has its own marketing mechanism; no two are exactly alike. The differences sometimes are a matter of tradition rather than of necessity, but usually they have developed because of the very nature of the problems of producing or consuming the individual metal. This description, because of limitations of space, can do no more than indicate the major aspects of the trade and touch lightly on the marketing structure of each metal. The dictionary states that a market is a "meeting of people for selling and buying." In the case of nonferrous metals this meeting may occur on a half-dozen different occasions between the time the ore has been first mined and the time the refined metal is available for use by industry; or it may not occur at all until after the metal itself has been rolled, drawn, stamped, cast, or forged into a useful semifabricated shape. To illustrate: A Chilean miner may sell his small ore production to a custom mill, which produces concentrates that are sold to an ore dealer, who finances the shipments of the concentrates to a United States custom smelter, which buys these' concentrates for conversion into blister, which is subsequently refined into electrolytic copper and sold. Conversely, much of the production of aluminum is in the hands of integrated concerns that mine bauxite, convert bauxite to alumina, smelt the alumina to produce aluminum, and then fabricate the aluminum into semifinished or even finished products before title to the material changes hands for the first time. Some nonferrous ores are not converted into metal at all but are sold by the miners or dealers directly b the ultimate consumers. A good example would be chrome ores used by the chemical industry. And of course a substantial part of the commerce in nonferrous metals is in scrap, which is the reconversion into useful form of metals that have long since been mined and smelted. Thus, one-third of all the lead used in the United

Jan 1, 1959

By R. M. Goldhoff, H. J. Beattie

The high-temperature properties of a 1 Cr-Mo-V forging steel are described. A series of controlled heat treatments was designed to delineate the effects of austenitizing and tempering treatments, temile strength, and grain size on such properties. Studies indicate that the mechanical properties and their varlations under creep can be described by the initial metallurgical structures and their changes droPirzg exposure, particulavly the carbide reactions. Such structures are described and correlated with the mechanical properties. FOR many years the large steam turbine industry has relied on the 1 Cr-Mo-V type forging steel for critical applications. Because of its adequate heat resistance and relative economy, it is currently in use in the temperature range up to about 1050" to 1075°F. Attempts to understand the large property variations attainable in this steel involve the structural modifications due to the wide latitude in its heat treatment. The heat treatment essentially involves a two-step process which includes solution-ing of carbides in the austenite range followed by a suitable tempering treatment below the critical to adjust the level of properties. The latter step is referred to as "secondary hardening" and is basically an ordinary aging reaction involving carbides. In the commercial heat treatment of large components of such steel, homogenizing and stress-relief anneals may be included and have some importance in determining subsequent properties. Several studies of the engineering properties of this steel as a function of transformation micro-structure have been reported.1 3 However, in this steel the carbide reactions, which are a function of composition and heat treatment, appear to be the property-controlling factor rather than the micro-structure defined as a transformation product. Thus, the tempering resistance of this type of alloy steel is mainly a function of the size and distribution of alloy carbides.4 However, it is also necessary to consider the stability of the microstructure and the effect of dynamic carbide reactions on subsequent properties. It is the purpose of this paper to show the interdependence of properties and corresponding structures, particularly carbide reactions, developed for a limited set of controlled heat-treatment conditions applied to 1 Cr-Mo-V steel. MATERIALS AND PROCEDURE The material for this work came from a large production forging whose chemical composition is shown in Table I. The property data accumulated on this steel as a function of heat treatment were room-temperature tensile and smooth- and notch-bar creep rupture at 1050°F (notch geometry: shank diameter = 0.357 in., depth = 50 pct, radius = 0.005 in.). To achieve controlled structural variations the temperature and time of both austenitizing and tempering were varied in a manner to produce a series of eight steels each at one of two grain sizes and one of two hardness levels in proper combination for valid comparisons. This will be clear upon examination of Table I. Structural studies involved the use of optical and electron microscopy as well as X-ray and selected-area electron diffraction. To reveal the nature of carbide precipitations, electrolytic extraction techniques were used with subsequent analysis of the residue by X-ray diffraction. Weight losses of the steel specimens during electrolysis were measured and successive chemical fractionations of the residues were applied and checked by X-ray examination. The details of fine structural distributions, morphologies, and crystallography of the precipitates as well as dislocation distributions were investigated by examining in the electron microscope three common types of preparation. a) Relief Replicas. Mechanically polished sections were etched in 2 pct nital, replicated with a nitrocellulose film, which was shadowed by chromium vapor deposited at a glancing angle of 20 deg. b) Extraction Replicas. A thin film of carbon was vapor-deposited on the polished and etched surface. The carbon films were then etched off and gathered on electron-microscope supporting grids. The carbides left imbedded in the carbon replica in their original distribution were then examined crystallo-graphically by selected-area electron diffraction. c) Thin Films. Specimens were mechanically ground and polished down to a thickness of 0.001 to 0.003 in. Final thinning was done electrolytically in a "chrome-acetic" electrolyte. When holes began to appear in the foil, the voltage was interrupted and applied in several 1-sec bursts. Sections of the foil between holes were thin enough to pass a 100-kv electron beam that carries an image.

Jan 1, 1965

By P. N. Richards, M. K. Ormay

Commercially hot-rolled low-carbon steel strip may have one of two basic types of orientation texture, depending upon the amount of a iron which was present during the finishing passes. The changes in these textures with varying amounts of cold reduction up to 95 pct have been determined for the sheet surface plane and for parallel planes down to the mid-plane. The development of cold reduction textures has been reassessed on the basis of (200), (222). and (110) stereographic pole figures and pole density or inverse pole figure values. In agreement with the literature, it is shown that the textures can be described in terms of partial fiber textures but alternative descriptions are given for one of the fiber textures, in order to more closely correlate with experimental data. One partial fiber texture consists of orientations of the type (hkk)[011] extending from (100)[011] to {322}(011) in agreement with the literature. At moderate amounts of cold reduction, a second partial fiber texture forms with a <331> fiber axis inclined 20 deg to the sheet normal and a range of orientations centered on one close to (1 11)[112] and reaching to (232)[101] or (322)[011]. An alternative description involves a (111) fiber axis parallel to the sheet normal but capable of rotation about the rolling direction with rotation about the fiber axis. ORIENTATIONS developed in low-carbon steel strip after cold reduction are of commercial importance because they control, in part, the final preferred orientations after subsequent annealing. The method of control however is not understood completely. Some preliminary work indicated that the cold-reduced orientations and the subsequent annealing textures of commercial low-carbon steel were dependent on the orientations present in the material before cold reduction, that is, those present in the hot-rolled strip but, to date, the effects of initial orientations have not been extensively investigated. For this reason, much of the information given in the literature on development of preferred orientation is difficult to assess as details of initial texture and processing conditions are often inadequate or are altered by a subsequent heat treatment such as normalizing.&apos; It is known2 that anomalous results for near surface orientations may be obtained if lubrication during cold rolling is not adequate but whether lubricant was used during the experiments has not always been given, nor has the exact depth below the surface at which determinations have been made. A comprehensive review of cold rolling textures has been made recently by Dillamore and Roberts&apos; and more restricted recent reviews are due to stickels4 and Abe.5 Based largely on the experimental work of Bennewitz,1 reviewers have accepted that the preferred orientations produced on cold reducing low-carbon steel can be described in terms of two partial fiber textures as follows: Partial Fiber Texture A which has a (011) direction in the rolling direction and includes orientations within the spread from (211)[011] through (100)[Oll] to (211)[011.]; there is some controversy as to whether it extends as far as the orientation (111)[011]. As Dillamore6 has observed, the extent of this partial fiber texture depends on the intensity levels selected. Partial Fiber -texture B which has a (011) direction located 60 den from the rolling direction in the plane containing the rolling direction and the sheet normal. There are two directions which satisfy these conditions and orientations in this partial fiber texture extend from (21l)[0ll] through (554)[225] to (121)[101]. The orientations {211}(011) are members of both partial fiber textures A and B and it can be noted that a variant of {554)<225> is within 6 deg of a variant of {111}(112). Barrett7 had postulated earlier that, in addition to orientations which would fall into partial fiber texture A, a true fiber texture with a (111) direction in the sheet normal was present after heavy cold reduction. This fiber texture would include orientations such as {111}(011) and {111}(112). Later investigators, notably Bennewitz,&apos; have discounted this, mostly on the ground that the partial fiber textures A and B, as described above, contain all the strong orientations that have been observed. However in other work it has been reported2 that (222) pole density or inverse pole figure values show a continuing increase with increasing reduction by cold rolling and give values considerably greater than for any other low indices plane. Thus it could be inferred that a (111) fiber texture as described by Barrett would be one which becomes more dominant with increasing cold reduction, whereas Bennewitz&apos; concluded that components such as {554)(225) in partial fiber texture B began to decrease in intensity at high reductions. Following Bennewitz, one would expect a decreasing (222) pole density value (parallel to the sheet normal) with increasing cold reduction. Because fiber textures consist of grains with a range of orientations that have one axis in common, it has been inferred that during deformation the crystal orientations rotate about the fiber axis&apos;74 and that the orientations of crystals that at one stage belong to one fiber texture can rotate on further cold reduction into the other fiber texture through an orientation in which the two fiber textures intersect.&apos; For example,

Jan 1, 1970

By Allan Martin, R. A. Swalin

Diffusion rates of manganese, aluminum, titanium, and tungsten in nickel were measured at temperatures between 1100° and 1300°C. Activation energies, Q, and values of the frequency factor, Do, were calculated for each system. Values of Q were found to be within 15 pet of that for self-diffusion of nickel in agreement with present theories of diffusion. ONE of the most interesting problems in diffusion concerns factors governing the order of diffusion coefficients of various solutes in a common solvent metal at low solute concentrations. An early suggestion by Rhines and Mehl&apos; was that diffusion coefficients might each approach that of the self-diffusion coefficient of the solvent itself. Later Thomas and Birchenall&apos; pointed out correlations between the order of the diffusion coefficients and the freezing point depressions of the solvent by the various solutes. Other correlations have been sought. To settle this question it seems likely that much more data will be needed and, in particular, data collected at low solute concentrations. This type can be obtained by special analytical techniques as well as by use of radioactive tracers. The following study was made of diffusion of manganese, aluminum, titanium, and tungsten in a common solvent, nickel, at relatively low solute concentrations: 1—Production of alloys of nickel with manganese, aluminum, titanium. and tungsten at concentrations of the order of 1 atomic pet. 2—Use of pressure-welded diffusion couples in cylindrical form. 3—Diffusion anneals in the temperature range of 1100" to 1300°C. 4—Lathe sectioning of the diffused couples. 5—Spectrophotometric analyses of lathe turnings for the solute being studied. 6—Calculation of the diffusion coefficient for each of the solutes as a function of temperature. 7—Interpretation of results with current theories of diffusion. Experimental Work Materials—Two types of nickel were used in this research. The grade designated as Vacuum melted Mond nickel was used for all diffusion systems except the Mn-Ni system for which the Vacuum melted electrolytic nickel was used. Analyses of the two grades are given in Table I. The manganese used in making alloys was 99.9 + pet pure, aluminum 99.99 pet pure, titanium 99.9 pet pure, and tungsten of C.P. grade powder. Alloys used in this investigation were prepared by melting in vacuo or under a low pressure of argon. After melting, all heats except those of nickel-manganese were poured into a cylindrical copper mold 3 in. long and 1 in. ID. In the case of nickel-manganese, the alloys were solidified in the melting crucible. For nickel-aluminum heats alumina crucibles were used and for all other heats, zirconia crucibles.

Jan 1, 1957

By L. V. Pirela, S. M. Farouq Ali

Some interest has been expressed recently in the application of solvents in conjunction with a thermal drive, such as a steamflood. At least one field project of this type has been reported. This paper makes the first attempt to provide some of the basic information necessary for choosing a solvent for such an application. Results of displacements conducted at elevated temperatures are also discussed. This paper shows that, in the case of alcohol-hydrocarbon-water or brine ternary systems, the system miscibility may increase, decrease, or both increase and decrease within the same system when the temperature increases. The distribution coefficient was consistently found to increase in favor of the oleic phase with an increase in temperature, which is advantageous from the standpoint of oil recovery. Results of solvent displacements in a sandstone core showed that even a relatively small temperature effect in the favorable direction (increase in miscibility and distribution coefficient) can lead to a 50 percent increase in oil recovery. On the other hand, if the system miscibility decreases with the temperature, even though the distribution coefficient increases, the oil recovery at the higher temperature may not increase. INTRODUCTION Miscible displacement has been the subject of many investigations. Miscible-phase solvent flooding, employing solvents such as alcohols that are miscible with both oil and water, has received considerable attention. Investigations conducted by Gatlin and Slobod,l Taber, Kamath and Reed,2 Holm and Csaszar,3 and Farouq Ali and Stah14 have helped in understanding the mechanism of solvent flooding. While the use of alcohols and similar solvents as oil recovery agents is economically unattractive, these solvents nevertheless provide a means of understanding the mechanistic aspects of important miscible-phase oil recovery processes such as the Maraflood process (discussed by Gogarty5). As shown by Taber et a1.,2 the phase behavior of a solvent-oil-water system is of .utmost importance in determining the efficiency of the oil displacement. This paper makes the first attempt to obtain the ternary phase behavior data for nine alcohol-hydrocarbon-water/brine systems at elevated temperatures. Results of core tests at elevated temperatures are also presented which corroborate the effect of temperature on oil recovery, as judged on the basis of phase-behavior data. The use of solvents at elevated temperatures has been suggested earlier by Farouq Ali.6 At least one field test of this type has been reportedO7 With the widespread use of thermal recovery techniques, it is possible in some situations (especially in steamflooding) that the use of a suitable solvent in conjunction with the heat carrier may be economically feasible. This paper attempts to provide some of the basic information needed for judging such feasibility. LOCATION OF THE PLAIT POINT The phase behavior of a typical ternary system consisting of a solvent, hydrocarbon and brine (or water) can be represented by a triangular diagram such as the one shown in Fig. 1 (for temperature TI). Point Pon the binodal curve represents the plait point, being the limit of tie lines such as Y1 Y2 The compositions of the coexisting oleic and aqueous phases are given by points Y2 and Y1, respectively, for any mixture composition along Y1Y2. The characteristics of ternary diagrams have been discussed by Findlay8 and others. Taber et aL3 have shown that the position of the plait point in a particular ternary system plays the decisive role in determining whether or not theoleic phase would be displaced in a continuous manner during an alcohol displacement. The area above the binodal curve also is important, since it represents

Jan 1, 1969

By Samuel Daniels

The Al-Cu-Ni-Mg alloy is much benefited by heat treatment and, in such condition, is preferable to the Al-Cu-Fe-Mg alloy either as cast or as heat-treated, when both are reheated to temperatures of from 400" to 600" F. and compared, cold, with respect to strength and to hardness. The main differences between the alloys do not arise until the reheating temperature exceeds 400" F., above which they gradually soften. This softening is characterized metallographically by the appearance of intragranular precipitate. The Al-Cu-Ni-Mg alloy is weakest and least hard after being reheated at 600" F., the Al-Cu-Fe-Mg alloy at about 700" F. The former starts to reharden at 700" F., the latter at 800&apos; F. There is a tendency for both alloys to lose strength and hardness with prolongation of time at the reheating temperatures of 500" and of 700" F. The Al-Cu-Ni-Mg alloy is considerably stronger and harder than the Al-Cu-Fe-Mg alloy when both are heat-treated and reheated for long periods of time at 500" and 700" F. Although the latter can be made harder initially than the Al-Cu-Ni-Mg alloy by suitable quenching and aging, heat treatment, in general, favors the retention of this initial (strength and) hardness after reheating to a much greater degree in the Al-Cu-Ni-Mg alloy. The percentage of elongation of the two materials in any condition is very small. Certain aluminum alloys have been used for pistons and other parts operating at temperatures up to 650" F. because of their lightness, high thermal conductivity and specific heat, fair strength and hardness at elevated temperatures, excellent machineability, and moderate resistance to corrosion. In the piston, the inertia forces and the bearing loading, and with this the vibration, are decreased. The piston head functions at a lower temperature (about 200" F. below one of cast iron), so that, because of the lessened tendency toward carbonization and detonation, higher compression ratios may be used. On the other hand, the aluminum alloys do not have the wearing and bearing qualities of cast iron; also they have a large coefficient of expansion, allowance for which must be made in the design. The range in analyses of aluminum alloys, used for pistons in domestic and in foreign internal-combustion engines is shown in Table 1. There seem to be three general types of composition; one containing about 10

Jan 1, 1926

By W. O. Philbrook, L. D. Kirkbride

IN the normal operation of the iron blast furnace, reduction of the iron oxides is accomplished almost entirely above the tuyeres.&apos; Blast furnace slags usually contain less than 0.5 pct FeO, although higher values may occur with abnormal operation. There is reason to conjecture, however, that incompletely reduced ore may sometimes reach the hearth and enter the slag as a result of heavy slips or, perhaps, even from cores of excessively large lumps of a charge material of poor reducibility. The possibility of reoxidation of iron droplets falling in front of the tuyeres has been considered by several writers. It would be of interest, to know how rapidly iron oxides reaching the slag for any of these reasons could be reduced by reaction with coke or with the high carbon liquid iron in the hearth. In comparison with the hundreds of papers that have appeared on various aspects of the reduction of solid iron oxides by gases and in the presence of several forms of carbon, little work has been published on the reductioin of liquid oxides or slags. Dancey measured rates of reaction of the pure liquid oxides, both FeO and Fe,O,, with molten iron containing about 4.3 pct C. The oxide was dropped into the cup formed in the upper surface of the iron by rotating the crucible and melt. Under these conditions, reduction of either FeO or Fe,O., was completed in less than 10 sec. The present study was concerned with the reduction of FeO from blast furnace-type slags containing less than 5 pct FeO and melted over carbon-saturated iron in stationary graphite crucibles. The results were considerably different from those found by Dancey, as will be discussed later. Although this work is of interest in relation to hearth reactions in the blast furnace, interpretations must be made with caution because the experimental conditions do not duplicate those within a furnace and may not even lead to the same reaction mechanism. The authors were motivated in undertaking this work by an additional interest—the part played by FeO reduction in the mechanism of de-sulphurization of iron by slags under similar experimental conditions. Derge, Philbrook, and Goldman eveloped detailed experimental evidence to support a three-step mechanism for desulphurization like that originally proposed by Holbrook and Joseph&apos; (These reactions are written in molecular form for convenience, but this is not intended to imply the existence of molecules of FeS in the bulk metal phase nor to deny the likelihood of ionic reactions in the slag.) Earlier work by Chang and Goldman" had shown that the overall reaction follows first-order kinetics with respect to sulphur and that the rate of reaction is proportional to the slag-metal interface area, which observations have been confirmed by subsequent work. Later studiese,&apos; have established the influence of al.loying elements on the first and last steps of the reaction. This paper reports a study of step 3 alone, uncomplicated by the simultaneous process of sulphur transfer. Apparatus and Procedure The experiments were made in a conventional high frequency induction furnace powered by a 35 kva Hg spark gap converter. The graphite crucibles used for most of the runs were 14 cm (5.5 in.) deep and 4.8 cm (1.9 in.) ID with 0.75 cm (0.3 in.) wall. An insulating cover with a small opening for withdrawing samples was used to minimize heat loss and infiltration of air into the furnace. The crucible was charged with 300 g of carbon-saturated iron and either 65 or 100 g of prefused slag analyzing 38.0 pct SiO,, 15.4 pct A10 and 47.1 pct CaO. To obtain the cleanest possible interface at the start of the reaction, the metal and slag were brought to temperature together to prevent the rejection of kish graphite that would have been caused by the chilling effect of a large addition of cold slag to carbon-saturated iron. After temperature control had been established, the desired amount of iron oxide was added in the form of a prefused slag of composition 73.6 pct FeO, 7.7 pct AWX and 19.0 pct SiOl. This slag addition was observed to be molten in somewhat less than 1 min, and a very vigorous reaction proceeded for 1 to 2 min after its introduction. Zero time was taken as 2 min after the ferrous silicate slag addition. Slag samples weighing about 0.5 g each were taken periodically by a copper chill sampler." The weight of the initial slag was large relative to the weight of samples removed, so that the slag weight never varied by more than 5 pct during any run. Temperature was measured by a calibrated W/Mo thermocouple immersed in the metal, with a graphite tip cemented over the fused silica protection tube to prevent attack by slag and metal. After some difficulties with uncertain temperatures during the first two runs, the practice adopted to position the thermocouple for reproducible results was to lower the protection tube to touch the bottom of the crucible and then raise it 0.5 cm. The apparent temperature gradient between the bottom of the crucible and the top of the slag was found to be 15°C (27°F). but much of this spread was probably the result of inadequate immersion of the protection tube to off-set conduction losses along the graphite tip when the thermocouple was inserted only into the slag. The temperature of the bath was controlled within 25°C (9°F) during a run.

Jan 1, 1957

By J. H. Swisher

In measuvements of the solubility of nitrogen in fer-rilic Fe-P alloys, tile nitrogen solubility is found to be Less in pIrospliorus-bearing alloys than in pure iron. The reduction in solubility is about 20 pct in a 1.0 wt pct P alloy at 1300°C and about 30 pct in a 0.23 wt pct P alloy at 440°C. Diffusion coefficient measurements at 1150 and 585°C show that phosphorus also decreases the nitrogen diffusivity in iron. In previous work on the Fe-P-N system, phosphorus was found to reduce the nitrogen solubility in liquid iron slightly.&apos; Indirect evidence for similar behavior in a Fe at low temperature was obtained by Dickenscheid and Brauner.&apos; These authors found that phosphorus reduces the height of the internal-friction peak due to dissolved nitrogen. The results of Dickenscheid and Brauner were confirmed by J. C. Swartz of this Laboratory in a single internal-friction experiment using the same specimen stock as in the solubility measurements described below. In the present investigation, the solubility of nitrogen in a fer rite-stabilized Fe-1.0 wt pct P alloy was measured in the temperature range from 800" to 1300°C. Additional experiments were performed in the temperature range from 440° to 585°C, using an Fe-0.23 wt pct P alloy and NH3-H2 gas mixtures. EXPERIMENTAL The experiments were performed in a vertical tube furnace wound with platinum wire. For experimental temperatures of 800°C and above, a mixture of 5 pct Hz in N2 was used as the reacting gas. The gas mixture was prepurified from oxygen by passage over platinized asbestos at 450°C, and subsequently over anhydrone to remove water. Flow rates of the gases were measured with capillary flow meters. The temperature was measured before and after each experiment with a Pt/Pt-10 pct Rh thermocouple. The specimens used for the high-temperature solubility measurements were in the form of rectangular plates, 0.534 by 1.6 by 3.8 cm. The specimens were cleaned in trichloroethylene and annealed for 2 hr in hydrogen at the beginning of each experiment. In measuring the nitrogen solubility, the specimens were held in the reacting gas until equilibrated, then cooled in a water-cooled copper block at the bottom of the furnace. The time needed for equilibration at 1150°C was determined by measuring the average nitrogen content of the 1.0 pct P alloy as a function of reaction time. As will be described, the nitrogen diffusivity in the alloy at 1150°C is only slightly less than its calculated diffusivity in pure iron. At temperatures other than 1150°C, the reaction time used in measuring the nitrogen solubility was about twice the calculated equilibration time for pure iron at the same temperature. With a few exceptions, the procedure for the low-temperature solubility measurements was the same as that described above. The compositions of the NH3-H2 gas mixtures were determined by collecting gas samples from the gas train and analyzing them for NH3 by titration with HC1. The specimen thicknesses were less than those used for the high-temperature experiments, eg., 0.124 and 0.051 cm for measurements at 585° and 440°C, respectively. Nitrogen concentrations were obtained by chemical analysis, using the Kjeldahl method. The Fe-P alloys were made by adding ferrophos-phorus to electrolytic Plastiron (Type 104 A). Commercial ferrophosphorus, containing 3 pct Mn and 0.35 pct Si as the major impurities, was first purified by melting under an FeO slag. In a separate heat, the electrolytic iron was melted and vacuum-carbon-deoxidized prior to making the ferrophosphorus addition. The principal impurities and their concentrations in weight percent in the 1.0 pct P alloy are as follows: Mn, 0.01; Si, <0.01; C, 0.01; 0, 0.003; and N, 0.0012. The impurity levels in the 0.23 pct P alloy are con-

Jan 1, 1968

By Earl Bardwell

THE structural relations existing between cuprous oxide and copper -were first systematically studied by Heyn1&apos;, who suggested that a study of the microstructure of refined copper might be substituted for the analytical methods in vogue for determining the oxygen content of copper coming from the refining furnace. Hofman, Green and Yerxa,2 in their paper A Laboratory Study of the Stages in the Refining of Copper, working along the lines suggested by Heyn, showed that a study of the microstructure could be made to yield a correct estimate of the oxygen content of the specimen of refined copper under examination. In order to determine the oxygen content of the specimen of refined copper under. examination a photomicrograph was first made. From the relative areas of copper and eutectic, the percentage of cuprous oxide and the corresponding percentage of oxygen were then readily calculated. It was found that the values for oxygen thus obtained corresponded closely with the analytical results. With the idea of utilizing this method of determining the oxygen content of each charge dipped from the refining furnaces at the Boston & Montana Reduction Plant, the physical testing laboratory was equipped with suitable apparatus for carrying out the work. It may be of interest to describe certain of the methods which have been worked out in this connection and give such data as have been obtained bearing on the effect of the oxygen content of refined copper upon its conductivity. Apparatus.-For the benefit of those who may be unfamiliar with metallographical apparatus and methods and may be interested to know what equipment is required, a few words with regard to the apparatus is in place at this point.

Jan 7, 1913

By Earl S. Bardwell

The structural relations existing between cuprous oxide and copper were first systematically studied by Heynl; who suggested that a study of the microstructure of refined copper might be substituted for the analytical methods in vogue for determining the oxygen content of copper coming from the refining furnace. Hofman, Green and Yerxa,2 in their paper A Laboratory Study of the Stages in the Refining of Copper, working along the lines suggested by Heyn, showed that a study of the microstructure could be made to yield a correct estimate of the oxygen content of refined copper. In order to determine the oxygen content of the specimen of refined copper under examination a photomicrograph was first made. From the relative areas of copper and eutectic, the percentage of cuprous oxide and the corresponding percentage of oxygen were then readily calculated. It was found that the values for oxygen thus obtained corresponded closely with the analytical results. With the idea of utilizing this method of determining the oxygen content of each charge dipped from the refining furnaces at the Boston & Montana Reduction Plant, the physical testing laboratory was equipped with suitable apparatus for carrying out the work. It may be of interest to describe certain of the methods which have been worked out in this connection and give such data as have been obtained bearing on the effect of the oxygen content of refined copper upon its conductivity. Apparatus.—For the benefit of those who may be unfamiliar with metallographical apparatus and methods and may be interested to know what equipment is required, a few words with regard to the apparatus are in place at this point.

Jan 1, 1914

By K. Adam

Grinding in steel mills adversely affects the flotation of pyrrhotite. The electrochemical nature of inter action between pyrrhotite and active metals was investigated by contacting pyrrhotite with platinum at different applied potentials. Flotation tests, scanning electron microscopy, Auger electron spectroscopy, and X-ray photoelectron spectroscopy were wed to examine the surface properties of pyrrhotite. The formation of hydroxide or oxide and sulfate species of iron through the oxygen reduction reaction at the cathodically polarized surface of pyrrhotite was shown to be the mechanism responsible for the reduced floatability of pyrrhotite.

Jan 1, 1985

By R. G. Hawthorne

This report is concerned with fluid displacement in porous media, in those cases where viscous and gravitational forces control the displacement. Such a system would usually be found in a sand body of large physical dimensions such as an oil reservoir, although it is possible to create such a system in the laboratory. It is shown that the position of the fluid interface can be predicted by numerical calculations using a basic idea presented by Dietz. Fluid flow is considered in a vertical plane in a homogeneous, porous medium of sufficient thickness that the capillary transition zone is small in comparison with the total reservoir. A theory developed by Dietz&apos; is used to make numerical calculations of the position of the fluid interface. The results for several conditions are compared with scaled model experiments. The results show that, for gas drive in a reservoir of steep dip, a relatively low flow rate can displace large volumes of oil before gas breakthrough. On the other hand, water injection at favorable mobility ratio and low dip may show best performance at high rates. Water tends to underride the oil and, given sufficient rime, will break through without much oil displacement. For certain conditions, which include relatively low flow rate, the interface is a straight line and its behavior is simple to calculate. At higher flow rates, the interface is unstable, and a numerical solution was programed for an automatic computer. In general, good agreement is shown between the fluid model and the computed results so long as gravitational forces have control. For a water drive at very unfavorable mobility ratio, many small water fingers appear. These viscous fingers are not controlled by the relatively small gravitational forces. When viscous fingering becomes the controlling factor, the mathematical model is oversimplified, and results do not check the fluid flow model. INTRODUCTION Present methods of reservoir analysis depend upon certain simplifying assumptions to obtain mathematical descriptions of practical use. Material-balance methods (Muskat2 or Tarner2) assume uniform fluid saturations in the entire reservoir, or in a few subdivisions of the reservoir. An unsteady-state flow calculation by West, er at considered pressure and saturation changes in flow to a well during solution gas drive, and neglected gravity effects. Results showed only a 4 per cent difference for ultimate oil recovery by the Muskat method, even though the case chosen for study was one in which unsteady-state effects should be high. The Buckley-Leverett5 method commonly assumes a one-dimensional flow system. It is applicable at high flow rates where viscous forces predominate over gravity forces. Simultaneous, parallel flow of the two fluids is assumed, and the concept of a fluid interface is not introduced. Permeabilities to each fluid for a given saturation must be known. The method is not applicable for a two-dimensional system where cross flow becomes possible. Less well known is the displacement equation derived by Dietz. This method is designed for two-dimensional flow systems and assumes a definable fluid interface within the porous medium. Dietz showed that, for a range of low flow rates, the interface would be stable. straight and at an angle of inclination which could be simply calculated. At a certain critical flow rate, the calculated interface tilt would equal the formation dip. For higher flow rates, a finger of displacing fluid would invade the displaced fluid. Dietz indicated that his method applied only to macroscopic reservoir behavior, while the Buckley-Leverett method applied to the small transition zone at the fluid interface. The examples worked out in this report are based on the fluid-displacement theory of Dietz. It is shown that the Dietz theory may be used to derive equations analogous to the Buckley-Leverett equations. In contrast to the Buckley-Leverett method, flow is considered in a plane rather than being limited to a line. Rather than a frontal advance, the movement of a fluid interface is followed. For flow rates substantially exceeding the critical rate and for high viscosity ratio, many fingers of invading fluid occur-—rather than the single finger assumed by Dietz. On the other hand, so long as some gravitational influence remains, the flow is not entirely parallel to the bedding planes as assumed by Buckley and Leverett; therefore, both methods fail to give an adequate descrip-

By M. E. Wadsworth, J. S. Cho

Colloidal silica dissolved in aqueous suspensions of high surface area thoria was permitted to adsorb on the thoria surface. Silica in three forms was identified by means of infrared spectroscopy and characterized by Si-O vibrational modes in the 9.0 to 10.5 region. A band at 9. 1 was attributed to free unad-sorbed silica, while adsorbed silica resulted in bands of greatest absorbency at 9.4 or 10.3p, depending upon the character of the surface bonding. Size considerations, the amount of silica adsorbed, and the character of the infrared spectrum for strongly adsorbed silica has been interpreted as evidence of formation of chain or layer silica linkages on the thoria surface. Infrared spectroscopy has been used successfully in recent years for the identification of minerals and synthetic inorganic substances. Unfortunately, infrared studies of silicate minerals have not proceeded to the point that unambiguous assignments may be made for Si-O vibrational modes as affected by lattice substitutions and structures. Several investigators have presented infrared spectra of silicate minerals, 1,7 and their work has pointed to the potential value of infrared to identify minerals as well as to note the sensitivity of various Si-O modes to structural and substitutional environments. The strong infrared absorption of various Si-O vibrational modes makes the infrared method a very useful tool for the study of silica adsorbed on the surface of solids of high surface area. Spaepen et a18 studied the adsorption of silica on thoria surfaces from aqueous solutions of silicic acid up to 300°C. A general review of the application of the infrared method to the study of surface adsorption has been presented by Pliskin and Eischens.9 EXPERIMENTAL Du Pont colloidal silica, Ludox SM (16.36% SiO2) and Ludox HS (30.25% SiO2) in aqueous suspensions were used as the sources of silica for the adsorption studies. The thoria used for this study was supplied by Union Carbide Nuclear Co.* under the preparation *Chemical Technology Div., Union Carbide Nuclear Co., Oak Ridge, Tenn. . number D-16-650. It was fired from the oxalate at 650°C and had a surface area of 32.4 ± 0.6 m2 per g measured by nitrogen adsorption. The chemical analysis of the D-16 thoria in ppm was: CO3= (5500), NO3- (< 4), so4±PO4 (100), and Si (20). The Ludox silica was placed in contact with the thoria in a two-liter autoclave10 between room temperature and 250°C. Slurries were made by placing 1 g of thoria in one liter of distilled water containing various additions of the silica sol. Samples were removed from the autoclave by opening a small stainless steel valve. Extracted samples were centrifuged for 10 min and excess solution was decanted. The sample was then dried for several hours at 80°C. Infrared samples were prepared by thoroughly mixing 10 mg of the thoria with 400 mg KBr in polystyrene vials on a "Wig-L-Bug" amalgamator. Pellets were pressed under vacuum and had final dimensions of 1.2 cm diam and 1.2 mm thick. Infrared spectra were

Jan 1, 1963

By S. Shapiro, J. A. Ford

The crystallo graphy of several grains of the lamellar Ni-Ni3 B eutectic solidified under conditions appvoachirt equilibriun has been examined.. A preferred interlace relationship has been observed in this system which may be described as: A detailed study of this interface by means of an atomistic model reveals the interface Plane to be puckered and more accurately describable as: Analysis of the atomic configuration on these planes reveals that this interface conforms to the orientation criteria proposed for directionally solidified lanzellar eutectics. In addition, a model is proposed to help explain the growth of a "puckered" interface. DURING the past several years an increasing number of unidirectional solidification experiments on eutectic alloys have been reported in the literature. The primary emphasis, in most cases, has been the effect of growth variables on microstructure. Some authors have, however, studied the crystallographic orientations and interfacial relationships resulting from these experiments. Four crystallographic studies have been published;&apos;-4 in each of these there is a factor which tends to prohibit the extension of the observations beyond the particular system. In the Al-CuA12 system, the approximately equal volume fractions of the phases have resulted in sorrie controversy as to which phase constitutes the matrix. In the Mg-Mg,Sn eutectic the presence of several interconnecting lamellar systems2 complicates the analysis. The two remaining eutectics. 1nSb-b and Al-Ali, are both rodlike (the latter exhibits a plate morphology at low solidification rates): the matrix in each of these alloys is the simpler (fcc) phase. Studies of nucleation in eutectic alloys indicate that the more complex constituent is the nucleating -.phase.&apos; For the purpose of an analysis of interface crystallography it was deemed desirable to study a lamellar system in which the matrix was the more complex and, presumably. the nucleating phase. Recently it has been shown that there is a eutectic in the Ni-B system between Ni3B and i; preliminary investigation by the authors indicated that the matrix in this eutectic is the boride phase. The structure of Ni,B is reported to be orthorhombic, the compound being isostructural with cementite. This eutectic is therefore analogous to that between austenite and cementite. Furthermore, the Ni-B system is not susceptible to a competing eutectic reaction as occurs in the Fe-C alloys; nor does it exhibit a eutectoid decomposition. For these reasons the study of the interfacial relationship in the Ni-Ni3B eutectic was undertaken. PROCEDURE Ingots of nominal composition 3.5 and 3.6 wt pct B were induction-melted in boron nitride crucibles within a graphite susceptor under a boric oxide slag; a dynamic argon atmosphere was maintained over the melt to prevent rapid oxidation of the susceptor. The raw materials used were 99.97 pct Ni from Huntington Metals Division of International Nickel Co. and 99.8+ pct B chips supplied by the United Mineral and Chemical Co. The analyses of the starting materials are listed in Table I. The melt was held at 1500cC for 2 hr to insure complete reaction and allowed to cool to room temperature. The castings were chemically analyzed for boron and were metallographically examined for uniformity. The metallographic samples were mechanically polished through 0.1 p A1,0, and etched with Carapella&apos;s reagent. Each master casting was cut up to make several specimen blanks which were remelted, in boron nitride crucibles, to form ingots of 1/2 to 3/4 in. in diarn by 7 in. long. These ingots were unidirectionally solidified using a modified vertical Bridgman technique. The rate of solidification was assumed to be equal to the uniform rate at which the crucible-susceptor assembly was withdrawn from the induction coil. This rate was varied from 1.18 to 2.21 cm per hr. In order to perform these experiments it was found necessary to redetermine the eutectic composition. This was accomplished by the zone-melting technique described by Yue and lark.&apos; An ingot of 4.5 wt pct B was zone-melted in a horizontal boron nitride boat 7-1/2 in. long with a 112-in.-square cross section. A

Jan 1, 1967