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By E. J. Rapperport, J. P. Pemsler

The thermodynamic activities of zinc in six solid solution Cu-Zn alloys ranging from 5 to 35 at. pct Zn were determined experimentally in the temperature range 400° to 600°C. This low temperature investigation was canducted in order to evaluate techniques developed to utilize the inherently high sensitivity of atomic absorption flocesses in the measurement of thermodynamic activities. Analytical expressions ,for the activity and actizlity coeflcient are given for the six alloys in the temperature ranges investigated. RELATIVELY few experimental methods are available for investigation of thermodynamic activities of alloys, especially in the solid state. The techniques most frequently used have been the electrochemical potential and the effusion methods, both of which have severe limitations in many instances. It is therefore desirable to expand the ability to perform such measurements in order to obtain new information as well as to provide an additional independent verification capability. In this work, we present a significant improvement in the spectrophotometric method for sensing small vapor pressures in static absorption cells. Similar techniques have been used previously;1"5 however, applications had been limited to relatively high pressures, often greater than 1 torr. Prior investigators have, for the most part, used broad spectral sources such as xenon or mercury lamps, and high intensity arcs. Hollow cathode sources were first suggested in 1956 6 and were used soon afterwards.4'5 These sources offer significant improvements in sensitivity and freedom from interfering spectral lines.'-' EXPERIMENTAL High purity zinc was obtained from Cominco Products, Inc., and copper from American Smelting and Refining Co. Both elements were of 99.999 pct purity. Copper-zinc alloys were vacuum melted in a high fired carbon crucible with each alloy pulled from the melt as a 4 -in. diam bar. The bars were swaged to -1/4 in. rods and vacuum annealed for 160 hr at 800° + 1°C. Samples for gross chemical analysis were taken at intervals along the length of the rods to ascertain the axial zinc gradient. Electron microprobe analysis of homogenized specimens indicated that the alloys had uniform compositions over their cross sections on a macro (200 p) and micro (1 u) scale to better than *1 pct (20) of the gross composition. This tolerance was determined by counting statistics, rather than assured composition fluctuations. All SiO 2 windows were high-ultraviolet-transmission grade to minimize intensity losses. Silica absorption cells were scrupulously cleaned consecutively in organic solvents, dilute HF, and distilled water before use. The empty cells were then flamed while under a dynamic vacuum, cooled, and removed to an argon-filled glove bag. Alloy pieces were cut and filed in the glove bag to produce fresh surfaces, and then loaded into the cells. The loaded cells were temporarily sealed, removed from the glove bag, reevacuated to 10-5 torr or better, and permanently sealed. The instrument used is schematically shown in Fig. 1. The spectral emission from a commercially made hollow cathode lamp (A) of a selected element is focused through an absorption cell (B) inside a well-controlled furnace (C). The intensity of the transmitted beam is measured using the spectrometer* (D) 'Techtron model AA4 atomic absorption spectrometer. which contains a grating (E) that disperses the light prior to impingement on the photomultiplier (F). The monochromator grating is adjusted so that only the wavelength of interest is measured. The power supply delivered an interrupted voltage to the lamp, causing a chopped radiation output to be transmitted. The detector read only the intermittent component of radiation incident upon it, so that all continuous noise signals (furnace radiation, and so forth) were eliminated. Three recording thermocouples contained in the muffle furnace were positioned along the length of the absorption cell: one at each end and one at the center. An effort was made to keep the ends of the cell several degrees hotter than the center to avoid window condensate. Appropriate thermal corrections were then necessary to relate cell pressure to radiation attenuation. Water-cooled heat shields, as shown in Fig. 1, were found to aid signal stability by protecting the hollow cathode and the photomultiplier from furnace radiation. The furnace had a 2-in. diam muffle, Kan-thal wound, with SiO 2 windows at its ends to minimize convective effects. The hollow cathode radiation was masked and focused to form a conic beam that was a maximum of { in. diam within the furnace. Thus, the 1.5 in. diam absorption cell easily contained the entire beam. The furnace was mounted on ball-bearing slides with positive positioning detents. This arrangement allowed the removal of the entire furnace assembly from the radiation path, position [I], Fig. 1, so that frequent sampling of the unattenuated beam intensity could be obtained. In all cases the beam intensity was kept constant to 0.1 pct as judged by readings taken immediately before and immediately after data collection. Only data for absorptions of less than 80 pct were utilized, as systematic deviations from linearity were found for greater absorptions.

Jan 1, 1970

By Willard L. Hunter

Four solvent extraction systems were studied to determine their efficiency jor extraction and separation of tantalum and columbium. Aqueous feed solutions of varying HF-HCl concentrations and metal content were contacted with equal volumes of cyclohexanone, 3-methyl-2-butanone, and 2-pentanone and solutions of varying HF-H2S04 concentrations were contacted with equal volumes of 2-pentanone. One multistage continuous test was made in a polyethylene pulse column using cy clohexanone as the organic phase. In each system studied, columbium and tantalum purities in excess of 95 pct with respect to each other were obtained in single-stage tests at low acidities in the feed solution. Separation factors ranging from 1700 to 2400 were obtained when rising HF-HCl mixtures in the aqueous phase. Best results were obtained when a solution of HF-H2S04 was used as the aqueous phase and 2-pentanone as the organic phase. A separation factor in excess of 6000 was obtained in one stage with aqueous solution concentrations of 2 _N HF and 2N H2S0,. When acid concentrations were increaszd to 52 HF and 10 _N H2S0,, 99.9 pct of the tantalum and 98.2 pct of the columbium initially present in the feed solution were transferred to the organic phase. The separation of columnbium and tantalum obtainable by means of the solvent extraction systems presented in this paper was found to corn -pare favorably with other systems, including the HF-H2SO4-methyl isobutyl ketone system currently used by most producers for the extraction and separation of these metals. TANTALUM and columbium are always found together in minerals of commercial significance, although the proportion of the two metals in ores varies within broad limits. Columbium is estimated to be 13 times more abundant than tantalum. Five methods generally employed for the separat:ion of these metals are: 1) fractional crystallization (the Marignac process),2 2) solvent separation, 3) fractional distillation of their chlorides, 4) ion exchange, and 5) selective reduction. Of these methods, the one currently used by industry to the greatest extent is that of solvent separation. One of the early technical developments in solvent separation of tantalum from columbium was reported by the Bureau of Mines: the HF-HC1-methyl isobutyl ketone system; data were presented for both laboratory and pilot-plant experimentation.3 Of twenty-eight organic solvents tested for their ability to extract tantalum from an HF-HC1 solution of columbium and tantalum, 3-pentanone (diethyl ke-tone), cyclohexanone, 2-pentanone, and 3-methyl-2-butanone were chosen for further study. Data on the HF-HC1-diethyl ketone system has been published4 and data describing the use of cy clohexanone, 2-pentanone, and 3-methyl-2-butanone as the organic phase are included in this report. RAW MATERIAL The source of tantalum and columbium oxides for this study was ('Geomines" tin slag from the Manono Smelter, Cie Geomines, Gelges, S.A., Congo. In order to extract the valuable Ta-Cb content, the slags were carbided, chlorinated, and the sublimate from chlo-rination was hydrolized and washed free of chloride with water. The washed material was air-dried and stored in a stoppered container. Throughout the paper, "feed material" refers to this mixture of hydrated oxides which was employed because of its high solubility in aqueous solutions. Typical analysis of the hydrated oxides is shown in Table I. I) HF-HC1-CYCLOHEXANONE SYSTEM Batch Separation. Effect of Acid Concentration. To determine the effect of varying the acid concentration upon the transfer of tantalum and columbium, a series of tests was made in which approximately 2.5 g of feed material was added to 25 ml solutions of 2, 4, 6, 8, and 10 N HF and 0 through 5 N HC1. Tantalum pentoxide concentration of the solu%ons was approximately 21 g per liter and columbium pentoxide was 14 g per liter. These starting solutions were shaken with equal volumes of cyclohexanone in 100 ml polyethylene bottles for 30 min. The phases were carefully separated in 125 ml glass separatory funnels. The time of contact of the solutions with the separatory funnels was kept at a minimum to reduce silica contamination. The measured phases were separated into 400 ml polyethylene beakers and the metal contents of each were precipitated by addition of an excess of ammonium hydroxide. Precipitate from each phase was filtered on ashless filter paper, ignited at 800" to 1000°C for 45 min, weighed, and analyzed by X-ray fluorescence.5 Data tabulated in Table I1 and illustrated in Fig. 1, show that maximum separation of tantalum from columbium for each HF concentration was obtained with no HCl present. The purest tantalum product was obtained with some HCl present. The highest separation factor was obtained at 2 N HF and

Jan 1, 1970

By C. W. Kovach, A. Moskowitz

Studies were undertaken to investigate the effects of manganese content on the machinability and other Properties of a free machining martensitic stainless steel (AISI Type 416). Machinability was found to be significantly improved in steels of high manganese content, and a direct relationship was obtained between machinability and steel Mn:S ratio. As the manganese content of the steel increases, the sulfide Phase present changes from CrS to (FeMn)Cr2S4 to (MnFeCr)S, and finally to MnS. The average sulfide inclusion hardness decreases through the same range of increasing manganese content. The mechanism for machinability improvement is discussed in terms of a soft ductile sulfide affecting deformation in the secondary shear zone. Type 416 containing relatively high manganese for improved machinability shows good general properties. The effects of increasing manganese content on mechanical properties, cold formability, and corrosion resistance are described. THE addition of sulfur is commonly used to improve the machinability of stainless steels. However, little attention has been paid in the past to the composition and characteristics of the sulfur-containing phase or phases present in these resulfurized steels. Recent information on the properties of sulfide phases, and their role in metal cutting, suggests that variations in these phases could have critical effects on machin-ability, as well as important effects on formability and other properties such as corrosion resistance. Manganese, chromium, and iron are strong sulfide forming elements present in stainless steels! of these, manganese has the greatest sulfide forming tendency and iron the least.1"1 The manganese content of resul-furized 13 pct Cr steels, often about 0.5 pct, can be insufficient or only barely sufficient to combine with the sulfur that is present; thus, the precise level of manganese can strongly influence the nature of the sulfide phase. Sulfide phases which may be present in stainless steels have been reported to include CrS, a spinel-type sulfide, chromium-rich manganese sul-fide, and manganese Sulfide.5,6 Detailed phase relationships for the Fel3Cr-Mn-S system have been reported by the present investigators,7 and a portion of this work will be referred to subsequently in this paper. Recent work by Kiessling6 and Chao et a1.8 has shown that sulfide phases can display wide variations in hardness, and may undergo considerable plastic deformation under isostatic loading.9-12 Early theories of metal cutting attributed the influence of sulfur to a lubricating effect. It is now apparent that the influence of the nonmetallic inclusions and their properties on crack initiation, deformation in the shear zones, and boundary films must also be considered in relation to the machining process. This paper presents the results of studies conducted to relate machinability to the various sulfide phases which occur in stainless steels. This work has led to the development of alloys with improved machinability, and has generated information on the effects of inclusions on metal cutting processes. Effects of sulfide inclusions and steel composition on other important metallurgical properties are also discussed. MATERIALS For drill machinability and inclusion studies, 10 lb laboratory heats were melted in an air induction furnace. These heats were made with sulfur contents be tween 0.10 and 0.50 pct and manganese contents be tween 0.05 and 3.0 pct. Residual elements were added to the heats in amounts typical for commercial steels. The typical compositional range covered by the heats is shown below: C Mn P S Si Ni Cr Mo Cu N 0.10 0.05 0.007 (M0 0.40 0.40 13.0 0.20 0.10 0.03 3.0 0750 The laboratory ingots were forged in the temperature range of 1800" to 2100°F to 3/4-in. sq bars, and all bars tempered to a hardness aim of 200 Bhn prior to testing. Because of differences in composition and tempering response, the tempered bars showed some variation in hardness (175 to 275 Bhn) as well as variations in delta ferrite content (0 to 50 pct). Composition, hardness, and delta ferrite content were considered in the analysis of the machinability data. Additional tests involving tool-life evaluation and determination of other properties were conducted on materials from commercially melted and processed 15-ton electric furnace heats. TESTS AND PROCEDURES Machinability of the laboratory heats was evaluated in a drill test. In this test, 1/4-in. diam holes, 0.4 in. deep, were drilled alternately in a test bar and in a standard bar for a total of four holes in each. This sequence was repeated three times using a freshly sharpened drill each time. The average time required to drill a hole in the test bar was compared to that for the standard bar. A drill machinability rating was assigned to the test bar relative to a rating of 100

Jan 1, 1970

By D. H. Desy, L. C. Fincher

The magnesium-rich end of the Mg-Ti phase diagram was investigated. The liquidus, solidus, and solvus boundaries to 1 pct Ti were established. All alloys were prepared by saturating molten magnesium with titanium in a consumable titanium crucible under inert gas maintained at 230 psig. The liquidus of the Mg- Ti system was determined by analysis of dip samples taken from 700° to 1300°C under equilibrium conditions in a pressurized inert atmosphere furnace and by analysis of small ingots rapidly poured and quenched from 1400° to 1500°C. The solubility of titanium in magnesium ranged from 0.018 wt pet Ti at 700°C (0.012 wt pet at 650°C by extrapolation) to 1.035 wt pet Ti at 1500°C. The solidus for compositions ranging from 0.03 to 1.00 wt pet Ti was determined to be 650° ± 1°C by thermal analysis. The titanium solid solubility values ranged from 0.08 wt pet at 350°C to 0.19 wt pet by extrapolation to 650°C. The freezing reaction is peritectic. No intermetallic compounds were found in the system; the phase in equilibrium with molten magnesium saturated with titanium was found to be titanium with magnesium in solid solution. Solid titanium will dissolve at least 1.32 wt pct Mg. PREVIOUS investigations of the Mg-Ti system have shown considerable disagreement on the solubility of titanium in liquid magnesium. Furthermore, the solid solubility of titanium in magnesium has not been well established. Liquidus curves for previous work and for the present investigation are shown in Fig. 1. Aust and Pidgeon1 used a dip-sampling method on molten magnesium held in equilibrium with solid titanium under a protective atmosphere to determine the solubility and found that it ranged from 0.0025 wt pet Ti at 651°C to 0.015 wt pet Ti at 850°C. Eisenreich2 introduced titanium into molten magnesium by means of TiCL4 adsorbed on BaCl2. Ingots were then cast at various temperatures. Making the assumption that only the titanium dissolved in magnesium at the time of casting was soluble in H2SO4, Eisenreich determined the solubility of titanium in molten magnesium to range from 0.003 wt pet at 655°C to 0.115 wt pet at 800°C. Eisenreich also determined the solid solubility of titanium in magnesium to be 0.015 wt pet at room temperature and 0.045 wt pet at 500°C. Since the solid solubility just below the freezing temperature for the bulk of the alloy was much larger than the liquid solubility just above the freezing temperature, Eisenreich concluded that the freezing reaction was peritectic. Obinata et al.3 equilibrated molten magnesium with titanium in hermetically sealed titanium containers which were then furnace-cooled. The titanium content of the magnesium was then determined and found to range from 0.170 wt pet at 700°C to 0.85 wt pet at 1200°C. No intermetallic compound was found in the system. The Armour Research Foundation4 determined two points on the solvus by electrical resistivity methods: 0.00057 wt pet at 200°C and 0.0008 wt pet at 300°C. At higher temperatures, data were meaningless with no trends observable. The authors of this report believed that the lack of significant data at the higher temperatures was due to variations in specimen geometry, although there was no positive evidence to verify this supposition. The present investigation was undertaken to clarify the uncertainty in both the liquidus and solvus of the magnesium-rich end of the Mg-Ti system. EQUIPMENT AND MATERIALS The equipment used in this investigation, with some modifications, was essentially that used by Crosby and Fowler5 in their determination of part of the Mg-Zr phase diagram. The equipment, as modified for this work, is shown in Fig. 2. It consists of a sealed furnace chamber which can be pressurized with inert gas so that melts can be made above the boiling point of magnesium at atmospheric pressure. Melts are made by induction heating in a titanium crucible which, after diffusion of sufficient magnesium into the walls of the crucible to saturate the titanium at the sampling temperature, comprises the solid phase in equilibrium with the molten magnesium. Dip samples may be taken with the sampling tube, or the entire furnace may be tilted so that ingots may be poured into a mold in the side chamber. The principal difference from the earlier apparatus is in the thermocouple, which in the present equipment is enclosed in a protection tube and immersed directly in the melt. The tips of both the thermocouple protection tube and the sampling tube, which dip into the melt, are made of high-purity titanium. The 4 1/2-in.-long titanium tip of the sampling tube is threaded into a steel tube, O in Fig. 2, which extends through the top of the furnace. To determine whether the temperature at the tip of

Jan 1, 1969

By P. G. Shewmon, F. N. Rhines

THE determination of the self-diffusion coefficient of magnesium has been made possible recently by discovery1-1 of a radioactive isotope, Mg28 having a half-life of 21.3 hr,1 and subject to manufacture in useful quantity. In the present research this material was condensed from the vapor phase upon a surface of high purity magnesium. The progress of diffusion of the tracer atoms into polycrystalline magnesium was followed by machining layers and measuring the change in the intensity of radiation as a function of the distance of each layer from the surface. The self-diffusion coefficient was found to be 2.1 X 10-8 sq cm per sec at 627°C, 3.6 X 10-9 sq cm per sec at 551°C, and 4.4 X 10-10sq cm per sec at 468°C; the activation energy is about 32,000 cal per mol. Experimental Procedure Since there was no other published measurement of a diffusion velocity in any magnesium-base material, is was necessary to employ a number of new experimental techniques. The short half-life of Mg28 made it necessary to complete the entire experimental procedure within three or four days. This meant that the work had to be done where a cyclotron was readily accessible and that all operations, prior to the diffusion heat treatment, had to be so designed as to minimize their time requirements. Unusual problems were imposed also by the chemical reactivity of magnesium, its high vapor pressure, and the fact that no satisfactory method for elec-trodepositing magnesium on magnesium is presently available. Finally, the machining and handling of the easily air-borne radioactive-magnesium chips involved certain health hazards, resulting in the need for further experimental restrictions. Preparation of Mg28 The Mg28 was produced in the Carnegie Institute of Technology syncrocyclotron by the neutron spallation of chlorine.5 his involved bombarding a 2 gram crystal of high purity NaCl with a beam of 350 mev protons for a period of 2 hr, after which the crystal was dissolved in warm water and the Mg28 was concentrated and purified by chemical means (see Appendix). About 50 microcuries of Mg28 thus were obtained in the form of magnesium oxinate (8 hydroxyquin-olatc?), which was ignited in air to produce MgO. This in turn was reduced to magnesium metal vapor, by the method of Russell, Taylor, and Cooper," in the vacuum apparatus shown schematically in Fig. 1. Here the essential part is a tantalum ribbon, slightly dished to receive the MgO. The ribbon, pre- viously outgassed at high temperature, is heated to about 1700°C by passing an electric current through it, whereupon tantalum oxide is formed, magnesium vapor is released almost instantaneously, and condensed partly upon the diffusion sample. Diffusion-Sample Preparation: Hot-extruded magnesium rod, 21/32 in. round was used in making the diffusion specimens. The magnesium analyzed as follows: 0.004 pct Al, 0.027 pct Fe, 0.040 pct Mn, 0.0004 pct Cu, 0.0002 pct Ni, and less than 0.01 pct Ca, 0.0004 pct Pb, 0.0011 pct Si, 0.001 pct Sn, and 0.001 pct Zn. A brief study of the crystal texture of this material revealed a sharp fiber texture with the (001) plane roughly parallel to the extrusion axis. Cylindrical samples 1/2 in. long by 5/8 in. were machined from this rod, the end faces dressed on 3/0 emery, and lightly etched with 20 pct HC1 in water. These samples then were annealed for at least twice the intended time of diffusion, at the intended diffusion temperature, in order to stabilize the grain structure at about 1 mm average diameter. The annealing treatments were conducted in argon in the same apparatus and in the same manner as the subsequent diffusion treatments, which will be described presently. Thus, a strain-free plane surface was produced, but there remained a layer of MgO which had largely to be removed before the layer of Mg28 was deposited. Most of this layer was taken off by two light passes over 3/0 emery paper. The balance of the oxide and a thin layer of metal were then removed by etching 5 to 10 min in 4 pct nital (4 pct HNO3 and 96 pct ethyl alcohol) made with absolute alcohol. There followed immediately three quick rinses in: 1-49 1/2 pct methanol, 49 1/2 pct acetone, and 1 pct formic acid, 2-50 pct methanol and 50 pct acetone, and 3-pure benzene. This procedure is essentially that of Sturkey.7 The resulting surface, which was of almost elec-tropolished brightness, remained plane and was free of cold work. It could be kept clean by storing under benzene, or in a desiccator; short exposure

Jan 1, 1955

By S. G. Proctor, D. L. Baaso, W. V. Conner

A double crucible system was developed for I-g scale plutonium reductions. The equipment consists of an inner MgO crucible, an outer MgO crucible, and a stainless steel pressure vessel. The reduction charge is PIaced in the inner crucible and the annulus between the inner and outer crucibles is filled with a mixture of calcium and iodine. The exothermic reaction between the calcium and iodine in the annulus supplies the heat required for complete reaction of the reduction charge ana' good metal coalescence. Metal yields of 80 to 85 ,pct were obtained from I-g scale reductions and yields as high as 97.5 pct were obtained from 0.5-g scale reductions. The system was used to reduce charges containing as little as 0.1 g of Pu resulting in metal yields up to 90 Pct. THIN metal foils of highly enriched plutonium isotopes are used as targets for cross section and other measurements. The isotopes are separated in the calutrons at Oak Ridge and are very expensive to prepare. Often, only 1 or 2 g of material are available thereby emphasizing the need for a method of preparing these small quantities of metal. Procedures for 1-g scale plutonium reductions have been described, but these procedures require elaborate or expensive equipment. For example, the procedure described by Anselin et al.1 requires an inert atmosphere glovebox and induction heating equipment. The procedure described by Baker2 also uses induction heating equipment to obtain the recommended heating rates and liner temperatures. Baker's procedure also requires high purity PuF4 with very little PuO2 present. The procedure described in this paper resulted from a search for a simple and inexpensive method for making 1-g scale plutonium reductions. EXPERIMENTAL Equipment. The equipment required for the double crucible system consists of a pressure vessel, two MgO crucibles, a MgO crucible lid, and a resistance-heated, vertical crucible furnace. The crucibles were slip cast from high purity MgO and were supplied by the Coors Porcelain Co. and the Norton Co. The pressure vessel and lid were fabricated from 316 stainless steel. Materials. The PuF4 used for this study was obtained from the P1utoniu:m Metal Production Department at Rocky Flats. The PuF4 was prepared in a con- tinuous hydrofluorinator by reacting Pu02 with HF at 650°C. The isotopic composition of the plutonium was approximately 93 pct 239PU, 6 pct 240PU, and 0.5 pct 241PU. Some of this PuF, contained less than 1 pct Pu02 (Batch No. 6 and 7), while other batches contained up to 15 pct Pu02 (Batch No. 3). The chemical analyses of all the PuF4 used for this study is given in Table I. The calcium was 99 pct pure, AEC grade, and only that fraction which would pass through a 20 mesh screen was used. The I2 was USP grade re-sublimed I2 which was ground before being used. Procedure. Various charge compositions and methods for loading the double crucible system were tested. The optimum conditions for 1-g scale reductions are described below. The double crucible system was loaded as shown in Fig. 1. The outer crucible was placed in the pressure vessel and the annulus between them was filled with MgO sand. The inner crucible was placed in the outer crucible, supported by a layer of MgO sand in the bottom of the outer crucible. A mixture of 5.2 g of Ca and 25 g of I2 was placed in the annulas between the two crucibles. The upper portion of the annulas was filled with MgO sand. Next, a layer of a mixture of calcium and I, equal to 20 wt pct of the calcium and I2 used in the main charge was placed in the bottom of the inner crucible. The PuF, to be reduced was mixed with a 30 pct excess of calcium and 1 mole of I2 per mole of Pu and this mixture was placed in the inner crucible. The charge was topped with a layer of a mixture of calcium and I2 equal to 20 wt pct of the calcium and I2 used in the main charge. The pressure vessel was sealed with a flat copper gasket and was purged by alternately evacuating and filling with argon. The purge valve was closed and the vessel was placed in a vertical crucible furnace which was preheated to 950°C. The furnace was turned off after 20 min of heating and the vessel allowed to cool. Experience has shown that. this amount of heating is sufficient to assure complete reaction of the charge. RESULTS AND DISCUSSION The double crucible system has been used to produce plutonium metal on a 0.1- to 1-g scale. Reduction

Jan 1, 1970

By S. Storchheim

MORE and more attention is being paid to the bonding of metals in their solid states. For a better understanding of this technique for joining metals and how it is affected by changes in temperature, pressure, and time at temperature and pressure, a detailed report concerning nickel to aluminum bonding has been published.' In order to broaden the knowledge accrued, some additional work concerning solid state joining of aluminum to copper and aluminum to zirconium was performed. The investigation of the Al-Cu system was considerably more extensive than the investigation of the Al-Zr system. For the A1-Cu system, not only were tensile sudies made but intermetallic penetration rate investigations also were carried out. The effect of temperature on intermetallic penetration rate for the A1-Cu system was determined at 11 tsi pressure, held 2 min. Procedure Apparatus: The hot pressing technique was the means of solid state reaction used and required the equipment depicted in Fig. 1. The following procedure was involved: The two metals to be reacted were placed in an aquadag-lubricated 18-4-1 tool steel die, 16 in. high by 1.440 in. ID, between punches of 1.366 in. diam made of the same material. A thermocouple well was located in the die body 3½ in. down from the top of the die, while another well was located centrally in the bottom punch 8½ in. from the bottom of the die. This die assembly was located in three cylindrical ceramic heating furnaces placed in tandem. Each furnace was controlled individually by a Variac power transformer. In turn, the die and furnaces were placed in a water-cooled stainless steel pot which could be evacuated. A cover, which contained a centrally located Wilson seal with an 18-4-1 1 in. diam ram running through it, was bolted on the pot. After sealing, the pot was evacuated by a roughing pump to 200 microns pressure, after which a diffusion pump was used to bring the pressure down to 5 to 15 u. At this pressure, the furnaces were turned on. As soon as they started to heat, out-gassing of the entire unit raised the pressure to 30 to 400 p. By the time the specimens were at temperature ready to be pressed, approximately 4/2 hr, the vacuum pumps had re-established the 5 to 15 u pressure. Once the desired temperature was reached, the required pressure was applied for a predetermined length of time to the 1 in. ram, through to the top punch, and to the specimen. When the time for keeping the specimen under pressure had elapsed, the pressure was released, the energizing coil current turned off, and the assembly allowed to cool. After cooling, the die was removed from the pot and the specimen was ejected. Specimen Preparation: Two different types of specimens were made for this investigation. One was for subsequent tensile testing, while the other was for determination of intermetallic alloy zone penetration into the parent metals. Tensile Bars—Commercially rolled copper pieces in. thick or zirconium sheet pieces 1/32 in. thick and 1.366 in. diam were placed between commercial 2-S aluminum rod 1 in. thick and 1.366 in. diam. This sandwich in turn was slipped into a 2-S aluminum sleeve 1.438 in. OD and 1.370 in. ID. This sleeve lined the couple up and prevented the aquadag lubricant from getting in between either the A1-Cu or Al-Zr interfaces. Immediately prior to the specimen assembly, the copper or zirconium was abraded on the flat surfaces with 320 grit silicon carbide paper, producing clean smooth surfaces. The aluminum was chemically cleaned just before assembly by: l—degrease in acetone, 2—distilled water rinse, 3—immersion for 3 min in 5 pct NaOH at 70" to 80°C, 4—distilled water rinse, 5—immersion for 2 min in 50 pct HNO3 solution at room temperature, 6—distilled water rinse, and 7—drying in a blast of gas. After the A1-Cu sandwiches were hot pressed and ejected, the specimens were machined such that the aluminum sleeve was removed, and the remaining aluminum was then threaded; the bar so produced was tested later for tensile strength. In all the instances where Al-Cu couples were tested, the specimens broke during the test at the Cu-A1 interface and never within the aluminum or copper. The ultimate tensile strength values at times showed considerable scatter for a set of given reaction conditions. Because of this, as many as three to five specimens were made for a particular set of conditions. The trend of the average tensile strengths obtained was not as conclusive as was the trend of the maximum tensile strengths, the latter values being obtained under optimum reaction conditions. Therefore, the values of ultimate tensile strength given herein are maximums.

Jan 1, 1956

By Earle E. Schumacher, Alexander G. Souden

IN the field of physical metallurgy it is becoming increasingly difficult to keep abreast of the recent develop¬ments since the diversity of investigations is so great and the literature so voluminous. The purpose of this review is to present the more important advances in the nonferrous field during the past few years, the topics discussed being classified broadly as fundamental and practical. The former includes those studies that have done most toward developing the basic science of metals and alloys, and the latter includes technical developments and applications. With the rapid growth of the metal

Jan 1, 1938

By N. M. Langdon

INTRODUCTION. IN considering the magnificent success of Mr. Gayley's Bold experiment of applying dry blast to the blast-furnace, whereby , saving of 20 per cent. of fuel per ton of iron is effected, the question arises whether, still further economy in fuel is possible, and, if so, how it is to be attained? The manner in which the heat generated in the furnace is utilized in the production of pig-iron may be determined, by the method of Bell and Gruner, for any furnace for which the necessary data are obtainable ; and the study of the operation,. tinder various conditions, of a number of furnaces, for which such information has been worked out., should enable us to form some conclusion on the subject. The tables and calculations given below cover the operations of several furnaces reported in our Transactions; also the two furnaces using natural and dry blast in ,Mr. Gayley's experiment, for which the heat-equation has been worked out by Prof. Joseph W. Richards in his admirable discussion' of Mr. Gayley's paper, The Application of Dry Air Blast to the Manufacture of Iron, and, finally, various hypothetical furnaces.. The full list is as follows : A. Isabella furnace, with natural blast. B. Isabella furnace, with dry blast. The data stated. for A and B in Table III. are those given by Professor Richards; except that the heat-units are given for one unit of iron instead of 100 units, and some items of heat supplied, as stated by Richards, have been subdivided, the total being the same as given by Richards. (Columns A and B are introduced in Table III. for comparison with C and D.)

Oct 1, 1909

By H. J. Ramey, I. S. Bousaid

Experimental results on the oxidation reaction kinetics in the forward combustion oil recovery process are presented. A total of 48 runs were made wherein a stationary thin layer of coked, unconsoli-dated sand was burned isothermally in a combustion cell. Individual runs were made at various temperature levels to permit determination of the effect of temperature upon the reaction. An expression was obtained for the burning rate of carbon as a function of carbon concentration, combustion temperature and oxygen partial pressure. The carbon burning rate for two types of crude oil indicated a first order reaction with respect to both carbon concentration and oxygen partial pressure. The effect of combustion temperature on the reaction rate constant matched the Arrhenius equation. The activation energy was similar for the two crude oils examined. The activation energy decreased for a porous media containing clay. The rate of oxidation of crude oil at reservoir temperature was found to be significant. Other significant findings included information on hydrogen-carbon content of fuel residues, fuel reactivity and the products of combustion. INTRODUCTION The production of crude oil by underground combustion has been studied in the laboratory by many investigators.1-5 Results of laboratory and field experiments have been reported in the literature describing the forward combustion process. But as yet, no qualitative or quantitative study of the kinetics of fuel combustion involved in this process has been reported. The fuel concentration and the rate at which fuel is burned at the front are important factors governing the air requirement in a forward combustion operation. Although the fuel is essentially unrecoverable crude, the air required to burn the fuel is an important economic factor in this process. Because fuel is burned, the heat transport associated with forward combustion is a key and unique feature of this new oil recovery method. Many investiga-tors5-9 have presented information on the heat transmission and fluid mechanics involved in forward combustion. Berry and Parrish10 demonstrated the utility of considering reaction kinetics in reverse burning. From differential thermal analysis, Tadema11 presented a qualitative discussion of the nature of reactions between oil and oxygen in combustion oil recovery. Although little quantitative work has been done on the reaction kinetics involved in forward combustion oil recovery, an extensive literature does exist on combustion of carbons and oils, and carbonaceous residues from cracking catalyst pellets. Dart, et al., 12 studied the combustion rate for oxidation of carbonaceous residues on clay catalyst pellets, and found the reaction to be second-order with respect to carbon concentration, and first-order with respect to oxygen partial pressure for carbon concentrations less than 2 weight percent of the catalyst weight. The reaction appeared to be first-order with respect to carbon concentration for concentrations greater than 2 percent. Metcalfe13 noted that other workers had found that aging of the fuel during the combustion process was responsible for changing coke properties, and it accounted for the apparent second-order carbon concentration effect found by Dart, et al. It appears that burning of residues from cracking pellets is first-order with respect to both carbon concentration and oxygen partial pressure. Dart, et al., also observed that hydrogen in the hydrocarbon residue appeared to react faster than the carbon. Lewis, et al.,14 studied oxidation of charcoal, coke and graphite in a fluidized bed. Gas velocities were high enough to partially lift and circulate the carbon particles. Their results indicated first-order reaction dependency with respect to both carbon concentration and oxygen partial pressure. One

Jan 1, 1969

By C. A. Stewart

I. INTRODUCTION AND GENERAL STATEMENT OF RESULTS. The field-work upon which this paper is based was done in the summer of 1910, and was made possible by the courtesy of the Imperial Copper Co., which gave me access to its property. For their kindness in this respect I wish to express my thanks to W. F. Staunton and Meade Goodloe. Moreover,. B. F. Smith and G. B. Gentry, mining engineers in the employ of the company, gave invaluable assistance by placing maps,. etc., at my disposal, and by discussing with me the problems of the district; and it is a great pleasure to acknowledge this indebtedness to them. In order that the significance of some of the details that follow may be better appreciated at first reading, a general outline of the conclusions reached is given here. In the Silverbell mining-district a series of Palaeozoic limestone blocks is completely surrounded by post-Palaeozoic igneous rocks, intruded in the following order: alaskite, alaskite-porphyry, biotite-granite, andesite, and quartz-porphyry. The biotite-granite is believed to represent a differentiation of the. magma from which the alaskite-porphyry came ; and this conclusion-has an important hearing on the origin of the ores. The intrusion of both alaskite-porphyry and biotite-granite was followed by the emission of magmatic waters, which sericitized and silicified the alaskite-porphyry and granite, and produced in the limestone, by the addition to it of silica, iron, and alumina, great masses of garnet, quartz, and wollastonite. Following close upon these solutions came metal-bearing magmatic waters, which impregnated porphyry, granite, and alas kite with cupriferous pyrite, and deposited in the garnet zones chalcopyrite and copper-bearing pyrite that make important bodies of contact-metamorphic ores. Secondary enrichment has taken place in the disseminated ores in the igneous rocks,. raising their copper-content to 2 per cent. in some cases,. and extensive drilling has been undertaken to block out these deposits. East of the contact-metamorphic deposits there is a fissure-vein of lead-silver ore in the quartz-porphyry. This rock is distinctly younger than the alaskite-porphyry and the granite; and the lead-silver ores belong, therefore, to a period of mineralization distinctly later than the copper-deposition.

May 1, 1912

By Randall L. Neal

This paper discusses the impact of taxes at the state and federal level on typical on-shore oil and gas exploration economics in the USA. Taxes considered are the windfall profits excise tax, state production (or severance) taxes, state income tax, and federal income tax. Also considered will be market prices for oil and gas in the USA. The effect of government take as a percent of revenue, on rate of return, discounted Payout, and discounted cumulative cash flow is shown on the attached tables. The conclusion drawn is that tax laws, while rarely the most important factor to be considered when drilling a well, can have significant impact on the profitability of oil and gas ventures, and should be considered when determining where to drill. Hypothetical exploration wells were analyzed for the impact of tax laws on project profitability. The results of this study show that when factors other than taxes are postulated to be the same (such as producing rate, capital, operating costs, and prices), cash flow can vary by as much as 68% due to the differences in the tax laws. Other significant findings for the cases studied include: (a) that discounted payout varied by as much as 1.8 years, (b) that rate of return differed by up to 67% and (c) the total tax rate as a percentage of revenue had a maximum variance of 33%.

Jan 1, 1982

NEW MEMBERS The following list comprises the names of those persons who became .members during the period of Jan. 10, 1918, to Feb. 10, 1918. ANTISELL, TONER, Min. Engr.; Supt., Great Falls Mine of Maryland, Chevy Chase, R: F. D. No. 4, Washington, D. C. BAKER, RAYMOND FRANK, Geol:, The Texas Co., Producing Dept., Box 362, Tulsa, Okla. BERTON, ADRIEN, Chief Engr., Corocoro United Copper Mines, Ltd., Corocoro, Bolivia. Buck, WILMER EARLE, Met., Curtis & Co. Mfg. Co., Hamberger & Kienlein Aves., St. Louis, Mo. BUELL, WILLIAM H., Asst. Director, Experimental Station, E. I. duPont de Nemours & Co., Wilmington, Del. CARDENAS, FEDERICO F., Mgr., Cia. Minera Nazareno y Alicante, S. A., Allende, No. 112, Saltillo, Coah., Mexico. CHEVALIER, JEROME A., Pet. Geol., The Carter Oil Co.; Exchange National Bank Bldg., Tulsa, Okla. CLEAVES, DANIEL LUNT Supt., St. Joseph Lead Co., Herculaneum, Mo. CLOTHIER, GEORGE A., Resident Min. Engr., Province of British Columbia,

Jan 3, 1918

By Marcus A. Grossmann

This paper offers for consideration certain somewhat radical modifications in the iron-carbon diagram, these modifications being the result of the presence of notable amounts of alloying elements. When only small amounts of alloys are present, the standard iron-carbon diagram (Fig. 1) can be used with but insignificant changes; when larger amounts of alloys are present, however, it assumes a distinctly altered appearance. No comment is offered for the present except to call attention to the delta area, A4BM, which represents a region of mixtures of austenite and delta iron, just as area A3SP represents mixtures of austenite and alpha iron. Absence of Carbon We may turn at once to the effect of the presence of alloys. It has been found that in the complete absence of carbon, the gamma change will sometimes disappear entirely when sufficient alloying element is

Jan 1, 1927

By B. W. Veal, B. S. Chandrasekhar

THE Laue method of orienting single crystals requires the use of tables of angles between crystal-lographic planes, and between zone axes. Such tables have been published for cubic crystals, and some rhombohedra12 and hexagonal3 crystals. A table of angles between planes in ß-tin has also been published;4 these angles refer to only low-index planes, and are not particularly helpful in the actual indexing of spots on a Laue photograph. Furthermore, it is often useful to know the angles between zones which share a common low-index plane. We have calculated such tables of angles for ß-tin and indium, both between planes in principal zones, and between zones passing through principal planes. The results are given in Tables I and 11. The standard formulas were used, with c/a = 0.54554 for 0-tin, and 1.07586 for indium.

Jan 1, 1962

By G. W. Mao, A. M. Gaudin, D. W. Fuerstenau

Activation of sphalerite with copper salts has long been thought of as a chemical reaction of the following form: ZnS + Cu++ [=] CuS + Zn++ [ 1 ] Early experimentation1-3 showed that the reaction seemed to be stopped by the coating of insoluble copper sulfide, but since the analytical methods were crude, it was only surmised that the reaction could proceed by diffusion. Probably the most conclusive evidence for reaction (Eq. 1) was obtained by Cooke,4 who found a stoichiometric replacement of Zn++ by Cu" after 50 days' reaction at about 100°C. Cooke also found the sphalerite to be covered with a rather thick coating of covellite, which in¬dicates that activation is a continuing replacement of Zn++ by Cu" rather than diffusion of Cu" throughout the sphalerite lattice. However, the occurrence of diffusion at high temperatures has been observed.5,6

Jan 4, 1959

By Horace Pops

THE martensitic transformation occurring at cryogenic temperatures in the bcc ß-phase Cu-Zn binary alloys has been discussed in a number of publication~.1-3 Addition of a second solute element to the binary Cu-Zn alloys enables the ternary martensitic phase to be stable at temperatures above room temperature, and the variation of the MS temperature with third element content has been determined recently4 for a series of Cu-Zn based alloys in which either the zinc content or the electron concentration was maintained at a constant value. The present paper describes some characteristic growth features of martensite observed in ternary alloys. Alloys were prepared by adding small amounts of Ni, Ag, Au, Cd, Ga, In, Si, Ge, Sn, or Sb to a a -brass Cu-Zn master alloy. Details of the melting and casting technique, homogenization, examination by cold-stage microscopy, and the determination of the

Jan 1, 1968

By Joseph Singewald

AMONG the genetically interesting iron ores of the United States are those of the St. Francis Mountains near Ironton and Iron Mountain, Missouri. They are specular hematite in porphyry. The Iron Mountain and Shepherd Mountain deposits are generally spoken of as veins and those of Pilot Knob, Cedar Hill, and Russell Mountain as bedded deposits. Iron Mountain has produced nearly 4,000,000 tons of ore and Pilot Knob about 1,500,000 tons. The output of the other three localities has been insignificant. Pilot Knob is no longer worked as an iron mine, but the rock is now being crushed for use as road metal. Iron Mountain has continued as an active producer. In 1927, the property was acquired by the M. A. Hanna Co. and an extensive prospecting and exploration campaign was undertaken, so that the ultimate production of Iron Mountain will doubtless greatly exceed the figures mentioned.

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 Jasper Johnson

Taken in all its bearings there is, perhaps, no more interesting coal-field than that locally known and designated as " Wilmington," both on account of the superior qualities of its product as a household and steam fuel, when compared with other Illinois coal, and its geological position. The territory underlaid with coal, to which this name was originally given, embraced a very small area, including only the south half of sections 31 and 32 (township 33 north, range 9 east) in Wilmington township, and sections 5, 6, 7, 8, 17, 18, 19, 30, and 31, with occasional outliers in sections 3, 4, and 9, and, possibly, in sections 20, 28, 29, 30, and 32 (township 32 north, range 9 east) of Reed township, in Will County, comprising eleven square miles of workable coal within the known basin. Borings indicate the presence of coal on sections 30 and 33 in Wilmington