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By AIME AIME

FEATURES of the second fall meeting of the Petroleum Division for 1941, held at the Ambassador Hotel, Los Angeles, Oct. 29-30, were the forum on the Paloma Plan on Thursday after- noon, the large attendance from east of the Rockies, and the dinner on Wednesday evening sponsored by the Southern California Section and at which President Suman spoke on the strategic minerals and metals situation. The attendance was large and the technical fare uniformly good ; the presiding officers had the proceedings well in hand at all times and kept things humming. Some- times it was necessary to taper off the discussion because of pressure on time. All this was due to careful groundwork before the respective sessions. These presiding officers deserve citation: L. W. Huebel, Howard Pyle, E. K. Parks, Carlton Beal, E. G. Trostel. R. W. French, Jr., John Dodge, and H. N. Marsh. The Los Angeles local commit- tees and the Southern California Section deserve much credit for the arrangements, which were recognized by suitable resolutions at the end of the meeting.

Jan 1, 1941

By DONALD H. McLAUGHLlN

Few factors have had more influence in maintaining the strength and stability of the United States than our persistent habit of providing .checks and balances to the dynamic powers of free enterprise on the one hand and to the controls and guidance exercised by the State on the other. .Indeed, it is this same concern for matching forces against each other that has given our republic its ability -to preserve a democratic basis of life for its citizens, and yet maintain a ,government that is able to protect the rights of all and to resist and minimize the danger of excessive concentration of authority. Our current efforts to clarify the nation's mineral policies and to define more clearly the role that the governmental agencies should play in conjunction with the functions of private -enterprise again reveal the desirability and advantages of maintaining our traditional controls. At times, the equilibrium has been temporarily disturbed by too great enthusiasm for one or the other of these basic concepts. Sooner or later, however, the balance has been restored by the healthy opposition that is always created by excesses of one sort. At the current stage in our history, the swing toward undue enlargement of the powers of the State seems to have gone dangerously far and we would be untrue 'to our traditional behavior if the group that must demonstrate the virtues of free enterprise did not rally to its support with the utmost earnestness.

Jan 1, 1949

By L. Delisle

This work represents the first step of an attempt to test the applicability of the electron microscope to the study of subgrain structures in copper. Observations on annealed and deformed single crystals and polycrystalline samples of copper are described. IN the course of study of the structure of fine tungsten wires and tungsten rods with the electron microscope, well defined subgrain structures were observed. The size, size distribution, and orientation uniformity of the etch figures varied widely in different samples. Figs. 1 and 2, electron micrographs of a tungsten wire and of a tungsten rod, respectively, are illustrations of the difference in size and size distribution of the etch figures in different samples of the same metal. The observed differences, as pointed out in a previous paper,' appeared to be related to the heat and mechanical treatments of the samples. They were also consistent with the results reported in the literature on the mosaic structure of metals.' For that reason a program of research was initiated in an effort to obtain more systematic evidence of the possible relation of heat and mechanical treatments to the subgrain structure of metals as observed in the electron microscope. The purpose of this paper is to present observations made on the effect of cold work on the subgrain structure of copper. Procedure Starting Materials: Copper was the metal studied because it can be obtained in a high degree of purity, much information is available in the literature on its properties and its response to cold work and heat treatment, it shows no allotropic change, and it is sufficiently hard to be handled without great difficulty. Two groups of specimens were used: 1—single crystals cast from spectroscopically pure copper and 2—polycrystalline samples of oxygen-free high conductivity copper. Single crystals were studied because it was hoped that the elimination of a number of variables, such as grain boundaries, orientation differences, degree of purity, would simplify the problem and perhaps permit a better understanding of the phenomena that would be observed. The polycrystalline samples were designed to give a general picture of the changes considered. The single crystals were made of copper which analyzed spectroscopically to better than 99.999 pct Cu. They were cast in vacuum, by the Bridgman method, in crucibles made of graphite with a maximum ash content of 0.06 pct. The mold design is shown in Fig. 3. It permitted casting crystals of the size and shape required for the experiments, so that the danger of introducing cold work in the original samples by cutting or other machining would be eliminated. The polycrystalline samples were pieces, 3/4 in. long, cut from a rod of oxygen-free high conductivity copper, % in. in diameter. A flat surface, 1/4 in. wide, was milled along the rods, polished, and etched. The samples were then annealed in vacuum at 850°C for 1 hr. Polishing and Etching: Work previously done on tungsten,' polished mechanically and etched chemically," had shown that: 1—the general appearance of the etch figures of a given sample was not altered by repeated polishings and etchings under similar conditions; 2—variations in the time of etching and the concentration of the etchant changed the definition of the etch figures, but did not alter their general size nor orientation distribution within the limits of observation. Further work confirmed the reproducibility of the subgrain structures observed in, 1—single crystals and polycrystalline samples of copper when polishing and etching were repeated under similar conditions, and 2—specimens of tungsten and polycrystalline copper when electrolytic polishing and etching were substituted for mechanical polishing and chemical etching, respectively. On the strength of these observations, it was felt that, if conditions of polishing and etching were kept constant, changes observed in the subgrain structure of a sample upon deformation and annealing would be attributable to such treatments. For that reason the conditions of polishing and etching were kept as constant as possible. The single crystals were polished electrolytically in a bath of orthophosphoric acid in water, in the ratio of 1000 g of acid of density 1.75 g per cc to 1000 cc of solution, under a potential drop of 1.6 to 1.8 V. Electrolytic polishing was selected to prevent the formation of distorted metal in polishing. The same samples were etched by immersion in a 10 pct aque-

Jan 1, 1954

By d&apos, K. Mukherjee, C. R. Antonio, R. J. Maciag, G. J. Fischer

Tensile data indicate that over the range of strain rates 10-5 to 10-1 sec-1 and in the temperature range 298° to 743°K the flow stress at a given temperature may be expressed as: C0 = Cem where m changes abruptly at a critical strain rate of 10-2 sec-1. The Zener-Hollomon parameter was tested and found to be invalid except at temperatures exceeding 700° K. Values of AH calculated for temperatures above 700°K ranged from 30 to 47.5 kcal per g-mole. ThE flow characteristics of aluminum and aluminum alloys as a function of temperature and strain rate have been of interest to various experimenters for many years. Trozera et al.1 determined tensile flow curves for pure aluminum and concluded that the combined effect of temperature and strain rate on the flow stress could be related using the Zener-Hollomon parameter. More recently, Hockett2 proposed a relationship between compressive flow stress, temperature, and true strain rate which could be represented by a surface. Holt et al.3 studied strain rate effects on flow stress in a number of aluminum alloys at room temperature. It was determined that there is a critical strain rate above which a strain rate effect is observed. It was also reported that the strain rate sensitivity was significant in aluminum alloys in the "0" condition only. In a recent review paper McQueen4 has considered a number of mathematical expressions which have been used to describe the relationship between stress, strain rate, and temperature. These expressions have been applied to the flow characteristics of a number of different metals and alloys including aluminum. In the present work the strain rate sensitivity of 7075-0 aluminum was determined in the temperature range of 298° to 743°K. The tensile flow stress at 0.2 pct offset was obtained over a nominal strain rate range of 10-5 to 10-1 sec-1. EXPERIMENTAL Threaded tensile specimens were cut from a single heat of 7075-T6 aluminum. The composition of this heat is given in Table I. The test bars had a gage section 1.5 in. long by 0.250 in. diam and conformed to ASTM specification E-8-57T. After machining, the bars were annealed at 413° ± 10°C for 2 hr. They were then cooled to 260°C in 3 hr, and finally air cooled to room temperature. This treatment is commonly used to produce the "0" condition. Load-time curves at constant crosshead speeds were obtained at various temperatures using an Instron testing machine. Crosshead speeds ranged from 0.002 to 40 in. per min. A three-zone resistance tube furnace was used for the elevated-temperature tests. Temperatures were measured at three points along the gage length by means of suitably placed thermocouples. Each tensile bar was held at temperature for 30 min prior to testing and the maximum temperature variation along the gage length was kept below 1°C. In all, 275 samples were tested and each data point plotted is an average of at least two tests. In many cases the point represents up to six tests. RESULTS AND DISCUSSION Values of the flow stress at 0.2 pct offset at six different temperatures are plotted vs strain rate on log-log coordinates in Fig. 1. Over discrete ranges of strain rate, the data for each temperature fit the expression:

Jan 1, 1969

By Koert D. Burnham, John G. Broughton

WOLLASTONITE in Essex County, New York, occurs as a typical contact mineral in a series of rocks metamorphosed by anorthosite. Sole current use is in various types of electric welding fluxes. Its uniform lathlike shape suggests its use as a specialized filler.

Jan 1, 1944

By Edward B. Hughes, Frank G. Norris

OXIDATION is characteristic of all processes for making steel from pig iron. This thought has been aptly expressed by H. W. Graham13 in the most recent Howe Memorial Lecture, "The process of steel-making consists of using iron oxide to reduce the carbon content of the pig iron to the desired level." Direct oxidation refers to the reaction that results from introducing oxygen either alone or mixed with other gases directly into the steel bath. In working a heat, oxygen in some form is added to the steel to remove the undesirable constituents as oxides. There are two general methods of supplying this oxygen to the open hearth bath. The method in which the oxygen is added as a, compound such as C02-or iron ore is designated an indirect method because the steel bath must first decompose the compound to attain oxygen in a usable form. The other method in which oxygen is added to the bath in the elemental or gaseous form, more or less diluted by other gases such as nitrogen, is a direct, method because no decomposition is necessary before the oxygen reacts with iron to form FeO which is dissolved in the bath in a usable form. Bubble formation (at least of a macroscopic size) presents no problem in case of direct oxidation because the reacting agent (oxygen) is in the form of bubbles when entering the metal. Regardless of whether oxygen is introduced into the bath directly or indirectly, several reactions proceed concurrently. In the presence of the bath of molten iron, FeO is formed either by oxidation of iron by oxygen or reduction of oxides by iron. This FeO dissolved in the molten iron is the source of oxygen for the oxidation of manganese, carbon, silicon, and phosphorus if these are present. The oxidation of carbon from steel is the controlling steelmaking reaction. The introduction of oxygen into the bath, its reaction in the elimination of impurities, and its control by the use of de-oxidizing additions have been subjects of importance since steel was first made by the bessemer process. Direct oxidation is, in a sense, an application of the bessemer principle to the open hearth process. Graham13 states: "The use of oxygen or air jets introduced into the metal bath is essentially an effort to approach in the open hearth the turbulence, rapid interface reaction, and high production rate per hour that exists in the bessemer process." The general subject, "Oxygen in Steelmaking," was given new life by the studies of Herty and associates starting about1925. The current interest in elemental oxygen is intimately related to the large scale production of oxygen developed during the war period. Some of the first applications were made during the early summer of 1946 at the Steel Co. of Canada using oxygen with the fuel. Such a use is of considerable interest and importance in contributing to faster heats but is not the subject of the present discussion which deals entirely with the introduction of elemental oxygen directly into the open hearth bath. A recent article12 reviewing the current

Jan 1, 1948

By A. R. Marder

Fe-C alloys have been investigated at temperatures below the eutectoid transformation to determine whether the superplasticity phenomenon exists for these materials. As a result of void formation at the carbide-ferrite interfaces that led to void coalescence and premature failure, the large elongations characteristic of superplustic matem'als did not develop. It had generally been assumed that the conditions for obtaining superplasticity include: a) T/Tm =0.5, b) a strain rate sensitivity of the flow stress that results in m s 0.3, and c) fine-grain structure. Although superphsticity was not observed in the alloys studied, stress-strain rate measurements indicated that an additional condition for the existence of superplasticitv in Fe-C allovs is that the fine-wain structure be equiaxed in agveement with previous results on Zn-Al al1oys. MANY investigations have been made on the hot deformation of iron-base alloys in order to obtain an understanding of the variables that may affect high-temperature strength and ductility.'-6 However, only a few papers have studied the effect of carbon content on the high-temperature properties of iron-base alloys. Peretayat'ko and Zaikov and Wallquist and carlen4 studied the effect of carbon on strength in the y temperature range, and recently Robbins, Shepard, and sherby6 studied the influence of carbon on the torsional behavior of iron in the a and cu-plus-cemen-tite temperature ranges. In addition to studying hot deformation behavior, current investigations have also been concerned with the phenomenon of superplasticity in nonferrous materials, and, in particular, ferrous alloys. Superplasticity is identified by the increased resistance to necking that results from a high strain rate sensitivity of the flow tress. ackofenr proposed the strain rate hardening coefficient m = d log a/d log e as a measure of strain rate sensitivity and showed that m must be "-0.3 for superplasticity to exist. In addition, a fine-grained microstrcture,- a eutectic or eutectoid ornosition,- and a test temperature in the creep range (TITm > 0.5)" have also been advanced as necessary conditions for superplasticity. Although many workers""23 investigated superplasticity associated with the allotropic transformation in iron and the eutectoid transformation in steel, and recently chadler " and orrison have studied superplasticity in the a - y phase region, no one has measured the superplastic effect in the a + cementite temperature region. Therefore, the purpose of this investiga- tion was to determine the effect of carbon content, microstructure, and test temperature on the strain rate sensitivity of Fe-C alloys at temperatures below the eulectoid transformation. EXPERIMENTAL PROCEDURE Fe-C alloys with carbon contents of 0.2, 0.4, 0.6, 0.8, and 1.0 wt pct were prepared as 100 lb 54 in. ingots by vacuum-induction melting. The compositions are listed in Table I. All the ingots were soaked at 2100°F for 2 hr prior to rolling to 4 in. plate. The minimum finishing temperature for rolling was 1800°F. The plate was sheared in 10-in. lengths and tensile bars were rough-machined prior to heat treatment. The samples were heat-treated according to the schedule in Table I1 in order to obtain a fine-grained microstructure consisting of finely dispersed carbides in a matrix of small ferrite grains. All the tensile specimens were heat-treated prior to finish machining, and tensile testing was accomplished on an Instron machine in conjunction with a clamshell furnace. The buttonhead specimen configuration is shown in Fig. 1. An inert atmosphere, helium, was maintained during testing with a steel tube shroud in a bell jar arrangement. Predried helium was continually purged over the buttonhead specimens and exhausted through ceramic fiber at the bottom of the tube to keep oxidation at a minimum and to prevent

Jan 1, 1970

By J. D. Sullivan, Chester R. Austin, J. L. Nunes

IT is characteristic of most shales and surface clays that a bloated or vesicular structure is produced by burning to a sufficiently high temperature, usually about 150° to 200°F. above the normal maturing temperature used when making common brick of the same material. Early investigators recognized this phenomenon and attributed it to the release or expansion of gases in the vitrified piece. A number of theories have been advanced on the source of the gas and the manner in which it is evolved, but none has been proved conclusively. T. E. Jackson's1 early theory that bloating was due to oxygen evolved by ferric oxide in forming ferrous oxide or ferrous silicate was never substantiated by experimental work. Orton2 thought this explanation unlikely, as all clays should bloat at the same temperature, if this were true. He found that clays bloated in the range from 1100° to 1706°C. Also, many clays containing iron did not bloat at all, but fused. Orton also stated that oxidation of different types of carbon was a source of gas during burning of clay and should be expelled before vitrification was reached. Seger3 said that he had dissolved ferric oxide in glass with no apparent evolution of gas. Matson4 came to the conclusion that ferruginous days burned to vitrification in an oxidizing atmosphere did not have the iron in a ferrous form. According to Wilson,5 the gases responsible for bloating might be entrapped air, water, sulphur dioxide, carbon monoxide, oxygen, and hydrocarbons. He spoke of two causes of bloating: (I) incomplete oxidation below the vitrification temperature, and (2) decomposition of compounds and evolution of gases above the vitrification temperature. Decomposition of calcium sulphate was given as the principal example of the latter. Bleininger and Montgomery6 stated that if any time after vitrification began the evolution of gaseous matter was rapid enough so that pressure was produced within the day, bloating was certain to take place, and a vesicular structure would be formed. They recognized that initial structure, rate of heating, kiln atmosphere, and many other variables affected bloating. Work done by the Emergency Fleet Corporation7 indicated that clays suitable for bloating should be high in compounds of metallic oxides, carbon, sulphur, sodium, potassium, or other equivalent compounds, which either act as a flux or give off gas. Orton2 studied the chemical status of the carbon, iron, and sulphur in clays during various stages of burning, using a Huron shale that bloated under oxidizing or reducing conditions. He found that only a small amount of sulphur remained in the clay and that it could be detected only by dissolving the clay in hydrofluoric acid; i.e., the sulphur was in combination with the silica. Orton said that this sulphur was probably in the form of iron sulphide dissolved in the glass phase. The iron sulphide was not broken down by heating, but was dissolved in the basic slag or glass,

Jan 1, 1942

By Ross Blake

THE St. Joseph Lead Co. became interested in the Tri-State district in 1921 through acquisition of prospecting and development rights on approximately 20,000 acres of land extending northeastward from the Picher mining field, mostly in Kansas. Prospecting with churn drills was begun the same year and the first commercial ore body was found on the Jarrett tract at the then northern limit of the main Picher field. Operations at this mine began in 1923. Kansas Explorations, Inc., was organized in 1923 by the St. Joseph Lead Co. as a wholly-owned subsidiary to carry on its operations in the Tri-State District from an office at Joplin, Mo. As prospecting of the original acreage proved largely negative, attention was subsequently turned to other sections of the district. Numerous additional leases were acquired and prospected. The Company was successful in developing into operating properties the Jarrett, Isherwood, Robinson, Sullivan and Lotson tracts and, in more recent years, the Ritz, Snapp, Buckingham, Gibson and Jasper mines.

Jan 1, 1947

By J. M. Smith, D. Kunii

Effective thermal conductivities of sandstones filled with stagnant fluids were measured using a steady-state technique. Data were obtained for seven sandstone samples, taken from four different locations and ranging in permeability from 18 to 590 md. The measurements with gases (helium, nitrogen, air and carbon dioxide) covered a pressure range from 0.039 psia to 400 psig. Data were taken for four liquids — n-heptane, methyl alcohol, 79.8 weight per cent glycerol-water solution and pure water at atmospheric pressure. The experimental results were used to evaluate the theoretical equations for predicting stagnant conductivities developed earlier 4 The low-pressure measurements permitted evaluation of the consolidation parameter bpDp/ks (necessary to utilize the theory) for the various types of sandstones. Using these characteristic values, the tbeoretical equations correlated well with the experimental conductivity data for the several fluids and rock samples. INTRODUCTION An aspect of heat transfer in solid-fluid systems of considerable current interest is the effective thermal conductivity of porous media. The stimulus for study of the subject arises from the need for sound procedures for designing thermal methods of petroleum production. The general system occurs when there exists a flow of fluid through the pores of the solid material. However, a logical starting point in developing a theory for predicting the effective thermal conductivity in the general system is to attack the special case when the porous solid is filled with stagnant fluid. Since the flow rates anticipated in thermal production processes are very low, such stagnant conductivities k,O are also of practical significance. Kunii and Smith4 recently reviewed the existing data for stagnant conductivities and proposed a theory for heat transfer in porous rocks. This leads to equations for predicting the stagnant conductivity as a function of the properties of the fluid and solid phases. The existing experimental information1-3,5,7,8 covered a range of porosities and agreed well with the theory. However, the available data were insufficient to examine critically the effects of two important properties on koe, — the thermal conductivity of the fluid and the pressure. The objectives of the present study are twofold: (1) to measure the effect on koe of (a) the pressure for gases, and (L) the thermal conductivity of the fluid kg for bloth gases and liquids; and (2) to determine for rocks of different porosities and permeabilities the apparent solid conductivity ks and the consolidation parameter bpDp/ks required in applying the theoletical equations. Measurements extrapolated to zero pressure are helpful in evaluating ks and the consolidation parameter. However, the extrapolations must be based upon data obtained at low pressures because in small pores the molecular conductivity of the fluid may be unusually depressed. This occurs when the mean free path of the molecules is of the same order of magnitude as the pore diameter, that is, in small-diameter pores at low pressures. The phenomenon has been studied recently by Schotte6in beds of unconsolidated fine particles. With particles in the size range of 45 to 200 microns, a significant reduction of kg with pressure was found even at absolute pressures greater than 1 atm. In the sandstones employed in the present investigation, pore diameters lower than those experienced by Schotte are likely, so that the effect would presumably be greater. SCOPE OF MEASUREMENTS Stagnant conductivities were measured for four types of sandstones using a total of seven samples. The characteristics of the samples, including porosity and permeability values, are given in Table

By M. Kaufman, D. Rosenthal

IT would be of great importance to our understanding of the phenomena of fracture in metals if a unique relationship could be established between stress and some easily measurable parameter of deformation up to the fracture. It is known that no such relationshir, has been found when the parameter was the mechanically measured strain,' the major part of which is plastic. The present investigation was initiated to determine, among other things, if the X-ray or lattice strain" might be a • For the definition of lattice strain see ref. 2. more suitable parameter. To this end, annealed stress free*' specimens of 61s aluminum alloy were ** Freedom of stress in this particular case means absence of those stresses which can be checked by the technique employed. tested at room temperature and liquid nitrogen temperature (—195OC), by first maintaining the same temperature from the beginning until the end of the test, and then with crossovers from one temperature to the other. Three major factors had to be taken into consideration in designing the specimens and testing equipment. The test setup must allow X-ray pictures to be taken while the specimen is under load (for as much as 2 hr at a given load). Provision must be made for maintaining the test specimen at the temperature of liquid nitrogen as well as at room temperature. In addition, the specimen must be able to rotate to allow the X,ray beam to take in as large a sample of grains as possible, to maintain centering, and to correct for effects of large grains. The final design of the specimen and equipment is shown in Figs. 1 and 2. The specimen and grips are hollow, enabling liquid nitrogen to be poured in through a funnel-container arrangement while the specimen is rotating. The diameter of the specimens at the 2 in. gage section is 5/16 in. with a 3/16 in. diameter hole through the center. A small pilot valve in the lower grip allows a very small stream of liquid nitrogen to escape, thus assuring circulation of the liquid at all times. A low temperature silicone grease-tissue paper packing is used to seal all joints. The specimen is held in the grips by a pin. Spherical socket joints at top and bottom are used to allow for proper alignment. The grips are connected to the thrust bearings by means of plastic couplings to decrease the heat flow. Rotation is accomplished by means of a motor which drives a plastic gear (integral with the lower coupling) through a semiuniversal joint to allow for deforma- tion of the specimen. The torque applied to the specimen is very small. The maximum stress caused by this torque at the highest loads reached was found to be less than 200 psi, The whole unit was mounted in a 10,000 Ib testing machine. An insulation cage was placed around the specimen to cut down air circulation, and consequent frosting of the specimen, and also to reduce radiation and convection heat losses. A narrow window, covered on both sides with a thin plastic materiai allows the X-ray beam to reach the specimen. Thermocouples placed just outside the pilot hole at the lower grip, in the bottom of the funnel container and near the top of the funnel container permitted checks of the

Jan 1, 1955

By A. H. Daane, J. J. Hanak, F. H. Spedding

IN the study of the rare earths at the authors' laboratory, methods have been devised for preparing pure rare earths and many of their properties'- have been determined. Very little information is found in the literature on the properties of europium metal, which is the scarcest of the naturally occurring rare earths. Since we have recently prepared europium in appreciable quantities, we are in a position to describe the method of preparation and some of the properties of this metal. Metallic europium was first prepared by Klemm and Bommera who heated a mixture of potassium and EuC1, in vacuo, and obtained a mixture of europium metal and KC1. Trombe4 electrolyzed a molten salt bath containing NaC1, KC1 and EuC1, and collected the europium in a molten cadmium electrode as a cadmium alloy. The cadmium was subsequently removed by distillation but the properties of the residue indicate that pure europium was not obtained. McCoy attempted to prepare europium by distilling mercury from europium amalgam, but the stability of the Eu-Hg intermetallic compounds prevented a complete separation of the two elements. The preparation of very pure europium was suggested by previous work in this laboratory1,4 in which ytterbium and samarium were prepared by heating the respective sesquioxides with lanthanum metal turnings to 1450°C in vacuo and distilling ytterbium and samarium from the mixtures. Subsequently, small test experiments showed that europium also could be prepared by this method. A more detailed version of this method was used in the work described in this paper. Klemm and Bommer3 found by X-ray analysis that the metal had a body-centered cubic (bcc) structure with a lattice constant a, = 4.582 ± 0.00A (converted from kX units), with a bulk density of 5.30 g per cu cm. They found europium to be weakly ferromagnetic. Spedding, et al,7 found a,, to be 4.606 ± 0.001A. Barrett' showed that the bcc structure persists throughout the temperature range 5 to 3000K with a, at 5, 78, and 300°K being 4.551 ± 0.003, 4.551 ± 0.004 and 4.577 ± 0.001A, respectively. Trombe1 described europium as being iron gray, malleable, about as hard as neodymium and not attacked by cold water. He estimated the melting point to be between 1100 and 1200°C. Previous work in this laboratory indicated that the pure metal corrodes rapidly in air and reacts with cold

Jan 1, 1959

By K. T. Aust

It is proposed that the intergranular corrosion of austenitic stainless steels is associated with the presence of continuous grain houndary paths of either second phase, or solute segregate resulting from solute-vacancy interactions. Experimental observations of structural changes and crrosion behavior of different types of austenitic stainless steel provide support for this poposal. On the basis of this model, it is shown that the intergranular -corrosion susceptibility of austenitic stainless steels in nitric-dic hromate solution may be substantially reduced either by suitable heat treatments or by impurity control. AUSTENITIC stainless steels, such as Type 304, generally have excellent corrosion resistant properties when properly solution heat-treated and used at temperatures where carbide precipitation is slow. However, several corrosion environments have been found which produce intergranular corrosion of solu-tion-treated stainless steels, that is, those steels with no detectable carbide precipitation.''2 Of the various corrosion environments, the most widely used test solution has been the boiling nitric-dichromate solution. In these acid solutions, stainless steels have been found to be susceptible to intergranular attack despite the addition of carbide-forming elements such as titanium or columbium, or despite lowering of the carbon content or use of high-temperature solution treatments. Studies of the electrochemical mechanism of corrosion attack have been made by several worke1s3'4 who found that oxidizing ions such as crt6 depolarize the cathodic reactions and consequently raise the open-circuit potential of stainless steel immersed in nitric acids. As a result of this, the anodic reaction is accelerated. The reason for the localization of anodic activity at the grain boundaries, and resulting intergranular corrosion, has not been conclusively determined. Several workers, e.g., Streicher,3 and Coriou et al.,4 have suggested that the strain energy associated with grain boundaries provides the driving force for the accelerated intergranular corrosion. This argument would predict that alloys of high purity would still be susceptible to intergranular attack. However, work by chaudron5 and by ArmijO,6 has shown that high-purity alloys are immune to attack, in disagreement with this argument. An alternative suggestion is that chemical concentration differences exist between grains and grain boundaries, that is, impurity segregation at boundaries, and that these chemical differences provide the driving force for localized attack. It is this impurity segregation which can lead to accelerated dissolution of grain boundaries when the alloy is exposed to a suitable corrodant. This mechanism would predict the immunity of high-purity alloys to inter-granular attack, which is in agreement with experi-mental observations. In the present paper, some recent studies on inter-granular corrosion of austenitic stainless steels which were conducted by coworkers and myself will be re-tibility A simple model will be described in which it is proposed that the intergranular corrosion of aus-tenitic stainless steel is associated with the presence of continuous grain boundary paths of either second phase or solute-segregated regions.* On the basis of this model, it is suggested that the intergranular corrosion rate can be markedly reduced by the formation of a discontinuous second phase at the grain boundaries if the discontinuous second phase incorporates the major part of the segregating solute, drained from the grain boundary region. Results are presented of corrosion tests and electron microscopic studies of different types of austenitic stainless steel after various heat treatments which provide experimental support for this model. Finally, a solute clustering mechanism, based on a solute-vacancy interaction, is shown to be consistent with the results obtained for inter-granular corrosion of solution-treated austenitic stainless steels. EXPERIMENTAL Corrosion tests using weight loss measurements were made on sheet specimens, which were lightly electropolished, washed, and immersed in boiling (115°C) 5 N HN03 containing 4 g crt+6 per liter added as potassium dichromate. Studies in which the inter-granular penetration depth was measured both by electrical resistance and metallographic methods have shown an empirical correlation between the rate of intergranular penetration and the weight loss per unit time for identically treated specimens of stainless steel." As a result, although all the corrosion data reported here are in terms of simple weight loss measurements, these data are considered to reflect primarily the rate of intergranular dissolution. Fig. 1 shows a typical result of intergranular attack of a solution-treated Type 304 stainless steel after 4 hr in a boiling nitric-dichromate solution. The wide grain boundary grooving at the surface, and the attack at incoherent twin boundaries, are evident; very little corrosion attack is seen at the coherent twin boundaries. INTERGRANULAR CORROSION MODEL

Jan 1, 1970

Jan 1, 1963

By J. Chipman, N. J. Grant, R. Rocca

Desulphurization of liquid iron by reducing slags of the electric-furnace type was studied from 65 heats. Variations were made in basicity over a wide range and in FeO up to about 5 pct for their effects on desulphurization. The role of FeO in desulphurization from the blast furnace, to the electric furnace, to the oxidizing conditions of the open hearth is shown to fit a relatively simple pattern of behavior. THE mechanism which controls the desulphurization of molten iron by basic slags has been the object of several investigations. In particular, equilibrium determinations have been made both in the field of basic open-hearth slags, which have a high iron-oxide concentration, and in the field of blast-furnace slags which have a very low iron-oxide concentration. In both cases the desulphurization ratio has been found to increase with increasing basicity of the slags; however, the mechanism of desulphurization differs in the two cases. In basic open-hearth slags desulphurization occurs mainly as a partition of iron sulphide:&apos; FeS * (FeS) and the desulphurization ratio is approximately independent of iron-oxide concentration in the slag. In blast-furnace slags the concentration of iron oxide is very low as a result of the highly reducing conditions in which they are formed. The controlling reaction for desulphurization is then:2,3 FeS + (CaO) <=* (CaS) + (FeO) The slags of the reducing stage in the electric furnace have an iron-oxide concentration which is intermediate between blast-furnace and open-hearth slags. The study of the mechanism of desulphurization for these slags has been the object of this investigation. The importance of low (FeO) in the slag for desulphurization was first verified by Bardenheuer and Geller,& who found that high desulphurization ratios were obtained in highly reduced slags. It was recognized" hat iron oxide in the slag becomes a controlling factor in desulphurization only at FeO concentrations approximately under 5 pct. A recent investigation conducted by Buehl,7 upon the suggestion of one of the authors, confirmed this opinion from the results obtained from a heat conducted in a small arc furnace. In the present investigation, slags of very high basicity, such as often are encountered in the basic electric furnace, could not be studied, but equilibrium data have been obtained for slags in a wide basicity range. The iron-oxide concentration in these slags ranged from 0.08 to 15 pct and was controlled by the addition of silicon to the metal. Other constituents of the slags were mainly CaO, MgO, SiO2, A120,, and CaF,. The experimental technique was essentially the same as that of previous investigations.1 8-lo In an open magnesia-lined induction furnace, 65 lb of Armco ingot iron was melted. An atmosphere of hydrogen was maintained over the melt for 1 hr to bring the carbon content down to approximately 0.010 pct maximum. The bath then was exposed to air for 25 min to remove hydrogen. The electrodes were put in place, and the furnace was operated from this point on in an atmosphere of nitrogen. A synthetic slag was added to which additions of silicon and iron sulphide were made. A rate study conducted at the beginning of this investigation had

Jan 1, 1952

By C. S. Smith, L. H. Beck

KNOWLEDGE of the Cu-Zn constitution diagram was critically examined in 1944 by G. V. Ray-nor,1 who suggested the diagram reproduced in Fig. 1 as the best evaluation of available data. No pertinent work on the constitution has been published since that time, although a number of authors have discussed transformation kinetics and theory. Despite the large amount of work that has been done on the constitution of these industrially important and scientifically interesting alloys, minor uncertainties still exist. For example, it is still not possible to say definitely whether a two-phase region exists between the ordered and disordered forms of the 8 phase. A careful re-examination of the phase boundaries in this part of the diagram was therefore undertaken. Two methods were selected for the new investigation—quantitative metallography for the higher temperatures and precision lattice parameter measurement for lower temperatures. Because of the relatively narrow two-phase regions flanking the ß phase in these alloys, quantitative metallography is particularly suited for their examination, since the relative amounts of the two phases are very sensitive to their compositions. The method, however, is useless below about 350°C because of the inadequate resolution of the two constituents. Below 400°, however, the X-ray diffraction method is applicable, although it is of somewhat lower sensitivity in this system. The changes of composition that occur during quenching from above about 500°C entirely vitiate X-ray measurements at room temperature though they do not affect metallographic area measurements. The two methods overlap and supplement each other admirably. Both methods depend on the attainment of equilibrium composition of the two phases in a more or less intimate mixture and thus avoid the difficult problems of nucleation and long range diffusion involved in the conventional metallographic bracketing method. The alloys were melted from a master alloy made from re-electrolyzed cathode copper and Horsehead 99.99 pct Zn. Melting was done under a cover of either borax or charcoal and the alloys cast into a 7/8 in. sq graphite mold for the a-ß alloys or a 3/8 in. diam cylindrical graphite mold for the ß-? alloys. The a-ß alloys were rolled at 750°C to 5/8 in. sq; annealed for 24 hr at 800°C and quenched; then rolled and swaged at 200°C to 3/8 in. diam rods, annealed 24 hr at 200°C, quenched and cold rolled 2 pct reduction. This treatment was intended to obtain a small grain size and to produce many nuclei of the minor phase for growth on subsequent heat treatment. The unworkable ß-? alloys were given preliminary treatment by sealing in Vycor tubes in vacuum and annealing for 4 hr at 800°C followed by cooling in air. Samples of homogenized alloys were checked spectrographically for impurities, but the principal components were determined on samples subsequent to heat treatment. The impurities analyzed averaged approximately as follows: Ag, 0.0002 pct; Fe, 0.004; Si, 0.0008; Cd, 0.005; Mg, 0.0002; and Pb, 0.002. For metallography, samples of appropriate composition were cut into rods 5/8 in. long, sealed in pyrex tubes in vacuum and annealed for eight weeks at temperatures of 470°C and below, two weeks at 480°, 500°, and 600°C, and 4 hr at 700°C, followed by quenching in cold water. Temperatures were accurate to ±2°C. The cylinders were then machined to 8.7 mm diam and a slice weighing 1.5 g cut with a thin saw transversely from the center of each. This

Jan 1, 1953

By T. P. Papazoglou, N. A. D. Parlee, W. C. Phelps

PRACTICAL designs for good "home made" molybdenum furnaces are hard to find in the literature. The one described briefly below left something to be desired but was good enough to operate as a rather long (30 in.) two-zone furnace for periods of over 2 months at temperature (1400° to 1600°C) without shutdown. The principal problem in our application was to establish a temperature profile with two distinct constant-temperature zones and no dip between the zones. This and other problems mentioned below would not arise, however, if both zones were operated at the same temperature and if a shorter furnace were acceptable. Since molybdenum windings oxidize very rapidly when heated in air, impervious refractory tubes were used for both the furnace core and the outer jacket tube shown in the accompanying figures. A protective atmosphere of forming gas (10 pct H2, 90 pct N2) was continuously passed through the gas-tight annular volume between the core and outer jacket. The water-cooled copper ends shown in Figs. 1 to 3 sealed the ends of the tubes. Annealed molybdenum wire (40 mil) was wound on the recrys-tallized alumina core (35.5 mm OD by 28.5 mm ID by 30 in.) at a spacing of 0.36 in. The spacing was reduced to 0.29 in. close to the ends to partially compensate for end heat losses. Fig. 2 shows two molybdenum-ground lead taps off the center of the winding to produce the two independect temperature zones. The ground lead was insulated with 1/4-in. alumina tubing and connected to the grounded copper end by passing the wires through the gas port tube and crimping each wire into notches cut at the mouth. To prevent sagging of the core at high temperatures, refractory "troughs" were cut from alumina and mullite tubing to cradle the core. The support "troughs" which were 6 in. long and located about 5 in. from each end of the annular volume also served as radiation shields. In view of the different expansion coefficients and operating temperatures of the core and outer jacket (3.5 in. OD by 3 in. ID by 30 in.), the ends of the tubes were smoothed and squared to produce good sealing surfaces, and the core was ground 1/32 in. shorter than the outer tube. The power terminals were passed through their respective conductor ports which were internally lined with alumina tubing and sealed with Armstrong adhesive A-6 leaving about 1 in. of protruding lead wire for external connections. (Adhesive A-6 is a two-component system consisting of an epoxy-type resin with a mineral fibrous filler and an amine catalyst.) Figs. 1 and 3 show the entire assembly of concentric refractory tubes, copper ends, and sealing o rings, held together with two brass flanges and 3/8-in. bolts with heavy springs for dimensional flexibility. The furnace shell (19 by 19 by 30 in.) consisted of a steel frame with sheets of transite forming a box. The copper ends protruded through two 3.75-in. circular holes cut at the center of each transite square end. Thermal insulation next to the transite exterior was effected by K-23 B&W bricks alld in a central volume of approximately 9 by 9 by 30 in. a row of K-30 bricks was lined up to support the hot assembly. The rest of the volume around the outer

Jan 1, 1965

By Avnulf Muan, P. V. Riboud

The effect of Cr2O3 on melting relations of iron oxide at oxygen pressures slightly above those prevailing in contact with metallic iron has been determined. Liquidus and solidus temperatures of wüstite are raised by the addition of Cr2O3, from 1385°C for pure iron oxide to 1420°C at the peri-ledie point where wüstite, iron chromite, liquid, and gas coexist in equilibrium under the atmospheric conditions used in the present investigation (CO2/H2 = 1). It has been shown in a previous investigation1 that the liquidus and solidus temperatures of iron oxide are drastically increased by the addition of Cr2O3 under the relatively oxidizing conditions prevailing in air. This is to be expected in view of the easy substitution of cr3+ for Fe3+ in crystalline oxide structures which are stable at high oxygen pressures, as demonstrated for instance by the completeness of the solid solution series Fe2O3-Cr2O3 at high temperatures (>1000°C). The stable phase of iron oxide at oxygen pressures approximating those prevailing when metallic iron is present is wüstite. This phase, although commonly represented by the simplified formula FeO for sake of convenience, in reality has a defect structure in which a part of the iron ions are present as Fe3+. It is to be expected that at least a limited amount of cr3 ions will substitute for Fe in this structure when Cr2O3 is added to wüstite. Depending on the ease of this substitution in comparison with that of cr3 substitution for Fe in iron oxide-Cr2O3 liquids under the same atmos- pheric conditions, the liquidus and solidus temperatures of wüstite may increase or decrease upon addition of Cr2O3. The methods of establishing these melting relations and the results obtained are presented in the following. I) EXPERIMENTAL METHOD 1) General Procedure. The quenching technique was used in this study. Oxide mixtures were heated at chosen constant temperatures in an atmosphere consisting of equal parts of CO2 and H2 until equilibrium was established among gas and condensed phases. The samples were then quenched in mercury to room temperature, and the phases present were determined by microscopic and X-ray investigation. 2) Preparation of the Mixtures. Starting mixtures were prepared by weighing and thoroughly mixing Fe2O3 and Cr2O3, or wüstite and Cr2O3. The Fe2O3 and Cr2O3 used were "Baker Analyzed" reagent grades, whereas wüstite of composition was synthesized by reducing Fe203 at 1325°C in an atmosphere consisting of equal parts of CG andHz. In order to avoid contact with crucibles, the equilibration runs were made with small pellets suspended from thin (-0.004-in.) platinum wires. Mixtures made from FOs and Cr203 were readily pelletized at a pressure of 500 atm in a 9.5-mm die, whereas mixtures made from wüstite and Cr203 when treated identically were too weak for handling. In order to obtain a stronger product, these pellets were sintered by heating for 2 min at -1200°C in the same atmosphere as was subsequently used for the equilibration runs (CG/H2 = 1:1). During the sintering, these pellets were wrapped in thin (0.0004-in.) platinum foil, which was stripped off before the equilibration runs. In order to reduce the time needed for equilibrium to be attained, preliminary equilibration of relatively large pellets of each mixture was carried out at -1200°C for 4 to 12 hr. Smaller pellets

Jan 1, 1964

By C. C. Herrick

The vapor pressure of indium has been measured by the torque-effusion technique, as a function of temperature between 1102o and 1422oK. For liquid indium, the vapor pressure (in atmospheres) can be represented by the equation -R In P = 5.782 x104/T - 25.29from 1000o to 1422oK. Extrapolation yields a calculated normal boiling point of 2329°K and a heat of vaporization at 298 oK of 58.09 kcal per mole by the third-law method and of 58.39 kcal per mole by the second-law method. Calculations indicate that the free-energy functions of Hultgren are to be preferred to those of Guruich. BECAUSE of the potential uses of liquid metals, it is important that convenient experimental methods be developed which will lead to a sufficient body of thermodynamic data so that reasonable estimates of properties of liquid metals can be made. Indium is particularly well-suited to investigation, since it remains liquid over a long temperature interval, it alloys readily, suitable containers for it are easily procured, and relatively few investigations of its thermodynamic properties in the region above 1000°K have been made. PREVIOUS RESEARCH The first determination of the vapor pressure of indium was made by Anderson,&apos; using the Knudsen method and silica-lines stainless-steel cells. Kohlmeyer and spandau2 determined the normal boiling point, and a mass-spectroscopic investigation has been made by Lyubimov and Lyubitov.3 (Unfortunately, only an equation representing the data of the latter investigators has been available to us.) Hultgren et al.4 and Gurvich5 have published discordant tables of the free-energy functions for indium. EXPERIMENTAL METHOD The torsion-effusion principle has been described amply in the literature.8,7 With this method, one observes the angular deflection induced by effusion of vapor from a multihole effusion cell which is suspended from a filament producing a small rotational restoring force. The pressure within the effusion cell can be computed from the relation ziaifiai where k is the torsion constant of the filament, 6 is the observed angular deflection, and ai, fi, and qi are the area, force factor, and moment arm of the ith effusion orifice. The force factor f is analogous to the Clausing factor,&apos; and corrects for the reduction in effusive force attributable to the finite geometry of the effusion orifice. Schultz and Searcy&apos; have tabulated the force factors for various tube geometries. EXPERIMENTAL APPARATUS The physical arrangement employed in this study is shown in Fig. 1. The furnace elements are six Globar heat rods with 15-in. hot zones. Temperature is maintained to * 1°K by a Beck mechanism driving two 26-amp Powerstats in parallel. A Pt (Pt, Rh 10 pct) thermocouple serves as the sensing element. Four inner tubes act as vibration isolators; the air pressure required for maximum isolation was determined empirically, and is maintained by a solenoid valve. The tungsten fiber, 9 by 0.002 in., is joined to an 0.008-in. tungsten wire or graphite rod via a machined lightweight chuck.

Jan 1, 1964

By K. R. Garr, D. Kramer, A. G. Pard

EXPOSURE of steels to a fast-neutron flux results in helium generation by (n,a) reactions. The elements Fe, Ni, Cr, and N are major participants in the (n,a) reaction and helium concentrations of up to 5 x 10"5 atom fraction could accrue in fuel clads after a year of service in proposed fast reactors.&apos; Such concentrations of helium can severely reduce the ductility of alloys at temperatures of reactor service. The phenomenon of helium embrittlement has been studied in austenitic alloys which were irradiated with particles as a rapid means of producing significant helium concentrations.2-5 The pres-ent work is a continuation of those studies and is concerned with helium effects in a ferritic stainless steel. I) EXPERIMENT Small sheet tensile samples with a gage length of 0.50 in. and a cross-section of 0.009 by 0.040 in. in the gage length were punched from cold-rolled type 405 stainless steel. The composition of the steel used in this work is given in Table I. Prior to helium injection, the samples were annealed 24 hr at 760°C which caused complete recrys-tallization with a resulting grain size of 40 u. This treatment rendered the alloy completely ferritic and carbide particles, 0.5 to 2 uin size, were present at a density of 1 x 1011 cm-3, Fig. 1. These carbide particles were probably a mixture of the M7C3 and M4C types.6 Helium was injected into the samples by irradiation with a particles from a cyclotron, which produced uniform concentrations through the center two-thirds of the sample thickness. Details of this procedure were previously described.&apos; The average helium concentration, as measured on a gas-source mass spec- 11) RESULTS A) Tensile Tests. The results of the tensile tests are given in Table I1 where the values shown are averages of two samples. There was no significant effect of helium on either the yield strength or tensile strength at 550" or 650°C but an increase in both is apparent at 750°C. Samples with helium showed a 20 pct loss in total elongation at 650°C which increased to a 55 pct loss at 750°C. The uniform elongation is not affected by helium at 550" or 650°C but shows an increase at 750°C.

Jan 1, 1970