Search Documents

By A. Gittens

In two recent papers stevens13,14 has compared the methods used by various investigators to calculate the contribution of grain boundary sliding to the total creep strain. In previous work Gittins15 has shown that the strain due to grain boundary sliding Egb may be estimated from the lateral, d, and vertical, v, displacements of a longitudinal marker line as it crosses a grain boundary. He obtained the formula, where nL is the number of grains per unit length measured on the specimens before creep, and \p and ?2 are, respectively, the angle between the grain boundary and the stress axis in the plane of the surface and normal to the surface (see Ref. 13, Fig. 1). The subscript L indicates that observations are made in a longitudinal direction parallel to the stress axis. It was generally found more convenient to measure the grain size of a specimen before creep; this was necessary to characterize the specimen. Stevens13,14 however prefers to define Egb in terms of NL, the number of grains per unit length after creep. Since nL - NL(l + €1) where cr is the total strain, Eq. 1 11 becomes The quantities d and ?, can be determined directly from the marker lines, while v and ?2 are found by sectioning normal to the surface. In the interior when symmetry considerations suggest that v = d and ?1 - ?2 the strain due to grain boundary sliding may be estimated from a suitable internal longitudinal marker line by the equation To determine cgb at the surface using either Eqs. |1| or [2] requires a large number of observations, particularly if many estimates of cgb are required, and also it is impossible to determine the variation of cgh with creep strain on the same specimen because the specimen must be sectioned to determine ?2. Gittins15 found that for a number of materials the sliding vectors d and v were related to each other so that provided one was measured the other could be estimated. Also during creep, grain boundaries tend to migrate to meet the surface at angles close to 90 deg,16 so that the term nL(v/tan?2)L was comparatively small when 4,- 90 deg. By determining the frequency distributions of ?2 on control specimens this term can be estimated without sectioning the creep specimen. In this way an empirical equation based on Eqs. |1| and |2| enables cgb to be determined with reasonable accuracy with fewer observations of the angles and sliding components. For B brass, the relationship between the sliding vectors indicated that ceb = 0.85nLVL . In Table I of Stevens paper this equation is stated to be incorrectly derived. However it should be pointed out that this is an empirical equation derived from Eq. |1|, based on a knowledge of the relationship between d and v and on the frequency distributions of ?1 and ?2 for a particular material under given experimental conditions. It was used only when these relationships were known, to reduce the number of observations required to estimate cb. Therefore the comment "derivation incorrect does not apply. Gittins did in fact make use of Eqs. |1| and 131. Author's Reply I must apologize to Dr. Gittins for the inadvertent misrepresentation of his work. Other slight errors in Table I have been pointed out to me. Langdon (No. 12 Table I), Gifkins (No. 7, Table I), and possibly other workers did not measure the number of boundaries per unit length after creep (A') but the corresponding quantity bejove creep (n). As Dr. Gittins points out, a completely analogous set of equations to those given in the paper can be derived by the same method: using the number of boundaries per unit length before instead of after creep. The basic equations corresponding to Eqs. [2] and 171 of the paper, from which all the others can be derived, are

Jan 1, 1968

By N. K. Chen, R. Maddin

THE textures of straight-rolled and of cross-rolled molybdenum were first determined with the aid of pole figures by Custers and Riemersma.' These authors have shown that for straight-rolling, the main texture was (100) [0111 with a considerable spread about the rolling direction. After cross-rolling a second texture was obtained in which there was a [111] axis perpendicular to the rolling plane, possessing a rotary symmetry. Recently Semchy-shen and Timmons2 in their study of preferred orientation of arc-cast molybdenum sheet obtained similar pole figures. In these two investigations, polycrystalline materials were used. In the main, the textures of molybdenum in these cases are qualitatively consistent with rolling textures of other body-centered cubic metals, such as iron and Fe-Si alloys." In the present investigation, single crystals of molybdenum were deformed by rolling with respect to specific crystallographic planes and directions. Since the deformation textures of polycrystalline aggregates have been related intimately to the behavior of individual grains,4 a study of possible correlations of final textures with respect to the initial orientations of the single crystals might conceivably lead to a better understanding of the textures. Annealing treatments were carried out after deformation in order to study the recrystallization characteristics as well as the recrystallization texture. Rolling of Single Crystals Single crystals of molybdenum (about 1/8 in. in diarn x 1-in. long), grown by the method previously described,5 were cold-rolled without intermediate anneals. Except for specimens MR-1 and MR-2, which were rolled at random in the preliminary test in order to find a proper rate of reduction, all other specimens were carefully documented as to their respective orientation before deformation by means of X-ray Laue back-reflection methods. A stereo-graphic projection was constructed from which it was possible to determine a particular plane and direction to be considered for rolling. Parallel flat surfaces were then polished metallographically with respect to a reference scratch on the specimen which was mounted in sealing wax. These flat surfaces contained the plane chosen for rolling. After etching, a Laue back-reflection photogram was again made of one of the flat surfaces to determine the exact plane of rolling. The initial orientations of all the specimens (specified by two elements for each crystal, direction of rolling and the pole of the rolling plane) are summarized in Fig. 1. The specimens were mounted in plasticene between two hardened Si-Fe plates. The sandwich was then rolled down, keeping the direction constant in the case of straight-rolling. In cross-rolling (MR-10, MR-11, and MR-12) the sandwich was rotated 90" after each pass so that every first and third pass contained the same rolling direction. Specimens MR-14, MR-15, and MR-16 were compression-rolled following the manner of Barrett." In these cases the direction of the sandwich through the rolls was changed by 3" to 5" for each pass until the specimens were rolled to the desired reduction in thickness. It was found that if extreme care was exercised in rolling, i. e., the amount of deformation per pass was extremely small, the specimens could be rolled to a large reduction in thickness. The rate of reduction used, with a single exception of MR-1. was generally 0.001 in. per 10 passes. Thus, it took about 800 passes to reduce a specimen to a final reduction in thickness of 87 to 98 pct. The results of rolling are shown in Table I. Cold-Rolling Textures The final orientations were determined by the conventional Laue transmission method," using molybdenum radiation, with or without a zirconium filter. Pole figures were plotted from (1101 and (200) reflections in which three degrees of intensity— heavy, medium, and light—were determined visually. Three main types of textures have been observed from the deformed single crystals. These are: 1—a

Jan 1, 1954

By S. E. Haszko

Fused alumina or silica crucibles were used as the containing vessel. X-ray powder photographs were taken with CrKa radiation and the use of Straumanis type Norelco cameras of 114.6 mm diam. Crystallographic data for these compounds are shown in Table I. These results are in agreement with others of this series reported previousiy by Wernick and Geller.l The abnormally large atomic volume of Eu and Yb metal3 is manifested in EuA12 and YbAl2, when one compares them with the compounds reported in Ref. 1. However, the behavior of Yb in the Ni compound is the same as that observed in Ni5Yb having the Cu5Ca structure.4 Thus, it appears that Yb has a valence closer to 3 only in the Ni compounds; i.e.. the 2s and Id electrons are lost to the conduction band. 1,4 Europium in EuAl2, appears to have a valence closer to 2. In previous work.' X-ray patterns of ingots of NdCo2 indicated a multiphase material with faint indication of the presence of a phase having the MgCu2 structure. It was thought that NdCo2 formed peri-tectically from the melt, resulting in a multiphase system when cooled under nonequilibrium conditions. An X-ray pattern of a sample from a melt cooled more slowly than in past work showed that the major phase was NdCo2. The lattice constant, Table 1, is in excellent agreement with the value one can predict from the data of Ref 1. One of the other phases was identified as Co,Nd. The author wishes to thank J. H. Wernick for his guidance in this work, and D. Dorsi for the preparation of these compounds. 'J. H. Wernick and S. Geller: AIME Trans., in press. 'J. H. Wernick and S. E. Haszko: to be published. 'F. H. Spedding and A. II. Daane: Progress in Nuclear Energy, Series 5, Eds.: H. M. Finniston and J. P. Howe, McGraw-Hill Book Co., 1956. 'S. E. Haszko: to be published. 'J. H. Wernick and S. Geller: unpublished work. 6J. 11. Wernick and S. Geller: Acla Cryst., 1959, vol. 12, p. '162. The Influence of Hydrogen on the Lattice Parameters of Ti-Sn Alloys A. Coucoulas and H. Margolin A reinvestigation of the lattice parameters of Ti-Sn alloys by the present authors has revealed consistently higher c and a values than those obtained by Worrier. The difference is most pronounced in the c-parameters which are, therefore, used as a basis of comparison. This discrepancy was not due to air contamination, since precautions were taken to exclude this possibility. Specimens for Debye-Scherrer photograms were prepared by arc-melting 15-g buttons of Bureau of Mines titanium and 99.99 pct Sn, with compositions of 6, 8, 10, and 12 at. pct Sn. These buttons were forged under an oxygen-acetylene torch to 1/8-in. sq rods to produce relatively fine grained material. Scale and some surface were ground off, and the rods, after wrapping in molybdenum and titanium sheet, were vacuum annealed 15 min at 800 °C to remove hydrogen. Heat treatment of one of the samples at 875°C to produce ß and reveal a at the surface showed no surface contamination. Following the vacuum treatment, the specimens were wrapped in molybdenum and annealed for 1week at 800°C under two atmospheres of argon. After water-quenching, the rods were ground so that the thickness tapered to 0.1 mm at the tips. The ground specimens were then recapsuled as previously and reannealed 1 hr at 800°C to remove cold work. The

Jan 1, 1961

By H. Margolin, A. Coucoulas

Fused alumina or silica crucibles were used as the containing vessel. X-ray powder photographs were taken with CrKcll radiation and the use of Straumanis type Norelco cameras of 114.6 mm diam. Crystallographic data for these compounds are shown in Table I. These results are in agreement with others of this series reported previousiy by Wernick and Geller.l The abnormally large atomic volume of Eu and Yb metal3 is manifested in EuAl2, and YbAl2, when one compares them with the compounds reported in Ref. 1. However, the behavior of Yb in the Ni compound is the same as that observed in Ni5Yb having the Cu5Ca structure.4 Thus, it appears that Yb has a valence closer to 3 only in the Ni compounds; i.e.. the 2s and Id electrons are lost to the conduction band.1,4 Europium in EuAl2 appears to have a valence closer to 2. In previous work.' X-ray patterns of ingots of NdCo2 indicated a multiphase material with faint indication of the presence of a phase having the MgCu2 structure. It was thought that NdCo2 formed peri-tectically from the melt, resulting in a multiphase system when cooled under nonequilibrium conditions. An X-ray pattern of a sample from a melt cooled more slowly than in past work showed that the major phase was NdCo2. The lattice constant, Table 1, is in excellent agreement with the value one can predict from the data of Ref. 1. One of the other phases was identified as Co5Nd. The author wishes to thank J. H. Wernick for his guidance in this work, and D. Dorsi for the preparation of these compounds. 'J. H. Wernick and S. Geller: AIME Trans., in press. 'J. H. Wernick and S. E. Haszko: to be published. 'F. H. Spedding and A. II. Daane: Progress in Nuclear Energy, Series 5, Eds.: H. M. Finniston and J. P. Howe, McGraw-Hill Book Co., 1956. 'S. E. Haszko: to be published. 'J. H. Wernick and S. Geller: unpublished work. 6J. 11. Wernick and S. Geller: Acia Cryst., 1959, vol. 12, p. '162. A reinvestigation of the lattice parameters of Ti-Sn alloys by the present authors has revealed consistently hiher c and a values than those obtained by Worrier. The difference is most pronounced in the c-parameters which are, therefore, used as a basis of comparison. This discrepancy was not due to air contamination, since precautions were taken to exclude this possibility. Specimens for Debye-Scherrer photograms were prepared by arc-melting 15-g buttons of Bureau of Mines titanium and 99.99 pct Sn, with compositions of 6, 8, 10, and 12 at. pct Sn. These buttons were forged under an oxygen-acetylene torch to 1/8-in. sq rods to produce relatively fine grained material. Scale and some surface were ground off, and the rods, after wrapping in molybdenum and titanium sheet, were vacuum annealed 15 min at 800 °C to remove hydrogen. Heat treatment of one of the samples at 875°C to produce ß and reveal a at the surface showed no surface contamination. Following the vacuum treatment, the specimens were wrapped in molybdenum and annealed for 1 week at 800°C under two atmospheres of argon. After water-quenching, the rods were ground so that the thickness tapered to 0.1 mm at the tips. The ground specimens were then recapsuled as previously and reannealed 1 hr at 800°C to remove cold work. The

Jan 1, 1961

By H. C. Vacher, C. J. Newton

EXTENSIVE investigations in the field of residual strain measurement by X-ray diffraction have been made by Bollenrath, Hauk, and Osswald,1 by Smith and Wood,2'3 by Greenough; by Rosenthal and Norton." and many others. Since X-ray strain measuremeits apply only to those crystals of the test body which are of the proper condition and orientation to diffract and since the residual strains revealed may be accompanied by either body or tex-tural stresses, there has been considerable disagreement among investigators with respect to the validity of conclusions in this field. Although the experi-mentors have employed a variety of loading schemes, surface preparations, and X-ray wave lengths, the observations almost invariably have been made only on the outer surfaces of the specimens. The present note is not to be construed as an exposition of a new method of stress analysis by X-ray strain measurements on sections but as a presentation of some results which point to interesting possibilities for further experiments with sections. The two test rods used in this study were of ingot iron annealed at 910°C. The initial length of the gage section was 2 in. and the diameter was 0.415 in. Cross-sections were cut from the ends of the annealed rods to provide strain-free material. The tensile rod was axially loaded the desired amount in a commercial testing machine. A 1 in. portion of the gage length was cut from the other rod and was subjected to compression in the same machine. Details of this plastic straining of each rod are given in the upper half of Table I. A half-cylinder piece about 1/4 in. long was obtained by making a short longitudinal plane cut containing the axis of the rod near the center of the gage length. From adjacent material a disk about 1/8 in. thick was cut to provide the cross-section specimen. Later another section was cut from this same region with an angle of 30" between the normal to its surface and the axis of the test rod. A cross-section and a longitudinal section were cut from the compression rod in a similar manner. All of these as well as the strain-free cross-sections were mounted in Bakelite and used as specimens for the following X-ray strain measurements. During the course of the study, it became apparent that the condition of the surface of a specimen was a highly critical factor. One of the annealed strain-free specimens as a control was subjected to about 24 hr of polishing with fine alumina, interrupted about every 2 hr for etching with 1 pct nital. Its lattice parameter was determined at intervals from measurements on back-reflection X-ray diffraction patterns, which were calibrated with diffraction from tungsten powder. The parameter gradually approached the value found in the literature for strain-free iron and remained there, within the limits of the experimental error. This determined a long polishing and etching procedure which was adopted for all the specimens and which gave X-ray results from the surfaces believed to be representative of each specimen as a whole. A large number of back-reflection patterns were made with cobalt and chromium radiation, all at normal incidence. Except for some preliminary stationary exposures made to monitor the removal of cold work from the surfaces, each exposure was made with the specimen slowly translating and the film slowly rotating. In appropriate cases a thin layer of a standard metal powder, tungsten with cobalt radiation and silver with chromium, was dusted over a film of vaseline on the surface of the specimen to serve to calibrate the X-ray patterns. After the preliminary work, four films were made,

Jan 1, 1956

By C. S. Smith, Chih-Chung Wang

TURNBULL and his collaborators1,2 have developed the theory of homogeneous nucleation as applied, inter alia, to solidification of liquid metals. Vonnegut³ and Turnbull4 have shown that if a liquid metal is subdivided into small droplets a vast majority of them will undercool very considerably before solidification, generally to as low as about 0.8 of the freezing temperature on the absolute scale. The nuclei effective at small degrees of supercooling in bulk metal seem to be internal or surface heterogeneities, relatively small in number. If the metal is subdivided, those droplets that happen to contain such nuclei will solidify at a temperature not greatly below the true freezing point, but only a small part of the whole volume will be affected and the majority of the drops will under-cool to the much lower temperature at which homo- geneous nucleation occurs as a result of fluctuations. It occurred to one of the authors that an appropriate subdivision to give effective freedom from random nuclei is produced during the solidification of many alloys that contain a minor amount of a phase of low melting point, and that one might then expect marked undercooling of the distributed phase. Experimental: The alloys selected for initial study were copper with minor amounts of lead and bismuth, and aluminum with tin. In all these alloys, the major component freezes at a temperature not much below that of the pure metal, and there is little further change in constitution on cooling until the lower melting point constituent freezes in an almost pure state. Cooling curves were taken using the controlled heat flow method permitting approximate specific heats to be obtained. Chromel-alumel thermocouples were used, with the standard emf tables, since extreme precision was not needed. The crucible (3/4 in. id, 5/16 in. wall) was made of B & W K-20 insulating brick. It held about 10 cc of the alloy being investigated. The cooling rate was 2.5" to 2.9°C per min under a controlled temperature difference of 20°. Approximate specific heats were computed from the inverse rate curves together with data from a blank run and from a standard run with a copper cylinder of known heat capacity. The alloys for investigation were made from high-purity metals (99.99+pct) and cast into graphite molds. The castings were machined to fit the crucible and to provide a hole for the inner thermocouple. Cooling curves were taken after heating to a temperature about 50" above the melting point of the minor, lower melting-point, constituent. Results The lead phase in an alloy of copper with 5 pct lead did not undercool more than 3" below the melting point of lead (327°C) either as cast or after annealing to produce a new dispersion of the liquid phase. A copper-zinc-lead alloy with 23.75 pct zinc and 5 pct lead undercooled more but showed no thermal effect below 319°C. A cast alloy of copper with 5 pct bismuth undercooled to 249°C (M.P. bismuth 27l °C), but once solidification started it was completed at the same temperature. This was anticipated, since the bismuth forms a nearly continuous phase between the grains of copper, and a solid crystal nucleated anywhere would rapidly* con- sume the entire network of liquid, unless the physical continuity of the liquid were broken through volume changes, inadequate fluidity, or gas evolution. Similar arguments apply in the case of copper-lead alloys, where the lead-rich liquid forms a network along grain edges, though not grain faces. In both cases there would be a few isolated particles

Jan 1, 1951

By T. Szaplonczay, D. E. Light

The auto-oxidation of sulfur dioxide to form sulfuric acid in commercially produced barren and recycle liquors, containing 1.66 and 4.56 gpl Fe respectively, from Elliot Lake was studied. A gas mixture, containing 3.5% SO2 and air was introduced into these liquors through a frit at a rate of 6.0g SO2 per hour per liter of solution. The barren and recycle were heated to 60°C. At the end of the first 24 hours of the process the concentrations of acid produced were 158 and 220 gpl H2SO4 for the barren and recycle respectively. Corresponding conversion efficiencies were 70 and 83%. In the period from 24 to 36 hours the rate of acid production decreased so that the H2SO4 concentrations at the end of 36 hours were 180 gpl for the barren and 260 gpl for the recycle; average conversions for the initial 36 hours were 55 and 68% respectively. Many investigators1'2'3 have considered the oxidation of sulfur dioxide to form sulfuric acid in aqueous solutions containing metallic ions. A summary of the work performed on this subject prior to 1946 has been presented by Keyes4 who described the auto-oxidation process as follows. Keyes also suggested that in this second reaction ferric ion serves as a catalyst for the conversion of sulfur dioxide to sulfuric acid. Neytzell-de Wilde and Taverner5 have reported on the use of auto-oxidation to produce a 4 to 5% sulfuric acid solution for use in a cyclic leach process at South African uranium plants. This paper describes investigations carried out to determine the feasibility of using the auto-oxidation process to produce sulfuric acid solutions of as high concentration as possible using commercially produced uranium plant barren and recycle liquors from the Elliot Lake region of Ontario. These liquors contained 1.66 and 4.56 gpl respectively of iron, chiefly in the ferrous state. This investigation is of particular interest to the uranium producers in Elliot Lake where the ores contain 3 to 4% sulfur, as sulfides. Flotation of these sulfides and roasting of same to produce SO, bearing gases have been successfully demonstrated using conventional methods.6'7 Barren and recycle solutions, as described previously, are also produced in large tonnages by these uranium producers. The experimental method and apparatus used to examine the auto-oxidation process will be described first. Then the tests carried out on laboratory prepared aqueous solutions containing ferric sulfate to determine optimum conditions will be presented. The next section will describe the tests using the commercial barren and recycle liquors. A final section will summarize the conclusions of the work. EXPERIMENTAL APPARATUS AND PROCEDURES Two types of solutions were used in the tests, a laboratory prepared aqueous solution containing definite amounts of ferric sulfate, and commercially produced iron bearing solution obtained from a uranium leaching plant in the Elliot Lake area. Two liters of a solution to be examined were placed in a 3 in. diam by 30 in. long glass cylinder with a cross-sectional area of 7 sq in. A mixture of air, and SO2 supplied from a lecture bottle for convenience, was introduced into the bottom of the vessel through a standard 30 mm glass frit, 700 sq mm in area. The temperature of the apparatus was controlled by a heating tape and variable transformer. Exhaust gases were vented to atmosphere. At the end of the test period the gas flow was shut off and the solution was analysed for H2SO4, Fe ++, and Fe +++, by conventional means. Four variables were examined using the laboratory prepared aqueous solution of ferric sulfate. First, the effect of SO2 concentration, from 1 to 1076, in the feed gas mixture was considered. Second, the temper-

Jan 1, 1964

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

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

Jan 1, 1969

By Donald L. Johnson

REVIEWS on the applications of optical ellipsometry to the study of polycrystalline metal surfaces and oxidation-corrosion processes have been presented by Kruger and Hayfield, and white.' In view of the ability of this method to measure differences in film thicknesses to below 10A, ellipsometry was used to study nitrogen chromium surface reactions during the early stages of growth. Chromium specimens in the form of a vapor-deposited film on glass substrate were exposed to purified nitrogen for selected time increments at 700°F. This temperature was selected because it gave the best combination of exposure time and thickness change. Ellipsometer readings were taken immediately after exposure to determine polarizer and analyzer angles using monochromatic light at 5000A.2 After each set of readings was obtained, the specimens were exposed for an additional increment of time in nitrogen and a new set of readings taken. Film thickness was computed from LUCy's3 equation for nonabsorbing thin films. In Lucy's derivation, two equations for computing thickness were obtained. Peterson and Bashara4 have discussed the validity for using one of these equations when an independent value of the refractive index is used. The film was assumed to be Cr2N (Ref. 5) and was determined to be optically isotropic. Optical isotropy was determined by rotating the films about the surface normal and noting that the azimuth and phase difference did not change. Since Cr2N is reported to be hexagonal, it is assumed that optical isotropy results from randomly oriented grains of very small size. The thickness was computed using refractive indexes varying from 1.6 to 2.0. The maximum variation in computed thickness over this range for a given exposure was 20 pct. The data reported are based on a refractive index of 1.8. Reference readings on the metal surface were taken just prior to nitrogen exposure. No attempt was made to deoxidize or denitride the metal surface after vapor deposition, although specimens were observed to gain approximately 2A per day in air at room temperature. Twelve experimental exposures were made on a single sample over a total accumulative time of 132 min. Additional experiments over longer time intervals were made to determine the effect of heat up and cool down during and after exposure. As a result of these experiments, the thickness computed for each exposure was increased by 4A. Time profiles based on the linear law are similar to the oxidation profiles for many metals.' The rate of accumulation of the nitride film is rapid at first and slows down as the film thickness increases. The parabolic law x2 =k1t +k2 [11 gives a straight line in Fig. 1; therefore, it is concluded that the kinetic behavior is parabolic. Sey-bolt and Haman5 reported similar results for CrlN on chromium at 1000°C although the order of the thickness was much greater (10-3 cm). Analysis of thickness data based on other values of refractive index shows that the curves are shifted vertically but retain the same shape. According to Mott,7 it is expected that for thin films k2 is zero in Eq. [I]. Since the plot in Fig. 1 is linear through the origin, k2 is zero and the parabolic nature of the film growth is further indicated. The parabolic rate constant, calculated from the slope in Fig. 1, is 4.4 x 10-16 sq cm per sec. The corresponding work (+) required to bring an electron from the metal into the oxide is estimated to be 1.5 ev.7 The author thanks professor N. M. Bashara and D. W. Peterson, Electrical Materials Laboratory, University of Nebraska, for making the ellipsometer available and providing technical assistance. The Electrical Materials Laboratory is supported by the office of Naval Research, NONR 3718 (01). This work was partially supported by the Engineering Experiment Station and the Mechanical Engineering Department, University of Nebraska.

Jan 1, 1967

By Nicholas J. Palethorpe

BACKGROUND Before addressing the above topic in any detail, it is pertinent to provide some background on Australia for those people who have not been there or who have a limited knowledge of our continent. Australia is approximately the size of the continental U.S.A. (excluding Alaska) covering an area of approximately 7 million square kilometres. It has a very dry climate which has led to a concentration of people in major cities scattered around the continents perimeter. Australia's population is currently approximately 15 million. Of the work force of 6.3 million, 72% work in tertiary industries, 20.2% in manufacture, 6.5% in agriculture and 1.3% in mining. Agriculture accounts for 46% of exports, mining for 31% and manufacturing for 23,. Economic activity is based on:- Agriculture This is capital intensive and covers extensive areas and is reliant on low cost farming. A.range of foods and fibres are produced with over 70% of production being exported. Such products are of course subject to the usual vagaries of world market demand and market access, particularly in regard to the operation of trade blocks such as the E.E.C. Mineral Resources A wide range of minerals and an abundance of iron ore, coal, gas and uranium resources provide an increasing volume of exports. However, Autralia's oil resources at present only supply approximately 70% of local requirements. Industry This is diverse and encompasses the processing of agricultural products and mineral ores as well as helping to supply the consumer and capital goods needs of the whole community. However, the small scale of local markets, the geographic isolation of Australia and relatively high wage costs have limited the scale of Australia's industry. Advanced technology has overcome some of these difficulties and high tariff and import quotas protect local producers from the full force of international competition. In 1980/81 Australia's Gross Domestic Product amounted to $130 billion with approximately 24% of this being devoted to investment. In the past decade Australia has experienced inflation rates ranging from 5% to 17% and only modest real growth rates ranging from 0.4% to 5% per annum. We have also experienced, as have many other industrialised nations, continuing wage and price increases. Unemployment presently stands at 6%. MINERAL DEVELOPMENT As the above figures indicate, Australia's continuing prosperity is very dependent on the mineral and agricultrual sectors of our economy. The dependence on these sectors is highlighted by the table below which indicates our position in a global context. [Australian Production of Minerals in a World Context Western World % Total Western World Position Mineral Production 1980 1st Rutile 75 Ilmenite 31 Zircon 70 Bauxite 36 Iron Ore 11 Tungsten 14 2nd Lead (Conc.) 15 3rd Manganese Ore 14 Brown Coal 11 (1979) Zinc (Conc.) 10 4thSilver (Conc.) 10 Nickel 6 5th Tin (Conc.) 5 6th Black Coal 5 Gold 2 Source: Mining Annual Review 1981] The total value of all mineral and fuel exports in 1980/81 is estimated at $5.9 billion. This prominence in the world mineral production has largely been achieved in the last 15 - 20 years. In fact, in the early 1960's, Australia had only 2 major mining export centres, Broken Hill in New South Wales and Mt. Isa in Queensland. This growth is highlighted by the fact that in 1963, for example, we exported only 9 tonnes of iron ore and less than 4 million tonnes of coal. In 1980/81 we exported 75m. tonnes ',of iron ore (valued at $1,117m.) and 47m. tonnes of coal valued at $1,965m.). The growth in our mineral industry has come about because of a number of factors. Abundance of Mineral Resources We are particularly well endowed with mineral resources, as indicated below.

Jan 1, 1982

By J. L. Carne

ORE control is a matter of planning and supervision based on a foreknowledge of the content and distribution of ore. The Inspiration orebody is predominately a copper-sulphide blanket, overlain by an oxidized zone of copper silicates, copper carbonates, and barren capping. Most of the ore is treated by leaching, and the optimum requirement of this method is the goal toward which the mining schedule is aimed. Both open-pit operations and underground mining are used. The problems of ore control at Inspiration are: I—maintenance of metallurgical balance, 2—conservation of oxide ore, and 3—mining out of the orebody at an average grade which parallels that of the reserve figure. Prior to the fall of 1926 all of the Inspiration division ores were treated by flotation, but the mixed ores of the Live Oak—Keystone section carried too large a proportion of copper in the form of chrysocolla for satisfactory flotation. For this type of mixed ore the leaching process now in use had been worked out, and the plant was put into operation in the fall of 1926. The process is known as the ferric sulphate leach, and the leaching solvents contain both ferric sulphate and free sulphuric acid. Sulphide copper in the form of chalcocite is leached by the ferric sulphate, and the oxidized copper minerals are dissolved by the sulphuric acid. From the beginning of operations to the present time the plant has treated some 67 thousand tons of ore having an average copper content of 1.142 pct, of which 0.605 pct has been in the form of oxidized copper minerals. The plant is currently being operated at the rate of 11,500 tons per day, 7 days per week. However, this tonnage is produced in 6 days of mine operation. The average current grade is approximately 1 pct copper, of which about 50 pct is present as oxidized or acid-soluble copper. Close control of metallurgical procedures is a vital factor in operation of the plant and is in turn dependent upon careful regulation of feed. An excess of sulphide copper requires the presence of more ferric sulphate in the leaching solvents. On the other hand, an excess of ferric sulphate in the presence of a low sulphide feed seriously reduces the efficiency of electrolytic precipitation in tank house operations. This condition must be avoided at all costs. An additional factor must be considered. It is known that the sulphide content is predominant in the ore which remains in the reserve. To maintain the necessary sulphide-oxide proportion, so that the entire reserve will mine out at both a grade and a sulphide-oxide ratio that will be permissible throughout the remaining life of the property, it is obvious that the oxide reserve must be currently preserved to as great an extent as possible. Fortunately much of the oxide reserve is found in the open-pit operation. This happy circumstance adds flexibility to the procedure and makes it possible to maintain the close regulation necessary to insure best overall results, both mining and metallurgical. The two ore streams from the pit and underground operations join at the coarse-crushing plant, and proper control must be exercised before the ore reaches this point. The open pit is currently providing about 55 pct of the ore and underground operations the balance of production. Both operations are under a single superintendent so that the closely interrelated problems may be more readily controlled. The least flexible of the two producing units is the underground mine, where the mining method is block caving. Although a block of ground may be undercut and developed, characteristics of the material determine its caving action. The ore in the chutes must be drawn. The area currently mined from underground is in a zone predominately sulphide and is generally

Jan 1, 1953

By Norman F. Schulz, Emert W. Lindroos, Strathmore R. B. Cooke

DURING the course of an investigation of the effects of various starch products on hematite and quartz in regard to their separation by flotation, it was found that whereas most starches flocculated suspensions of hematite in water, they did not flocculate similar suspensions of quartz. However, a derivative of whole corn starch containing approximately one tenth aminoethyl group (-—CH,CH2NH2) per glucose unit proved to be an exception. This aminoethyl starch was a very good flocculant for both hematite and quartz, and also possessed the property of depressing both minerals in cationic flotation tests. In view of the widespread use of starch as a flocculating agent of solids in tailing water, pulps, and for coal slimes, ore and various other purposes in sulphide and nonsulphide flotation, attention is called to the effective surface activity of aminoethyl starch in flocculating suspensions of the two minerals investigated. Test Materials The starch products employed included Globe Pearl starch No. 144 and fresh aminoethyl starch, both supplied by the Corn Products Refining Co. Dr. A. L. Elder" has kindly furnished a description The minerals used in the various tests are listed in Table I. Their specific surfaces were determined by the air permeability method, which gave results reproducible to within plus or minus 3 pct. Surface areas obtained by krypton adsorption were greater than the air permeability values by a factor of 2.0 for quartz and 62.4 for hematite. Starch Adsorption on Mineral Surfaces Starch adsorption data were obtained by agitating for 1 hr measured volumes of neutral starch solutions of known concentrations with weighed quantities of finely divided mineral of measured specific surface. The mineral then was separated from the pulp liquor by centrifugation and the residual starch content determined by chemical analysis. The analytical procedure consisted of oxidizing the starch with an excess of dichromate in acid medium at elevated temperature and titrating the excess dichromate by the ferrous ammonium sulphate—potassium permanganate method. Analytical results were reproducible to within less than 1 pct. Adsorption data obtained in unbuffered solutions near the neutral point are plotted in Fig. 1. The adsorption on either mineral was far greater for the aminoethyl starch than for the Pearl starch. Flocculation The degree of flocculation was determined for a given pulp by measuring the time required for the supernatant liquid to reach a certain degree of clarity. This was accomplished by passing a standard light beam through the pulp, contained in a glass settling tube, and measuring the time required after agitation ceased for the intensity of the transmitted beam to reach a predetermined value. Starch reagent was added to each pulp in small uniform increments, and the settling time was determined after each such addition. Increase in pulp liquor volume due to the added starch reagent was ignored in these tests. Pulps were maintained at or near neutrality. of the preparation of the aminoethyl starch: "Three hundred and sixty grams of powdered unmodified corn starch was slurried in 3 liters of water and stirred during gelatinization. Eighty-six grams of ethylenimine was added slowly during reflux which was continued for 4 hr. The yellow solution set to a gel upon cooling. This was broken up and neutralized with HC1. The thick paste was dried on hot rolls. Adsorbed polyethylenimine and salts were removed from the yellowish products by washing first with acidified aqueous '60 per cent' alcohol. The white product contained nitrogen corresponding to about one aminoethoxy group per ten glucose residues." Only laboratory samples of this starch derivative have been prepared. The starch reagents for use in flocculation, flotation, and adsorption tests were made up by dispersing the appropriate quantities of air-dry starch in cold water, adding boiling water, and heating for 30 min at 120°C under pressure. When used ip adsorption tests, the starch solutions first were cleared of insoluble matter by centrifugation.

Jan 1, 1953

By Strathmore R. B. Cooke, Emert W. Lindroos, Norman F. Schulz

DURING the course of an investigation of the effects of various starch products on hematite and quartz in regard to their separation by flotation, it was found that whereas most starches flocculated suspensions of hematite in water, they did not flocculate similar suspensions of quartz. However, a derivative of whole corn starch containing approximately one tenth aminoethyl group (-—CH,CH2NH2) per glucose unit proved to be an exception. This aminoethyl starch was a very good flocculant for both hematite and quartz, and also possessed the property of depressing both minerals in cationic flotation tests. In view of the widespread use of starch as a flocculating agent of solids in tailing water, pulps, and for coal slimes, ore and various other purposes in sulphide and nonsulphide flotation, attention is called to the effective surface activity of aminoethyl starch in flocculating suspensions of the two minerals investigated. Test Materials The starch products employed included Globe Pearl starch No. 144 and fresh aminoethyl starch, both supplied by the Corn Products Refining Co. Dr. A. L. Elder" has kindly furnished a description The minerals used in the various tests are listed in Table I. Their specific surfaces were determined by the air permeability method, which gave results reproducible to within plus or minus 3 pct. Surface areas obtained by krypton adsorption were greater than the air permeability values by a factor of 2.0 for quartz and 62.4 for hematite. Starch Adsorption on Mineral Surfaces Starch adsorption data were obtained by agitating for 1 hr measured volumes of neutral starch solutions of known concentrations with weighed quantities of finely divided mineral of measured specific surface. The mineral then was separated from the pulp liquor by centrifugation and the residual starch content determined by chemical analysis. The analytical procedure consisted of oxidizing the starch with an excess of dichromate in acid medium at elevated temperature and titrating the excess dichromate by the ferrous ammonium sulphate—potassium permanganate method. Analytical results were reproducible to within less than 1 pct. Adsorption data obtained in unbuffered solutions near the neutral point are plotted in Fig. 1. The adsorption on either mineral was far greater for the aminoethyl starch than for the Pearl starch. Flocculation The degree of flocculation was determined for a given pulp by measuring the time required for the supernatant liquid to reach a certain degree of clarity. This was accomplished by passing a standard light beam through the pulp, contained in a glass settling tube, and measuring the time required after agitation ceased for the intensity of the transmitted beam to reach a predetermined value. Starch reagent was added to each pulp in small uniform increments, and the settling time was determined after each such addition. Increase in pulp liquor volume due to the added starch reagent was ignored in these tests. Pulps were maintained at or near neutrality. of the preparation of the aminoethyl starch: "Three hundred and sixty grams of powdered unmodified corn starch was slurried in 3 liters of water and stirred during gelatinization. Eighty-six grams of ethylenimine was added slowly during reflux which was continued for 4 hr. The yellow solution set to a gel upon cooling. This was broken up and neutralized with HC1. The thick paste was dried on hot rolls. Adsorbed polyethylenimine and salts were removed from the yellowish products by washing first with acidified aqueous '60 per cent' alcohol. The white product contained nitrogen corresponding to about one aminoethoxy group per ten glucose residues." Only laboratory samples of this starch derivative have been prepared. The starch reagents for use in flocculation, flotation, and adsorption tests were made up by dispersing the appropriate quantities of air-dry starch in cold water, adding boiling water, and heating for 30 min at 120°C under pressure. When used ip adsorption tests, the starch solutions first were cleared of insoluble matter by centrifugation.

Jan 1, 1953

By H. A. Deans

A three-parameter mathematical model for one-dimensional flow in porous media is developed. The objective of the model is to predict accurately the longitudinal dispersion associated with the flow of either gases or liquids over a wide range of Reynolds number. A qualitative analysis of the model parameters is given. Published experimental pulse-response curves are compared with results predicted by the model. Several general types of problems are given for which the model can be used. INTRODUCTION The problem of multicomponent single-phase flow through porous media is encountered in the study of petroleum reservoirs, gas chromatographic and ion-exchange columns, industrial fixed-bed con-tacters and elsewhere. These particular examples span the wide range of flow conditions possible; Reynolds numbers of less than l0-4 are not unusual in oil-production problems, while values in excess of 103 are common in large fixed-bed operations. The study of flow-dependent transport phenomena is complicated both by the changes in the character of the flow over this range, and by the irregularity of the flow boundaries inherent to porous media. Dispersion is one of the important phenomena known to depend fundamentally on flow conditions as well as on fluid and medium properties. As used in this paper, the term "dispersion" refers to the observed mixing of fluid elements of different composition which occurs in flow systems. The actual mechanism may be one or more of a number listed below. Only dispersion in the direction of the mean flow (referred to as axial or longitudinal dispersion, or mixing) is considered here, although lateral dispersion arises as part of certain coupled mechanisms. MECHANISMS FOR LONGITUDINAL DISPERSION A number of distinct mechanisms are known3,5,7,8 to contribute to the phenomenon of longitudinal dispersion. The more important of these are as follows. 1. Molecular diffusion in the flow direction. 2. Turbulent (cell) mixing. 3. Lateral transport processes coupled with velocity and/or residence time distributions, including: (a) "Taylor" diffusion caused by the interaction of velocity profiles in individual voids with lateral molecular diffusion; (b) separation and remixing or interdiffusion of streams having different velocities around particles; and (c) the couplipg of gross velocity profiles, caused by viscous instability or inhomogeneous porosity, with lateral dispersion. 4. Finite mass-transfer rate between a porous matrix and the flowing phase, and finite diffusion rate inside elements of the porous matrix. It is a well documented fact that these mechanisms, whether acting individually or in combinations, produce essentially similar integral effects. The observed dispersion can be described approximately by solutions of the diffusion equation with a properly chosen dispersion coefficient. Necessary conditions for equivalence between dispersion and diffusion are discussed by Klinkenberg and Sjenitzer.7 Apparently these conditions are not satisfied exactly in many real systems. "Best fit" solutions of the diffusion equation often depart appreciably from measured breakthrough curves for the usual pulse- or step-forced experimental systems. In particular, pulse response curves usually show some degree of asymmetry and "tailing" which cannot be reproduced by the one-parameter diffusion model. The three-parameter model proposed herein attempts to produce these effects in a realistic manner. Asymmetry and tailing are predicted for certain sets of parameter values, while for other sets the new model agrees with the diffusion model. VELOCITY DEPENDENCE OF DISPERSION Molecular diffusion apparently controls at sufficiently low Reynolds number in both gas and liquid systems.*l3 At Re > 20, turbulent cell mixing is dominant for gases flowing at low pressure; the data of McHenry and Wilhelm8 show that the mixing cell is approximately 1 particle diameter long in random sphere packs. on the other hand, the data

By J. L. Carne

ORE control is a matter of planning and supervision based on a foreknowledge of the content and distribution of ore. The Inspiration orebody is predominately a copper-sulphide blanket, overlain by an oxidized zone of copper silicates, copper carbonates, and barren capping. Most of the ore is treated by leaching, and the optimum requirement of this method is the goal toward which the mining schedule is aimed. Both open-pit operations and underground mining are used. The problems of ore control at Inspiration are: I—maintenance of metallurgical balance, 2—conservation of oxide ore, and 3—mining out of the orebody at an average grade which parallels that of the reserve figure. Prior to the fall of 1926 all of the Inspiration division ores were treated by flotation, but the mixed ores of the Live Oak—Keystone section carried too large a proportion of copper in the form of chrysocolla for satisfactory flotation. For this type of mixed ore the leaching process now in use had been worked out, and the plant was put into operation in the fall of 1926. The process is known as the ferric sulphate leach, and the leaching solvents contain both ferric sulphate and free sulphuric acid. Sulphide copper in the form of chalcocite is leached by the ferric sulphate, and the oxidized copper minerals are dissolved by the sulphuric acid. From the beginning of operations to the present time the plant has treated some 67 thousand tons of ore having an average copper content of 1.142 pct, of which 0.605 pct has been in the form of oxidized copper minerals. The plant is currently being operated at the rate of 11,500 tons per day, 7 days per week. However, this tonnage is produced in 6 days of mine operation. The average current grade is approximately 1 pct copper, of which about 50 pct is present as oxidized or acid-soluble copper. Close control of metallurgical procedures is a vital factor in operation of the plant and is in turn dependent upon careful regulation of feed. An excess of sulphide copper requires the presence of more ferric sulphate in the leaching solvents. On the other hand, an excess of ferric sulphate in the presence of a low sulphide feed seriously reduces the efficiency of electrolytic precipitation in tank house operations. This condition must be avoided at all costs. An additional factor must be considered. It is known that the sulphide content is predominant in the ore which remains in the reserve. To maintain the necessary sulphide-oxide proportion, so that the entire reserve will mine out at both a grade and a sulphide-oxide ratio that will be permissible throughout the remaining life of the property, it is obvious that the oxide reserve must be currently preserved to as great an extent as possible. Fortunately much of the oxide reserve is found in the open-pit operation. This happy circumstance adds flexibility to the procedure and makes it possible to maintain the close regulation necessary to insure best overall results, both mining and metallurgical. The two ore streams from the pit and underground operations join at the coarse-crushing plant, and proper control must be exercised before the ore reaches this point. The open pit is currently providing about 55 pct of the ore and underground operations the balance of production. Both operations are under a single superintendent so that the closely interrelated problems may be more readily controlled. The least flexible of the two producing units is the underground mine, where the mining method is block caving. Although a block of ground may be undercut and developed, characteristics of the material determine its caving action. The ore in the chutes must be drawn. The area currently mined from underground is in a zone predominately sulphide and is generally

Jan 1, 1953

By C. F. Baes, H. H. Kellogg

The effect of dissolved sulphur on the surface tension of liquid copper has been measured by a sessile-drop method at 1120°C. Sulphur is highly "surface active" in liquid copper; the surface tension lowering is about 650 dynes per cm for a sulphur content of 0.6 pct. The degree of adsorption of sulphur on the liquid copper surface has been calculated, and various models of the surface layer have been tested against the results. THE science and technology of surface chemistry and physics at room temperature are relatively advanced, and the engineer possesses a background of information that allows him to predict and control many phenomena—such as frothing, emulsifica-tion, wetting of solids by liquids, flow through capillaries, adsorption, mineral flotation, penetration of porous bodies by liquids—which are related to the behavior at interfaces. Surface phenomena in high temperature systems are probably of equal importance to the metallurgist and ceramist, but at present are incompletely understood. Frothing of liquid slags, penetration of refractories by liquid metals and slags, infiltration of powder metallurgy "skeletons" by liquid metals, bonding of metals to ceramic oxides in the manufacture of "cermets," wetting of one metal by another for purposes of soldering and welding, are but a few of the many phenomena of metallurgy that are controlled by surface behavior. Concerning the most elementary of surface properties—the gas-liquid surface tension—the existing data on liquid metals are inadequate. For the surface tension of "pure" metals the results of different investigators differ by 10 or 20 pct. The role of surface-active agents in liquid metals is relatively unknown, and it is not unlikely that the discrepancy in the values for the surface tension of pure metals is due to the presence of traces of surface-tension-lowering impurities in the samples. Based on analogy to room-temperature systems, the highly surface-active impurities in liquid metals should be elements or compounds of limited solubility in the liquid metal and possessing considerably weaker in-termolecular bonding forces than the metal itself. The nonmetals of the V, VI, and VII groups of the periodic table might be expected to act in this way. The experimental work in this paper represents a study of the surface tension of pure liquid copper in hydrogen at 1120°C, and the effect of dissolved sulphur (which is a strongly surface-active agent in liquid copper) on the surface tension of copper. The Gibbs equation has been applied to the results and an attempt made to correlate the surface tension behavior with two models of the interfacial layer. The sessile-drop method for surface-tension measurement at high temperatures which was used in this investigation has been described by several investigators.1,2 It involves the measurements of the dimensions of a stationary liquid drop on a horizontal surface. From these dimensions and the liquid density, the surface tension of the liquid may be calculated either by means of various approximate formulas, or more accurately by means of the Bash-forth and Adams tables.- or liquid drops which exhibit a contact angle greater than 90°, by far the simplest dimensions to measure are those indicated in Fig. 1, i.e., the diameter of the maximum horizontal cross section (2X) and the maximum height (Z) above this plane. In order to calculate the contact angle and the volume of the drop, the diameter at the base of the drop (2a) and the total height (h) also must be measured. Upon investigation of the literature, the authors failed to discover a concise statement of the accuracy of the method when used in conjunction with the Bashforth and Adams tables, hence a careful examination of the tables was made and the curve shown in Fig. 2 was constructed. The "error factor," plotted as the ordinate, is the factor by which the

Jan 1, 1954

By J. P. G. Farr, R. Brownsword

THE role of solute segregation in the formation of cellular solidification substructures in tin and its dilute alloys is well-established, see, e.g., Ref. 1. Segregation has been shown to persist during cooling, enabling solidification structures to be studied from sections taken at some distance behind the interface. In the present work, a single crystal of commercial nickel, 99.965 pct, was examined in this way. The crystal was cut from the center of a rod given a single pass in an electron beam floating zone melter. Polished sections of a nickel specimen taken normal to the growth direction showed a very fine precipitate phase, the distribution of which varied over the section. The identification of the phase proved difficult because of the small amount present and the small particle size, about 1 p: but it was shown by probe microanalysis to contain only nickel and oxygen in detectable concentrations and was probably nickel oxide, NiO. Bulk analysis of the material before melting showed there to be only 3 to 4 ppm of oxygen present, thus demonstrating a very considerable segregation concentration effect. In some areas of the section the precipitate formed a discontinuous hexagonal network suggesting decoration of the cellular boundaries known to be present in the sample2 whereas in a restricted region the precipitate formed small clusters. Occasionally it could be seen that the clusters were at the intersections of an hexagonal network of cellular dimension. It was suggested3 that this was the result of enhanced segregation to the cell boundary intersections whereas general cell boundary segregation was insufficient to give a precipitate. Enhanced nodal segregation has since been demonstrated in a number of systems.1, 4-8 The development of a suitable electrolytic etching technique (perchloric acid 20 pct v/v; ethyl alcohol 70 pct; glycerol 10 pct; current below electropolishing plateau; 1 to 2 sec etching) suggested the association of the phase with regions of solute segregation (where ko < 1); in these regions anodic attack produced grooves or depressions. In a study of the variation of solidification substructures with degree of constitutional supercooling, Biloni et a1.&apos; appear to have used standard growth conditions and varied the solute concentration. They were able to produce in a series of individual tin crystals examples of substructure ranging from planar interface through various cellular structures to den- Fig. 1—Electroetched section taken normal to the rod axis; the center of the rod lies to the left and the periphery to the right of the micrograph. The variation of structure across the section is evident. Magnification 60 times. drites. It was possible in the present nickel crystal to observe a continuous range of substructures varying with degree of supercooling across a single section as shown in Fig. 1. Growth rate, 13 mm per min, and temperature gradient were essentially constant; the variation in structure is thought to be due to a radial gradient in solute concentration ahead of the solid interface. The liquid at the interface is likely to have been richer in solute toward the periphery of the zone, the result of curvature of this interface. The type of substructure was seen to vary with increasing constitutional supercooling as follows: a) region free of precipitate. top left, Fig. 1: 6) region of nodal precipitates which became arranged in hexagons on passing from the center of the rod: c) irregular hexagonal cells with incomplete boundary precipitation; d) regular hexagonal cells of decreasing size with complete boundary precipitation. Fig. 2 shows the transition from stage 6 and Fig. 3 shows the structure in stage d. Within stage 0, the range of conditions over which irregularly positioned nodes occur appears to be small and the nodes are soon recognizable as taking up positions at the intersections of an hexagonal network as the supercooling increases.

Jan 1, 1970

By T. L. Joseph

S. T. Killian (Johnstown, Pa.)—This is one of the finest papers I have read. Tying in stoichiometric calculations with furnace performance and practice is a step which had to be taken sooner or later. The noteworthy difference between Dr. Joseph&apos;s type of calculations and regular blast furnace calculations is that the Ib mol system is used as a basis. With the Ib mol system, weights, volumes, and chemical reactions can all be expressed in the same equation. In the paper, wind, ore, flux, and fuel are all expressed as lb or lb mols. Probably Dr. Joseph does not realize it, but the vague word coke appears only twice in the entire paper. Lb of C and Ib mols of C are followed through reactions but the word coke appears only as 1560 lb coke per ton of pig and 1700 lb of coke per ton of iron. Obviously in order to understand furnace reactions, the coke should be expressed as lb or lb mols of C. Furnaces can also be compared more easily. In some respects the paper is too thorough and too complete. The effects of the metalloids reduced into the iron upon the top gases represents a difference of less than 3 pct of the CO formed in the bosh. Due to the completeness of the calculations in relation to the CO/CO2 ratio, this was included and was necessary. However, the exclusion might have enabled more furnace men to follow the lb mol system of calculations through the blast furnace to a better degree. By considering only irons of similar analysis, this part of the calculations might have been omitted. However, if this had been done, total rewriting of the paper later would have been necessary in order to make the work complete as it is now. It also would not have been nearly as authoritative. In the paper, there appears the reaction: H2O + CO ? CO2 + H2 [I] Dr. Joseph states that he did not take this reaction into consideration in any calculations pertaining directly to the paper. The piobable reason- for this is that although it contains all the main reacting top gases except N2, it is rather inflexible since it is monomolecular in relation to each of the reacting gases and does not tie in with the gasification of C. Actually the reactions: H2O + C ? CO + H2 [2] 2H2O + C ? CO2 + H2 [31 and the solution loss reaction: CO2 + c ? 2c0 [41 tend to assume an equilibrium through the reaction: H2O + CO ? CO2 + H2 [I] which should be considered a balancing or equilibrium reaction. Reactions 2, 3 and 4 permit furnace conditions to balance with the CO/CO2 ratio and H2 formation. They tie in with the solution loss. Reaction 1 unites them chemically. Probably the best calculation to make at this time would be to try to find the relative importance of the CO2 from the flux and the H2 in the dilution on an actual furnace gas analysis. For this purpose the Dob-scha-Carnegie-Illinois paper—"Effect of Sized and Sintered Mesabi Iron Ores On Blast Furnace Performance" is chosen. This paper was presented before the blast furnace section of the AIME in 1948. This represents the best large scale furnace operation available to me. Unfortunately the changes were brought about by beneficiation of the burden and not by changes on one burden. In choosing the basis for the calculation in relation to the furnace, 100 mols of dry top sgas is chosen. This leaves something to be desired inasmuch as the nitrogen basis is changing but I believe it will be better understood than any other type and it is the easiest to use.

Jan 1, 1952

By Robert M. Lewis

Can wet-ground mica be produced from mica schist ores, and if so, would its properties be comparable with products now on the market? This was the problem which prompted the development of a flowsheet for the beneficiation of mica schist. The fine-ground mica industry relies on weathered pegmatites and alaskite ores as sources of raw material. The mica concentrates obtained from these ores are relatively clean and require moderate beneficiation to meet color and bulk-density specifications. Mica obtained from mica schist is iron-stained and decrepitated and requires additional beneficiation to produce a wet-ground mica product. Despite these adversities, there are several advantages to be gained by mining and processing mica schist ores. The mica content of these ores is considerably higher than that of the pegmatites and alaskite ores now being mined, often containing in excess of 40% mica. This higher-grade mica feed should promote a lower mining and milling cost. The mica schist ores with their higher mica content would mean less tailings to handle; however, there would have to be a means for disposing of acid and sulfate wastes. A flowsheet was developed whereby mica could be recovered from mica schist ores and beneficiated in a way that would result in a high-quality end product.&apos; The essential phase of the process involves using reducing reagents to increase the magnetic susceptibility of iron contaminants which then can be removed with a magnetic separator. General Treatment Procedure The mica is floated by either of two methods, an amine float in an acid circuit&apos; or the U.S. Bureau of Mines (USBM) amine-fatty acid float in an alkaline circuit&apos; The flotation mica is ground in a pebble mill to liberate contaminated particles and expose iron-stained surfaces. The concentrate is then conditioned with a reducing reagent and passed through a Frantz Ferrofilter for the removal of magnetic material. The nonmagnetic product is acid-leached to further reduce the iron contamination. The leached material is then ground to product size and checked for specifications. Discussion of Flowsheet and Its Development Flotation: The mica is concentrated by flotation using either of two methods: an amine float in an acid circuit, or the USBM amine-fatty acid float in an alkaline circuit.&apos; The writer does not wish to elaborate on the relative merits of the two flotation procedures; however, after investigating ores from various localities, it was felt that the amine float in an acid circuit was more consistent when using a standard procedure. Iron Reduction and Magnetic Separation: This phase of the flowsheet may be considered the key to the process. It was developed when it became apparent that hot acid leaching had just about reached its maximum effective¬ness for color improvement. S. C. Sun and William Hirsh in "Hydrochloric Acid Leaching of Iron From Pennsylvania Aluminous Clays,"` reported iron extraction for -20-mesh minerals of 82.20% for hematite and only 33.46% for magnetite. The test procedure employs a 19% hydrochloric acid solution, 104°C temperature, and 10% solids. It was felt that magnetic removal of some of the iron contaminants before leaching therefore would be advantageous. Since the iron minerals present as contaminants vary in magnetic susceptibility, it was decided to experiment with reducing reagents as a means of influencing their magnetic properties. Zinc hydrosulfite or sodium hydrosulfite were the reagents used throughout the tests. The procedure developed consists of conditioning the mica concentrate in a closed container at approximately 5% solids with a reducing reagent. Approximately 10.0 lb of zinc hydrosulfite per ton of mica concentrate is used. The ferric iron is reduced to the ferrous state (magnetic) and oxidation is retarded by isolation from the atmosphere in a closed container. After the desired conditioning time has elapsed, the material is passed through a Frantz Ferrofilter where the magnetic particles are retained and discarded as

Jan 1, 1972

By Kehsin Kuo

DIE steel with 1.47 pct C, 0.42 pct Mn, and 8.22 pct W contains Fe,C and WC in the annealed state and WC embedded in a martensitic matrix in the hardened state (quenched from 800°C). The presence of a large amount of undissolved angular WC carbide particles makes this steel extremely wear-resistant. However, the WC carbide begins to dissolve in the austenite when the heating temperature is raised above 1000°C, but this solution process is still not complete at 1250°C although partial melting has already taken place at the austenite grain boundaries. At 1325 C, this steel contains austenite and liquid metal but no WC carbide, Fig. 1. On quenching into brine, the liquid metal solidifies into a constituent which etches differently from the austenite-martensite matrix. This constituent appears lighter than the matrix at the 1250°C stage when etched with 2 pct nital but darker in Fig. 1 when etched with Murakami&apos;s reagent. Such a constituent has also been found in burnt tungsten high speed steels. This constituent has been isolated from the matrix by anodic dissolution in a 5 pct HC1 electrolyte and was found by the X-ray powder method to be iso-morphous with &manganese, Table I. The agreement in line intensity between these two phases indicates that there is no ordering in this new phase. The calculated cube edge of this phase is 6.395A, somewhat larger than that of ß-manganese (6.30A). Besides this phase, the anodic residue also contains free carbon from the matrix and amorphous WO,, although the X-ray powder pattern of the residue shows the presence of only this phase. This makes it impossible to determine directly the composition of this phase from the residue. Attempts to prepare an alloy containing only this phase have hitherto been fruitless. The following experiments serve to show that this phase can only be obtained by drastic quenching from the liquid state and that its tungsten and carbon contents must be lower than those in the Fe,W,C carbide. On air cooling from 1325oC, the liquid metal solidifies into a eutectic consisting of austenite and the Fe3W3C carbide. The nature of this dark-etching Fe3W3C has also been ascertained by X-rays. This eutectic becomes coarser on furnace cooling. The solidification of a specimen cooled for 5 min from 1325" to 1200°C and water quenched is still not complete and the fine eutectic is formed during the quenching. Since this new phase can be replaced by a eutectic of austenite and the Fe,W,C carbide, its composition must lie somewhere between the latter two phases. The special features of this phase are: 1—it can only form directly from the liquid state by drastic quenching and 2—it is a ternary phase of iron, tungsten, and carbon. The ß-manganese structure of this phase is also interesting. In the Periodic Table, iron and tungsten lie on opposite sides of manganese; a certain combination of these two elements, in the presence of carbon, may have average properties similar to those of manganese. It has already been established that the x phase, a ternary one of iron, chromium, and molybdenum, has the a-manganese structure."&apos; A similar phase has also been found in the ternary system Fe-Cr-W and in the following binary systems: Re-Cb, Re-Ta, Re-Mo, and Re-W.6 References 1 G. D. Preston: Philosovhical Magazine 11928) 5. 7th Series, p. 1207. - K. W. Andres: Nature (1949) 164, p. 1015. 35. G. McMullin, S. F. Reiter, and D. G. Eberling: Trans. ASM 11954) 46, p. 799. &apos; J. S. Kasuer: Acta Metallurgica (19541 2, p. 456. • H. J. Goldschmidt: Trans. ASM (19541 46, p. 807. P. Greenfield and P. A. Beck: Private communication.

Jan 1, 1957