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By Herbert H. Kellogg

Graphs representing the standard free-energy of formation as a function of temperature for 21 fluorides are presented, along with estimated values for the standard free-energy of formation of 20 atedadditional fluorides. A few of the many possible uses of these data in metallurgical calculations are discussed, including the fluorination of oxides, sulphides, metallurgicaland chlorides, and the reduction of metal fluorides. RECENT papers which have presented free-energy data for oxides, sulphides, chlorides, carbonates, sulphates, and silicates in the form of free energy vs. temperature plots,1-5 have found important uses in teaching and metallurgical development work. This method of presentation of thermo-dynamic data serves to make available in readily usable form thermodynamic constants which are scattered throughout the literature, and to show by graphical means the stability relations which exist between the compounds of a given type. It is certainly desirable to have these free-energy-temperature diagrams for as many types of compounds as are of present or potential use in metallurgical processes. Thus, even though there are but few uses of metallic fluorides in extractive metallurgy today, the potential uses of fluorine processes are of great importance and serve as the principal justification of this paper. Recent developments in the production of fluoro-carbons have resulted in vastly improved methods for the production and handling of fluorine and corrosive fluorides, with consequent reduction in costs.".' The extractive metallurgist should no longer overlook possible fluorine processes when development of a new process for a relatively high unit-price metal is being considered. In a previous paperv he author outlined in some detail the importance and use of free-energy data in metallurgical calculations and also discussed the properties of a standard free-energy vs. temperature diagram. The same method of presentation is adopted in this paper, and the reader is referred to the earlier work for explanations of the use of free-energy data. Thermodynamic Data This paper presents standard free-energy vs. temperature diagrams, Figs. 1 and 2, for those fluorides for which the major thermodynamic constants are known. In the calculations of the standard free-energy of formation (AGO), values of the enthalpy of formation at 298°K (?Ho,) were taken from "Selected Values of Thermodynamic Constants"8 most of the values of standard entropy at 298°K (S°298) were taken from "Selected Values"," but in a few cases the values given by Kelley9 ere preferred; data for the Phase changes came from "selected Values" and several of Kellley's publics- tions;0-12 and most of the specific-heat data were taken from Kelley.l0 The appendix gives a detailed list of the sources of the data. As explained in an earlier paper,6 he accuracy of some of the standard free-energy relationships is not high. An error of +1 kcal at 1000°C is expected in most of the curves of Figs. 1 and 2. The error may be as high as +3 kcal in some of the curves. Rather than attempt to estimate the reliability of each curve, the source of the data used is reported in the appendix, and the reader may compare these data with newer values as they become available. Figs. 1 and 2 fail to show values for the fluorides of many important metals. In most cases this is because the entropy of the metallic fluoride is unknown. For preliminary calculations it is often useful to have available the best estimate of an unknown datum, rather than no information at all. With this in mind, Table I lists estimated standard free-energy values for a number of important metallic fluorides not included in Figs. 1 and 2. The values reported in Table I were, calculated by Brewer et al.13 and are based on estimated entropy values. The estimated uncertainty of the values for each fluoride were calculated from the uncertainty values given by Brewer1' for ?H°, and the entropy function.

Jan 1, 1952

By AIME AIME

HENRY DAYTON WILDE-"Date," informally- manager- of the technical and research department of the Humble Oil & Refining Co., was born at Aguascalientes, Mexico, Sept. 25, 1900. He is a graduate in chemical engineering: M.S. from the University of Texas and I Sc.D. fro111 the Massachusetts Institute of Technology. t For a year and a half in 1926 and 1927 he was a research : associate in the research laboratory of applied chemistry at M.I.T., under W. K. Lewis. In the latter year Dr. Wilde went with the Humble as head of the laboratory experimental division of its refining development department. In 1929 he was made director of production research. Dr. Wilde is the author of important papers in the TRANSACTIONS of the Institute, wherein are also mans dis-

Jan 1, 1938

By M. A. Bryant, J. C. Goodwin, T. B. Faddies, L. D. Kornze

The Mercur Gold Mine is located 56 km (35 air miles) southwest of Salt Lake City in north central Utah; In July 1981 Getty Mining Company made the decision to put Mercur into production. The first gold bar was poured in April 1983. This paper provides details on: 1) the history of the camp, 2) past production, 3) geology of the deposit, 4) the exploration and development program, 5) ore reserve estimates, 6) detailed geologic pit mapping, 7) production blasthole sampling techniques and 8) the use of geostatistics (kriging) in handling assays and gold extractions to produce the required mill feed.

Jan 1, 1985

By J. Alfred Berger, O. M. Katz

The Zv-Hf-H ternary system was studied between 500° and 900°C at pressures less than 1 atm of hydrogen gas between 1 and 60 at. pct H. A new and unique microgravimentric apparatus was used. Cizanges of slope on pressure-hydrogen composition isothernis delineated phase boundaries. These boundaries separatecl the three regions, a, 0, and y—so designated to correspond to the regions of the Zr-H binary system—from the multiphased areas between them. A eutectoidal decomposition was found with the ß region phase or phases decornposing into a lamellar product on quenching to rool ter,zperatuve. Reproducible decomposition-pressure hysteresis occilrved lnainly at lower hydrogen cornpositions and at lower temperatures across multiplzase vegions between a and 0 and a and y. Tire effects of hqfniur7z on the hydriding charactevistics of zirconiurrz weYe as follows: 1) stabilization of the a and y vegions while destabilizing the 0 region; 2) a/?preciable elevation of the decomposition pressrkres in the multiphase region between the a and /3 field; 3) ~nouenzent of the eutectoid reaction to high te~nperatures; 4) reduction in the total qiiantity of hydrogen absorbed under one atmospheve of Hz p7-essure; and 5) introduction of a split deconzposilion at the eiitectoiclal poinl in pa?? of the ternavy. Assuru~ptions based on an ir-2terstitial vandonl-solulion rtioclel 0.f hydrogen in metals slzowed that the bindit~g energy between solute sites prednnzinatecl at low /i?!dvogen concentrations. However, at high hydrogen contents the entropy was the predorninatlt factor in determining the stability of the Zr-Hf-H al1o.s. This was interpreted to mean a scarcity of filrtlzer itltevslilinl solute sites caused by hydrogen-hydvogen intet-actions in the metal lattice. INTEREST in the reaction of hydrogen with metals has increased in the past few years for the following reasons: 1) the formation or use of high hydrogen potential environments in nuclear reactors; 2) the reaction of hydrogen with alloys in nuclear reactors with the accompanying deleterious effects on the mechanical and corrosion properties; 3) the theoretical implications of thermodynamic data on the theory and rules of alloy formation in the metal-hydrogen systems; 4) the use of hydrogen-containing fuels in rocket engines; 5) the need for a process of making fine metal powders of high-melting reactive metals; and 6) the beneficial impregnation of superconducting alloys with hydrogen. In nuclear pressurized-water reactors, the problem exists of limiting the hydrogen pickup of zirconium alloys which are utilized as fuel cladding, heat shields, and support members. In general, zirconium alloys have good mechanical and corrosion-resistant properties in high-temperature water. However, hydrogen is absorbed from the corrosion reaction between metal and water, greatly accelerating the formation of the corrosion product ZrOz as well as mechanically embrittling the underlying metal. In addition, recent observations1 at zirconium to hafnium welds showed that secondary elements in zirconium can have an appreciable, and somewhat unexpected, effect on hydrogen absorption. This paper lists the thermochemical data in the range 500" to 900°C for the equilibrium reaction of four high-purity Zr-Hf alloys with hydrogen. Phase boundaries and thermodynamic functions are determined while the structural data will be presented in a future paper. In general, the Zr-Hf-H system approximates the well-known, eutectoidal, Zr-H diagram2,3 with modifications introduced through the behavior of hafnium.4,5 The Hf-H system,' published while this work was in progress, provided a consistent trend with the Zr-Hf-H data. PREPARATION OF Zr-Hf ALLOYS Table I presents a complete flow chart of the preparation procedure. The zirconium and hafnium crystal bars were completely immersed in high-purity kerosene and slowly cut into thin wafers. Wafers were then cold-sheared into approximately 1-g pieces, thoroughly cleaned, weighed, and inserted into the furnace. The alloys, B-2, B-4, B-6, and B-8, were then nonconsumable arc-melted under 500 mm of purified argon. Additional purification of the argon was accomplished by melting a large titanium button each time an alloy was re-melted or a different alloy melted. Each alloy button, which weighed 25 g, was remelted four times in an approach to complete homogeneity. Material losses were less than 0.02 wt pct. Alloy buttons were alternately cold-rolled and vacuum-annealed into 10- and 20-mil sheets. Table I1 gives the composition of the four alloys used. Very little elemental segregation existed be-

Jan 1, 1965

By R. E. Ogilvie, J. I. Goldstein

The a and y solubility limits in the Fe-Ni phase diagram have been redetermined at temperatures above 500°C. Both a diffusion-couple and a quench and anneal technique were used. The solubility limits were measured with an electron-probe micro-analyzer. The nickel concentration at the phase boundary is increased below 700°C and the a solid-solubility range is much larger than had been previously measured. The solubility limits are also extrapolated to 300°C. It is suggested that the solubility of nickel in a FeNi reaches a maximum in the temperature interval 400o to 500°C. THE equilibrium diagram has been of great use in the field of meteoritics, where the phase relations between kamacite (a) and taenite (?) in metallic meteorites can be described by means of the Fe-Ni diagram. The study of metallic meteorites by electron-probe microanalysis has cast some doubt on the accuracy of the presently available Fe-Ni diagrams.1, 2 Recent thermodynamic studies of the Fe-Ni system also suggest that the diagram may be in error.3 For these reasons the high-temperature (800o to 500°C) part of the diagram was redetermined. INTRODUCTION The currently accepted Fe-Ni diagram is that of Owen and Liu.4 Above 910°C, there is a region of complete solid solubility, ? (fee). Below 910°C, the a (bee) phase is stable in pure iron. The effect of increasing amounts of nickel is to stabilize the y phase. The phases that form when Fe-Ni alloys are heated or cooled bear little relation to the equilibrium diagram. If an alloy is cooled from the y state and held at a temperature within the a + y field, no evidence has been found for the occurrence of the y - a transformation.5 If the alloy is cooled to low enough temperatures the y phase breaks down into a supersaturated bee phase called a2. In fact, in alloys over 27 pet Ni the y phase is retained at room temperature.6 The a, phase has the same composition as the original y. The temperature at which a2 forms, the M, temperature, has been determined experimentally.' A state of equilibrium can be approached by cooling below M, to form a2 and then reheating the alloy into the two-phase region of the diagram. The y phase will then begin to precipitate out of the a2 phase and grow. The growth of the phase, however, is quite slow. Using the interdiffusion coefficients -Da of Goldstein et al.,8 it is estimated that it takes about 1 year to grow a 10-µ-wide region of ? at 700°C in a 5 pet Ni alloy. Owen and Liu4 used the technique just described to form the equilibrium phases. The phases present were determined by means of X-ray analysis. The accuracy of their diagram depends on the number of alloys available near the phase boundary at a given temperature. In this study two different techniques were used to determine the a/a + ? and ?/a + ? solubility limits. The inherent accuracy of both techniques was greatly improved over that used by previous investigators because the phase-boundary compositions were measured with an electron-probe microanalyzer. PROCEDURE The two methods used to determine the Fe-Ni diagram are the diffusion couple (D.C.) and the quench-and-anneal (Q.+A.) techniques. In the first method, diffusion couples whose diffusion path goes through a two-phase region of the phase diagram were used. A description of the technique used for making the diffusion couples has been described in a previous paper.' After the diffusion treatment a discontinuity in the resultant concentration vs distance profile was measured. The nickel concentrations in the a and ? phases at the interface of the discontinuity are the solubility limits of the a and ? phases in the phase diagram at the diffusion temperature. If the interface com-

Jan 1, 1965

By Hansheinz Portisch, Harold Margolin

A surface expansion was found to occur sometime after etching in Ti-A1 alloys containing 9.5 to 12.5 wt pct Al. The structure formed, grew, and disappeared with tzrrze. The surface expansion was followed by microscope observations and interferometric and lattice parameter measurements. Activation energy measurements for the growth of the "expansion structure" and chemical analysis indicated that the phenomenon occurred as a result of hydrogen pzckup during etching. It is proposed that hydrogen initially enters octahedral sites of Ti3Al coherent with a Ti and later shifts to the tetrahedral sites. It is postulated that expansion occurs when hydrogen enters the tetrahedral sites. The expansion structure disappeared, it is proposed, because of diffusion of hydrogen from the surface into the body of the alloy and because of loss of coherency of Ti3Al. In examining Ti-A1 alloys, Ence and arolinl observed markings on the surface of specimens. These markings did not appear after electropolishing only, but rather appeared only after etching. The markings appeared to grow as a function of time after etching and later seemed to disappear. Although the markings had some similarity to precipitates, showing, frequently, a Widmanstatten type of arrangement, the observation that other microstructural markings continue to be seen within the new structure suggested that it was actually not a precipitate. The source of this structure was unknown and an attempt was made in the present investigation to develop some understanding of its nature. It has been labeled expansion structure. 1) EXPERIMENTAL PROCEDURE A) Alloys. Alloys in the range 6.5 to 14.5 wt. pct A1 were studied. Bars, 4 in. sq, forged from Bureau of Mines (73 Bhn) titanium consumably arc-melted 4-lb ingots,' as well as 50-g arc-melted buttons of desired aluminum contents were used. The 50-g buttons also used Bureau of Mines titanium (73 Bhn) and aluminum of 99.99 pct purity. Buttons containing up to 8.5 wt pct A1 were hot-rolled from a furnace at 900' . Those with higher aluminum contents were hand-forged on a titanium anvil, and heated with an oxygen-hydrogen torch in the region of 1200" to 1300°c. Frequent reheating kept the samples at the desired temperature range. After a reduction of about 30 pct, the samples were water-quenched. To eliminate any contamination picked up either during hot rolling or forging, at least 1 mil of the surface of the sample was taken off. B) Heat Treatment. Prior to heat treatment all alloys were vacuum-annealed to remove hydrogen. Samples were annealed at 900' until a vacuum of 10'5 mm Hg was established. After this treatment, the samples were wrapped in molybdenum sheet and heat-treated in argon-filled quartz capsules, which were broken under water or iced brine at the conclusion of the heat treatment. All heat treatments under dynamic vacuum were performed in a rapid-quench furnace. This consisted of a molybdenum-lined quartz tube attached to a vacuum system and through a stopcock to a beaker of water. At the completion of the heat treatment the vacuum stopcock was closed, the furnace shut off, and dropped below the quartz tube. Then immediately the inlet stopcock was opened and water admitted until the tube was filled. The steam formed was allowed to escape through the inlet stopcock. This method was used in heat treatments up to llOO°C. C) Metallography. Specimens for metallographic examination were ground, then electropolished using a Disa Electropol machine with a perchloric acid electr01te. Specimens were etched with R-etch.3 A standard etching time of 3 min was used, with the specimen being agitated during immersion. D) Sample Preparation for X-ray Analysis. Samples 0.2 to 0.5 mm in diam were produced from heat-treated rods which were turned to 2 mm diam on a lathe and then rotation-etched. An etchant consisting of 1 pt HF, 7 pt HN03, and 12 pt HzO was satisfactory. With the rod rotating in a vertical position at 50 to 100 rpm, a needle with uniform dimensions could be obtained. Care had to be taken to insure that the rod was at the center of rotation, otherwise cavitation developed. If a small unevenness developed, it was possible to grind it off with a fine emery paper. E) X-ray Diffraction. All X-ray work was done on a North American Phillips X-ray diffraction apparatus and a Jarrell Ash microfocus X-ray unit. The Phillips unit was used with a copper target and nickel filter. The Jarrell Ash unit was fitted with a cobalt target and iron filter. For the Phillips unit 35 kva and 20 ma were used, whereas for the microfocus unit with the 100-p fixed-focus gun 40 kv and 1.5 ma were used. It was found that alignment of cameras on the Jarre11 Ash unit was very critical. The X-ray beam contains an intense area which is not the beam center. The cameras were aligned with the intense region by monitoring the beam coming out of the camera with a Geiger counter. Adjustments were made until a maximum intensity was obtained. A Phillips diffractometer with a Brown chart recorder furnished some of the lattice parameter data. The divergence slit up to 80 deg 28 was I deg; above 80 deg, a 4-deg opening was used, while the scatter slit was1 deg and the receiving slit had a 0.003-in. opening. The general scanning rate was 1 deg per min, while peaks of special interest were rescanned at -j deg per min. For elevated-temperature X-ray diffraction a Uni-cam High Temperature Camera with a film diameter

Jan 1, 1969

(Members are urged to send in for this column any notes of interest concerning themselves or their fellow-members.) Members and guests who registered at Institute headquarters during January: A. Neustaedter, Jersey City, N. J. William Jones, Kent, England. A. J. Sweetser, Boston, Mass. Percy E. Barbour, Candor, N. C. Algernon Del Mar, Los Angeles, Cal. Herbert S. Kohlberg, El Paso, Texas. W. B. Cogswell, Syracuse, N. Y. I. N. Knapp, Ardmore, Pa. R. E. Chambers, New Glasgow, N. S.

Jan 2, 1914

By F. O. Garrabrant

POWER is furnished to the Climax Molybdenum Co. by the Public Service Co. of Colorado over two 100,000-volt line to a bank of three 3333-kva. Transformers 100/13.8 kv. These transformers arc so designed that with the addition of forced cooling their capacity may be increased 33 1/3 per cent at 12,000-ft. altitude. Under present conditions, these transformers are operated at 140 per cent of their rating with forced air cooling. On the secondary side of this bank there is a 15-kv., 1200- amp. Westinghouse oil circuit breaker provided with automatic reclosing relays allowing three successive short circuits before lockout. From this breaker 13.8-kv. power is transmitted to a central switching station (Fig. I) where all circuits radiate to the different operations of the property. Each circuit is protected by a 23-kv., 600-amp. oil circuit breaker with by-pass and isolating disconnecting switches. MINE Power at 13.8 kv. enters the mine through a ventilation raise over a three-conductor, size 1-0 varnished cambric insulated, leaded, steel-wire armored cable, insulated from 17 kv. This power is received and distributed through one switching station and four underground substations, shown in Fig. 2. No. 370 substation (Fig. 3) contains three 250-kva, 13,800/440-volt, single-phase Pyranol transformers protected on the high-voltage side by a 600-amp. manually operated oil circuit breaker. This station serves 20 slusher-hoist motors, a 45-kw., three-phase, 220-volt electric furnace, a Massco hot miller for tempering and milling Timken detachable bits and a hoist with 175-hp. motor on the No. 3 development shaft. Also at this shaft are three pumps. One two-stage pump, 1200 gal, per min., 100-ft. head, 3600 r.p.m., driven by a 150-hp. motor, is at the bottom of the shaft. Two deep-well pumps, 500 gal. per min., 500-ft. head, are at the collar of the shaft. Under normal operation the one pumping 1200 gal. per min. is controlled by a float switch to take care of the water. If this pump fails, or if its capacity is insufficient, the first 500-gal. pump is automatically started, and if still more capacity is needed the second 500-gal. pump automatically starts. Time delay relays are provided on the deep-well pumps, so that if power fails the column will have time to drain before the pumps restart. On failure of any of these, an alarm is sounded in the train dispatcher's office, so that mechanics can be sent to ascertain the cause of failure and make repairs. The cable from No. 370 substation is run to the switching station, in which are four15-kv., 600-amp. direct-current solenoid-operated oil circuit breakers. The current for operating and tripping is furnished by a 125-volt storage battery. All breakers are operated from the switchboard in the compressor room. One circuit from this switching station goes to the

Jan 1, 1944

Discussion of the paper of K. Huessener, (Trans., vol. 53, pp. 402 to 4333, and of the papers of Linn Bradley, H. D. EGbert and W. W. Strong, pp. 303, 319. R. J. WysoR, So. Bethlehem, Pa. (communication to the Secretary*). —At our plant (Bethlehem Steel Co.), we have had several Bradshaw burners under course of construction and erection for some time, but up to the present we have not had opportunity to put them in service. I regret that I can not take part in the discussion with some actual results from these burners. Mr. Huessener properly emphasizes the importance of obtaining the highest combustion temperature practicable in boiler practice, which demands a near approach to perfect combustion conditions. The ideal burner is the one which, while meeting the various mechanical requirements, fulfills the above condition under a wide range of gas pressure. The question as to the relative value of hot raw gas and cold washed gas for boiler use is a very interesting one. I think that in the past the importance of low temperature of washed gas sometimes has been overemphasized. Mr. Huessener has pointed out that so far as temperature is concerned, no advantage accrues in washing gas below 100" F. In many plants, there is a notable operating economy in using furnace cooling water, which is appreciably warmer than the supply water. However, in a given type of washer, other conditions being constant, the lower the exit gas temperature the lower will be the dust content; this is equivalent to saying that the more washing water is used, other conditions being constant, the lower will be the dust content of the exit gas. For each type of washer there is a certain desired average temperature difference between inlet water and exit gas, concomitant with known average dust and moisture contents, and with economical operation. With the present tendency toward smaller stove checkers, it is generally agreed that gas for stove use should be cleaned to a dust content of 0.20 grain or less. The method employed and extent of gas cleaning are clearly problems for individual furnace plants. As a general proposition, wet washing is decidedly more attractive for furnaces smelting soft, fine Lake ores than for those reducing chiefly hard, lumpy ores, such as the foreign and domestic magnetites. In the former case the average moisture content of the gas is probably 35 grains per cubic foot, the dust content is relatively high and the top temperature relatively low. In our plant, the ore mixtures consist almost exclusively of hard magnetites. The average dust content of the gas leaving the dust catcher will average only about 2 grains and the moisture about 12 grains per cubic foot, corresponding to saturation at about 83" F. The temperature is fully 100" F. higher

Jan 1, 1917

By C. R. Simcoe, T. J. Koppenaal

The effect of direct and alternating currents on the quench aging behavior in an Al-4 pct Cu alloy has been investigated by use of resistivity measurements. The reaction rate increases with direct current density in the investigated range of 1000 to 3000 amps per sq cm. Alternating current of a specific frequency is observed to decrease the reaction rate by a factor of about two. ErDMANN-JESNITZER et al.,1,2 investigated the effect of direct and alternating current on the quench and strain aging behavior of low-carbon iron. In both cases they observed that direct current accelerates the aging reaction and that an alternating current can completely inhibit the aging process. The purpose of the present research was to investigate these phenomena in the quench aging behavior of an Al-4 pct Cu alloy and to determine the correlation, if any, between the increase in the observed reaction rate and possible heating effects accompanying the aging with direct current. EXPERIMENTAL PROCEDURE The aluminum-base alloy used in this investigation contained 3.98 wt pct Cu (1.72 at. pct) with impurities of 0.003 pct Si, 0.002 pct Fe, and 0.001 pct Mg. The alloy was rolled into a ribbon about 0.36 mm thick and 3.7 mm wide. The ribbon was split end from end with the ends being used as electrical contacts and the central unsplit section, about 5.3 cm in length, serving as the specimen. Solution treatment was accomplished by quenching from a salt bath at 520° ± 2°C into water at 25° ±0.5°C; the specimen was immediately transferred to a liquid nitrogen bath. All aging was done at 75° ± 0.2°C in a rapidly stirred ethylene glycol bath. Resistivity measurements were made by the double potentio-metric method employing a standard resistor; for purposes of convenience, the resistance measurements were made at 77°K. The transfer of the specimen from the aging bath to a liquid nitrogen dewar was accomplished in less than 1 sec. The aging kinteics were studied with the specimen being aged under the influence of direct current, alternating current, and without any type of current. The amount of heating caused by direct currents was investigated by soldering a thermocouple on the specimen surface and measuring the temperature change after applying various current densities. The temperature was observed to increase (from 75°C, the aging temperature) about 0.8°, 3.0°, and 8.5°C with direct currents of 1000, 2000, and 3000 amp per sq cm, respectively. When employing alternating current, the circuit was monitored with an oscilloscope and adjustments made to produce a normal sine-wave pattern. RESULTS Prior investigations3'4 in the aging characteristics of A1-4 wt pct Cu have shown that the resistivity initially increases, reaches a maximum, and then decreases to values significantly lower than the as-quenched resistivity. This type of behavior is seen in Fig. 1 which shows the resistivity at 77°K as a function of aging time at 75°C observed in this investigation. At this aging temperature, the resistivity maximum is seen to occur in about 1 to 1-1/2 min and it further decreases to the as-quenched value in about 24 min. The behavior observed with the application of direct currents of 1000, 2000, and 3000 amp per sq cm during aging is shown in Fig. 2. With increasing current densities, (+) ?pmax decreases and the rate of the aging process increases. The time necessary to reach the as-quenched resistivity value decreases from 24 min for aging without current to about 16, 10, and 7 min for aging with 1000, 2000, and 3000 amp per sq cm direct current, respectively. Fig. 3 shows the results obtained when two changes were made during the aging with 2000 amp per sq cm

Jan 1, 1963

By T. H. Alden, H. W. Schadler

The strain rate dependence of the flow stress of the eutectoid Zn-Al alloy has been determined as a function of mechanical processing, microstructure, and temperature. The best superplastic properties result from the ultrafine, equiaxed structure produced by solution treatment and isothermal transformation at 0°C. Lamellar structures produced by isothermal transformation and coarse equiaxed structures produced by annealing also exhibit strain rate sensitivity in excess of 0.5, but at higher stresses and lower strain rates than the finest structure. Solution treatment and isothermal transformation eliminate the effect of prior processing history. Small composition variations in the binary alloy do not influence the mechanical properties. Below the eutectoid transformation temperature (.275C) increasing temperature lowers the flow stress at all strain rates. The data do not favor any of the present proposals for the mechanism of superplastic flow. ALLOYS of zinc and aluminum, near the eutectoid composition, have been investigated for: 1) the flow stress-strain rate and elongation behavior,1, 2) the transformation kinetics,3 and 3) structure,3"5 but the structure sensitivity of the mechanical properties is poorly understood. Using a near eutectoid alloy water-quenched from 380°C, Backofen et aL2 estab- high and increases with increasing strain rate. They found a correlation between strain rate sensitivity and tensile elongation as expected from the increased resistance to necking that a high strain rate sensitivity provides.296 The large elongation at high strain rates is attractive for metal forming. Since most other superplastic alloys7-l3 do not show high strain rate sensitivity at such a high strain rate (for the exception see Ref. 12) there is the possibility of a unique deformation mechanism for this alloy. The sensitivity of the mechanical properties of the eutectoid alloy to thermal history1 suggests a structure sensitivity that has not been demonstrated. Gar-wood and Hopkins3 identified a lamellar product for material transformed between 200" and 260°C. The size of the lamellae decreased with decreasing temperature. They also demonstrated that an unresolved transformation product formed below 200°C. A granular two-phase material was resolved for specimens quenched to below 150°C by Mitbauer and sauerwald4 who observed coarsening of the structure after annealing. The role of grain boundaries in superplastic deformation is suggested by the strong effect of grain refinement in encouraging this phenomenon at high strain rateS7-11, 13 and is emphasized in several proposals about rnechanism7, 8, 12 and in a theory14 of high-temperature deformation. Alden8 showed metallographic evidence that grain boundary sliding is occurring extensively at strain rates where m is large but less at high strain rates where normal plasticity is observed. Holt and Backofen10 have shown that sliding also oc-

Jan 1, 1969

By Huey-Lin Luo, T. R. Anantharaman, William Klement

Two new metastable phases have been obtained in Au-Ge alloys by rapid cooling from the melt. One is of the hep structure with near-ideal axial ratio and may be considered a Hume-Rothery phase. The other has a complex tetragonal structure (a = 11.627Å and c = 22.191Å for the Au60Ge40 alloy) and may be looked upon as a superlattice made up of forty-four fee unit cells. Alloys with the tetragonal phase are charactevized by marked preferred orientation. The metastable constitution of the Au-Ge alloys is discussed with reference to the rate of cooling from the melt. THE Au-Ge equilibrium diagram features a rather deep eutectic near 27 at. pet Ge with a maximum solid solubility of 3.2 at. pet Ge in gold and is similar to the Ag-Ge, Ag-Si, and Au-Si diagrams.' The present study of the effects of rapid cooling from the melt on the structure of Au-Ge alloys constitutes an extension of similar investigations2-8 in this laboratory on alloys of noble metals with germanium and silicon. Nonequilibrium hep structures have so far been obtained by quenching Ag-Ge2, 3 and Ag-Si4, 5 alloys from the melt; an Au-Si alloy of approximately eutectic composition has been found6 to solidify in a noncrystalline state. EXPERIMENTAL PROCEDURES Twenty-nine alloys prepared from gold of 99.9+ pet and germaium of 99.999 + pet purity were investigated. The method of alloy preparation, the technique of rapid quenching from the melt, and the X-ray diffraction procedures were similar to those described previously.3, 4 Essentially, small sections (-20 mg) of thin alloy rods (-1 mm diam) were rapidly heated up to 1200°C in a graphite crucible under argon and the liquid alloy ejected by a helium blast onto a polished copper strip held on the inner periphery of a rotating wheel. The resulting thin foils were examined with or without the copper substrate in a G.E. X-ray Diffractometer or in a 114.6-cm-diam Debye-Scherrer camera. RESULTS Table I gives the constitution of liquid-quenched Au-Ge alloys, as estimated from intensities of X-ray reflections from the corresponding phases, viz., a (fee solid solution), ß (hep phase), ? (tetragonal phase), and diamond-cubic (dc) germanium. Despite unavoidable variations in the quenching rates, the proportions of the phases in different alloys were generally reproducible and stable at room temperature. There was no evidence of quenching strain, since the a doublets were well-resolved in high-angle Debye-Scherrer reflections in all cases except where stacking faults in the a fee and ß hep structures contributed to X-ray line broadening. The ß and ? metastable phases showed signs of decomposition to the equilibrium a phase and germanium only after a few hours annealing above 100°C. A few alloys around the eutectic composi-

Jan 1, 1965

By N. J. Grant, D. S. Bloom

N recent reports, Sully' and Beck and coworkers' I have advanced hypotheses concerning the formation of the phase. Both of these hypotheses are based on Pauling's theories of the electronic configuration of the elements of the first transition group. Sully considered that the number of electrons which can be absorbed in filling electron "holes" is the factor which determines whether or not the structure can form. Beck suggested that the presence of a certain concentration of electron "holes" is the controlling value. It can be shown that a similar criterion can be developed without making reference to Pauling's theories. Table I shows the elements of the first transition group and the incidence of the a structure in the binary systems of these elements according to the data presently available. Also appended is the number of electrons considered to exist in the 3d-4s levels of these elements. If the atomic percentages for the phase are listed as shown in Table 11, and if the number of electrons in the 3d-4s levels per atom is calculated for the a boundary values, the results are as shown in the last column. It can be seen that the numerical values are all in the vicinity of 7 electrons per atom. This is true also for the ternary Cr-Mo-Ni IT phase, which occurs in a system in which none of the binary compositions are known to develop the phase. In the Fe-Mo binary, the high temperature a phase, which occurs at a composition of 50 atomic pct of each element, also yields a ,;1 e of 7 electrons per atom. From inspection of Tables I and 11, it develops that any series of sequential numbers which is assigned to the elements under consideration will result in the numbers pertaining to a compositions grouping themselves around one specific number. It does not follow, however, that this random number necessarily has physical significance. Such a point has already been discussed by Hume-Rothery." One interesting point develops from this study, however, and that is the position of manganese with reference to the other elements and to the phase. In the system used here, the formation of phase is associated approximately with the value of 7 electrons per atom, which is also the number of electrons per atom that manganese has. Manganese, it will be recalled, exists in three different crystal forms, none of which are the usual, simpler metallic forms; on the other hand, elements just to the left of manganese (in Table I) generally have lower coordination-number structures (body-centered cubic) than do elements to the right of manganese (face-centered cubic). The contribution to a complex crystal structure by the interalloying of elements from opposite sides of manganese is significant in that the a phase is formed in binary systems including one element from each side of manganese, with manganese capable of participating with both sides. It is indeed an interesting coincidence that manganese, with 7 electrons per atom, solidifies in complex crystal forms, and that when alloys of the transition elements are made which have seven 3d-4s electrons per atom, they, too, tend to assume a complex crystal form. From the above, it might be deduced that the study of the a phase might be advanced by a critical examination of the element manganese and how its structure is affected by small additions of elements which change the 3d-4s electrons per atom number. The role of atom size would also be of interest in formation. References ' A. H. Sully: The Sigma Phase in Binary Alloys of the Transition Elements. Journal Inst. Metals (1951) 80, Part 4, p. 173. 2 S. Rideout, W. D. Manly, E. L. Kamen, B. S. Lement, and P. A. Beck: Intermediate Phases in Ternary Alloy Systems of Transition Elements. Trans. AIME (1951) 191, p. 872; Journal of Metals (October 1951). "W. Hume-Rothery, H. M. Irving, and R. J. P. Williams: The Valencies of the Transition Elements in the Metallic State. Proc. Royal Soc. (September 1951) 208A. p. 431.

Jan 1, 1954

By Joseph C. Kieffer

The Duquesne property of the Callahan Zinc-Lead Co. is about 20 miles east of Nogales, in southern Arizona. One mine is near the mill, but most of the mill feed is hauled in by truck from a number of small mines. The same sulphides are found in all the ores, in general, but the amounts vary considerably. All ores contain silver, copper, lead and zinc minerals but one mine ships ore high in silver and lead and low in copper and zinc; while another mine ships ore high in copper and zinc, and low in silver and lead. The common sulphides are galena, carrying most of the silver; chalcopyrite; sphalerite, carrying iron in solid solution; and pyrite, in a gangue consisting of limestone, quartz and garnet. Mineralization is fairly coarse. At the present grind of about 66 per cent minus 200 mesh most of the sulphides are liberated A small amount of chalcopyrite is locked up with the sphalerite and cannot be liberated at an economic grind, and the copper carried into the zinc concentrate with the sphalerite accounts for the comparatively poor recovery of copper in the copper-lead concentrate. Production oF Two Concentrates The milling problem, which was complicated by the extreme variation in the grade of the feed, was first attacked with the idea of producing a silver-copper-lead con- centrate and a zinc concentrate, both with satisfactory grades and recoveries. By February 1941, it was felt that these objectives had been attained, when the grades of the various products and the recoveries were as shown in Table I. A rough outline of the flowsheet and reagents used is as follows: Minus ¾-in. feed to a 7-ft. by 36-in. Hardinge ball mill working in closed circuit with a 36-in. Wemco classifier. The classifier overflow passes to the second cell of an 8-cell bank of No. 18 Special Denver Sub-A flotation machines (volume, 22.5 cu. ft. per cell). A rougher concentrate is removed from the second to the fifth cells inclusive, and returned to the first cell, which is the cleaner. A scavenger concentrate is removed from the sixth, seventh, and eighth cells, and returned to the third cell. Consump-

Jan 1, 1943

By Joseph C. Kieffer

The Duquesne property of the Callahan Zinc-Lead Co. is about 20 miles east of Nogales, in southern Arizona. One mine is near the mill, but most of the mill feed is hauled in by truck from a number of small mines. The same sulphides are found in all the ores, in general, but the amounts vary considerably. All ores contain silver, copper, lead and zinc minerals but one mine ships ore high in silver and lead and low in copper and zinc; while another mine ships ore high in copper and zinc, and low in silver and lead. The common sulphides are galena, carrying most of the silver; chalcopyrite; sphalerite, carrying iron in solid solution; and pyrite, in a gangue consisting of limestone, quartz and garnet. Mineralization is fairly coarse. At the present grind of about 66 per cent minus 200 mesh most of the sulphides are liberated A small amount of chalcopyrite is locked up with the sphalerite and cannot be liberated at an economic grind, and the copper carried into the zinc concentrate with the sphalerite accounts for the comparatively poor recovery of copper in the copper-lead concentrate. Production oF Two Concentrates The milling problem, which was complicated by the extreme variation in the grade of the feed, was first attacked with the idea of producing a silver-copper-lead con- centrate and a zinc concentrate, both with satisfactory grades and recoveries. By February 1941, it was felt that these objectives had been attained, when the grades of the various products and the recoveries were as shown in Table I. A rough outline of the flowsheet and reagents used is as follows: Minus ¾-in. feed to a 7-ft. by 36-in. Hardinge ball mill working in closed circuit with a 36-in. Wemco classifier. The classifier overflow passes to the second cell of an 8-cell bank of No. 18 Special Denver Sub-A flotation machines (volume, 22.5 cu. ft. per cell). A rougher concentrate is removed from the second to the fifth cells inclusive, and returned to the first cell, which is the cleaner. A scavenger concentrate is removed from the sixth, seventh, and eighth cells, and returned to the third cell. Consump-

Jan 1, 1943

By William Sellers

tested without knowing anything of their chemical composition. I had these pieces separately placed upon 10-inch bearings under a 7-gross ton lianlrner, a piece of 2½-inch round iron laid upon them as a fuller, and the hammer allotved to fall from 20 inches above the fuller, which, according to Haswell, gave a ldow of 67.75 gross tons. The pieces were then turned orcr, the fuller placed upon the convex surface, and the harnnler allowed to fall from 13 inches above the fuller, giving a blow of 58.46 gross tons. You will see that the rails do aot show ally bigrls of ruptnre, and their color at the points of torture prove them to have been absolutely cold when the test was made. I thirk these rails ought to be reasonably safe in the track. As you see by this piece of the head of one of these rails, I had it plarred, and then some teeth cut in it by a cold clrisel, and one-half of them pounded down with a hammer. The teeth of my rack did not break off. The analyses of these rails substquently made are: I. 11. Carbon,... 0.110 0.880 Silicon,..0.050 0.058 Phosphorus ,..0.086 0.082 Manganese,.. 0.042 0 840 In conclusion, I will say that Dr. Dudley's paper as a contribu tion to our knowledge of steel rails is valuable and interesting, but I protest against his conclusions king reoeived as manufacturing or comtnercial axioms. From its being presented in the form-of a report to the leading railroad of the country from one of its trusted officers, as well as from the tone of the concluding deductions, it is liable to be so received by railroad men. If any railroad com pany desires rails made under either of Dr. Dudley's formulas, and are willing to pay a price large enough to cover the loss in making them, dl and good; but so long as the rail makers are compelled to gwrrantee the wear of their rails for a given number of years, justice reqnires that. the composition of the steel from which these rails are made should be left to them. WILLIAM SELLERS, PHILADELPHIA: The very interesting paper upon the wear of steel rails that has just been read preseak the record of a series of investigations that are extreniely valuable, and the deduction that bas been drawn from the results noted seems to be unavoidable; the tests, however, to which it is proposed steel rails shall be subjected hereafter, with a view to determine their quality, sllould

Jan 1, 1881

By E. M. Wise

IT is known qualitatively that the recrystallization behavior of platinum is dependent upon the amount and particularly the nature of impurities present, the amount of prior cold-work and the annealing time and temperature, but published data are limited. A study of the effects of cold-work and annealing temperature on the hardness of a sample of very pure platinum was undertaken to supply part of this information. CONCLUSIONS 1. The platinum used in the experiments had a probable platinum content of 99.99+ per cent, and had the following mechanical properties in the completely softened condition: Vickers hardness number, 39.4; ultimate tensile strength, 19,340 lb. per sq. in.; proportional limit, very low; elongation, 37.5 per cent in 2 inches. 2. The effect of cold-rolling on the hardness is shown in Fig. 1. The hardness increases rapidly up to 10 to 15 per cent reduction and more slowly up to about 75 per cent reduction, beyond which it increases more rapidly. 3. The recrystallization temperatures for a 15-min. anneal, after cold-rolling 19, 39.5, 50.8, 66, 80.5 and 89.5 per cent reduction in thickness, are approximately 765°, 700°, 635°, 600°, 545° and 425°C., respectively. 4. The recrystallized grain size of this platinum is a function of the percentage of cold reduction, being larger the lower the percentage of cold-work. 5. Little or no grain growth resulted from subjecting recrystallized samples to higher temperatures or annealing for longer times.

Jan 1, 1940

By M. E. Tyrrell, Alan H. Goode

The application of a simple, two-dimensional computer technique for evaluating rock burst potential in cut-and-fill stopes was investigated. The principal purpose of the study was to compare the effectiveness of high-modulus fill and destressing as aids in the control of rock bursts. Two conclusions that are probably of general applicability are drawn. First, high-modulus fill is ineffective as a means of increasing the mine stiffness and acts to control rock bursts only if it supports enough load to reduce substantially the stresses on the unmined vein material. Second, destressing is most effective if it is performed when the vein material is near the point of failure.

Jan 1, 1975

By W. L. Hill, W. H. Armiger, S. D. Gooch

The physical properties, chemical behavior under thermal treatment, and fertilizer value of fluorine-containing pseudowavellite (hydrous calcium aluminum phosphate) that occurs as phosphate clay admixed with quartz sand in an extensive deposit near Bartow, Fla., were determined by experiments in laboratory, pilot-plant, and greenhouse. When the mineral was heated at 500°C, 80 pct of the phosphorus become citrate soluble. The heated product, however, deteriorates markedly under moist conditions such as obtain in the soil. EXTENSIVE beds of a soft aluminiferous phosphate lie in the Bartow-Pembroke region of Florida. Although the extent of the deposit is unknown, it is thought that the equivalent of at least five million tons of material containing 25 pct P,Os exists on one large mine property alone, and soft phosphates similar in nature are known to occur elsewhere in the state. This aluminum phosphate, unlike fluorapatite, is rendered fairly soluble in neutral ammonium citrate solution merely by heating it at a temperature below 600 °C, a property made the basis of a process patent by the junior author.' The possibility of producing an available form of phosphorus from what has hitherto been a worthless natural phosphate prompted the Bureau of Plant Industry, Soils, and Agricultural Engineering to make a brief study of the Pembroke phos- phate during the war years with a view towards determining the optimal temperature for heat treatment and the reactions involved in the process. The results of this study supplemented by data and information furnished by the junior author are presented in this paper. Description of Natural Phosphate: The phosphate with admixed quartz sand and siliceous matter occurs as a low-grade (8 to 9 pct P2O5) clay-like material that can be beneficiated cheaply by making a water separation of the very fine material from the sand, floating off the fine material, settling the suspension to a thick slurry, and finally de-watering the slurry by vacuum filtration followed by drying. The product dried at 100 °C contains about 16 pct water and 25 pct P2O5, about 1/12 of which is citrate soluble. Partial analyses of representative samples of the crude ore and corresponding concentrate are given in table I. The concentrate is light yellow in color and even after being dried at 100°C sticks very noticeably to laboratory grinding and screening equipment. Under the microscope the ground material is predominantly light brown crystalline aggregates with index of refraction near 1.61. The principal phosphate mineral constituent was identified as pseudo-wavellite with admixed phosphosiderite.2 Pseudo-

Jan 1, 1951

By W. L. Hill, W. H. Armiger, S. D. Gooch

The physical properties, chemical behavior under thermal treatment, and fertilizer value of fluorine-containing pseudowavellite (hydrous calcium aluminum phosphate) that occurs as phosphate clay admixed with quartz sand in an extensive deposit near Bartow, Fla., were determined by experiments in laboratory, pilot-plant, and greenhouse. When the mineral was heated at 500°C, 80 pct of the phosphorus become citrate soluble. The heated product, however, deteriorates markedly under moist conditions such as obtain in the soil. EXTENSIVE beds of a soft aluminiferous phosphate lie in the Bartow-Pembroke region of Florida. Although the extent of the deposit is unknown, it is thought that the equivalent of at least five million tons of material containing 25 pct P,Os exists on one large mine property alone, and soft phosphates similar in nature are known to occur elsewhere in the state. This aluminum phosphate, unlike fluorapatite, is rendered fairly soluble in neutral ammonium citrate solution merely by heating it at a temperature below 600 °C, a property made the basis of a process patent by the junior author.' The possibility of producing an available form of phosphorus from what has hitherto been a worthless natural phosphate prompted the Bureau of Plant Industry, Soils, and Agricultural Engineering to make a brief study of the Pembroke phos- phate during the war years with a view towards determining the optimal temperature for heat treatment and the reactions involved in the process. The results of this study supplemented by data and information furnished by the junior author are presented in this paper. Description of Natural Phosphate: The phosphate with admixed quartz sand and siliceous matter occurs as a low-grade (8 to 9 pct P2O5) clay-like material that can be beneficiated cheaply by making a water separation of the very fine material from the sand, floating off the fine material, settling the suspension to a thick slurry, and finally de-watering the slurry by vacuum filtration followed by drying. The product dried at 100 °C contains about 16 pct water and 25 pct P2O5, about 1/12 of which is citrate soluble. Partial analyses of representative samples of the crude ore and corresponding concentrate are given in table I. The concentrate is light yellow in color and even after being dried at 100°C sticks very noticeably to laboratory grinding and screening equipment. Under the microscope the ground material is predominantly light brown crystalline aggregates with index of refraction near 1.61. The principal phosphate mineral constituent was identified as pseudo-wavellite with admixed phosphosiderite.2 Pseudo-

Jan 1, 1951