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By S. T. Wlodek

The surface and subscale oxidation reactions were followed by means of continuous weight-gain and metallographic techniques over the range 1600" to 2200°F (871° to 1204 °C) for up to 400 hr. Full identification of all scale and subscale reaction products was obtained by electron and X-ray diffraction. At or below 1800°F (982°C) a linear rate of reaction (QL = 46.0 kcal per mole) governed the oxidation process, extending for up to 100 hr at 1600°F (871 "C). During linear oxidation the surface scale consisted of an amorphous SiO2 film overgrown with Cr 2O 3 and NiCr204. This initial linear process was followed, and above 1800°F completely replaced, by two successive parabolic rate laws (Qp = 60 and 57 kcal per mole). This parabolic reaction involved the formation of a complex scale consisting of Cr2 O3 and smaller amounts of NiCr2O4. Parabolic oxidation appeared to coincide with the disruplion of the silica film present during linear oxidation and was followed by subscale (internal) oxidation of crystobalite and NiCr2O4. The balance between the subscale and surface oxidation reactions controls the oxidation of this commercial alloy. The amorphous silica film appears to result in the linear rate and diffusion through Cr2O3 is the more likely rate-limiting step during parabolic oxidation. THE oxidation of a multicomponent composition is a complex phenomenon not presently amenable to a rigorous classical interpretation. Nevertheless, even a qualitative understanding of the scaling and subscale reactions that occur in a commercial composition can illuminate the reactions that limit its high-temperature stability in an oxidizing environment. This study of the oxidation of Hastelloy Alloy X presents the first of a series of studies with the above approach in mind. Hastelloy X exhibits one of the best combinations of strength and oxidation resistance available in a wrought, solution-strengthened, nickel-base alloy. Although during long time exposure some precipitation of M6C and M23C8 carbides as well as a complex Laves phase occurs, the amounts are probably small enough to have no appreciable effect on the chemistry of the matrix. Radavich has identified the oxidation products on Hastelloy X oxidized for 5 min to 10 hr at 1115°F as NiO and the NiCr2O4 spinel. Oxidation for 5 to 15 min at 1500°F produced a scale of spinel, NiO, and a rhombohedra1 phase, probably Cr2Os. Sannier et 2. have reported continuous weight-gain data for Hastelloy X at 1650" and 2010°F and internal-oxidation measurements after 150 hr at 2010°F. In addition, much of the data on binary Ni-Cr alloys recently reviewed by Kubaschewski and okins' and Ignatov and Shamgunova4 as well as studies of binary Ni-Mo alloys5 are also pertinent to the oxidation of this composition. EXPERIMENTAL Continuous weight-gain measurements and metallographic measurements of subscale reactions were the main experimental techniques used in this study. X-ray and electron diffraction backed up by a limited amount of electron-microprobe analysis served to characterize the nature of the scale- and subscale-reaction products. Two heats of commercial sheet of the composition given in Table I and identified as A and B were used in the bulk of this study. Internal-oxidation measurements were made on a third heat of material in the form of a 0.5-in.-diam bar. In order to assure homogeneity, all heats were reannealed 4 hr at 2175°F prior to sample preparation. weight-Gain Measurement. All specimens (1.5 by 0.4 by 0.03 in.) were abraded through 600 paper, electropolished, and lightly etched in an alcohol-10 pct HCl solution. An electrolyte of 150 cu cm H,O, 500 cu cm HsPO4 (85 pct conc), and 3 g CrO3 at a current density of 0.9 amp per sq cm or a solution of 10 pct HaW4 in alcohol used at 4 v and 0.3 amp per sq cm was used for electropolishing. The resultant surface exhibited a finish of 3 ± 1 p rms. Continuous weight-gain tests were made at 1600°, 1700°, 1800°, 1900°, 2000", and 2200°F on auer' type balances capable of recording a total weight change of 110 mg with an accuracy of k0.1 mg. All tests were made in air dried to a dew point of -70°F and metered into the 2-in.-diam reaction

Jan 1, 1964

By R. W. Stormont, F. Wald

The phase diagram of the Pseudobinary section PbTe-Fe was determined. It was found to contain a monotectic and a eutectic reaction, the latter one taking place at 14 at. pct Fe and 875° * 5°C. The solid solubility of iron in PbTe was found to be 0.3 at. pct by electronmicroProbe analysis. No solubility of PbTe was detected in iron. Slight deviations from true pseudobinary behavior were found to occur in the range of - 5 to 10 at. pct Fe. In the course of a general investigation of reactions of various metals with lead and tin telluride,' the lead telluride-iron system was reinvestigated. It had been established much earlier than iron does not chemically react with lead telluride but forms a eutectic with a melting point of 879" The eutectic composition or other related information has never been reported, but for a number of years iron has been in general use for contacting of lead telluride and lead telluride alloys for thermoelectric applications. It seems therefore desirable to clarify the exact constitution of the system to furnish a base for the long-term evaluation of bonds made between lead telluride and iron either by pressure contacting or by brazing methods. I) EXPERIMENTAL METHODS Lead telluride-iron alloys were prepared in 10-g charges, using premelted lead telluride. This material was prepared from high-purity, semiconductor-grade lead and tellurium obtained from the American Smelting and Refining Co. and described as 99.999 pct pure. The iron used was "Armco" iron; the major impurities found here were 0.02 pct C, 0.018 pct Si, and 0.015 pct Cr. All remaining impurities were less than 0.01, the total of all impurities not exceeding 0.15 pct. Charges were prepared in closed quartz arnpoules which were evacuated and in some cases backfilled with high-purity argon to retard excessive lead telluride evaporation and deposition in slightly cooler parts of the ampoule. For high iron concentrations, this can lead to total separation of the constituents, since the vapor pressure and the sublimation rate of PbTe are quite high.4 Nevertheless, since the ampoules are closed, no change in overall composition was expected and the nominal composition of all alloys was assumed to be retained. X-ray diffraction analysis, thermal analysis, and microsections were used in the evaluation of the alloys. The nature of the system was such that X-ray diffraction was not particularly helpful. It merely served to establish that at all concentrations PbTe and a! iron were in equilibrium at room temperature. Thermal analysis was carried out by taking direct temperature vs time curves on a Sargent recorder where a width of 10 in. was kept as 1 or 0.5 mv by use of an automatic bucking voltage network. Quartz ampoules with minimized dead space, coated with boron nitride and fitted with a thermocouple reentrant, were used as containers for the charge. At high temperatures and over long periods of time, boron nitride reacts with iron. For the thermal analysis runs, however, this was not significant. More significant was the fact that the vapor pressure of PbTe at some of the meas -uring temperatures apparently exceeded I atrn quite considerably. This, in some cases, caused the slightly softened quartz tubes to blow out if great care was not taken to contain them and minimize time and temperatures used. As containers pure nickel tubes were used which also served to avoid temperature gradients in the quartz ampoule. Nevertheless, the experimental difficulties at high temperatures were severe and the monotectic temperature could therefore not be determined accurately. In general, the accuracy reached by the thermal analysis setup in this case is *4"C as determined with gold, silver, and tin, under the conditions of analysis here. Inherently, the apparatus is capable of reaching accuracies better than i 1°C. Also, difficulties were encountered in microsection-ing. They were related to polishing, since it is rather difficult to avoid pulling the iron out of the weak and brittle lead telluride matrix. It proved best to follow a procedure where, after grinding to 600 grit on carborundum paper, a polish with 6 p diamond was used on nylon cloth. Finally, #3 "Buehler" alumina and an automatic polisher were used for -5 min only, to avoid relief. The best etching results were achieved with

Jan 1, 1969

By C. L. Magee, H. W. Paxton

The effects of testing temperature, frorn 77" to 420" K, and volume fraction of martensite on the micro-plastic response of unaged Fe-31Ni martensite-austenite aggregates have been determined. The kinetics of the aging phenomena which lead to a decrease in the microplastic response were also characterized. These determinations, supplemented by other experimental results, show that at least two mechanisms of plastic deformation give rise to the apparent softness of the quenched structures. Only one of these mechanisms is fully discussed in this paper The transformation of retained austenite to martensite during the application of stress leads, in specified conditions, to large microplastic strains. This deformation behavior cannot be described by normal transformation plasticity theory but is shown to result from the fact that stress-assisted formation of martensite is a possible deformation mode. The present results and further considerations of previous work lead to the conclusion that it is unnecessary to postulate a special work-hardening mechanism to explain the mechanical properties of unaged martensite. It is now generally accepted that dislocation motion can occur in many solids at stresses very much below the L'macroscpic" yield stress, e.g., 0.1 pct offset. This phenomenon has been investigated by a variety of techniques including measurements of elastic limit,' effective static elastic modulus,~ and irreversible deformation following stressing at low levels.3"5 Of particular interest to the work to be described are exper -iments conducted on the deformation of martensite in attempts to decide whether freshly quenched ferrous martensites are "hard" or "soft".6 Muir, Averbach, and cohenl and McEvily, Ku, and ~ohnston' have shown that as-quenched ferrous rnartensites can be plastically deformed at relatively low stresses. A difference between these two sets of experiments exists in that some diffusion of carbon would take place before testing in the experiments of Muir et a1. because the plain Fe-C alloys which they have tested transform to martensite well above room temperature. McEvily et a1. examined Fe-Ni-C alloys with Ms of about -30"~ and tested the alloys directly after quenching to — 195" ~ —a technique which obviates any appreciable carbon diffusion. Unfortunately, a characteristic of the alloys which transform below room temperature is that they do not transform entirely to martensite. The results discussed below will show that, because the transformation of this retained austenite under stress leads to plastic deformation, one cannot investigate the properties of martensite by such experiments. The existence of a second deformation phenomenon, which is not caused by retained austenite, is also established in the present work. In line with a previous suggestion,' it is believed that the second microdefor-mation mode is principally due to the internal stresses generated by the formation of martensite. To avoid confusion in the present report, the evidence we have found for this interpretation will be discussed separately in a brief note.7 EXPERIMENTAL Materials. The alloys were induction-melted and cast under vacuum; the resulting compositions are given in Table I. The ingots were hot-swaged to 2-in.-diam bar and further cold-swaged and/or cold-rolled prior to specimen preparation. The standard tensile specimens were machined from sheet. The gage section was 0.05 by 0.2 by 5 in.; 0.75-in.-wide ends had 0.2 5-in. centered holes for pinloading. The three-point bend samples were 0.075-in. thick and 0.6 in. bide. The distance between the outer loading points was 5.5 in. In order to establish a standard starting condition, all specimens were quenched to 77°K prior to annealing in vacuo for austenitizing. The temperature of the austenitizing anneal was controlled to + 5"~. The testing and aging temperatures were maintained by various liquid baths (nitrogen, 77"~; freon, 130° to 200°K; acetone, 200 to 300°K; silicone oil, 300' to 450°K) to better than il°K. Strain Measurement. The results herein were derived from both uniaxial tension and three-point bending experiments. For bending tests, the stresses and strains reported are those corresponding to the maximum fiber values. Normally, because of the small strains involved, very sensitive strain measurements are necessary to make microplastic measurements. However, because of the magnitude of the dilatation and shear involved in the martensitic transformation, the requirements in the present experiments proved to be less rigorous. In most experiments the plastic strain was evaluated by measuring stress relaxation and modulus defects. In this method, specimens are loaded rapidly to some predetermined load on an In-

Jan 1, 1969

By Charles M. Packer, Oleg D. Sherby, Roy H. Johnson

Originally round tensile specimens of a eutectic Zn-A1 alloy develop elliptical cross sections during superplastic deformation. This observation, coupled with a detailed study of the microstructure and preferred orieniation, suggests that crystallographic slip and continuous grain boundary migration or re-crystallization are important processes during super-plastic deformation. In spite of the extensive activity in superplasticity1-15 and the numerous explanations proposed, no single model has had universal acceptance. It has been established, however, that the general requirements for superplastic extension of two-phase alloys include an extremely fine, stabilized grain size of the order of a few microns, a temperature about equal to or greater than one-half the melting point, a critical range of strain rate, and a similarity in the mechanical strength of the major phases. The proposed models can perhaps best be characterized in terms of the important phenomena associated with them. These phenomena include: phase instability,1 diffusional creep by volume diffusion3 or grain boundary diffusion4,5 slip and continuous grain boundary migration or recrystalliza-tion,= grain boundary Sliding,7-9,13,14 and dislocation glide.'5 In this paper, experimental observations will be reported which support a model involving slip and continuous grain boundary migration or recrystalliza-tion. Specifically, a correlation will be made between this model and the development of elliptical cross sections as originally round specimens are superplas-tically deformed. For the most part, superplasticity studies have been conducted with eutectic or eutectoid alloys. Probably the most thoroughly studied material has been the monotectoid Zn-A1 alloy.1,2,6,12,13,15 No attention to the eutectic Zn-A1 alloy has previously been reported, and the results discussed in this paper represent part of a general study of the superplastic properties of this alloy. MATERIALS The alloys used in this investigation were prepared by melting appropriate quantities of 99.99+ pct A1 and 99.999 pct Zn in air, mixing, and pouring into a water- cooled stainless-steel mold. Wet-chemical analysis was conducted with each heat of alloy prepared, using the procedure of Fish and smith.16 The composition of the eutectic alloy was 95.1 wt pct Zn. Ingots about 2 in. thick were rolled to 0.4-in. plate at about 300°C with a reduction of 5 to 10 pct per pass. Specimens were machined from the plate with the tensile axis parallel to the rolling direction. The specimens were round, with 0.150-in.-diam, 1.25-in.-long gage length, and 0.25-in.-diam threaded grip sections. EXPERIMENTAL PROCEDURE Specimens were mounted inside a uniform-temperature quartz tube which was surrounded by a double elliptical radiant furnace with a 12-in.-long uniform-temperature hot zone and a low thermal capacity. The tube extended through the top and bottom of the furnace and permitted rapid quenching of the loaded specimens when quickly filled with cold water at the conclusion of the test. The quench precluded any effects on specimen microstructure from a normal, slow cool. Constant stress was applied to test specimens by suspending a load on a constant stress cam of the type described by Hopkin.17 The design of this cam permitted application of a constant stress for elongations up to 200 pct. For greater elongation, approximately constant stress conditions were maintained by systematically reducing the load manually. RESULTS As part of an investigation of the superplastic properties of the eutectic Zn-A1 alloy, evidence was obtained for the development of elliptically shaped cross sections as originally round specimens were extended. For example, after an elongation of about 100 pct, a round specimen with an initial diameter of 0.150 in. became elliptical with major and minor axis of 0.128 and 0.88 in., respectively. Photographs are presented to illustrate the ellipticity developed during superplastic deformation, Fig. 1. The specimen shown was deformed at a stress of 500 psi, at a temperature of 285°C, and a strain rate of 2.28 x 10-2 min-1. The strain-rate sensitivity exponent* was measured at *The strain-rate sensitivity exponent, m, is defined as d In o/d In c where o is the steady-state flow stress and E is the strain rate. this temperature and in the strain rate range 10"3 to 10-1 min-1 was found to be about 0.5. This value is typical of those observed with superplastic materials. The material studied exhibited negligible strain hardening during superplastic deformation, the creep rate remaining constant under constant stress and temper-

Jan 1, 1969

By E. S. Bartlett, D. N. Williams

QUANTITATIVE values for the oxidation rate of unalloyed molybdenum in air at temperatures above the melting point (1460°F) of the characteristic oxide are contained in the literature as a result of previous investigations. Lustman' reported values corresponding to 0.36 in. penetration per day (IPD) at 1500 and 1600°F in still air, noting essentially no variation in rate with temperature. Jones, Spretnak, and Speiser' reported values corresponding to 0.14 and 0.13 IPD at 1500 and 1800°F, respectively, in still air, attributing the decreased oxidation rate at higher temperatures to a lesser accumulation of the corrosive molten oxide on the surface at the higher temperature as a result of increased volatilization rate. Harwood3 ecently summarized work in the field, presenting generalized data corresponding to 0.48 to 0.96 IPD at 1800°F and 0.55 to 0.83 IPD at 1700°F in slowly flowing air. In a recent program at Battelle, it became desirable to know more about the characteristic oxidation behavior of molybdenum under varying conditions of temperature and atmosphere. Using oxidation-test apparatus designed for dynamic, continuous recording of weight change during testing,' values for the oxidation rate of molybdenum were obtained at temperatures from 1400 to 2150°F. In addition the effect of air flow on the oxidation rate was studied briefly at temperatures of 1600, 1800, and 2000°F. Exhaust of the contaminated atmosphere from the oxidation chamber was effected by an impeller pump attached to a 3/16-in.-diam opening in the oxidation chamber. The volumetric exhaust rate (cubic feet per hour) was normally maintained slightly in excess of the input rate to avoid condensation of MOO,,' on the sample suspension rod. The entering atmosphere was preheated prior to admission to the oxidation chamber by a 1 1/2-in.-diam cup packed with shredded asbestos. The experimental data are presented in Table I. Comparing conditions 2 and 3 (taking into account the temperature difference) and conditions 8 and 9. shows that in the absence of forced exhaust an atmosphere of moving air results in greater oxidation rate than a stagnant atmosphere. The use of forced exhaust, as shown by comparing conditions 3 and 4 and conditions 14 and 15: resulted in an even greater increase in oxidation rate. By virtue of the size of the atmosphere input and exhaust openings, it was calculated that the exhaust velocity was about 60 times that of the input velocity for essentially equal volumetric flow rates. Because of the proximity (about 3/4 in.) of the exhaust port to the specimen, it is logical to assume that cleansing of the atmosphere immediately surrounding the specimen was accomplished much more efficiently by the exhaust flow than by the input flow at a constant-volumetric flow rate. Also, it can be seen by comparing conditions 4 through 7 and conditions 11 through 13 that increasing the rate of atmosphere flow (by increasing input velocity with a proportional increase in exhaust velocity) above some optimum value has little, if any, further effect on the oxidation rate. These results suggest that there is a maximum oxidation rate for molydenum at a given temperature which is obtained when conditions are maintained such that the partial pressure of MOO3 in the atmosphere surrounding the specimen is at a low value. By controlling the partial pressure of MOO, surrounding the sample, it is possible to control the rate of volatilization of MOO:, from the surface. This, in turn, affects the rate of oxidation, since the thickness of the MOO3 layer determines the amount of oxygen which will be able to reach the reaction surface.' When the liquid oxide layer is less than some critical thickness, i.e., when the volatilization rate is high, enough oxygen is transported to the active surface to permit oxidation to proceed at the maximum rate allowed by the kinetics of the oxidation reaction. However, if the volatilization of MOO,, is suppressed, the thickness of the layer of MOO3 on the surface increases, and the diffusion of oxygen through the oxide layer becomes the rate-controlling step in the oxidation process. The lack of agreement between the present results and those of previous investigators is presumed to be due to differences in removal of the oxidation product (Moo,) from the immediate vicinity of the sample. By comparing conditions 1, 5, 10, 12 and 14, it is seen that when forced exhaust was used the oxidation rate of molybdenum increased with increasing temperature. A rapid increase was observed between 1400 and 1600°F, attributable to the effects

Jan 1, 1959

R. Schuhmann, Jr. (Purdue University)— Fulton and Chipman's results on rate of silica reduction from slags are analogous in many was to the results of Parlee, Seagle, and Schuhmann10 on rate of alumina reduction from alumina crucibles. Both investigations have given comparably low rates of reduction and slow approaches to equilibrium. Accordingly, we may hypothesize that the rate-determining step is the same in both kinds of experiments; that is, oxygen diffusion across the stagnant boundary layer on the liquid-metal side of the interface between the liquid metal and the oxide phase (slag or solid oxide). I suggest that silica reduction involves the following consecutive steps: I) At the slag-metal interface: SiO2(slag) Si+ 20 II) Transport of oxygen from slag-metal to gas-metal interface: a) diffusion across liquid-metal boundary layer at slag-metal interface. b) convection within the body of liquid metal. c) diffusion across boundary layer at metal-gas interface. 111) At the metal-gas interface: C +O- CO (gas) Iv) At the graphite-metal interface: C (graphite) -C At steelmaking temperatures it is reasonable to assume that equilibrium is attained in all three chemical reactions (I, 111, and IV) right at the respective interfaces. Convection within the stirred liquid metal (step IIb) is also rapid. Transport of Si and C should be orders of magnitude easier than transport of 0, because of the relatively high concentrations of Si and C. Accordingly, we might expect the overall reaction rate to be determined by boundary-layer diffusion of oxygen, either IIa or IIc. Fulton and Chipman's demonstration that bubbling CO through the system had no major effect on reaction rate indicates that IIc is not the slowest step. Therefore, it becomes logical to estimate the maximum rate for step IIa and to compare this theoretical estimate with Fulton and Chipman's experimental data. If oxygen diffusion across the liquid metal boundary layer at the slag metal interface (step IIa) is rate-determining, In this equation, dn sio, /dt is the rate of silica reduction in moles per sec,A is the area of slag-metal interface in sq cm, Do is the diffusivity of oxygen in sq cm per sec, 6, is the boundary layer thickness in cm, c,* is the oxygen concentration right at the slag-metal interface in moles per cubic cm, and co is the oxygen concentration in the body of the liquid metal, also in moles per cubic cm. Equilibrium data" on the silicon deoxidation reaction in liquid iron and steel at 1600°C indicate that the oxygen contents of the liquid metal in Fulton and Chipman's experiments at 1600°C probably fell in the range of 0.5 x10-3 x10-3wt pct. That is, the maximum conceivable value of co*-co for the system under consideration was on the order of 10"5 mole oxygen per cubic cm. On the basis of previously published data,1O,11 it is estimated that Do/0 will fall somewhere in the range from 10-3 to 10-1 cm per sec. The surface area A in Fulton and Chipman's experiments was approximately 20 sq cm, and the weight of metal involved was about 500 grams. Combination of all these figures with the above rate equation leads to an estimate that the rate of silica reduction should fall within the range from 0.002 to 0.2 wt pct Si per hr. This estimate is consistent with the experimental data. For example, Fulton and Chipman's Fig. 2 shows a change of about 0.3 pct Si in 10 hr, corresponding to an average rate of 0.03 pct per hr. According to the proposed hypothesis, increasing the temperature will increase the reaction rate ill two ways: 1) by increasing oxygen diffusivity and 2) by increasing the oxygen concentration (oxygen solubility) in the liquid metal. The combination of these two effects accounts for the high value of the observed activation energy. Summarizing, I propose that the rate of silica reduction, like that of the carbon-oxygen reaction, is diffusion controlled and that low oxygen concentration in the liquid metal is the major factor accounting for the very low observed rates of silica reduction. John Chipman (author's reply)—The authors thank Professor Schuhmann for his interesting contribution. His proposed explanation may well prove to be the correct one. There is clearly a need for much further experimental work on this problem, and further research is in progress.

Jan 1, 1961

By J. H. Swisher

When an Fe-Mn alloy is internally oxidized, the inclusions formed are MnO which contains some dissolzled FeO. In the internal oxidation reaction, not all of the manganese is oxidized; some remains in solid solution as a result of the high Mn-0 solubility product in iron. Taking these factors into consideration, the rate of internal oxidation of an Fe-1.0 pct Mn alloy is computed as a function of temperature, using available thermodynanzic data and recently published data for the solubility and diffusivity of oxygen in iron. The predicted and experimentally determined rates for the temperature range from 950 to 1350°C are in good agreement. ThE rates of internal oxidation of austenitic Fe-A1 and Fe-Si alloys have been studied extensively.1"4 Schenck et al. report the results of a few experiments with Fe-Mn alloys at 854" and 956C, and Bradford5 has studied the rate of internal oxidation of commercial alloys containing manganese in the temperature range from 677" to 899°C. When Fe-Mn alloys are internally oxidized, the inclusions formed are solutions of FeO in MnO, the composition depending on the experimental conditions. Since the thermodynamics of the Fe-Mn and FeO-MnO systems have been investigated,6"9 and since the solubility and diffusion coefficient of oxygen in y iron have been determined recently,' it is possible to predict the rate of internal oxidation from known data. The calculations used in predicting the rate of internal oxidation will first be outlined, then the results of the prediction will be compared with the experimental results of this investigation. PREDICTION OF PERMEABILITY FROM THERMODYNAMIC AND DIFFUSIVITY DATA Oxygen is provided for internal oxidation in these experiments by the dissociation of water vapor on the surface of the alloy. The dissociation reaction is: + H2(g) + [O] [1] where [0] denotes oxygen in solution. The equilibrium constant for this reaction is known as a function of temperature:' log As oxygen diffuses into the alloy, oxide inclusions are formed which are MnO with some FeO in solid solution. The reactions occurring are: [Mn] + [0] = (MnO) [31 and [Fe] + [0] = (FeO) [41 where [ Mn] is manganese dissolved in iron and (FeO) is iron oxide dissolved in MnO. The overall reactions may be written as follows: [Mn] + HOte) = (MnO) + H2(£) [5] and [Fe] + H20(g) = (FeO) + Hz(R) [61 The standard free-energy changes and equilibrium constants for Reactions [5] and [6] are known.6 Therefore the equilibrium constants for Reactions [3] and [4] may be obtained by combining known thermodynamic data for Reactions [I], [5], and [6]. For Reactions [3] and [4]: K = and For the present purpose, both the Fe-Mn7,8 and FeO-~n0' systems can be considered to be ideal, i.e., [amn] = [NM~] and (aFeO) = (NM~~) = 1 - (NFeO) where the Ns are mole fractions. These relations, together with Eqs. [I] and [8], permit us to compute both the oxide and metal compositions as a function of temperature and oxygen potential at any point in the specimen. For cases where the oxygen concentration gradient between the surface and the subscale-base metal interface is linear, the kinetics of internal oxidation is an application of Fick's first law: where dn/dt is the instantaneous flux of oxygen into the specimen, g-atom per sq cm sec; 6 is the instantaneous thickness of the subscale, cm; Do is the diffusion coefficient of oxygen in iron, sq cm per sec; p is density of iron, g per cu cm; h[%O] is the oxygen concentration difference between the surface and sub-scale-base metal interface, wt pct. B6hm and ~ahlweit" derived an exact solution to the diffusion equation for systems in which there is a stoichiometric oxide formed. They showed that the oxygen concentration gradient is given by a rather complex error function relation. For the Fe-Mn-0 system and for most other systems that have been studied, however, variations in oxide compositions are small and rates of internal oxidation are sufficiently slow that the deviation from linearity in the concentration gradient of oxygen is negligible. The mass of oxygen transported across a unit area of the specimen for the total time of the experiment is given by the mass balance equation:

Jan 1, 1969

By Pol Duwez

IN the course of an investigation of the V-CO system, two intermediate phases were found. One of these phases corresponds approximately to the stoichiometric composition VCo and is isomorphous with the sigma phase in the Fe-Cr system.' The second phase has the composition V3Co; its crystal structure is described in the present note. The alloys were prepared by mixing the two metals in the powder form, pressing a small disk weighing about 5 g at 80,000 psi, and arc melting this disk on a water-cooled copper plate in an atmosphere of pure helium. The details of this technique have been described.' The vanadium powder was obtained from Westinghouse Electric Corp., Bloomfield, N. J. This powder is probably of very high purity, since when it is properly sintered or melted in the above-mentioned arc furnace, ductile specimens are obtained. The cobalt powder, from Charles Hardy, Inc., New York, contained 0.5 pct Ni, 0.1 pct Cr, and traces of Si and Fe. After melting, the V,Co samples were sealed in evacuated quartz tubes and homogenized for ten days at 800°C. Powder diffraction patterns were obtained with a 14.32 cm diam camera, using Ka copper radiation. The patterns were readily indexed on the basis of a primitive cubic lattice with a parameter equal to 4.675A. The density, determined by the immersion method, was 6.71 g per cu cm; hence the number of molecules per unit cell is approximately 1.95; i.e., 2. At this point, the possibility that the structure might be that of beta tungstena became apparent. The beta tungsten structure is described as follows: Space group 03,, — Pm3n 2 Co in (a) : 000; ?4lhYZ (hhl) reflection present only if 1 = 2n. Assuming this structure to be the correct one, intensities were computed by means of the usual eauation: 1 + cos220 I oc p F sin 0 cos 6 where F is the structure factor, 0 the Bragg angle, and p the multiplicity factor. The observed and calculated values of sin 0 and the intensities are given in Table I. The agreement between the observed and the calculated sin 0 is good and there are no flagrant discrepancies between the calculated intensities and those estimated visually. The (hhl) reflections for which 1 is odd are not observed, as required by the space group. In addition, the (410), (430), and (531) reflections are missing as expected, because of the special (a) and (c) positions in0%. However, six reflections—(llo), (220), (310), (411), (422), and (510)—which have very weak computed intensities were not observed. For these reflections, the structure factor is proportional to the difference between the scattering factors of the two atoms in the structure. Since the scattering factors of vanadium and cobalt are not very different, these reflections are weak. However, by using Ka chromium radiation, whose wavelength is just above the absorption edge of vanadium, the effective scattering factor of vanadium may be decreased by one or two units; consequently the difference between the cobalt and vanadium scattering factors is increased. It was, indeed, found that in a powder pattern taken with chromium Ka radiation, the three reflections (110), (220), and (310) were actually present. The three other reflections (411), (422), and (510), with spacings smaller than half the wavelength of chromium Ka, were obviously not obtainable with chromium radiation. All the experimental results appear to confirm the beta tungsten structure for V,Co. In this structure, each cobalt atom is surrounded by twelve vanadium atoms at 2.61A; each vanadium atom is surrounded by two vanadium atoms at 2.34A, four cobalt atoms at 2.61 A, and eight vanadium atoms at 2.86A. Acknowledgment This work was done at the Jet Propulsion Laboratory, California Institute of Technology, under contract number W-04-200-ORD-455 with the Army Ordnance Department, Washington, D. C. The author wishes to thank this agency for the permission to publish the results of this investigation. References 'P. Duwez and S. R. Baen: X-Ray Study of the Sigma Phase in Various Alloy Systems. Symposium on the Nature, Occurrence, and Effect of Sigma Phase. ASTM Special Tech. Pub. No. 110, pp. 48-54. Philadelphia, 1951. 2 C. H. Schramm, P. Gordon, and A. R. Kaufmann: The Alloy Systems Uranium-Tungsten, Uranium-Tantalum, and Tungsten-Tantalum. Trans. AIME (1950) 188, pp. 195-204; Journal of Metals (January 1950). 3 M. C. Neuburger: The Crystal Structure and Lattice Constants of Alpha and Beta Tungsten. Ztsch. fiir Krist. (1933) 85, pp. 232-237.

Jan 1, 1952

By Charles H. Jacoby, Leo E. Read

IN diamond coring salt beds to evaluate deposits, special techniques are applied to standard slim hole drilling to obtain a representative sample of the water soluble sodium chloride. Industrial consumers generally require a run-of-the-mine material of 98.0 pct sodium chloride. Since no commercial beneficiation has yet been devised to upgrade the lower quality salt beds, the only processing is crushing and screening to the size required by the customer. Coring salt sections has recently become important not only in dry mining, but also in the development of brine cavities by hydraulic fracturing and the formation of jugs for storing liquid petroleum products. Drilling Fluid: The fluid used in coring salt beds in New York, Ohio, and Michigan is a thoroughly saturated brine made from 3.0 lb rock salt per gal of make-up water. This mined rock salt, -4 mesh +10 mesh, is dissolved in a lixator, a double-bottomed cone hopper that turns fresh water to fully saturated brine.

Jan 5, 1957

By David Burgess, Hershiel H. Hayden

Experiments at the Somerset mine, Colo., under an agreement between US. Steel Corp. and the US. Bureau of Mines are described. A test was made of the tube bundle method of mine air sampling which was developed for European longwall mines; some 300,000 running feet of tubing provided continuous monitoring at 38 locations. Carbon monoxide concentrations were obtained with standard deviations of less than 1 ppm and oxygen concentrations with standard deviations of less than 0.2%. A base level of CO index (ppm CO evolved per percent 0, removed) was determined to be zero to 20 through most of the passageways of the mine. However, in one working section where the coal was initially hot (about 180°F within a pillar) the CO index was demonstrably higher, 120 trending upward to about 60 when smoke appeared and the section was sealed. The data are discussed in terms of laboratory experiments on CO evolution from coals.

Jan 1, 1977

By B. J. Steblay

Roof bolts are the primary means of supplemental support in coal mines and are widely used in other mines. Presently, post installation loads are measured infrequently on only about 10% of the bolts by using standard torque wrenches that limit accuracy to about ± 30%. Because mine roof bolts are long, slender, non-uniformly sized, roughly forged, placed in a difficult environment, and subject to severe bending on installation, researchers have been unable to use ultrasonic reflection techniques to measure strain. A complete measurement system has now been assembled by the US Bureau of Mines, Denver Research Center. Obstacles such as bolt preparation, transducer mounting, reliable reflection, and calibration have been dealt with. The seemingly simple concept of measuring the time of flight of an ultrasonic pulse to a reflector is actually complex due to the need to measure to 0.0025 mm (0.0001 in.) accuracy, the sensitivity of velocity to temperature, and stress, and the stability required to make measurements over several years.

Jan 1, 1986

By Vassiliki G. Stavropoulou

Although plane-strain is the preferred method of analysing many rock mecahnics problems, little is known about the behaviour of rock under this loading condition. A simple and inexpensive apparatus has been built for laboratory testing of rocks in plane-strain conditions. A thorough .investigation of the specimen geometry and the friction end effects showed that the results can be considered as reliable. The behaviour of a brittle sandstone in the simplest plane-strain condition [(03 = 0)] is significantly different than that of the uniaxial compression [(02 = U3 = 0)]. The plane-strain values of the Young's Modulus and the Poisson's Ratio are decreased in comparison to the corresponding uniaxial values. Dilatancy is also reduced in plane-strain, whereas the pre-failure brittleness of the rock increases. The most dramatic effect of the plane-strain condition is that on the strength of the sandstone, which increases by 49 per cent in comparison to its uniaxial compression value.

Jan 1, 1982

By Robert G. Woolery, S. Ramachandran, James A. Weber, Donald J. Hansen

Union Carbide began looking seriously at heap leaching in 1971. At that time some 1.6 million tons of mineral averaging 0.40 kg U308 /t) (0.80 lb U308) were stockpiled at various sites around the Gas Hills, Wyoming, uranium facility. Several alternatives for economically exploiting these reserves were considered and heap leaching seemed the most attractive. At the time, Western Nuclear Inc. was operating a heap leaching project nearby in which the low-grade ore was leached with sulfuric acid, the product liquor treated in an on site solvent extraction circuit, and the stripped product liquor re-acidified and recycled. The operators were most generous in allowing us to visit their site and in answering our questions. They were also helpful in discussing the problems associated with heap leaching. Their experience confirmed our belief that it was possible to operate a heap leach profitably on material too low grade for conventional milling.

Jan 3, 1978

DISCUSSION, A. Y. Bethune presiding M. E. Wadsworth and W. M. Fassell (University of Utah, Salt Lake City)—The authors of this paper should be complimented on the experimental techniques they have employed to investigate the rate of solution of galena in sodium hydroxide solution. Studies of this type are important not only as a practical means of leaching normally non-leachable substances, but also to determine the mechanism of solution at the solid-aqueous solution interface. There is some question, however, as to the conclusions which have been drawn by these authors concerning their proposed mechanism. Unfortunately, the contribution of OH- was not definitely established in their work, and concentrations less than 0.5 N NaOH evidently were not investigated. The pressure data at 123°C and 0.5 N NaOH were used to determine pressure dependency and the subsequent model proposed was taken as correct on the basis of the three points presented in Fig. 5 of the paper. In developing the

Jan 1, 1954

By R. P. Smith

THE carbon content of iron-silicon and of iron-manganese alloys at fixed activities of carbon has been reported previously.' It seemed desirable to investigate a system which allows a more extended range of alloy composition within a single phase region. The iron-nickel system is ideal in this respect, in that all alloys from 100 pct Fe to 100 pct Ni are face centered cubic ("austenitic") at 1000 °C. The experimental procedure was similar to that previously described.1,2 The alloys, in the form of pieces about 2 by 2 by 0.2 cm thick, together with a similar specimen of pure iron, were equilibrated with each of a series carbon monoxide-carbon dioxide tnixtures of fixed composition, quenched in the carburizing gas in the top of the furnace and then analyzed for carbon. The carbon content of samples containing more than 0.3 wt pct C was determined by the usual combustion method; those with less carbon

Jan 1, 1961

By J. D. Cannon

SLAGS studied in this investigation were from 0.25 to 0.35 pct plain carbon steels and were melted in a 3-ton acid-lined Lectromelt furnace with a 2500-kva transformer. The melting process employs a short, violent boil, which is partially blocked, and the desired carbon content is adjusted by pig iron or iron ore, depending on the preliminary carbon. A relatively small volume of slag is used in refinement. Bottom is here defined as that portion of the furnace that comes in contact with the molten metal, or all the surface below the slag line. Bottom trouble-i.e., holes in the bottom lining-is very seldom experienced at our plant. We have been watching the bottom lining over a period of some boo heats in the hope of having holes large enough to supply data for this report, but none occurred during that period. The bottom is eroded uniformly, occasionally with slightly deeper depressions around the taphole.

Jan 1, 1947

By Frank A. Crossley

The work described has one serious shortcoming: grain size was not monitored during heat up to the temperature (1675°F) of isothermal anneal. The chief obstacles to p grain growth in titanium a-ß structures are the a grains. Heating a structure such as that shown in Fig. 1 to a temperature close to ß transus causes dissolution of a grains in order to adjust the a/ß ratio, compare Figs. 1 and 2. During this process there is a concomitant growth of the ß grains—otherwise ß grains would have to be nucleated in order to adjust the a/ß ratio. When the annealing temperature is reached the a/ß ratio stabilizes and this initial phase of ß grain growth ceases. After an incubation period growth resumes as described. Some 0 grain boundaries can be clearly seen in Fig. 1. (Skilled metallography commonly produces photomicrographs which show more structural detail than direct observation.) These boundaries suggest that the average ß grain size is approximately 0.002

Jan 1, 1970

By L. H. Lange

It is the author's opinion, based on many field experiences over several years, that it is usually better to design a rougher flotation circuit with long rows of rougher cells for high tonnage capacity for maximum recovery and better operating efficiency than the alternative of a greater number of shorter rows with proportionately less tonnage of feed per row. Recent plant studies and tests in the 12,000 ton per day flotation plant of the Atlas Consolidated Mining and Development Corp., Cebu, P. I., have given further substantial support to this opinion. There are two flotation sections in this concentrator: 1) Section 1, treating half the tonnage to the total mill, has eight rows of rougher cells, each row containing 360 cu ft of cell volume. Accordingly, each row of cells receives, on the average, 750 tons per 24 hours which assays about 0.65 to 0.75% copper. The main copper mineral is chalcopyrite with minor

Jan 11, 1963

By George W. Lower, Robert B. Booth

The use of cyanides in the extraction of gold and silver is well known1 Such extractions employ concentrations of cyanide in the range of 0.02-0.25% sodium cyanide equivalent in leaching cycles of 24-48 hr and frequently longer. Copper minerals, even though minor components of precious metal ores, dissolve in these cyanide leaching solutions, consume cyanide, cause fouling of mill solutions, and thus interfere with the precipitation and recovery of gold.2,3,4 This paper presents a summary of laboratory investigations on the use of cyanide solutions as extractants for copper from various copper-bearing ore fractions. In view of the metal contents involved, it will be apparent that larger quantities of cyanide are required to extract copper than for the extraction of precious metals. In cyanide solutions of concentrations generally favorable to copper extraction, sulfide and oxide copper minerals were found to dissolve rapidly at room temperature and atmospheric pressure.

Jan 11, 1965

By J. S. Browning

The pegmatites of the Kings Mountain-Lincolnton, N. C., area constitute the largest known domestic reserve of beryl and spodumene. The reserve is estimated to contain 90 million tons of pegmatic material with 1,280,000 tons of recoverable Li2O (lithia) as spodumene.1 The pegmatites also contain 0.4 to 0.5 pct beryl disseminated throughout the orebodies. The pegmatites may contain a potential reserve of 240,000 tons beryl, equivalent to approximately 34,000 tons of BeO. Different flotation methods for separating beryl from feldspar or quartz, or both, have been developed by various investigators.2,3,4,5,6,7 On the other hand, published information is limited on concentration of spodumene-beryl ores. As the response of beryl and spodumene to flotation is essentially the same, a successful separation of the two minerals depends upon use of a selective depressant or a selective collector for one of the minerals.

Jan 7, 1961