Search Documents

By O. D. Gonzalez

Existing measurements for the steady-state permeation of hydrogen in a iron above 100°C have been examined for contribution of determinate errors. The analysis leads to a recommended equation for the permeability of hydrogen in a iron: o= (2.9 ±0.5) x 10-3 exp - (8400 ± 400)/RT cu cm (ntp H2) cm-1 sec-1 atm-1/2 THE permeability of a iron to hydrogen has been the subject of numerous investigations over the past 40 years, and at present there are thirteen sets of published results for the rate of steady-state permeation of hydrogen in a iron above 100°C. The numerical values in each set of results are entirely self-consis-tent, but the spread among the sets is too large to be attributed solely to experimental error, i.e., to error other than in the specimen itself. Several reasons have been advanced to explain the disparities, but to date the relative importance of experimental inaccuracy to the spread remains uncertain. The purpose of this report is to examine in detail the sources of determinate errors inherent in the experiments and to assess as far as possible the contribution of the errors to the results. The ultimate goal is the selection of values for the permeability and heat of permeation most nearly representative of hydrogen in a iron. The analysis is limited to those experiments in which the permeation rate was observed at steady state—a condition in which traps for hydrogen within the metal are filled to a fixed level15 so that the trapping mechanism is not reflected in the rate of passage of the gas. Furthermore only data are examined in which surface processes are judged to have little or no influence on the flow. It is hoped with these restrictions to obtain values of the permeability and the heat of permeation which will be as closely related as possible to the mechanism of lattice diffusion. I) DEFINITION OF TERMS; UNITS In this report the data for permeation are given in terms of a coefficient oj permeability, ?, which is defined by the equation: jt=?A/?x{p1/2-po1/2) [1] where jt is the total flow of gas normal to the surface of a membrane of planar geometry, e.g., a disc, of area A and thickness ?x; pi and po are the pressures in the input and output sides, respectively. For flow radial to the walls of a membrane of cylindrical geometry, e.g., a tube, the corresponding equation is: where 1 is the length of the cylinder, and ri and ro are the inner and outer radii, respectively. The flux normal to the surface is given by Fick's law: j= -D(dc/dx) [3] At steady state the concentration gradient will be constant, and integration of Eq. [3] gives for the total flow through a disc of area A and thickness Ax: h =-DA(co - ci) [4] where c, and ci are the concentrations of solute at the output and input surfaces, respectively. When surface control is absent, co and ci are given by Sievert's law c = Kp1/2, and substitution therewith into Eq. [4] gives directly Eq. [I] where ? = DK. Integration of Fick's Eq. [3] in cylindrical coordinates will give Eq. [2] where again ? = DK and is thus shown to be independent of geometry (provided that surface control is negligible). The coefficient of permeability, or simply the permeability,* must be expressed in proper units. In *The term permeability will refer in this report always to the coefficient defined above; permeation will be used to specify the general phenomenon of gas passage through a membrane. this report ? will be expressed in the units of cu cm (ntp H2) cm-1 sec-1 atm-1/2. The variations of D and K with temperature are given by D = Do exp(-Ea/RT) and K = KO exp(-?Hs/RT) where E, is the activation energy for diffusion and AH, the heat of solution, each usually expressed in calories per mole of solute. The variation of permeability with temperature will thus be given (for conditions where surface control is negligible) by ? = ?o exp(-?Hp/RT) where ?0 = DoKo and ?Hp = Ea + ?Hs. The units of ?0 are the same as those of 6, and??Hp will be expressed in calories per mole H. 11) SUMMARY OF PERMEABILITY RESULTS Table I gives the values reported to date for the permeability of H2 in a iron in terms of ?o and ?Hp. Except where noted the parameters listed were taken directly from the numbers reported by the various investigators with only a change in units. The temperature limits within which the listed ?o and ?Hp hold are given in column 7; the limits marked in parentheses in this column indicate the entire temperature range covered in each investigation. The listed values of ?o and ?Hp are those giving a linear plot of ln? against T-1 at the higher temperatures in each set of measurements, and thus presumably represent the case for which surface control was negligible. Column 6 gives values of 9 at a representative tem-

Jan 1, 1970

By Hans-Jürgen Schaller, Horst A. Brodowsky

Activity coefficients of boron in palladium were determined at concentrations up to PdB0.23 by reducing B2O3 between 870" and 1050°C in a controlled H2-H2stream and measuring the resulting weight gain. The deviations from ideal behavior closely resemble those of the system Pd-H and are interpreted in terms of three principles: 1) The solute atoms occupy octahedral interstitial positions. 2) They donate their valence electrons to the 4 d and 5s bands of palladium, raising its Fermi energy. 3) The lattice strain energy is lower for two nearesl -neighbor interstitial particles than for two farther separate ones. SOLID solutions of hydrogen in palladium are a useful subject for studying thermodynamic aspects of the formation of alloys and of nonstoichiometric systems.1-3 The activity of hydrogen is readily measurable to a high degree of accuracy,4'5 even at low temperatures where the deviations from ideal behavior are more pronounced, and its simple structure facilitates an interpretation of these deviations in terms of a detailed model. Two effects are discussed to account for the non-ideal properties:3 An "electronic" effect, connected with the rise of the Fermi energy, as electrons of the interstitial hydrogen atoms enter the electron gas of the metal, and an "elastic" effect, due to an interaction of the regions of strain around each interstitial atom. The electronic effect is based on the idea that the lowest energy levels of the dissolved hydrogen atoms are higher than the Fermi energy, so that the electron will not occupy a localized state but enter into the electron band of the metal.6 The elastic effect is based on the observation that dissolved hydrogen distorts and expands the palladium lattice. The hypothesis is put forward that the elastic strain energy is lower for two adjacent dilatational centers than for two separate ones; i.e., they attract each other. The resulting pair interaction can be used to calculate an elastic contribution to the thermodynamic excess functions by means of one of the statistical methods. This model permitted a detailed description of the solution properties of hydrogen in palladium3 and in palladium alloys.798 An extension of the approach to describe the excess functions of substitutional palladium alloys is possible.9 In order to further test and refine the model, an investigation of other interstitial alloys was started. Palladium dissolves considerable amounts of boron in homogeneous solid solution.10 The palladium lattice expands linearly up to nB = 0.23 (nB = B/Pd atomic ratio), the highest concentration studied." The expan- sion, extrapolated for 1 mole of interstitial per mole of palladium, is 17 pct of the lattice constant of pure palladium vs 5.7 pct in the case of hydrogen.12 The fact that the lattice expands rather than contracts is a strong indication that interstitial positions are occupied. According to neutron diffraction experiments, hydrogen occupies the octahedral sites of the fcc lattice.13 Unfortunately, this direct evidence is not available for the Pb-B system, mainly because of the high-reaction cross section of boron with thermal neutrons. However, by way of analogy and on the grounds of the rather close similarities between the two systems to be reported here, it seems safe to attribute octahedral positions to the dissolved boron, too. At higher boron contents, compounds of stoichiomet-ric compositions are reported such as Pd3B, which has the structure of cementite,14 so that a close structural relationship seems to exist with the system r Fe-C. In their study of hydrogen absorption in Pb-B alloys, Sieverts and Briining noted that alloys with an atomic ratio of about nB = 0.16 are no longer homogeneous15 This observation was confirmed in an extensive X-ray investigation.11,16 The phase boundaries of two miscibility gaps were established. One two-phase region was stable below a transition temperature of about 315°C and extended from nB = 0.015 to 0.178. The other one extended from nB = 0.021 to 0.114 slightly above the transition temperature and had an apex at nB = 0.065 and 410°C. All phases involved have the fcc structure of pure palladium with lattice expansions proportional to their boron contents. The occurrence of miscibility gaps, i.e., the coexistence of dilute and concentrated phases, points to an energy of attraction between the dissolved particles, in the Pb-B system as well as in the Pd-H system. The filling up of the electron bands seems to be analogous, too, in the two systems, as indicated by the hydrogen absorption capacit15,17,18 and by the suscepti bility of Pd-B alloys.l8 In both types of experiments, boron acts as an electron donor. A chemical method was used to measure the activity of boron in palladium. Boron trioxide was reduced in a moist hydrogen stream: B2O3 + 3H2 = 2B + 3H3O [l] At known activities or partial pressures of boron trioxide, hydrogen, and water, the activity of boron could be calculated from the law of mass action. The equilibrium concentration of boron corresponding to this activity was determined as the weight gain of the sample. EXPERIMENTAL The samples consisted of small pieces of foil of 0.1 mm thickness and about 100 mg weight. The palladium was supplied by DEGUSSA, Germany, and stated to be

Jan 1, 1970

By J. Chipman, T. Fuwa

The effects of various elements on the activity coefficient of carbon in liquid iron have been studied by two experimental methods: 1) equilibration with controlled mixtures of CO and CO2; 2) the solubility of graphite in the melt. Activity coefficient of C is increased by Al, Co, Cu, Ni, P, Si, S, and Srz. It is decreased by Cr, Cb, Mn, Mo, W, and V. THE thermodynamic properties of the iron-carbon binary system have now been fairly well established, although some uncertainty remains with respect to the exact location of some of the phase boundaries. The activity of carbon in ferrite and in austenite has been measured in the classic researches of R. P. smith' while similar measurements by Richardson and ~ennis, and by Rist and chipman3 have established the values of the activity of carbon in liquid iron up to 1760°C. On the other hand, our knowledge of the effects of alloying elements on the activity of carbon in dilute solutions is restricted to Smith's experiments on systems Fe-C-Mn and Fe-C-Si in the austenitic range and to some more recent experiments of schwarzman4 in the a range. In addition there have been a number of determinations of the effects of various elements on the solubility of graphite in liquid iron, and from these the corresponding effect in saturated solution may be obtained. The purpose of the present study was to extend the investigation of the liquid system to include the effects of alloying elements upon the activity coefficient of carbon, principally in dilute solutions. Equilibrium measurements were made on the reaction C + co, = 2 CO (g) The prepared mixture of CO and CO,, diluted with argon, flowed over the surface of the liquid metal which, after several hours' exposure to the gas, was quenched and anqlyzed. As in the earlier experiments, the principal experimental difficulty was in the deposition of carbon on the parts of the furnace at temperatures slightly below that of the metal bath. In order to minimize this difficulty, the ratio (Pco)2 /PCo2 was restricted to values not much higher than 100 atm, and correspondingly the carbon concentration in the metal seldom exceeded 0.30 pct. EXPERIMENTAL METHODS The method and apparatus were essentially the same as used by Rist and Chipman.3 The gaseous mixture consisting of highly purified CO, CO,, and argon, each controlled by a flowmeter, was led into the furnace and passed over the surface of the liquid-iron melt which was heated and stirred by high-frequency induction. One slight modification was made in that a molybdenum susceptor was placed outside the crucible for the sake of uniformity of temperature and to combat the tendency of carbon to precipitate on the crucible wall. Pure alumina crucibles approximately 25 mm ID were used. The charge consisting of about 30 g was made up of electrolytic iron, the alloying element to be added, and enough graphite to supply slightly more or less than the anticipated equilibrium carbon concentration. All metals used were of high purity. Metallic chromium, columbium, and vanadium were from special lots supplied by the Electro Metallurgical Co. Tin, copper, molybdenum, tungsten, cobalt, and nickel were of purest commercial grades. The electrolytic iron, after being cut to the proper size for charging, was prereduced by hydrogen at 850° to 1000°C to remove surface oxidation. The oxygen content of the reduced material was 0.002 pct. This treatment made it easy to control the carbon content of the initial melt. The charge was melted under the gas mixture to be used for the entire run. In some earlier melts the charge was melted under a stream of argon, but in this case some alumina was reduced from the crucible, and the aluminum thus absorbed in the melt was subsequently oxidized with the formation of a solid film of alumina on the surface of the melt. AS another safeguard against film formation, overheating of the bath was carefully avoided. All runs were made at a temperature of 1560°C. Under experimental conditions a charge of pure iron picked up 0.17 pct C in 3 hr and 0.23 pct C in 6 hr under an atmosphere for which the equilibrium concentration of carbon is 0.27. It is clear that the time required to reach equilibrium from an initially carbon-free melt would be very great. For this reason each experiment was started with a melt of known carbon concentration not far above or below the expected equilibrium value, and each melt was held at temperature for a period of at least 5 hr. Under such circumstances it was possible to chart the approach to equilibrium from both high-carbon and low-carbon materials. Temperature was controlled by frequent optical observation and adjustment and the metls were timed in such a way that the final 2 hr occurred during a time when electric power was steady; for example, 2 to 4 pm or after 11 pm. In melts containine volatile metals such as copper, tin, and mangane\e the time of holding was decreased somewhat in

Jan 1, 1960

By N. L. Svensson

The model developed by Tuylor for the calculation of Polycrystalline yield strength has been applied to the case of an aggregate hawing a preferred orientation. In general this procedure requires the specification of texture by means of weighting factors applied to specific orientations. The problem to which the model has been applied is that of the yield-strength aniso-tropy of cold-rolled aluminum whose rolling texture was described as a combination of (110)[112] and (311) [112] In this case yield-strength anisotropy is defined by the rutio of yield strength measured at an angle 8 to the rolling direction to that measured along the rolling direction. The method of calculation of yield-strength ratio as a function of ? is described and the results show good agreement with experimental values. The orthotropic yield criterion suggested by Hill has been applied to the results and the strain ratio R also calculated as a function of ?. This has been compared with calculations using the method suggested by Elias, Heyer, and Smith which does not exhibit suck good agreement with observation. one deficietlcy of the method presented is that the strain ratios used by are those applying to iso-Irobic materials. The method should therefore be reg-clrded only as a first abbroximation to the prediction of anisotropy. THE problem of calculating the stress-strain characteristics of polycrystalline aggregates from the properties of single crystals has attracted attention for a number of years. The most important contributions to this study have been those due to: Sachs,' Cox and sopwith,2 Taylor,3 Kochendorfer,4 Batdorf and Budiansky,5 Calnan and Clews,6 Bishop and Hill,7,8 Kocks,9 Budiansky, Hashin, and sanders, 10 Kroner,11 Cyzak, Bow, and payne, 12 Budiansky and Wu,13 and Lin.14 While the earlier work has been largely superseded, recent developments tend to support Taylor's solution" within the restriction imposed by his assumptions. The essential features of Taylor's approach were: 1) the material is rigid-plastic; 2) each grain experiences the same strain components as the aggregate as a whole (the problem was that of uniaxial deformation with principal strain components in the ratio 3) all regions of each grain deform uniformly; 4) work hardening occurs equally on all slip systems. While Bishop and Hill7 have generally validated this approach, there has been some criticism offered. Kocks? as pointed out that since multiple slip must occur the single-crystal data must be determined from orientations arranged such that polyslip takes place. Boas and Hargreaves,15 and others, have shown experimentally that the strain distribution within grains is not uniform, the strains in the vicinity of grain boundaries being less than those in the center of the grains. Both of these criticisms can be largely offset by the suitable choice of single-crystal critical shear stress. However, for the problem analyzed below, the critical shear stress is not directly used and, consequently, these criticisms lose their importance. The more recent contributions have attempted to obtain a more complete analysis by considering an elas-toplastic material and considering interactions between grains of differing orientations. Lin14 has considered the early stages of yielding for a polycrystalline aggregate having specific regions of defined slip plane orientations. On the other hand, Budiansky and Wu13 have allowed for these interactions for randomly disposed grain orientations and have calculated the polycrystalline stress-strain curves for crystals exhibiting either elastic-ideally plastic or kinematic hardening characteristics. This work has shown that yielding commences when the macroscopic stress is 2.2 times the critical shear stress for slip in a single crystal (7,). The yield stress-strain curve then rises becoming asymptotic to a value of 3.072 7,. This is close to the value obtained by Bishop and Hill (3.06) in their confirmation of Taylor's method. This, of course, is to be expected since, at large strain values, the elastic strains are negligible and the rigid-plastic model is satisfactory. The results of Budiansky and Wu indicate that the result obtained by Taylor is 7.7 pct high at a plastic strain which is two times the elastic strain at the initiation of yield. By defining the anisotropy in terms of relative values, the ratio of yield strength at orientation ?, to that measured in the rolling direction, the effect of the discrepancy in Taylor's solution is considered to be of lesser consequence. Therefore, it is anticipated that an analysis based on Taylor's solution, which can be quite straightforward, should provide a reasonable estimation of the anisotropy of materials having a preferred orientation texture. OUTLINE OF TAYLOR'S METHOD In fee metals there are four possible slip planes (the octahedral planes) and in each there are three possible slip directions (the edges of the octahedron), that is a total of twelve possible slip systems. von Mises16 has shown that at least five independent slip systems must become operative in each grain of the polycrystalline aggregate in order to preserve continuity of strain. With this geometrical requirement as basis and the assumptions previously listed, Taylor determined the operative slip systems for a number of orientations of the tensile stress axis specified in the unit stereographic triangle. For the ith slip system, the critical shear stress

Jan 1, 1967

By W. D. Robertson, W. L. Phillips Jr.

Stress-strain curves were obtained for single crystals of alpha brass in tension and in direct shear. Specimens were strained various amounts in a given slip direction, unloaded, and immediately strained in a second slip direction 60°, 120°, or 180&apos; from the original slip direction. Crystals strained in tension and direct shear had comparable critical resolved shear stresses and stress-strain curves. The density of slip lines in direct shear and in tension was essentially the same. The stress-strain curves obtained in shear were independent of initial orientation, choice of {111 } slip plane, choice of <110> slip direction, prior annealing temperature, and rate of cooling after annealing. There was no recovery after annealing for 4 hr at room temperature or 200°C; recovery was observed after 4 hr at 400°C. The crystals showed no asterism and mechanical properties were completely recoverable up to 20 pct strain. It was found that there is a barrier to slip in all latent close-packed directions, and that the magnitude of these barriers, evaluated at 3 pct strain, is proportional to prior strain and independent of the choice of latent direction in the {111} plane. The formation of Cottrell-Lomer barriers is discussed as a possible explanation for the hardening of the latent systems. AN idealized concept of plastic deformation indicates that a single crystal should yield at some stress that is dependent on crystal perfection and it should then continue to deform plastically by the process of "easy glide," which is characterized by a linear stress-strain curve and a low coefficient, ds/dE, of work-hardening. Hexagonal metal crystals generally conform to this ideal concept of laminar flow. In face-centered cubic metals the range of easy glide is always restricted in magnitude and it is strongly dependent on orientation, composition, crystal size, shape, surface preparation, and temperature. Since one of the principal differences between the two crystal systems, both of which deform by slip on close-packed planes, is the existence of secondary (latent) slip planes in the face-centered cubic crystals, it has been proposed that the transition from easy glide to turbulent flow, characterized by rapid linear hardening, is due to slip on secondary planes intersecting the primary plane.&apos;-.; However, the characteristic differences between individual face-centered cubic metals remain to be explained; in particular, it is not clear why the range of easy glide should vary so greatly in different metals and alloys similarly oriented for single slip. An investigation and comparison of different metals with respect to latent hardening on the primary slip plane should provide some of the information required to specify the necessary and sufficient conditions governing the transition from easy glide to turbulent flow. But, in order to accomplish this purpose, plastic strain must be produced by simple shear in a chosen plane and in a predetermined direction by some form of directed shear apparatus, the results of which must be correlated with the corresponding tension experiments. Two such experiments have been performed previously with zinc and with aluminum. Edwards, Washburn, and Parker" and Edwards and Washburn7 found that the strain-hardening coefficients in two latent directions in the basal plane of zinc were the same as in the primary direction. However, to initiate and propagate slip in either the [2110] or the [1210] direction, following primary slip in the [1l20] direction, it was necessary to increase the stress above that required to continue slip in the primary direction; when the direction of shear was reversed 180 deg plastic strain began at a much lower stress than that required to initiate slip in the original direction and the stress to propagate slip in the reverse direction was lower than the stress to continue slip in the forward direction, indicating a permanent loss of strain-hardening. Rohm and Kochendorfer observed softening in aluminum for all latent close-packed planes and directions. They also found that the critical resolved shear stress obtained from their direct shear apparatus was 50 pct lower than the value obtained from conventional tension tests, that the stress-strain curve was linear at 50 pct plastic strain, and that slip lines were not visible at strains less than 30 pct. At present it is uncertain whether these diverse results correspond to real differences in work-hardening characteristics of the close-packed planes of aluminum and zinc or to differences in experimental technique. In view of Read&apos;s analysis &apos;" of the stress distribution in the experimental arrangement of Rohm and Kochendorfer, there is some reason to question the significance of the latter results. In order to resolve this problem it is necessary to re-valuate the direct-shear technique and either repeat the previous measurements or investigate a third system. The latter choice seemed most likely to produce significant results with respect to work-hardening, and accordingly, it was decided to examine the hardening characteristics of the latent slip directions in alpha-brass. The choice of alpha-brass was dictated by the fact that easy glide is more extensive in this alloy than in any other face-centered cubic metal or alloy and, presumably, more nearly like the idealized hexagonal system. Experimental Procedure Crystals were made in graphite by the Bridge-man method in the form of cylinders, 11/2 in. diam and 8 to 9 in. long. Material for the crystals was 70/30 brass containing the following impurities:

Jan 1, 1959

By E. T. Turkdogan, M. T. Hepworth, R. P. Smith

The permeability of oxygen in 0 iron in the tempera-ture range 700" to 900 C and in 6 iron at 1450°C was determined by the rate of internal oxidation of iron, containing -0.1 pct Al. The solubility of oxygen in zone-refined iron was determined by equilibration with hydrogen-water vapor gas mixtures at 1450" and 1510°C; oxygen solubilities , for iron in equi1ibriu.rn with molten oxide, are found to be 66 and 83 ppm for these two temperatures, respectively. The diffusivity of oxygen in iron at 14500C3 as calculated from the permeability and solubility data, is (4.1 * 0.6) x 10 "B sq cm per sec. OXYGEN is one of the most common impurities present in iron or steel, mainly in the form of oxide inclusions. In the study of many metallurgical problems concerning solid iron, it is often desirable to know with a reasonable accuracy the solubility and diffusivity of oxygen over a wide temperature range. The solubility of oxygen in solid iron has been the subject of numerous studies yielding highly discordant results as seen for example from the literature surveys made by Meijering &apos; and Schenck et a1.&apos; As shown by Kitchener et aL3 and by Sifferlen, the high oxygen solubilities reported by many investigators are the result of oxidizable impurities which are often present in iron. In addition, there have been experimental problems associated with icaccuracy of oxygen analysis of iron containing less than 100 ppm 0. A number of studies have been made on the permeability of oxygen in a and y iron using Fe-Si, Fe-Mn, and Fe-A1 alloys in the internal-oxidation experiments.1&apos;2&apos;5&apos;6 However, no direct measurements have been made of the diffusivity of oxygen in iron. In the present work two sets of experimental measurements were made: permeability and solubility studies at 1450" and 1510°C and permeability studies only in the range 700 to 900°C. In both sets of permeability measurements slab-shaped specimens containing small predetermined amounts of aluminum in solution were exposed at constant temperature to gas mixtures of hydrogen, water vapor, and argon for varying times. These specimens were quenched, sectioned, and examined for oxygen penetration by metallographic observation of aluminum oxide particles which formed. From these data, it is possible to calculate the ratio of the diffusivity of oxygen in iron, D, to the equilibrium constant K for the reaction Hz(g) * O (dissolved in iron) = H,O(g). EXPERIMENTAL Permeability Measurements at 1450°C. An ingot of vacuum-carbon deoxidized iron containing 0.086 pct A1 was prepared, using commercial "Type lO4A Plas-tiron"; after hot rolling, specimens were machined into slabs a by 2 by 2 in. The impurity contents were: S, P < 0.002 pct; C, Mn < 0.01 pct; each of all other Usual impurities < 0.004 pet. The amount of oxide inclusions in this material, determined by a bromine-methyl acetate extraction, corresponded to about 20 ppm 0 in the iron which agreed well with the results of vacuum-fusion analysis. Each specimen was annealed at 1450°C for 1 hr in purified hydrogen, polished to a smooth surface, and then introduced into a controlled oxidizing atmosphere in a recrystallized alumina tube at 1450°C. The constant temperature zone (*3"C) was about 3 in. in length. The gas composition was controlled by mixing argon with hydrogen (using calibrated constant-head flow meters) and passing the mixture through a column of a mixture of oxalic acid dihydrate and 10 pct anhydrous oxalic acid, to establish a required water-vapor content in the gas mixture. The temperature of the oxalic acid dihydrate column was controlled by a thermostat. The total gas flow was in the range 800 to 1000 cu cm per min. The exit gas from the reaction tube was passed through a weighing bottle containing a desiccant, to cross-check the degree of water-vapor saturation, which for all experiments was about 97 pct of those derived from the data of Baxter and Lansing.1 For a typical experiment, a specimen was introduced into the furnace in a stream of dry argon and hydrogen. The specimen was then rapidly raised by a Pt-Rh alloy wire into the hot zone and allowed to reach the reaction temperature, at which time the oxidizing gas mixture was introduced. The oxygen potentials employed were sufficient to oxidize aluminum but not to cause liquid iron oxide to form. After a specified time, the experiment was ended by dropping the specimen onto a water-cooled copper block at the bottom of the reaction tube. The depth of the internally oxidized zone, hereafter called the "case", was determined by sectioning the specimen at right angles to the long direction. The section was then examined under a microscope equipped with a micrometer stage. In general, the oxide particles were fairly uniform in size and distribution, forming a reasonably well-defined interface between the oxidized and unoxidized region. A typical cross section as observed at X30 is shown in Fig. 1. A thermal macroetch was used in one selected specimen to delineate the case. A cross section of a previously oxidized slab was polished and reheated at 1450°C in a hydrogen atmosphere for about 10 min. Upon quenching, the surface relief shown in Fig. 2 was produced; causes of this effect are unknown. Permeability Measurements Below 900°C. A slightly

Jan 1, 1967

By S. Usui, I. Iwasaki

The effect of pH on the adsorption of dodecylamine at the mercury-aqueous solution interface was investigated by differential capacity and electrocapillary measurements. With dodecylammonium acetate, the differential capacity curves showed two desorption peaks in the cathodic branch with their relative intensities varying with the solution pH. With dodecyltrimethylammonium chloride, only one cathodic de-sorption peak was observed in the same pH range. Through thermodynamic analysis of the electrocapillary curves, the adsorption density of undissociated amine was evaluated separately from that of aminium ion. The adsorption densities of the un-dissociated amine and of the total amine increased with increasing pH. The ratio at the interface of undissociated amine to aminium ion was several orders of magnitude greater than the ratio in the solution and increased with increasing pH. The potential at the closest distance of approach of counter ions to the mercury surface was compared with values of zeta potential on quartz previously reported. The most important variable in the flotation separation of minerals is probably the pH of the pulp, and a number of theories have been proposed to explain its effect on the condition of the mineral surfaces, on the dissociation of collectors and of inorganic and organic species (accidentally present or intentionally added) in the pulp, and on the mineral-collector interaction. In the development of a theoretical background for oxide flotation systems, an experimental approach based on electrokinetic measurements has been of much value, although the effect of pH becomes confounded since it governs both the electrochemical conditions of the oxide surface and the dissociation of the collector. For investigation of the adsorption behavior of long-chain collectors on oxide minerals, however, electrokinetic potential measurements are the most widely used technique. Hydrogen and hydroxyl ions are found to be the potential determining species, thereby governing the interfacial electrical conditions. The electrostatic interaction between the charged mineral surfaces and ionized collectors is regarded as the driving force for the adsorption of the collectors. An association of alkylamine collectors adsorbed on quartz surfaces has been postulated from streaming potential measurements, and a term "hemi-micelles" has been proposed.&apos; The possibilities of coad-sorption of undissociated amine along with aminium ion has been inferred from contact angle measurements? and from adsorption studies.~ Electrochemical titration as applied to silver sulfide provides a more quantitative approach to the analysis of the electrical double layer at an ionic solid-solution interfaceqG and the electrochemical evidence for the adsorption of amine at pH 4.7 indicates a specific affinity of dodecylammonium ion towards silver sulfide surfaces, whereas at pH 9.2 the adsorbed species might be free arnine." A combination of differential capacity and electrocapillary measurements on a dropping mercury electrode was reported to be a sensitive method of provid- ing reliable information on the adsorption behavior of dodecylammonium acetate (DAA) at a natural (near neutral) pH.? It was also shown that there were striking similarities in the properties of the double layer and in the adsorption behavior of the amine on mercury and on such ionic solids as quartz, silver sulfide, and silver iodide. The effect of pH on the differential capacity curves at a mercury-sodium fluoride solution interface has been investigated by Austin and Parsonss who reported that between pH 7 and pH 11 there was very little effect. In the present paper, the adsorption behavior of DAA was investigated as a function of pH through differential capacity and electrocapillary measurements and the information gathered was correlated with that available in literature on quartz and silver sulfide. Experimental The apparatus and the method used for determining the differential capacity and the electrocapillary curves were identical to those described previously.&apos; The ionic strength of the supporting electrolyte was fixed at 0.1 M with potassium fluoride, and the pH of the solution with potassium hydroxide. Only the neutral to alkaline range was covered in order to avoid the dissolution of the glass vessel with hydrofluoric acid. Results In Fig. 1 the differential capacity has been plotted against the applied potential at a DAA concentration of 10-&apos; M at three different pH values. The curves are characterized by one capacity peak in the anodic branch, by two capacity peaks in the cathodic branch, and by a marked depression in capacity between the peaks. The depression indicates an adsorption of the arnine in this potential range. One of the cathodic peaks appears at pH 7.3 near -1.4 v and decreases with increasing pH. The other appears at pH 8.9 near —1.2 v and increases with increasing pH. At pH 9.6 only the latter peak is observed. Beyond the cathodic peaks, all the curves tend to converge with the curve in the absence of DAA, implying that two different species are being desorbed in this potential region. The anodic peak near 0.0 v increases markedly with increasing pH. The well-defined anodic peaks at pH 8.9 and 9.6 were accompanied by an appreciable increase in the current flow (in excess of O.luA), and, therefore, is a "pseudo-capacity"&apos;" due to a

Jan 1, 1971

By L. T. Larson, M. L. Picklesimer

The relationship between the apparent angle of rotation of monochromatic plane polarized light and the tilt of the basal pole from the surface normal has been experimentally determined for zirconium over the wavelength range of 500 to 655 mp. This relationship allows the determination of the spatial orientation of the basal pole of an individual grain in a polycvystal-ling zivrconium specimen to within ±3 deg by three simple tneasurements with a polarized-light metallurgical microscope. The method of measurement is discussed in detail. THE optical anisotropy of materials having noncubic crystal structures has long been used to reveal features by polarized-light microscopy. Petrographers have used measurements of certain optical properties to identify and classify transparent or translucent minerals. More recent work (i.e., Cameron1) has extended such measurements to opaque minerals in reflected light. Few attempts have been made to make similar measurements on noncubic metals. Couling and pearsall2 have reported that a sensitive tint plate can be used in a polarized-light metallurgical microscope to determine the position of the basal-plane trace in a grain of polycrystalline magnesium. Reed-Hill3 has reported that the same technique can be used for zirconium. We have found that the precision of measurement can be increased to about ±0.5 deg by using a Nakamura plate4,5 to determine the exact extinction position after the sensitive tint plate has been used to locate approximately the basal-plane trace. This report describes a method for measurement of another optical property, the apparent angle of rotation. This measurement permits determination of the angle between the basal pole of a grain of a hcp metal and the normal to the surface of the specimen. When the two measurements are combined, the orientation of the basal pole in space can be determined from three simple measurements on a single surface. One to two hundred such determinations will permit plotting of a basal-pole figure for the polycrystalline material with reasonable accuracy. When normally incident, monochromatic, plane-polarized light is reflected from the surface of an optically anisotropic material, the light may be converted to elliptically polarized light, the plane of vibration may be rotated, or both may occur. The el- lipticity, the angle of rotation, and the reflectivity can be related to the indices of refraction and the absorption coefficients of the material.6,7 Ellipticity values can be determined with an elliptical compensator, but not with the ease and precision desirable for the present purposes. Measurement of the angle of rotation requires only the determination of the angle from the crossed position (90 deg to the polarizer) that the analyzer must be rotated to obtain extinction when the trace of the optical axis in the surface is at 45 deg to the vibration direction of the polarizer. The angle of rotation of the analyzer is approximately 6/5 that of the true angle of rotation of the light as reflected from the specimen because there is a small amount of additional rotation produced during the passage of the reflected light through the mirror of the microscope. Since we are presently interested only in determining the tilt of the basal pole, the angle of rotation of the analyzer (the apparent angle of rotation of the light, i.e., uncorrected) can be used. Precision of the measurement can be increased substantially by the use of a Nakamura plate4,5 in determining the extinction position. In an optically uniaxial material (hcp or tetragonal crystal structure) the angle of rotation depends only on the optical properties of the material and the orientation of the optical axis of the grain relative to the plane of incidence of the plane-polarized light.7,8 Thus, in a metal such as zirconium, the apparent angle of rotation at the 45-deg position in any given wavelength of light is a direct measure of the tilt of the basal pole from the normal to the surface. If the optical properties vary with wavelength, the apparent angle of rotation for any given tilt of the basal pole will vary. None of the required information exists in the literature for zirconium nor for any other non-cubic metal. MEASUREMENTS ON SINGLE-CRYSTAL ZIRCONIUM A single-crystal sphere of zirconium 9/16 in. in diam was spark-cut from a single-crystal rod grown from iodide bar by an electron-beam zone-melting process.9 The damaged surface was removed by chemical polishing in a 45/45/10 mixture (by vol) of water, concentrated HNO3, and HF (48 pct) and then electropolishing at 50 v in a bath1&apos; of methyl alcohol and perchloric acid (95/5 by vol) at -70-C. The single-crystal sphere was mounted in a five-axis goniometer stage having a removable eucentric X-ray diffraction goniometer head for the two inner orientation axes. The basal pole of the single-crysta sphere was aligned parallel to a third axis of the goniometer stage by using the sensitive tint method to determine the basal-plane trace at several rotational positions of the sphere. The alignment was then checked by removing the sphere and eucentric gonio-

Jan 1, 1967

By D. S. Flett, D. W. West

The solvent extraction of chromium 111 has been studied for the system Cr 111, H,SO., H,O/RNH/RNH., xylene, where the primary amine used was Primene JMT. Rate studies have shown that extremely long equilibrium times are required, ranging from 1 hr at 80°C to 20 days at room temperature. Heating the solution prior to extraction increases the rate of extraction. The variation in the amount of Cr 111 extracted is an inverse function of the acidity of the aqueous phase. Thus, the slow rates of extraction appear to be connected with the hydrolysis of the Cr I11 species. Extraction isotherms for the extraction of Cr 111 have been obtained for two sets of experimental conditions, namely at 60°C and for a heat-treated solution cooled to room temperature. The separation of Fe 111 from Cr 111 and Cr 111 from Cu 11 in sulfate solution by extraction with Primene JMT has been studied and shown to be feasible. A survey of the literature relating to the solvent extraction of chromium showed that, although many systems exist for extraction of Cr VI, only a very few reagents have been found to extract Cr 111. The extraction of Cr III by di-(2-ethyl hexyl) phosphoric acid has been reported by Kimura.&apos; A straight-line dependence of slope —2 was observed between log D,, and the log mineral acid concentration at constant extractant concentration. Since the slope of this plot reflects the charge on the ion extracted, it must be concluded that a hydrolyzed species of Cr III is being extracted. Carboxylic acids generally do not form extractable complexes with Cr III but di-isopropyl salicylic acie does extract Cr 111. Simple acid backwashing of the organic phase, however, failed to remove the chromium. Similar difficulty in backwashing was found by Hellwege and Schweitzer8 in the extraction of Cr I11 with acetyl-acetone in chloroform. The extraction of Cr 111 from chloride solutions by alkyl amines has been reported4-&apos; but the maximum amount of extraction achieved in these studies did not exceed 10%: From sulfate solutions, however, Ishimori" has shown that appreciable amounts of Cr I11 were extracted by amines. The amines used were tri-iso-octyl amine, Amberlite LA-1 (a secondary amine, Rohm & Haas) and Primene JMT (primary amine, Rohm & Haas). The efficiency of extraction with regard to amine type was primary>secondary> tertiary. Appreciable extraction of Cr I11 was recorded for Primene JMT as the aqueous phase acidity tended to zero. The major difficulty with Cr I11 in solvent extraction systems stems from the nonlabile nature of the ion in complex formation. This accounts for the slow rate of extraction generally experienced and the difficulty encountered in backwashing the Cr I11 from the organic phase in the case of liquid cation exchangers. Consequently, the possibility of extraction of Cr I11 as a complex anion is attractive since the backwashing problems should be minimized in this way. From published data, it appeared that the extraction of chromium from sulfate solutions of low acidity by primary amines afforded the best chance of success for a useful solvent extraction system for Cr iii This paper presents the results of a study of the extraction of Cr I11 from sulfate solution by Primene JMT and examines the application of such an extraction procedure for the recovery of chromium from liquors containing iron and copper. Experimental Chromium solutions were prepared from chrome alum in sulfuric acid and sodium sulfate so as to maintain a constant concentration of sulfate ion of 1.5 molar. Solutions of Primene JMT were prepared in xylene and the amine equilibrated with sulfuric acid/sodium sul-fate solutions, of the same acidity as the chromium solution, until there was no change in acidity between the initial and final aqueous phases. The solutions of Primene JMT conditioned in this way were then used for the equilibration experiments. Equilibrations at 25°C were carried out in stoppered conical flasks shaken in a thermostat; equilibrations at all other temperatures were carried out in stirred flasks in a thermostat. After equilibration, the phases were separated and analyzed for chromium. In the tests on the rate of extraction, small samples of equal volume of both phases were withdrawn from time to time and the chromium distribution determined. The chromium analyses were carried out either coloi-imetrically using diphenyl carbazide, or volu-metrically using addition of excess standard ferrous ammonium sulfate and back titration of the excess iron with potassium dichromate. The oxidation of Cr 111 to Cr VI in the case of the raffinate solution was effected by boiling with potassium persulfate in the presence of silver nitrate and, for the backwash solution, by boiling with sodium hydroxide and hydrogen peroxide. Results Preliminary experiments indicated that extraction results were effected by the age of the chromium solution, higher distribution coefficients being obtained with solutions which had been allowed to stand for some time. Consequently a stock solution of chrome alum, 10 m moles per 1 Cr I11 in 1.4 M Na,SO,/O.l M &SO,,

Jan 1, 1971

By A. Grant Elliot, H. W. Lavendel

qualitative picture has been developed to describe the oxidation behavior of TaSi2-coated tantalum and CbSi2-coated columbium. These systems have a significantly lower inherent oxidation resistance than MoSi2-coated molybdenum does. This stems primarily from the fact that Ta2O5 and Cb2O5 are nearly as stable thermodynamically as SiO2, whereas MoO2 or Moos are not. Further, diffusion of silicon in the Ta- and Cb-Si system is considerably slower than in the Mo-Si system. These ,factors prohibit the mechanism of selective oxidation of- silicon which accounts for the oxidation resistance 01- MoSi2-coated molybdenum. The silicide can be stabilized by adding suitable Modifiers which increase the thermodynamic stability of the silicate formed during oxidation. Modifiers, such as aluminum, can be inroduced into solid solution in the coating. in controlled amounts through proper selection of the source in the pack cementation process of coating fov~rzatiorz. Addition of aluminum to TaSi2, coatings on tantalum was effective in moderately increasing the oxidation resistance. EXTENSIVE experimental work and analysis have established the nature of the oxidation behavior exhibited by MoSi2- and MoSi2 -coated molybdenum-base alloys, and defined the conditions for maximum protection against oxidation of the substrate.&apos;-* The oxidation resistance of MoSi2 in the temperature-pressure range of 1100°C-PO2 > 10-5 atm to 1900°C— PO2 > 10-1 atm is due to the formation at the surface of a continuous film of SiO2 which results from selective oxidation of silicon. Under the prevailing kinetic conditions, this film is stable toward the molybdenum silicide with which it comes in contact. Initially molybdenum oxidizes also, but it forms volatile species. SiO2, however, nucleates and grows as a condensed phase. Once a continuous film of SiO2 has formed, the oxidation rate falls to that observed for the oxidation of pure silicon indicative of diffusion through the oxide film as the rate-controlling mechanism. This oxidation behavior is of course highly dependent upon temperature and oxygen pressure. Bartlett and Gage13 and Bartlett, McCamont, and Gagelb define precisely this dependence in terms of the oxygen partial pressures and silicon diffusivities required to support a stable SiO2 film. At low temperatures (near 500°C—the "pest" region) silicon diffuses too slowly to be selectively oxidized. Hence, molybdenum and silicon oxidize readily in proportion to their stoi- chiometry. At high temperatures and low pressure, SiOz dissociates to form volatile SiO(g), and a protective film cannot be maintained. Application of the MoSiz/Mo system is limited to temperatures below 1900oC, the eutectic between MoSi, and MO5Si3.5 The oxidation behavior of MoSi2-coated molybdenum is essentially the same as that outlined above with the exception that the MoSi2 is not in equilibrium with the molybdenum substrate. At the temperatures under consideration silicon will diffuse rapidly into the molybdenum eventually converting the coating to MosSi3.4 The rate constant for subsequent decomposition of Mo5Si3 into Mo3Si plus silicon, and/or the diffusivity of silicon through Mo3Si then becomes low enough to allow active oxidation of both molybdenum and silicon with subsequent degradation of the specimen. A stable silica film can be formed but at temperatures and/or oxygen partial pressures higher than those required with MoSi2 present as a source of si1icon.l, 4 Because of the similarity between the silicides of molybdenum and those of columbium and tantalum one would expect similar oxidation behavior for coatings in the respective systems. This is not entirely the case, however, as shown by the experimental results reported herein. Regarding tantalum and columbium disilicide coatings on tantalum and columbium substrates, respectively, the oxygen arriving at the surface of the coating partitions itself nearly equally between the metal and the silicon, and a two-phase oxide layer (Me2O5 plus SiO2) is always formed. The diffusion of silicon in the tantalum and columbium silicides is relatively slow, compared to that in the molybdenum silicides, which further enhances this equipartitioning of oxygen. Thickening of the coating during service by inward diffusion of silicon into the substrate is correspondingly slow, and the effective thickness of the coating at the roots of cracks and defects is only slightly changed providing high probability for premature coating failure. Furthermore, the SiO2 glass that is generated is not thermodynamically stable with respect to the coating. The metal silicide tends to reduce the SiO2 liberating either free silicon or SiO. The situation can be improved by suitably modifying the coating such that the stability of the protective glass which is generated during service is increased. Thus, selective oxidation of silicon and the modifying agent will occur, and the silicide coating will not tend to reduce the oxide layer. Modifying agents can be introduced into the coating by the pack cementation process. Using sources containing the modifier at controlled chemical potentials allows control of the coating composition. Partially substituting aluminum for silicon in TaSi2 coatings by forming a Ta(Si,Al)2 solid solution was effective in moderately increasing the oxidation protection.

Jan 1, 1968

By Eugene S. Meieran

The effects of methods of crystal growing, wafer sawing, polishing, routine handling, diffusion, and epitaxial growth on the defects in GaAs are reviewed and studied using reflection and transmission X-ray topographic techniques. In general, it was found that boat-grown crystals exhibited fewer defects than Czochralski crystals, although all crystals showed large numbers of precipitates visible when examined in the electron microscope. Mechanical surface treatments such as sawing and mechanical polishing introduce damage to a depth of about 5 µ, most of which can be removed by suitable chemical or chem-mechanical polishing. In addition, defects can be introduced through routine handling of wafers, for example with metallic tweezers. These defects can be quite severe, and have been observed 20 µ below the wafer surface. Defects can also be introduced through diffusion and epitaxial growth. These defects, which include precipitates, growth pyramids, stacking faults, dislocations, and so forth, can be detrimental to device fabrication. It is shown that wafers or films which appear defect-free optically can contain defects visible in the X-ray topographs. WHILE the use of GaAs in the semiconductor industry has increased very rapidly in the last few years, due mainly to the recent development of many important GaAs devices,1,2 the major limit to the production of commercial quantities of many GaAs devices remains a severe lack of suitable materials technology. This lack is apparent in two critical areas. First, production quantities of high-quality GaAs crystals, reproducibly doped and precipitate-free, simply are not available commercially, although some reasonable quality material is available on a limited first-come, first-serve basis. Second, in comparison to silicon technology, little is known about the effects of processing variables on the defects either present in as-grown GaAs or introduced through processing and handling of wafers. These areas are now receiving some attention from semiconductor device manufacturers, who are studying defects in GaAs in order to better understand how either to prevent their occurrence or to cope with their existence. Most investigations of the defects in GaAs have been made by optical microscopy3-5 or transmission electron microscopy techniques.&apos;-&apos; Recently, however, the imaging techniques of X-ray topography, electron mi-croprobe analysis, and scanning electron microscopy are being applied to the study of GaAs.9-14 In the case of X-ray topography, a one-to-one image is obtained that must be photographically enlarged. In compensa- tion, the defects within entire wafers may be imaged by simple scanning (Lang technique15) if the wafer is reasonably perfect, or by using the scan oscillation technique developed by Schwuttke16 if the wafer is warped or distorted. The purpose of this paper is to both review and extend the general application of X-ray topographic techniques to GaAs. Emphasis will be placed on the effects of growth and process variables on the quality and perfection of both bulk and epitaxial GaAs. Reference to optical or electron microscopy results will be made when useful. Since the effects on defects of a wide variety of processing variables such as crystal growing, sawing, polishing, diffusion, and epitaxial growth will be somewhat superficially reviewed, a fairly extensive bibliography of the most important recent results in these areas is included. However, for completeness, important defects will be illustrated here, although such defects have been previously shown by others. While this paper is concerned with defects rather than with the physics of X-ray scattering, the mechanisms of contrast formation in the topographs will of necessity be briefly mentioned. EXPERIMENTAL GaAs crystals, both boat-grown18 and Czochralski-grown,&apos;8 containing a variety of dopants of various concentrations, were purchased from outside vendors. Wafers were sliced from the crystals using a Hamco ID saw and were mechanically polished using 1 µ diamond paste. Chem-mechanical polishing was done in bromine-methanol as described by Sullivan and Kolb.18 Chemical polishing was done using a modified sulfuric-peroxide solution, 11 parts H2SO4, 1 part 30 pct H2O2, 1 part DI water.5 Zinc diffusion was carried out in a closed tube, using a 10 pct Zn-In source at 825°C for 1 hr. Oxide masking techniques were used to select the area to be diffused. Epitaxial wafers were either purchased or prepared here. All epitaxial runs prepared here were carried out using a Ga-GaAs-AsC13 source in a closed tube at a substrate temperature of 750°C. Wafers were chem-mechanically polished and gas-etched prior to deposition. The X-ray topographs were taken on a Krystallos Lang camera, operating in the transmission scanning geometry (Lang technique15) or in the reflection scanning geometry (modified Berg-Barrett technique20,21). MoKa, radiation was used for all transmission topographs using a Jarrell-Ash 100-µ spot focus. CuKal radiation was used for all reflection topographs using a General Electric CA-7 1-mm spot focus X- ray tube. Topographs were printed from an intermediate contrast inversion film, so the contrast shown in all figures here is the same as that of the original 50-µ-thick emulsion L4 Iiford nuclear plate used to record the topograph.

Jan 1, 1969

By B. W. Christ, P. M. Giles

Mossbauer effect measurewents have been made on I-mil-thick foils of commercial 1 wt pct C steel and Fe-2 wt pct C alloy. The experimental method required about 3 to 5 vol pct of a phase in the nzultiphase steel sample for detection. Room-temperature Md&apos;ssbauer patterns obtained on austenitized atid quenched samples exhibit fifteen, and possibly twenty-one, lines. A sharp parama&tetic singlet and a quadrupole doublet, poorly resolued from the singlet, are attributed to austenite. Remaining lines are due to tnartensite. Accurate evaluation of austenite line paranzeters is not feasible if significant amounts of other phases such as carbides or martensite occur simultaneously with austenite. This is demonstrated by comparison of hyperfine interactions determined for austenite in multiphase high-carbon samples with those reported for Fe-C austenite in a nearly 100 pct austenitic sanple. Lines from carbides are incompletely resolced from austenite lines, as demonstrated by comparison of austenite line positions with carbide line positions calculated frow published values of hyperfine interactions. One martensite line overlaps an austenite line in the pattern for commercial 1 wt pct C steel. Results of this study suggest that the usefulness of e M6ssbauer pectroscopy for quantitatizle analysis of austenite in bulk samples of quenched and tempered high-carbon steels is restricted by poor resolution. Use of Mossbauer spectroscopy for phase identification and for evaluation of atomic and electronic structures appears quite feasible, however, The Mijssbauer effect has been widely discssed,&apos;-and e Mossbauer effect measurements have been reported on materials of metallurgical interest.7"20 In particular, it has been proposed that e Mossbauer patterns of commercial steels and laboratory-made Fe-C alloys, in the quenched condition, are composed of lines originating in two phases, Fe-C austenite and Fe-C martenite.-&apos; Evidence accumulated in this study demonstrates that three absorption lines found in the central region of the e Mossbauer pattern obtained on quenched steels are attributable to retained austenite. This interpretation is supported by parallel decreases in the intensity of these three lines caused by subambient cooling of commercial 1 wt pct C steel samples after water quenching to room temperature. A second result of this study is to clarify effects of line resolution and sensitivity in the Mossbauer patterns of multiphase steels on the accu- rate determination of austenite line parameters. Experimental line widths (full width at half height) are generally 1.5 to 3 times larger than the natural line width of 0.19 mm per sec. At least two lines, and sometimes more, from a single phase such as cementite (Fe3C), other carbides, martensite, and austenite fall in the energy band, i0.85 mm per sec. hhis band width is employed simply for convenient reference. It represents approximately the energy interval between the + 112 to 112 transitions in ferrite and is expressed as the velocity needed to Doppler shift a 14.4kev 7 ray to the aforementioned ferrite energy levels. This energy band is referred to as "the central region of the Mossbauer atttern:: in this paper. Hence, due to the large number of lines from different phases in a multiphase steel falling in a relatively narrow energy band, absorption lines from the different phases may overlap. Analysis of available data, presented below, indicates that this occurs to a significant extent for phases which commonly occur in quenched and quenched and tempered high-carbon steels. One consequence of limited resolution in the Mdssbauer patterns from multiphase steels is difficulty in accurate determination of such line parameters as position, width, and intensity. In fact, it appears that quantitative analysis for retained austenite in quenched and tempered high-carbon steels is not practical with the present experimental method. Line resolution is influenced to some extent by sensitivity. We point out below that atom or volume fractions of less than about 3 to 5 pct are not detected by the present experimental method. Thus, the presence of a multiplicity of phases does not always lead to impaired resolution. Finally, we report in this paper room-temperature MGssbauer parameters determined for austenite in a freshly quenched, commercial 1 wt pct C steel and in a freshly quenched laboratory heat of an Fe-2 wt pct C alloy. These parameters are compared with others reported in the literature. Three types of hyperfine interactions are detectable in a Mossbauer effect measurement: isomer shift, quadrupole interaction, and magnetic dipole interaction. These interactions are evidenced by one, two, and six line patterns, respectively.&apos;-4 More than one type of interaction has been reported in certain metallurgical phases thus far studied by this method. Isomer shift is the experimentally measured displacement of line position from some arbitrarily defined reference position. In the case of a multiline pattern, isomer shift is given by the displacement of the centroid (center of gravity) of that pattern from the reference position. All isomer shifts measured at finite temperatures contain a second-order Doppler effect characteristic of that temperature. The isomer shift is related to the total s electron density at the nucleus, becoming more negative with increasing s electron density. The first-order quadrupole effect arises from the interaction between the nuclear quadrupole moment and any axially symmetric electric field gradient in

Jan 1, 1969

By J. H. Swisher

The rate of internal sulfidation of austenitic Fe-Ti alloys in H2S-H2 gas mixtures is controlled primarily by sulfur diffusion, with counterdiffusion of titanium playing a minor role. At temperatures below 1100°C, enhanced diffusion along grain boundaries becomes important. The rate of internal sulfidation at 1300°C is approximately equal to the rate computed from the sulfur diffusion coefficient. The diffusion coefficient of titanium in y iron has been determined from electron microprobe traces in the base alloy near the subscale interface. The solubility of sulfur in Fe-Ti alloys has been measured in the temperature range from 1150° to 1300°C. The equilibrium sulfur content is found to increase with titanium content, due to the large effect of titanium on the activity coefficient of sulfur. The Ti-S interaction becomes stronger as the temperature decreases. TITANIUM as an alloying element in stainless steels is an effective scavenger for interstitial impurities, carbon in particular. Titanium is known to form stable sulfides; however extensive thermodynamic data on the Ti-S system are not available. Schindlerova and Buzek1 have shown that the Ti-S interaction in liquid iron is moderately strong. There have been no previous studies of the Ti-S interaction in solid iron. Internal sulfidation of Fe-Mn alloys was the subject of a recent investigation by Herrnstein.2 He found the rate of internal sulfidation to be an order of magnitude greater than predicted from available solubility and diffusivity data. A satisfactory explanation for the discrepancy could not be given. In the present study, the solubility of sulfur in austenitic Fe-Ti alloys was measured using a standard gas equilibration technique. Fe-Ti alloy specimens were also internally sulfidized. The rate of internal sulfidation was measured as a function of temperature and alloy composition. Supplementary electron micro-probe measurements were made to provide additional information on the nature of the internal sulfidation process. EXPERIMENTAL The starting materials were alloys containing 0.12, 0.24, 0.38, and 0.54 wt pct Ti. The alloys were made in an induction furnace by adding titanium to electrolytic iron that previously had been vacuum-carbon-deoxidized. The major impurity in the alloys as determined by chemical analysis was carbon. The carbon content of the alloys averaged about 100 ppm; metallic impurities were presented in concentrations of 50 ppm or less. Specimens were made in the form of flat plates, 0.03 by 2 by 4 cm for the equilibrium measurements and 0.5 by 1.5 by 3 cm for the rate measurements. The experiments were performed in a vertical resistance furnace wound with molybdenum wire and containing a recrystallized alumina reaction tube. In the gas train, flow rates of the reacting gases were measured using capillary flow meters. The source of H2S was a mixture of approximately 2 pct H2S in H2, which was obtained in cylinders from the Matheson Co. A chemical analysis was provided with each cylinder. The H2-H2S mixture was diluted with additional hydrogen to obtain the desired ratio of H2S to H2, and the resulting mixture was diluted with 30 pct Ar to minimize thermal segregation of H2S in the furnace. Argon was purified by passage over copper chips at 350°C and subsequently over anhydrone. Hydrogen was purified by passage over platinized asbestos at 450°C and then over anhydrone. The H2-H2S mixture was purified by passage over platinized asbestos and then over Pas. The samples used in the solubility measurements were analyzed for sulfur by combustion and iodometric titration. The subscale thickness in the internally sulfidized samples was measured on a polished cross section, using a microscope with a micrometer stage. Electron microprobe traces for titanium in solution were made on several samples that had been internally sulfidized. A Cambridge microanalyzer was used, and the known titanium content at the center of the specimen was used as a calibration standard. The procedure for the microprobe measurements will be described further when the results are presented. RESULTS AND DISCUSSION Equilibrium Data. Fig. 1 shows the sulfur concentration as a function of gas composition for three alloys equilibrated at 1300°C. The dashed line is based on data published by Turkdogan, Ignatowicz, and pearson3 for pure iron. The breaks in the curves are the saturation points for the alloys. The fact that the initial slope decreases with increasing titanium content indicates that titanium interacts strongly with sulfur in solution. To obtain information on the composition of the precipitating sulfide phase, the measurements described in Fig. 1 were extended to higher sulfur partial pressures. These results are shown in Fig. 2. (The initial portions of the curves are reproduced from Fig. 1.) The highest PH2s /pH2 ratio used is believed to be below the ratio required for the formation of a liquid sulfide phase. Time series experiments were used to study the approach to equilibrium in the samples. It was found that equilibrium with the gas phase was reached in less than 4 hr at 1300°C.

Jan 1, 1969

By P. R. Sahm, T. V. Pruss

Mixtures of fine GaSb and Gds as well as preal-loyed GaSbl,As, powders were hot-pressed at 690°C and 25,000 psi. Dense alloys with compositional gradients of less than 5 pct were obtained from mixtures containing about 20 mol pct GaAs. For x < 0.2, there were increasing compositional gradients, and for x > 0.2 a GaAs-rich second phase appeared in the microstructure. Densification as well as alloying wlechanisms were enhanced by dissociation and, possibly, oxidation reactions of the powders. Densification of coarse prealloyed material, however, primarily depended on plastic flow phenomena and required temperatures just below solidus and pressures of 50,000 psi Thermal and electrical properties were measured. Although in no case was the figure of merit of melt growth materials approached closer than to within 25 pct, the better overall thermoelectric properties were found in coarse-grained, prealloyed materzals which had been compacted to near theoretical density and where grain regrowth had been induced. Similar results are believed to hold in other binary 111-V compound systems if processed under similar conditions. The densification of unalloyed GaSb powders during pressure sintering (= hot pressing) was shown to depend strongly on powder particle size.&apos; Fine powders displayed a "liquid skin effect" that enhanced compaction through the presence of liquid gallium, whereas coarse powders compacted predominantly by plastic flow. The liquid skin effect, in particular, appeared attractive for alloying GaSb with other, higher-melting, III-V compounds, and to densify these in a one-step operation. This is of special interest in the case of III-V compound alloys as the conventional techniques of melt growth or long-time annealing of powders2 is very time-consuming, especially in cases where a large separation of liquidus and solidus can be expected, such as in GaSbl alloys.2 It was felt that experimentation with this system, a particularly unfavorable example, would allow us to extrapolate to several other, more favorable, cases. Uses of Ill-V alloys are most evident in thermoelectric energy conversion devices.&apos; For this reason certain thermal and electrical properties were measured and compared to those of melt-grown material and to hot-pressed prealloyed powders. EXPERIMENTAL PROCEDURE The pressure-sintering apparatus has been previously described.&apos; Using this equipment, both powder mixtures of GaSb with GaAs and prealloyed GaSbl-,As, powders were hot-pressed. The mixtures were pre- pared from cast GaSb and melt-grown GaAs. The prealloyed material was obtained from stoichiometric melts, initially heated to 1200°C in an evacuated quartz ampoule, and then annealed in the solidus-liquidus interval. A typical annealing cycle consisted of a heating to 850°C (1 hr), extended successive annealing at 750°C (65 hr), and slow stepwise cooling (25 hr) to below solidus. The GaSb, GaAs, and GaSbl-,As, materials were ground in a vibrational mill to particle sizes below 500 . A jet mill reduced these further where necessary. Fine powders were analyzed by Coulter counting for their size distribution. Average sizes by volume were calculated from the data. Mixing of the powders, where necessary, was carried out through rapid vibrational motion. The hot-pressing operation consisted of a degassing period of 15 hr, in most cases at 690°C, followed by several hours of compression, normally 25,000 psi at 690°C for powder mixtures and 50,000 psi at 710°C for prealloyed powders. The chemical compositions were confirmed by X-ray fluorescence analysis. To estimate the degree of solid solution achieved, lattice parameters were determined and interpreted according to Vegard&apos;s rule. In addition, optical microscopy helped to correlate the relative amounts of the phases present as well as the degree of porosity to the measured density. To reveal grain boundaries, polished surfaces were etched4 with H 2 O:H 2 O:HCl = 2:l:l. In several cases microscopic concentration gradients were monitored by electron-probe analysis-. RESULTS AND DISCUSSION Alloying and Densification of GaSn-GaAs Powder Mixtures. After preliminary experiments showed that no appreciable alloying took place in mixtures of coarse GaSb (22.5 p) and fine GaAs (2.5 p) powders, hot pressing of mixtures was confined to fine powders only (3.1 and 2.4 p, respectively). Alloying and densification apparently occurred simultaneously with a grain regrowth mechanism which depended on the presence of a liquid phase.&apos; The liquid phase was provided by the dissociation of GasbS particles into liquid gallium and antimony above 555°C. This not only enhanced grain regrowth and densification, as in unalloyed GaSb,&apos; but took on additional importance here for the alloying process. Alloying was speeded up by the resulting liquid-solid interaction as compared to the very slow solid-state diffusion process normally expected at these temperatures.&apos; The results obtained with a series of powder mixtures have been compiled in Table I. It is seen that for mixtures with less than 20 mol pct GaAs, x < 0.2, the compositional ranges increased and for x > 0.2 a GaAs-rich phase and free antimony appeared in the microstructure in sizable amounts.

Jan 1, 1968

By H. Doi, Y. Fujiwara, K. Miyake

In order to throw light on the mechanism of plastic deformation of WC-Co alloys, compressive tests of WC-(7 to 43) vol pct Co alloys have been carried out at room temperature, and stress-micro strain relation has been investigated in detail. The analysis of the factors affecting the yield stresses reveals that the yield stresses can be predicted by modified Oro-wan&apos;s theory if one properly estimates the planar in-terfiarticle spacings. Conzpressive straining of some of the alloys by 0.066 to 0.17pct increases the decrements by a factor of as much as 3.4 to 14, whereas the corresponding increase in the electrical resistivities is less than 10 pct. The analysis of the decrement data in terms of -Gramto and Lücke theory shows that the marked increase is attributed to increased dislocation darnping itt the binder (cobalt) phase. By cornbilling the decrement data and the conzjwession duta, one obtains the relation between flow stress in shear (?t) and increase in dislocation density (p): At = const . v6 . This is interHeted to mean that the mechanism of strain hardening of CirC-Co alloys is essentially sarne as the one for dispersion strengthened alloys. The possible effect of bridge formations between the carbide particles has also been examined. OWING to the combination of hardness, strength, and other physical and chemical properties, WC-Co alloys have opened the way for unique fields of applications, the recent ones being, for instance, anvils for super-high-pressure generation apparatuses. In such applications, the alloys are frequently subjected to very high compressive stresses: these stresses may cause the alloys to deform plastically and eventually to fail. However, much remains obscure regarding the nature of the plasticity of the alloys. Evidently, the alloys owe their high strength to the hard carbide particles which frequently occupy as much as 80 to 90 pct in volume fraction, whereas the ductility required for practical applications is provided by the small amount of the binder phase between the carbide particles. When the volume fraction of the carbide phase is not very large, deformation behavior of the alloys may be described by some of the current dispersion strengthening theories. However, greatly increasing the carbide phase is thought to lead to some carbide skeleton structure or bridge formations owing to the increased chances for direct contacts between the carbide particles;1,2 this may appreciably affect the plasticity of the alloys. Regarding the effect of formation of the carbide skeleton structure, it is interesting to note the work by Ivensen et al.3 on compression tests of the alloys containing somewhat large carbide particles; they observe extensive generation of slip bands in the carbide particles after application of some preliminary compressive stresses. They interpret the results in terms of plastic deformatiot: of the carbide particles which are supposed to have formed a skeleton structure; the binder phase plays only a passive role, at least in the early stages of the deformation. That carbide crystals exhibit microplasticity at room temperature is apparent from the work of Takahashi and Freise4 and French and Thomas5 on indentation of WC single crystals. On the other hand, Dawihl and coworkers6-10 maintain that even when volume fraction of the carbide phase is very large (for instance, more than 90 pet), a very thin binder layer generally exists between the carbide particles. They interpret the results of the extensive mechanical tests in terms of the plasticity of such a layer. Gurland and Bardzil11 point out that decrease in ductility of the alloys with increase in the carbide phase is caused by the effect of plastic constraint exerted by the dispersed carbide particles. Drucker12 further develops this concept from a continuum-mechanics approach on an assumption that a continuous thin binder layer separates the carbide particles. A common feature of the studies reported so far on the plasticity of the alloys is that the information deduced is invariably qualitative in nature. Thus, very few systematic experiments for obtaining reliable and sufficiently detailed stress-strain curves of the alloys varying widely in the microstructural features have been carried out. In particular, it may be of special interest to investigate in detail the early stages of the plastic deformation of the alloys in order to shed light on the strengthening mechanism. However, such work appears to be extremely rare. Doi et al.13 recently reported a first brief account of the results of some quantitative analysis of the plasticity of the alloys in terms of dislocation theory. Their experiment was rather limited in the composition range covered (volume fraction occupied by the carbide phase: 79 to 83 pct), and thus they could not necessarily elucidate the controlling mechanism of plastic deformation of the alloys of a more general composition range. Consequently, in the present investigation, deformation behavior and some other physical properties of the alloys were investigated and discussed in more detail over a much wider composition range. SPECIMEN PREPARATION WC-Co alloys used in this experiment were prepared in cylindrical or rectangular form by sintering in vacuo compressed mixtures of tungsten carbide and cobalt

Jan 1, 1970

By S. Shapiro, G. Krauss

The strutural and cr~stallo~aphic features of the plates of austenite produced by the martensite to aus-tenite or reverse martensitic tramformation have been determined in an Fe-33 wt pct Ni alloy. Micro-focus X-ray techniques and single-surface trace analysis 072 bulk samples yielded two distinct habit planes, (0.174, 0.309, 0.~35)~ and (0.375, 0.545, 0.749jM. The former plane uas the one predorninantly observed and its existence was verified by transn~ission electron microscopy. The orientation relation-ship between the reversed austenite and the parent martensite was approximately the same as the Nishiyamna and other relationships reported for the direct tramformation. Replica and thin-joil obser-vations show that both high densities of tangled dis-locations and occasional twins constitute the fine structure of the reversed austenite. Application of the phenomenological theory to a variant of the predominant habit plane defines an irrational plane and direction for the second shear in accordance with the comnplexity of the fine structure. The shear accompanying the reverse martensitic transformation is at least 0.51, the maximnum value of- the tangent oJ the tilt angle measured on surface replicas. A mechanism relating the fine transformation twins in martensite to the nucleation of reversed austenite of the predominant habit is proposed. The reversal of Fe-Ni martensite takes place both at the edges of martensite plates and in a piecewise fashion within them.&apos; The shear-type nature of the reverse transformation is verified by the surface relief which accompanies both edge-type reversal2 and the fragmentation of plates of martensite&apos; as a result of rapid heating above the A, (austenite start temperature). The orientation relationship between the edge-type reversal product and the parent martensite, as determined by transmission electron microscopy, is reported to be within 4 deg of either the Kurdyumov-Sachs or Nishiyama relationships,&apos; but there is no work at present in the literature relating to the crystallography of the platelike reversed austenite. The fine structure of reversed austenite after heating to 50°C above the Af is reported4 to be composed primarily of tangled and jogged dislocations in concentrations up to 10" per sq cm. A replica investigation of partially reversed Fe-Ni martensites5 corroborates the increase in dislocation density following reversal and presents indications of other possible modes of fine structure. This paper reports on an investigation performed to examine in detail the morphology and crystallography of the plates of reversed austenite and the shear which accompanies their formation in a matrix of Fe-Ni martensite. EXPERIMENTAL PROCEDURE Discs of a high-purity Fe-32.9 wt pct Ni single crystal served as the starting material. The single crystal had been produced in the course of an earlier investigation6 and the carbon content was determined at the time to be 0.006 wt pct. The M,, and the A,, were respectively -120" and 300°C. Partial transformation to martensite was performed at -125°C and reversal of some of the martensite was accomplished by heating in the temperature range 340" to 355°C. Most samples were heated to the reversal temperature by immersion&apos; in a salt bath for 2 min. For surface-relief studies some polished and etched Samples were heated in a tube furnace for ten min in a hydrogen atmosphere maintained over the samples throughout the heating and cooling cycles. Samples were prepared for metallographic examination by electropolishing and etching with an HC1-HNOs-H20 et~hant.~ On one of the surface-relief samples two sets of fiducial scratches were placed on the etched sample by drawing it over a slurry of 0.06 p alumina on a "microclothJ&apos;. The orientations of individual plates of martensite were determined by X-ray analysis. A Rigaku-Denki microbeam X-ray generator in conjunction with a Micro-Laue camera with facility for precision location of the sample in front of the beam was employed for this purpose. The collimator size was 30 p and the specimen to film distance was 5 mm. The Laue photograms were enlarged to an equivalent 3-cm specimen to film distance for analysis. The orientation of each of the plates of martensite was compared to that of the parent austenite and the relationship be -tween the two phases was, in all cases, within a few degrees of those predicted for the direct transformation. The orientation relationship between one of the larger plates of reversed austenite and its parent martensite was determined in a similar manner. The habit plane of the islands of reversed austenite in the X-rayed plates of martensite was determined by a single-surface trace analysis. Each reversal island had with the parent phase one comparatively straight boundary which was presumed to represent the habit plane trace. The pole locus technique7 was applied to traces from six different plates of martensite to determine the indices of the habit plane. A 40-cm stereographic net was employed for this analysis The morphology and fine structure of the reversed austenite were studied by electron microscopy of pre-shadowed direct carbon replicas,5 and the macroscopic shear was evaluated by a two-stage replica technique similar to that employed in electron fractog-

Jan 1, 1968

By P. K. Strangway, H. U. Ross

Briquets consisting of pure artificial magnetite, pure artificial hematite, and mixtures of the two were reduced by hydrogen in a loss-in-weight furnace at temperatures in the range 500° to 1000° . The rate of reduction of the pure hematite briquets increased continuously with increased temperature. In contrast, the pure nmgnetite briquets exhibited a pronounced rate ninimutn at about 700°C. Metallographic studies of partially reduced briquets rerlealed that, at this temperature, the he.matite samples reduced in a topo-chemical manner while the magnetite ones reduced uniformly throughout, and after partial reduction their cross sections contained a mixture of iron and unreacted wustite grains. No iron shells could be detected on the surfices of any of these uwstite grains. X-ray diffraction investigations indicated that these grains had a rzinimum lattice parameter when they had been formed at the rate rninimum temperature. Also, it was found that an activation energy of 41,000 cal per mole zoas required for reduction when only these wustite grains were present. Thus, it is suggested that the overall reduction rate of the rnagnetile su?nples at temperatures in the range influenced by the rate nzinirnum phenomenon was limited by the rate qf iron ion diffusion in the unreacted wustite grains. THE rate minimum phenomenon, which has often been observed when reducing iron oxides at a temperature of about 700°C, is one of the most interesting, yet unresolved, problems in the field of reduction kinetics. Basic principles of chemical kinetics and &apos;In some instance, a second rate minimum has been observed at about 900°C. Since most investigators are in agreement that this minimum is directly related to the transformation from a to y iron (which takes place at 911°C) and since it was not encountered during the present reduction tests, it will not be referred to in this vaver. fundamental laws of diffusion all agree that, as the temperature is increased, the rate of reduction should also increase. However, with certain ores, it has been found that their reduction rate actually decreases with an increase in temperature up to some value X where a minimum reduction rate is reached. With further temperature increases beyond X the rate becomes more rapid again. Temperature X is usually referred to as the "rate minimum temperature", while the overall type of behavior constitutes the "rate minimum phenomenon". This phenomenon has been reported by numerous investigators. They have found rate minima during the reduction of both artifiial&apos; and natural374 magnetites and artificia15j6 and natural5" hematites. Rate minima have been observed when reducing high-purity material2 or low-grade ores,3&apos;4 when studying particles in the micronsize range5 or relatively large agglomerates,g10 and during reduction with either hydrogen7 or carbon monoxide.11"2 Previously, this phenomenon has been attributed to many factors; these include sintering and recrystallization of the iron formed during reduction374 changes in microporosity of the ore upon redction,"" formation of dense iron shells around retained wustite grains,11716 and chem-isorption,17 to name only a few. However, most investigators who have reported a rate minimum merely speculated as to what seemed to influence it and they did not examine the fundamental causes. Consequently, the present experimental study was initiated in order to evaluate the basic factors which could be associated with this phenomenon. MATERIALS AND METHODS The experimental techniques, followed during this investigation, are similar to those which have been described previously.18 The chemically pure magnetic powder was prepared by partially reducing Fisher reagent-grade hematite with a gaseous mixture of carbon monoxide and carbon dioxide in a rotating-drum furnace. Three-quarter-inch diam cylindrical briquets which weighed about 12 g were formed from this magnetite powder and pure hematite powder. All of the briquets were sintered while they were slowly raised through the 1200°C hot zone of a vertical tube furnace. An argon stream was continually flushed through this furnace in order to prevent oxidation of the magnetite briquets, while in the case of the pure hematite briquets sintering was carried out in air. The sintered hematite briquets had a density of 5.06 g per cu cm while the density of the sintered magnetite briquets was 4.27 g per cu cm. The sintered briquets were reduced by purified hydrogen in a loss-in-weight furnace at temperatures in the range 500" to 1000°C. In all instances, the critical reducing gas velocity was exceeded and, in order to ensure that the results were reproducible, duplicate briquets of each type were reduced under each set of experimental conditions. A continuous record of the weight loss during reduction was obtained with the aid of a Statham transducer. The present experimental setup was capable of detecting a change in weight as small as 10 mg. Since a weight loss of over 2 g usually occurred during each reduction test, an accuracy of better than 0.5 pct of the total weight loss could be achieved. RESULTS AND DISCUSSION Reducibility Tests. In the first set of experiments, pure hematite and pure magnetite briquets were used.

Jan 1, 1969

By Y. C. Liu, G. A. Alers

The effect of rolling reduction on the textures of Cu-A1 alloys has been investigated both by pole figure and by modulus methods. In alloys which exhibit complete copper or brass types of rolling texture, the rolling reduction has little effect on the texture except to increase the degree of preferred orientation. In alloys which exhibit a transition texture, however, increased rolling reduction increases the amount of brass-type texture at the expense of the copper-type texture. The present experimental results show that there is no one-to-one correspondence between the SFE and the rolling texture of fcc metals. Additional data taken from the literature for fcc metals also support this conclusion. On the other hand, the present and previous experimental results are shown to be in good agreement with the suggestion that the texture transition occurs at a critical value for the separation distance between two partial dislocations—a consequence of the "dislocation interaction" hypothesis for texture. formation. This critical separation occurs when the parameter .r/ub is 3.75 x 10&apos;3. From this, a value for the SFE of 39 ergs per sq cm may be deduced for a Cu-2.85 at. pct A1 alloy. ThE correlation between the rolling texture of fcc metals and the stacking fault energy, SFE, was one of the first attempts to relate atomistic properties with the type of rolling texture.&apos; This correlation gives a qualitative explanation for the experimental observation that the addition of alloying elements, which generally lower the SFE, changes the copper-type texture to a brass-type texture. The simplicity of this correlation had led to its general acceptance and even its quantitative use.&apos; However, it is only a correlation and is largely based on descriptive features of pole figures, and on the poorly known SFE values in dilute alloys. Quantitative verification of this phenomenologi-cal correlation is, in fact, completely lacking. One purpose of the present study is to test this correlation. Another atomistic description for the formation of rolling texture is the "dislocation interaction" hypothesis of texture formation.3 In this hypothesis, the factor controlling the type of rolling texture depends on whether or not the separation distance between two partial dislocations exceeds a critical value. Materials having a separation of less than the critical value are supposed to exhibit a copper-type texture while those with a separation above the critical value are supposed to have a brass-type texture. At the critical value, it is expected that the material should show equal amounts of copper- arid brass-type orientations in their textures, i.e., a 50 pct transition texture. The SFE appears in this hypothesis as only one of several factors which determine the separation distance between partial dislocations. It is possible to test the validity of these two concepts by studying the rolling texture as a function of rolling reduction. Since the SFE per se is an intrinsic property of the metal, it should not, by definition, be influenced by local irregularities, such as variable stress conditions. Thus, no change in texture-type is expected to occur with changes in rolling reduction. On the other hand, according to the "dislocation interaction" hypothesis, any factor that effectively influences the separation distance of partial dislocations would be expected to change the rolling texture. Since the separation distance between partial dislocations is known to depend upon local stresses,4-6 it is anticipated that there would be an effect of the degree of reduction on the texture-type. Also, since applied stresses are more likely to increase, rather than to decrease, the separation between partials,4&apos;5 the overall effect would be to increase the amount of material in the brass-type orientations as rolling reduction is increased. Furthermore, this reduction dependence would be most prominent in alloys exhibiting the transition texture since the distance between partials in those alloys is thought to be close to the critical value. Experimental data in the literature is insufficient to distinguish between these two alternatives. Haessner studied the effect of rolling reduction on textures in a series of Ni-Co alloys by means of the X-ray intensity-ratio technique,&apos; and found that while one texture parameter indicated no reduction dependence the other indicated a slight dependence of the rolling texture on reduction in the range of 96 to 99 pct. As has been noticed previously, the intensity-ratio technique is a convenient but controversial method7 because there is no a priori reason to suggest which intensity-ratio would describe the texture most meaningfully. A more quantitative method of describing textures is found in terms of the orientation dependence of Young&apos;s modulus. Here, the type of modulus aniso-tropy associated with the copper-type texture is sufficiently different from that observed for the brass-type texture to allow the two types to be easily distinguishable and a quantitative measure of the amount of each can be deduced from the numerical results. This ability to provide quantitative data is particularly valuable when the two textures occur simultaneously in one alloy as is the case for the transition textures. In this paper the modulus method, supplemented by pole figure data, is used to look for an effect of roll: ing reduction the texture. Also by combining the texture measurements with recent determinations of the SFE in Cu-A1 alloys&apos;0&apos;" it should be possible to test for a relationship between the SFE and textures.

Jan 1, 1970

By T. R. A. Davey

IN 1947 the author became interested in the fundamental aspects of the desilverizing of lead by zinc, conducted some experimental work, and searched the technical literature for all available fundamental data. Since then a revival of interest in the subject in Europe resulted in the appearance of quite a number of papers. It became evident that it would be more profitable to collect together and examine thoroughly the results of various workers, than to attempt to duplicate the experimental determinations. There are many inconsistencies in the various publications, and it is opportune to review at this time the present status of knowledge on the Ag-Pb-Zn system. There is also a need for a clear description, in fundamental terms, of the various desilverizing procedures. This paper is presented in four sections: 1—There is an historical review of the origins of the Parkes process, of the results of many attempts to find a satisfactory fundamental explanation for the phenomena, and of the modifications proposed to date. 2—A diagram of the Ag-Pb-Zn system is presented. This is believed to be free of obvious inconsistencies or theoretical impossibilities, although thermodynamic analysis subsequently may reveal errors. 3—The fundamental bases of the various desilverizing procedures, which have been used up to the present day, are described; and a new method is suggested for desilverizing a continuous flow of softened bullion in which the bullion is stirred at a low temperature in two stages producing desilverized lead at least as low in silver as that from the Williams continuous process and a crust which, on liquation, yields a very high-silver Ag-Zn alloy. 4—A suggestion is made for the revival of de-golding practice, following a recently published account which does not seem to have attracted the attention it deserves. The terms "eutectic trough" and "peritectic fold" as used in this paper are synonymous with "line of binary eutectic crystallization" and "line of binary peritectic crystallization" as used by Masing.&apos; The German literature on ternary and higher systems is rather extensive and a fairly general system of nomenclature has arisen, whereas in English usage the corresponding terms are not as well established. For this reason the meanings of terms used in this paper, together with the equivalent German terms, are given as follows: 1—Eutectic trough—eutektische rinne: line at which a liquid precipitates two solids S1 and S2 simultaneously. If the composition of a liquid which is cooling reaches this line, it then follows the course of this line until a eutectic point is reached, or until all the liquid is exhausted. The tangent to the eutec-tic trough cuts the line joining S1S2. 2—Peritectic fold—peritektische rinne: line at which a solid S1 and a liquid L transform into another solid S2. If the composition of a liquid which is precipitating S1 reaches the line, on further cooling only S2 is precipitated. The liquid composition moves from one phase region (L + S1) into the other (L + S2), and does not follow the course of the boundary. The tangent to the peritectic fold cuts the line S1S2 produced nearer S,. 3—Liquid miscibility gap, or conjugate solution region—mischungslucke: the region within which two liquid phases coexist in equilibrium over a certain range of temperature. A system whose composition is represented by a point in this region comprises one liquid at high temperature; then as the temperature is progressively reduced, two liquids, one liquid and one solid, one liquid and two solids, and finally three solids. 4—Liquid miscibility gap boundary—begrenzung der flussigen mischungsliicke: the line along which the surface of the miscibility gap dome, considered as a solid model, intersects the surrounding liquidus surfaces. 5—Tie lines—konoden: lines joining points representing the compositions of two liquids, a liquid and a solid, or two solids, in equilibrium. In binary systems the only tie lines customarily drawn are those through invariant points, e.g., through the eutectics of the Pb-Zn and Ag-Pb systems, or the various peritectics of the Ag-Zn system, as in Figs. 1 to 3. In ternary systems it is desirable to draw sufficient tie lines to indicate the slopes of all possible tie lines. 6—Ternary eutectic point—ternares eutektikum: point at which liquid transforms isothermally to three solids, S1, S2, and S Such a point can lie only within the triangle 7—Invariant peritectic (transformation) point— nonvariante peritektische umsetzungspunkt: (a) — On the miscibility gap boundary, the point at which two liquids and two solids react isothermally so that L, + S, + L, + S2. (b)—On the eutectic trough, the point at which a liquid and three solids react iso-thermally so that L + S, + S2 + S3. Such a point must lie on that side of the line joining S,S which is further from S,. (c)—A further possibility, not found in this ternary system, is that the point is at the intersection of two peritectic folds when the reaction concerned is L + S, + S, + S Historical Introduction Karsten discovered in 1842 that silver and gold may be separated from lead by the addition of zinc.2 Ten years later Parkes used this fact to develop the well known desilverizing process which bears his

Jan 1, 1955

By S. K. Asunmaa, W. D. English, N. A. Tiner, W. A. Cannon

This paper discusses the reaction of metal surfaces with fluorine. Fluorination reactions result in the formation of metal fluoride films which are "passive" toward further reaction of the metal with fluorine. These films are very adherent, and do not easily detach from the substrate metal by mechanical flexing or thermal shock. Exposure of passive films to a humid atmosphere produces hydrated metal fluorides which cause secondary fluorination reactions upon reexpo-sure of the metal surface to fluorine. The surface films formed range from 10 to 30A in thickness and they pow at the expense of surface oxide films. The apparent film formation is completed rapidly in 15 to 30 min on stainless steel and nickel surfaces. On copper and on Monel surfaces, the film at first grows rapidly, then increases slowly over an extended period of time. Passive films are formed at all fluorine pressures in the range from 0.1 to 1.4 atm at room temperature. ALL metals react when exposed to fluorine. These reactions generally produce surface films which consist of metal fluorides. The rate of reaction is largely determined by the extent to which these films are protective. Although there is an extensive literature concerning reactions of oxygen with metals, there are very few investigations reported concerning fluorine-metal reactions. Brown, Crabtree, and ~uncan&apos; investigated the kinetics of the reaction of gaseous fluorine with copper metal which had been freshly reduced in hydrogen. The reaction rate was independent of pressure over the range from 6 to 60 torr. A logarithmic rate law was obeyed in the temperature range from 25" to 300" ~. There was some deviation at higher temperatures which could have been the onset of a parabolic law. The calculated film thicknesses ranged from about two molecular layers, 10A, for 5 hr exposure at room temperature to thirty-five molecular layers for 5 hr exposure at 200" . The authors concluded that no single mechanism could explain all the observations. O7Donnell and spatkowski2 studied the reaction of fluorine with copper at 450°C at pressures from lo to 133 torr. The reaction was found to be pressure -dependent and followed a logarithmic rate law. It was not entirely diffusion-controlled, and fluorine was thought to be the migrating species in the reaction. Miscellaneous metal-fluorine reactions were investigated by Haendler et ~1.~ Reaction products were identified but no rate data were determined. Air Prod- ucts and Chemicals, Inc., have conducted an investigation of reactions between fluorine and various metal powders at room temperature and 85° C. Fluoride film thickness as a function of time of exposure was reported on the assumption that the reaction takes place between fluorine and metal to form the normal metal fluoride. Surface areas of the powders were only estimated so the relative film thicknesses may not be exact. The data showed reaction rates which were generally logarithmic in character, the rate of film growth virtually ceasing after a few hours exposure time for some alloy powders. The effect of moisture on fluoride films was also investigated by measuring additional reaction with fluorine after exposure of passivated powders to atmosperic moisture. The fluorination of iron was studied by 0&apos;~onnell~ at temperatures from 225" to 525" ~ and at pressures ranging from 20 to 200 torr. In all ranges, the reaction followed a logarithmic rate law and was dependent on the square root of the gas pressure. The author concluded that fluorine gas passes through pores in the film. As the film grows, the blocking of pores leads to a rapid decrease in reaction rate; hence a logarithmic rate law is observed. Jarry, Fischer, and Gunther&apos; investigated the mechanism of the reaction of fluorine with nickel at about 600" to 700°C. On the basis of the metallographic examination of fluoride scales growing on the nickel and from separate radioautographic data, it was claimed that fluorine is the migrating species in the reaction. This is in sharp contrast to the growth of oxide films on nickel where it has been shown that nickel ions migrate through the scale to the gas-solid interface to react with oxygen. Few investigations have been reported of the reaction of fluorine with metal oxides. Such investigations should be of great significance for a better understanding of passivation in view of the ubiquitous oxide films on technical alloys. Haendler et al.3 studied the reaction of fluorine with oxides of copper, tin, titanium, zirconium, and vanadium. Copper (I) oxide reacted as follows in the temperature range 150" to 300"~: temperature above 300" ~ was required for the CuO to react to form additional copper fluoride. Ritter and smith7 also investigated the reaction of fluorine with copper (11) oxide. An oxide powder comprised of spherical particles with a fairly high surface area was reacted with fluorine, starting at room temperature and increasing to 100° C over a period of 3 or 4 hr. The initial reaction was slow until the fluoride film thickness reached about to or 15R at which time the reaction rate accelerated, then decreased again. Most of the kinetic data was obtained during this final phase of reaction. The authors conclude that the film grows slowly at first until the stresses developed in the distorted lattice are sufficient to rupture the initial

Jan 1, 1969