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By R. P. Abendroth

The hydrogen-water vapor ratio at which Fe-Cr alloy, chromium oxide, andiron chromite coexist in equilibrium was determined between 900" and 1200°C. A thermogravimetric method was used to determine equilibrium conditions. The results fit a straight-line relationship in the temperature region studied, and are given by Reduction experiments were also performed to confirm the results of the equilibrium investigation. ThE oxygen pressures at which Fe-Cr alloy, chromium oxide, and iron chromite coexist in equilibrium have been previously determined by Boericke and angert,' Morozov and Novokharski,' and Katsura and uan. Only one determination (at 1300°C) was made by Katsura and Muan, but it agrees with the results of orozov and Novokharski. The results of Boericke and Bangert, however, differ appreciably from the results of these investigators. Previous studies have assumed that the equilibrium metallic phase is pure iron, but Dahl and Van vlack have shown that the iron contains from about 1 wt pct Cr at 1000°C to over 2 wt pct above 1300°C. The chromium oxide also contains a small amount of iron in solid solution. In the present study, hydrogen-water vapor mixtures were equilibrated with the condensed phases, using a therrnogravimetric method to determine equilibrium conditions. The reaction can be written EXPERIMENTAL General Procedure. The starting material was a sintered pellet of Fe2O3-Cr2O3 solid solution with a hole in the center, and was placed on a fused silica hook. This assembly was raised into the preheated hot zone of the furnace in a helium atmosphere, hooked onto a fused silica hangdown suspended from one arm of an Ainsworth Model RV-AU-1 recording balance, and the starting weight determined. A flowing hydrogen-water vapor atmosphere was then exchanged for the helium by evacuation, and the sample reduced until the weight loss indicated the sample composition to be in the alloy-Cr2O3-chromite field. The tem- perature was adjusted incrementally until constant sample weight was achieved for several hours, to within 0.02 mg. A hydrogen-water vapor atmosphere of different composition was then admitted, and the same procedure carried out. At the end of a series of determinations, the sample was examined by X-ray diffraction to verify the presence of the desired phases. Microscopic examination of the silica hook showed no interaction with the sample, nor did it lose any weight. Several criteria were used to insure equilibrium besides constancy of weight. For a given hydrogen-water vapor composition, equilibrium was approached from both oxidizing and reducing sides by varying the furnace temperature slightly. The resulting slow weight loss or gain was observed for several hours. Constant weight could be re-established by returning to the original furnace temperature. The last criterion used was varying the relative amounts of the phases by further reduction or oxidation, and observing any changes in temperature required for constant weight for a given hydrogen-water vapor atmosphere. None were observed. This procedure was essentially the same as approaching the equilibrium from oxidizing and reducing sides, but larger weight excursions were carried out. Sample Preparation. Reagent-grade Fe2O3 and Cr83 powders were mixed in the desired proportions and heated in air at 1250°C for 2 hr. The mixture was re-ground and heated in air overnight at 1250°C. X-ray diffraction showed complete solid-solution formation as a result of this procedure. The solid solution was then pressed into l/2-in.-diam pellets using Carbowax 4000 as a binder. The hole was drilled in the center, and the pellets were sintered 24 hr at 1250°C in air on a bed of Fe2O3-Cr2O3 of the same composition, contained in an alundum boat. After cooling, the pellet surfaces were abraded with 310 paper to remove any surface compositional differences, such as loss of Cr2O3. Chemical analysis of the sintered pellets was 67.16 wt pct CrP3 and 33.02 wt pct Fe203. Atmosphere Generation and Control. The hydrogen-water vapor atmospheres were generated by passing Matheson ultrahigh-purity hydrogen, with no further purification, through two water bubblers contained in a constant-temperature water bath. Since the water-vapor dew points required in this study were below room temperature, the bath was insulated, and was cooled by thermoelectric-immersion devices. The bath temperature was controlled to 0.0l0C. Since rather high flow rates of about 900 ml per min were used through the furnace tube, an independent check of the dew point was made to insure saturation of the hydrogen by the water vapor. Although the dew point could only be determined to within 1/2"C, the determined dew points agreed with the water-bath temper-

Jan 1, 1967

By J. J. Tietien, R. O. Clough

A technique previously used to prepare alloys of InAs1-xPx and GaAsl-x Px, miry: the gaseous hydrides arsine and phosphine, has been extended to grow single -crystalline GaAs 1-x Sb x by replacing the phos-phine with stibine. Procedures were developed for handling and storing stibine which now make this chemical useful for vapor phase growth. This represents the first time that this series of alloys has been grown from the vapor phase. Layers of P -type GaSb and GaSb-rich alloys have been grown with the carrier concentrations comparable to the lowest ever reported. In addition, a p-type alloy containing 4 pct GaSb exhibited a mobility of 400 sq cm per v-sec which is equivalent to the highest reported for GaAs. RECENTLY, interest has been shown in the preparation and properties of GaAs1-xSbx alloys, since it was predicted1 that for compositions in the range of 0.1 < x < 0.5, they might provide improved Gunn devices. However, preparation of these alloys presents fundamental difficulties. In the case of liquid phase growth, the large concentration difference between the liquidus and solidus in the phase diagram, at any given temperature, introduces constitutional supercooling problems. It is likely that, for this reason, virtually no description of the preparation of GaAs1-xSbx by this technique has been reported. In the case of vapor phase growth, problems are presented by the low vapor pressure of antimony, and the low melting point of GaSb and many of these alloys. In previous attempts1 at the vapor phase growth of these materials, using antimony pentachloride as the source of antimony vapor, alloy compositions were limited to those containing less than about 2 pct GaSb. This was in part due to the difficulty of avoiding condensation of antimony on introducing it to the growth zone. A growth technique has recently been described2 for the preparation of III-V compounds in which the hydrides of arsenic and phosphorous (AsH3 and pH3) are used as the source of the group V element. With this method, GaAs1-xPx and InAs1-xPx have been prepared2&apos;3 across both alloy series with very good electrical properties. Since the use of stibine (SbH3) affords the potential for effective introduction of antimony to the growth apparatus, in analogy with the other group V hydrides, this growth method has been explored for the preparation of GaAs1-xSbx alloys. In addition to GaSb, these alloys have now been prepared with values of x as high as 0.8. In the case of GaSb, undoped p-type layers were grown with carrier concentrations equivalent to the lowest reported in the literature. Thus it has been demonstrated that, with this growth technique, all of the alloys in this series can be prepared. EXPERIMENTAL PROCEDURE A) Growth Technique. The growth apparatus, shown schematically in Fig. 1, and procedure are virtually identical to that described2 for the growth of GaAs1-xPx alloys, with the exception that phosphine is replaced by stibine.* HCl is introduced over the gallium boat to *Purchased from Matheson Co., E. Rutherford,N+J. transport the gallium predominantly via its subchlo-ride to the reaction zone, where it reacts with arsenic and antimony on the substrate surface to form an alloy layer. The fundamental limiting factors to the growth of GaAs1-xSbx alloys from the vapor phase, especially GaSb-rich alloys, are the low melting point of GaSb (712°C) and the low vapor pressure of antimony at this temperature (<l mm). Thus, relatively low antimony pressures must be employed, which, however, imply low growth rates. To provide low antimony pressures, very dilute concentrations of arsine and stibine in a hydrogen carrier gas were used. Typical flow rates (referred to stp) were about 4 cm3 per min of HC1 (0.06 mole pct)+ from 0.1 to 1 cm3 per min of ASH, (0.002 to 0.02 mole pct), and from 1 to 10 cn13 per min of SbH3 (0.02 to 0.2 mole pct), with a total hydrogen carrier gas flow rate of about 6000 cm3 per min. Although no precise data on decomposition. kinetics exist, it is known4 that stibine decomposes extremely rapidly at elevated temperatures. However, the high linear velocities attendent with the high total flow rate (about 2000 cm per sec) delays cracking of the stibine until it reaches the reaction zone and prevents condensation of antimony in the system. To improve the growth rates of the GaSb-rich alloys, growth temperatures just below the alloy solidus are main-

Jan 1, 1970

By W. H. Bassett

IN the commercial annealing of cartridge brass there are four points regarding which definite data are essential. They have to do with the correct interpretation of grain count in its relation to annealing temperature and, incidentally, to Brinell hardness. These points are: 1. The comparison of the grain sizes of two cartridge-brass mixtures: 69 copper, 31 zinc, 0.376-in. (9.5-min.) gage; and 68 copper, 32 zinc, 0.130-in. (3.3-mm.) gage. 2. The comparison of the grain sizes of annealed metal that had previously been reduced by rolling varying amounts; for instance, 20.0, 36.6, 50.9, and 59.1 per cent. 3. The determination of standards for grain sizes on annealed brass of the composition 68 per cent. copper, 32 per cent. zinc and 69 copper, 31 zinc. 4. The comparison of grain size with Brinell hardness on identical samples of annealed metal. In their comprehensive and thorough investigation of the recrystallization of cold-worked alpha brass on annealing,1 Mathewson and Phillips have discussed the relations between temperature of anneal, degree of deformation, and structural alteration in alpha brass. They have also shown certain comparisons between the ordinary physical properties and the grain size of annealed brass. The purpose of the present investigation is mainly concerned with the grain size of cartridge brass, its relation to Brinell hardness, and the publication of sufficient data to enable those engaged in the inspection of such material to have a correct foundation upon which to work.

Jan 1, 1919

By R. V. Higgins

This paper presents a computer method to obtain the shape factors and equal cell volumes of the channels for any well spacing pattern from a potentiometric model. By using this program the authors have processed the data for the seven-spot, direct line-drive and the staggered line-drive patterns. The data for the five-spot pattern had been previously processed by a noncomputer method and are included for completeness. The shape factors and volumes for the channels are presented in tables for those who want to use them to process data using their own permeability relationships and viscosities of their reservoir oils. The authors have used the data and sets of representative permeability curves to process sample calculationr of waterflood performances. The comparison of the calculated results shows that the influence of well spacing is small. The permeabilities of the reservoir rock to oil and water had a greater influence on oil recovery for a given pore-volume throughput of water than the well spacing pattern. The more water-wet the reservoir rock, the better the possibility of permeabilities which are conducive to good recovery. The viscosity of the reservoir oil also influences the recovery more than the well spacing pattern. The reduction in the percentage recovery of oil with increase in viscosity of the reservoir oils is small when oil viscosities are in the range of 0.1 to 3. Above this range the reductions in recoveries are extensive. Sample comparisons of the time required for different patterns to recover the oil are presented. Results of an example calculation are given to show the effect of the permeability profile on recovery. INTRODUCTION The effect of well spacing pattern on the recovery of oil when flooding with either gas or water has been studied by many investigators. Muskat et al.1 presented an analysis using conductivity, sweep efficiency and unit mobility to the time of breakthrough. Dyes et al.2 used experimental techniques (X-ray shadowgraphs) and different mobility ratios. They presented quantitatively the relationship between mobility and sweep efficiency at and after breakthrough. Hauber3 presented a method to predict waterflood performance for arbitrary well spacing patterns and mobility ratios. Craig et al.,4 using techniques similar to Dyes et al. to determine sweep efficiency for a five-spot pattern, added the use of relative permeability curves at breakthrough and thereafter. Douglas et al.5 sed rela- tive permeabilities and continuously changing saturations throughout the entire five-spot flood pattern. In obtaining their solutions they used finite-difierence equations. Hig-gins and Leighton6,7 also used relative permeabilities and continuously changing saturations throughout the pattern before and after breakthrough. They employed techniques that process a flood-pattern calculation on the computer in about one minute. The methods of Douglas et al. and Higgins and Leighton both checked closely the laboratory results for a wide range of mobility ratios. This paper presents some sample performances calculated by the Higgins and Leighton method that show the effect on recovery of different permeabilities and viscosities using the seven-spot, the line-drive and the staggered line-drive, as well as the fivespot flood pattern. No previous paper has presented these data using different permeability curves and continuously changing saturations throughout the flood patterns. The paper also presents (1) the results and analyses of the flood-pattern prediction, (2) the computer techniques for determining the shape factors and volumes from the potentiometric models for the foregoing flood patterns, and (3) the shape factors and volumes of the channels of the flood pattern in the event reservoir engineers may like to process waterflood calculations using their own permeability curves and reservoir oils. DESCRIPTION OF METHOD VOLUMES AND SHAPE FACTORS The use of channels taken from a potentiometric model (see Fig. 1) to aid in calculating the performances of water floods of nonlinear patterns has been thoroughly explained in the literature.0,7 Therefore, very little theory, discussion, or proof regarding this phase will be repeated in this paper. The computer method presented in this paper to calculate the volumes and the shape factors of the channels of potentiometric models employs the trapezoidal rule for the volumes and the Pythagorean theorem (the hypotenuse equals the square root of the sum of the squares of the two sides of a right triangle) for the shape factors. In calculating the volume of a channel, the area of each cell in the channel is determined and then multiplied by the thickness to obtain the volume. In determining the areas of the cells, trapezoids are constructed whose vertical sides are spaced Ax apart, as shown in Fig. 2. The length of the sides is the difference between an ordinate cut off by the top and bottom of the cell — usually equipo-tentials. The coordinates of the points along an equipo-tential or streamline are obtained by Lagrange&apos;s8 equation of interpolation for which the constants are coordinate points at the intersections. Three intersections for con-

Jan 1, 1965

By AIME AIME

MINERAL production of the United States is valued at over five billion dollars a year at present and the industry employs close to a million workmen, yet such maps as are available that might indicate the geographical distribution of this industry show only the location of coal and oil fields and of other mineral deposits. No recent map is available that shows this distribution in a quantitative way. The purpose of the maps and graphs here presented is twofold: (1) to give the mining engineer a clear conception of the relative value and the pattern of distribution of minerals in the United States; (2) to test the so-called block-pile (or grouped pillar) system of statistical mapping, which makes this presentation possible. (I discussed this method of mapping in an article which appeared in Economic Geology in 1939, Vol. 15, p. 185-188.)

Jan 1, 1941

By W. C. Ellis, E. S. Greiner, M. E. Fine

Discontinuous changes of Young&apos;s modulus, internal friction, coefficient of expansion, electrical resistivity, and thermoelectric power are evidence for a transition in chromium near 37OC. Although the X-ray diffraction pattern gives no clue, a difference between the thermal expansivity and the temperature dependence of the lattice parameter suggests a crystal-lographic change. Young&apos;s modulus data disclosed another transition near THE thermal dependence of a number of proper- ties of chromium indicates a transition occurring over a temperature range near room temperature. Bridgman&apos; noted this first from a minimum in the electrical resistivity near 12°C. In a sample of greater purity, Sochtig&apos; observed the minimum at 41 °C. Erfling3 reported an inflection in the thermal expansivity curve at 36°C. These temperature-dependence curves are reversible with no hysteresis being detected. No discontinuity or inflection has been observed in the heat capacity&apos; or the paramagnetic susceptibility.&apos; Likewise, no one has noted a change in crystal symmetry. In the present investigation Young&apos;s modulus, internal friction, coefficient of expansion, electrical resistivity, illustrated in Fig. 1, lattice constant, Fig. 2, thermal electromotive force, Fig. 3, and paramagnetic susceptibility, Fig. 4, were measured over an extended temperature range. The samples were prepared in two ways: (1) By cold pressing a sintered electrolytic powder compact,&apos; and (2) by electroforming from an aqueous solution. The electroformed samples were prepared by R. A. Ehrhardt and G. Bittrich by plating on copper or nickel tubes from an aqueous solution according to the method of Brenner, Burkhead, and Jennings.&apos; The pressed powder samples (method 1) were finally annealed at 1400°C in purified helium: the electroformed samples, packed in powdered chromium, were vacuum-annealed at 1000°C. From the composition of the original powder&apos; the purity of the pressed powder samples is estimated to be 99.8 pct Cr. Spectrochemical analysis furnished by E. K. Jaycox, revealed only slight traces of impurities in the electroformed sample (less than 0.001 pct), neither iron nor nickel being detected. Chromium deposited by this method is reported to contain approximately 0.05 pct 0.- Methods and Data Young&apos;s Modulus: For measurement of Young&apos;s modulus, an annealed, pressed powder sample, 0.114 x0.237x1.845 in., and an electroformed sample, 0.10 in. od, 0.01 in. id, and 1.86 in. long, were prepared. The resonant frequencies of the rod samples in forced longitudinal vibration were measured at a series of temperatures from —192" to 200°C by a method previously de~cribed.6,7 Because the samples were nonferromagnetic, iron- silicon or molybdenum permalloy tips (0.013 in. thick) were soldered to the ends. The softening temperature of the solder limited the temperature of measurement. Young&apos;s modulus, E,, of chromium at temperature, T, may be calculated from the resonant frequency of the composite rod, f,; the thickness of the tips, t; the length of the chromium sample at 25°C, l,.; the density of chromium at 25°C, pc (7.20 g per cc);5 and the thermal expansivity, Al/l25. Modulus differences for two temperatures, ET and E, are accurate to +0.002x10" dynes per cm2. ET = 4PAlc+2tyf Young&apos;s modulus at 25°C, Fig. la, is 28.2~10" dynes per cm&apos; (40.8xlO" si) in wrought chromium (upper curve). The modulus of the electroformed sample is apparently lower due to cracks. From the modulus measurements two transitions were observed: one with a critical temperature at 37°C, the other at —152°C. Internal Friction: The internal friction, 1/Q, was determined from the width, Af, of the strain amplitude-frequency curve at 0.707 times the strain amplitude at resonance;&apos; the internal friction, 1/Q, then equals Af/f. Fig. lb shows a sharp peak in internal friction at 38°C. The internal friction of the electroformed sample had a similar maximum. Thermal Expansion: The expansivity measurements, shown in Fig. 2, covering the temperature range —195" to +400°C were made by D. MacNair in an interferometric dilatometer8 sing a sample consisting of three pyramids 0.25 in. high prepared from wrought electrolytic chromium. Below —120°C the experimental points deviated up to ±2x10 from the drawn expansivity curve in Fig. 2 because of decreased precision of the quartz wedge thermometer at low temperatures. Near 38°C the thermal expansivity curve, Fig. 2, goes through an inflection corresponding to a minimum in the coefficient of expansion, Fig. ld, and a relative volume decrease on heating. Electrical Resistivity: The variation of electrical resistivity with temperature measured by the po-tentiometric method is also shown in Fig. l. The resistivity of the wrought chromium (upper curve) at 20°C is 13.6 microhm-cm; of electroformed chromium (lower curve) 12.8 microhm-cm. The lower value reflects higher purity and agrees closely with a published value." A minimum at 40°C occurs in the resistivity curves of both samples. No conclusive evidence for a transition near — 150°C was observed, but the points, Fig. 1, appear to deviate from a smooth curve between —120" and —160°C.

Jan 1, 1952

By C. A. Heiland, W. H. Courtier

The investigations described were made on a portion of Clear Creek basin near Golden, Colo. (-4 portion of the area under survey is shown in Fig. 1. The photograph was taken in the vicinity of station No. 2 of Line 11.) Three principal purposes were in the minds of the investigators: 1. To repeat with modern, more sensitive and more reliable instruments magnetometric placer investigations previously made. 2. To disprove the recently advanced theory that deposits of the glacial period have no pronounced magnetic effects. 3. To develop in detail the theory of the magnetic effects produced by placer deposits. Six years ago, the first magnetic observations were published, which proved that it is possible to locate gold-bearing channels with relatively crude instruments.&apos; Two years ago, K. C. Laylander published results obtained with similar instruments.2 The measurements of the latter were discussed by the senior author of this paper.3 At that time, however, the material available for such a discussion was somewhat scarce and not made with the most modern magnetic instruments, although very brilliant results were obtained. Therefore, the senior author felt that magnetic investigations should be made on very clear geologic conditions with the most modern instruments. Comparison of Magnetometers The junior author undertook this work in the spring of 1928. The magnetic field balances, for vertical and horizontal intensities, designed by Schmidt were used (Figs. 2 and 3). The scale value of these instruments was approximately 257 and 157, respectively. The middle

Jan 1, 1929

By J. D. McBeth, G. M. Potter, Ramon Pizarro

Heap leaching is used by the Carlin Gold Mining Co., Carlin, Nev., to supplement conventional processing of gold ore by agitation-leaching and countercurrent decantation. Selected open-pit ore containing about 0.072 oz Au per ton is crushed to 3/4 inch, dumped by truck on an asphalt pad, and leached by sprinkling with dilute cyanide solution for 7 days. The heap is then drained and removed by front-end loader to tailings disposal. About 70 percent of the gold is dissolved. Leach solution from the heap joins the pregnant solution from countercurrent decantation for gold recovery by zinc precipitation. Four leach pads, each with a capacity of 1,400 tons of ore, are in use. About 10,000 tons of ore are heap leached monthly from about April through October. Heap leaching is recessed during freezing weather. Labor, equipment, and reagent requirements for heap leaching are presented.

Jan 1, 1974

By W. A. Foster

NINETY years after the Riddle nickel deposit N was discovered in Oregon in 1864, Hanna Coal & Ore Corp. began mining operations. Until 1954 much prospecting and preliminary development work had been done on the property, but no ore had been shipped other than for metallurgical testing. The deposit is being explored by churn drilling and trenching, and a few test shafts have been put down for the purpose of studying the ore in place, determining volume and moisture factors, and gathering bulk samples for pilot plant and smelter tests. In churn drilling, 6-in. casing is driven down 2 or 3 ft behind the drill bit and bottomed at each 5-ft interval. All the sludge for each cased 5-ft interval is dumped through a splitter and one eighth is saved and analyzed. Drillholes are stopped after going through the ore zone and penetrating fresh peridotite in which the nickel content is less than 0.5 pct.

Jan 8, 1957

By D. A. Belforti, M. P. Lepie

Spectroscopically pure copper was melted on sapphire plaques in a zydrogen atmosphere. The surface tension of the liquid metal was determined using the sessile drop technique. Measurements were made by direct observation with the aid of a specially const,mcted telescope. The value obtained, 1268 dynes per cm, is compared to that found in the literature. THERE is at this time considerable interest in the use of ceramics for vacuum tubes. The crystalline material is superior to the more conventional glass in mechanical strength, chemical inertness, dielectric properties, ability to withstand high temperatures, and so forth. However, ceramics are much more difficult to seal hermetically with metals than are the glasses. For this reason an investigation was undertaken to determine the wetting and adhesion of metals to ceramics. The sessile drop technique offers a convenient means at elevated temperatures for measuring liquid surface tension, wetting angle, density, spread- ing coefficient, and work of adhesion. Thus, from the contour of a drop of liquid at rest on a solid surface one can obtain a quantitative evaluation of the degree to which the two substances will bond. To this end a special apparatus was constructed so that various molten metals could be observed. Standardization of the apparatus was done initially by measuring the surface tension of copper since this is well documented in the metallurgy literature. Although there are many methods available for the measurement of surface energy,&apos;+ the sessile drop technique has been used most extensively for molten metals and ceramics.5"&apos; Fig. 1 illustrates the dimensions to be measured. From these values, the surface tension of the liquid can be obtained using the Bashforth and bdams&apos; equation and tables.

Jan 1, 1963

By John W. Lane, Richard A. Ronzio, Frederick N. Bender

Climax Molybdenum Co. operated a hydrometallurgical plant at Climax, Colo., from August 1966 to August 1968 to recover molybdenum from an oxidized ore. The feed, tailings from sulfide flotation, was first upgraded by cycloning. The concentration plant handled 6000 tpd of feed and produced 2000 tpd of slime concentrate. The concentrate was leached by a sulfuric-sulfurous acid solution at 65°C. The molybdenum was solubilized in the form of "molybdenum blue." Activated charcoal was added to the leach tailings in a resin-in-pulp type circuit. Molybdenum was adsorbed on the charcoal. The charcoal was screened from the pulp and washed. The washed charcoal was pumped to columns where it was ammoniated and air-blown. The oxidized molybdate then was washed from the charcoal. The eluate was evaporated until ammonium dimolybdate crystallized out. The ammonium dimolybdate was calcined to molybdenum trioxide.

Jan 1, 1973

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

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

Jan 1, 1969

By P. G. Winchell, J. K. Jackson

The strtcture of body-centered Fe-Ni-C alloys (0 to 16.5 wt pct Ni) containing less than 0.015 wt pct C was investigated by measuring the carbon-diffusion peak at low frequencies with a torsion pendulurrr. By determining the Snoek damping in ferrite and in quenched alloys of identical composition, the effects of nickel content and heat treatment were separated, and the existence of a structure in which Snoek damping is greatly reduced was revealed in the quenched ternary alloys. The relative amount of this structure increases with increased nickel content and cooling rate. It is proposed that this structure may be highly imperfect or tetragonal. In Fe-Ni-C alloys containing only ferrite the addition of nickel (0 to 5.1 wt pet) decreases tke area of the carbon-diffusion peak and shifts its position to lower temperatures but broadens the peak only slightljl. The decrease in peak area with increasing nickel implies that short-range interactions with the nickel atoms prevent some of the carbon atoms from participating in the relaxation process. The shift in the peak position indicates a long-range effect of nickel on the movement of carbon atoms so that at 300°K the diffisivity of carbon in -ferrite is increased by about 35 pct by the addition of 5.1 tut pct Ni. The results are presented as distributions of relaxation strength 072 the activation energy under the assumption that the frequency factor is invariant. BODY-CENTERED iron-base solid solutions dissolve carbon interstitially in the octahedral sites. The occupation of an octahedral site produces a tetragonal distortion of the surrounding lattice. These sites fall into three sets according to the orientation of the tegragonal distortion associated with each and may be identified by their lattice coordinates as: type 1/2 0 0, type 0 1/2 0, type 0 0 1/2. At low carbon levels in cubic ferrite the carbon atoms are distributed at random1 among these sites. In high-carbon body-centered iron-base solid solutions, which are unstable with respect to several two-phase mixtures, a tetragonal structure occurs as the product of the diffusionless transformation of austenite. This transformation is commonly accompanied by appreciable microstrain and its product is called martensite. The tetragonality of martensite, a supersaturated solution of carbon in a iron, is maintained prior to decomposition even though local diffusion of carbon occurs as evidenced by carbide precipitation. The tetragonality is taken as evidence that one set of octahedral sites is preferentially occupied by carbon. (This preferential occupation is called ordering below.) Support for this view is presented by the absence of strain-induced carbon-atom diffusion in high-carbon solid solutions (martensite). Such diffusion occurs in ferrite and produces the 40°C internal-friction peak observed at 1 cps frequencies.&apos; Thus, there appears to be qualitative evidence favoring the view that at sufficiently high carbon levels tetragonality arises spontaneously as a result of the ordering of the carbon atoms; however, no experimental evidence exists concerning an equilibrium between cubic and tetragonal body-centered solid solutions. Moreover, attempts to estimate the energy of ordering7-&apos; predict a value too low to maintain the tetragonality observed at medium carbon levels, 0.3 to 0.6 wt pct C. In the present work an attempt using internal-friction measurements is made to establish the presence or absence of tetragonality in low-carbon body-centered solid solutions formed by quenching austenite. Fe-Ni alloys containing about 0.01 wt pct and 0 to 15 wt pct Ni were selected for the study. While the work was in progress Gilbert and Owen10 reported that the transformation which occurs in these alloys during quenching at rates up to 5000°C per sec is not martensitic but is more properly categorized as massive. Thus, the solid solution

Jan 1, 1964

By Leon W. Dupuy

SUPPLEMENT THESE tables should accompany Figs 6, 7, 8, 9 and 10, respectively. To follow Fig 6: TABLE 2[a]-Drill Rod [ ] To follow Fig 7: TABLE 3-Rod Coupling [ ]

Jan 1, 1947

By J. J. Predali, J. M. Cases

J. J. Predali and J. M. Cases (Attachè de Recherche and Charge de Recherche, respectively, Centre de Recherches sur la Valorisation des Minerais, Institut Polytechnique de Nancy, Nancy, France)-The role of CO, in carbonate flotation is one of the parameters of a complex phenomenon: the adsorption of salts of fatty acids onto minerals. The authors therefore must be congratulated for their work. Their experimental results suggest some questions: 1) Recovery with C02, benzoic acid, or HCl, look very similar [(Fig. 1)] to that with the use of air; however, the recovery decreases very slightly (<10%). But in these two kinds of experiments, two parameters are different: the pH which is near 5.8 (with C02) becomes 9.1(without C02) and the concentration of Ca* I x 10-3 mole per 1 (without C02) becomes 1.9 X 10&apos; mole per 1 (without COO. 2) Adsorption experiments (Fig. 2) permit computing the surface coverage 9 which is 7.4% (without C02) and 8% (without CO_.) for an initial concentration of 12 X 10-6 mole per 1 in sodium oleate. It seems doubtful to us that this small variation can produce large increases of the recovery in flotation. 3) It is difficult to correlate adsoption and flotation experiments because they do not seem to have been done with the same size of particles. The concentration needed to obtain 95% recovery (Fig. 1) is about 3.0 X 10_" mole per l, that is, 1.13 X 10-6 mole for about

Jan 1, 1973

By Valentine Garfias

THE various phases of the Mexican oil industry have received so much publicity that there is little to add to the discussion of present and future production, extent and importance of prospective fields, and status of petroleum legislation, to mention but a few of the angles of the Mexican oil problem. However, out of this wealth of information, which is generally of contradictory nature, the average petroleum man is at a loss to know something definite regarding the various questions involved so, keeping the foregoing in mind, it has been the writer&apos;s aim to record in a concise form the most reliable and up-to-date information regarding the salient features of the Mexican oil situation. PRESENT STATUS OF MEXICAN OIL INDUSTRY Production During 1921 The Mexican oil fields, during 1921, produced in round numbers 203,000,000 bbl. of which 176,000,000 bbl., or 86 per cent., were exported, the bulk of -these exports, or about 73.3 per cent., going to the United States. The Mexican exports were divided by grades as follows: Light crude, 47.0 per cent.; heavy crude, 22.0 per cent.; tops, 3.5 per cent.; fuel oil from light crude, 24.0 per cent. The balance, or 3 1/2 per cent., includes the bunker fuel shipments and the coastwise trade in Mexico, which is not classified as to grades. The figures show that, in importance, the light-oil fields from about 755 per cent. of the Mexican petroleum industry.

Jan 4, 1922

By W. T. Burns

Attempts were made in 1908, at the Great Falls Works, to produce ingots direct from the Butte precipitate by smelting the material in a reverberatory refining furnace. The ingots produced in this manner averaged 99.4 per cent. of copper and 0.40 per cent. of arsenic and antimony. The copper content being considered too low, it was decided to cast the copper into anodes and to treat the anodes in the electrolytic plant. No. 1 Furnace, in which the precipitate was treated, was a regular cathode refining furnace previously employed in making wire bar, cake, and ingot from electrolytic cathodes. The hearth of the furnace was 24 by 12 ft., having a capacity of 100,000 lb. of cathodes. The furnace was coal fired, and the copper was dipped by means of trolley ladles. The average composition of the furnace charges was as follows: Per Cent. Peer Cent. Copper. Precipitate,..........7.5.3 40 to 80 Purification cathodes,.....1.9 92 Refinery slag (oxide slag),.. 10.1 50 to 60 Electrolytic cathodes,... 2.1 99.9 Precipitate anode scrap,.... 3.1 99.0 Scrap copper,.........7.5 99.2 100.0 The slag from this furnace amounted to 46 per cent. of the total amount charged and was of the following average composition: Per Cent. Cu..............16.86 SiO2.............34.7 FeO.............18.8 A12O3.............13.0 CaO.............9.4 MgO.............2.7 S............... 0.47 As..............0.11 Sb...............0.006 Ag, oz per ton.....0.18

Jan 1, 1914

By L. Graydon Carpenter, Donald E. Garrett

Probably the largest single tungsten deposit in the U. S. is one that has yet to produce any tungsten; it is not even listed in tables showing U. S. reserves. This deposit is at Searles Lake, Calif., where the brine contains about 70 ppm WO3. Small though the concentration is, the amount of brine in the lake is so great that it is estimated at 170 million lb of WO3 (8.5 million units), equaling the total of all other known reserves in the U. S. This dry lake is located in the basin formed by the Argus and Slate ranges in the northeastern corner of the Mojave Desert (Fig. 1). It consists of a massive salt body some 35 sq miles in extent, varying in thickness from 0 to 120 ft and containing more than 3 billion tons of salt. A central section of about L. G. CARPENTER and D. E. GARRETT are with the Research Dept., American Potash & Chemical Corp., Trona, Calif. TP 47881. Manuscript, Nov. 4, 1958. AlME Trans., Vol. 214, 1959. 8 sq miles is exposed salt; the remaining area is overlain by mud. Except for the exposed sodium chloride (10 to 15 ft thick) the body consists of a very complex and heterogenous mixture of soluble crystals, containing at least eight major phases. It is only about 53 pct solid, the voids being occupied by a dense brine which is the raw material for two chemical companies operating in the valley.

Jan 3, 1959

By Frank C. Smith

The following article covers the history of a metallurgical campaign, commenced in March, 1905, at the mines of the Socorro Bold Co., in the so-called desert region of Yuma county, Arizona. The results obtained were simply a function of necessity, as will be seen from the description of the local economic conditions and the character of the ores treated. The mines and mill of the Socorro Gold Co. are located near the small village of Harrisburg, about 60 miles from Congress Junction, Ariz., which, at the time this work was undertaken, was the nearest railroad station, and from which all supplies were brought by wagon through the desert, at a cost varying from $10 to $15 per ton in addition to the railroad freights. Wood, the only available fuel, cost $7 per cord. Water for all purposes was pumped to the plant from a well in the valley about 4 miles away. Under the Arizona law, a working-shift is 8 hr. Wages were $6 per day for foremen and mill-men, $4 per day for blacksmiths and engineers, $3.50 per day for miners, and $3 per day for shovelers and trammers. The ore consisted of quartz, in which, above the 250-ft. level, the iron-minerale were largely oxidized and some free gold was visible; below that level few traces of oxidation occurred, and pyrite constituted the principal mineralizer in the quartz, together with occasional pockets of galena and a few eccentric specks of covellite. The 20-stamp mill was equipped with plates for amalgamation, and three Standard tables for concentration. The tails from the tables mere elevated by a centrifugal pump to a launder, by which they were conveyed to a 60-ton cyanide-mill for further treatment. The cyanide-mill was erected at so great a distance from the stamp-mill that a separate crew of workers and a separate power-plant were necessary. No arrangement had been made for the treatment of the concen-

Jan 1, 1907

By D. M. Dunbar, H. C. SCHLILTZ

HE Chile Exploration Co.&apos;s mine and reduction plant are at Chuquicamata, Chile, on the eastern edge of the Atacama Desert, 163 miles northeast of Antofagasta, 80 miles from the Pacific Ocean, and 70 miles from the Bolivian border and at an altitude of 10,000 ft. Guggenheim Brothers started prospecting in -4pri1, 1912, and purchased the main property, in October of that year; the property is now controlled by the Anaconda Copper Mining Co., which acquired it in January, 1923. The orebody strikes north 10" east, and has a dip of about 64" west. The length, as far as developed, is approximately 1% miles; the width averages sightless than mile.

Jan 1, 1925