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By K. Tangri, M. Chaturvedi

On water-quenching from within the (a + ß) phase region Zr-2.5 Nb and Zr-2.5 Nb-0.5 Cu alloys can undergo w transfirmation. This transformation has been attributed to the enrichment of ß Zr phase, at the solution-treatment temperature, by the solute atoms. The ß—w transformation is accompanied by a hardening 01 the alloys and in the optimum condition w-bearing specimens of the ternary alloy are about 14 pct harder than those bearing only a' phase. On aging crl reverls thermally to more stable phases, which results in a considerable softening of the specirnens, as follows: w quenched -waged + ß Zr (enriched) waged - a + ß Nb The high-temperature bcc ß Zr in certain zirconium alloys can transform to a metastable w phase which has a primitive hexagonal structure. In the Zr-Nb alloy system w phase has been observed in the composition range of 7 to 15 wt pct Nb by a number of investigators.'-' In this composition range w can form by water-quenching ß Zr or by aging. known as athermal and thermal w, respectively. Hatt and Roberts' have found that thermal w has a constant c/a ratio of 0.622 +0.002 regardless of the composition and tha: the lattice parameters are of the order of a = 5.02A and c = 3.0 ?. The actual lattice parameters depend upon composition and the temperature of aging. The lattice constants of athermal w. however, depend upon alloy composition.3 The presence of w phase in zirconium alloys can cause substantial strengthening which has been attributed as probably due to the coherency between w and parent ß Zr phase. Robinson et al.' found that the presence of w can raise the strength of Zr-5.0 Nb-2.0 Sn and Zr-5.0 Mo-2.0 Sn alloys to about 170.000 psi: however. the ductility is considerably reduced. With the growing use of Zr-2.5 Nb and Zr-2.5 Nb-0.5 Cu alloys in the nuclear reactors, and the significant effect of w transformation on the mechanical properties of zirconium alloys studies were undertaken to study the w transformation in Zr-2.5 Nb and Zr-2.5 Nb-0.5 Cu alloys. This paper is concerned with the formation and reversion of w phase in these alloys. 1) MATERIALS AND EXPERIMENTAL TECHNIQUES The following two alloys were studied: 1) Zr-2.5 Nb-0.5 Cu (referred to as the ternary alloy): 2) Zr-2.5 Nb (referred to as the binary alloy). The chemical analysis of the alloys is given in Table I. The alloys, in the form of 3/8-in.-diam rods and 1/8-in.-thick sheets, were supplied by the Chalk River Nuclear Laboratories of the A.E.C.L. Initial fabrication for preparation of various specimens was carried out by cold rolling and swaging with intermediate anneals at 1000°C. All the heat treatments were carried out after the specimens were wrapped in zirconium foils and encapsulated in silica tubes under a vacuum of 5 x 10-% m of Hg. For optical metallography and hardness measurements disc specimens + in. diam by + in. thick were used. After the required heat treatments the specimens were mechanically and then chemically polished in a 45 pct HNO3, 45 pct H20. and 10 pct HF solution. The hardness measurements on the chemically polished specimens were carried out on a Vickers hardness tester using a 10-kg load. For each specimen at least fifteen indentations were made in order to obtain a representative hardness value. The phase identification and structural analysis were carried out using X-rays and electron diffraction techniques. Wires of 1.5 mm diam reduced to 0.12 mm diam by chemical etching were used for making Debye-Scherrer powder patterns using copper K-a radiations in 114.6-mm-diam camera. Thin films for transmission electron microscopy were prepared by electropolishing heat-treated a by 7 by 0.005-in.-thick strips using a modified Bollmann-Window technique. The 10 pct perchloric acid-90 pct methyl alcohol electropolishing bath was kepl at -5OCC and polishing was done at 5 to 10 v. The thinned specimens were washed in ethyl alcohol at -30" to -40°C and dried between filter papers. The thin films

Jan 1, 1970

By D. C. Seidel, M. C. Fuerstenau, R. J. Roman

The existence of a surface charge on the alkali halide salts is shown, and a flotation mechanism involving surface charge and collector solubility is developed. Data suggest that KC1 is positively charged and that NaCl is negatively charged in saturated brines, and that the neutral molecule RNH,Cl is the collector in the amine-KC1 system, RSO, is the collector in the sulfonate-KC1 system, and RCOONa) is the collector in the fatty acid-NaCl system. A number of hypotheses have been advanced to explain the mechanism of soluble salt flotation; one of these involves exchange between collector ions and surface cations. With this mechanism Gaudin1 suggested that the differences in flotability of halite and sylvite with primary amines are due to the ionic size of the RNH;, Kt, and Na t ions. Fuerstenau and Fuerstenau expanded this hypothesis to include many other alkali halide salts. Several exceptions to this hypothesis are known. That is, this model does not explain why salts containing the same cation, or why salts of different degrees of hydration, respond differently to flotation. For example, why NaI is floated with an amine whereas NaI .2H,O is not. Further, no correlation between ionic size and flotation response can be made with sulfonate or car-boxylate as collectors. In addition, this hypothesis does not explain the effect of magnesium or lead activation, nor does it offer any explanation of the role of temperature in salt flotation. Rogers and Schulman3 realized some of the inadequacies of the ion exchange mechanism and proposed another mechanism based on the heat of solution of the salts. They concluded that weakly hydrated salts can be floated with alkyl amines and sulfonates, that strongly hydrated salts can be floated with fatty acids, and that excessively hydrated salts cannot be floated at all. Their work was not limited to the al-

Jan 1, 1969

By P. Chiotti, R. J. Hecht

Vapov pressure data of solid and liquid alloys along with phase diagram data WERE employed in calculating the thermodynamic properties for the Ca-Zn system. The relative excess partial molal free energy for zinc in the liquid alloys was fitted to the relation wnvre i is we tvmpvrutiirc in ucgrees neivtu ana in is the tr~ole fvaction. Relations for the standard free energy of fortnation for the eight cornpounds were developed. ThE phase diagram for the Ca-Zn system as determined by Messing et a1.' is reproduced in Fig. 1. Earlier work on the phase diagram has been summarized by Hansen and Anderko2 and the very limited thermodynamic information for this system has been reviewed by Hultgren et a1.3 The heat of fusion for the compound CaZn2 has recently been determined to be 9260 cal per mole.4 Solubility data for calcium in zinc for the temperature range of 650" to 725°C were fitted by the relation and reported by Johnson and Dilloon5 In the present investigation zinc vapor pressure data were obtained by both the dewpoint and Knudsen methods in order to calculate the thermodynamic properties for liquid and solid alloys. The dewpoint method as employed in this work requires that only one of the components be significantly volatile, in this case zinc, and that the vapor pressure of pure zinc be known. For calculation purposes the vapor pressure data for pure zinc3 were fitted to the relations; for temperatures below 692.7K, the melting point of zinc. The corresponding free-energy relations for vaporization and sublimation of pure zinc are respectively. Some of the calculations also required knowledge of the free energy of fusion of zinc and calcium and the free energy for the 721°K allotropic transformation of calcium. The free energy of fusion of zinc was taken to be the difference between Eqs. [4] and [5], or The free energy of fusion and transition for calcium were based on the enthalpy values of 2040 and 222 cal per g-atom, respectively, as reported by Chiotti et al. 4 and the heat capacity data given by Hultgren et a1.3 and are represented by the relations, In the latter expression the difference in heat capacity between the a and 0 forms of calcium was neglected. MATERIALS AND EXPERIMENTAL PROCEDURES The metals used in preparing the alloys were Bunker Hill slab zinc, 99.99 pct pure, and Ames Laboratory calcium. The average impurities in the calcium in parts per million by weight, ppm, were N-17, H—77, Ba—216, Mg-15, Si—7, C—157, and Fe—9. The zinc was cleaned in dilute nitric acid and the calcium was used as received. The calcium was stored and handled in an argon-filled glove box and when removed from the dry box it was kept in an argon-filled desiccator. Tantalum was found to be a suitable alloy container. The alloy components were contained in a 1-in.-diam cylindri-

Jan 1, 1968

By Lewis Reeve

As part of a program of investigation of the properties of electric arc welds carried out in the laboratories of the A. 0. Smith Corporation, considerable work has been done on the determination of the oxygen, nitrogen and hydrogen content of different types of weld metal, employing for this purpose the so-called "vacuum fusion method." It is the purpose of this paper to describe certain improvements that have been introduced in this method of determining the gas content of metals, with particular references to the steel specimens examined in this investigation. The method and apparatus used at the beginning of the investigation were essentially those of the Bureau of Standards as described by Vacher and Jordan.' Later a number of changes were introduced which resulted in more rapid evacuation of the graphite crucibles employed and which enabled larger volumes of gas to be dealt with than could be handled conveniently in the Bureau of Standards equipment. In addition, the analyzing of the gases evolved from a melt in the same apparatus as collected was abandoned in favor of analysis outside the equipment using standard methods of gas analysis. The time required for gas analysis in the apparatus itself, as described by the Bureau of Standards, was found to be considerable, and during this time the rest of the equipment was tied up, preventing its use for the analysis of further steel samples. As a result of the modifications introduced, the time required for the analysis of a steel sample for gas content was reduced from about 8 hours to less than 3 hours. Subsequently, the whole procedure of melting the sample and collecting the gases evolved was modified so as to enable a distinction to be drawn between the easily reducible oxides such as iron oxide and the more stable oxides such as silica and alumina. At the same time evidence was obtained indicating the probable existence in the steels of other nitrides than those of iron alone and making possible their quantitative etermination.

Jan 1, 1934

By D. C. Hilty, W. Crafts

The solubility of oxygen in iron containing aluminum has been determined at 1550°, 1600°, and 1650°C and found to be much higher than predicted from theoretical considerations, possibly due to equilibria with an iron-aluminum spinel phase rather than pure AI,O.. The presence of manganese greatly increased the deoxidizing power of aluminum. DEOXIDATION and inclusion formation in steel have proved to be elusive phenomena that are difficult to control in spite of much effort to understand and evaluate the reactions. Study of the problem indicated that more accurate data on the solubility of oxygen in iron containing deoxidizers were essential to further progress, and an empirical determination of oxygen solubilities has been initiated at the Union Carbide and Carbon Research Laboratories, Inc. The investigation has included the effects of aluminum, silicon, manganese, and combinations of these elements at 1550°, 1600°, and 1650°C. The equipment and experimental procedure as well as the results of a study of the effects of aluminum are described below. In general, it was found that the solubility of oxygen in iron containing aluminum is much higher than predicted, possibly because of the formation of complex nonmetallic phases, and that manganese greatly increases the deoxidizing power of aluminum. The generally accepted deoxidation curves for 1600°C are summarized in fig. 1, from "Basic Open Hearth Steelmaking"'. These curves are assumed to represent the solubility of oxygen in the presence of deoxidizers and should indicate the limits of mis-cibility gaps in the phase diagrams of the systems that control the formation and character of non-metallic inclusions as described by Benedicks and Lofquist'. They were derived mainly by application of the methods of thermodynamics to the available experimental observations, and by calculations based on the thermal constants of the pure substances when experimental data were lacking. Among the more notable researches contributing to the development of knowledge of oxygen solubilities are those of Korber and Oelsen8, 4, C. H. Herty, Jr. and associates5,6, Krings and Schackmann7, Went-rup and Hieber8 Schenck and Briiggeman9, Vacher and Hamilton'" and Chipman and co-authors 1,11,12,13 Practically, the deoxidation curves are of limited value in predicting oxygen content and rationalizing deoxidation practices. The reasons for this inadequacy appear to be error from inaccurate data, oversimplifying assumptions, interacting effects of combined deoxidizers, and possibly unknown extra-equilibrium and side reactions. Although inclusion formation is a very complex reaction it must be re-

Jan 1, 1951

By W. A. Backofen, G. Y. Chin, W. F. Hosford

The ductile fracturing process was studied in single-crystal and poly cvystalline aluminum deformed in tension over a temperature range from 295° to 4.2°K. At temperatures as low as 77°K, the fracture of "inclusion-free" material, including zone-refined aluminum, was by rupture (-100 pct RA). At 4.2 OK, fracture was brought on by adia-batic shear. Metallographic examination did not disclose any voids or slip-band microcracks, thus negating for inherently ductile metals any mechanism of void nucleation by vacancy condensation or of cracking due to dislocation pile-ups. In Izigh-purity aluminum not treated to be inclusion-free, fracture at temperatures as low as 45°K was of the double-cup type and a result of void formation. The reduction-of-area decreased as temperature was lowered, corresponding to the earlier appearance of voids. Such behavior was rationalized in terms of a larger increase, with decreasing temperature, in the .flow stress relative to the strength of the inclusion-matrix interface. Evidence for low-temperature adiabatic shear was found in discontinuous flow at 4.2"K, in the transition to a localized shear fracture at low temperatures, and in the suppression of shear fracture with an elastically hard pulling device. A simple analysis for the initiation of adiabatic shew permitted a general correlation of the various contributing factors. It has been pointed out that the duration of shear depends upon effective mass and elastic stiffness of the deformation system. IT has long been recognized that fracture* may Throughout this paper, the term "fracture" is taken to mean any process that results in the separation of a material into two (or more) parts. Thus rupture as it may be encountered in a tension test leading to 100 pct reduction-of-area is included in this category. occur in a ductile mode, and that the process can be of great practical as well as general interest. Much information about ductile fracture has also been accumulated over this period, but only recently has an understanding of mechanism begun to appear. Ludwik,' in 1926, first reported fracture in a tensile specimen starting with a central crack in the necked section. Since then, other studies have disclosed that such cracks may form by the coalescence of voids nucleated in this region where hydrostatic tension is highest.2-4 Rogers and Crussard et al.' have emphasized void formation and reori-entation along localized shear bands as a mode of crack propagation. pines6 has considered the tensile rod as a bundle of fibers joined by weak interfaces, which subsequently separate to allow individual fiber contraction. The notion of cavity growth and coalescence by purely plastic processes was discussed by Cottrell: who added that the tensile reduction-of-area ought not to be sensitive to temperature. On the other hand, it has been observed that the reduction-of-area is greatly increased if tests are carried out at high temperaturesa or under high hydrostatic pressure.' Fracturing anisotropy in wrought products lends support to the idea of void formation from preexisting flaws strongly aligned by earlier processing.''-l2 There is evidence that many voids result from the fracturing of inclusions or separation at the inclusion-matrix interface Another possibility is that voids grow out of pore volume produced in the initial solidification and never fully removed in later working. In general, a structure 3f particles, pores, and weak interfaces can be expected, at least in materials of engineering interest. Vacancy condensation has been suggested as an alternative mechanism of void formation for materials considered to be inclusion-free.13 Yet experience has shown that tensile reduction-of-area increases with purity, to the extreme of rupture as so often observed in single crystals. Adiabatic shear has an important bearing on ductile fracture. It occurs when the decrease of flow stress, as a result of local temperature rise from heat generated during straining, becomes larger than the increase due to strain and strain-rate hardening. As demonstrated by experiments on punching of plates,14 a large temperature rise may be brought about by rapid straining. Adiabatic flow as a result of the high strain rate reached in an ordinary tensile specimen just prior to separation may account for the cone formation in cup-and-cone fracture;14 evidence of such local heating has been presented.15 For geometrical reasons, however, pure sliding along the conical surfaces is unlikely, and separation under tensile forces is probably an important accompanying feature of the shear.7 In deformation processing operations, a high shear-strain rate may exist at boundaries between plas-

Jan 1, 1964

By John F. Elliott, John R. Rawling

The rate of reduction of silica to silicon by carbon at 1550° to 1700°C in iron blast-furnace type slag-metal systems has been investigated. In the tower portion of the temperature range oxygen transport in the metal boundary layer at the slag-tal interface is probably rate limiting. A second step, which apparently involves a chemical process in the slag at the slag-metal interface, appears to be rate limiting when the oxygen-transport limitation is avoided. Above 1650°C rate control of the reduction by carbon probably is mixed between the two steps. INVESTIGATIONS1.2 into the equilibrium distribution of silicon between graphite-saturated slags and metals typical of iron blast-furnace practice show that, under the experimental conditions specified, the reduction of silica to silicon is relatively slow compared with the rates of other slag-metal reactions under similar conditions. For this reason, the reduction of silica in blast-furnace slag-metal systems was considered to be an interesting subject for further study. Investigations of the kinetics of the reaction3-5 suggest that several possible steps may be rate controlling, and that the rate-controlling step depends not only on the physical state of the systems but also on the configuration of the apparatus. The main objects of the investigation reported here were to sug- gest plausible reaction paths for the reduction of silica under the experimental conditions chosen and to determine the step or steps which control the rate of reduction of silica. EXPERIMENTAL Two types of experiments involving the reduction of silica from the slag were carried out. In the first, the only reducing agent present was carbon (graphite), for which the over-all reaction is (SiO2) +2C(gr) —Si + 2Co(g) [l] The second type was a graphite-saturated ferro-silicon-iron concentration cell. In it silica in the slag could be reduced either by carbon according to Eq. [I], or by a reaction of electrochemical nature in which silicon was oxidized at the ferrosilicon-slag interface and silica was reduced at the slag-iron interface without the formation of CO. The two types of experiment are described below. Reduction of Silica with Carbon as the Only Available Reducing Agent. The reduction of silica was accomplished by allowing a liquid lime-alumina-silica slag and graphite-saturated iron to react in an induction-heated graphite crucible. The crucible was 2.25 in. diameter and 5 in. deep; it was fitted with a graphite stirrer which penetrated through the slag and into the metal, Fig. 1. The slag and metal charges weighed 350 g each. Pure carbon monoxide at a pressure of 1 atm was maintained above the melt by passing the purified gas through the crucible at a rate of 0.5 liter per min. The gas did not stir either the slag or metal. Temperature measurements were made by sighting an optical pyrometer down the hollow stirrer rod into a 1/4-in. hole drilled in the stirrer blade. The crucible temperature was maintained within *15"C of the required value by manual control of the power supply to the

Jan 1, 1965

By M. Baeyertr

Since 1915 many papers and books have covered industrial applications of X-rays from various angles. Two of the more recent are a paper by Fink and Archer, which describes in detail the technique of radiography, and a paper by Clark2, which embraces the whole field of X-ray metallogmphy. This paper, therefore, is confined to work of the X-ray Laboratory of the Western Electric Co., which naturally divides into two categories: radiography and diffraction patterns of various types. Radiography Radiography is the field in which the application of X-rays has had most general appeal among the industries which produce or use metals and alloys. Equipment permitting the examination of heavy sections of metals less permeable than aluminum or other light alloys requires apparatus capable of generating hard X-rays over a considerable period of time. The equipment used in the work presented in this paper is practically identical with that described by Fink and Archer in their paper on radiography in industry and is easily capable of penetrating 1/8 in. of lead. Radiography is used in two major groups of problems: (1) in the development of cquipment and tools and (2) in studies of materials. So far there has been no instance in which the use of radiography for routine inspection is justified. This is partly due to the fact that the manufacture of telephone apparatus involves the production of many identical parts by standardized procedures and equipment that has had development and trial before being put on a regular production basis. It is during this stage of development of equipment and tools that radiography has been used to particular advantage.

Jan 1, 1931

J. W. Tomlison—It seems probable that the author's conclusion, that the conductivity of the slags decreases with increasing content of FeO, is erroneous due to the method of plotting the data. Thus, the results of other workers2,3,13,15 show that the conductivity of molten oxide slags increase with increasing temperature, indicating that the trend of the curve shown by the authors is due to the fact that the data for the slags containing relatively small amounts of FeO are at higher temperatures than those for the slags containing relatively large amounts of this oxide. In this connection the work of Wejnarth2 may be mentioned in which in an investigation of a series of iron silicate slags, the conductivity was found to increase with increasing content of FeO; the fact that the author's slags contained TiO2 probably does not affect the issue since it has been shown15,16 that, at least as far as conductivity is concerned, this oxide behaves essentially the same as silica and that mixtures of the oxide with silica have a very low conductivity of the order of 10-4 mhos at 1750°C. In connection with the experimental technique it may be noted that bubbles of carbon monoxide would probably be produced at the surface of the graphite electrodes in contact with the melts thus rendering the accuracy of the measurements somewhat open to question. J. L. Wyatt (author's reply)—Dr. Tomlinson makes reference to works by Martin and Derge, which indicate that slag systems containing no TiO2 are characterized by an increase in conductivity with an increase in temperature. Further, I have cited his examples, which indicate a drastic increase with small temperature change. The results of Dr. Derge's work have no bearing whatsoever on the results of this paper, since the slags under study here contained up to 70 pct TiO2 One cannot generalize on slag systems as a whole on the basis of any one family, for there are definite compounds of ionic nature formed in each system, and the ionic mobilization of these is something that cannot be determined without actual experimentation. Dr. Tomlinson makes reference to an unpublished work which, he claims, shows that titanium dioxide behaves the same as silica in regard to conductivity. Since I have not had 'an opportunity to see the paper I cannot make any comments, but unless the same slag system was studied there can be no specific comparison of results. If the decrease in conductivity of the slag was due entirely to temperature phenomena, as Dr. Tomlinson indicates, then one is without an explanation of the values shown in the paper for slags containing from 10 to 20 pct FeO. I cannot agree that the deviation in findings was appreciably related to temperature change; further, I believe this point was completely covered in the paper. References 13 Endell and Hellbrügge: Glasstech. Ber. (1942) 20, 277. 14 Bockris, Kitchener, Ignatowicz and Tomlinson: Faraday Society. Discussion (1948) 4, 265. 15 Tomlinson: Thesis, London 1949. 10 Bockris, Kitchener, Ignatowicz, and Tomlinson: Unpublished work.

Jan 1, 1951

By E. S. Leaver

The authors of the paper above mentioned have sent the following statement to correct erroneous com-ments and implications in their article with the re-quest that it be published: "In the above mentioned article the reference to Bendelari jigs is used in the generic sense as applying to the mechanically driven diaphragm jigs. No attempt was made to dif-ferentiate between the various machines as installed on different dredges. The Natomas Company use a jig of their own manufacture. The Yuba Company installed the Placer jig as manufactured by the Pan American Engineer-ing Company. "The Pan American Engineering Company also manufactures the Crangle jig under their own name. This is a diaphragm jig in which the pulsations are produced by intermittent flow of water through the patent Crangle Valve and it has no driving mechanism."

Jan 1, 1937

By F. R. Brotzen, L. D. Whitmire

Single crystals of high-purity molybdenum were de-formed at temperatures from 195°to 473°K, and the effect of deformation on the electrical resistivily was deler-mined. To separale the resislivity components of point and line defecls some cryslals were annealed at 473°K. The vale of resislivily increase wilh strain was nearly linear and was strongly dependent upon the deformation temperature. Point dejects are annealed out without any effect on the flow stress. At low temperatures the flow stress is a linear function of the square root of the resistivity increase attributable to dislocations. ELECTRICAL-resistivity measurements have been used successfully to gain information on structural changes in metallic materials. During plastic deformation the electrical resistivity rises because of electron scattering from newly created lattice defects. Such measurements lend themselves, therefore, to corroborating results from direct observation of lattice defects and, to a certain extent, to correlating defect densities and distribution with mechanical properties. Published information on research with single crystals of the bcc metals of Group VI, particularly molybdenum, is still limited. Yet, molybdenum single crystals of relatively high purity can be readily prepared by electron-beam-melting techniques. Furthermore, some valuable information on the defect structure of deformed crystals by direct observation is available. Lawley and Gaigher,1 for example, have examined dislocation configurations in deformed molybdenum crystals by means of transmission electron microscopy. Their results revealed that the dislocation density and distribution were strongly dependent upon the deformation temperature. These findings differed from those by Keh and weissmann,2 who found that the average dislocation density in polycrystalline iron deformed between 138° and 298°K depended only on the degree of strain and not on the deformation temperature. Martin3 and peiffer4 showed that point defects introduced in polycrystalline molybdenum by cold work can be eliminated by annealing at a relatively low tempera-ture. In view of their work it became apparent that resistivity measurements of suitably annealed crystals could disclose changes in their dislocation structure and contribute to the understanding of the work hardening of molybdenum crystals. EXPERIMENTAL PROCEDURE Crystals were grown by electron-beam zone melting5,6 of 0.062-in.-diam molybdenum rods (99.99 pct) supplied by General Electric Lamp and Wire Division, Dover, Ohio. The crystals, about 4 in. long, were prepared by using five zone-refining passes at a speed of about 6 mm per min in a vacuum of about 5 X l0-6 Torr. The resistivity ratio of the crystal, p(4.Z°K)/p(273°K), was generally near 10-3. These crystals were used as tensile specimens of uniform diameter in the "as-grown" condition. They were oriented for maximum shear on the (011)[111] slip system (Schmid factor >0.49). The specimens were held in spherically seated Templin-type grips so as to minimize bending. Samples were deformed on an Instron machine at a strain rate of about 5 X 10-5 sec-1 in an isopentane bath with dry ice at 195°K, in ice water at 273°K, and in a vegetable-oil thermostat at 373° and 473°K. The temperature in the latter was maintained constant within +2°K. Resistance measurements were carried out with a Kelvin double bridge. The resistance of the potential leads was kept low by using large-diameter wires outside the low-temperature bath. Many of the resistance data were checked by measurements made with an ac bridge. Current and potential leads were spot-welded to the specimens. The distance between the potential leads, about 3 in., was also considered to be the gage length for the strain measurements. Diameter and gage length of the samples were measured optically with an error of less than 2 pct. These measurements were used also to insure that the deformation had been uniform over the gage length of the specimen. Resistivity changes were then determined from the resistance measurements at 4.2°K assuming constancy of volume. In the course of a test, the crystal diameter, gage length, and resistance at 4.2°K were determined first in the initial state and subsequently for various amounts of elongation.

Jan 1, 1968

By Frank C. Aplleyard

The two calcium sulfate minerals-gypsum and anhydrite-occur in many parts of the world, and gypsum has long been of economic importance in the family of industrial minerals. Gypsum, the dihydrate form of calcium sulfate (CaSO4•2H2O) and anhydrite, the anhydrous form (CaSO4) are frequently found in close association, and it is seldom that a calcium sulfate deposit will consist exclusively of one mineral or the other. Although known gypsum deposits are extensive, anhydrite makes up the largest part of total calcium sulfate reserves. However, it has very minor economic use, and most of the following discussion will be devoted to gypsum. Calcium sulfate is one of the principal constituents of evaporite deposits, and when pure, has the following composition: [Sulfur Combined Lime Trioxide Water (CaO) (SO,) (H2O) Gypsum 32.6% 46.5% 20.9% Anhydrite 41.2% 58.8% -] Deposits of pure gypsum or of pure anhydrite which are large enough to be considered commercial have never been found because of both the metastable relationship between the two minerals, and the presence of impurities such as calcium or magnesium carbonates, chlorides, other sulfate minerals, clay minerals, or silica. As a result most mine production of gypsum will range between 85 and 95% pure. Often it is used as mined, although in certain cases, one or more forms of mineral beneficiation are employed to upgrade the product. End Uses The largest use for gypsum is based upon the unique property which calcium sulfate has of readily giving up, or taking on, water of crystallization. With the application of a moderate amount of heat in a process known as calcining, gypsum is converted to plaster of paris (the hemihydrate of calcium sulfate, CaSO4 ½ H2O) which when mixed with water will set or harden as the calcium sulfate returns to the dihydrate form. This semifinished product, usually called stucco, is then manufactured into a large variety of plasters, wallboard, and block for construction use, or into plasters for industrial applications. About 75% of the gypsum used in the United States is calcined for these purposes. Uncalcined uses of gypsum are principally as a retarder for portland cement, as a soil conditioner, as a mineral filler, and other minor industrial applications. About 25% of the gypsum mined in the United States goes into these markets; however, in less developed countries where construction and other industrial uses may be quite limited, the use of uncalcined gypsum for portland cement retarder may well be the dominant-if not the only-market for the mineral. It has often been noted that calcium sulfate constitutes the world's largest reserve of sulfur, and minor use of both anhydrite and gypsum has been made to produce sulfuric acid or other sulfur compounds such as ammonium sulfate. However, because sulfur is readily available at lower cost from other sources, use of calcium sulfate has been limited to only a few locations where it could compete economically. No such use is reported in the United States at this time. Mineralogy Anhydrite, CaSO4 because of its geologically rapid conversion to gypsum, and relatively high solubility (about 0.2 g per 100 g H2O) is not often found outcropping in climates wet enough to support abundant vegetation except on steeply dipping slopes or other places where hydrated material is continuously removed. Anhydrite rock is most often light to bluish gray in color, and under the microscope, varies

Jan 1, 1983

By J. L. Wyatt

J. W. Tomlison—It seems probable that the author's conclusion, that the conductivity of the slags decreases with increasing content of FeO, is erroneous due to the method of plotting the data. Thus, the results of other workers2,3,13,14 show that the conductivity of molten oxide slags increase with increasing temperature, indicating that the trend of the curve shown by the authors is due to the fact that the data for the slags containing relatively small amounts of FeO are at higher temperatures than those for the slags containing relatively large amounts of this oxide. In this connection the work of Wejnarth2 may be mentioned in which in an investigation of a series of iron silicate slags, the conductivity was found to increase with increasing content of FeO; the fact that the author's slags contained TiO2 probably does not affect the issue since it has been shown15,16 that, at least as far as conductivity is concerned, this oxide behaves essentially the same as silica and that mixtures of the oxide with silica have a very low conductivity of the order of 10-4 mhos at 1750°C. In connection with the experimental technique it may be noted that bubbles of carbon monoxide would probably be produced at the surface of the graphite electrodes in contact with the melts thus rendering the accuracy of the measurements somewhat open to question. J. L. Wyatt (author's reply)—Dr. Tomlinson makes reference to works by Martin and Derge, which indicate that slag systems containing no TiO2 are charac-terized by an increase in conductivity with an increase in temperature. Further, I have cited his examples, which indicate a drastic increase with small temperature change. The results of Dr. Derge's work have no bearing whatsoever on the results of this paper, since the slags under study here contained up to 70 pct TiO2. One cannot generalize on slag systems as a whole on the basis of any one family, for there are definite compounds of ionic nature formed in each system, and the ionic mobilization of these is something that cannot be determined without actual experimentation. Dr. Tomlinson makes reference to an unpublished work which, he claims, shows that titanium dioxide behaves the same as silica in regard to conductivity. Since I have not had 'an opportunity to see the paper I cannot make any comments, but unless the same slag system was studied there can be no specific comparison of results. If the decrease in conductivity of the slag was due entirely to temperature phenomena, as Dr. Tomlinson indicates, then one is without an explanation of the values shown in the paper for slags containing from 10 to 20 pct FeO. I cannot agree that the deviation in findings was appreciably related to temperature change; further, I believe this point was completely covered in the paper. References 13 Endell and Hellbrügge: Glasstech. Ber. (1942) 20, 277. 14 Bockris, Kitchener, Ignatowicz and Tomlinson: Faraday Society. Discussion (1948) 4, 265. 15 Tomlinson: Thesis, London 1949. 10 Bockris, Kitchener, Ignatowicz, and Tomlinson: Unpublished work.

Jan 1, 1951

By CARLE R. HAYWARDC

BEFORE discussing this subject it is necessary to define somewhat the meaning of the tern metallurgical.. When I was a student at M. I. T. ore-dressing was not thought of as metallurgy in any sense of the word, but it was considered as more closely allied to mining, enabling the miner to market an otherwise unmarketable product, or at least to market it to better advantage. Progress in ore-dressing has gradually allied it more closely with smelting, for at present the raw material received by the smelter is predominantly concentrates and smelting practice has been profoundly affected by the products of the concentrating mill. It is not surprising therefore that in many schools ore-dressing is frankly considered as metallurgy and although there may be some dissenting opinions it will be considered as such in this discussion. Twenty-five years ago at M. I. T. metallography was taught in a few optional lectures. This subject has developed rapidly and been expanded into the new and increasingly important field of physical metallurgy. To many metallurgists the -term metallurgy means only physical metallurgy. They know little or nothing about smelting and leaching and even less about ore-dressing. Having then broadened the scope of the term metal¬lurgy to cover ore-dressing, smelting, leaching and phys-

Jan 1, 1930

By H. N. Eavenson

Prior to 1907 nearly all coke was made in beehive ovens, and most of the gas produced was made in the old-style gas retorts, and while there were a few coke plants in southern West Virginia, southwest Virginia and Kentucky operating on high-volatile coals the proportion of the total product made by them was small and usually was used locally. The greater part of the coke made, and the coal gas produced, came from the Pittsburgh seam of western Pennsylvania and northern West Virginia, which was then regarded as the standard coking and gas coal of the country, and the best coal available anywhere for these purposes. With the advent of the byproduct oven and the building of coke plants at the furnaces, the restriction of the use of one grade of coal for making coke was removed and the use of mixtures of low-volatile and high-volatile coals began. The change in the locations of the coke plants removed the necessity of using Connellsville coal and also made sources of gas available to the public utilities other than of their own manufacture. Most of the first oven plants were built at points distant from the Connellsville region and this afforded an opportunity for the use of coals from the southern Appalachian fields, which were then at approximately equal distances from the ovens. Since that time development has been made on a number of seams of coal of great purity in southern West Virginia, southwestern Virginia and eastern Kentucky, which have been largely used for gas, cokemaking and metallurgical purposes where low amounts of ash, sulfur and phosphorus are determining factors. These coals are much lower in the objectionable elements than most of the coal shipped from the Pittsburgh seam, or than any northern coal, and when blended with low-volntile cod produce coke in byproduct ovens that is not excelled for any purpose by any coal mined in this country, and is equaled very seldom. Coal from several of these scams is shipped in great quantities without beneficlation and is lower in ash and sulfur than any but the best washed product from the Pittsburgh seam in the north. The writer has made a study of these coals to ascertain their relative qualities and the areas and reserves of coal available in each of them. No attention has been paid to the coals of Alabama, which do not compete with any of these coals, and no coal of equivalent quality is found in

Jan 1, 1934

By George Comstock

Results are given of scleroscope and Brinell tests on specimens of cast 10-per cent. aluminum bronze, quenched and reheated at various low temperatures. The scleroscope was not found as reliable as the Brinell machine for measuring the hardness, for the size of the piece tested seemed to affect the scleroscope results. The maximum hardness was obtained by quenching and reheating to between 315° and 370° C. Softening was produced by reheating above 370° or 400° C. A series of polished and etched microsections showed a more reddish color in those that had been reheated above 400° C., and a change in microstructure above 500° C. IT HAS been known for many years that the alloy containing 90 per cent. copper and 10 per cent. aluminum can be hardened, like steel, by quenching from a suitable temperature, and that the hardened alloy can be softened again by annealing or drawing the temper. It does not seem to be generally appreciated, however, that the effect of the first slight reheating after quenching is actually increased hardness, the softening effect not taking place until a certain temperature of "drawing" has been exceeded. This paper gives the results of a few experiments on various specimens of cast 10-per cent. aluminum bronze, quenched for maximum hardness, and subsequently annealed at different temperatures. The hardness measurements were made with both a scleroscope and a standard Swedish Brinell machine; some peculiarities of the scleroscope test on this material are described. The author is not aware of many previous investigations of the hardness of this alloy when quenched and drawn, but two important papers on the subject should be mentioned. The earliest was by Portevin and Arnou,1 in which it was stated that tempering quenched 10-per cent. aluminum bronze at 400° C. increased the hardness as compared with the quenched untempered alloy and that reheating above that temperature was necessary to obtain any softening effect.

Jan 7, 1924

By C. S. Harloff, Frank R. Corwin

THE Nichols Copper Co., associated with the Phelps Dodge Corp. and the Calumet & Arizona Mining Co., has constructed at El Paso, Tex., and is now operating a copper refinery with a yearly capacity of 100,000 tons of anodes. Transportation facilities were perhaps the most important of the considerations that led to the selection of this site. The rapid industrial development of the Middle and Far West has increased the consumption of copper there. The advantage of local refining as against shipping the copper to the Atlantic sea- board is apparent. Copper refined in the Southwest is equally competitive for export shipment, either from the Gulf or the Pacific Coast ports. The tonnage of copper produced in the Southwest not only justifies the construction of this plant, but may warrant considerable expansion in years to come.

Jan 1, 1930

By M. E. Straumanis, J. -P. Krumme

In basic ([KOH + KCl] with a total polarity of 2) or acidic (2N H2SO4) electrolytes and at anodic current densities of more thun 2 to 4 ma per sq cnz, n-type GaAs single crystals of lozo resistivity preferentially dissol~je forming etch tunnels with triangular or civc~ilay cross sections and of a width between 0.5 arid 5 p. These etch tunnels are oriented along any one of the four possible (111) directions of GaAs. However, their growth occurs only in one direction of a given (111) whick apparently is determined by the atomic sequence Ga —As (and not the rezlerse) in respect to an individual valence bridge in the crystal. It is concluded from comparison with the cubic lattice structure of GaAs that the etch tunnels represent macroscopic evidence for the tetrahedral bonds and their polar properties. If the anodic current density is increased the tunnel fomation results in the development of a fibrous surface layer consisting of GaAs. The latter separates frorn the substrate (in an anodic s~irface disintegration process) by the growth pressure of an As,0, filnz forming in the interior of the fibrous layer, 100 to 200 µ under the surface, at more than about 50 ma per sq cni. The fibrous GaAs film has the same crystallographic orientation as the substvate and represents a skeleton of the original crystal. Since the etch-tunnel density in a separated GaAs layer is about 108 c?n-', and the etch tunnels develop only along (111) in a given polar direction, it is assurraed tlmt the dislocations have no influence on the growth of these tunnels. ElECTROLYTIC treatment of smooth surfaces of poly- and single-crystalline GaAs at high anodic current densities causes the formation of porous surface layers.' This phenomenon suggests comparison with effects being observed with magnesium,' indium,, gallium,4 and aluminum5 and known as "anodic disintegration". The purpose of the present paper is to explore and to explain the reasons for the formation of such surface layers on GaAs and, in particular, to investigate the influence of the lattice polarity of this III-V compound semiconductor in the (111) direction on the anodic dissolution behavior. GaAs SINGLE CRYSTALS For the experiments described below GaAs single crystals from the Monsanto Co., St. Louis, Mo., were used. Their impurity levels were below 1 ppm and their dopant levels between 1 and 100 ppm. They were grown in (111) using the Czochralski or the gradient-freeze technique. The crystals had n-type conductivity and electric resistivities between 1 and 5 ohm-cm. EXPERIMENTAL The GaAs single-crystal rods were cut perpendicularly to (111) into wafers of about 1 mm thickness using a wire-blade crystal slicer and an aqueous slurry of Sic or a diamond saw. The orientation of the faces of these wafers were checked by Laue back-reflection patterns. If there was a deviation from (111) the faces were abraded under a certain angle using grinding paper and distilled water. The damaged surface layer was removed from each crystal by chemical etching with a mixture of 1HF:1HNO3: 1H20 or 2HF:1HNO3:2HAc (glacial). {110) faces were obtained by mechanical cleavage, producing surfaces which did not require a further treatment. The GaAs wafers were mounted using "alligator" clamps instead of soldered electrical contacts.' Only the bare crystal surfaces were dipped into the electrolyte. The clamps were coated with insulating wax to prevent any contact with the electrolyte. The experiments were carried out in aqueous 2 N H2so4,' or in an aqueous solution of KOH and KCl1 (1 mole KOH + 1 mole KCl in 1000 cu cm solution). Anodic current densities up to several hundred ma per sq cm were applied for periods between 30 sec and 2 hr. For the purpose of investigating the initial steps of disintegration the anodic current density applied never exceeded 20 ma per sq cm. The films which partially separated from the anodic surfaces under high-field conditions were treated with KOH to further their detachment by dissolving the As2O3 formed. The washed and dried films were pasted to strips of filter paper, and Laue pictures were made. The back-reflection patterns obtained were compared with those of the original anode surface before and after anodic dissolution. Furthermore, space reciprocal lattices7 were constructed from asymmetric rotation crystal patternsa which permitted the determination of the crystallographic orientation of the detached films of the corrugated anodic surfaces. The disintegration products were identified from assymmetric powder patterns.8 The polarity of the {111) faces was determined by chemical etching with mixtures of 1HF:1H2O2(30 pct): 2H2O or 1HNO3:2H2O. Different patterns on each of two inverse (111) sides appeared.'-l8 The correlation of these patterns to the Ga{111) or the As(111) side has already been established by the use of light figures,18-20 by X-ray diffraction near the absorption edges of gallium and arsenic,'lmZ4 and by LEED measurements.25 The geometric structure of these surfaces and the interior of the anodically attacked crystals were observed and photographed with a high-power microscope using oil immersion objectives up to magnification of X1720.

Jan 1, 1968

By Charles Morgan

AN increased demand for brown iron ore in the Birmingham district during the past 18 months has caused renewed activity both in prospecting and mining these ores. In recent years the production in Alabama has ranged from 41,559 tons in 1932 to 639,351 tons in 1928. During the last 9 years about 83 per cent of the total brown ore produced in the United States has come from Alabama (Tables 1 and 2). PROSPECTING Two methods of prospecting are used in this district: (1) test pits, (2) churn-drilling. Usually there is certain quite definite information on an area to be prospected; some of the indications are float ore suck as small gravel or small and large boulders known as "dornicks” scattered over the surface, and ore exposed by erosion in gulleys and ravines, which have cut or eroded through the overburden. Often these natural erosions furnish an indication of the thickness of the ore and to some extent of the area of the ore body. Deposits of brown ore are very irregular both in thickness and extent. Deposits are often lens-shaped or long narrow leads, some of which may be parallel and separated from one another by sand, clay or gravel. The bottom-the footwall-is also very irregular. This footwall is usually lime clay-disintegrated limestone, locally called "white horse," which usually is found at a depth of 6 in. to 20 ft. overlying the limestone. At some places sand and gravel is found under the ore instead of clay. No ore is found under the lime clay, although often the ore has sunk or slumped and is found in the upper portion of this clay, as at some of the Sloss workings at Russellville. The origin of these ores has been discussed by Major E. C. Eckel and Dr. E. F. Burchard in U. S. Geological Survey Bulletin 400, and recently the latter has done further work on ores in the Russellville district, of which reports undoubtedly will be published.

Jan 1, 1937

Member ship L P MATHEWSON, Chairman GEORGE D BARRON LOUIS D HUNTOON JOHN A CHURCH, JR H N SPICER Alternates LEWIS W FRANCIS WILBER JUDSON F T RUBIDGE Increase of Membership JOHN A CHURCH, JR, Chairman Other members to be appointed

Jan 1, 1923