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By C. E. Tsoutrelis

A new method for determining rock drillability in diamond drilling is discussed; the method takes into consideration both penetration rate and bit wear. The method is based on drilling a rock specimen under controlled laboratory conditions using a model bit. The technique used for determining the experimental variables is extremely simple, quick, and reliable. Drillability is then determined by the mathematics of drilling. In considering the different factors that affect diamond drilling performance, the nature of the rock to be drilled is of outmost importance since it affects significantly the drilling costs and such other variables as bit type and design, drilling thrust, and bit rotary speed. Many attempts have been made to study this effect by correlating actual drilling performances either to certain physical properties of the rock being drilled1-? or to test drilling data obtained under laboratory conditions.7-13 These attempts were aimed at providing a reliable method of predicting by simple means the expected rock behavior in actual drilling, thus giving the engineer a tool to use in estimating drilling performances and costs in different types of rock. The purpose of this paper is to describe such a method by which rock drillability (a term used in the technical literature to describe rock behavior in drilling) could be determined in diamond drilling. It is believed that the proposed simple and reliable method will cover the need of the mining industry for a workable method of measuring the drillability of rocks. It should be emphasized, however, that since drill-ability depends on the physical properties of rock and each drilling process (diamond, percussive, rotary) is affected by different or partly different rock properties,14-l6 the proposed method of determining rock drillability cannot be extended to the other drilling processes. The results presented in this paper form part of an extensive three-year research program carried out by the author in the laboratories of the Greek Institute of Geology and Subsurface Research. During this period the effects of the physical properties of rocks and of such operational variables as drilling thrust and bit rotary speed in diamond drilling were investigated in detail. DRILLABILITY CONCEPT The literature is not devoid of drillability studies. While there are a number of investigators1,3,5-7,9-0,12-13,17 who have attempted to establish by direct methods (i.e., drilling tests under laboratory conditions) or indirect (i.e., through a physical property of rock) an index from which the drilling performance in a given rock may be estimated, very few6-7,9,12, of the proposed methods seem to be of much practical value to the diamond drilling engineer and none to date has been universally accepted. Commenting on the proposed methods for assessing rock drillability, Fish14 remarks that "for a measure of drillability to be accepted it is essential that penetration rate at a given thrust and bit life are elucidated as otherwise the method is of little value." This statement should be examined in more detail by making use of the penetration rate-drilling time diagram obtained in drilling a rock under constant operational conditions. Furthermore, the merits of using this diagram to describe rock drillability will be pointed out. At the same time reference will be made to this diagram when discussing some previously proposed methods. Fig. 1 illustrates such a diagram for three rocks,A, B, and C, which have been diamond drilled under identical conditions. It is assumed here that rocks A and B have the same initial penetration rate, i.e., VOA = Vog, but since rock B is more abrasive than A, rapid bit wear occurs and as a result the fall of its penetration rate with respect to time is more vigorous than in rock A. This is shown graphically by a steeper V = f(t) (0 curve in this rock than in rock A. Rock C has a lower initial penetration rate, due to higher strength properties16 but since it is not very abrasive, only a slight fall of its penetration rate occurs during drilling (in this category are some limestone and marbles with compressive strength above 1000 kg per sq cm). It follows from the foregoing considerations that the characteristic for each rock curve (I) is a function of (i), the penetration rate of the rock Vo recorded at the instant of commencing drilling, which determines the starting point of the curve (1) on the y-axis and (ii), the abrasive rock properties which determine the rate of fall of Vo with respect to time. Thus, curve (I) provides an actual picture of the rock behavior in drilling for given operational conditions, and it can be used with complete satisfaction to assess rock drillability. It can be seen clearly from Fig. I that proposed methods for assessing rock drillability by measuring the

Jan 1, 1970

By Carl J. McHargue

Mechanical twins were produced in electron-beam melted columbium by high-speed impact at room temperature and by slow or fast compression at -196°C. The composition plane of the twins was { 112} and the shear direction was <111>. Notches in the twin bands often corresponded to traces of {110) of the matrix and appeared to be untwinned regions. Markings within the twin bands were interpreted as resulting from {110} slip in the twins. THERE has been much work in recent years concerning plastic deformation by glide, and the dislocation theory relating to glide has reached a relatively high degree of development. On the other hand, there have been fewer studies of deformation by mechanical twinning, and understanding of this process is far from satisfactory. This method of deformation is of interest for at least two reasons. First, it provides a mechanism in addition to glide for the relief of stresses, and, in the bcc and hexagonal close-packed metals may result in significant amounts of plastic flow. Secondly, there is the possibility that twins may act as barriers for dislocation movement, resulting in pile-ups which could nucleate cracks. As might be expected, the bulk of the literature on mechanical twinning in the bcc metals is concerned with iron. A good summary of the work done prior to 1954 is contained in the book by all.&apos; Recently the refractory bcc metals have become increasingly important. Limited studies have shown that tantalum,2,3 molybdenum,4,5 vanadium,6,7 tungsten,&apos; and columbium9-11 deform by mechanical twinning under some conditions. Alloys of molybdenum with rhenium and tungsten with rhenium show extensive deformation by twinning at room temperature.I2-l4 Most of these studies have dealt primarily with mechanical properties at low temperatures or have shown the existence of twins, and there is only a small amount of information concerning the conditions under which they form. The subject of the present paper is the formation of twins under stress in columbium with a consideration of their morphology. EXPERIMENTAL PROCEDURE The material used for these studies was taken from an ingot of columbium which had been melted twice by the electron-be am-method. The analysis of the ingot was (in ppm): B < 1, C = 10, Fe < 100, The cast ingot contained very large grains, and it was possible to obtain single-crystal prisms which measured from ¼ to 3/4 in. on a side. A few experiments were conducted on polycrystalline plate which was prepared by rolling material from the same ingot at room temperature and annealing at 1000 in a dynamic vacuum of 10-6 mm Hg. This gave a plate in which the grains had an average diameter of 3 mm. After the specimens were cut from the ingot, the six faces were metallographically polished and elec-tropolished to remove all traces of cold work. Most of the observations were made on the surfaces of the deformed specirllens without further treatment. Occasionally, etching after deformation was desirable. In these cases, an etchant of the composition 50 parts H2O, 5 parts HNO3 25 parts HF, and 10 parts H2SO4 was found to delineate the twins very well. Unless considerable care was taken to ensure the removal of all disturbed metal left by the mechanical polishing, etching failed to reveal many of the features discussed in this; paper. The specimen&apos;s were deformed either by impact or slow compression at 77°K (liquid-nitrogen coolant), 198°K (dry ice and acetone coolant), and 298°K. The impact load was delivered by a hammer except in one case where the load was delivered by a bullet. Slow compression was carried out on a hydraulic testing machine equipped with a chamber to hold the coolant. EXPERIMENTAL RESULTS It has been generally believed that the conditions favoring the formation of deformation twins are large grains, low temperature, and impact loading. In fact, Barrett and Bakish2 found twins in tantalum only after impact deformation at 77°K, and Adams, Roberts, and Smallman10 observed twins in columbium only at 20 For these reasons, the initial experiments of this study used impact loading. Hammer blows caused many bands resembling twins in single crystals a.t 77" but not at 198°K. Only a few slip lines were observed on any of the single-crystal specimens of this study—essentially all the deformation occurred by twinning. The appearance of the twins on the as-deformed surface is shown in Fig. 1. Although both Figs. 1(a) and l(b) are photomicrographs of twins taken at the same magnification and from the same crystal, they are startlingly different in appearance. Fig. 1(a) was taken from the crystal face approximately perpendicular to the shear direction, whereas Fig. 1(b) was taken from

Jan 1, 1962

By H. H. Kellogg

Equations representing the standard free energy of formation as a function of temperature, for thirty metallic chlorides, are presented and plotted on a free-energy vs. temperature diagram. The use of these data for calculations on reduction of metallic chlorides, refining of metals with chlorine, and chlorination of metallic oxides and sulphides is illustrated. CHLORINE metallurgy&apos; has attracted metallur- gists for more than a century because the unusual properties of the metallic chlorides—low melting point, high volatility, and ease of formation from the oxides—make possible many useful extractive processes. Interest in chlorine processes is undergoing a renaissance due to present availability of chlorine at relatively low prices, and to recent advances in technology. During the present century there have accumulated a considerable number of reliable values of the thermodynamic constants for the metals and their chlorides. These data permit the calculation of free-energy equations for many metallurgically important reactions. Consideration of free-energy values makes possible certain predictions of the direction and extent of a given reaction, as well as the effect of temperature, pressure, and composition upon the result. Reaction rate, although not predictable from free-energy data, is usually sufficiently great at elevated temperatures that diffusion of the reactants and products to and from the zone of reaction determines the actual rate. Thus, if the free-energy indication is favorable, the chances are good that a high temperature metallurgical reaction will proceed at a reasonable rate, if adequate provision for rapid diffusion has been made. This paper presents standard free-energy equations for a number of metallic chlorides, based on data which are scattered throughout the literature. The equations are presented in a form that simplifies their use, and typical examples are given of the application of free-energy data to metallurgical processes. Free Energy of Reaction The free-energy change (AG) of a reaction is the true measure of the "driving force" of the reaction under a given set of conditions, and this is related to the standard free-energy change (AGO) of the reaction as follows: For the reaction: bB + cC = dD + eE ?G = ?G°+RTln ADd. AEA / ABb. ACc where A, = activity of constituent (i) T = absolute temperature, OK R = gas constant The criterion of a spontaneous reaction from left to right, at constant temperature and pressure, is a negative value for the free-energy change (?G). The standard free energy of the reaction is equal to the free energy of the reaction when all the reactants and products are at unit activity, since under these conditions the second term on the right-hand side of eq 1 is equal to zero. The concept of activity is treated fully in many textbooks on chemical thermodynamics1 and in a recent article by Chipman.2 Briefly, the activity (A,) of a constituent (i) is a measure of the reactivity of this constituent relative to its reactivity in some arbitrary standard state. For liquids and solids the standard state most often used is the pure liquid or solid constituent. Thus the activity of a pure liquid or solid in a metallurgical reaction is equal to unity. Gases under moderate pressure and at elevated temperatures behave very nearly as &apos;idea1 gases,&apos; and the standard state is chosen as the gas at 1 atm pressure. The activity of an ideal gas is therefore equal to its partial pressure, and this relation is sufficiently exact for real gases in most metallurgical reactions. For a liquid or solid solution there is in general no simple way to express the activity of a constituent as a function of its concentration, and activity must be determined by experiment. A few solutions follow a so-called &apos;ideal&apos; behavior, and if the pure constituent is chosen as the standard state, the activity of a constituent in an ideal solution becomes equal to its mol fraction. When a reaction reaches a state of thermodynamic equilibrium at constant temperature and pressure, AG becomes equal to zero and eq 1 reduces to: [ADd . AEe ?G°=RTln Abb ¦ Ac c equilibrium [2] The brackets surrounding the activity term are used to emphasize that each of the activities is an activity under equilibrium conditions—not just any arbitrarily assigned value. The bracketed term is the equilibrium constant (K) of the reaction. Eq 2 makes possible the calculation of equilibrium activities for a given reaction, if AGO is known at the desired temperature. The standard free-energy equations presented in this paper were calculated from the fundamental thermodynamic values of enthalpy of formation at 298°K (AH°,), standard entropy at 298°K (So298), heat capacity as a function of temperature (Cp), and enthalpies of transition, fusion, vaporization, and sublimation for the various constituents. Where possible the data reported in the recent "Selected Values of Chemical Thermodynamic Properties," published by the Bureau of Standards," were used. A large number of data came from the publications

Jan 1, 1951

By W. L. Phillips

Stress-strain curves were obtained for single crystals of 70 pct Ag-30 pct Zn tested in tension and shear. Samples tested in tension and shear had comparable resolved shear stresses and stress-strain curves. The {111} <110> slip system was observed. It zoas found that the9.e is a barrier to slip in both latent close -packed directions and that the magnitude of these barriers is proportional to prior strain during easy glide. It was observed that cross-slip in tension and shear was most frequent in crystals with an initial orientation near <100> "Oershoot" zoas observed in tension. The amount of this "overshoot" was independent of initial orientation. AN idealized concept of plastic deformation indicates that a single crystal should yield at some stress that is dependent on crystal perfection and it should then continue to deform plastically by the process of easy glide which is characterized by a linear stress-strain curve and a low coefficient, d/dy, of work hardening. Hexagonal metal crystals generally conform to this ideal concept of laminar flow. In fcc metals the range of easy glide is always restricted in magnitude and it is strongly dependent on orientation, composition, crystal size, shape, surface preparation, and temperature. Since one of the principal differences between the two crystal systems, both of which deform by slip on close packed planes, is the existence of latent slip planes in the fcc crystals, it has been proposed that the transition from easy glide to turbulent flow, characterized by rapid linear hardening, is due to slip on secondary planes intersecting the primary plane.ls Several theories have been proposed to explain the linear hardening and parabolic stages of the stress -strain curve.6"10 The easy-glide region is the least understood of the three stages. The stress-strain characteristics of Cu-Zn, which shows a long easy-glide region, have been extensively investigated."-" In light of recent ideas on dislocations, cross-slip, effect of solute atoms, and stacking fault energy, it was felt that the certain features of this earlier work might be compared with another alloy, Ag-30 pct Zn, which also exhibits a long easy-glide region. Tension and shear stress at room temperatures were employed. The results obtained, together with some interpretation of the observations, are described below. EXPERIMENTAL PROCEDURE The silver and zinc used for mixing the alloys were 99.99 pct pure. The two components were weighed to within 0.1 pct of the weights required fo the alloy composition. They were then placed in a closed graphite mold and the mold and contents were heated in 100°C stages from 500&apos; to 900°C with sufficient time and vigorous agitation at each stage provided to dissolve the silver. The crucible was then heated to 1150°C and agitated violently before being quenched in oil. The resulting alloy rod was machined free of sur face defects and then placed in a graphite mold designed for growing single crystals. The graphite mold was closed with a graphite plug and was encased in a pyrex glass tube which was connected to a vacuum system. The tube and mold assembly were placed in a furnace; the tube was evacuated and the furnace was rapidly heated to a temperature sufficient for fusing and sealing the glass. The glass-encased evacuated mold and contents were then lowered through a vertical furnace. The top section of the furnace was held at 100 °C above the melting point of the alloy. The lowering rate was 1.5 in. per hr. The tension specimens were 1/4 in. diam; the shear specimens were 1/2 in. diam. These specimens were then removed from the mold, etched, and chemically polished with hot (60°C) Chase etch reagent (Crz03-4.0 g, NH4C1-7.5 g, NHOs-150 cc, HzS04-52 cc, and Hz0 to make 1 liter). In preparation for tensile testing, the specimens were carefully machined to a diameter of about 0.200 in. to permit a gage length of 6 in., annealed for 16 hr at 800&apos; to reduce coring, and then cleaned and polished. A modified Bausch-type shear apparatus which has been described previously18 were employed. The gage length was 1/8 in. This shear apparatus was placed in an Instron tensile testing machine. EXPERIMENTAL RESULTS A) Tension. Several specimens were extended at room temperature to determine the effect of initial orientation on the stress-strain curves of Ag-30 pct Zn. The initial orientation and the resolved shear stress supported by the active slip system at various total strains are plotted in Fig. 1. The critical resolved shear stress, t,, initial rate of work hardening, d/dy, and length of the easy-glide region are independent of orientation. The arrival at the symmetry line is shown by an arrow in Fig. 1. During the easy-glide region of the stress-strain

Jan 1, 1963

By Paul F. Kerr, Raymond F. Robinson

Uranium mineralization occurs in the footwall of the Sunshine vein from the 2900 to the 3700 level. Veinlets of uraninite associated with pyrite and jasper have been so extensively divided and recemented that units more than a few feet in length are seldom observed. The wall rock is St. Regis quartzite of the Belt series. The age of the uraninite, on the basis of isotopic analyses, is 750 * 50, which agrees with geological data suggesting that phases of the Sunshine mineralization are pre Cambrian. THE Sunshine mine in the Coeur d&apos;Alene district, Idaho, is well known for its silver-bearing veins but prior to the summer of 1949 had not been recognized as a possible source of uranium. At that time, during a geiger counter reconnaissance by T. E. Gillingham, R. F. Robinson, and E. E. Thurlow, high radioactivity was noted and radioactive specimens were collected from the footwall of the Sunshine vein.&apos; The detection led to the identification of uraninite-bearing veins, since explored jointly by the Atomic Energy Commission and the Sunshine Mining Co. After the occurrence was noted, the geology of the uranium deposit was studied by the Sunshine staff, and a laboratory examination of the ores was conducted at Columbia University. Several types of laboratory work were undertaken. Differential thermal curves were made of selected siderite samples and results from many more were secured through the work of Mitcham.2 X-ray diffraction and X-ray fluorescence analyses were employed on uraninite, jasper, and siderite. Chemical analyses were made through the cooperation of the Division of Raw Materials of the Atomic Energy Commission. General Geological Features Several silver-bearing veins cut the overturned north limb of the Big Creek anticline as mapped by Shenon and McConne1,³ while the Osburn fault, a long-recognized regional feature about a mile away, marks the north boundary of the Silver Belt. The Sunshine vein, Fig. 1, has a south dip more or less parallel to the 60" axial plane of the fold and cuts rocks of the Belt. Series, starting with the Wallace formation near the surface, continuing downward through the St. Regis formation, and probably extending into the Revett quartzite which lies below the bottom or 3700-ft level. The limb of the anticline is locally modified by secondary folds, one being prominently exposed in the uranian area along the Jewel1 crosscut near the Sunshine vein. Crumpling of the limb resulted from compression which formed the anticline and probably preceded the faults in which the vein deposits accumulated. Evidence of drag along these faults points to reverse movement in the uranium-bearing area and elsewhere. This is true of major faults in the mine workings, and the majority of faults which can be mapped, as pointed out by Robinson.&apos; The St. Regis formation, as measured in the mine, appears to have an initial thickness of some 2000 ft, but the apparent thickness due to thickening during folding is some 3400 ft. Along the Sunshine vein the purple and green rocks characteristic of the Wallace formation in the nearby Military Gulch section p. 37 of ref. 5) have been completely bleached because of introduced sericite. Hydrothermal solutions acting on the wall rock have substituted for the original color a pale greenish cast, although no pronounced mineralogical change has resulted, as Mitcham has observed.&apos; The silver and the uranium depositions appear to belong to distinct epochs resulting from several periods of emplacement. Likewise, multiple periods of deformation account for the faulting. Uraninite is generally associated with silicification, while silver . mineralization accompanies carbonate veins. Rarely, uraninite may be found in a matrix of siderite. Ordinarily uraninite formed prior to ar-gentian tetrahedrite. Where clusters of veins form a stockwork, uraninite-jasper veins often favor one trend while tetrahedrite-siderite veins favor another. During deformation, brecciation of the St. Regis quartzite provided openings between broken rock fragments for precipitation from vein-forming solutions. Fractures due to major breaks were filled during the first stages of vein formation, while later deformation displaced the first veins and provided new channels along which further mineralizing solutions proceeded. The uraninite veins, as the first formed, have suffered fracturing, displacement, and segmentation. Uranian vein segments uncut by faults and more than a few feet in length are rare or nonexistent. Siderite veins are more massive and often extend without a break for tens and even hundreds of feet. In general they show much less segmentation. While the siderite is usually later, there is an overlap in the periods of deposition, some earlier siderite veins being extensively segmented in much the same way uraninite veins have been broken. Vein silica is more extensively distributed than the uranium and iron mineralization it carries. Along the vein course concentrations of uraninite frequently fade away and barren white quartz continues, the transition often occurring within a few feet along strike or down dip. An example appears on the 3700-ft level where a uraninite vein, see Fig. 2a,

Jan 1, 1954

By Y. A. Chang

Phase relationships in the system Cr-Si have been established based on the melting point, X-ray, metallo-graphic, and DTA studies. The three intermediate phases, Cr3Si, Cr5Si,, and CrSi,, melt congruently at 177V ± I@,Cr3Si, 1680"i 20°, and 1490" *20°C, respectively, while the fourth intermediate phase CrSi, melts peritectically at 1413" i 5°C to Cr5Si3 and a melt containing 51 at. pct Si. The temperatures and compositions of the four eutectic isotherms occurring in this system are given below: DTA and metallographic evidences indicate that Cr5Si, undergoes a phase transformation at 1505" i20°C. The high-temperature form of this phase could not be retained by the quenching techniques used in this study. TECHNOLOGICAL interest in the developing of composite systems, consisting of Sic on the one hand as a fiber-reinforced material and metallic substances such as chromium, nickel, or Cr-Ni alloys as a binding agent on the other hand, stimulated the present investigation of phase relationships in the binary system Cr-Si. Earlier works concerning this system have been evaluated and summarized by ansen and Anderko.&apos; Their phase diagram was based mainly on the works of Kieffer, Benesovsky, and schroth2 and Kurnakov.~ According to these authors, the three intermediate phases Cr3Si, CrSi, and CrSi, all melt congruently at approximately 1730°, 1600°, and 1550°C. However, they did not agree on the compositional stability of the fourth intermediate phase between Cr3Si and CrSi. Later Parthe, Nowotny, and schmid4 determined the structure of this phase to be tetragonal T-1 type using the single-crystal method, and concluded that this phase had a formula of Cr5Si3. Since the compilation of Hansen and Anderko,&apos; a new phase diagram for the system Cr-Si has been proposed by Elliott5 based on the works of Goldschmidt and rand,&apos; Guseva and ~vechkin,~ and Trusova, Kuzev, and Ormont8 and the earlier works quoted by Hansen and Anderko.&apos; According to this proposed phase diagram, all four intermediate phases have large ranges of homogeneity and all melt congruently. More recently, Svechnikov, Kocherzhinskii, and yupkog studied the system Cr-Si by the DTA-method. According to their findings, the three intermediate phases, Cr3Si, Cr5Si3, and CrSi,, melt congruently at 1700°, 1720°, and 1475"C, respectively, while the fourth intermediate phase, CrSi, melts peritectically at 1475°C to Cr5Si3 and a melt containing 50 at. pct Si. The temperatures and compositions of the four eutectic isotherms were found to be: In view of the discrepancies existing in the literature concerning the system Cr-Si, it was decided to rein-vestigate the phase relationships in this system. EXPERIMENTAL a) Starting Materials. Chromium disilicide and chromium or silicon powders were used in the present study to prepare the melting point and DTA samples. CrSi, was obtained by directly reacting cold-pressed elemental powders in an atmosphere of Hz at a temperature of about 1250°C. Chromium powder, purchased from Stark Chemical Co., had the following impurities in ppm: Fe, 200; Mg, 1000; and 0, 250; while silicon powder, purchased from the Welded Carbide Co., had the following impurities in ppm: Ca, 700; and Fe, 3500. b) Melting-Point Determination and Differential Thermal Analysis. Cylindrical melting-point samples of approximately 13 mm in diam and 30 mm in length with a rectangular groove in the center were prepared by hot-pressing of well-mixed powder mixtures in graphite dies. Before the melting-point determination, the hot-pressed samples were ground on a sand paper to remove any minute surface contamination of graphite. A small hole of 1 mm in diam, drilled on the center portion of the samples, served as a blackbody cavity for the temperature measurements. DTA samples approximately 13 mm in diam and 15 mm in length were prepared in a manner similar to the melting-point samples. Melting points were determined using the Pirani technique under a helium atmosphere of 40 psi. The design, performance, and operation of this apparatus have been described in detail by Rudy and ~ro~ulski.&apos;~ The temperature measurements were carried out with a calibrated disappearing-filament-type micro-pyrometer. The measured temperature was corrected for losses from the quartz window of the melting-point furnace and for deviations from blackbody conditions of the observation hole. The procedure for temperature correction has also been previously described." The DTA method of Heetderks, Rudy and Eckertl&apos; was also used to check any phase transformations of selected alloys in the system Cr-Si. It was not possible to make remated runs on the same sample once melt-

Jan 1, 1969

By John Chipman

The concentration of a solute in a dilute ),zetallic solution may be measured by any of several parame- ters including weight percent, atom fraction, atom ratio, and lattice ratio. The ratio of filled to unfilled interstitial sites is useful for interstitial solutes. A variable 2 proportional to this ratio is used as a measuve of concentration. For component 2 irz a bitzary solution z2 = n2/Ym - nz/b) where b is the numberber of interstitial sites per lattice atom. For a t~lul-ticortzporzent solution this becomes zz = n2/(nl + Cvjnj) in which Vj = - l/b for an interstial solute and +1 for a substitulional solute. In the infinitely dilute solution the activity of an interstitial solute 2 is proportional lo z2. At finile concentration the departure from this limiting law is expressed us an activity coefficient, his coefficient is a function of concentra1io)z expressed as tevactiolz coeffcient 8; is analogous to the jark~iliar e£ bul is found to be independent of concentvation in certain solutions for which data are available. It is found that the same equations may be used to express the activity of a nonmetallic solute, sulfur, in liquid solutions of iron containing other solutes, both metallic and nonmetallic. For a nonmetallic solute or for one which strongly increases the actiuity of sulfur, it is convenient to assign arbitvarily a value vj = — 1. When this is done the derivative is found to be constant in each of the ternary solutions studied. The activity coefficient of sulfur in a complex liquid iron solution may be expressed as where nk is a second-order cross product determined in the quaternary solution Fe-S-j-k. The equation is used to calculate tlze activity of sulfur i)z three sevetl- component solutions. IN thermodynamic calculations concerning dilute solutions it is unnecessary to invoke laws and relations which extend across the concentration range to include concentrated solutions. In most binary metallic systems, as arkeen&apos; has recently pointed out, there exist two terminal composition regions of relatively simple behavior, connected by a central region of much greater complexity. When the solute is a nonmetal there is only one such region and in many systems the concentration range is extremely limited. It is the purpose of this paper to suggest a method for the calculation of activities in such a terminal region in which one or more solutes are dissolved in a single solvent of predominantly high concentration. HENRY&apos;S LAW In the usual textbook statement of Henry&apos;s law, concentration is stated in mole fraction. This has the advantage that it makes Henry&apos;s law thermodynamically consistent with Raoult&apos;s law. Since all measures of concentration at infinite dilution are related by simple proportion it follows that mole fraction, molality, atom ratio, weight percent, or any other unit of concentration can be used with the appropriate constant. At finite concentrations, however, calculations based on the law depend upon the unit employed. Deviations from Henry&apos;s law at finite concentrations depend upon the composition variable employed. They are evaluated in terms of activity and interaction coefficients2 which have become familiar features of metallurgical thermodynamics. It is the purpose of this paper to propose a measure of concentration for metallic solutions containing interstitial or nonmetallic solutes by means of which the calculation of activities in complex solutions may be simplified. The discussion will be restricted to free-energy interaction coefficients3 typified by Wagner&apos;s c|a BINARY SOLUTIONS The several measures of concentration which are to be considered are shown in line a of Table I. The corresponding activity coefficients are in line b and the deviation coefficients, sometimes called self-interaction coefficients, are in line c. Henry&apos;s law simply states that the activity coefficient approaches a constant value at infinite dilution. By adoptihg the infinitely dilute solution as the reference state and defining the "Henrian" activity as equal to the concentration in this state, the activity coefficient is always unity at infinite dilution. This convention is far sim~ler and more useful in dilute solution than emploiment of the &apos;Raoultian" activities and it will be used in the following discussion. The several definitions and equations of Table I will be referred to by means of their coordinates in the table. Early observations of deviations from Henry&apos;s law in metallic solutions were shown graphically4 rather than analytically. For the case of sulfur in liquid iron5 the slope of a plot of logfs vs (%S) was constant in the range 0 to 4.8 pct S, indicating constancy of eh2&apos; in Ic. He was proposed by wagnerz and has been widely adopted. The a function of IIIc recently employed by ~arkenl was designed specifically for dilute solutions. Darken has shown that the value of a12 remains essentially constant for many binary solutions within a substantial range of compositions. The atom ratio is directly proportional to the molalitv.<, a conventional measure of concentration. IVb and C served as the basis for smith&apos;s6 classic studies of

Jan 1, 1968

By W. Philippoff

ALTHOUGH Gaudin1 and more recently Sutherland2 have calculated the probability of collision of a falling mineral particle with a rising bubble, there is no published information concerning the details of the mechanism of attachment of a collector-coated particle to a bubble. During the past year the writer has developed a theory for the mechanism of attachment, which has been substantiated experimentally.&apos; Funds for the investigation and for some of the equipment used have been supplied by the Mines Experiment Station of the University of Minnesota. Motion picture studies of the phenomena involved in the collision between mineral particles and bubbles, such as those of Spedden and Hannan,3 show that the contact can be completed within 0.3 millisec. Formulas developed for rigid bodies have hitherto been used&apos; for the calculation of the motion of bubble and particle, but it is obvious that a bubble cannot be regarded as a rigid body. On the contrary, Spedden and Hannan&apos;s pictures show a great degree of deformation during the collision. The time of attachment was calculated as the time the particle drifted past the bubble. Time of Collision The theory presented in this paper enables calculation of the time of collision; using the concept that the bubble, or more generally, a liquid-air interface, acts as an elastic body. The elasticity, defined as the restoring force on a mechanical deformation, is caused by, the surface tension and is the result of the principle of the minimum of free surface energy. It is well known that an elasticity together with a mass determines a frequency of vibration. The vibrations of jets and drops caused by the elasticity of the interface are known to comply exactly with the classical theory of capillarity.5 However, the vibrations of isolated bubbles, as distinct from foams, have not been investigated previously. The following equation, presented elsewhere,&apos; has been deduced for these frequencies: [3fB = 9.20•&apos;./V•Vn- (n-1) • (n+2) /8[1]] in which fB is the frequency of a harmonic of the bubble in cycles per second, V the volume of the bubble in cc, n a number determining the order of the harmonic, and n = 2 the basic vibration. The first (basic) harmonic describes a change of the spherical bubble to an ellipsoidal bubble. The higher harmonics are more complicated, for the circumference of the bubble is divided approximately into as many parts&apos; as the order of the harmonic. As an example, Spedden and Hannan&apos;s published motion picture of, a vibrating bubble corresponds to the sixth harmonic. Eq 1 shows that only the first and third harmonics are simple multiples (1 and 3), all the others being irrational fractions of the basic frequency. This means that the shape of the vibration can change with time and is in general unsymmetric in respect to the time axis. Such conditions prevail when there is a distributed elasticity or mass, as in the case of vibrating membranes or rods. The constant 9.20 is valid for water at room temperature, but a general solution involving the physical constants of the liquid has not been found. The case of the floating particle is much easier to treat I than that of the bubble. It can be assumed that the elasticity is caused exclusively by the interface and that the mass is concentrated in the particle together with some adhering water. The following expression for the frequency of a system, of one degree of freedom can be applied: [1E/m[2] fP = 27] Here f, is the frequency of the particle vibration in cycles per second, E the elasticity in dynes per cm, and m the mass in grams. The classical theory of impact phenomena gives the time of collision during the striking of a spring (in this case the surface of the bubble) by a mass, as: [t~ = 2/f = 7r\/m/E[3]] It is now possible to develop an expression for the elasticity of a floating cylindrical particle. The force equilibrium of a cylinder floating end on at the air-liquid interface is given by the well-known equation (Poisson&apos; 1831) [aP = 4 D2.pL•g•h +7rD•y sin a[4]] which accounts for the buoyancy and the action of the surface tension where P is the force acting on the particle in dynes (weight-buoyancy), D the diameter of the cylinder in cm, pL the density of the liquid in grams per cc, g the acceleration of gravity = 981 cm per sec2, h the depression of the cylinder below the surface of-the liquid in cm, y the surface tension in dynes per cm and a the supporting angle&apos; or the one required to insure equilibrium, a being smaller than the contact angle ?. Although demonstrated by Poisson, it has not

Jan 1, 1952

By R. L. Bell, T. G. Langdon

A technique was developed- for determining the grain strain, and hence the grain boundary sliding contribution, occurring during the high- temperature creep of a magnesium alloy, from the distortion of a grid photographically printed on the specimen surface. The results were compared with those obtained from measurements of grain shape, both at the surface and interrwlly, and it was concluded that the grain shape technique may substantially underestimate the grain strain and overestimate the sliding contribution due to the tendency for migration to spheroidize the grains. ALTHOUGH a considerable volume of work has been published on the role of grain boundary sliding in high-temperature creep, many of the estimates of Egb (the contribution of grain boundary sliding to the total strain) have been in error due to the use of incorrect formulas or inadequate averaging procedures.&apos; One of the most easy and convenient measurements from which to compute Egb is that of v, the step normal to the surface where a grain boundary is incident. Unfortunately, this parameter is also the one associated with the treatest number of pitfalls. Values of v have been used to calculate Egb from the equation: egb =knrVr [1] where k is a geometrical averaging factor, n is the number of grains per unit length before deformation, v is the average value of v, and the subscript ,r denotes the procedure of averaging along a number of randomly directed lines. If the dependence of sliding on stress were assumed, it would be possible, in principle, to calculate k from the known distribution of angles between boundaries and the surface. This in itself is difficult because the distribution depends on the history of the surface,&apos; but the problem is even further complicated by the fact that v depends on other factors such as the unbalanced pressure from subsurface grains.3 However, the great simplicity of the measurement procedure for v makes it highly desirable that this problem of k determination should be overcome. In the present experiments, this was achieved by the use of an indirect empirical method in which the grain strain, eg, at the surface was determined by the use of a photographically printed grid. The assumption here is that the total strain, et, is simply the sum of that due to grain boundary sliding, egb, and that due to slip or other processes within the grains, eg. SO that: Et = Eg + Egb [2] Thus k is given by: In practice, it is customary to indicate the importance of sliding by expressing it as a percentage of the total creep strain; this quantity is termed y (= 100Egb/Et). The determination of Eg from a printed grid within the grains avoids the difficulties due to boundary migration which should be considered when the grain strain is calculated from measurements of the average grain shape before and after deformation. As first pointed out by Rachinger,4,5 however, this latter technique has the particular advantage that it can also be applied in the interior of a polycrystal. Recently, several workers have produced evidence on a variety of materials6-&apos;&apos; to support the observation, first made by Rachinger on aluminum,4,5 that 7 can be very high, 70 to 100 pct, in the interior, even when the surface value, determined from boundary offsets, is very much lower.10&apos;11 Although there have been criticisms both of the shortcomings of the grain shape technique&apos;&apos; and of the different procedures used to determine y at the surface,&apos; it seemed important to check whether measurements of sliding by grain shape gave values of y which were truly representative of the material. In the present experiments, grain shape measurements were therefore made both at the surface and in the interior for comparison with one another and with the independent measurements of grain strain using the surface grid technique. EXPERIMENTAL TECHNIQUES The material used in this investigation was Magnox AL80, a Mg-0.78 wt pct A1 alloy supplied by Magnesium Elektron Ltd., Manchester. Tensile specimens, about 7 cm in length, were prepared from a 1.27-cm-diam rod, with two parallel longitudinal flat faces each approximately 3 cm in length. The specimens were annealed for 2 hr in an oxygen-free capsule, at temperatures in the range 430° to 540°C, to give varying grain sizes, and, prior to testing, the grain size of each was carefully determined using the linear intercept method. This revealed that the grains were elongated -0.5 to 5 pct in the longitudinal direction. Testing was carried out in Dennison Model T47E machines under constant load at temperatures in the range 150" to 300°C. At temperatures of 200°C and below, tests were conducted in air with the polished flat faces coated with a thin film of silicone oil to prevent oxidation; at higher temperatures, an argon atmosphere was used. To determine v,, each test was interrupted at regular increments of strain and the specimen removed from the machine. At the lower strains, when v, was less than about 1 pm, measurements were taken on a Zeiss Linnik interference microscope;

Jan 1, 1969

By W. A. Backofen, R. L. Fleischer

Single crystal, bicrystal, and polycrystal tensile tests of aluminum at 4.2°K, 77°K, and 300°K have been used to examine the role of grain boundaries in the deformation process. Results indicate that a grain boundary may affect the extent and slope of easy glide. The stage II hardening rate, on the other hand, is independent of the presence or absence of grain boundaries. This conclusion allows the size of the region of multiple slip caused by an incompatible grain boundary to be determined. For the size of bicyystal sample used in this study, multiple slip occurs in about half of the cross section. PREVIOUS studies of the stress-strain characteristics of bicrystals of face-centered-cubic metals have been limited to aluminuml-5 at room temperature. Recent results, however, indicate that the stress-strain curves of single crystals of such metals may be separated into at least three stages6 in which different deformation processes are occurring7 provided testing is done at sufficiently low temperatures.&apos; Since for aluminum a well-defined stage II develops only below room temperature, previous studies have not been able to relate effects of grain boundaries to all of the three stages of deformation. It is therefore to be expected that low-temperature deformation of aluminum single crystals and bicrystals should clarify the effects of grain boundaries on the different processes of deformation. EXPERIMENTAL PROCEDURE Single crystals and bicrystals were grown from the melt by the standard techniqueg with aluminum reported by Alcoa to be 99.993 pct pure. Ridges in the boat were used to guide the grain boundary during growth, assuring that the boundary would bisect the sample.10 The rate of furnace motion during growth was 1.0 cm per hr. During growth zone purification resulted, as evidenced by the ability of the first material to freeze to recrystallize at room temperature following severe deformation. Samples were approximately 4.4 X 6.6 mm in cross section and 103.5 mm in length between grips. Samples were annealed at 635" i 5°C for 40 hr and furnace cooled over a 7-hr period. They were then electropolished in a solution of 5 parts methanol to 1 part perchloric acid at a current density of 15 amp per sq dm for about 30 min at temperatures below 0°C. Tensile testing was performed at 295" (room temperature), 77" (sample in liquid nitrogen), and 4.2"K (sample in liquid helium) on the hard-type machine indicated schematically in Fig. 1. The machine con- sists basically of a tube surrounding a rod; one end of the sample is attached to each member, and the rod is pulled up the tube to extend the sample. The rod is rigidly mounted and is moved vertically by a system described by asinski." The pulling force is measured continuously by an electrical strain gage load cell, and the relative displacement of the tube and rod is also recorded continuously by a soft cantilever beam with electrical strain gages. Maximum stress and strain sensitivities were ±2g per sq mm and * 3-10-5. In all tests the strain rate was approximately 5.10-5 per sec. The thin wires in the tensile apparatus introduce softness, which may be corrected for, however, by measuring load vs displacement with the sample replaced by an elastic member. For loads greater than 15 kg the spring constant is 1.875.106 g per cm. The flexible wires also served to reduce substantially the large shearing forces which may arise in the case of grips having horizontal rigidity.&apos;&apos; As in any gripping system, however, bending moments will arise in the course of deformation by single slip. Engineering stress, s = (load)/(original cross-sectional area), and strain, E = (increase in length)/ (original length), are used for stress-strain curves unless otherwise indicated. Tables list resolved shear stress, T=mo and shear strain ? = dm, where m is the usual Schmid resolved shear stress factor for the primary slip system at the start of deformation. The first group of samples to be described forms an isoaxial set, all of the crystals making up the single crystals or bicrystals having the same tensile axis, the orientation of which is indicated by the cross in Fig. 2. For this orientation the primary slip plane and slip direction make angles of 45 deg with the tensile axis and the Schmid factor m has its maximum possible value of 0.5. Rotations about the tensile axis are indexed by means of an angle 0 between the small-area surface of the samples and the projection of the primary slip direction onto the cross section, as defined in Fig. 3. In single crystals, values of 0 were 0 and 90 deg, while in bicrystals 0 values were (0 deg, 180 deg), (90 deg, 270 deg), and (0 deg, 90 deg) as indicated in Fig. 4.

Jan 1, 1961

By R. R. Judd, H. W. Paxton

The rate of dissolution of cementite was studied in three low-carbon materials: a zone-refined Fe-C alloy, an Fe-0.5pct Mn-C alloy, and a commercial low-carbon steel. The materials were spheroidized, ad then held isothermally at temperatures above the Al. The isothermal anneal was interrupted periodically by a water quench and the specimens were analyzed by quantitative metallography for the amount of aus-tenite formed during the anneal. The results of this study were compared with an analytical model for the process, which assumes that carbon diffusion in aus-tenite is the rate-controlling step for the cementite dissolution process. The correlation between the model and the experimental data is excellent for the zone-refined Fe-C alloys; however, the Fe-0.5 pct Mn-C alloys and the commercial steel deviate from the calculated model. This deviation is thought to be a result of manganese segregation between the carbide and the matrix. The rate of nucleation of austenite at carbide interfaces was reduced by the manganese addition and enhanced by the presence of ferrite-ferrite grain boundaries. PREVIOUS investigations of the nucleation and growth of austenite from ferrite-carbide aggregates are not entirely satisfying for at least one of several reasons. The most prevalent of these is a lack of quantitative data. Engineering studies have been run on many steels with little control over important parameters such as composition and initial aggregate structure. The data obtained are valid only for material with identical chemistry and thermal history. A more informative approach to the problem of aus-tenitization would be to determine the mechanism that controls the rate of solution of carbide in austenite and how it is modified by alloying elements. This information could then be used to calculate an austeniti-zation rate for any material, provided its composition and structure are known. The object of the present work is to establish the rate-controlling step for cementite dissolution in Fe-C austenite and to investigate the modification of this rate by small manganese additions. The composition and structure of the material used were carefully controlled and all measurements were designed to allow a quantitative analysis of the kinetic process that controls the austenitization rate. A MODEL FOR DISSOLUTION OF CEMENTITE Cementite dissolution has been analyzed mathematically by a model that approximates the material used in the experiments. This model postulates a regular ar-array of identical cementite spheroids with 4 C( diam, embedded in a grain boundary- free ferrite matrix. The analysis provides a detailed description of the dissolution of one carbide spheroid and a generalization of the solution by summation over all the carbides in the material. The carbides may be isolated by defining identical, space-filling cells of ferrite around them. If the cell dimensions are greater than the diameter of the austenite sphere resulting from complete dissolution of the carbide, and no interaction (through diffusion in ferrite) takes place between cells during the dissolution process, the model need concern only one cell, since the solution in each cell is identical. In the experimental material, the dimensions of the cell, the carbide, and the final austenite sphere are approximately 24, 4, and 8 p, respectively; use of the single cell is therefore justified. The experimental observations are made on the austenite nodules that form around each carbide during the dissolution process. The model concerns the growth of these austenite nodules. The attendant shrinking of the carbide can be obtained from the same analysis by an extension of the calculations. Several a priori assumptions are necessary to make the analysis of the growth problem tractable. They are: 1) carbon diffusion through the austenite nodule is the rate-controlling process; 2) local equilibrium exists at all interfaces, 3) the austenite nucleus that forms on each carbide instantaneously envelops the carbide; 4) during the austenite growth process, the diffusion flux of carbon in ferrite is insignificant; 5) a quasi-steady state exists in the austenite concentration field; that is, at any instant during the dissolution process, the austenite carbon concentration gradient closely approximates that for a steady-state solution; and 6) the effects of capillarity on the dissolution rate of the carbides can be neglected. Referring to Fig. 1, a mass balance at the y-a interface for an infinitesimal boundary movement gives: Where rb is the outer radius of the austenite shell, C1 and C are carbon concentrations at the interface in austenite and ferrite, respectively, see Fig. 2, is the diffusion coefficient of carbon in austenite for the concentration of carbon at the interface, and t is time. The fifth assumption permits the austenite carbon concentration to be approximated by the Laplace solution for the spherical case. Therefore, where C(Y) is the carbon concentration at r, and A and B are constants. Local interfacial equilibrium fixes the boundary conditions for the diffusion problem. They are:

Jan 1, 1969

By M. E. Wadsworth, K. C. Bowles, H. E. Flanders, R. M. Nadkarni, C. E. Jelden

The kinetics of precipitation of copper on iron of various purity were carried out under controlled conditions. The rate of reduction has been correlated with such parameters as copper and hydrogen ion concentration, geometric factors, flow rate, and temperature. The character of the precipitated copper as a function of flow conditions and rate of PreciPitation has been observed under a variety of conditions. ThE precipitation of copper in solution by cementation on a more electropositive metal has been known for many years. Basile valentine&apos; who wrote Currus Triumphalis Antimonii about 1500, refers to this method for extraction of copper. Paracelsus the Great2 who was born about 1493 cites the use of iron to prepare Venus (copper) by the "rustics of Hungary" in the "Book Concerning the Tincture of the Philosophers". Agricola3 in his work on minerals (1546) tells of a peculiar water which is drawn from a shaft near Schmölnitz in Hungary, that erodes iron and turns it into copper. In 1670, a concession is recorded4 as having been granted for the recovery of copper from the mine waters at Rio Tinto in Spain, presumably by precipitation with iron. Much has been published in recent literature on the recovery of copper by cementation, the majority of the articles being on plant practice.5-24 The rest include articles on investigation of the variables involved25-28 and a review of hydrometallurgical copper extraction methods." This literature has established: a) The three principal reactions in the cementation of copper are Cu + Fe — Fe+4 +Cu [ 11 One pound of copper is precipitated by 0.88 lb of iron stoichiometrically. In actual practice about 1.5 to 2.5 lb of iron are consumed. 2Fe+3 + Fe — 3Fe+2 [21 Fe +2H&apos;-Fe+2 + H2 [3] Reactions [2] and [3] are responsible for the consumption of excess iron. Wartman and Roberson&apos;28 have established that Reactions [ I] and [2] are concurrent and much faster than Reaction [3]. b) Acidity control is important in the control of hydrolysis and the excessive consumption of iron. he commercial workable range is approximately from pH = 1.8 to 3." c) Iron consumption is closely related to the amount of ferric iron in solution. Jacobi" reports that, by leaving the pregnant mine waters in contact wi th lump pyrrhotite (Fe7S8) for 3 hr, all the iron was reduced to the bivalent condition and scrap iron consumption was cut to 1.25 lb scrap per pound of copper precipitated. He also reported that SO2 has been used successfully to reduce ferric iron to the ferrous state. d) The ideal precipitant is one that offers a large exposed area and is relatively free of rust. e) High velocities and agitation show a beneficial effect upon the rate of precipitation, as it tends to displace the layer of barren solution adjacent to the iron and also dislodges hydrogen bubbles and precipitated copper to expose new surfaces. Little work, however, has been published on the reaction kinetics of copper precipitation on iron. Cent-nerszwer and Heller20 investigated the precipitation of metallic cations in solutions on zinc plates. They found the cementation reaction to be a first-order reaction. The rate constant was independent of stirring for high stirring rates and they concluded that the rate is governed by a diffusional process at low stirring speeds and by a "chemical" process at higher stirring speeds where the rate reaches a constant value. This conclusion has been challenged by King and Burger30 who could not find any region where the rate was independent of the stirring speed, although the rate constant they had obtained for high stirring speed was greater than the maximum value of the rate constant reported by Centnerszwer and Heller (by a factor of six). King and Burger, therefore, concluded that the rate of displacement of copper was controlled only by diffusion. Cementation of various cations on zinc has been summarized by Engfelder.31 APPARATUS A three-necked distillation flask of 2 000-mm capacity was used as a reaction vessel. A pipet of 10-mm capacity was introduced through one of- the side necks, the sample of sheet iron, mounted in a rigid sample holder, through the other, the stirrer being in the middle as shown in Fig. 1. The whole assembly was immersed in a constant-temperature bath. The stirrer was always placed at the same depth in the solution. EXPERIMENTAL PROCEDURE Reagent-grade cupric sulfate (J. T. Baker Chemical Co., N.J.) was used to make up a stock solution containing 10 g of copper per liter which was then diluted to various concentrations as required. Experimental data were obtained by measuring the amount of copper and iron ions in solution at successive time intervals. The initial volume of the solution was always 2000 ml, 10-ml aliquots being removed each time for chemical analysis. Because the total volume change of the solution was less than 10 pct, no correction was used for solution volume change. Nitrogen was bubbled through the solution before and

Jan 1, 1968

By E. W. Felegy

THE need for improved mine communication to increase efficiency and to insure greater safety has long been recognized. General and unrestricted communication between all points underground, and between the surface and all points underground, is probably the least advanced phase of the mining industry. An ideal system of mine communication must require no fixed wire installations. The equipment must be small, lightweight, and readily portable, and the power requirements low. A system that can be used not only under normal circumstances but also in an emergency, when the continuity of wires, tracks, and pipelines may be disrupted, must function independently of any aid furnished by standard installations. Radio communication offers possibilities of meeting all the requirements necessary for an ideal communication system in underground mines. Transmission of signals must be achieved through one or both of two mediums, through the air in mine openings or through the strata. The results or lack of results obtained by early investigators showed conclusively that radio communication by space transmission cannot be accomplished effectively beyond line-of-sight distances in underground passageways. A radio system underground therefore must depend solely upon transmission through soil and strata. The application of radio to underground mine communication was investigated by many individuals and agencies at different times in the last several decades, but little success was achieved before World war 11.2-0, The results of experiments during the war, and further knowledge gained in experiments with vastly improved communication methods and equipment after the war provided the background for additional research in radio communication in underground mines. During 1950 to 1.952 the University of Minnesota sponsored an investigation to determine the possibility of developing: a system of radio communication universally applicable in underground metal mines in the Lake Superior district. The possibility of using radio equipment to determine the imminence of rock bursts in deep copper mines in that district also was investigated. The investigation supplemented previous and concurrent emergency mine communication studies of the U. S. Bureau of Mines. Testing equipment and laboratory facilities maintained by the Bureau of Mines at Duluth, Minnesota, were used in the research program, which was conducted as a mining engineering graduate research problem by the present writer under the direction of T. L. Joseph and E. P. Pfleider. The radio units used in the research program were designed and built to specification solely to conduct tests of radio communication in mines. Two identical units were used in all tests. Each unit contained a transmitter section, a receiver section, and a power-supply section, mounted on a single chassis. The entire unit was enclosed in a single 10x12x18-in. metal case provided with a leather-strap handle for carrying purposes. The front of the case was hinged to open upward and provide easy access to the single control panel on which all controls were mounted. Storage batteries supplied the operating power for all tests. Standard 6-v automobile batteries were utilized to provide adequate capacity to conduct tests for a full day without exhausting the battery. A frequency range from 30 to 200 kc was covered in eight pre-fixed steps on each unit. The carrier frequencies were crystal-controlled and amplitude-modulated. The receiver employed an essentially standard superheterodyne circuit and was sufficiently sensitive to detect signal strengths of 5 micro v. A heterodyne circuit was employed in the transmitter to obtain the low-carrier frequencies used in the units. Power output of the transmitter, usually less than 2 w, rarely exceeded 3 w in any test. Tests were conducted in mines on the Vermillion iron range in Minnesota, the Gogebic iron range in Wisconsin, the Menominee and Marquette iron ranges in Michigan, and a copper mine in the upper Michigan peninsula. All tests were conducted when the mines were operating normally, and usual mining, maintenance, and transportation activities were in progress, so that any interference caused by normal production activities could be evaluated during the tests. Tests were made between different points underground in each mine, and between underground and surface points at some mines. Test readings obtained at any one mine were calibrated in the laboratory before another series of tests were begun at the next mine. The transmitter and receiver were separated by one or more levels in each test, and generally there was no other means of communication between test points. Two 100-ft lengths of rubber-covered wire were used for antenna wires on each unit in both transmission and reception. The ends of the wires were connected to ground points in one of several methods, depending upon physical conditions at each test site. The wires were clipped to metal rods about 200 ft apart in the back, side, or bottom of the mine opening where the character of the rock permitted driving rods. Both wires were clipped to points about

Jan 1, 1954

By J. W. Spretnak, D. A. Chatfield, G. W. Powell, J. R. Eifert

In nzost cases, the driving force for a lattice transformation is produced by supercooling below the equilibriunz transformation temperature. The interfnce reaction in isothermally annealed, multiphase diffusion couples may involve a luttice transformation which also requires a driving force. Direct experinzental evidence has been obtained for the existence of the driring force in the form of a supersaturated phase at the aocc)-0@cc) interface in Cu:Cu-12.5 ult pct A1 couples; the super saturation is equivalent to an excess free energy of approximately 3 cal per mol at 905. A tentatiue interpretation of the dynanzic situation a1 the interface based on the free energy-composition diagram is proposed. THE presently accepted theory of diffusion in multiphase couples1 states that there will be a phase layer in the diffusion zone for every region which has three degrees of freedom and which is crossed by the diffusion path in the equilibrium phase diagram. For binary systems, this restriction excludes all but single-phase fields and, for ternary systems, only one- and two-phase fields are included. In addition, Rhines"~ as well as other investigators3 6 have reported that the compositions of the various phases adjacent to the interfaces are, for all practical purposes, the compositions given by the intersections of the diffusion path with the solubility limits of the single-phase fields of the equilibrium phase diagram. Some studies of the rate of thickening of these intermediate diffusion layers indicate that the thickness of the layer changes para-bolically with time, or: where x is the position of the interface relative to an origin xo, t is the diffusion time, and k is a temperature-dependent factor. crank7 shows mathematically that, if the compositions at an interface are independent of time and the motion of the interface is controlled by the diffusion of the elements to and from the interface, then the segments of the concentration penetration curve for a semi-infinite step-function couple will be described by an equation of the form: hence, Eq. [l] follows from Eq. (21 if the interface compositions are fixed and if the motion of the interface is diffusion-controlled. Although the concept of local equilibrium being attained at interfaces has assumed a prominent role in the theory of diffusion in multiphase couples, experimental evidence and theoretical discussions which challenge the general validity of this concept have been reported in the literature. arkeen&apos; has stated that strict obedience to the conditions set by the equilibrium phase diagram cannot be expected in any system in which diffusion is occurring because diffusion takes place only in the presence of an activity gradient. Darken also noted that it is usually assumed that equilibrium is attained locally at the interface although the system as a whole is not at equilibrium, the implication being that the transformation at the interface is rapid in comparison with the rate of supply of the elements by diffusion. ISirkaldy3 indicates agreement with Darken in that he believes the concept of local equilibrium is at best an approximation because the motion of the phase boundary requires that there be a free-energy difference and, hence, a departure from the equilibrium composition at the interface. Seebold and Birks9 have stated that diffusion couples cannot be in true equilibrium, but the results obtained are often in good agreement with the phase diagram. The initial deviation from equilibrium in a diffusion couple will be quite large because alloys of significantly different compositions are usually joined together. Kirkaldy feels that the transition time for the attainment of constant interface compositions (essentially the equilibrium values) will be small, although in some cases finite. Castleman and sieglelo observed such transition times in multiphase A1-Ni couples, but at low annealing temperatures these times were quite long. Similarly, ~asing" found departures, which persisted for more than 20 hr, at phase interfaces in Au-Ni and Fe-Mo diffusion couples. Braun and Powell&apos;s12 measurements of the solubility limits of the intermediate phases in the Au-In system as determined by microprobe analysis of diffusion couples do not agree with the limits reported by Hiscocks and Hume-Rothery13 who used equilibrated samples. Finally, Borovskii and ~archukova&apos;~ have stated that the determination of the solubility limits of phase diagrams using high-resolution micro-analyzer measurements at the interfaces of multiphase couples is not an accurate technique because of deviations from the equilibrium compositions at a moving interface; diffusion couples may be used to map out the phase boundaries in the equilibrium diagram, but the final determination of the solubility iimits should be made with equilibrated samples. The purpose of this work was to investigate the conditions prevailing at an interface in a multiphase diffusion couple and to compare the interface compositions with those associated with true thermodynamic equilibrium between the two phases. Microanalyzer techniques were used to measure interface compositions in two-phase Cu-A1 diffusion couples annealed at 80@, 905", and 1000°C for various times.

Jan 1, 1969

By A. L. Pranatis, G. M. Pound

Changes in length of copper foils of varying thickness and grain size were measured under such conditions of low stress and high temperature that it is believed that creep was predominately the result of interboundary diffusion of the type recently discussed by Conyers Herring. The surface tension of copper was calculated and results confirmed previous work within the limits of experimental error. Under the assumption of viscous flow, viscosities were calculated as a function of temperature and grain size. Predictions of the Nabarro Herring theory of surface grain boundary flow were borne out fully and the Herring theory of diffusional viscosity is strongly supported. ONLY a relatively few techniques for obtaining the surface tension of solids are presently available. Of these, the simplest and most straight forward is the direct measurement of surface tension by the application of a balancing counterforce. Thin wires or foils are lightly loaded and strain rates (either positive due to the downward force of the applied load or negative if the contracting tendency of surface tension is sufficiently greater than the applied stress) are observed. By plotting strain rates against stress, the load which exactly balances the upward pull is found and a simple calculation yields a value for the surface tension. The technique is of comparative antiquity, and solid surface tension values were reported by Chapman and Porter,&apos; Schottky; and Berggren" in the early part of the century. Later, the filament technique became fairly well established as a method for determining the surface tension of viscous liquids, and Tammann and coworkers,&apos;. " Sawai and co-worker and Mackh howed good agreement between the values of surface tension for glasses and tars obtained by the filament technique and by more conventional methods. With the increased confidence in the technique gained in these experiments, the method was applied to solid metals and the first reliable values of surface tension of solid metals were reported by Sawai and coworkers10&apos; " and by Tammann and Boehme." More recently, Udin and coworkersu-&apos;" have reported the results of experiments with gold, silver, and copper wires. Similar experiments with gold wires were carried out by Alexander, Dawson, and Kling.&apos;" The excellent review articles of Fisher and Dunn" and of Udinl@ should be referred to for detailed criticism of the foregoing work and for discussion of underlying theory. In all the foregoing calculations, it is assumed implicitly that the material contracts or extends uni- formly along the length of the specimen and also that it flows in a viscous fashion, i.e., that strain rates are proportional to stress. For an amorphous material, such as glass, tar, or pitch, the assumptions are quite valid and good agreement is obtained with values of surface tension measured by other techniques. The values reported for metals, however, are occasionally regarded with misgiving, since it can be argued that, because of their crystalline nature, true solids can not deform in a viscous fashion. If this is true, then the results reported for solid metals over a long period of years are of only doubtful value. Thus it is clearly necessary that a mechanism be established that would explain both the viscous flow and the uniform deformation that has been assumed. Such a mechanism has been proposed by Herring."&apos; Briefly, he suggests that, under the conditions of the experiment, deformation takes place by means of a flow of vacancies between grain boundaries and surfaces. This is a direct but independent extension of the theory proposed by Nabarro" in an attempt to explain the microcreep observed by Chalmer~.In a condensed form the Herring viscosity equation is TRL there 7 is the viscosity, T the absolute temperature, R and L grain dimensions, and D the self-diffusion coefficient. In its complete form, all constants are calculable and it includes such factors as grain shape, specimen shape, and degree of grain boundary flow. When applied to existing data, good agreement was obtained between predicted and observed flow rates. The theory received provisional confirmation from the work of Buttner, Funk, and Udin" who observed viscosities in 5 mil Au wire much higher than those in the 1 mil wire used by Alexander, Dawson, and Kling.&apos;" More significant were the completely negligible strain rates found by Greenough" in silver single crystals. Opposed to these observations were those of Udin, Shaler, and Wulff&apos;" who found indications of viscosity decreasing as grain size increased. Thus, complete confirmation of the theory was lacking in that the data to which it could be applied contained only a limited number of grain sizes. Hence, it was proposed that a series of experiments be carried out with thin foils of varying grain size up to and including single crystals, where, according to the Herring theory, deformation would occur only at almost infinitely slow rates.

Jan 1, 1956

By V. Pasupathi, R. E. Hummel, J. W. Koger

Specimens of P1 brass were plastically deformed at room temperature to various degrees of deformation and subsequently cooled in order to transform them to low-temperature martensite. Deformation shifts Ms. A, , and the temperature of minimum resistivity to lower temperatures, and also decreases the temperature coefficient of electrical resistivity. These properties change rapidly up to about 15 pct reduction but vary very little with higher deformation. The possible relationships between martensite formed by deformation and the M, temperature of low-temperature martensite are discussed. Evidence is given that deformation martensite delays the formation of low-temperature martensite. BETA&apos; brass undergoes at least two different types of martensitic transformations. One of these transformations (B1- B2) was first observed by Kaminski and ~urdjumov&apos; and occurs when 81 brass with a zinc content between 38 and 42 wt pct (quenched from the single-phase region) is cooled below room temperature. Jollev and Hull&apos; determined the structure of 0" from X-ray and electron-diffraction data as ortho-rhombic. Kunze came to the conclusion that the super-lattice cell of 0" is one-sided face-centered triclinic (pseudomonoclinic). The second martensitic transformation (B1-A1) occurs when the specimens are deformed at or somewhat above room temperature. This type of martensite will be called deformation martensite. Horn-bogen, Segmuller, and Wassermann4 determined the structure of deformation martensite to be bct. (An intermediate phase, az, occurs before the final phase appears.) At deformations higher than 70 pct, a, transforms into a.4 A critical temperature Md exists above which no transformation occurs during deformation and is estimated to be around 400°C in P1 brass.5 This martensite has elastic properties.6 When the sample is stressed, martensitic plates appear; when the stress is released, the plates disappear. The present paper studies the effect of deformation martensite on the formation of low-temperature martensite. The experiments involved samples of 8, brass which were plastically deformed by various amounts and were subsequently cooled below the transformation temperature. EXPERIMENTAL PROCEDURE The 13 brass investigated was made from 99.999 pct pure copper and 99.9999 pct pure zinc and contained 38.8 wt pct Zn. The specimens, consisting of foils 0.1 mm in thickness, were heat-treated at 8&apos;70°C for 15 min in an argon atmosphere and then quenched into ice water. They were then deformed by cold rolling and subsequently cooled at a rate of 1°C per min. The martensitic transformation that occurred during cooling was followed by electrical resistivity measurements. The resistance measurement technique and its accuracy have been described in a previous paper. Because the transformation 81 —-8" occurs below room temperature, the samples were placed in a cryo-stat which contained isopentane as a cooling medium. The isopentane was cooled by liquid nitrogen pumped under pressure through a 15-ft coil of copper tubing which was immersed in the isopentane. The nitrogen flow was regulated by a temperature controller using two thermistors in the cooling medium. The cryogenic liquid could be heated with an immersion heater. The useful temperature range with this device was from +25° to approximately -155~C. EXPERIMENTAL RESULTS Resistivity Measurements. The following abbreviations are used in this paper to label the characteristic temperatures during the martensitic transformation. M, is the starting point of the martensitic transformation and is defined as that temperature where the resistivity vs temperature curve on cooling first deviates from a straight line. Mf is the temperature at which the martensitic transformation is completed. On reheating, the transformation from martensite to the parent phase starts at a temperature A, and ceases at a temperature Af. Fig. 1 presents five different resistivity vs temperature curves corresponding to the transformation of brass from Dl to 8" after different degrees of reduction in thickness. The following observations can be made from these curves. 1) With increasing degree of deformation the Ms temperature is shifted to lower temperatures. This shift ranges up to 35°C compared to the undeformed state. This is also indicated in Fig. 2, where AM, (the shift of Ms, compared to the undeformed state) is plotted vs the degree of deformation. AM, increases rapidly until a reduction of about 15 pct is reached. With higher deformations, no additional increase in AM, was found. 2) With increasing degree of deformation the temperature of minimum resistivity (M) is also shifted to lower temperatures. The shift, attains a maximum of about 61°C compared to the undeformed state. In Fig. 3, AM is plotted as a function of deformation. It can be seen that, as in 1 above, AM increases rapidly and no further shift of M occurs for deformations greater than 15 pct. 3) The temperature coefficient of resistivity, is given by the slopes (dp/dT) of the linear portions of

Jan 1, 1969

By G. M. Yocom

Blowing acid Bessemer converters with oxygen-steam produces steel of below 0.002 pct N2 content. This method of blowing, combined with a dephosphorizing treatment in the steel ladle, results in low-carbon steels of low nitrogen and low phosphorous (under 0.035 pet) contents, which has physical properties equivalent to open-hearth steels of similar analysis. Using a 50-50 mixture of oxygen and steam, the refinitzg rate is increased 25 pct over blowing with natural air, and scrap charge increased from 3 to 10 pet. Bottom life is normal with proper tuyere area and arrangements, fumes are decreased, yields increased, and hydrogen content is normal. THE acid Bessemer plant at the South Works of Wheeling Steel Corp., consists of two 15-ton bottom blown converters with a monthly capacity of 57,000 N.T. The product of the shop is skelp billets for continuous welded pipe and slabs for ordinary drawing and forming quality sheets. Approximately 50 pct of ingot production is regular Bessemer steel of natural Phos content and the remainder is a dephosphorized grade of steel made by a special treatment of the blown metal as it is poured into the steel ladle. The low Phos grade of steel has certain advantages over the higher Phos grade but since both grades were produced by blowing natural air, the N2 content was in the range of 0.015 pct which limited its application. In 1954 it was decided to explore the possibilities of blowing with a steam-oxygen mixture for the production of steel of both low N2 and low Phos contents. The necessary equipment was installed to operate one converter in this manner and early in 1955 an experimental run of 160 heats was made by blowing with a steam-oxygen blast and excluding natural air entirely. During this period the proper operating techniques were established, such as blast pressures, steam-oxygen mixtures, valves and instrumental control equipment, tuyere arrangement in the bottoms, blowing times and production rates, and a thorough study made of the final steel quality. Also during this experimental period the dephosphorizing practice was improved by the use of a tap hole below the lip of the vessel. This provided a clean separation of the acid converter slag and blown metal which made the dephosphorizing treatment more effective. The results of this experimental run dictated further development of this practice and a second run of 720 heats was made in 1957. The quality features and conversion cost results were in line with expectations and accordingly a 400-ton per day oxygen plant is now being installed. The plant is scheduled for completion in September of this year. This will provide sufficient oxygen to operate both vessels on steam-oxygen blast and delete natural air blowing entirely. The steel will then be below 0.002 pct N2 bar content and the dephosphorized grades will be between 0.015 and 0.040 pct Phos. STEAM-OXYGEN BLOWING The steam for the process is fed to the plant at 220 psig pressure through a 6-in. line. The high-purity oxygen is compressed to 200 psig and conducted through an 8-in. line. The oxygen from the main line is valved down to 100 psig and passed through a steam heated heat exchanger. The heat exchanger is regulated to supply oxygen at 300°F to the steam-oxygen mixing station. It is essential that the incoming oxygen be held at this temperature to avoid condensation of the steam with resulting excessive erosion of the clay tuyeres in the vessel bottom. Oxygen is admitted to the mixing chamber by a 6-in. hydraulically operated valve driven by the ratio control regulator on impulse from the flow of steam. Steam is admitted to the steam-oxygen mixture station through a 2 1/2-in. hydraulically driven valve. The ratio control regulator acts to increase or decrease oxygen input as the steam flow increases or decreases with changing positions of the Blower&apos;s control lever. The important point to note here is that steam flow always precedes the oxygen flow as a safety measure. The control valves have sufficient capacity to afford protection should blow pipe trouble develop. A 50-50 mixture for these 15-ton heats demands an oxygen flow of 3800 standard cu ft per min along with 317 lb of steam. The Blower&apos;s stations is provided with an indicating blast pressure gage, and indicating steam and oxygen flow meters. Signal and warning lights indicate the valve positions and line pressures. A control room at the real of the Blower&apos;s pulpit room houses the ratio control and pressure regulators, as well as the various meter bodies. The hand actuated wheels used to change the conditions are mounted on a panel on the front of the meter control house. The recording steam and oxygen meters used for totalizing and accounting purposes are also mounted on this panel.

Jan 1, 1962

By W. V. Green

Creep of tantalum was measured at temperatures from 0.6 to 0.89 of the absolute melting temperature. The creep curves include first, second, and third stages. Steady-state creep rate depends on the fourth power of stress. The activation energy for creep throughout this temperature range is approximately 114 kcal per mole, measured by the aT technique. Subgrain formation occurs as a result of creep strain, and pile-up dislocation arrays are observed in etch-pit patterns. BECAUSE of its high melting point-which is exceeded only by those of rhenium and tungsten—and its high room-temperature ductility compared to most of the other high-melting-point metals, tantalum will undoubtedly be utilized in an increasing number of high-temperature applications. Alloying studies directed toward increased high-temperature strength must use data on tantalum itself as a base line in order to evaluate the effectiveness of the alloying additions. However, to date, no systematic study of creep of tantalum at temperatures above one-half of its melting point has been reported in the literature. Conway, Salyards, McCullough, and Flagella1 have measured linear creep rate of tantalum sheet as a function of stress, but at only one temperature, 2600°C. This paper describes a relatively thorough study of the high-temperature creep of tantalum. METHOD Material Tested. The commercially supplied, l/2-innch-diameter tantalum rod used for this work was electron-beam-melted, cold-forged, rolled, swaged, cleaned chemically, and vacuum-annealed for 1 hr at 1000°C, all by its manufacturer. The vendor&apos;s analysis included 60 to 170 ppm C, 3.4 to 4.2 ppm H, 60 to 80 ppm 0, 15 ppm N, and a hardness ranging from 66 to 81 Bhn and averaging 76 Bhn. Creep eimens Used. Two creep-tested specimens are shown in Fig. 1. The 1/4 in.-diameter gage section was 3/4 to 1 in. long, and terminated either at shoulders 5 mils high or at 20-mil-diameter tantalum wires spot-welded to the circumference of the gage section. Both kinds of shoulders served equally well as fiducial marks for optical strain measurements. The spot welding did not alter the creep behavior in any detectable way; the 5-mil- high sharp shoulders did not result in any detectable localized effect on the strain. Before testing, each tensile bar was first mechanically polished -id then electrochemically polished according to the method referred to by Forgeng2 as the "Thompson Ramo Woolridge" method, which was suitable for tantalum after small adjustments of technique were made. Two tensile bars tested at low stresses had 1/8-in.-diameter gage sections and utilized only the weight of the bottom grip for the applied load. Although these diameters were smaller than were desired for other reasons, applied loads were known with high precision in the tests in which they were used. Testing Procedure. Two different constant-load creep-testing machines were employed, one of which has been described by Smith, Olson, and Brown.3 In both, the tensile bar is held vertically on the axis of a cylindrical tungsten tube or screen heater by threaded tungsten grips. The tensile bars and associated grips are heated by radiation from the incandescent heaters, which are heated by their own electrical resistance. Both testing machines use pins to hold the bottom grips in place. The load is applied to a tensile bar through hanging weights, a constant force-multiplication lever, a pull rod sealed to the chamber lid, and a top grip threaded to the pull rod at one end and to the tensile bar at the other. In one machine, the vacuum seal is a bellows with a low spring constant; in the other, the seal involves a rotating "0 ring". With the latter, rotation is converted to translation with a crank shaft, so that elongation of the tensile bar is accommodated with no change of tensile load. The incandescent tensile bar is viewed by an external optical system through slots in the radiation shields and heater, and an enlarged image is projected on a ground-glass screen. Gage-length measurements are made on this image with cathetometers on traveling microscopes. With regard to creep-test results, the two machines were identical. Thorium oxide coatings were applied to the threaded ends of the tensile bars, to prevent diffusion welding of the tensile bars to the grips during testing. Specimen temperatures were measured with an L. & N. optical pyrometer which had been calibrated against a standard carbon arc, and were corrected fir window absorption by calculation from the measured spectral transmittance of the quartz observation windows. Longitudinal temperature gradients in the tensile-bar gage length and temperature drifts during testing were detectable but small, and were estimated to be 10°C or less. Accuracy of temperature measurement was confirmed by comparing the temperature measured on the surface of a special

Jan 1, 1965

By Robin O. Williams

AN investigation has been made of the Ni-Cr system for the purpose of elucidating certain points, namely the nature of aging in both terminal solid solutions and the nature of the phase diagram. Information pertaining to solubilities and precipitation has been obtained. Experimentation Five alloys, Table I, were arc melted in a cold copper crucible using electrolytic chromium and car-bony1 nickel, both dry hydrogen treated. These 100 g buttons were homogenized 24 hr at 1300°C in dry hydrogen and air cooled. Powders were prepared by filing or pulverizing and subsequent heat treatment was done in vacuum or helium using titanium chips as a getter. Powder of —80 mesh was filed from the 60 pct Ni alloy quenched from 1000°C and was sealed in silica under vacuum using a 250 °C outgassing. After aging as indicated in Table I1 the lattice parameters were measured on the quenched samples using the standard cos" 6 extrapolation. These parameters are considered accurate to roughly 0.0001A. In all cases chromium lines of 2.8812 ± 0.0005Å at 30°C were found. Drastic quenching from sufficiently high temperatures produced very sharp body-centered-cubic lines in the first four alloys without indications of transformations. Temperatures to 1250°C were used. Solid samples less than 1/16 in. thick were quenched in water without transformation and the powders could be adequately quenched in small helium filled thin wall silica tubing using a water quench. For those powder samples which were quenched from the two phase field the relative intensity of the body-centered-cubic lines and the face-centered-cubic lines were estimated and extrapolated to give the indicated solubility data in Fig. 1. The data for the two higher alloys were somewhat limited, the plotted points being the lowest temperature where no nickel phase was found. Neither filing, abrading, pulverizing, nor cooling to —190°C produced any new diffraction lines for solid samples quenched from the single phase region, nor did the character of the body-centered-cubic lines change Single phase body-centered-cubic powders likewise did not change on cooling to —190°C. Also, samples which had some precipitation due to inadequate quenching showed no additional changes under these conditions. The first change apparent by X-ray diffraction form samples quenched almost fast enough to prevent precipitation was the diffuseness of the body-centered-cubic lines, particularly on the low angle side, For slower cooling rates the diffuse face-centered-cubic lines appeared. Work on the large grained castings showed profuse streaking through some of the Laue spots while oscillating patterns showed broad body-centered-cubic and face-cen-tered-cubic lines as well as some new lines. For the 23.6 pct Ni alloy the new lines corresponded to 2.16, 1.96, and 1.86A and were more similar in character to the face-centered-cubic lines than the body-centered-cubic lines. Samples which were air cooled gave only face-centered-cubic and body-centered-cubic lines which were still broad. One pattern indicated that face-centered-cubic (111) plane was parallel to a body-centered-cubic (110) plane. For those samples which were examined by light microscopy there were details which were not resolved. However, varied and beautiful structures were obtained. Fig. 2 is of an alloy quenched in a helium filled silica tube from the single phase region and shows particles associated apparently with dislocations which are arranged in low angle boundaries. Finer, general precipitation has also taken place within the grains. Figs. 3 to 5 show the variety of structures produced in these alloys on continuous cooling. It appears that there are four distinct modes of precipitation as evidenced by these, figures. Annealing these structures at higher tem-peratures in the two phase field gives structures as shown in Fig. 6, which shows nickel plates in the chromium matrix which reprecipitated nickel on a much finer scale of the final quench. Lower annealing temperatures and shorter times naturally give finer plates of the nickel-rich phase. Samples of the first four alloys were annealed for appreciable times between 900º and 1250°C and gave structures like Fig. 6. The relative amounts of the two phases were measured and extrapolated to give solubility data as indicated in Fig. 1. The point at 1250°C was deduced from data of Oxx.1 These and most of the other samples were checked for ferromagnetism but none was apparent. In fact, it appeared that the magnetic susceptibilities were not more than three times that for paramagnetic chromium. Discussion In Fig. 1 it is seen that the solubility of nickel in chromium can be represented by a slightly curved line on the usual log X vs 1/T plot, These data are believed to be accurate to roughly 5 to 10º. There is only fair agreement with the data of Taylor and

Jan 1, 1958

By R. E. Powers, E. H. Kinelski, H. A. Morrissey

A group of 17 American blast-furnace sinters, an American open-hearth sinter, an American iron ore, and a Swedish sinter were used to evaluate testing methods adapted to appraise sinter properties. Statistical calculations were performed on the data to determine correlation coefficients for several sets of sinter properties. Properties of strength and dusting were related to total porosity, slag ratio, and total slag. Reducibility was related to the degree of oxidation of the sinters. THIS report to the American iron and steel industry marks the completion of a 1949 survey of blast-furnace sinter practice sponsored by the Subcommittee on Agglomeration of Fines of the American Iron & Steel Institute. The use of sinter in blast furnaces, sinter properties, raw materials, and sinter plant operation have been reported recently.1,2 After preliminary research and study," test procedures were adapted to appraise the physical and chemical properties of sinter to determine what constitutes a good sinter. During the 1949 to 1950 plant survey each plant submitted a 400-lb grab sample to research personnel at Mellon Institute, Pittsburgh, Pa. A 400-lb sample was also submitted from Sweden. In addition, 2 tons of group 3 fines iron ore were obtained from a Pittsburgh steel plant. The following tests were performed on the iron ore sample and on the 19 sinter samples: chemical analysis; impact test for strength and dusting; reducibility test; surface area measurements, B.E.T. nitrogen adsorption method; S.K. porosity test; Davis tube magnetic analysis; X-ray diffraction analysis for magnetite and hematite; and microstructure. Results of these evaluations are discussed in this paper and supply a critical look at testing procedures used to determine sinter quality. Sinter Tests and Results Each 400-lb grab sample of sinter was secured at a time when it was believed to represent normal production practice at each plant. It was not possible to use the same sampling procedures throughout the survey; consequently samples were taken from blast-furnace bins, cooling tables, and railroad cars. These were very useful for evaluation of test methods, since they were obtained from plants with widely divergent operations. With the exception of Swedish sinter and sinter sample N, which were produced on the Greenawalt type of pans, all survey sinters were produced on the Dwight-Lloyd type of sintering machines. Sinters submitted for test were prepared in identical manner by crushing in a roll crusher (set at 1 in.), mixing, and quartering. To secure specific size fractions for tests, one quarter of the sample was crushed in a jaw crusher and hammer mill to obtain a —10 mesh size. The remainder was screened to obtain specific size fractions. The group 3 fines iron ore was dried and screened and samples were taken from selected screen sizes to be used for various tests. Prior to testing, each ore sample except the —100 mesh fraction was washed with water to remove all fine material and was then dried. This iron ore, a hematitic ore from the Lake Superior region, was used as a base line for comparing results of tests on sinters. The iron ore did not lend itself to impact testing, since it was compacted rather than crushed in the test, and no impact tests are reported. However, the iron ore was subjected to all remaining physical tests to be described. Chemical Analysis: Table I presents chemical analyses performed on the survey sinter samples. Included in this table are data obtained from determination of FeO and the slag relationships: CaO + MgO and total slag (CaO + MgO + SiO, SiO2 + Al2o3 + TiO2). The percentage of FeO was used as an indication of the percentage of magnetite in the sinter. It was believed that slag relationships could be correlated with sinter properties. During initial determination of FeO great disagreement arose among various laboratories, both as to the results and the methods of determining values. Table I lists the values of FeO resulting from the U. S. Steel Corp. method of chemical analysis,&apos; which reports the total FeO soluble in hydrochloric and hydrofluoric acids (metallic iron not removed) with dry ice used to produce the protective atmosphere during digestion. Use of dry ice was a modification required to obtain reproducible results. In this method, the iron silicates and metallic iron are believed to go into solution and are therefore reported as FeO. This is important, for in the study of the microstructure of sinters, glassy constituents suspected of containing FeO as well as crystallized phases of undetermined identity which may also contain FeO have been observed. Strength Test by Impact: In evaluating sinter quality, one of the properties stressed most by blastfurnace operators is strength. This strength may be described as the resistance to breakage during handling of sinter between the sinter plant and the blast-furnace bins. It is also the strength necessary to withstand the burden in the blast-furnace. After

Jan 1, 1955