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[Title 1 Contents Page . 3 Officers and Directors 5 Past and Present Officers 6 Standing Committees 9 Professional Divisions 11 Technical Committees 12 Institute Representatives on Boards 17 United Engineering Society 17 Engineering Societies Library Board 17 Engineering Foundation Board 17 Other Committees 17]

Jan 1, 1928

By S. A. Braley

THE first commercial production of bituminous coal in the United States was in 1820, and formation of acid in the areas from which the coal was removed began at that time. Thus it is 130 years since the development of mine acid began. The coal operator has had to deal with the acid water produced in his mines, and his losses from corrosion of pumps and equipment have been tremendous. Other industries and the public have been forced to spend large amounts for their water requirements because of the acid discharge from the mines. There are many contradictions in the literature on this subject probably because of variations in the analytical procedures followed and differences in the methods of calculation and reporting. The opinions previously expressed may be summarized as follows: The production of mine acid has been looked upon as a simple chemical reaction wherein the oxygen of the air has reacted with pyrite to produce ferrous sulphate and free sulphuric acid. This reaction appears in many chemistry texts and generally has not been considered worthy of further study. Since the measurement of hydrogen ion concentration or activity was developed and expressed in terms of pH, indicator and instrumental methods for pH determination have become readily available, making it natural to think of it as a measure of acid content. Special purpose analytical methods applicable to potable waters, sewage effluents, and boiler waters, based in general upon the determination of what may be regarded as impurities, have been applied to more concentrated solutions constituting mine discharges, without reference to the fact that these specialized procedures had been developed to serve as operating guides for water-treatment plants. It has been assumed that the pounds of acid deliv- Table I. Showing pH and Titratable Acid of Varying Concentrations of Ferrous and Ferric Sulphates Ferric Ferrous ion Acldfty Ion Acidity (Fe+++) ppm CaCO3 We++) ppm CaCOa ppm PA equiv. PPm pH equiv. 11.200 1.80 30,000 11,200 3.98 20,000 5,600 2.01 15,000 5,600 4.15 10,000 2,800 2.21 7,500 2,800 4.41 5,000 1.120 2.48 3,000 1,400 4.68 2.500 560 2.60 1,500 140 5.00 250 280 2.65 750 28 5.00 50 112 2.81 300 56 3.07 150 28 3.38 75 ered by a mine was roughly a constant varying with the number of acres mined, and that the concentration of the acid in the drainage was inversely proportional to the volume of flow. Increased flow was thought to result in a dilution of the acid produced. When the Sanitary Water Board of the Commonwealth of Pennsylvania established a fellowship at Mellon Institute, the first approach to the problem was to review some of the chemical reactions involved and their relation to acid production. Since the sulphates of iron were among the principal constituents of coal-mine drainage, the first studies were based upon solutions of chemically pure ferrous and ferric sulphate. These are both neutral salts, that is, the iron and the sulphate are equivalent, but they produce acid reactions in water solution because as salts of strong acids with weak bases, they hydrolyze to form acid solutions. Solutions of each salt, of varying concentrations, were prepared and the pH, titrable acidity and iron and sulphate

Jan 1, 1952

By W. A. Tiller, D. H. Lane

A simple zone melting technique for investigating the effect of ultrasonic irradiation upon ingot solidification is described. The effect of i) ultrasonic power level, ii) freezing velocity, iii) constant or variable frequency, iv) direction of irradiation, and v) transducer-cozlpling bar joint upon the grain size of type 316 stainless steel have been investigated. The results of this study support the postulate that the ultrasonic vibrations increase the nucleation probability in the layer of liquid adjacent to the freezing interface. In the first paper of this series,l the possible mechanisms whereby ingot structure may be altered by irradiating a solidifying melt with ultrasonic vibrations have been discussed. A new technique for efficiently introducing the ultrasonic energy into the solid-liquid interface region was presented and applied to ingot preparation by the consumable-electrode arc-melting technique. The experimental results support the postulate that the ultrasonic vibrations may refine the ingot structure by increasing the nucleation probability in the zone of liquid adjacent to the solid-liquid interface. The present paper describes the application of the same technique to a relatively simple laboratory-scale zone-melting apparatus. This apparatus is found to be well suited to the detailed study of ultrasonic technology in this area and allows one to determine, in particular, the minimum ultrasonic power level needed to produce a certain grain size in a particular material. The results of this study support the nucleation mechanism for grain refinement, but do not provide any deeper insight into the specific nucleation mechanism responsible for the effect. EXPERIMENT The apparatus used in these experiments is shown in Fig. 1 and illustrated schematically in Fig. 2. The material to be studied, type 316 stainless steel, was in the form of a 3/4-in. sq bar 30 in. long. This bar was placed in a square open-topped mold with open ends made from high-purity graphite coated with a flame-sprayed Al2O3, skin. Surrounding the crucible was a molybdenum susceptor with 3/8-in. diam holes spaced at 1-in. intervals along its length to serve as sight ports. A tapered transducer horn was brazed to one end of the specimen. The entire assemblage was enclosed in a quartz tube, the transducer itself projecting out one end and resting in a cooling tank. A vacuum seal between the coupling bar and the end plate enclosed one end. A similar plate and seal enclosed the other end. The system is gas tight and can be operated under vacuum or an inert atmosphere. For these experiments, flowing argon at 15 in. of Hg pressure was used. The heat source for melting the stainless steel specimen was a 2-in. long 3-kc induction coil placed around the quartz tube; this source heated the susceptor, inductively melting about a 3-in. zone of the sample by radiation. To move the molten zone at a specified rate, the induction coil was moved down the tube at this rate with the aid of a simple pulling device. Thus, the sample could be irradiated at varying ultrasonic frequencies and power levels and could be solidified at varying rates. The power input to the transducer was measured using a "John Fluke Model 120 VAW-Meter." 1 The power delivered to the interface region is probably only about 50 pct of that measured on the VAW-meter. In a typical run, when the ultrasonic power was turned on, the interface of the molten zone closest

Jan 1, 1961

By R. E. Maringer, B. A. Wilcox, A. H. Clauer, J. H. Sovik

Internal friction measurements from 25° to 1100°C have been made on specimens machined from TD nickel bar. The use of miniature torsional pendulum specimens alloived damping measurements to be made on specimens whose axes were parallel to the original bar axis, at 45 deg to the bar axis, and at 90 deg to the bar axis. There was a marked difference in damping with varying specimen orientation, and this was related to the pronounced micro structural anisotropy of this material. Varying the microstructure by cold working plus re crystallization annealing also greatly affected the damping behavior. Recrystallization essentially removed the broad peak found at 400° to 650°C in as-received TD nickel, and in addition greatly lowered the background damping. DlSPERSION hardened metals such as SAP-type alloys (Al + AI2O3) and TD nickel (Ni + 2 pet ThO2) have been developed primarily to improve high temperature strength properties. There have been numerous damping studies on SAP-type alloys,1"9 and one of these6 showed that the damping capacity was greater than that of 99.5 pet pure Al from 25° to 600°C. Several preliminary observations on TD nickel10 and an experimental Ni-ThO2 alloy11 indicated that here, too, the damping capacity was quite high. A high damping capacity in TD nickel, combined with its relatively good high temperature creep strength, could provide an additional benefit for some high temperature structural applications. This work was undertaken to study the internal friction behavior of TD nickel bar over the temperature range 25° to 1100°C. In Ni-ThO2 and Ni-Cr-ThOz alloys, other properties such as steady-state creep rate,12 creep rupture life,12'13 modulus of elasticity,14 and ultimate tensile strength,14 are sensitive to orientation with respect to the primary working direction. Thus, in order to examine anisotropy effects in damping, studies were made on specimens machined with their axes parallel, at 45 deg, and transverse to the original bar axis. MATERIAL DESCRIPTION AND EXPERIMENTAL PROCEDURES The material used in this investigation was from the same £ in. diam TD nickel bar that has been studied previously.13'15 The structure typical of the as-received TD nickel is shown in Fig. 1, and additional details of the structure can be found in Refs. 13 and 15. Elongated grains are parallel to the bar axis and are about 10 to 15 u long and about 1 u in diam. This structure is very stable, since no recrys-tallization or grain growth occurred after annealing for 3 hr at 1300°C.13 The total ThO2 content was 2.3 vol pct and the particles ranged in diameter from 100 to 1000. The average particle diameter was 370Å and the mean planar center-to-center particle spacing was 2340Å. To examine the influence of grain and subgrain structure on damping, a section of TD nickel bar was swaged and drawn at room temperature from 1/2 in. diam bar to 0.040 in. diam wire (99.3 pct re-duction in area). The structure in Fig. 2 resulted after the wire was annealed for 3 hr at 1250°C. The recrystallized grains were much larger than the grains in as-received bar, but still showed considerable elongation in the direction of working. A high

Jan 1, 1970

By G. Ansell, J. Weertman

G. Ansell and J. Weertman (Rensselaer Polytechnic Institute and Northwestern University, respectively) —The great increase in creep strength that you found in your indium-glass composites is quite striking. You ruled out a decrease in the dislocation source density as an explanation of the reduced creep rates. Could you tell in greater detail why you feel this is an inadequate explanation of the phenomenon. It appears to us that it is a reasonable one. Consider the spacing between the glass spheres in your composites. It is of the order of 10-3 cm. The spacing between dislocations in a (single-phase) annealed metal with a dislocation density of the order of 106 to 107 cm per cm3 also is of the order of 10-3 cm. Therefore it is not reasonable to expect that the arrangement of the dislocation lines is the same in the composite material as it is in pure indium. If the dislocation arrangements are different the density of the dislocation sources likewise will be different. Another way of saying the same thing is the following. The presence of the glass spheres reduces one of the dimensions of the metal phase to 10-3 cm. Thus the metal phase, in effect, is equivalent to a metal whisker or a thin metal film. These are strong because they have so few dislocation sources within them. T. D. Gulden and J. C. Shyne (authors' reply)—It is to be expected that the arrangement of dislocations in the indium-glass composites would be quite different than that observed in annealed pure metals. The dislocations probably exist primarily as segments connecting the dispersed particles. These segments and discontinuities at the very large area of particle-metal interface could act as dislocation sources. For this reason it was considered unlikely that the very high observed creep strengths were due to a low density of dislocation sources. A more likely explanation is that the distance a dislocation can glide is limited by the interparticle spacing. The particles averaged about twenty in diam and were less than 10 µ apart in the 40 pet composite. It seems reasonable to assume that a dislocation loop in a volume of metal surrounded by these relatively large particles would not bow out around them but would be restricted to the region between particles. A general expression for creep rate is given by the product of the dislocation source density, the average rate at which loops are generated from a source, and the average area swept out by a loop times the Burgers vector magnitude. Assuming that the area swept out is limited by the interparticle spacing and the rate of generation of loops is controlled by the rate of climb of loops over second-phase particles, as suggested by Ansel and Weert-men,9 a calculation of the dislocation source density may be made from the experimentally observed creep rates. The result comes out 10" to 10" per cm3 which seems reasonable in view of the assumptions involved. Thus it is concluded that the anomalously low creep rates that were observed were due not to a low dislocation source density but rather to a limitation on the area swept out by each dislocation loop.

Jan 1, 1964

By S. K. Basu, H. H. Kellogg

THE physical-chemical behavior of the system Pb-S-0 is of prime importance to the understanding of lead smelting processes, yet little accurate information is available on either equilibrium or kinetic behavior in this system. This paper is the first report of a program designed to fill gaps in our knowledge of this system. In the total ternary Pb-S-0, the region of greatest metallurgical interest is that bounded by the compositions Pb-PbS-PbS0,-PbO-Pb. Systems richer in sulfur, or richer in oxygen,* than those essentially pure SO2. This conclusion follows from the fact that all systems are in a highly reduced state, since either PbS or Pb is a constituent of all the equilibria. The content of 02, SO3, S2, S6, S8, and so forth, can be shown to be negligible compared to SO, in all such systems.* corresponding to this region can only be obtained at gas pressures exceeding 1 atm, a condition seldom met in lead smelting practice. Not only is the present study limited to condensed phases within this portion of the total system, but it is limited to temperatures at which all phases are pure solids, except for lead, which is liquid. In this limited system the following seven condensed phases are known to exist: Pb(l), PbS(c), PbO(c), PbSO,(c), PbSO,•PbO(c), PbSO4 • 2PbO(c), and PbSO, -4PbO(c). PbO exists in two crystal modifications,' but only the high-temperature yellow form is considered here. Schenck and co-workers2-4 reported the compound PbSO4 3Pb0 to be stable at high temperature, but the more recent work of Lander,5 and the present work, prove that the tetra-basic sulfate, rather than the tri-basic sulfate is stable. Fig. 1 shows the composition diagram for the binary PbO-PbSO2, based primarily on the work of Lander. In this study the univariant boundaries and invariant points existing among these seven condensed phases and the gas phase have been determined. In a ternary system, the phase rule indicates that an invariant point involves the simultaneous equilibrium of five phases—four condensed phases and the gas phase. A univariant relation involves four phases—three condensed phases and the gas phase. The gas phase in the systems studied is The following stable univariant equilibria between SOz and the condensed phases were identified: (a) PbS + 7PbS04 = 4(PbSO, - PbO) + 4SO2 (b) PbS + l0(PbS04 • PbO) = 7(PbSO4- 2PbO) + 4SO2 (c) PbS + 8(PbSO4 • 2PbO) = 5(PbSO4 . 4PbO) + 4SO2 (d) Pb + PbSO, • 4PbO = 6PbO + SO2 (e) 3PbS + PbSO4 . 4PbO = 8Pb + 4SO2 (f) 3PbS + 16(PbS04 PbO) = 7(PbSO4 . 4PbO)+ 12SO2 (g) 2PbS + PbSO,2PbO = 5Pb + 3SO2 (h) Pb + 3(PbSO4 . 2PbO) = 2(PbSO,. 4PbO) + SO, Of these eight univariant equilibria, five were measured in this work (a, b, c, d, and g) and the behavior of the other three (e, f, and h) was calculated by thermodynamic analysis of the measured data. Two invariant points were found corresponding to simultaneous equilibria as follows: Point 1: PbS, PbSO4PbO, PbSO4.2PbO, PbSO, - 4PbO, and SO2 Point 2: Pb, PbS, PbSO, . 2PbO, PbSO, - 4PbO, and SO2, From the measurements it was also possible to calculate the thermodynamic properties of the three basic sulfates of lead at 298.16°K. EXPERIMENTAL Apparatus—The experimental method consisted of the measurement of the gas pressure exerted by a given reaction mixture at a given temperature. An iridium crucible was used to contain the reaction mixture. There was no evidence of attack of the iridium,* but after use at high temperature for a week

Jan 1, 1961

By P. Bardzil, J. Gurland

An experimental study of the variation of transverse-rupture strength with composition Anexperimentaland grain studysize has shown that the strength reaches a maximum for values of the mean free path between carbide particles of 0.3 to 0.6 microns. The fracture oforiginates in and proceeds through the carbide grains mainly. Impact strength and hardness also were recorded. MOST of the physical properties of sintered carbides vary linearly with composition. The transverse-rupture strength, however, shows a unique behavior. As the amount of binder metal is varied from 6 to 25 pct by weight, the strength at first increases; then, between 15 and 20 pct Co, it reaches a maximum of nearly 400,000 psi, and finally decreases with further additions of binder metal. This behavior of the transverse-rupture strength has been reported, among others, by Englel and Sandford and Trent.' The significance of these observations has not been discussed in the literature. That it may be of more than specific importance is indicated by the very similar variation of strength with composition encountered in other systems sintered in the presence of a liquid phase, such as Tic-Ni3 and Fe-Cu.' Experimental Details All compacts were prepared and sintered according to normal industrial practice. The average diameter of WC grains and the mean free path between grains were measured on metallographically prepared samples by a method of linear and planar analysis sing the relations where d is the average diameter of dispersed grains; Nl is the number of noncontiguous grains intersected on a metallographic plane by a line of unit length; N, is the number of noncontiguous grains per unit area; P is the mean free path between grains of dispersed phase; and f is the volume fraction of dispersed phase. Approximately 1000 grains were counted on each sample. For each composition d2 was plotted against P, the resulting straight lines serving as a check on the measurements. The distribution curves of the WC powders of different average diameters were homologous, and no attempt was made to influence the grain size by blending powders, adjusting the sintering conditions, or otherwise altering the particle size distribution. Densities were measured by differential weighings in air and water. The degree of densification did not vary consistently with either composition or grain size. The density is influenced by slight amounts of impurities, specifically by 0.1 to 0.2 pct Fe which enters the powders during ball milling. As an illus- -tration of the experimental variations, a number of measured densities are listed in Table I. They are expressed in percentage of theoretical density, as calculated from the published X-ray densities of WC and Co.' For the purpose of determining the transverse-rupture strength, rectangular test specimens (3/16x 3/8x3/4 in.) were broken by loading at the center of a 9/16 in. span. The average strength of five or more samples is reported for each composition and grain size. The compacts were ground on two parallel surfaces only. The load was applied at an average rate of 6,800 psi per sec. Since the elongation after fracture of the alloys is very small, it was assumed that the compacts deform elastically to failure and the fracture stress was calculated by the conventional beam formula. The data for one alloy are presented in Table II as an example of the results and scattering ranges encountered. The precision of the test, as measured by the average difference between duplicates, is of the order of 15,000 psi. The results are strictly comparable only to compacts prepared and tested in the manner described and of similar chemical composition and grain size characteristics. Unnotched Charpy specimens were used for impact testing. Each point represents the average of 3 to 20 samples, the larger number being used in an attempt to determine the influence of grain size. Considerable scatter was encountered, the range from lowest to highest value often amounting to 30 pct of the impact strength. The hardness is reported as a Ra reading, using a 60 kg load with diamond brale indenter. Compositions are given in weight percent.

Jan 1, 1956

By N. E. Rogen, N. J. Grant

WHILE direct measurements of the growth of precipitate particles during aging is of fundamental value, few such measurements have been made. Direct measurements by means of optical or electron-microscopy and X-ray techniques are preferred, however, many of the aging studies have been based on indirect methods such as electrical resistivity and hardness. Because of the minute size of most precipitate particles (less than 1000A) the light microscope is of limited use while electron microscopy is subject to slowness, etching problems and consequent resolution problems. It is fortunate that alloys of the Nimonic type, based on Ni-Cr-Ti-Al, lend themselves to accurate and relatively easy particle size measurements. With proper balance of titanium and aluminum, the only aging precipitate is the gamma prime (r') Ni3,(Al, Ti)2 phase and this phase is the basis of the high-temperature strength of these allos.3-6 The Ni3(Al, Ti) phase is a face-centered-cubic, ordered structure with nickel atoms occupying the cube faces. Titanium atoms can replace three out of every five aluminum atoms and when substituting do so preferentially.2 Electron microscopy has shown that during aging of most of the commercial alloys of this type, precipitate particles are unusually uniform in size and distribution, and that the volume of (r') phase is large (20 pct).4,7 The aim of this investigation was to measure the growth of (y') phase during aging. In so doing, it was hoped that a clearer understanding of the aging process would be attained. X-ray line broadening was used as the measure of precipitate particle size. This technique was selected because it can measure and average the diameter of thousands of particles in one operation. The variations in hardness and matrix lattice parameter with aging were also studied and related to the particle size. EXPERIMENTAL PROCEDURE An alloy of the following composition was studied: Cr Ti A1 C Ni Wt pct 20.71 2.98 1.43 0.04 bal. At. pct 22.06 3.47 2.95 0.18 bal. The alloy, a 15- lb vacuum melt, was forged to 1/2-in. diam at a temperature of 1900" to 2200°F; was solution heat treated for 4 hr at 2000°F and water quenched; and was then aged in various ways. The ASTM grain size was 4 to 5. No (7') phase could be detected by X-ray analysis after solution treatment and electrolytic extraction. Aging was performed on 2-in. long specimens at 1400°, 1500°, and 1600°F for increasing times. One-half inch sections were removed after each time increment and were then electropolished in a solution of H3P04 saturated with chromium trioxide at a potential of 30 v and rectified with a tantalum electrode. Rockwell hardness measurements were taken using one side of the polished specimen. Matrix lattice parameter determinations were made on the other side using filtered chromium radiation references with the position of the (220) line of a silicon standard. To enable the precipitate particles of the (y') phase to be measured using X-ray line broadening techniques, it is first necessary to separate and concentrate this phase by electrolytic extraction. Extraction is necessary because the difference between matrix and precipitate lattice parameters is only approximately 0.5 pct and intensities of.the (y') phase lines are very weak relative to those of the matrix. The extraction techniques employed have been described before and found to produce a reasonably quantitative separation.398 A water solution of 15 pct H3Po4 is used at a current density of 0.5 amp per sq in. at 6 v. The precipitate particles are separated from the liquor by centrifuging and decanting and are then washed, dried and repowdered. A plot of the X-ray intensity vs diffraction angle for the (111) line of the precipitate particles was used as a measure of particle size. The intensity curve approximated the shape of Gaussian distribution function and its breadth was measured at the half height. The (220) line of a silicon standard was used to correct the measured line breadth for instrumental and other broadening errors. The Scherrer formula was used to calculate particle

Jan 1, 1961

By G. Venturello, C. Antonione, G. Della Gatta

Results from work on the effect of inferstitials on recovery and recrystallization of' very pure iron (99.995 pet) doped with nilrogen up to 400 ppm are reported. Nitrided specimens were obtained by heating the iron in a static atmosphere of NH3 + H2. The samples were cold-rolled 80 pet, subjected to a series of isochronal and isothermal anneals, and submitted to examination by X-rays, micrographs, and hardness tests. Small additions of nitrogen show a strong effect in reducing recovery of' the mechanical properties of high-purity iron. At the temperatures of. the experiments, this effect proved greater than in the case of carbon. At 400°C pure iron recovers more than 50 pet of the total hardness increase, carburized iron vecovers 25 pet, and nitrided iron only 10 pet. On the other hand. the addition of nitrogen has, similarly to carbon, a very small effect on recrystallization; the effect is, however, slightly higher than that of carbon. When the concentration Of nitrogen is above the solubility limit in a iron at the temperattue of the experiments, an increase in the frequency of nu -cleation is also observed. THE object of the present work is to improve knowledge on the effect of interstitials both on recovery and on primary recrystallization of pure iron. In fact. at present there are no available data on the effect of nitrogen on high-purity iron. The only work which at present can be somewhat related to this problem is a work of Leak et al.1 in which grain boundary internal friction at high temperature in the presence of increasing amounts of nitrogen is studied by a torsion pendulum. The present work is a continuation of a previous one2 on the effects of carbon. EXPERIMENTAL PART Preparation of the Material. Pure iron was prepared following the same methods used in the pre- vious work2 and was nitrided using controlled quantities of ammonia in an apparatus similar to that used for carburizing. The apparatus consists essentially of a gas-tight quartz tube containing the specimens. The tube, maintained at constant pressure by means of a mercury seal, is placed in a resistance furnace. For nitriding, the NH3 + H2 atmosphere with a suitable concentration of NH3 was introduced into the tube, which had been previously carefully evacuated and degassed by heating at 600°C. The hydrogen used was carefully purified by passing it through a palladium filter. The ammonia required was prepared with the following reaction: CaO + 2NH4CI —CaCl2 + H2O + 2NH3 by heating the mixture of CaO and NH4C1 in a glass flask and then collecting the ammonia in a graduated Hempel burette. For each nitriding program a given amount of NH3 prepared by this method was introduced together with the H2 into the tube previously evacuated. Nitriding of the sample was then performed at 570°C for 48 hr. After this, to ensure a homogeneous distribution of nitrogen, the samples were further heated for 72 hr at 800°C. With this method which uses a static nitriding atmosphere, carefully controlled conditions of purity are obtained. Contrarily, with the conventional continuous-flow methods, using large quantities of circulating gas, there is a greater risk of introducing impurities into the samples. Furthermore, the required nitrogen concentration in the specimen is easily predetermined and obtained. A plot of the relation observed between the initial concentration of NH3 in the gas and the quantity of nitrogen introduced into the iron samples is given in Fig. 1. The data refer to samples of 1.2-mm thickness and to the nitriding conditions previously described. Furthermore, as a comparison, the data relative to two 0.5-mm-thick samples are reported. The presence of a reservoir in the cold zone of the reaction bulb made possible the gradual dissociation of ammonia on the sample in the hot zone. Internal-friction methods were used to determine the content of nitrogen dissolved in the iron samples. Some analyses were also carried out with chemical methods. The following table, Table I, shows a comparison of data obtained with chemical and internal-friction methods. The correspondence between chemical methods and internal-friction

Jan 1, 1964

By P. A. Flinn

ALTHOUGH many physical properties of superlat-tices have been studied intensively, relatively little attention has been paid to their mechanical properties until recently. Even for the well-known transformation in 0 brass, the effect of the transformation on plastic behavior has only lately been extensively investigated.''' A partial analysis of dislocation structure in superlattices has been given by cottrel13 and his theory agrees well with the experimental results on CU3AU.4,5 His analysis, however, is implicitly limited to low-temperature effects, since it does not include the behavior of dislocations at temperatures high enough for diffusion, and hence climb, to occur. The work of Herman and Brown2 on the creep of 0 brass indicates that important effects occur under such conditions, and consequently, the theory should be extended to include them. Such high-temperature effects cannot be observed in Cu3Au, since it disorders below the temperature at which diffusion occurs at a reasonable rate. There are materials of the same structure, however, such as Ni3A1, which retain their order up to, or close to, the melting point. GEOMETRY OF THE COMMON SUPERLATTICES The two best-known ordered structures are the 0 brass type, B2, shown in Fig. 1, and the Cu3Au type, Ll2, shown in Fig. 2. In the B2 structure the (000) and (1/2, 1/2, 1/2) sites are different in that they are occupied by different types of atoms. The symmetry of the structure is then lowered from a body-centered cubic, A2, in which the sites are equivalent, with atoms located randomly in the sites, to simple cubic. This lowering of symmetry has the consequence that two types of regions may occur within a crystal: regions where A atoms are in the (0, 0, 0) sites, and regions where they are in (1/2, 1/2, 1/2) sites. The boundary between two such regions will contain bonds between like atoms, and be a surface of higher energy. These regions are known as antiphase domains and the boundary as antiphase boundary. In the B2 structure, boundary formed during the ordering process should disappear as a result of domain growth, since any domain growing to the boundary of two others will join one and engulf the other.' In any well annealed crystal, only a single domain should exist, with antiphase boundary present only in connection with dislocations, as discussed below. The L1, structure is related to the A1 (face-centered cubic) in much the same way as the B2 is to the A2. The face-center sites are occupied by A atoms, and the corner sites by B atoms. The symmetry is again lowered to simple cubic, and antiphase domains can exist. In this case, however, there are four initially equivalent sites in the unit cell: (0,0,0), (0, 1/2, 1/2), (1/2,0, 1/2) and (1/2, 1/2, 0). In the ordered structure any one may be occupied by a B atom and the other three by A atoms. Thus four types of antiphase domains can occur in this structure. This is sufficient to permit a metastable "foam structure" to exist within a crystal.''7 Antiphase boundaries along three different planes are shown in Figs. 3, 4, and 5.* *The presence of a layer of disordered material between antiphase domains, as suggested by Jones and Sykes8 does not seem likely. Such a layer would be a region of unnecessarily high energy which could readily be reduced by the formation of the type of boundary discussed here.__________________________________________________________ The notation (111) [110] means a boundary lying along a (111) plane between antiphase regions related by a 1/2 [I10] translation. It may be seen in Figs. 3 and 4 that an antiphase boundary usually results in incorrect nearest neighbors (shown connected by braces). However, as pointed out by Wilson, a boundary of the (001) [I101 type can exist

Jan 1, 1961

By G. R. Palmer

The occurrence of mercury minerals in precious metal-bearing ores has long been noted. During cyanide leaching of these gold-silver ores, some mercury forms a soluble cyanide complex, which is present in the pregnant leach solution and passes through the process operations of the cyanidation mill. As a result, mercury is found on the electrowinning cell cathodes, on the stripped carbon before It is volatilized during carbon regeneration, or in theme tailings pond. The U.S. Department of the Interior's Bureau of Mines is examining the effectiveness of two ion-exchange resins to adsorb gold and/or mercury from a cyanide leach solution. The resins, Duolite A-7 and Ionac A-305, were contacted with leach solutions containing varying concentrations of mercury, gold, and silver. The resin A-7 reached a maximum mercury loading of 0.0165 lb Hg/ft3, and A-305 reached a maximum mercury capacity of greater than 0.44 lb Hg/ft3. Adsorption of gold by both A-7 and A-305 is influenced by the presence of additional ions in the solution.

Jan 1, 1984

Crushed limestone is now being "de-dusted" at the Warner Co. plant in Bellefonte, Pa., by a new high-efficiency classifier utilizing aerodynamic principles not previously employed in classifiers. Crushed limestone for certain glass industry requirements must not have more than 10 pct fines in the overall aggregate, and it is the function of the new-type classifier to separate these fines from the coarse material. During the development of this classifier by the Buell Engineering Co. of New York, it was found to have possible applications for separating pulverized coal, sintered metals, ores, mineral flours, and fillers, among other items. Limestone from Warner's deep mine is initially crushed and particles larger than 3/8-in. mesh are burned in kilns to provide calcium oxide for the chemical industry. The 3/8-in. screenings are dried and crushed to -16 mesh for use by the glass industry. For those applications requiring a minimum of fines, no more than 10 pct -100 mesh material is allowable in the end product. Hence the need for high-efficiency separation.

Jan 11, 1960

By S. Mellgren, W. Opie

AN equilibrium state of importance in the process of electrolytically depositing titanium from fused chloride electrolytes is that which exists between titanium metal, titanium dichloride, and titanium trichloride. This can be expressed by the reaction titanium concentration of the solution, temperature, and the proportion of strontium chloride and sodium chloride in the solution. Procedure The general procedure used consisted of the following steps: 1) Development of an analytical method for determining Ti+2 and total titanium. 2) Preparation of batches of fused salt solutions containing various amounts of total titanium, Ti+2 and Ti+3 3) Blending of the prepared batches and excess titanium metal in Vycor tubes and allowing the solutions to come to equilibrium. By blending, solutions with different total titanium content could be prepared and equilibrium could be approached from the high Ti+2 and low Ti+2 sides. 4) Studying the effect of titanium concentration, temperature, and the mole ratio of the solvent chlorides, SrC1, and NaC1, upon the equilibrium.

Jan 1, 1958

By Malcolm J. McPherson, Michael Hood

Sunnyside Mines, owned and operated by the Kaiser Steel Corporation, are situated near the city of Price, Utah. The complex comprises three adjacent mines, named simply Nos. 1, 2 and 3, all connected underground. Two seams, the upper and lower Sunnyside have been worked. These dip at about 10 percent to the north-east. The surface cover is variable due to the mountainous nature of the topography. The Sunnyside upper seam varies from 5 1/2 ft (1.7m) to 9 ft (2.7m) In thickness whilst the lower seam remains at about 6ft (1.8m). The separation between the two seams has ranged from 7 to 45 ft over the mined area (2 to 14m). Longwall mining has been practiced at Sunnyside for over 20 years due to difficulties of roof control encountered when using the roan and pillar system. Number 3 mine is bounded on the north and south sides by mines Number 1 and 2 respectively. Whilst current production is concentrated into Number 1 mine, much of the future of the complex lies in the further development of deeper reserves in Number 3 mine. Workings in this latter mine were curtailed in 1978 due to difficulties in ventilation. Present developments are ventilated partially from the neighboring Number 2 mine where no workings are in progress. The layout of Number 3 mine is illustrated on the schematic Figure 1. Trunk airways extend down dip from the surface at No. 2 Canyon and the Water Canyon for a distance of some 9,600 ft. (2930m). The area between the two sets of trunk airways has been worked extensively in both seams as have the corresponding reserves on either side in the connected adjacent mines. At the present time exhausting fans are sited at the top of a shallow shaft in No. 2 Canyon and an 8 ft (2.4m) diameter shaft sunk to a depth of 1013 ft (310m) closer to the current developments (Figure 1). The current airflow system, even with an additional 116,000 cfm (55m3/s) entering from No. 2 Mine, is adequate only for the development work now in progress but will be unable to support new longwall faces further downdip. The basic ventilation problem of this mine may be stated quite simply. In a situation where all intake and return airways pass through extensive old workings, a ventilation system design was required that would be effective, efficient and economic for the foreseeable future of the mine. ORGANIZATION OF THE PLANNING PROCEDURE The procedure followed during the study is illustrated on Figure 2. Initial ventilation surveys established the current state of the airflow system and provided the necessary data for setting up a Basic Network File in a computer store. The data in this file was a mathematical model of the ventilation system of the mine. The basic network was analysed by a ventilation network analysis program in order to correlate the measured and computed airflows and to establish the basic network as a true representation of the mine as it stood at the time of the surveys. The network model could then be extended to simulate the future development of the mine and alternative ventilation designs investigated. The remaining sections of the paper outline the work involved in each of these main phases of the planning procedure. VENTILATION SURVEYS Conduct of Surveys Two types of measurements were conducted simultaneously throughout the air-carrying routes of the mine: (i) Airflow measurements were made by anemometer traverse or smoke tube at 221 selected stations. Anemometer traverses were repeated at each station until at least three gave results to within 5 per cent. (ii) Pressure drop measurements were made across ventilation doors, regulators and, wherever possible, across stoppings. Additionally, frictional pressure drops were measured along airways where such pressure drops were significant (above 0.01 inches of water gauge or 2.5 Pa over a 100m distance). The trailing hose method was used to determine these frictional pressure drops. This involved laying out 100m of abrasive resistant plastic tubing (3 mm internal diameter) with a 4 ft. pitot-static tube facing into the airflow at either end and a low range pressure gauge connected into the line. The trailing hose method was preferred to the alternative barometer technique for this study because of (a) the relative ease of access between measuring points and (b) the greater accuracy within individual airways. The anemometers used were Davis Biram Type A/2-3" (30 to 5,000 ft/min) and Airflow Developments AM-5000 digital (50 to 5,000 ft/min). The pressure gauges employed were Dwyer magnehelic instruments. These were preferred to liquid in glass manometers because of their portability and dependability under adverse mining conditions. A checklist of the equipment used in the survey is given in Appendix 1. The instruments were calibrated before and after the surveys in the mine ventilation laboratory at the University of California, Berkeley. The survey occupied two teams, each of three men, for ten working days. The work consisted

Jan 1, 1982

By R. A. Burmeister, G. P. Pighini, P. E. Greene

An open tube vapor phase epitaxial growth system has been used for large area (multiple substrate) growth of GaAs1-xPx on GaAs substrates. The GaCl-GaCl transport reaction is used with either a GaAs or Ga (nonsaturated) source. Selenium and tellurium have been used for donor impurities, and zinc as an acceptor. The useable substrate area in this system is approximately 20 sq cm. The uniformity of thick-ness of the epitaxial layers are typically better than ±5 pct across a given wafer. Electrical and optical measurerments indicute comparable uniformity in electrical and luminescent properties within a wufer. The application of this system to the large scale pro-duction of GaAs1-x Px for display devices, both discrete and arrays, is discussed. Typical electrical and luminescent properties of light emitting diodes fabricated front material produced by this technique are presented. THE most promising materials currently being utilized for visible injection electroluminescence are GaAs1-xPx, Ga1-xAlxAs, and Gap. All have reasonably efficient emissions in the red portion of the visible spectrum at room temperature; Gap also has an efficient green emission.' At present, GaAs1-xPx has a technological advantage over Ga1-xAlxAs and Gap for display applications, since relatively large (several sq cm) areas of GaAs1-xPx suitable for use in electroluminescent devices may be readily grown by vapor phase growth techniques. In contrast, the preparation of Gap and Ga1-xAlxAs for electroluminescent device applications generally employs solution growth techniques which are at present not well suited for the growth of large areas of uniform thickness and doping level. The capability of uniform growth over large substrate areas and the use of multiple substrates is necessary for the practical utilization of electroluminescent devices. This is particularly important when quantity production or monolithic devices are required. Furthermore, in many display applications arrays of light emitting devices are used, the individual elements of which are of a size resolvable by the unaided eye. Thus the overall dimensions of display are substantially larger than those of most semiconductor devices. It is also necessary to achieve a high degree of control over the growth parameters to attain the required degree of reproducibility of materials properties for electroluminescent devices. In the case of GaAs1-xPx it is necessary to accurately and precisely control the phosphorus content of the alloy, both on a macroscopic and microscopic scale, in addition to the parameters generally associated with epitaxial growth such as thickness and doping level. This value is critical, as it has a major effect on the performance of electroluminescent devices. This paper describes the epitaxial growth of GaAsl-xPx suitable for electroluminescent display devices using a system developed specifically for this purpose, and which contains several novel features. The results of studies of selected physical properties of the epitaxial layers are also discussed. Finally, a brief summary is given of the characteristics of display devices fabricated from GaAsl-xPx grown in this system. EXPERIMENTAL A) Reactants. A number of techniques suitable for the vapor phase epitaxial growth of GaAs1-xPx have been reported in the literature.'-' The method selected for this investigation is that in which the Ga is transported by the GaC1-GaCI3 reaction in an open tube process. The results reported here were obtained using either the combination of GaAs, AsC13, and pH3, or Ga, AsH3, pH3, and HC1 as the initial re-actants.* The ASH3 and pH3 were obtained as dilute *Several different sources of supply were used for these reactants, y~elding comparable results._____________________________________________________ mixtures in HZ; the HC1 was obtained from the reduction of AsC13 by Hz at elevated temperatures. Both selenium and tellurium were employed as donor impurities, and zinc as an acceptor impurity. Selenium was introduced in the form of H2Se, tellurium in the form of tellurium-doped GaAs, and zinc in the form of diethy1 zinc. B) Apparatus. The prinicipal difference between the apparatus used in the present study and that of Tietjen and Amick,8 in addition to size and other related design features, is that RE induction heating is utilized in place of resistance heated furnaces. Induction heating was selected for this application because it appears to have several advantages, including: 1) It is possible to keep all fused silica portions of the apparatus at temperatures well below those of the reaction zone, thus minimizing a possible source of contamination. 2) The thermal mass of an induction heated system can be made small, thus reducing the total time required for the growth process. 3) Sharp temperature profiles (desirable for high deposition efficiency) are easily achieved. 4) The volume of the system for a given substrate area can generally be made smaller than a comparable resistance heated unit. This results in shorter time

Jan 1, 1970

By W. H. Porter, M. E. Wadsworth, J. R. Lewis, K. L. Leiter

The oxidation of Cu2S in oxygen and the sulfating of Cu2O in oxygen-sulfur dioxide atmospheres was carried out under a variety of conditions. The oxidation of Cu2S was found to be retarded by entrapment of SO, and O2, which stabilized internal sulfates for long periods of time. The course of the reaction was followed by measuring weight changes and also by SO, evolution. Sulfating of Cu2O was a maximum at ratios of SO, to O2 approximating maximum SO, production. At elevated temperatures SO, was found to increase the rate of oxidation of Cu2 O to CuO even though sulfates did not form. All sulfating reactions followed the parabolic rate law indicating diffusion. MANY studies of the roasting of copper sulfides have been reported in recent years. Diev et al.1 investigated the roasting of chalcocite (Cu2S) in air, and oxygen enriched air. Lewis et al.2 also studied the oxidation of natural and synthetic chalcocite in air and oxygen atmospheres and their studies indicated that the maximum formation of water soluble sulfates occurred at approximately 450oC. Ashcroft3 reported that oxide production during the roasting of chalcocite resulted only from secondary decomposition of sulfates which were formed as primary products. peretti4 refuted this claim by showing that a layer of Cu2O appeared directly adjacent to the Cu2S during roasting of cylindrical briquettes of cupric sulfide, CuS. The linear advance of the Cu2S-Cu2O interface was used as a measure of the kinetics of the roasting reaction. The reactions proposed were: 2 CuS—Cu2S + 1/2 S2 [4-1] 1/2 S2 + O24 SO2 [4-2] cuzs +3/2 O2 4 Cu2O + SO2 [4-3] cu2o + 1/2 O2—2 cuo [4-4] At temperatures above 663oC, CuO was the only final solid phase reported. Below 663" C increasing amounts of sulfate were found mixed with the CuO. McCabe and Morgan5 investigated the roasting of discs of synthetic chalcocite and reported the following sequence of products beginning at the sulfide surface: Cu2O, a mixture of Cu2O and CuSO4, Cum,, CuO . CuSO4, and CuO. The principal reactions were reported to be: Cu2S + 3/2 O2-Cu2O + SO2 [5-1] CU2O + 2 SO2 + 3/2 O2—2 CUSO4 [5-21 2 CUSO4— CUO . cum, + SO3 [ 5-31 cuo . cuso4—-2 cuo + SO, [ 5-41 Eq.15-11 supports the claim of Peretti, Eq. [4-31, that CuzO is formed directly from Cu2S rather than as a secondary product from a sulfate as suggested by Ashcroft. On the other hand CuO was found to form as a secondary product from the decomposition of copper sulfate and basic copper sulfate, Eqs. [5-31 and [5-41. The formation of sulfates was explained by McCabe and morgan5 to be a direct reaction of Cu2O with 0, and SO, or SO, at distinct regions in which the partial pressures of each were such as to form the sulfate. Thornhill and pidgeon6 roasted both natural and synthetic chalcocite grains in air at temperatures between 420" and 550° C. They found a dense primary oxidation layer in contact with the sulfide. A secondary layer of porous oxidation products was found to expand with roasting time. The oxide products were leached away and the remaining core was studied by X-ray diffraction. The X-ray patterns showed an increased conversion of chalcocite to digenite with time. Digenite,7 a defect structure of cuprous sulfide, occurs naturally as Cu,-,S where x = 0.12 to 0.45, with an average analysis of Cu, ,S. The mechanism of digenite formation was proposed as: Cu2S + oxygen—Cu1-8S + 0.1 Cu2O [6-1] Cuj.eS + oxygen—0.9 Cu2S + SO2 [6-2] It is apparent from the above studies that the oxidation of Cu2S, ultimately ending in CuO, may be divided into ihree general stages (all of which may occur simultaneously): 1) primary oxidation to Cu2O; 2) secondary sulfate formation; and 3) sulfate decomposition. Consequently reactions of O2 and SO, with Cu20 constitute important aspects of the roasting of chalcocite. Virtually no studies have been made regarding sulfating reactions involving Cu,O. Mills and Evans8 noted the effect of sulfur dioxide on the oxidation of copper at low temperatures and low SO, partial pressures. They reported a measurable increase in the oxidation rate of copper when SO2, was present. Interest in the Cu2O-CuO-0, system has been limited predominantly to misciblllty studies and determinations of heats of formation by

Jan 1, 1961

By W. M. Robertson

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

Jan 1, 1969

By C. E. Lundin, M. Hansen, D. J. McPherson

PRIOR work on the Zr-Cu phase diagram by Alli-bone and Sykes,' Pogodin, Shumova, and KUGU cheva,' and Raub and EngeL3 as confined largely to copper-rich alloys. The investigations of Raub and Engel were the most recent and seemingly the most complete of these. Alloys from 0 to 68.3 pct Zr were studied principally by thermal analysis and microscopic examination. These authors reported an inter metallic compound ZrCu, (1116°C melting point) and two eutectics, one at 86.3 pct Cu (977°C mp) and the other at 49 pct Cu (877°C mp). The solubility of zirconium in copper was reported to be less than 0.1 pct at 940°C. The zirconium melting stock consisted of Westing-house "Grade 3" iodide crystal bar (nominally 99.8 pct pure). It was treated by sand blasting and pickling (HF-HNO, solution) to remove the surface film of corrosion product, resulting from grade designation tests. The crystal bar was cold rolled to strip, lightly pickled again, and cut into pieces approximately 1/32 in. thick and 1/4 in. square. These were cleaned in acetone, dried, and stored for charging. The high-purity copper (spectrographic grade) was supplied by the American Smelting and Refining Co. with a nominal purity of 99.99 pct. These copper rods were rolled to strip, cut into squares the same size as the zirconium platelets, cleaned in acetone, dried, and stored. Equipment and Procedures The equipment used for melting and annealing the zirconium binary alloys and for the determination of solidus curves has been described in connection with previous work on the Ti-Si system' and in recent papers in this series describing the studies on eight binary zirconium systems.5-' Techniques employed for preparing and processing the alloys were also similar to those used in the above references. Ingots of 20 g were melted under a protective atmosphere of helium on water-cooled copper blocks in a nonconsumable electrode (tungsten) arc furnace. The ingots were homogenized and cold-worked prior to isothermal annealing to aid in the attainment of equilibrium. The specimens were heat-treated in Vycor bulbs sealed in vacuo or under argon, depending on the temperature of the anneal. Quenching was accomplished by breaking the Vycor bulbs under cold water. Temperature control was within ±3OC of reported temperatures. Thermal analysis was primarily relied on to determine eutectic levels, peritectic levels, and compound melting points. The induction furnace incipient melting technique was also used but did not provide the accuracy obtained by thermal analysis in this system, which involves much lower solidus temperatures than the other zirconium systems. A special technique for the determination of characteristic temperatures was employed in the case of several intermediate phases and their eutectics which displayed very small differences in melting temperatures. Specimens were sealed in Vycor bulbs and annealed at a series of very accurately controlled temperatures. Metallographic examination was then employed to reveal incipient melting. Furnaces and techniques in general were described previously.' The echant used was 20 pct HF plus 20 pct HNO3 in glycerine unless otherwise stated. Results and Discussion The chemical analyses of the majority of alloys prepared for the determination of phase relationships in this system are given in Table I and a brief summary of the equilibrium anneals employed is given in Table 11. In a preliminary program, alloys containing 1, 4, and 7 pct Cu were annealed for three different times at each of the temperatures 700°, 800°, and 900°C. No change in the relative amounts of phases present was detected after 350, 150, and 75 hr at the above temperatures, respectively. The times listed in Table II were accordingly chosen as a result of these preliminary tests. Zirconium-rich alloys containing from 0.1 to 10 pct CU were reduced by cold pressing from 58 to 8 pct, depending upon thk alloy content, homogenized for 7 hr at 900°C, and then reduced 80 to 13 pct by cold rolling, again depending upon copper content. Other alloys were studied in the cast, or cast and annealed conditions. The contracted scope of investigation for this system included the range 0 to 50 atomic pct Cu. This approximate region is shown in Fig. 1. Due to evidence of phase relationships departing considerably from those proposed by Raub and Engel" in the 50 to 100 atomic pct range, the investigation was extended to cover this composition area rather thoroughly also. Fig. 2 is a drawing of the entire diagram. The labeling of some phase fields was omitted in Fig. 2 for the sake of clarity. An expanded view of the zirconium-rich region, with the experimental points necessary for its construction, is given in Fig. 3. The generally accepted value of Vogel and Tonn8 or the allotropic transformation a + 862' ±5OC, was employed in the construction of these diagrams. A careful study revealed that the "Grade 3" crystal bar used in this investigation actually transforms over the approximate range 850" to 870°C, due to impurities. It must be expected that this two-phase field in unalloyed zirconium will cause some departures from binary ideality in the very dilute alloys. Zirconium-rich Alloys: The a + ß transformation temperature is decreased from 862" to about 822°C by increasing amounts of copper. Thus, a eutectoid reaction, fi ß a+ Zr,Cu, occurs at a composition of about 1.6 pct Cu. The eutectoid level was determined to lie between the alloy series annealed at 815" and 830°C. The placement of this eutectoid temperature

Jan 1, 1954

By K. Osseo-Asare

The thermodynamics of solid-aqueous solution equilibria up to 200°C In the systems Me-NH3 H2 0 (Me=Cu, Ni, Co) are summarized with predominance area diagrams generated with the DIAGRAM computer program. The implications of the diagrams to ammonia hydrometallurgy are discussed.

Jan 1, 1981

By William E. Ford, Edward Salisbury Dana

WheweUite. Calcium oxalste CaCz04.Hz0. In small colorless monoclinic crystals. Optically +. j3 = 1.555. From haxony, with coal; also from Bohemia, and Akace. Oxammite. Ammonium oxelate, (N&)rC20r.2HzO. From the guano of the Gudape Isbnds, Peru.

Jan 1, 1922