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By P. L. Weston, S. E. Khalafalla

A systematic study was made by the Bureau of Mines on the effect of so me hypothesized accelerators for the process of wustite reduction in carbon monoxide. When small concentrations of promoter materials in the order of 0.69 at. pct were added to the reducible charge, the rate of reduction to iron was increased. Promotion phenomenon prediction was made in light of a suyface reduction mechanism with the aid of Vol'kenshtein's effect regarding the propagation of crystal lattice disturbances by small amounts of relatively larger interstitial ions. The acceleration produced by a typical promotor, such as potassiunl, increases with protnoter concentration up to a maximum, beyond which the reduction rate decreases. Concentration for maximum promotion depends on the nature and physicochemical properties of the promoter. The extent of reduction rate enhancement is found to be directly proportional to the atomic volume and electronic charge of the additive. DESPITE the enormous volume of literature on iron oxide reduction, very little is reported concerning additive or impurity effects on this important metallurgical process. The beneficial effect bf calcium compound additions on the reducibility of iron oxide sinters has been reported by Tigerschiold,1 vor dem Esche,2 and Edstrom. Doi and Kasai~ found that the addition of lime or limestone to iron ores helps to break up any unreducible compounds, such as fayalite or ilmen-ite. and thus free the combined iron for reduction. Schenck et al. 5 suggested that the increased reduction rate obtained when adding lime could be accounted for by the instability of wustite in the presence of lime. Acid-base slagging reactions resulted in wustite disproportionation according to The dicalcium ferrite formed will yield iron and calcium oxide during reduction. Regenerated calcium oxide dissociates more wustite. This mechanism has been used by Seths and white7 to explain their experimental results. Recently, Strangway and ROSS' attributed the calcium carbonate acceleration of iron oxide agglomerate reduction to increased porosity, both initial as well as that developed during reduction. Aside from calcium carbonate, or oxide, no other promoter was noted in the literature, except for a brief mention by Barrett and woodg on the effect of sodium carbonate and aluminate as activators for the hydrogen reduction of magnetite at 600°C. The present investigation systematically studied a host of other promoters, including calcium and sodium, in an attempt to elucidate the mechanism by which promotion takes place and to fit the results into a simple chemical model. To attain this goal, the effect of promoter physical properties, such as atomic volume, electronic charge, and concentration are related to wustite reduction kinetics in this paper. Wustite reduction to iron, rather than the overall hematite reduction, was chosen since this reaction is known to be the slowest, and hence the rate-deter mining step for the overall iron oxide reduction process. EXPERIMENTAL PROCEDURE Raw Materials and Their Preparation. The pure or impregnated wustite pellets were prepared from minus 400-mesh chemically pure hematite powders. A known weight of hematite was thoroughly and uniformly mixed with a calculated weight of the additive. The mixed paste containing 35 wt pct water was gradually heated from 400" to 1200° C and fired at 1200°C for approximately 4 hr in an air atmosphere. After cooling, the sinter was pulverized to minus 100 mesh and pelletized into minus 4- plus 5-mesh spheres. Pellets were fired, similarly to the paste mix, air-cooled, sized, and stored. An appropriate weight of the charge (20 g) was placed in a zirconia reduction tube maintaining a uniform oxide bed height of 1 cm and a cross section of 7.1 sq cm for all of the test runs. The samples were supported in the vertical reaction tube by a bed of fragmented insulating firebrick plus 3- to 6-mesh alumina beads. The hematite was then transformed to wustite by reduction with a 30 pct CO2-70 pct CO gas mixture at 1000°C in a globar furnace. Complete conversion to wustite was ascertained by a continuous infrared gas analyzer recording the CO-CO2 content of the effluent gas until no carbon monoxide was absorbed from the inlet gas, and inlet-outlet gas analysis remained constant for 30 min. The wustite sample was then reduced with 100 pct CO at 100WC. From the recorded data, an initial rate of reduction was determined by the initial slope of the graph percent reduction vs time. In order to estimate the accuracy of the data, five separate determinations of the reduction curve of pure wustite, under otherwise identical conditions, were performed. The maximum deviation from the average reduction at 14 min amounted to 2 2 pct reduction. This deviation corresponds to 3.8 pct variation based on the percent reduction of the sample. Aiiy impurity effect below the limits of this maximum deviation was considered a spurious result. If the effect exceeded + 4 pct, then it was considered as a positive one. Considerable care was exercised in determining the initial rate from the slope of the initial segments of the curve. Each reduction curve was examined separately on large graph paper and the best tangent to the curve at zero time was drawn. The slope of this tangent was taken as a measure of the initial fractional reduction per minute. Although the time required to reach 50 pct reduction may be of special practical significance, initial rate measurements are invaluable in fundamental studies. These rates provide a measure of the process kinetics on the initial

Jan 1, 1968

By C. H. P. Lupis, R. Hocine, G. Bernard

The necessary and sufficient conditions for the stability of a multicomponent phase with respect to infinitesinzal fluctuations are derived and transformed to be written in terms of activity coeffcients and mole fractions rather than in terms of the customary second deritlatives of the free energy. NECESSARY conditions for the stability of a multi-component system were derived by Gibbs as early as 1876.' However, as the usefulness of these conditions is greatly enhanced by the simplicity of their translation in terms of functions of common usage, the present contribution establishes these conditions in terms of activities or activity coefficients-and mole fractions. It was shown in another article2 that not only may these conditions be used for the prediction of the appearance of new phases, but they may also provide a check on the orders of magnitude of the interaction coefficients involved. "Spinodal" decomposition is said to occur when, at constant temperature and pressure, the system is unstable with respect to infinitesimal fluctuations in composition. As a result, the "phases" which appear may be attained through continuous changes in the system rather than discontinuous ones, and, consequently, the free energy of these phases may be described by a unique continuous free-energy function. For a binary system, the familiar curve of Fig. 1 illustrates the case we wish to extend to a multicom-ponent system. The conditions to be written pertain to the decomposition of a system of n moles into moles of phase moles of phase v, ...hen moles of phase 9, where the phases a, ...v, ...9 are—at least initially-arbitrarily close in composition to that of the original phase. Each A, is positive and since the total number of moles n in the system remains constant: Each phase v contains hv(nl +dnY) moles of component (I), ...xV(ni +dny) of component + dnk) moles of component (m). The total number of moles ni in the system remaining also constant, it is clear that:

Jan 1, 1968

By J. Larsen-Badse

The resistance to dry sliding abrasion us been measured for some hardened and tempered carbon steels. The wear resistance, defined as the reciprocal of the volume loss per unit sliding distance, is found to vary linearly with the hardness of the abraded surface. The data fit two lines, one, of high slope, for the pure metals and for the annealed steels and another, of smaller slope, for the hardened and tempered carbon steels. A relationship is developed showing the alwasion resistance to be proportional to the hardness of the material and to en, where n is the exponent of work hardening. The values of n and of the hardness FOR most materials a high resistance to abrasion is generally associated with a high value of indentation hardness. Brine11 even used the abrasion resistance as a measure of hardness in an attempt at expanding the hardness range covered by his indentation-hardness test.' When comparing different types of materials there is, however, only a very general relation between abrasion resistance and hardness. Sample brittleness seems to contribute to the deviation from a direct relationship. In general, increased brittle- are those relating to the heavily deformed abraded surface. However, for materials having n constant or varying m a regular manner over a wide range of strailts, the wear resistance will also be a linear function of the bulk hardness of the material. For tempered steels containing a dispersion of cementite in ferrite the increase in wear resistance due to the dispersion is found to be a linear function of the volume fraction of Fe3C and of the reciprocal of the mean free ferrite path. This indicates indirectly that the yielding of this material, when it is already heavily deformed, follows the Orowan criterion. ness leads to decreased abrasion resistance.' When comparing materials in the same group, e.g., the metals, the spread is less. Kruschov found that the abrasion resistance of pure metals and of annealed steels is directly proportional to the hardness of the metal. For hardened and tempered steels he obtained another linear relationship, one of smaller slope and intersecting the line for the pure metals at the location of the data for the annealed steels. He also found that the abrasion resistance of cold-worked metals is independent of the degree of cold working. This shows, as he concluded, that the process of abrasion work hardens the metal in the surface region to a very high degree.

Jan 1, 1967

By R. Lagneborg, R. Gullberg

An X-ray method for determinig volume fractions of phases in textured materials has been developed. The method involves measurements of the integrated intensities of reflections of each phase for one single orientation of the sample. The method was checked by evaluating the phase contents in samples from two stainless Cr-Ni steels containing austenite and ferrite in known amounts. In the present case measurements of about five reflections from each phase were required. The agreement between calculated and known volume fractions was found to be very close. AN X-ray diffraction method is often employed for determining the amounts of two or more phases in a material. The details of the method have been described at several instances.'" In short, the method is based upon the fact that the integrated intensity of a reflection is directly proportional to the volume fraction of the phase considered. In principle, the method only requires the measurement of the intensity of one reflection for each phase. The most severe shortcoming with this method is that it disregards influences from preferred orientation in the material. In a diffractometer, where this type of analysis is most conveniently carried out, the geometry is such that the diffracting planes for a specific Bragg peak are all parallel to the surface of the specimen. This implies that it must be required that the occurrence of the diffracting planes parallel to the specimen surface must be as frequent as for any arbitrarily oriented physical plane of the sample. This requirement will generally only be fulfilled for a material free of texture. Since all materials in reality always exhibit a preferred orientation to some extent. the deficiency of the method is quite serious. In cold-deformed material the texture is appreciable, but also annealed material will in many cases display a considerable texture. The problem of quantitative phase analysis in textured material is one of obtaining the integrated intensity averaged over all orientations of the specimen with respect to the X-ray beam. Lopata and ~ula~ have shown that this can be accomplished by integration of intensities over the whole pole figure, or by random rotation of the specimen in the X-ray beam, or by a combination of both. Hence, in this method the average integrated intensity for a specific reflection is obtained by directly determining the intensity for a sufficient number of physical orientations of the sample. However, since an excess of diffracting planes in a certain surface plane necessarily must be accompanied by a deficiency of another type of diffracting plane, it appears to be possible to obtain the correct average intensity for a specific diffracting plane by performing an appropriate averaging of intensities belonging to a large number of diffraction planes of different hkl when all intensities have been produced from one single orientation of the specimen surface. In the present work such a method has been attempted and tested experimentally for two stainless Cr-Ni steels containing austenite and ferrite. 1) THEORY The expression for the integrated intensity of a Bragg reflection diffracted from a phase in a polycrys-talline sample in a diffractometer is: where C is a constant only dependent on the incident X-ray power and the diffractometer geometry, v the volume of the unit cell, F the structure factor, m multiplicity of the diffracting plane, L Lorentz factor, P polarization factor, e-2 temperature factor, p average linear absorption coefficient of the irradiated vO1umej and V volume fraction of the phase 'Onsidered. Hence, the factor R in the abbreviated form of Eq. [I] can be calculated and depends only on 0 and the diffracting plane {hkl}. For an alloy containing two phases, a and y, we can write

Jan 1, 1967

By W. M. Robertson

The formation of grain boundary grooves on surfaces of poly crystalline samples of cobalt and iron immersed in liquid lead has been studied. The grooves form by volume diffusion of the solutes cobalt and iron in the liquid. The diffusion coefficients of the solutes in liquid lead are derived from the measured rate of grooving. The diffusion coefficients are described by the relation D = Do exp (-Q/RT), with, for cobalt, Do = 4.6 x 10-4 sq cm per sec and Q = 5300 ± 800 cal per mole, and for iron, DO = 4.9 x 10-3 sq cm per sec and Q = 10,500 ± 1500 cal per mole. LIQUID metal-solid metal interactions occur at solid-liquid interfaces. Interfacial energy provides a driving force to change the morphology of the interface. Mullins1,2 has derived expressions for the kinetics of interface morphology changes driven by capillarity. These expressions can be applied to an isothermal system of a solid in equilibrium with a liquid saturated with the solid. Surface profile changes can occur by volume diffusion of the solute in the liquid, by volume self-diffusion in the solid, and by interfacial diffusion at the liquid-solid interface. A groove will form at the intersection of a grain boundary with a solid-liquid interface, reducing the total interfacial free energy of the system. The solid-liquid interfacial energy ? must be greater than half the grain boundary energy of the solid ?6 for Mullins' calculations to apply. If ? is less than ?b/2, then the liquid penetrates the boundaries, separating the grains rather than forming grooves. Boundary penetration did not occur in the work described here. where CO is the equilibrium volume concentration of the solid in the liquid, Dv the volume diffusion coefficient of the solid in the liquid, ? the interfacial free energy of the solid-liquid interface, O the atomic volume of the solid crystal, k Boltzmann's constant and T the absolute temperature. Eqs. [1] and [2 ] also apply to grooving by volume self-diffusion in the solid,1 with CoODv = D Self, where DSelf is the volume self-diffusion coefficient of the solid. For a grooving mechanism of interfacial diffusion at the solid-liquid interface, the groove width is given by2 where CS is the interfacial concentration of the diffusing species, and DS is the interfacial diffusion coefficient. Eqs. [1] and [3] can be used to determine the mechanism of groove growth. A t1/3 dependence of the growth indicates volume diffusion and t1/4 indicates interfacial diffusion. In some cases, volume diffusion and interfacial diffusion both can contribute substantially to the grooving process, causing the time dependence to be intermediate between t 1/3 and t1/4.3 For these cases, the relative contributions of the two processes can be separated.4 However, in many cases, one process will be dominant, and the data can be analyzed on the basis of Eq. [1] or Eq. [3] alone. The time dependences for volume diffusion in a liquid and volume self-diffusion in a solid are the same. However, the self-diffusion contribution of the solid is usually negligible compared to volume diffusion in the liquid. After the grooving mechanism has been determined, Eq. [1] or Eq. [3 ] yields the kinetic parameter A or B. The kinetic parameter can be used to calculate values for the unknown quantities in the product CD?. Usually C is known or can be estimated. If ? is known, then D can be calculated. In a measurement of grain boundary grooving of copper in liquid lead,' the time dependence indicated volume diffusion in the liquid. The quantities Co, Dv, and ? were obtained from the literature, giving excellent agreement between the observed values of A and the values calculated from Eq. [2 ].5 In a study of the grooving of several refractory metals in liquid tin and liquid silver, A1len6 educed that grooves formed by volume diffusion in the liquid. In a study of nickel in a nickel sulfide melt, Steidel, Li, and spencer7 found volume diffusion grooving kinetics. Both Dv and ? were unknown, so they could not obtain either one separately, though they did obtain a reasonable value for the temperature dependence of the product Dv ?. Several methods have been used to obtain surface profiles. It can be done by sectioning through the interface7 or by chemically removing the liquid from the solid surface after solidification of the liquid.6 However, if the liquid dewets the solid on removing the solid from the melt, then the interface can be observed directly. This method was used previously' and was utilized also in the present study. EXPERIMENTAL PROCEDURE Lead of 99.999 pct purity was obtained from American Smelting and Refining Co. Cobalt sheet was obtained from Sherritt-Gordon Mines, Ltd., with a nominal purity of 99.9 pct, the principal impurities being nickel, iron, copper, carbon, and sulfur. The sheet was

Jan 1, 1969

By P. M. Kelly, E. P. Butler

The stability of a 70/30 Mn-Cu alloy aged to peak damping has been investigated using electron microscopy, X-ray diffraction, and torsional pendulum measurements. Storage at room temperature or at 100" C causes a reduction in damping capacity. This is shown to be due to the formation of subdomains which "lock" the main domain structure and so hinder their movement. After storage the damping capacity can be restored by a retransformation treatment, which generates structures identical to those found in newly aged specimens. Plastic deformation by rolling also causes a decrease in damping capacity. In this case the damping capacity can only be restored by retransformation if the amount of deformation is less than about 5 pct. THE general metallography and structure of these high damping capacity alloys has been discussed in Part I of this work.1 Part II deals with some of the variables that affect the damping capacity. In particular, the stability of the damping capacity of a 70/30 alloy aged for 2 hr at 425° C and quenched has been investigated. The temperature sensitivity of the damping capacity of a 70/30 alloy aged for 2 hr at 450° C has been reported by Birchon.2 The damping capacity begins to decrease with increasing temperature, and is very low above the M, temperature of 125°C. The cubic — tetragonal transformation is completely reversible and there is no apparent thermal hysteresis associated with the change in damping capacity. Another important effect was first reported by Dean and his coworkers.3 They noticed a decrease in the damping capacity with time for specimens of a quenched tetragonal alloy. More recently workers at the Admiralty Materials Laboratory 4 have studied the stability of an aged 70/30 alloy. They found that the damping capacity decreased to half its original value after about 1000 hr at room temperature. EXPERIMENTAL The techniques used for electron microscopy and X-ray diffraction have been described in Part I. The damping capacity was measured by means of a torsional pendulum, using rectangular specimens, 3 by 0.3 mm with a 6 cm gage length. The specific damping capacity, S.D.C., was calculated as a percent amplitude decay in free vibrations over 10 cycles, starting at an amplitude which corresponded to a 700 psi surface shear stress. Because of the stress dependence of the damping,' the values obtained were about a third those reported for a 5000 psi surface shear stress.' RESULTS a) Effect of Aging Temperature. The effect of aging temperature on the damping capacity is shown in Fig. 1. The damping capacity reaches a peak of 12 pct after aging at 400° to 425°C) then begins to decrease as the volume fraction of a Mn increases. At higher aging temperatures the structure becomes cubic again with a low damping capacity. b) Stability of the Aged Structure. The damping capacity of the aged alloy decreases with time at room temperature. This process could be accelerated by storing at 100°C, when about 100 hr were required for the damping to fall to half its original value. The results of room temperature and 100°C storage, for times up to 1000 hr, are shown in Fig. 2. The damping capacity starts to decrease after about 24 hr at 18° C and 1 to 2 hr at 100°C. It was found, however, that the damping could be almost completely restored by retransformation. The specimens were held at a temperature above the M, for a short time, 250° C for 5 min, and then quenched. The values of damping capacity for specimens that were aged, stored, and then retransformed are shown by the full points in Fig. 2. X-ray measurements of the c/a ratio and hardness readings on the specimens did

Jan 1, 1969

By J. F. Smith, J. E. Davison

The heat capacity of CaMg2 was measured over the temperature interval, 4.8° to 287°K, by the technique of low-temperature adiabatic calorimetry. Heat content measurements were performed with a drop calorimeter over the temperature interval, 273" to 673°K. From these data the thermodynamic functions, (FT - H0)/T, ST - So, and & - Ho, were evaluated. A third-Law calculation of the standard entropy of formation of CaMg2 yields a value of -0.25 * 0.06 cal per (°K g-atom) , and the free-energy function derived from this study when combined with existing equilibria data yields a value for the standard enthalpy of formation which is in agreement with direct calorimetric enthalpy measurements. The accompanying paper' shows that the enthalpy of formation of CaMg2 has been determined with good precision by three different calorimetric techniques.'-= TWO independent determinations of the Gibbs free energy of formation of CaMg2 have also been made; both determinations were based on vapor pressure measurements, being in one case hydrogen vapor pressures over ternary Ca-Mg-H alloys4 and in the other case magnesium vapor pressures over binary Ca-Mg alloys.5 The present determination of heat capacity of CaMg2 below room temperature and of the heat content of CaMg2 above room temperature was undertaken to provide supplementary data. These data are useful in their own right but can in addition be used to evaluate an entropy of formation for CaMg2 which, because of the interrelation of free energy, enthalpy, and entropy, can be used as a check of the self-consistency of the composite of the presently available information. LOW-TEMPERATURE HEAT CAPACITY The heat capacity of CaMg2 was measured over the temperature interval 4.87° to 286.64°K in an adiabatic calorimeter. The physical details of the calorimeter and the experimental procedure for measuring the heat capacity of a specimen have been adequately described by Gerstein et a1.6 The source and purity of the calcium and magnesium are described together with the methods of sample preparation and chemical analyses in the accompanying paper.' Results of chemical analyses of the material which was used in the present investigation are shown in Table I. These analyses show that, on the basis of the published phase diagram,7 the heat capacity sample contained a slight excess of a calcium while the heat content sample contained a slight excess of magnesium. However, in both cases the excess was small, and X-ray diffraction patterns showed reflections which were without exception attributable to CaMg2. The sample which was used for heat capacity measurements weighed 69 g while the sample container and addenda weighed 132 g. The sample was in the form of annealed powder, 50 to 60 mesh, and was sealed into the sample container under 0.1 atm of helium. Copper fins inside the sample container facilitated thermal equilibrium of the powdered Sample. Time intervals of the order of 10 min were required for thermal equilibration, and such times are normal for this calorimeter regardless of the form of the sample. The observed heat capacities were corrected for the small excess of a calcium through use of the heat capacity values tabulated by Hultgren et a1.8 The corrected heat capacities are tabulated as a function of temperature in Table II. The free-energy function and the absolute entropy of CaMg2, which were calculated from the experimental heat capacity data, are listed in Table 111. A smooth curve was fitted to a plot of the experimental values of the heat capacity and in only two instances above 30°K did the plotted points deviate from the curve by more than 0.2 pct. Below 10°K the deviation of several of the points was as much as 50 pct. These large percentage deviations were attributed to the small value of the heat capacity and to the low sensitivity of the platinum resistance thermometer in this temperature range. The deviations in the region of 10°to 30°K were less than 5 pct. Although the percentage deviations of some of the low-temperature measurements are large, the actual value of these deviations is small since the magnitude of the heat capacity in that temperature range is small. The error in the value of the third-law entropy at 298.15°K was estimated to be less than 0.01 cal per (°K g-atom). A value of -0.25 ±0.06 cal per (°K g-atom) was obtained for the standard entropy of formation at 298.15°K from the relation:

Jan 1, 1969

By P. Crowther, G. J. Lamprecht

The solubilities of silver, zinc, and cerium in liquid sodium, in the temperature ranges 100 to 270°C, 190° to 550°C, and 120" to 460°C, respectively, have been determined. From the solubility data the heat the entropy the partial molal enthalpy of mixing the excess entropy and the partial molal free energy of solution for the systems Nu-Ag and Na-Zn have been calculated. For the system Na-Ce the observed negative is discussed in terms of the solubility of the oxide Ce2O3. In an earlier publication the results obtained in the study of the solubility of tin' in liquid sodium are presented, as well as the detailed analytical procedures used. 1) REAGENTS Spectroscopically pure metals as supplied by Johnson Matthey and Co, were used to produce the following tracers: 253-day Ag110, 245-day zn65, and 325-day ce141. The tracers were prepared by irradiation in a thermal neutron flux of 4 x 10 13 neutrons cm-2 sek-1. To obtain a uniform amount of the required specific activity, needed for each solubility experiment, the radioactive metal was diluted with the corresponding inactive metal, by melting them together in an inert atmosphere. The liquid sodium used contained 11 ±2 ppm of O,1 determined by the vacuum distillation method.' The oxygen was assumed to be present as the oxide NaD. 2) THE SYSTEMS: SODIUM-SILVER AND SODIUM-ZINC Plots were made of the log of the mole fraction of silver, Fig. 1, and of zinc, Fig. 2, dissolved in the liquid sodium vs reciprocal absolute temperature. The equations for the solubilities, based on the least-squares fit to each plot, are: where Xi is the mole fraction metal dissolved in sodium, T is the absolute temperature, and s is the standard deviation in the value of log Xi. The heats and the entropies lution were calculated from the solubility data by In neither of the two cases was any intermetallic compound formed between sodium and the solute metal as was the case for tin.' Thus, for the silver and zinc systems the pure metal was taken as the reference phase. Since the solids in equilibrium with the liquid sodium were the pure metals, one can calculate the partial molal enthalpy of mixing and

Jan 1, 1969

By J. W. Downey, A. E. Dwight, M. H. Mueller, H. Knott, R. A. Conner

Sixty new ternary equiatomic compounds are reported with a hexagonal crystal structure that is isostructural with or very similar to Fe2P, D3h-P62m. HoNiAl is a typical example, with a, = 6.9893 ± 0.0003Å, C, = 3.8204 ± 0.003Å, and c/a = 0.54 7. Three holmium atoms occupy (g): x,0,1/2 three aluminum atoms occupy (f): x,0,0; one nickel atom occupies (b): 0,0,1/2; and two nickel atoms occupy (c): 4, + , 0. The nonequivalent 1(b) and 2(c) sites give rise to two sets of unequal interatornic distances (i.e., Ho-Ni and Al-NL in the case above), which account for the prevalence of Fe2P-type tertmry compounds and the scarcity of binary examples. Unit-cell constants are presented for the sixty compounds and density measurements on the compounds HoNiAl and UFeGa confirm that three formula weights are present per unit cell. Neutron and X-ray powder diffraction intensity measurements were made on CeNiAl and HoNiAl, respectively. The atomic posiLiotml parameters in CeNiAl were determined from neutron data to be x = 0.580 5 0.001 for cerium and 0.219 5 0.001 for aluminum. An investigation of the quasibinary section between the binary compounds CeNi2 and CeA12 revealed a new ternary compound CeNiAl. The compound has a hexagonal structure and is isostructural with the prototype compound Fe2P. Additional examples discovered or confirmed in this investigation provide a total of sixty ternary compounds that are isostructural with or closely related to Fe2P. Previous investigators1'2 reported the unit-cell constants for the hexagonal compounds UFeA1, UCoAl, UIrA1, ZrNiAl, ZrNiGa, HfNiAl, and HfNiGa and the present investigation has confirmed that the compounds are isostructural with Fe2P. Independently, Steeb and petzow3 reported the same structure type for UCoAl, UIrA1, and UNiA1. However, the present results suggest a different atomic site occupancy for the component atoms in the three compounds. A detailed investigation of the relative positions of the three kinds of atoms in the compounds CeNiAl and HoNiAl will be discussed. EXPERIMENTAL PROCEDURE The equiatomic alloys were prepared from elements of 99.9+ pct purity by arc melting under a helium-argon atmosphere. After homogenization at temperatures from 700" to 900' C, a metallographic examination was performed by conventional methods, and density measurements were carried out by the immersion method in CCl4. A powder sample was prepared for diffraction studies by crushing a portion of the annealed button. X-ray diffraction patterns were obtained with a Debye-Scherrer camera, in which the annealed powder was glued to a quartz filament, and indexed with the aid of a Bunn chart. Unit-cell constants were calculated from the computer program of Mueller, Heaton, and Miller4 and d spacings were obtained by the program of Mueller, Meyer, and Simonsen.5 The intensity values were calculated from the relation I, ~ (m)(L.P.)F2 by a computer program written by Busing, Martin, and Levy.6 The absorption and temperature correction factors were neglected. An X-ray study of HoNiAl was carried out to take advantage of: large differences in atomic scattering factors for holmium and aluminum, X-ray patters free of background darkening, negligible oxidation at room temperature, and negligible weight loss in the preparation of this alloy. The neutron diffraction studies were made on a powder sample of CeNiAl contained in a -in. diam V tube and a pattern was obtained with neutrons of wavelength The neutron scattering factors employed (x 10-12 cm). In contrast to the scattering amplitude for X-rays, cesium does not have the largest cross section, however, there is a sufficient difference in the neutron scattering amplitudes to distinguish between the atomic species. The neutron transmission was high, 86 pct; therefore, absorption corrections were not necessary for the cylindrical sample. Most reflections could not be observed individually, because of the relatively large unit cell (a = 6.9756 and c = 4.0206Å) and relatively short neutron wavelength; therefore, the intensity of grouped reflections was considered. The Kennicott modification7 of the Busing-Martin-Levy program6 was employed to determine the identity of the atoms at the various lattice sites and the positional parameters. RESULTS A structure for the prototype compound Fe2P was first reported by Hendricks and Kosting;8 however, the structure was in error. The correct structure, as reported by Rundqvist and Jellinek,9 is as follows. The unit-cell constants and volumes per formula weight (V/M) are given in Table I for the sixty compounds examined in this investigation and classified as Fe2P-type compounds. The structure type was determined initially from a comparison of the unit-cell constants of HoNiAl with other known examples of this structure type1' and from the density of HoNiAl, given in Table 11. The density indicated that three formula weights comprised a unit cell, as in the prototype compound Fe2P. The assignment of the three species to lattice sites was made initially on the basis of atomic size. The large holmium atoms were assigned to the 3(g) sites that have a relatively large interatomic distance to nearest neighbor positions, the small nickel

Jan 1, 1969

By Juan Sodi, John F. Elliott

The standard free energy of ReS2 has been measured in the range of 1050° to 1250°K using H2/H2S mixtures and a slight variation of the method described by Hager and Elliott.1 The result is: The experimental method and apparatus were modified slightly for this study. Measurements on Cu2S were made to verify the application of the method to the work on ReS2. THE EXPERIMENTS AND RESULTS Briefly, the experimental method consisted of exposing a chip of copper or rhenium at a known temperature for 8 hr to a slowly flowing gas stream at the same temperature in which Ph2S and PH2 were known. The chip was withdrawn quickly from the hot furnace, and subsequently it was inspected for the presence of a sulfided surface. In the experiments described here, there was no ambiguity in any case as to the presence or the absence of the sulfide. At a given temperature, gas compositions for sulfidization were explored systematically until two compositions were found whose values of ?G°, Eqs. [I] and [2], were within approximately 100 cal of each other, one of which was sulfi-dizing and the other was not. These are termed the "straddle" compositions and it is assumed that the equilibrium composition lies between them. The chief modification to the apparatus, which is shown schematically in Fig. 1 of Ref. 1, was to support the metal specimen on a small alumina boat which could be moved along the reaction tube, 6 mm ID, by platinum wires. An appropriate seal at each end of the reaction tube permitted the sample to be moved from the cold end of the tube into the hot zone in 2 to 3 sec, and the sample could be withdrawn equally rapidly. Thus, it was possible essentially to quench the specimen from the reaction temperature with the reaction gas or helium flowing and without danger of breaking the reaction tube. The usual practice at the end of the experiment was to switch the gas system to the helium tank, flood the reaction chamber with helium, and pull the sample out of the hot zone. The purpose of the modification was to permit study of the sulfidization of copper without the complication of the back-reaction between the gas and the specimen as the latter cooled during slow withdrawal of it from the hot zone; this was a problem in the earlier work.&apos; A further improvement located the tip of the temperature-indieating thermocouple and the specimen precisely at the hottest part of the furnace. A carefully calibrated thermocouple, with its tip at the position of the specimen and with other conditions duplicating those of an actual experiment, showed that in the temperature range of 900° to 1122°C the temperature of the specimen differed from that of the tip of the indicating thermocouple by less than 0.5°C. The two positions were 0.5 cm apart. The reaction gas was prepared from ultrahigh-purity hydrogen (<l ppm O2, <0.5 ppm H2O) and CP grade hydrogen sulfide (99.5 pct H2S). High-purity helium (99.995 pct He) was used. All of these gases were purchased from the Matheson Co. All flow meters were recalibrated by the soap-bubble method with hydrogen, H2S, helium, and several gas compositions used during the study. These calibrations gave a linear relationship with a slope of 1.0 for the plot of log flow rate vs log pressure drop across the flow meter, in accordance with the Hagen-Poiseuille equation. The analysis of the gas was determined in the same manner as was reported previously. Good checks were obtained between the composition of the gas established by the flow-meter settings and by chemical analysis of the gas taken after the mixing bulb and ahead of the furnace. The pressures of H2S, H2, S2, and HS in the equilibrium gas at temperature were calculated from the following data :3 The pressures of the species S and S8 were negligible for the conditions of the experiments.3 There was no sign of vaporization of ReS2 either by weight loss or deposits in the reaction tube. Thus it is not possible to account for the apparent volatility of the compound reported by Juza and Biltz.2 The inlet gas composition and the calculated equilibrium ratio of PH2 S/PH2 for the "straddle" points of each experiment are shown in Table I. The specimens of metal for the experiment were small clippings of annealed copper (99.9+ pct) sheet 0.005 in. thick that was obtained from Baker and Adamson and of "high-purity" rhenium (99.9+ pct) sheet 0.005 in. thick that was purchased from Chase Brass and Copper Co. A specimen was removed from the apparatus; inspected for the presence of the sulfide, and then stored in a sealed vial. A fresh clipping was used in each measurement. The condition of the surface of each specimen after the experiment is noted in Table I.

Jan 1, 1969

By L. H. Van Vlack, T. Y. Tien, R. J. Martin

The phase relationships of the MnTe-MnS system were studied by DTA procedures. There is an eutectic at 810°C with about 10 mole pct MnS-90 mole pct MnTe. An eutectoid occurs at about 710°C with approximately 7 mole pct MnS where the MnTe(NaCl) solid solution dissociates on cooling to MnTe(NiAs) and MnS. There is very little solid solubility of MnTe in MnS. ALTHOUGH MnS may exist in three different crystal forms,&apos; only the NaC1-type phase is stable.2 Above 1040°C, MnTe also has the cubic NaC1-type structure. Below that temperature, MnTe changes to the NiAs-type structure.3 This phase transition is rapid for both heating and cooling. As a result the high-temperature crystal form of MnTe cannot be retained at room temperature. Because MnO, MnS, and MnSe are all stable with the NaC1-type structure, and MnTe has this structure at high temperatures,4 solid solution formation could be expected among these compounds. It is interesting to note, however, that a complete series of solid solutions exist only in the MnS-MnSe system,&apos; and that the solid solution is quite limited in the MnO-MnS system.&apos; The MnSe-MnTe system possesses a complete series of solid solutions at high temperatures with separation at lower temperatures.7 Although ion size may be critical in the miscibility of MnO-MnS, it is quite possible that the bond type plays a more important role with the miscibility of MnSe-MnTe. This would permit us to speculate that the miscibility gap would be extensive in the MnTe-MnS system. EXPERIMENTAL Preparation. The samples were prepared by mixing and compacting MnTe and MnS powders. The MnS was previously prepared through the sulfur reduction of Mnso4.8 The MnTe had been prepared by mixing and compacting double vacuum distilled metallic manganese and high-purity tellurium in stoichiometric ratio modified with 1 wt pct excess tellurium. The compacted powders were put in a graphite crucible which was sealed in an evacuated vycor tube. The free space in the vycor tube was made minimal to reduce the loss of tellurium. The sealed assembly was then heated slowly to about 500° C where the free manganese and tellurium reacted vigorously, melting the MnTe which formed. Only one phase, MnTe, was detected by X-ray powder patterns and metallographic techniques. Each compact of MnTe-MnS was placed in a graphite crucible and then sealed in an evacuated vycor tube. The samples were heated at 1250°C for 4 hr and furnace-cooled. Microscopic examination revealed no third phase beyond MnS and MnTe. A typical microstructure is presented in Fig. 1. Identification. X-ray powder patterns were obtained using 114.6 mm Debye-Scherrer camera and Fe-Ka radiation. Mixtures of cubic MnS and hexagonal MnTe were observed in all of the compositions prepared. No lattice parameter change was noticed among different compositions, indicating no solid solution could be retained at room temperatures between these two end-members. A lattice parameter of 5.244Å for MnS was obtained by the Nelson and Riley9 extrapolation method using the diffraction lines of (h2 + k2 + 12) equal 12, 16, 20, and 24. The values, a = 4.145Å and c = 6.708Å, for hexagonal MnTe were obtained from the (006) and (220) lines in the back-reflection region. These values agree well with the values reported by Taylor and Kag1e.10 Differential Thermal Analysis. A differential thermal analysis procedure was used to determine phase relationships since the high-temperature equilibrium conditions could not be retained for examination at room temperature, even when the sealed samples (~0.5 g) were quenched in water. The samples were sealed in an evacuated 4 mm vycor tube with a recess in the bottom to accept a thermocouple. An Al2O3 reference was similarly prepared and the two placed within a piece of insulating fire brick to dampen spurious temperature changes within the furnace. The furnace was controlled by a mechanically driven rheostat which increased the temperature at a rate of about 15°C per min. Known phase changes in the Pb-Sn system1&apos; and the a-to-ß quartz inversion12 were used for calibration

Jan 1, 1969

By G. L. F. Powell, L. M. Hogan

Large degrees of undercooling have been produced in bulk samples, 400 g, of copper and Cu-O alloys by melting in a slag of commercial soda-lime glass. The maximum degrees of undercooling obtained for copper, hypoeutectic and hypereutectic Cu-O alloy samples were 208°, 218°, and 97°C, respectively. No grain refinement as a function of undercooling was observed for the pure copper samples although in Cu-O alloys there was a marked decrease in grain size at degrees of undercooling greater than 150°C. The grain size change is the result of recrystallization during or immediately following the freezing process. THE first report of a large degree of undercooling in a bulk sample of metal was that by Bardenheuer and Bleckmann1 who produced 258°C undercooling in a 150-g sample of iron by melting in a glass slag. Garbeck2 extended this technique to nickel, cobalt, and copper and reported maximum undercoolings of 220°, 230°, and 60°C, respectively, while Fehling and schei13 undercooled a large number of metals as 2 to 20-g samples slagged in glass. Subsequently, one of the authors4 applied the glass slag technique to bulk samples, -500 g, of silver and obtained a maximum undercooling of 250°C. It was concluded that impurities which normally catalyze nucleation at small degrees of undercooling could be removed by oxidation and solution in a glass slag. Large undercooling of bulk samples of iron, nickel, cobalt, and their alloys has also been reported by other authors.8&apos;10&apos;11 Of the five metals mentioned above, copper was the only one which had not been undercooled by at least 200°C in the form of a large bulk sample. Since copper exhibits high liquid solubility for oxygen, as do iron, nickel, cobalt, and silver, it was considered that a much larger degree of undercooling than that observed by Garbeck for copper should be possible. This was obtained by modification of the technique applied previously to silver and the results of undercooling experiments with 400-g samples of copper form part of this paper. The undercooling behavior of Cu-O alloys was also studied, and the influence of a small oxygen content on the grain structure of undercooled copper was observed metallographically. 1) EXPERIMENTAL The copper was obtained as oxygen-free high-conductivity copper, the major impurities of which were Fe 0.01 pct, Zn 0.015 pct, and Si 0.02 pct. Melting was carried out in an open-ended vertical cylindrical fur- nace wound with Kanthal wire. A schematic diagram of the experimental setup is shown in Fig. 1. The undercooling technique previously used for silver4 involved preoxidation of the samples by melting the silver in contact with the atmosphere. The oxygen content was subsequently reduced by freezing the samples under a glass slag, whereby the oxygen was evolved as gas and the continuous glass cover over the surface prevented re-solution of oxygen when the sample was remelted. Since oxygen is not released as gas when a Cu-O alloy is frozen. the technique had to be modified for use with copper. Also, copper is oxidized during fire refining so that an in situ preoxidation treatment of the samples was not considered to be a prerequisite to large undercooling. Experimentation proved that this supposition was correct. Instead, it was found that care was necessary during melting of the copper under glass to minimize oxygen pickup. Samples of copper weighing 400 g were prepared by adding 50-g pieces of copper to a vitreous silica crucible partly filled with soda lime glass at a temperature of approximately 1000°C. Each piece was quickly immersed in the glass slag and held at this temperature until the oxide coating on the surface decomposed. This change was easily observed and coincided with the formation of gas bubbles in the glass

Jan 1, 1969

By G. R. Belton, Y. K. Rao

A galvanic cell, using liquid MgCl2 or MgC12-CaC12 mixtures as the electrolyte, has been used to determine activities in Mg-A1 liquid alloys between 700&apos; and 880°C. The incovporation of a chlorine electrode in the cell also allowed measurements to be made of the standard free energy of formation of MgCl2(l). The results are shown to be in good agreement with thermo-chetrlical values from the literature, and this is taken as evidence that the small, known solubility of magnesium in iMgCl2 introduces no significant error in galcanic cell measurements. Within experimental error, the activity coefficients and relative partial molar enthalpies at 800°C are shown to be represented by the following "subregular" solution equations: logy~~ =-0.68(1 -xMgj3 log yAL =-1.02(1 - XMf + 0.68(1 - XMf H.M = -4400(1 - %)3 / cal Mg 7Ag&apos; HZ =-6600(1 - xA1)&apos; + 4400(1 - XMf cal SCHNEIDER and toll&apos; have used a transpiration technique to measure the vapor pressures of magnesium over Mg-A1 alloys between 544" and 594°C. amsstad,&apos; however, has since suggested that the extrapolation to zero flow rate, used by these authors in interpreting their apparent pressure vs flow rate data, gives unreliable results. Rogers, Tomlinson, and Richardson,3 in interpreting the results of solution equilibria between Mg-A1 alloys and liquid MgC12, also considered the measurements of Schneider and Stoll to be unreliable and preferred to derive activities for the alloys from the earlier boiling point determinations of ~eit~ebel~ and the partial molar heats recommended by Kubaschewski and ~atterall.~ These latter heats were based substantially on the early calorimetric work of Kawa-kami but, unfortunately, his work on other systems has sometimes been found to be inaccurate.7 Rogers et al., in the above-mentioned paper,3 tentatively concluded that the most likely species responsible for the limited solubility (0.3 mole pct at 800°C) of magnesium in MgC12 were Mg° (neutral) and Mg2++. Two more recent studies8,9 have supported Mg2++ as the soluble species. In the present study, activities in Mg-A1 alloys have been determined by means of a galvanic cell involving liquid MgCl2 or MgC12CaCl, mixtures as the electrolyte. Since the reactive nature of magnesium precluded simple Faraday yield experiments, a chlorine electrode was incorporated in the cell in order that the performance of the cell could be checked by measurements of the heat and free energy of formation of MgC12. This procedure was considered necessary since it has been suggested1&apos; that the solubility of a metal in a molten salt might introduce electronic conductivity; also, previous determinations of the standard electrode potential for MgC12 differed by as much as 70 mv11-13 EXPERIMENTAL Materials. Analyses of the materials used in preparing the alloys and the electrolyte mixtures are presented in Table I. The alloys were prepared by induction melting weighed amounts of the metals in a graphite crucible held under an argon atmosphere. Pure anhydrous magnesium chloride was prepared by heating the mixture MgCl, . 6H20 +NH4C1(1:1) to 650°C, followed by melting under dry argon. The melting point of the dry MgC12 was found by differential thermal analysis to be 714.8oC, which compares well with the accepted value of 714C.14 This agreement was taken to be an indication of the high purity of the dried salt. Table I. Compositions of Materials, wt pn Impurity Mg Al MgCI2 CaCI, Ba - - 0.005 Ca - - 0.010 Cu 0.02 0.02 Fe - 0.10 0.001 0.010 Pb 0.01 - 0.001 0.005 Mn 0.15 0.001 Si - 0.10 Sr - - 0.005 MBSO* - 0.040 ARGON TUNGSTEN CHLORINE LEAD—411 11 II ALUMINA &apos;A I / ave GRAPHITE on irA~_ ( ^"l ROD MAGNESIUM S>ILICA~^ /, OR ALLOY-. I /A] ___________ -«^- _ ELECTROLYTE I y FRITTED DISCS Fig. l—Arrangement of chlorine and metal electrodes in electrolytic cell.

Jan 1, 1970

By Byoung Whie Lee

In order to investigate the change in surface energy as a function of cold work ad environment, the contact angles between a liquid and the surface of elec-tropolislzed aluminum with various degrees of cold work were measured. Specinlens cut from aluminum rod (99.99 pct Al) were annealed at 600°C for 24 hr and then cold compressed parallel to the drawing di-rectzon of the rod in increments of approximately 10 pcl from 0 to 70 pct. The sections, taken transversely to the drawing direction, were mechanically and electro chemically polished. Contact angles between the sessile drop of distilled water, glycerin, and glycol and the specimen surface were measured optically. The differences in interfacial energy were calculated from the contact angle data. The effects of chemical washing and surface roughness of the specimen on the contact angle were also studied. The liquid contact angle was a linear function of the degree of cold working (D) ad changed markedly with differed liquids. THE plastic deformation of polycrystalline metals induces a preferred orientation in crystal structure. A preferred orientation changes the atomic density of a metal surface. This change in surface atomic density brings about the changes in surface interactions of the metals."&apos; Also, the plastic deformation of metals raises the internal energy by increasing the stored energy.&apos; Consequently, the total Helmholtz free energy of the metal increases and, in turn, the surface free energy of the metal. In order to study the effect of plastic deformation on solid surface phenomena, the liquid contact angle of a sessile drop made on cold compressed and elec-trochemically polished aluminum was measured. The preferred orientation in aluminum, due to uniaxial compression, is known to be [110] direction parallel to the compression axis. However, this description is only a first approximation of a rather complex orientation. In actuality, half the crystallites are more than 10 deg from this orientation, regardless of the amount of compression." For randomly oriented fcc crystals, the average surface atomic density can be calculated as follows: The number of atoms in a unit volume is 4/a3, where a is a lattice constant. Hence, the number of atoms per unit surface area is about (4/a3)2/3 = 2.52/a2 However, when the preferred orientation took place along [110] direction, the surface atomic density is as follows: The area of (110) plane of a unit cell, considering ridges and valleys, is BYOUNG WHlE LEE, Member AIME, is Research Metallurgist, Atomic Energy Research Institute of the Republic of Korea, Seoul, Korea. Manuscript submitted May 29, 1968. IMD 2 x J2- a x Ga = 6a2 Since this plane contains 4 atoms, the surface atomic density is 4i6a2 = 2.3/a2 Upon changing from random to preferred orientations, the surface atomic density decreases about 10 pct. The increase in the stored energy and the change in surface atomic density due to plastic deformation would certainly alter the surface tension of a metal. EXPERIMENT High purity aluminum rod of 6-mm diam (99.99 pct Al, obtained from Johnson, Matthey & Co., Ltd, London, England) was cut into sections approximately 1 cm long. The transverse cross section was mechanically polished. Then, the specimens were annealed in air at 600°C for 24 hr. Thus, eight annealed specimens were uniaxially compressed at room temperature from 0 to 70 pct of cold working with an increment of 10 pct. The extent of cold working was determined by the percentage of reduction in axial length to the original length. The specimens were further polished mechanically and, then, electrochemically with the Modern Battelle Type 1 electropolishing solution with a current density of 0.3 to 0.4 amp per sq cm and an electrode potential of 8 to 12 v at the solution temperature of 78" to 82°C for approxirr~ately 5 min. The Modern Whlte Diffusing Screen \t/ --------------- re Goniometer for Mercury Lamp ^-^ Sessile Drop ¦=• Condenser c=> Microscope l_*~_i bJ Mlcromster Filer with Protmcter Fig. 1—Schematic diagram of apparatus set-up for liquid contact angle measurement.

Jan 1, 1970

By C. W. Kovach, A. Moskowitz

Studies were undertaken to investigate the effects of manganese content on the machinability and other Properties of a free machining martensitic stainless steel (AISI Type 416). Machinability was found to be significantly improved in steels of high manganese content, and a direct relationship was obtained between machinability and steel Mn:S ratio. As the manganese content of the steel increases, the sulfide Phase present changes from CrS to (FeMn)Cr2S4 to (MnFeCr)S, and finally to MnS. The average sulfide inclusion hardness decreases through the same range of increasing manganese content. The mechanism for machinability improvement is discussed in terms of a soft ductile sulfide affecting deformation in the secondary shear zone. Type 416 containing relatively high manganese for improved machinability shows good general properties. The effects of increasing manganese content on mechanical properties, cold formability, and corrosion resistance are described. THE addition of sulfur is commonly used to improve the machinability of stainless steels. However, little attention has been paid in the past to the composition and characteristics of the sulfur-containing phase or phases present in these resulfurized steels. Recent information on the properties of sulfide phases, and their role in metal cutting, suggests that variations in these phases could have critical effects on machin-ability, as well as important effects on formability and other properties such as corrosion resistance. Manganese, chromium, and iron are strong sulfide forming elements present in stainless steels! of these, manganese has the greatest sulfide forming tendency and iron the least.1"1 The manganese content of resul-furized 13 pct Cr steels, often about 0.5 pct, can be insufficient or only barely sufficient to combine with the sulfur that is present; thus, the precise level of manganese can strongly influence the nature of the sulfide phase. Sulfide phases which may be present in stainless steels have been reported to include CrS, a spinel-type sulfide, chromium-rich manganese sul-fide, and manganese Sulfide.5,6 Detailed phase relationships for the Fel3Cr-Mn-S system have been reported by the present investigators,7 and a portion of this work will be referred to subsequently in this paper. Recent work by Kiessling6 and Chao et a1.8 has shown that sulfide phases can display wide variations in hardness, and may undergo considerable plastic deformation under isostatic loading.9-12 Early theories of metal cutting attributed the influence of sulfur to a lubricating effect. It is now apparent that the influence of the nonmetallic inclusions and their properties on crack initiation, deformation in the shear zones, and boundary films must also be considered in relation to the machining process. This paper presents the results of studies conducted to relate machinability to the various sulfide phases which occur in stainless steels. This work has led to the development of alloys with improved machinability, and has generated information on the effects of inclusions on metal cutting processes. Effects of sulfide inclusions and steel composition on other important metallurgical properties are also discussed. MATERIALS For drill machinability and inclusion studies, 10 lb laboratory heats were melted in an air induction furnace. These heats were made with sulfur contents be tween 0.10 and 0.50 pct and manganese contents be tween 0.05 and 3.0 pct. Residual elements were added to the heats in amounts typical for commercial steels. The typical compositional range covered by the heats is shown below: C Mn P S Si Ni Cr Mo Cu N 0.10 0.05 0.007 (M0 0.40 0.40 13.0 0.20 0.10 0.03 3.0 0750 The laboratory ingots were forged in the temperature range of 1800" to 2100°F to 3/4-in. sq bars, and all bars tempered to a hardness aim of 200 Bhn prior to testing. Because of differences in composition and tempering response, the tempered bars showed some variation in hardness (175 to 275 Bhn) as well as variations in delta ferrite content (0 to 50 pct). Composition, hardness, and delta ferrite content were considered in the analysis of the machinability data. Additional tests involving tool-life evaluation and determination of other properties were conducted on materials from commercially melted and processed 15-ton electric furnace heats. TESTS AND PROCEDURES Machinability of the laboratory heats was evaluated in a drill test. In this test, 1/4-in. diam holes, 0.4 in. deep, were drilled alternately in a test bar and in a standard bar for a total of four holes in each. This sequence was repeated three times using a freshly sharpened drill each time. The average time required to drill a hole in the test bar was compared to that for the standard bar. A drill machinability rating was assigned to the test bar relative to a rating of 100

Jan 1, 1970

By Richard A. Walker, John P. Hager

The thermodynamic properties of the Pb-Au system have been determined between 750" and 1075°C by means of the cell Mo, Pb(1) |(PbO-SiO2){l) , SiO2(s) |Pb-Au(1), Mo The activities of lead and gold exhibit negative deviations from ideal behavior; the values of ? pb and ? the raoultain activity coefficients at infinite dilution, being 0.24 and 0.25, respectively, at 1200°K. The liquidus curve for the gold-rich region of the Pb-Au phase diagram has been determined from measure-ments on seven alloy compositions in the two phase region (liquid + Au(s)). The standard free energies of formation of Au2O(l) and Ag2O (1) have been estimated from cell measurements obtained by replacing the alloy electrode with pure liquid gold and silver. A new integral molar heat of mixing curve for the liquid Pb-Au system is presented and the results of previous studies discussed. The contribution of HM to FE was found to be small relative to TSE. THE use of galvanic cells of the type A(l) |A+Za|A - B(l) [I] provides an accurate means for the thermodynamic study of liquid alloy systems. In Part 1&apos; it was shown that cells of type [I] may be extended to higher temperatures and to a wider range of alloy systems if the ion A+Za is incorporated in an appropriate molten oxide phase, rather than in the classical fused salt electrolyte. In the following investigation the experimental method is extended to an investigation of the thermo-dynamic properties of the Pb-Au system by use of the cell: Mo, Pb(l) | (PbO-SiO2)(l), SiO2(S) |Pb-Au(l), Mo [] Previous measurements on liquid Pb-Au alloys were obtained by Kleppa2 by electromotive force measurements on a galvanic cell involving a molten chloride electrolyte. These measurements were confined to temperatures less than 830°C and compositions with X Pb > 0.2 because of the instability of the cell at higher temperatures. Later measurements by Kleppa3 on the heats of formation in the composition range 0.67 < Xpb < 0.98 were not consistent with the results by electromotive force measurement. The purpose of the present study is to extend the temperature and composition range of the thermodynamic properties and to obtain an independent measure of the integral molar heat of mixing over the entire composition range.

Jan 1, 1970

By Charles Stein

The effects of several different prior treatments an the creep behavior of 99.9995 pct aluminum at 260°C and 1000 psi canstant stress are compared with annealed specimens. Quenching from 538oC, irradiation with 2 mev electrons, and tension-compression room temperature fatigue damage were used to change the substructure of the specimens prior to their creep testing. The quenched and the irradiated specimens showed a larger primary and transient stage contribution to the creep curve than those specimens which were only annealed prim to creep testing. The specimen receiving prior fatigue damage at room temperature showed no first stage or transient creep when tested under identical conditions as the above specimens and had an average creep rate seven orders of magnitude lower than that of either the annealed, the quenched or the irradiated creep specimens. In a previous electron transmission microscopy investigationl of the substructure developed during the creep of pure aluminum at 0.57 Tm, it was noted that a large concentration of vacancy loops and dislocation loops were present in and near the subboundaries while the interior of the subgrains contained few of these defects and had a low dislocation density, see Fig. 1. Yim and Grant2 and Hazlett3 have shown that the presence in nickel of a substructure developed by prior cold work effectively reduces the primary and transient contributions to the creep curve. Hultgren,4 McLean,5 Gervais, Norton, and Grant,6 Chang and Grant,7 and others have shown the same effect with the higher stacking fault energy material, aluminum. However, the specific defect responsible for the change in the creep behavior developed by the prior cold work was not established. Specifically, what effectively interfered with dislocation motion in these materials at elevated temperatures? Was it jogs on dislocations produced by their interaction with other dislocations or with vacancy or dipole loops, see Fig. 1, or did the subgrain walls determine the mean free path for glissile dislocations? This would be a realistic possibility only if subgrain boundaries are effective barriers to dislocation motion. The ability of a subgrain boundary to act effectively against glissile dislocations depends on the number and the arrangement of dislocations in the subboundary,8 which in turn is a function of the creep strain.&apos; This paper compares the creep rate of specimens possessing a large vacancy concentration to that of annealed specimens and with specimens having a stable subboundary wall containing Lomer locks produced by prior fatigue damage. EXPERIMENTAL PROCEDURE Vacancy Loops. Aluminum creep specimens, 99.9995 pct pure, were machined from zone refined rod to a 2-in. gage length and a cross-sectional area of 0.025 in. These specimens were annealed at 538oC, 1000°F, for 10 min and quenched into ice water. They were then reheated to the creep test temperature of 260°C, 500°F, and held at this temperature for 18 min to al-low for vacancy condensation and loop formation. The specimens were subsequently creep tested at 1000 psi constant stress at 260°C. The temperature along the gage length was monitored by three Pt-Pt, 13 pct Rh thermocouples, two embedded in the upper and lower shoulders of the specimen and one attached to the mid-point of the gage length- The temperature gradient was held to ± l°C or less throughout the Creep test. Elongations were measured by two LVDT&apos;s &apos;connected in an averaging &apos;On-figuration, with quartz extension arms placed against the specimen at the extremes of the 2-in. gage length. i K 3J?--&apos; * *H - >^> - &apos; ^L r 77 . *y J OJL, J Fig. 1—Transmission electron micrograph of pure aluminum strained 8.2 pct at 260°C and 1000 psi constant stress. Note the presence of numerous loops near the light dislocation tangle

Jan 1, 1970

By J. L. Tomlinson, B. D. Lichter

Electrical resistivities 01 liquid Cd-Bi, Cd-Sn, Cd-Pb, In-Bi, and Sn-Bi alloys were measured using an electrodeless technique. The resistivities ranged from 50 to 160 microhm -cm, temperature dependences were positive, and no sharp peaks in the composition dependence of the resistivity were observed. On the basis of these observations, it was concluded that the alloys are typical metallic liquids. The electron con-cent9,ation was calculated from the measured resis-tizlity and available thermodynamic data using a model which attributes electrical resistivity to scattering by density and composition flzcctuations. A correla-tion was shown between the departure of the electron concentration from a linear combination of the pure component valences and the value of the excess integral molar free energy. Calculation of the temperature dependence of the electrical resistivity showed a need for more detailed thermodynamic data in these systems and led to suggestions for improvement in the concept of residual resistivity in the fluctuation scattering model. THE electrical resistivity of liquid metals provides information regarding interatomic interactions and their effects upon structure. In this experiment an electrodeless technique was used to measure the electrical resistivities of liquid alloys of Cd-Bi, Cd-Sn, Cd-Pb, In-Bi, and Sn-Bi, and the results were used with thermodynamic data to calculate a parameter which reflects the tendency toward localization of electrons due to compositional ordering. It was found that the resistivities of these alloys are generally metallic in magnitude and temperature dependence. The electrical and thermodynamic properties are discussed in terms of the fluctuation scattering model&apos;22 which supposes that the electrical resistivity arises from scattering due to a static average structure and departures from the average due to fluctuations in density and composition. Further, this model is compared with the pseudopotential scattering model of Ziman et al.3-5 EXPERIMENTAL PROCEDURES Alloy samples were prepared from 99.999 pct pure elements obtained from American Smelting and Refining Company (except tin which was obtained from Consolidated Smelting and Refining Company.) J. L. TOMLINSON, Member AIME, formerly Research Assistant Division of Metallurgical Engineering, University of Washington, Seattle, Wash., is now Physicist, Naval Weapons Center, Corona Laboratories, Corona, Calif. 0. D. LICHTER, Member AIME, is Associate Professor of Materials Science, Department of Materials Science and Engineering, Vanderbilt University, Nashville, Tenn. This work is based on a portion of a thesis submitted by J. L. TOMLINSON to the University of Washington in partial fulfillment of the requirements for the Ph.D. in Metallurgy, 1967. Manuscript submitted May 31, 1968. EMD Weighed portions were sealed inside evacuated silica capsules, melted, and homogenized before the resistivity was measured. The resistivity of a liquid alloy was measured by placing the sample inside a solenoid and noting the change in Q. According to the method of Nyburg and ~ur~ess,~ the resistivity of a cylindrical sample may be determined from the change in resistance of a solenoid measured with a Q meter as T7--5--W =R7JT^ =&apos;Kc-lm(Y) [1] where L, R, and Q = wL/R are the inductance, series resistance, and Q of the solenoid. The subscript s refers to the solenoid with the sample inside; the subscript 0 refers to the empty solenoid. Kc is the ratio of the sample volume to coil volume and y = 2 [bei&apos;0(br)-j ber&apos;o(br)~\ br\_bero(br) +j bei0 (br) expressed with Kelvin functions which are the real and imaginary parts of Bessel functions of the first kind with arguments multiplied by (j)3&apos;2. The argument of the function Y is hr where r is the sample radius and b2 = po~/p, i.e., the permeability of free space times 271 times the frequency divided by the resistivity in rationalized MKS units. Since Eq. [I] cannot be solved explicitly for p, values of Kc. lm(Y) were tabulated at increments of 0.1 in the argument by. A measurement of Q, and Q, determined a value of Kc . lm (Y) and the corresponding value of br could be read from the table. From the known r, uo,, and w, the resistivity, p, was determined. The change in Q was measured after letting the encapsulated Sample reach equilibrium inside a copper wire solenoid. The solenoid was contained in an evacuated vycor tube in order to retard oxidation of the copper while operating at high temperatures and heated inside a 5-sec-tion nichrome tube furnace capable of obtaining 900°C. Temperature was determined with two chromel-alumel thermocouples, one in contact with the solenoid 30 mm above the top of the sample and the other inserted in an axial well at the other end of the solenoid and secured with cement so that the junction was 2 mm below the bottom of the sample. Temperature readings were taken with respect to an ice water bath junction, and the voltage could be estimated to the nearest thousandth of a millivolt. The lower thermocouple was calibrated by observing its voltage and the Q of the coil as the temperature passed through the melting points of samples of indium and tellurium. The upper thermocouple reading was systematically different from the lower thermocouple reflecting the temperature difference due to a displacement of 60 mm axially and 6 mm radially. Calculations show that the gradient over the sample was less than 2 deg. Q was measured by reading a voltage related to Q from a Boonton 260A Q meter with a Hewlett Packard

Jan 1, 1970

By A. S. Venkatadri, H. B. Bell

The equilibrium sulfur distribution between molten iron and Ca0-Mg0-Al203 slags containing iron oxide was investigated at 1550°C. The results were used to derive the iron oxide activities at low iron oxide concentrations in the slag by combining the sulfide capacity data obtained from gas-slag work with the free energies of both the sulfur solution in iron and the iron oxide formation in slag. The derived ferrous oxide activities were compared with values based on Tem-kin&apos;s kin&apos;s and Flood&apos;s ionic models. One difficulty in using these models is that the nature of the aluminate ion in slag is uncertain. Nevertheless, such indirect methods, in particular, those described in the present paper, are of value because of the difficulty of measuring small amounts of oxygen in liquid iron in equilibrium with slag. It is shown that these methods confirm the consistency of thermodynamics data on liquid iron and slags. It is well established that decreasing the iron oxide activity in the slag increases the desulfurization of molten iron at constant slag basicity. This effect is most pronounced at the very low iron oxide activities, characteristic of blast furnace slags. Yet a precise quantitative determination of the significance of low iron oxide contents in slag in blast furnace desulfuri-zation is not possible for the following reasons: a) difficulty of separation of iron "shots" from the slag, and b) errors in chemical analysis of small amounts of iron oxide in slags. In view of these obstacles, one must resort to indirect methods of calculating iron oxide activities. EXPERIMENTAL TECHNIQUE The apparatus for providing the sulfur equilibrium data has been described previously1 and was similar to that used by ell&apos; in connection with the study of slag-metal manganese equilibrium. The procedure consisted of: a) melting about 50 g of Armco iron in a magnesia crucible in a platinum furnace, b) adding a mixture of about 15 g of lime-alumina slag and varying amounts of Fe2O3 and CaS, and c) maintaining the temperature at 1550°C for more than an hour in an atmosphere of argon to enable the sulfur equilibrium to be attained. Several melts were made using lime-alumina slags with basic composition 55, 50, and 45 pct lime. During the experiment the temperature was controlled manually using a Pt/10 pet Rh-Pt thermocouple. After the experiment, the Power was shut off and the flow rate of argon was increased to freeze the melt as quickly as possible. The analysis of sulfur in the metal was carried out by the oxygen combustion method3 using uniform drillings from the top and bottom of the metal button. After crushing and grinding and removal of any iron particles with the aid of a hand magnet, the slag was analyzed for sulfur by the CO2 combustion method.4 The E.D.T.A. method was employed for the analysis of lime5,6 and magnesia,= the ceric sulfate method7 for the analysis of slag iron oxide, and the perchloric acid dehydration method5 for the analysis of silica. The remaining amount was taken to be Al2O3 precipitation with ammonium hydroxide in several preliminary melts had confirmed the propriety of using this simple procedure. RESULTS The activity of iron oxide in binary, ternary, and more complex slags has been the object of numerous investigations, and the two experimental methods for its determination are: 1) Equilibrating the metal with the slag in question and measuring the oxygen content of the metal. The ferrous oxide activity is then given by aFeO L%OJSat where [%0]sat is the oxygen content of the metal in equilibrium with pure iron oxide slag. This method was used by Chipman et al.8,9 2) Equilibrating the slag in iron crucibles with known partial pressures of H2/H2O or CO/CO2 mix-tures.10-12 This method is limited to temperatures between 1265" and 1500°C. The very low oxygen content of the melts in this investigation made it impossible to derive the ferrous oxide activity by the first of these methods. Therefore, the iron oxide activities were computed by means of: Sulfide capacity data from the gas-slag work" Temkin&apos;s concept14 Flood&apos;s approach15 a FeO from Sulfide Capacity. The method of calculating the aFeO involves the sulfide capacity of the slag (c,), the sulfur distribution coefficient (Ls), the free energy of dissolution of sulfur in iron, and the free energy of formation of iron oxide in the slag. Bell and Kalyanram13 have investigated the sulfur absorption characteristics of lime-alumina slags containing magnesia by the Carter-Macfarlane method16 (based on comparing the sulfide capacity of the slag in question with that of a standard slag of unit lime activity) and have derived lime activity values. The relation between sulfide capacity and their lime activity a&apos;CaO is given by: Cs= 3—: Xa&apos;CaO at 1500°C

Jan 1, 1970

By William A. Edmiston, R. E. Grace

A simplified model for the theory of reaction rates near equilibrium has been applied to the reduction of wustite. A linear relationship between the net rate of reaction and the Gibbs free-energy change, ?F, is predicted. The reduction of wustite in H2 -H2O gas mixtures was studied with a microbalance technique at temperatures from 850° to 950 °C. The predicted model was found to be valid to -?F/RT = 0.1 or approximately -200 cal per mole away from equilibrium. ThE theory of reaction rates near equilibrium has been developed by a number of authors. Prigogine, Outer, and Herbo1 have studied the catalytic hydrogena tion of benzene in an attempt to deduce some intrinsic connection between reaction rates near equilibrium and thermodynamics. Manes, Hofer, and weller2 have derived more general expressions for reaction rates near equilibrium from classical thermodynamics. Hollingsworth3,4 has commented briefly on the work of Manes et al. Benson5 has summarized in a general way the results of the earlier contributions. It is the purpose of this paper to apply the theory of reaction rates near equilibrium specifically to the reduction of wustite in H2-H2O gas mixtures. The basic premise is that the reduction of wustite proceeds by a surface reaction, rather than by solid-state diffusion ,or gaseous diffusion. Richardson and Dancy6 and Gellner and Richardson7 have suggested that the reduction of wustite may be governed by iron diffusion in wustite. Mckewan8-11 has proposed that reduced iron layers on various oxides are sufficiently porous to offer a negligible impedance to the reducing gas. The linear motion of interfaces reported by McKewan and discussed by Themelis and Gauvin12 indicates the lack of diffusive control during reduction. The reduction studies of magnetite reported by Quets, Wadsworth, and Lewis13 give additional evidence that reduction rates are linear when the reaction products are porous and nonprotective. The interpretation of measurements reported in this paper is predicated upon a surface-controlled reduction reaction, at least in the earliest stages of reduction when the reduced iron layer is thin.

Jan 1, 1967