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By Arnulf Muan, Klaus Schwerdtfeger, L. S. Darken

The equilibrium ratios CO/CO, of. a gas pharse coexislitrg with selected oxide phase assemblages of the system "FeO"-MnO-SiO2 and metallic iron have been determined at 1150°C. The data obtained are combined wilh the thermodynamic data on fayalite (Fe2SiOi) and "FeO"-MnO solid solutions to derive the actiuity-coiHpQsiUon relations for the various oxide components of the olivine (Fe2SiO4-,lIn2Si04) and pyroxenoid (standard free energies of formation of ferrosilile (FeSiO,), tephroite , and rhodonite from their oxides have been evaluated. In the Appendicc~s by Darken and Schivcerdtjeger the ideal solution law for solid deri oed. THE quaternary system Fe-Mn-Si-0 is of interest in many important phases of iron- and steelmaking. For instance, reduction in the blast furnace of ores containing Fe-Mn silicates, deoxidation of liquid steel with Mn-Si alloys, formation and subsequent alterations of oxide inclusions in steels, and the oxidation of manganese- and silicon-containing steels during processing are all governed largely by the thermodynamic relations existing in the system Fe-Mn-Si-O. Although the equilibria between liquid iron and Fe-Mn silicates have been studied in detail previously,' experimental data are lacking for equilibria among the solid phases. The present paper provides such data for a selected temperature, 1150°C. I) PREVIOUS WORK The general feature of subsolidus phase relations in the system iron oxide-manganese oxide-silica under strongly reducing conditions is known.' Fig. 1 represents an isothermal section at 1150°C. The phases present, in addition to silica, are three solid-solution series, viz.. the oxide solid-solution series "Fe0"-MnO (manganowiistite), the orthosilicate solid-solution series Fe2SiO4-Mn2SiO4 (olivine), and the metasilicate solid-solution series FeSi03-MnSi03 (pyroxenoid). The "FeO"-MnO solid solution is continuous between the two end members wustite and manganositeV3 as is the orthosilicate series between the two end members Fe2SiO4 and Mn2 SiO4. 4 The metasilicate solid solution, on the other hand, extends only part way from the MnSi0.l end member toward FeSiO because the latter end member is unstable relative to the phase assemblage fayalite + silica. The letters a through m in Fig. 1 identify end members of the individual solid phases dealt with [for instance, c designates fayalite (FeZSiO4) in equilibrium with wustite, e designates fayalite in equilibrium with silica, and so forth]. In addition to the phase relations there are some thermodynamic data available for the end members of the silicate solid solutions and for the "FeO" -MnO solid solution. The free energy of formation of fayalite (Fe2Si04) from its oxide components has been studied by several investigators. Unfortunately, the data obtained show considerable discrepancies. According to recent tabulations by Kelley, the change in standard free energy Affn for the reaction

Jan 1, 1967

By Ö. Valla, A. Muan, K. Grjotheim

The solid miscibility gap between CaO and "FeO" in the system CaO-"FeO" in contact with metallic iron gradually closes as MnO is added as a third component. On the liquidus surface of the system CaO-"FeO"-MnO, this situation gives rise to a boundary curve which originates in the bounding system CaO-''FeO", proceeds a short distance into the composition triangle of the ternary system, and then vanishes. A new approach has been used to follow the course of this boundary curve. It is shown that the curve vanishes at a much lower temperature and at much lower MnO contents than has been inferred previously. The oxides CaO, "FeO", and MnO together with SiO2 are the major components of the slag phase formed in the basic oxygen process. Hence, the system CaO-"Fe0"-MnO is of considerable technological interest. In addition, the system is theoretically interesting. The three oxides above all have sodium chloride structure. The size differences among the cations are such that in the bounding "binary"* systems CaO-MnO and "FeO"-MnO complete solid-solution series are formed,1,2 whereas in the system CaO-"FeO" there is only limited mutual solubility in the solid state,3 see Fig. 1. Hence, a solid miscibility gap exists in a part of the "ternary"* system Ca0-"Fe0"-Mn0, and a liquidus boundary curve originates at the peritectic point, point a in the insert in Fig. 1, in the system CaO-"FeO", extends a certain distance into the ternary system, and then vanishes. Very little quantitative information on the system Ca0-"Fe0"-Mn0 is available in previous literature. Fischer and Feischer4 sketched isothermal sections at 1600° and 1700°C, and estimated that the vanishing boundary curve extends to approximately 1650°C and a composition of 42 wt pct MnO. The work to be described in the following was aimed at locating experimentally the "vanishing" liquidus boundary curve, determining its end point, and deriving representative isothermal sections below and above the temperature of the end point of this curve. EXPERIMENTAL METHODS The phase relations were determined by the well-known quenching method. (For a description of this method as applied to oxide systems, see the original paper of Shepherd, Rankin, and wright.5) Prereacted oxide mixtures of desired compositions were contained in iron crucibles and heated in a vertical tube furnace in an atmosphere of purified nitrogen. After equilibrium was judged to have been attained, the samples were quenched to room temperature, the phases present were identified by microscopic and X-ray examination, and total iron oxide contents were determined by chemical analysis. "Fisher Certified" reagents (MnCO3, CaCO3, Fe2O3, and Fe) served as starting materials. The calcium carbonate and ferric oxide were heated in air at 400° and 800°C, respectively, for 24 hr prior to use. Manganese oxide was prepared by decomposing the carbonate in a graphite crucible in hydrogen atmosphere at 1000°C. The product was ground under acetone to -100 mesh. The iron powder was used directly without any preparation. Dicalcium ferrite was used as a starting material for some mixtures. It was made by mixing some of the above prepared CaCO3 and Fe2O3 in proportions corresponding to the formula 2CaO. Fe2O3. This mixture was then fired in air for

Jan 1, 1969

By M. E. Nicholson

The effect of boron on the austenitic transformation rate of iron is smaller than on low carbon steels. The influence of austenitizing temperature on B-Fe is the reverse of its influence on steels. THERE have been many studies made of the influence of boron on the hardenability of steel, but apparently none has been made of its influence on the y-a transformation of pure iron. There are several facts suggesting that boron should have a pronounced effect on the transformation rate of iron. First, Simcoe et a1.l indicated that boron reduces the nucleation rate of ferrite and bainite. Second, they showed, along with others,', " that the lower the carbon content of steel the greater the influence of boron on hardenability. If this trend extends to pure iron, the influence on rate of ferrite formation should be considerably greater for iron than for medium carbon steels. According to Rahrer and Armstrong," the multiplying factor for boron in pure iron should be about 2.40, compared with 1.50 in a 0.35 pet C steel. According to an extrapolation made by Grange and Mitchell,' the effect should be even greater, and the multiplying factor should be about 3.5 in iron. Many investigations of the boron influence'.7, 2, 5 indicated that boron is effective only when in solid solution. On the other hand, Chandler and Bredig" suggested that boron increases hardenability by combining with nitrogen, thereby preventing formation of AlN, which catalyzes the decomposition of austenite. If their hypothesis is valid, boron should have no effect on an alloy free from nitrogen. Digges et al." showed that so far as low nitrogen high purity Fe-C alloys are concerned this is not the case. No experiments, however, have been made on low nitrogen iron. To determine whether or not boron has an effect on low nitrogen iron and, if an effect exists, to determine whether it is as large as predicted from the investigations of boron treated steels, the following work was performed. Because of the rapidity with which iron transforms from austenite to ferrite at even a moderate degree of supercooling, it was decided to study the influence of boron on the transformation rate of iron by determining the effect of quenching rate on the temperature of the beginning of transformation. The technique, essentially that used by Greninger' and Duwez,H consisted of heating small specimens, 0.1 in. sq and 0.010 in. thick, in an atmosphere of purified helium with a resistance heater coil, and then quenching the sample in a jet of helium gas. At the time the jet was applied, the heating coil was removed from around the sample. The sample was suspended in the furnace on 30 gage chrome1 and alumel wires, one welded to each side of the specimen, which also served as a thermocouple for measuring the specimen temperature. Specimens were prepared from vacuum-melted iron obtained from the National Research Corp. which was rolled to a thickness of 0.060 in. and then decarburized in wet hydrogen for 51/2 hr at 700°C. This treatment also removed any boron present in the iron. The resulting iron contained 0.001 pet C. 0.0002 pet N, and 0.005 pet 0. One half of the piece was then boronized by surrounding it with 325 mesh boron powder and heating it for about 2 hr at 900°C in H,. The boronized iron was then homogenized at 1100°C for 24 hr. The iron boride case formed by boronizing was removed by grinding 0.010 in. from each side of the plate, and the piece was finally rolled to a thickness of 0.010 in. The resulting alloy contained

Jan 1, 1957

By Michael P. Robinson

It has been suggested that streaming potentials are not nomlally logged because the streaming potentials known to be generated across mud filter cakes are substantially cancelled by streaming potentials generated in contiguous shale beds. Laboratory measuments of streaming poterztials acrons hand specirnens of shale have been adduced as evidence to support the suggestion. The experiments show that streanzing potential depends on the resistivity of the equilibrating solution and on pressure drop. Meizsurenlents were made perpendicular to the bedding planes of the shales. The mechanism of streaming potential generation in shale which the suggested cancellation theory iniplies has been critically examined. Conclusions reached are tested by comparing self potentials logged before and immediately after changing the resistil~ity (but not the weight) of mud in a borehole. The resultant SP change is found to equal the theoretical electrochetnical potential change, i.e., cancellation of .strearning potential is independent of mud resistivity. Since streaming po/entials generateal across mud filter cakes depend critically upon mud reistivity, shale .strearlling potential in situ must he equally sensitive. Using plausible values for the pemleahility, porosiy arzd compressibility of shale, the van Ererdingerl-Hurst approach shows that the pressure drop between horehole pressure and formation pressure in a radially honzogeneous shale is unlikely to coincide with the zone of filtrate invasion. If, perchance. this coincidence occurs with one mud a chatzge 10 a second must result in non-coincidence, i.e., a .YP logged in the second mud should show a streaming potenlial. The dilernrna may he overcome by postrrlating: (I) perrneabilities of shale7 parallel to their beddine planes greatly exceed their cross-bedding permeabilities; (2) a resistivity-sensitive mud cake of low permeability forms either on the face of, or probnhly in the lanlinations of, many shales. These postulates are examined with reference to the pres.sure and SP histories of the McClosky and Aux Vases zones in the Illinois Basin and some srcpport for them found. It is concluded that a definitive solultion to the streaming potential problem does not exist. INTRODUCTION Recently Gondouin and Scala' published a contribution to the streaming potential problem which is notable particularly for the elegance of its experimental techniques. The conclusions drawn by Gondouin and Scala from their studies amplified those previously suggested by Schehck'. In essence they suggested that the streaming potentials known to develop across mud filter cakes" are not normally observed on SP logs because they are largely cancelled by streaming potentials generated in adjacent shales. This suggestion appears so reasonable that many workers in the logging field will be prone to accept it. We incline strongly to the view that the suggestion is basically correct. Nevertheless, it is important to realize that the cancellation hypothesis in the form put forward by Gondouin and Scala does not appear to meet all the known experimental facts. It is the principal intention of this note to call attention to what appears to be a flaw in the relevancy of the experimental evidence adduced by Gondouin and Scala and to suggest an alternative hypothesis to remove it. The consequences of the new hypothesis are compared with field data which, we believe, are unique. A second but not less important purpose of this note is to emphasize that even the new hypothesis does not fully explain all field observations. Hence we conclude that further study of the streaming potential problem is required before it can be said that a definitive solution to it has been attained. The bare experimental bones of laboratory data on streaming potentials appear to be as follows. 1. A streaming potential is developed across a mud filter cake. This streaming potential is virtually independent of cake thickness but depends on the mud resistivity. The relationship is of the form, 2. A streaming potential is developed across a shale. This potential is independent of shale thickness but depends on the resistivity of the permeating solution if the shale has been first equilibrated in this solution. The relationship is of the form, The relationship in (1) was determined first by Wyllie3, confirmed by Gondouin and Scala and qualita-

By L. K. Welch, C.W. Macgregor

The past 20 years has seen a revolutionary change in the testing of materials at elevated temperatures. This has largely been brought about by the practical importance of the creep problem in the design of equipment for operation at high temperatures. The short-time tension test carried out at elevated temperatures has consequently assumed in many cases only a secondary role compared with the longtime creep test. In many problems, however, a knowledge of the short-time high-temperature properties of a metal is essential. To mention a few cases in which this is so, we might include all hot-forming operations such as rolling, forging, etc., the welding problem if residual stresses are to be computed, the development of new alloys for high-temperature service where, in the initial stages, time does not permit of long duration creep tests, and others. Usually a knowledge of the short-time properties is desired, if only to serve as a background against which to compare creep behavior. In conducting short-time high-temperature tests, it has been almost the universal practice to determine stresses based on the original area and strains referred to the original gauge length which is usually chosen as 2 in. It has been pointed out1,2 that one of the reasons that the true significance of certain tensile properties is not understood, which perhaps curtails their usefulness, especially when the material is applied under conditions differing considerably from the test conditions, is that true physical stresses and strains are not determined. It is essential to have a knowledge of true stresses and strains in order to correlate the values present in the tension test with those existing, for example, in hot metal-forming operations and in the general problem of the yielding and failure of metals under combined stress conditions. Stress and strain values based on the original dimensions of the test piece do not exist physically except in the early stages of the test. Since at the present time there is very little information in the literature on true stress-strain relations in the short-time high-temperature tension test it is proposed in the following pages to describe a

Jan 1, 1943

By L. K. Welch, C. W. MacGregor

The past 20 years has seen a revolutionary change in the testing of materials at elevated temperatures. This has largely been brought about by the practical importance of the creep problem in the design of equipment for operation at high temperatures. The short-time tension test carried out at elevated temperatures has consequently assumed in many cases only a secondary role compared with the longtime creep test. In many problems, however, a knowledge of the short-time high-temperature properties of a metal is essential. To mention a few cases in which this is so, we might include all hot-forming operations such as rolling, forging, etc., the welding problem if residual stresses are to be computed, the development of new alloys for high-temperature service where, in the initial stages, time does not permit of long duration creep tests, and others. Usually a knowledge of the short-time properties is desired, if only to serve as a background against which to compare creep behavior. In conducting short-time high-temperature tests, it has been almost the universal practice to determine stresses based on the original area and strains referred to the original gauge length which is usually chosen as 2 in. It has been pointed out1,2 that one of the reasons that the true significance of certain tensile properties is not understood, which perhaps curtails their usefulness, especially when the material is applied under conditions differing considerably from the test conditions, is that true physical stresses and strains are not determined. It is essential to have a knowledge of true stresses and strains in order to correlate the values present in the tension test with those existing, for example, in hot metal-forming operations and in the general problem of the yielding and failure of metals under combined stress conditions. Stress and strain values based on the original dimensions of the test piece do not exist physically except in the early stages of the test. Since at the present time there is very little information in the literature on true stress-strain relations in the short-time high-temperature tension test it is proposed in the following pages to describe a

Jan 1, 1943

By John W. Burd

A system is described for the simultaneous deposition of epitaxial layers on as many as eight substrates. A high degree of uniformity of both physical and electrical characteristics is achieved in the films. Variation of film thicknesses is consistently less than ±10pct within a wafer and from wafer to wafer within a run with the variation typically on the order of 55 pct. Composition variation of GaAs1-x PX layers within a wafer and from wafer to wafer within a run is consistently less than 51 pct. Electrical evaluation of the films by several techniques indicates excellent doping uniformity within a wafer and from wafer to wafer within a run. Mobilities for lightly doped GaAs films at 300°K are consistently >6000 cm2 v-1 sec-1 and mobilities > 7000 cm2 v- 1 sec-1 are regularly attainable. Techniques for the preparation of material with carrier concentrations from 1 x 1015cm-3 to 1 x 1019 cm-3 n-type and 5 x 1016 to 5 x 1018 cm-3 p-type are discussed. METHODS for the preparation of 111-V compounds by vapor phase reactions have been extensively reported in the literature.1-6 Almost all of the apparatus described for these various methods are suitable for processing one or at the most a very limited number of wafers simultaneously. With the recent rapid advances in the use of vapor grown GaAs for microwave oscillators and GaAs1-xPx as visible light emitters the requirements for these materials are steadily increasing. In order to satisfy these requirements it is necessary to move from a laboratory scale apparatus to one which is capable of processing a large number of wafers simultaneously. Desirable features would be a high degree of uniformity among the wafers and good reproducibility from run to run. The apparatus to be described fulfills these requirements very well. DISCUSSION The various methods reported in the literature can be classified under three headings: 1) closed tube, 2) open tube, and 3) the close-spaced method. Of these three the open-tube method is the most amenable for scale-up to a manufacturing process. It is the most versatile and the various operating conditions can be more precisely controlled than with the other two methods. A number of chemical reactions may be used to achieve vapor-phase growth of 111-V compounds. Sev-era1 of the more generally used reactions are shown in Fig. 1. All of these reactions have the following points in common: 1) generation of a volatile group III(Ga) species by the reaction of the transport agent (halide or HC1) with either Ga or GaAs, 2) introduction of the Group V(As and/or PI component, 3) a method of adding dopant, if desired, and 4) a region in which deposition from the vapor will occur and form as a single crystal epitaxial film on the substrates. The laboratory scale reactors permit the hot re-actant gases to flow into the relatively cooler deposition zone and pass successively over the several substrates which are arrayed along the long axis of the tube parallel to the gas flow. With this arrangement the composition of the reactant stream is continually changing as solid material is deposited on each successive substrate. As a result of this changing gas composition the reaction driving force also changes from substrate to substrate and the degree of uniformity of layer thickness, doping level, and so forth, is poor. This effect can be partially overcome by imposing a controlled temperature gradient along the deposition region to compensate for change in gas composition. However, even when this is done variations in layer thickness on the order of 30 to 40 pct are common and as high as 50 pct are frequently experienced between adjacent wafers in the tube. To expand this arrangement to a large number of wafers would only increase the nonuniformity from the first to last wafer in the line. From the above discussion the two undesirable features of changing gas composition and temperature gradient become evident. A reactor system which eliminates or minimizes these undesirable features is one in which the apparatus is mounted vertically as shown schematically in Fig. 2. The vertical mounting permits the disposition of a number of substrates on a suitable support so that all wafers are at the same vertical height in the furnace and hence at essentially the same temperature. By using only a single row of wafers the reactant gas mixture passes over only one substrate in its path through the reactor. Thus the two undesirable features of changing gas composition and temperature gradient are minimized. An additional design feature which further minimizes temperature variations is rotation of the substrate holder. Rotation serves to integrate any radial temperature gradient existing around the resistance heated furnace. A photograph of a reactor assembly at the completion of a run is shown in Fig. 3. MATERIAL PREPARATION Apparatus. Although any of the several chemical systems shown in Fig. 1 are adaptable for use in this apparatus the one generally used is System 2, the hydride synthesis system. This system has been de-

Jan 1, 1970

By Harold L. Overton, Leonard B. Lipson

The first paper in this series1 outlined practical methods for applying the theory of steady-state flow of an ideal Bingham plastic liquid through a circular pipe and axially through a stationary concentric annulus to the enginekring analysis of friction loss problems. In the present paper the properties of another useful rheological model, the pseudoplastic generalized Newtonian liquid, are considered. The terminology applied to the rheological models is derived from the following classification of rheological models. The term "generalized Newtonian" is a class designation applied to models which do not have yield points but which exhibit a dependence on shear rate. The term "pseudoplastic" applies to a sub-group of models within this class which exhibit a decrease in "viscosity" with increasing shear rate. The term "power model" refers to a mathematical model proposed for describing the behavior of the pseudoplastic liquid. This model is of interest since certain of the salt saturated, oil emulsion, and "low solids" drilling fluids, inverted emulsion- and oil-base drilling fluids, aqueous gels, gelled crudes and blocking agents employed in hydraulic fracturing operations are of this type. The present treatment considers the equations describing steady-state Poiseuille flow through a circular pipe and a stationary concentric annul us, and Couette flow between concentric rotating cylinders for a particular pseudoplastic model. As in the previous paper' it is demonstrated how these equations can be applied to engineering calculations of friction losses. Graphical procedures for recovering the various flow curves and cxample calculations are included. A method for simplifying turbulent-flow correlations is also proposed. PROPERTIES OF PSEUDOPLASTIC GENERALIZED NEWTONIAN LIQUID In contrast to the Bingham plastic the generalized Newtonian liquid is yield point-free. However, in the flow region the relation between stress and rate of shear is not linear as it is with ordinary Newtonian fluids. If the stress increases with shear rate at a less than linear rate the system is called pseudoplastic. While there is no yield point in this system, the Bingham advocates' coined the term pseudoplastic to distinguish this kind of behavior from Bingham plastic behavior. For the pseudoplastic a plot of flow rate vs friction loss or rpm vs torque, from pipe flow or rotational viscometer measurements, respectively, generally has three qualities: (1) it can be clearly extrapolated toward the origin; (2) there is very little slope at the origin. This accounts for the high apparent viscosities at low mixing and pumping rates; and (3) the flow curve possesses a continuous curvature which gradually diminishes as the shear increases. Rheological measurements on a pseudoplastic liquid can be easily misinterpreted as indicating Bingham plastic behavior. A typical case in point is illustrated in Fig. 1. These data were obtained from measurements on an oil-emulsion mud using a commercially available rotational-type viscometer (Model 35 Fann V-G meter). Applying the "two-point"* method3 gives a plastic viscosity of 17 cp and a yield point of 24 lb/100 ft2; at the same time weighting material settles very easily in this system. This illustrates that it is not possible to distinguish between the pseudoplastic and the Bingham plastic from only two data points. It is possible to determine qualitatively which model is more appropriate by a combination of dynamic and static measurements. Experience indicates that the simplest criterion for the Bingham plastic liquid is that the calculated dynamic yield point should be of the same magnitude as the measured gel strengths. For the oil-emulsion drilling fluid illustrated in Fig. 1, a value of 4 lb/100 ft2 was obtained for gel strengths measured

By David V. Ragone, James A. Craig, Richard E. Balzhiser

The Gibbs free energies of formation of UC2 and UC were measured by equilibrating two-phase mixtures of UC2 + C and UC, + UC with liquid bismuth. The measured equilibrium concentrations of uranium in the bismuth combined with available activity coefficient information yielded uranium activities in these two-phase regions. Measurements on UC2 were performed over the range 1015 to 1160 K and on UC over the range 1115° to 1165°K. The values obtained for UC2 are in excellent agveement with values determined using combustton calorimetry and low-temperature heat capacity measurements. The UC values are in fair agreement with the calorimetric values, differing by about 10 pct from the calorimetric determination. MUCH interest has been shown in the uranium carbides in recent years because of their potential as nuclear fuels. As nuclear reactor operating temperatures have been raised to increase thermal efficiency, new fuels have been required. The uranium carbides are of interest because of their high melting points, >2000°C, high thermal conductivity, and resistance to irradiation damage. The manufacture and use of uranium carbides are aided by a knowledge of their stability and reactivity under various conditions. In this regard the thermo-chemical properties of the carbides, i.e., heat capacity, heat of formation, free energy of formation, and so forth, are particularly important. A great amount of work has recently been done on the thermodynamics of the U-C system. Unfortunately, however, there has not been good agreement among the various investigations. This study of the free energies of formation of uranium monocarbide and uranium di-carbide in the temperature region 1100°-1200° K was undertaken to help clarify the situation. It should be noted that in the temperature range of this investigation, 1100°- 1200° K, the thermodynam-ically stable phase in equilibrium with graphite is U2C3, not UC2, Fig. 1. However, U2C3 is reported to be stable only under extremely low oxygen and nitrogen pressure. Although UC2 is metastable below 150O°C, it exists under most experimental conditions. It should also be noted that "UC," never exists as UC2 but with compositions near UC1.9. However, "UC2" will be used to designate the dicarbide phase except when the stoi-chiometry is necessary for clarity. METHOD The approach taken in this study of the free energies of formation of UC and UC2 was to determine the thermo- dynamic activities of uranium in the two-phase regions UC, + C and UC + UC, by equilibrating the two-phase mixtures with the liquid bismuth. When a mixture of solid UC2 + C is brought to equilibrium with liquid bismuth, the reaction that occurs is: Neither carbon nor UC, could be detected as dissolved material in the bismuth. The standard free energy for this reaction may be written: In the two-phase region UC, + C, Fig. 1, the thermo-dynamic activities of UC2 and carbon are unity. The activity of uranium in this region was determined by measuring the concentration of uranium in a liquid bismuth melt in equilibrium with the two-phase mixture. This concentration was then used in conjunction with the activity coefficient data of uranium in bismuth reported by Tien et al.' to determine the activity of uranium in the two-phase region, UC, + C. All of the quantities in Eq. [2] were then known, and the AG; (uc,) was evaluated. UC + UC2. For the studies involving UC + UC,, the reaction taking place when the two-phase mixture is brought to equilibrium with liquid bismuth is: The standard free-energy change for this reaction is given by:

Jan 1, 1969

Edward Keller, Baltimore, Md. (communication to the Secretary*) :—The authors of this paper are to be commended for their industry and congratulated upon the many interesting results which were the fruit of their researches. While thoroughness has marked their work in general, yet on a few points in particular they have touched but lightly, for which reason, it would appear to me, they have hit wide of the mark in their respective conclusions. The work alluded to pertains chiefly to the occurrence of magnetic iron oxide (ferroseferric oxide) in copper-mattes. Because the authors find that the magnetic residue, left by the dissolved sulphides, varies largely in quantity according to the strength of nitric acid used (with potassium chlorate) in dissolving the mattes, they conclude :— "It appears, therefore, that the ferroso-ferric oxide is the result of precipitation by the oxidizing agent, rather than an original constituent of the matte." In this part of their investigation, Messrs. Gibb and Philp have ignored some well-established data,. In the first place, they have overlooked the fact that there are mattes which are strongly magnetic and others which scarcely show any magnetic property. There is nothing in their work tending to explain this variation. They Seem to have tested none of their products for magnetism. Secondly, they have overlooked the fact that magnetic iron oxide probably exists in all ore-charges in the copper-matting furnaces, and, under the given conditions, that this oxide is very difficult to reduce and to combine with silica to form slag. Thirdly, they pay no attention to the varying specific gravity of the several grades of copper-matte, which may exceed, equal, or fall below that of the magnetic oxide. These are .essential points which, I believe, clearly in-

Jan 1, 1906

By Carl H. Samans

In their recent complete review of the subject of age-hardening,' R. F. Mehl and L. K. Jetter classify the main types of precipitation-hardening alloys under two headings, depending upon the nature of the precipitate and the character of the precipitation. In the alloys falling under the first heading, which display "continuous precipitation" and are typified by the aluminum-copper alloys, "precipitation seems to occur without much regard to grain boundaries and apparently at much the same rate at every point," although an acceleration in regions plastically deformed has definitely been established.2 In the second type of alloys the precipitation is "discontinuous," as in the copper-silver system for example, and "seems to start in restricted regions, primarily those contiguous with the grain boundaries, and to spread inward in an advancing wave." The reasons for the occurrence of these two greatly different types of precipitation are unknown, as are those for many other reactions that take place in the solid state. In the present paper only the first or "continuous" type of precipitation will be dealt with, for which a complete crystallographic mechanism has been worked out for the process of precipitation from a supersaturated solid solution of copper in aluminum. Based upon this mechanism, an explanation of the various property changes found experimentally will be developed in the second paper of this series. In later papers ('discontinuous precipitation" in copper-silver alloys will be explained, and an effort will be made to rationalize the two processes and types of precipitation. Crystallography of the Precipitation Process Through the extensive investigation by R. F. Mehl, C. S. Barrett and F. N. Rhines3 on the Widmanstätten structure in aluminum-rich copper

Jan 1, 1940

By Harry L. McNeill

The Selective Media Process was developed by the author in a laboratory provided by The Steams-Roger Manufacturing Co. It is the outcome of an investigation into the possibilities of coarse beneficiation by sink and float without using the conventional heavy media. Commercial work to date has been limited to the treatment of minus 3/8-in. iron ore at the Hill Trumbull washing plant of the Cleveland Clifis Iron Co., at Calumet, Minnesota. Two cut away prints of the machine are shown (Figs. I and 2). A rotary conical impeller is mounted within a stationary cone (Fig. 2). This impeller is adjustable vertically by a 12-ton screw jack. The speed of the impeller can be varied from 14 to 32 r.p.m. by the Reeves variable-speed motor pulley mounted on the 7½-hp. motor drive. Attached to the bottom of the stationary cone is the automatic control valve for sink product, actuated by a ¼-hp. gear motor. The sink product is dewatered in a conventional drag driven by a 7½-hp. motor and discharged onto an inclined conveyor containing from 6 to 10 per cent moisture. Two plants are operated at the Hill Trumbull property. All the ore is first treated in a typical washing plant (Fig. 3). when treating "wash ore" a finished concentrate can be produced by the log washers and Akins classifiers, as the separation involves only fine silica (minus 48-mesh) and free iron. However, when "jig ore" is led to the washing plant the coarse

Jan 1, 1947

By Harry L. McNeill

The Selective Media Process was developed by the author in a laboratory provided by The Steams-Roger Manufacturing Co. It is the outcome of an investigation into the possibilities of coarse beneficiation by sink and float without using the conventional heavy media. Commercial work to date has been limited to the treatment of minus 3/8-in. iron ore at the Hill Trumbull washing plant of the Cleveland Clifis Iron Co., at Calumet, Minnesota. Two cut away prints of the machine are shown (Figs. I and 2). A rotary conical impeller is mounted within a stationary cone (Fig. 2). This impeller is adjustable vertically by a 12-ton screw jack. The speed of the impeller can be varied from 14 to 32 r.p.m. by the Reeves variable-speed motor pulley mounted on the 7½-hp. motor drive. Attached to the bottom of the stationary cone is the automatic control valve for sink product, actuated by a ¼-hp. gear motor. The sink product is dewatered in a conventional drag driven by a 7½-hp. motor and discharged onto an inclined conveyor containing from 6 to 10 per cent moisture. Two plants are operated at the Hill Trumbull property. All the ore is first treated in a typical washing plant (Fig. 3). when treating "wash ore" a finished concentrate can be produced by the log washers and Akins classifiers, as the separation involves only fine silica (minus 48-mesh) and free iron. However, when "jig ore" is led to the washing plant the coarse

Jan 1, 1947

By Carl H. Samans

In their recent complete review of the subject of age-hardening,' R. F. Mehl and L. K. Jetter classify the main types of precipitation-hardening alloys under two headings, depending upon the nature of the precipitate and the character of the precipitation. In the alloys falling under the first heading, which display "continuous precipitation" and are typified by the aluminum-copper alloys, "precipitation seems to occur without much regard to grain boundaries and apparently at much the same rate at every point," although an acceleration in regions plastically deformed has definitely been established.2 In the second type of alloys the precipitation is "discontinuous," as in the copper-silver system for example, and "seems to start in restricted regions, primarily those contiguous with the grain boundaries, and to spread inward in an advancing wave." The reasons for the occurrence of these two greatly different types of precipitation are unknown, as are those for many other reactions that take place in the solid state. In the present paper only the first or "continuous" type of precipitation will be dealt with, for which a complete crystallographic mechanism has been worked out for the process of precipitation from a supersaturated solid solution of copper in aluminum. Based upon this mechanism, an explanation of the various property changes found experimentally will be developed in the second paper of this series. In later papers ('discontinuous precipitation" in copper-silver alloys will be explained, and an effort will be made to rationalize the two processes and types of precipitation. Crystallography of the Precipitation Process Through the extensive investigation by R. F. Mehl, C. S. Barrett and F. N. Rhines3 on the Widmanstätten structure in aluminum-rich copper

Jan 1, 1940

By S. P. Ray, B. D. Sharma

THE activation energy values for self-diffusion in pure metals have been correlated with a number of physical properties such as melting points,1 valences,' Debye temperatures,3 and cohesive energy densities.4 Extending the melting point correlation, the self-diffusion activation energy values for the alloys can be similarly correlated with the solidus temperatures. For metals and alloys which exhibit phase transformations, such a correlation is not feasible because of the uncertainty of various physical properties of the corresponding phases. Using thermodynamical approach, Ardell5 calculated the hypothetical melting points of the low melting phases of the polymorphic metals. However, these calculated melting points do not show reasonable correspondence with the activation energy of self-diffusion. Recently, a new approach treating metals and alloys as electron concentration phases has been developed by Engel6 and Brewer.7 These workers have attempted to correlate the crystal structures with the electron configurations of the atoms existing either in ground state or in an excited state of low promotion energy. The basic postulate of this theory is that whereas the contribution to the bonding of the metal comes from the interaction of both d and (s-p) electrons existing either independently or in hybridized states, the existing crystal structure is controlled by the (s-p) electrons alone. Specifically, a metal is supposed to crystallize in bcc, hcp, or fcc phase provided the metal has one, two, or three valence electrons per atom in the (s-p) configurations. The diamond, or ZnO and ZnS structures, occur with four (s-p) electrons per atom. Secondly, the contribution of d electrons to bonding is supposed to increase with atomic number

Jan 1, 1970

By Sidney Sigel, J. Gardner Brooks, Irvin R. Kramer

In 1942 Grossmannl proposed that the hardenability of a steel may be calculated from its chemical composition by considering the base hardenability associated with its carbon content and grain size and multiplying this base by factors for each element present. Since Grossmann's original publication, several investigaton2-6 have reexamined the multiplying factors for the individual elements and in general have found that the multiplying principle is valid. However, some of the individual factor curves developed have been in poor agreement. Inasmuch as the carbon-factor curve obtained by Grossmann was dependent Lipon the factors for all the other alloying elements present in the steel, it logically followed that his results were in need of correction in the light of the new data available for manganese, silicon, and the other alloying elements. Furthermore, in order to avoid the possibility that errors in the manganese, silicon, or other curves might influence the carbon-factor curve, investigation of iron-carbon alloys containing little or no manganese and silicon was necessary. That the effect of carbon on hardenability was greater than indicated by Grossmann is shown by a comparison of the diameters of completely hardened rounds of iron-carbon alloys with the ideal critical diameter calculated from Grossmann's factors. These alloys have a greater hardenability in a finite quench than predicted by Grossmann's factors for an infinite quench (Table I). Among the other important variables that were in need of further investigation were the effect of deoxidation practice on the grain-size correction curves and the effect of stable carbide-forming elements on the depth of hardening. Most Of the work by Kramer, Hafner, and Toleman4 was done on silicon-killed steels. It was not known whether Gross-mann's grain-size correction curves, determined on aluminum-killed steels, was valid when applied to steels with different deoxidation practice. More data on the

Jan 1, 1947

By J. Gardner Brooks, Sidney Sigel, Irvin R. Kramer

In 1942 Grossmannl proposed that the hardenability of a steel may be calculated from its chemical composition by considering the base hardenability associated with its carbon content and grain size and multiplying this base by factors for each element present. Since Grossmann's original publication, several investigaton2-6 have reexamined the multiplying factors for the individual elements and in general have found that the multiplying principle is valid. However, some of the individual factor curves developed have been in poor agreement. Inasmuch as the carbon-factor curve obtained by Grossmann was dependent Lipon the factors for all the other alloying elements present in the steel, it logically followed that his results were in need of correction in the light of the new data available for manganese, silicon, and the other alloying elements. Furthermore, in order to avoid the possibility that errors in the manganese, silicon, or other curves might influence the carbon-factor curve, investigation of iron-carbon alloys containing little or no manganese and silicon was necessary. That the effect of carbon on hardenability was greater than indicated by Grossmann is shown by a comparison of the diameters of completely hardened rounds of iron-carbon alloys with the ideal critical diameter calculated from Grossmann's factors. These alloys have a greater hardenability in a finite quench than predicted by Grossmann's factors for an infinite quench (Table I). Among the other important variables that were in need of further investigation were the effect of deoxidation practice on the grain-size correction curves and the effect of stable carbide-forming elements on the depth of hardening. Most Of the work by Kramer, Hafner, and Toleman4 was done on silicon-killed steels. It was not known whether Gross-mann's grain-size correction curves, determined on aluminum-killed steels, was valid when applied to steels with different deoxidation practice. More data on the

Jan 1, 1947

By Heinrich Freyn

THE American iron and steel manufacturer finds himself to-clay barely at the threshold of enormous possibilities for practicing rational economy in the use of fuels. The fuel cost is by no means the smallest of items which enter into the cost of manufacture of iron and steel products, but the great wealth of this country in high-grade fuels, together with a protective tariff, has heretofore made fuel economy relatively unimportant. In Germany, the use of raw coal for the purposes of iron and steel manufacture has been all but abandoned and large sums of money, formerly irrevocably wasted, are now being saved. When scanning the literature of this country devoted to the application of gas power, but little information will be found on a subject which, however, is destined to become of considerable importance in the United States, namely, the use of coke-oven gas for the generation of power in gas engines. This lack of information can be traced to the fact that the regenerative by-product coke oven with its large amount of surplus gas is still far from having attained in this country the universal application which it has found in Europe. This statement needs hardy any corroboration other than the evidence of statistical investigations made by E. W. Parker of the United States Geological Survey, according to which only approximately 25 per cent. of the total coke produced in this country in 1912 was made in by-product coke ovens, whereas 75 per cent. was produced in bee-hive ovens. This entailed the enormous loss of over $80,000,000 in non-recovered by-products, such as gas, tar, and ammonia, without considering the substantial loss due to the non-recovery of benzol from the coal. There are two more or less distinct fields of application of the by-product coke oven: one, to furnish as the main product metallurgical coke of specified quality, and surplus coke-oven gas as the by-product, and the other, to carbonize high-volatile coals, and thus produce as the main product large quantities of gas, high in heat value and rich in illuminants, adapted primarily for domestic heating and lighting, while domestic coke becomes the by-product.

Jan 4, 1914

[Abstmct of remarks by R. II. Sweetser arid suhscqueut discussion at the New York Meeting, February, 1926. The Transactions mill ultimately contain a report of work resulting from these discussions. Need for a standard of ualuration.—There should be an accepted method for evaluating the different kinds of bituminous coals based on their carbon just as that for iron ores is based on iron. Variation in the classes of coals and their desirability fol the different industrial uses is analagous to the case of iron ores. The iron people have developed a standard. In the past coals have not been intelligently distributed because the public has not been informed as to its uses. Many operators have known nothing about the final disposal of the coal shipped from their mines. Sales agents and retailers have had no means of evaluating coals except to make the price as high as the market will stand. Producers and distributors need to know how much more valuable the coals would be if prepared so as to contain less objectionable material. Mr. Swectser cnlletl on the Goal and Coke Committee of the Institnte to organize a study through producers and users to develop a method scientifically and comnereially sound E. A holbrook said that the information exists but the public is unwilling to investigate. He praised Ashley's1 nomenclature of the different kind of coal which has been accepted by the Coal Mining Institute of America and recommended to the American Enginecring Standards Commitee. G. S. Rice pointed out the wider variety and distribution of consumption of coal compared to Iron ore. C'. M. Young approved Mr. Sweetser's remarks and hoped lor a research institution, probably endowed, to study utilization of coal after it comes from the ground. Mr. Sweetser cited incidents to prove his former statements. He said that a reduction of 1 per cent. ash in the coal would cut down the cost of pig iron at a blast furnace 30 c. a ton, that the coal men should tell what the iron men would have to pay to get better coal. H. J. Prryn endorsed the need of blast-furnace operators to know the kind of coal from which their- coke is made and the latler's ash content, as this affects coke consumption. A. C. Fieldncr explained that the difficulty of evaluating coal on the basis of chermical analyses for calorimetric tests is: (1) representativr

Jan 1, 1927

By H. M. Warren, E. J. Powell, A. S. Biesecker

In the past, steam engines were used in practically all cases for driving the machinery in and about an anthracite breaker, and hence few or no accurate data were available as to the power requirements for starting and operating the individual machines, which make up the complete equipment. It was impossible to segregate the power necessary to drive each individual machine, first, because the equipment was driven in groups, and second, because it was impracticable to obtain graphic, integrated, or instantaneous records of the horsepower used. As a result of these conditions, it was found, when individual electric motors were applied to the various machines, that more accurate and complete data were needed in order to provide motors of the proper power and design for the particular services to be rendered. In order to obtain the desired information, the writers made and collected a number of tests, from time to time, on the individual motor drives in electrically operated breakers, and as these tests have been of great value, it occurred to them that a paper giving the results might be of service to other engineers interested in similar installations. Table I shows the results of these tests. All the motors tested were of the three-phase, 60-cycle, 440-volt, induction, squirrel-cage type, except a few, which, on account of size and starting conditions, were of the wound-rotor type. The instruments used in making these tests were: An integrating watt-hour meter, a graphic ammeter, and a graphic voltmeter. These instruments were connected in each motor circuit, and a record of a day's run of 9 hours was obtained from each machine. From these tests, the running light load, the average all-day load, and the instantaneous peak readings in amperes, volts, and kilowatt input, were obtained. By means of the characteristic curves obtained from these motors at the factory, the power factor, the efficiency, and the horsepower output were calculated for each particular test. Starting tests were made by the brake-arm method, in which the torque in pounds was measured directly on a spring balance.

Jan 1, 1916