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By A. R. Amos, S. B. Patterson

Log washers have been used for many years in the washing of clay iron ores, phosphate rock and manganese ores, but not until the past 15 years have they been employed to any extent in the preparation of aggregate materials and fluxing stone. For a machine of such importance where tenacious clay or soft rock must be eliminated, there are few data generally available. The purpose of this paper is to set forth the results obtained from several operations, together with a few suggestions for planning a specific installation. Where the material to be washed out consists of loose surface soil, silt, or small amounts of quickly soluble clay, there is little competition with other forms of washers, because greater power and maintenance are required for the operation of log washers, but where the foreign matter is a stiff clay, such as occurs with high-calcium limestones and in marginal gravel deposits, the ability of other kinds of washers to eliminate completely the hard clay balls is at least uncertain. Then the log washer comes into its own field, for with the breaking and churning action of the logs it will clean out the toughest clay. Even with material from the hydraulic dredge, if it contains tough clay, the log washer is desirable unless the gravel is subjected to a costly soaking and rehandling process. Recently there has been a considerable development in other types of machines to accomplish these results but it is not within the scope of this paper to make comparisons between competitive types, but to present the best obtainable data on log washers only. From the primitive design that gave it its name, a long log hewn from a tree, with paddles forged to shape from strap iron and attached by lag screws, the log washer has gradually been developed to the present all-steel type. As now manufactured, the log washer consists essentially of two built-up logs on which are mounted a series of paddles, carried by shafts fitted at the ends of the logs on bearings fastened outside the enclosing steel box, or trough, which is set at an angle of about 5" to 10" and into which the material is fed. Stuffing boxes at the places where the shafts pass through the box at the lower end are equipped with water-

Jan 1, 1938

By N. J. Themelis, P. Spira

The efficiency of the reverberatory furnace operation in producing. slags of 1020 copper content depends on the mixing and flow conditions in the bath. Radioactize-tmcer tests have indicated the jkaction of bath volume engaged inflow and the mixing conditions in the bath. The factors controlling the flow pattern of slag have been classified as laminar transfer flow, natrsral convection, and flou, due to the rapid addition or removal of slag.. Similarity criteria for model studies have been developed. The pyrometallurgical processing of copper begins with the smelting of either flotation concentrates, or direct-smelting ores which have been partially roasted to calcines. These materials are generally smelted in a reverberatory furnace, Fig. 1, and separate into two liquid phases, a sulfide matte and an iron silicate slag. he matte is tapped and subsequently reduced to metallic copper in a converter, while the reverberatory slag is usually discarded without any further treatment. Molten slag from the converting operation is returned intermittently to the reverberatory in order to recover its high copper content (1 to 3 pct Cu). The reverberatory furnace is about 115 ft long by 30 ft wide. In general, the solid charge is fed at intervals through openings along the sides of the roof and forms sloping banks from which the molten materials trickle down into the bath; the charge banks extend over a length of about 70 ft from the firing wall. The depth of the slag and matte layers varies from smelter to smelter; in the Noranda furnaces, the slag depth is 24 to 30 in., while the depth of matte at the taphole is about 20 in. Apart from smelting, the functions of the reverberatory are to recover most of the copper content in the converter slag by physical and chemical interaction with the furnace bath, and to provide adequate time for optimum separation between matte and slag. The efficiency of these operations depends on the mixing and flow conditions in the bath and is reflected on the copper losses in the slag. In the present study, the reverberatory furnace is considered as an open-channel chemical reactor and the driving forces for material transport through the bath are examined by means of flow and mathematical models. FLOW CONDITIONS IN THE REVERBERATORY FURNACE To facilitate the study of mixing conditions in continuous-flow reactors, two idealized patterns of flow have been accepted by workers in this field.' The term "backmix" flow is used to describe complete and instantaneous mixing in the reactor (perfect mixing); all particles have the same chance of leaving the system, independently of their time of entrance, and the fluid is uniform in composition throughout the vessel. On the other hand, "plug" flow, or "piston" flow, assumes that a fluid element moves through the reactor without overtaking or mixing with fluid entering at an earlier or later time. In addition to the two idealized patterns of flow, "deadwater" flow accounts for that portion of the fluid which is moving so slowly that it may be assumed to be stagnant. According to the definition by evensppiel,' the cut-off point between active and stagnant fluid may be taken as material which stays in the vessel for a period twice the mean residence time. The flow patterns in real vessels may be approximated by a combination of the above flows. Thus, the vessel is assumed to consist of interconnected flow regions with various modes of flow existing between them. The flow pattern may be determined directly from the flow paths of fluid through the essel. -However, the difficulty of obtaining and interpreting such information has led to the alternate approach of determining the residence time distribution of fluid elements by means of stimulus-response studies. The stimulus is provided by introducing a tracer in the inlet stream and the response by the record of the change in tracer concentration in the exit stream from the reactor. Such tests have been conducted in glass tank furnaces using either chemical7"9 or radioactive tracers1'-'' and, in one case, experiments have been reported for a metallurgical furnace.'"

Jan 1, 1967

By H. H. Klepfer, M. E. Snyder

UNTIL very recently, the commercial availability of the rare earths as metals has been very limited. Fabrication of mill products from these metals has not been studied in most cases. This note reports the results of the development of fabrication techniques for thulium. Thulium has a melting point of about 1550°C and a hexagonal close-packed crystal structure. It oxidizes in air to give a black oxide (TmzO,). The procedures for producing thin thulium foil were developed on one ingot weighing about 220 g and were subsequently applied in processing about a pound of metal to foil. Several alternates for the various fabrication steps were investigated and will be discussed. The metal fabricated was in the form of commercial chill-cast ingots 1 in. in diam and 2 in. long weighing approximately 220 g. Impurities in the ingots were reported by the vendor to be 4000 ppni tantalum, 2000 ppm calcium, 200 ppm nickel, 100 to 200 ppm iron, 100 ppm europium, and less than 100 ppm copper, lutetium, and ytterbium. In addition to these impurities, several salt-like inclusions as large as l/8 in. in diam were revealed along the center line of the one ingot sectioned. Preliminary tests indicated that small wafers cut from the as-cast ingot would not fabricate readily by rolling. Forging of copper-jacketed wafers was therefore attempted. At 1550"F forging was satisfactory but an apparent reaction of copper with thulium demanded investigation of lower temperatures. Therefore, the remainder of the test ingot was forged at 1450°F—with only minor cracking. All ingots forged were inserted into copper tubes of 1 in. 1D and 0.125-in. wall thickness. The jackets were sealed by flattening the ends of the tubes and welding under helium. Heating time at 1450°F was 30 min. Press forgings of 1/8 in. per pass were used, followed by 10 min reheats. When the ingots had been squared and reduced to 0.250 in. in thickness, the original copper jacket was stripped off and replaced by a new jacket in preparation for hot rolling. Hot rolling at 1450" F without edge cracking was readily accomplished after forging. Excellent results were obtained with 10 pct reductions of thickness followed by 5 to 10 min reheats. After reduction of thickness from 0.250 to 0.100 in. the copper jacket was removed. It was found, in fact, that hot rolling in air was possible. A tenacious black oxide similar to that seen on zirconium was formed during 3 min reheats at 1450°F. Reduction in air to 0.010 in. foil was possible taking 10 pct reductions per pass. The oxide coat formed during hot rolling in air could best be removed by sand blasting and pickling. Common pickling solutions containing polar solvents were found to attack the metal too rapidly and a concentrated nitric-hydrofluoric acid mixture attacked neither the oxide nor the metal. The most satisfactory pickling solution was 52 vol pct concentrated nitric acid-48 vol pct glacial acetic acid. After forging to 0.250 in., vacuum annealing and cold rolling was found to be another satisfactory alternate to hot rolling in copper jackets. After forging. a hardness of Rockwell B76 was found. Annealing in vacuum (2 X l0-5 mm of Hg) for 1 hr at 1200"F did not alter this value. Annealing at 1470"F for 1 hr brought the hardness down to R;]63. With cold rolling (5 pct per pass) the hardness returned to about R,1:76 after 20 pct reduction and edge cracking became noticeable. However, cold rolling to a total of 40 pct reduction in thickness (RI,,83) was possible before edge crack propagation became serious. Good surface finish was obtained, and the metal loss due to oxidation was minimized by cold rolling and vacuum annealing. Using this procedure the yield of 1.25 in. wide by 0.010 in. thick foil from a 1-in. diam ingot was about 40 pct.

Jan 1, 1961

By G. J. Dickman, W. N. Thomas

The factors involved in selecting, a drive system for a grinding mill, including gearing arrangement, motor selection, and electric-supply system limitations are reviewed. Equipment costs are evaluated on a dollar per horsepower basis and starting performance is analyzed, the latter making use of a recently developed computer program. The present interest in large-diameter grinding mills and the rapidly rising cost of the drive in proportion to the cost of the mill establishes a need to explore the drive system in detail. The drive for a 7 to 8,000 hp mill will cost from $350 to $600,000 which represents nearly half the total cost of the mill package, and requires as much building space as the mill proper. Some of the drive components require a longer time to manufacture and the installation time and costs are equal to those for the mill. It is apparent that the drive has become a dominant factor in the overall mill design consideration. A new plant requires a tremendous investment in both time and money. With the high degree of competition in the mining industry, low capital cost is an exceedingly important factor in the development of a project. It is just as important, however, to insure that the equipment is going to perform satisfactorily for the anticipated life of the project without adding unplanned operating, maintenance, and replacement costs. This is the position in which the engineer or designer usually finds himself and is really one of his primary functionsestablishing a realistic compromise between cost and performance. Large primary grinding mills can represent a major portion of the cost of a plant and the drive system accounts for a substantial part of this cost. These facts justify a careful analysis of the drive requirements and all of the factors involved in ultimately arriving at the best system for the lowest cost. A number of excellent papers have been published on various aspects of mill drives. The authors have used information from these papers in making a study of a drive for a 7600-hp, 32 x 12-ft autogenous mill. This was a broad investigation, including mechanical and electrical design, layout, performance, and maintenance considerations, and overall economics leading to the selection of the optimum system for that mill. This paper was developed from the study and includes information applicable to large mills in general. For a successful and economical application, the drive must be considered as a system and all of the components analyzed to determine their effect on the system. This requires the participation of the mill designer, gear, and other mechanical component manufacturers, motor manufacturer, plant designer, and operator. A careful analysis of the mill torque requirements is first necessary to provide a basis for selection of the mechanical and electrical drive components. Because of manufacturing limitations on the size and capacity of gearing available for these low-speed applications, an evaluation of costs for various gear ratios and configurations in conjunction with motor speeds is required. Consultation with the power-supply company is necessary to determine limitations on motor-starting disturbances and to analyze operating costs on the basis of existing rate structures and low characteristics. Finally, consideration must be given to the drive arrangement and its affect on plant layout, space requirements, and location of auxiliary equipment for the selected process. There are presently three basic schemes for driving a mill. The first is a direct drive by a motor operating at mill speed with no gearing. The second is by a higher-speed motor through a trunnion-connected gear drive. The third is by a motor through the more conventional pinion and ring-gear with the option of an interposing gear box to permit greater motor speed than pinion shaft speed. [(Fig. 1.)] Several manufacturers have or are presently developing motors which drive the mill directly without the use of gears. One arrangement has the motor armature intimately surrounding the mill shell-discharge spout or extension of the trunnion journal. The motor stator is then supported independently and surrounds the shell or trunnion-mounted rotor. Another variation utilizes an independent mill-speed motor connected to the trunnion by a drive shaft and flexible couplings.

Jan 1, 1972

By Jean-Jacques Prompsy, J. S. Rinehart

The purpose of the present study was to arrive at a better understanding of the stress fields developed within drill bits under dynamic loading and the influence that these stress fields could have on the failure of the drill bits. Particular emphasis has been given to the influence that bit shape has on the establishment of highly localized, potentially destructive stress inhomogeneities within the bit. This paper covers one phase of a broad study involving three velocity regimes: impacts at very low velocities, 0 to 20 ft/sec, a velocity range in which dynamic effects are just beginning to be found; impacts at velocities ranging from 20 to several hundred ft/sec, arange commonly encountered in practical drilling operations; and impulsive loading through the detonation of explosives, a velocity range in which the dynamic effects are greatly exaggerated and made more identifiable. Specifically, fracturing which develops at the end of a cylindrical bar undergoing a shock produced by impact was experimentally investigated, the impacted area being the face of a truncated cone terminating the cylindrical bar. Fracture characteristics were looked at as a function of impact velocity, area of impacted face and cone angle — parameters of considerable importance in the design of drill bit. EXPERIMENTS The specimens were made of Plexiglas, which enabled the fracture pattern to be easily observed. In Plexiglas, the velocity of a longitudinal wave is about 8,700 ft/sec, and the velocity of the transverse wave about 4,200 ft/sec. The specimens were impacted by a steel cylinder whose lower face was parallel to the terminal face of the experimental bit, as shown in Fig. 1. The impacting mass was shifted up and down on two steel rods, dropping from a maximum height of 11 ft, with the velocity varied between 0 and 6.5 m/sec. The initial mass of the cylinder was 4.1 kg, which could be increased by steps up to 8.8 kg by addition of steel plates. The velocity of the steel cylinder was determined by using an electric circuit; as the cylinder dropped, it contacted two steel wires, the first one starting and the second one stopping an electronic counter. Two similar counters connected in parallel were used to corroborate each other. The velocity was checked at each drop as it had been observed to vary somewhat from drop to drop. The two contact wires were located just above the top of the specimen so as to give a value of the instantaneous velocity of the steel cylinder at impact. The distance between the wires was 40 ± 0.5 mm and the discrepancy between the counters was never more than 0.1 m/sec. Thus the velocity was known to within 3.25 per cent. This precision was sufficient with respect to the precision of the machining of the specimens. A very small lack of parallelism between the face of a specimen and that of the impacting hammer resulted in an oblique impact which required a much lower velocity to break the specimen. The experiments had a twofold purpose — (1) to observe the fracture pattern, and (2) to find relationships between the minimum velocity required to generate a fracture within a specimen and the

By J. A. Putnam, A. D. K. Laird

In laboratory research on the behavior of oil, gas and water in porous materials, no direct method has been devised to measure saturation without disturbing the flow. Indirect methods involving various forms of radiation have been developed for measuring one or two components. The X-ray absorption method for two components has been described previously1-3. The possibility of three component measurement has also been mentioned1. Since two component measurement still requires considerable care to insure accuracy, the fact that three components can be measured satisfactorily is not generally appreciated. The fraction of the energy of an X-ray beam of one wavelength transmitted through a material is given by the transmission factor. in which 1 is the beam's path length through the fluid. p is the fluid density, and 1,. is its mass absorption coefficient. Eq. 1 implies that all parts of the beam pass through equal amounts of the fluid. Practical applications are, therefore, limited to systems in which the fluid is distributed so that I varies negligibly over the cross-section of the beam. Typical variations of the transmission factor with X-ray tube potential arc shown in Fig. 2 from which experimental points have been omitted for clarity. The X-ray absorption of low pressure gases in a core is practically zero so it cannot he distinguished from that a vacuum by instruments that will differentiate between liquids. The transmission factor of a gas in a core is. therefore, unity. Consequently, the saturation of only one gaseous component can be found. If two fluids completely fill a core, their two saturations add to unity and, therefore, only one value of the transmission factor, T, is needed to determine both of them. When two liquids do not completely fill the core, their saturations do not add to unity and transmission factors at two wavelengths must be measured. At one of these wavelengths, 7 for one liquid must be different from T or the other liquid. The change of T for one liquid us the wavelength is changed between the two values must be different from the corresponding change of T in the other liquid. The two values of fluid saturation will also give that of the gas because the three saturations must add to unity. In Fig. 2 it can be seen that there are many large differences of T between various oil solutions and water solutions at any one potential, and between potentials for any one solution. Consequently, conditions for optimum accuracy of measurement of the saturations of a gas and two liquids can be chosen. Once the operating potentials have been selected, however. it is more convenient to cross plot the data from Fig. 2 on transmission factor-solution concentration coordinates for the chosen potentials, as shown in Fig. 3. Fig. 3 was used to plan the experimental procedure for Core N-38-1. Since the voltage control at 45 kv was good, the slopes of the curves in Fig. 2 at this potential would cause little error. At low potentials, however, the voltage control was not good, so 33 kv was chosen because the small slopes of the curves made voltage control less critical. The lowest strength beam that could be measured reasonably at 33 kv corresponded to a minimum T factor of 0.385. Fig. 3 shows that both 4.80 weight per cent of cadmium chloride in water and 24.0 per cent of iodobenzene in crystal oil had this T value, and, consequently, were indistinguishable to the X-rays at 33 kv. Thus, at 33 kv, the liquid saturation was given by the same curve regardless of the relative amounts of oil and water solutions present. This simple calibration curve from which the gas and liquid saturation can be read, is shown in Fig. 4. Fig. 3 also shows that at 45 kv, T for the aqueous solution is 0.610. and that T for the oil solution is 0.220. These values were transferred to Fig. 4 to give the triangular calibration plot from which the brine and oil saturations can be found, after the gas saturation has been determined at 33 kv.

By D. L. Sikarskie, B. Paul

A theory is presented for the static penetration of a single rigid wedge into brittle material. The material considered is one which exhibits both crushing and chipping phases in the penetration process. If the wedge angle and three parameters are specified, the theory predicts forces and associated penetrations during both the crushing and chipping phases. For certain ranges of the parameters agreement with the limited experimental data available is promising, except for the initial phase of the penetration process where refinements on the proposed theory are required. The theory also predicts that for certain values of the wedge angle and other known parameters, the chipping process does not occur and penetration is due entirely to crushing. When viewed in detail, the drilling of rock by percussive means involves, among other things, system dynamics, actuating forces, dynamic stress levels and the actual penetration mechanism of the bit into rock. If rock drills are to be significantly improved, a thorough understanding of the entire system would be highly desirable. In this paper, one aspect of the system, namely the mechanism of penetration of the bit, will be studied in detail. It has been found1 that for the velocities encountered in percussive drilling (of the order of 20 fps) a static analysis adequately describes the penetration process, at least for some rocks. Hence, we will only be concerned with describing analytically the static penetration of a single wedge shaped tool. It will further be assumed that the wedge is long enough to permit a two-dimensional analysis. Numerous authors have studied the static penetration of a wedge into rock. The following papers give some of this work and provide additional references to other work. Cheatham2,3 has assumed the rock to behave plastically and has obtained force-penetration equations for both Coulomb-Mohr and parabolic yield criteria. Evans and Murrell4 have studied the penetration of two types of coal and have found equations relating the penetration characteristic (P/dSc) to wedge angle for the various strength coals tested. race' attempted to find a correlation between hardness as determined by indenting the material and other mechanical properties and concluded that the results of such a test are generally inconclusive. His paper however contains a very extensive bibliography on the indenting of many different materials. Gnirk6 also has a fairly complete literature review on the static penetration of rock, of which he makes use in his indexing studies. A wide range of behavior is found in the wedge penetration of different rocks under different external conditions. For example, a rock that is essentially elastic-brittle at standard pressure may become elastic-plastic at a high confining pressure.7 It has also been observed4. " that some rocks will merely be crushed and indented by a wedge, whereas others will crack and form chips, furthermore the existence or non-existence of chips depends in great measure on the geometry of the indentor, type of rock and the depth of penetration. Hence, to attempt a theory which embraces all possible behavior is not practical at present. We, therefore, confine our attention to predicting the force-penetration characteristic and volume removal behavior for a type of rock which exhibits both crushing and chipping phases in the penetration process. Such behavior is characteristic of the harder rocks such as granites and represents a more difficult problem than the behavior of softer rocks such as coal and certain sandstones. In this preliminary study an attempt will be made to describe only the essential features of this complex penetration process. A qualitative description of these essential features is obtained with the aid of Fig. 1.1, where a wedge of vertex angle 28 is shown at some intermediate stage of the penetration process. As the wedge advances, the rock is fragmented (i.e. crushed) in some local region surrounding the wedge, the shape of this region being unknown. Simultaneous with the fragmentation in this local region, essentially elastic stresses are assumed to be building up in the surrounding rock. When a certain penetration level, di+1, is reached, the stresses along some surface are sufficient to cause failure and a chip is thus formed. The process now repeats, i.e., a crushing phase followed by the formation of a chip.

Jan 1, 1965

By W. O. Philbrook, A. E. El-Mehairy

The reduction by hydrogen of individual particles of dense hematite implanted in beds of inert spheres is controlled by single-particle kinetics. No evidence of reagent starvation was found down to low flow rates established by pressure gradients as low as 0.01 in. H2O per- in. of depth in beds of spheres as small as 3/16 in. diam. The optimum size for most rapid reduction of beds of homogeneous ores results from the effect on reducing potential of the gas of competing factors of supply and consumption. A recent publication1 presented the results of a study of the rate of reduction of iron ore in a fixed bed by hydrogen introduced at constant pressure differential. Under these conditions the reagent flow rate varied directly with the bed permeability, which was a function of particle size and shape and bed voidage, and inversely with the temperature-dependent viscosity of the gas. The present note adds data from supplementary experiments designed to reveal whether or not any partial reagent starvation arising from a flow-dependent transport resistance in the gas phase might have been operative. Kinetic studies were made of the reduction of individual spheres of iron oxide inserted into beds of inert spheres, so that the reagent flow rate and aerodynamic conditions were again determined by bed characteristics and temperature. The experimental techniques and apparatus were similar to those previously described.' The synthetic iron ore spheres were wet-rolled by hand from powdered, reagent-grade* Fe2O3 and subsequently dried and then fired in air at 1250°C. The indurated pellets has almost no porosity as indicated by their specific gravity of 5.10. The beds were made of dense alumina spheres, closely sized to the same dimension as the iron oxide spheres, in the following diameters: 3/16, 1/4, 5/16, and 3/8 in. Each bed was hand-packed of particles of a single size to a controlled voidage of 0.32 and depth of 3 in. within a capsule having an internal diameter at least 10 times the particle diameter. A few weighed iron oxide spheres were individually planted in the central plane of the bed of inert spheres at points away from the wall. Reduction was carried out at atmospheric pressure by purified hydrogen at 670°, 800°, and 985°c. The reagent was supplied at precisely controlled pressure differentials of 0.01, 0.02, and 0.03 in. of water per in. of bed depth. This gave a range of flow rates similar to that used in the study of beds of ore and comparable with blast-furnace practice in terms of mols of reducing gas per hr per sq ft of cross-section. Viscous flow prevailed in all beds under the experimental conditions of this study. The reduced particles were checked for loss in weight and then sectioned for metallographic examination. Occasional particles were found to have contained minute internal cracks that interfered with the concentricity of the reduction interfaces, and data for such particles were rejected. An experimental rate constant for the reduction of the imbedded Fe2O3 spheres was calculated on the assumption that the rate was proportional to the metal-oxide interface area by an equation that has been found by McKewan2 to describe the reduction of single spheres

Jan 1, 1962

Page Foreword. By Edmund M. Wise..................... 3 A.I.M.E. Officers and Dircctors...................... 4 Institute of Metals Division Officers and Committees............ 7 Institute of Metals Division Annual Award Certificate............ 8 Institute of Metals Division Lectures and Lecturers............. 9 Photograph of E. H. Dix, Jr., Institute of Metals Division Lecturer...... 10 PAPERS Acceleration of the Rate of Corrosion by High Constant Stresses. By E. H. Dm, JR. (Institute of Metals Division Lecture, T. P. 1204).......... 11 Variation of Internal Friction with Grain Size. By Clarence Zener and R. H. Randall. (T.P. 1146, with discussion) .............41 Changes in Damping Capacity during Annealing of Alpha Brass. By John T. NoRton. (T.P. 1168, with discussion)................49 An Electron Diffraction Study of Anodic Films. By R. A. HarrinQton and H. R. Nelson. (T.P. 1158).....................62 Determination of Orientations by Etch Pits. By Charles S. Barrett .and L. H. Levenson. (T.P. 1171, with discussion).............76 Process of Precipitation from Solid Solution, I—A Crystallographic Mechanism for the Aluminum-copper Alloys. By Carl H. Samans. (T.P. 1186). . . 85 Age-hardening of Aluminum Alloys, IV — Discussion of the Theory. By WilTJam L. Fink and Dana W. Smith. (T.P. 1083, with discussion). . . 95 Structure of Aluminum after Compression. By Charles S. BaRREtt and L. H. evensonON. (T.P. 1104, with discussion)................112 Recrystallization Texture of Aluminum after Compression. By ChaRlEs S. BarRett. (T.P. 1141, with discussion)................128 Plastic Deformation and Recrystallization of Aluminum Single Crystals. By J. A. Collins and C. H. Mathewson. (T.P. 1145, with discussion) . . . 150 Recovery and Recrystailization in Long-time Annealing of 70-30 Brass. By S. E. Maddigan and A. I. Blank. . (T.P, 1166, with disonssion).....170 Correlation of Deformation and Recrystallization Textures of Rolled 70-30 Brass. By R. M. Brick. (T.P. 1144, with discussion).........193 Tensile Deformation of Critically Oriented Brass Crystals. By H. L. Burghoff. (T.P. 1149).............................214 Recrystallization of Lead. By Paul A. Beck. (T.P. 1101, with discussion). . 222 Simple Method of Thermal Analysis Permitting Quantitative Measurements of Specific and Latent Heats. By Cyril Stanley Smith. (T.P. 1100, with discussion).............................236 Metallographic Study of Internal Oxidation in the Alpha Solid Solutions of Copper. By Frederick N. Rhines. (T.P. 1162, with discussion). . . . 246

Jan 1, 1940

By Edward Gridley

Members of the Institute who were present at the Amenia, N. Y., meeting, in October, 1877, will remember their visit to the hematite mines, just west of the village of Amenia, and some of them may perhaps recall the deposit of carbonate ore south of the opening made for the hematite. The smelting of this carbonate during the last few months, has produced an iron that seems worthy of being brought to your notice. A little more than a year ago, at the Wassaie Furnace, Dutchess County, N. Y., we made a few hundred tons of iron from a mixture of two-thirds ram carbonate and one-third Chateaugay ore, hoping that it would be suitable for steel purposes, but as the iron showed phosphorus 0.189 per cent., it, was not offered. This iron looked well and seemed quite strong, and gave good results in malleable castings; but no special tests of strength were made. About February 1st, of this year, we began using two-thirds roasted carbonate, and one-third Chateaugay, and noticing that the iron mas stronger than usual, we had two samples tested, which showed tensile strength of 32,014 and 34,176 pounds per square inch. After our stock of Chateaugay ore was exhausted, me put on one-third ram carbonate with the two-thirds of roasted carbonate, and the first test made of the iron, showed 40,008 pounds per square inch. The three tests given above were made by Mr. A. J. Copp and Mr. E. B. Manning, of the Phoenix Furnace, Millerton, N. Y., on a machine of Riehle Bros., Philadelphia. Since these tests were made, they have broken samples made with all carbonate ore as follows: 39,669, 40,816, 41,882, 42,281, 39,902, and 40,130 pounds per square inch. A test taken from the same bed of iron as the last-mentioned (40,130), was broken by Mr. A. Blass, at Irondale Furnace, showing 40,151 pounds per square inch. A sample broken on the Riehle Bros. machine, at Stevens Institute, under direction of Professor R. H. Thurston, showed 40,000 pounds per square inch. Another sample was broken by Professor Thurston on his torsion machine, and gave torsion 7", and tensile strength of 44,500 pounds. And

Jan 1, 1884

Page Foreword. By Edmund M. Wise..................... 3 A.I.M.E. Officers and Dircctors...................... 4 Institute of Metals Division Officers and Committees............ 7 Institute of Metals Division Annual Award Certificate............ 8 Institute of Metals Division Lectures and Lecturers............. 9 Photograph of E. H. Dix, Jr., Institute of Metals Division Lecturer...... 10 PAPERS Acceleration of the Rate of Corrosion by High Constant Stresses. By E. H. Dm, JR. (Institute of Metals Division Lecture, T. P. 1204).......... 11 Variation of Internal Friction with Grain Size. By Clarence Zener and R. H. Randall. (T.P. 1146, with discussion) .............41 Changes in Damping Capacity during Annealing of Alpha Brass. By John T. NoRton. (T.P. 1168, with discussion)................49 An Electron Diffraction Study of Anodic Films. By R. A. HarrinQton and H. R. Nelson. (T.P. 1158).....................62 Determination of Orientations by Etch Pits. By Charles S. Barrett .and L. H. Levenson. (T.P. 1171, with discussion).............76 Process of Precipitation from Solid Solution, I—A Crystallographic Mechanism for the Aluminum-copper Alloys. By Carl H. Samans. (T.P. 1186). . . 85 Age-hardening of Aluminum Alloys, IV — Discussion of the Theory. By WilTJam L. Fink and Dana W. Smith. (T.P. 1083, with discussion). . . 95 Structure of Aluminum after Compression. By Charles S. BaRREtt and L. H. evensonON. (T.P. 1104, with discussion)................112 Recrystallization Texture of Aluminum after Compression. By ChaRlEs S. BarRett. (T.P. 1141, with discussion)................128 Plastic Deformation and Recrystallization of Aluminum Single Crystals. By J. A. Collins and C. H. Mathewson. (T.P. 1145, with discussion) . . . 150 Recovery and Recrystailization in Long-time Annealing of 70-30 Brass. By S. E. Maddigan and A. I. Blank. . (T.P, 1166, with disonssion).....170 Correlation of Deformation and Recrystallization Textures of Rolled 70-30 Brass. By R. M. Brick. (T.P. 1144, with discussion).........193 Tensile Deformation of Critically Oriented Brass Crystals. By H. L. Burghoff. (T.P. 1149).............................214 Recrystallization of Lead. By Paul A. Beck. (T.P. 1101, with discussion). . 222 Simple Method of Thermal Analysis Permitting Quantitative Measurements of Specific and Latent Heats. By Cyril Stanley Smith. (T.P. 1100, with discussion).............................236 Metallographic Study of Internal Oxidation in the Alpha Solid Solutions of Copper. By Frederick N. Rhines. (T.P. 1162, with discussion). . . . 246

Jan 1, 1940

By Ralph E. Esarey, G. F. Fix

The oil and gas industry in Indiana in 1938 showed considerable improvement over the preceding year. Most of the drilling and development during the year, as in the past several years, was in the Indiana portion of the Illinois Basin, but increasing interest was apparent in the old Trenton area, for possibilities of further production in the Trenton formation and the underlying St. Peter sandstone. Interest in all other portions of the state was at a new peak, since many areas have never been prospected. Natural gas production continued to drop during 1938, since new discoveries have not been able to keep pace with the rapid decline in older areas. Oil production increased considerably, chiefly through the discovery of new fields. Older fields contributed about the same quantity of oil during 1938 as during the preceding year. There were 159 wells completed in Indiana during 1938, an increase of 25 over the preceding year. Of these, 48 were oil wells, 41 were gas, and '70 failed to find commercial production. Forty-three, or about 20 per cent, were wildcat. Six of these were productive—three oil wells and three gas wells. Thirty-nine wells on which operations started during the year had riot been completed by Dec. 31. Fourteen others were temporarily abandoned, with the possibility that several will be drilled to completion in the near future. A new oil field (Heusler) was discovered in May 1938, in sees. 1 and 12, T. 7 S., R. 12 W., Posey County. Production was found in the Waltersburg (Upper (Chester) sandstone at a depth of approximately 1775 ft. At the close of the year, Heusler field had nine producing wells and two drilling. The Point township area, Posey County, near the confluence of the Wabash and Ohio Rivers, held promise of good production from the McClosky lime, but offsets to the, discovery well had only shows of oil. The discovery well declined rapidly in production arid was finally plugged. In the Oaktown field, Knox County, a wildcat came in with a good flow of gas, extending the field to the east, and proving considerably more acreage. A new gas area was discovered in Sullivan County, and four good wells were completed. The discovery well was in sec. 35, T. 8 N., R. 10 W., and had an initial

Jan 1, 1939

By Ralph E. Esarey, G. F. Fix

The oil and gas industry in Indiana in 1938 showed considerable improvement over the preceding year. Most of the drilling and development during the year, as in the past several years, was in the Indiana portion of the Illinois Basin, but increasing interest was apparent in the old Trenton area, for possibilities of further production in the Trenton formation and the underlying St. Peter sandstone. Interest in all other portions of the state was at a new peak, since many areas have never been prospected. Natural gas production continued to drop during 1938, since new discoveries have not been able to keep pace with the rapid decline in older areas. Oil production increased considerably, chiefly through the discovery of new fields. Older fields contributed about the same quantity of oil during 1938 as during the preceding year. There were 159 wells completed in Indiana during 1938, an increase of 25 over the preceding year. Of these, 48 were oil wells, 41 were gas, and '70 failed to find commercial production. Forty-three, or about 20 per cent, were wildcat. Six of these were productive—three oil wells and three gas wells. Thirty-nine wells on which operations started during the year had riot been completed by Dec. 31. Fourteen others were temporarily abandoned, with the possibility that several will be drilled to completion in the near future. A new oil field (Heusler) was discovered in May 1938, in sees. 1 and 12, T. 7 S., R. 12 W., Posey County. Production was found in the Waltersburg (Upper (Chester) sandstone at a depth of approximately 1775 ft. At the close of the year, Heusler field had nine producing wells and two drilling. The Point township area, Posey County, near the confluence of the Wabash and Ohio Rivers, held promise of good production from the McClosky lime, but offsets to the, discovery well had only shows of oil. The discovery well declined rapidly in production arid was finally plugged. In the Oaktown field, Knox County, a wildcat came in with a good flow of gas, extending the field to the east, and proving considerably more acreage. A new gas area was discovered in Sullivan County, and four good wells were completed. The discovery well was in sec. 35, T. 8 N., R. 10 W., and had an initial

Jan 1, 1939

By G. Krauss, J. M. Thompson, H. Y. Kumagai

Boron-doped p-type and arsenic-doped n-type source materials were used to deposit thin silicon films on amorphous fused quartz substrates by cathodic sputtering in argon atmospheres. All as-sputtered films were found to have high electrical resistivities of about 104 ohm-cm, despite controlled variation of the substrate temperature from 50O to 400°C. The high resistivity of the n-type films persisted even after postdeposition heat treatments as high as 1000°C, while p-type films showed a sharp decrease in re-sistivity to values on the order of 1 ohm-cm or lower after heat treatments above 650°C. X-ray and electron diffraction, together with transmission electron microscopy of the p-type films, revealed that the improved electrical properties resulted from two distinct processes. A primary crystallization or recovery within the pains, which were approximately 200Å diam in the as-sputtered films, accompanied the initial sharp drop in resistivity at 650°C. Following this process, a secondary recrystallization or discontinuous grain growth was nucleated in films heated at 1000°C. The resulting significantly increased size of certain grains and the corresponding decrease in grain boundary area accompanied an additional decrease in resistivity after heat treatment at 1000°C. The properties of thin silicon films are of interest because of their possible application in device technology. Although evaporated silicon films on amorphous substrates1-3 and both sputtered and evaporated germanium films4-' have been studied in some detail, sputtered silicon films have not been widely investigated. It has been observed that evaporated silicon films deposited at substrate temperatures below approximately 600°C are amorphous.1,3,9,10 At substrate temperatures higher than this, the films are polycrys-talline, sometimes exhibiting a fiber texture with the fiber axis normal to the substrate surface.' Similar results have been obtained with germanium films, although in this case the substrate temperature for the amorphous to crystalline transformation is reported to be as low as 150OC.5 The mechanism of film deposition by cathodic sputtering differs markedly from that of thermal evaporation. It might be expected, therefore, that the properties of sputtered and evaporated silicon films would also differ. The purpose of our study was to determine the effects of deposition conditions and heat treatments on the electrical resistivity, structure, and composition of thin silicon films sputtered on fused quartz substrates. EXPERIMENTAL DETAILS Apparatus. A schematic diagram of the sputtering apparatus is shown in Fig. 1. The vacuum chamber was enclosed by an 18-in.-diam by 12-in.-high Pyrex bell jar mounted on a stainless-steel base plate. Access holes in the base plate were used to supply argon gas to the chamber, to allow for various electrical feedthroughs, and to provide mechanical motion to the shutter between the source material and substrate. The chamber was evacuated by a pumping system consisting of a 720 liter per sec oil diffusion pump backed by a 13 cu ft per min mechanical pump. Ultimate pressures of less than 1 x 10-6 torr could be achieved. The substrates were securely mounted on the stainless-steel substrate holder by quartz tabs held in place by stainless-steel screws. Temperatures of the substrate holder were measured by a thermocouple inserted within the holder. A quartz lamp was used to heat the holder and temperatures as high as 420°C could be maintained. Deposition Conditions and Procedure. The substrates used were polished fused quartz slides 116 by 1-12 by 3 in. and were outgassed at 200°C for 1 hr at a pressure less than 1 x 10-5 torr before film deposition. This was followed by a presputtering period of 2 hr during which the movable stainless-steel shutter was so positioned that deposition on the substrate was prevented. At a sputtering voltage of 5000 v dc and an argon pressure of 0.03 torr, the cathode cur-

Jan 1, 1967

By Winston A. Wong, John J. Jonas

Commercial purity aluminum was deformed by extrusion over the temperature range 320° to 616°C and the strain rate range 0.1 to 10 per sec. Flow stresses and strain rates were calculated from the experimenLa1 ram pressures and speeds. The stress-strain rate-lemperature relationship in extrusion was found to be similar to that in creep. Extrusion, torsion, compression, and creep data extending over ten orders of magnitude of strain rate and over two orders of magnitude of stress were correlated by a single creep equation. It was concluded that hot-working is a thermally activated process, in which the rate-controlling mechanism is either the climb of edge dislocations or [he motion of jogged screw dislocations. The microstructural changes observed during extrusion were consistent with the proposed deformation mechanisms. ALTHOUGH great progress has been made in understanding the technology of extrusion, very little is known about the actual deformation mechanisms operating during flow. Previous accounts describing extrusion have indicated that the relationship between ram speed (V), pressure (P), and temperature (T) can be given as follows:1 V = apb and P = A' exp(-AT). In these equations, a and b are constants which depend on temperature, A' is a constant which depends on ram speed, and A is a "coefficient" with a different value for each metal. Although these equations have fairly wide application, they do not contribute much to a fundamental understanding of the deformation. Furthermore, extrusion has not hitherto been considered as a thermally activated rate process. This lacuna is surprising because hot-working is similar to high-temperature creep in several respects. There is, in fact, a fair body of experimental evidence suggesting that the material response under hot-working conditions is similar to that occurring under creep conditions, in spite of the many orders of magnitude difference in strain rate.2"4 Since creep has been extensively analyzed in terms of dislocation mechanisms, the comparison of hot-working to creep is useful, for it can suggest the possible deformation mechanisms operating during hot-working. In this paper, the hot extrusion of aluminum will be examined from the point of view of thermally activated deformation mechanisms, such as operate during creep. EXPERIMENTAL PROCEDURE The experimental procedure consisted of extruding commercial purity aluminum* over a range of ram velocities and temperatures at constant die reduction by the direct method. Details of the experimental equipment have been published elsewhere.5 Extrusion was carried out at each of the following billet temperatures: 320°, 376°, 445°, 490°, 555°, and 616°C at the following constant ram speeds: 0.002, 0.008, 0.02, 0.1, and 0.2 in. per sec.* All results were obtained using a square-shouldered die with an extrusion ratio of 40:1, giving a reduction in area of 97.5 pct. The ram force was the dependent variable, and was measured by means of strain gages on the ram and was plotted as a function of ram travel. The sequence of events before making an extrusion was duplicated before each run so as to minimize as much as possible variations in experimental conditions. For example, after the equipment had been assembled, the billet was allowed to heat up to temperature inside the insulated container. Once the container attained the desired temperature, a period of 1/2 hr was allowed to elapse before the extrusion was made. This time was found to be required to allow the billet to reach a steady-state temperature, as determined from previous tests. When all was ready, extrusion was carried out without interruption; that is, the billet was upset and extruded in one operation. EXPERIMENTAL RESULTS AND DISCUSSION The two usual experimental approaches for investigating high-temperature deformation exhibit an important common feature. In the first approach, which corresponds to creep, a constant stress (or load) is applied to the material at constant temperature and the resultant strain is recorded against time. After an initial transient stage, a state of constant strain rate exists (secondary creep), in which a steady-state condition is established which is sensitive to variation in either applied stress or temperature. In the second approach, a constant strain rate is applied and the resultant flow stress is recorded. This corresponds to the situation in hot torsion or hot compression, where it is observed that, for a constant test temperature, there is an initial rise in stress to a steady value which is maintained up to very high strains. In tests of this type, a steady-state region is also established in which the stress is sensitive to variation in either the strain rate or the temperature.3,4,6-16 In both types of tests, therefore, a steady-state region is established after an initial transient. In the case of hot-working this region may be called steady-state hot-working, and it is analogous to steady-state creep with which it has many common features. Stress Dependence of the strain Rate in Extrusion. In order to assess the stress dependence of the strain rate under extrusion conditions, and to compare it to that of creep, as well as of hot torsion and hot compression, the extrusion data were analyzed according to power, exponential and hyperbolic sine creep equations.

Jan 1, 1969

By J. N. Butler, R. J. Morris

A series of organic collectors has been developed which successfully float synthetic secondary uranium minerals, such as autunite, carnotite, and torbernite. Recoveries up to 97 pct have been obtained. With cleaning of rougher concentrates, ratios of concentration as high as 15:1 are possible on head assays of 0.10 to 0.50 pct U 3 O 8. Additions of certain base metal salts aid in recovery and materially increase the rate of flotation and selectivity of the collectors for the synthetic minerals. Flotation tests on natural uranium minerals have not yet equaled results obtained on the synthetics, although these collectors do give better results than conventional collectors for nonsulfide minerals. RAPID increase in mining and milling uranium ores during the past seven years and the discovery of large tonnages of uranium-bearing material too low in grade to stand the cost of leaching have developed considerable interest in possible methods for beneficiating these marginal ores. Such ores are generally classed as those containing less than 0.10 pct U3O8. Development of a beneficiation method that would give both high recovery and high ratio of concentration would also make possible the beneficiation of higher grade ores and would provide higher grades of feed to existing leaching plants. Although considerable research and testing on physical or physico-chemical beneficiation of domestic uranium ores has been done in the past, to the best knowledge of the authors only a single application of physical beneficiation is now in operation on a commercial scale. Flotation has been attempted on the basis of mineral association rather than by direct concentration of the contained uranium minerals. Flotation studies conducted on this project on certain ores gave recoveries of 60 to 70 pct of the uranium by the use of conventional flotation agents such as oleic acid, but ratios of concentration were in the order of 1.5:1 to 2.5:1. Subsequent cleaning to upgrade the concentrates rapidly increased losses in the cleaner tailings, which were not later refloated in the rougher flotation. Selection of Collector: In selecting desirable organic collectors for these oxide systems, a thorough study was made of the relationship between structural characteristics and collector activity by an examination of the behavior of a number of different functional arrangements present in a variety of organic molecules, (see Fig. 1). It is generally accepted that a collector must have a relatively long-chain hydrocarbon radical and a chemically reactive elec-trophilic center. Such a requirement could be met by a large number of compounds, but steric effects at the uranium mineral surface, solubility, compat-ability with aqueous systems, air avidity, bond strength at the mineral surface, interfacial concentration of the collector, and diffusion rate of the formed complex from the air-water interface eliminated many as unsuitable for this purpose. Preliminary investigations were completed of possible collector designs consisting of aliphatic and aromatic hydrocarbon radicals attached to stable combinations of nitrogen, oxygen, sulfur, and halogen electrophilic centers, Fig. 1.Tests were made to determine melting point spans, solubility of mineral-collector combinations in various solvents, reactions with soluble uranium salts, contact angles, and floatability by semi-quantitative beaker methods.' Contact angle determinations were not too useful because of the fine particle sizes of available mineral samples. From the foregoing study it appeared that nitrogen-sulfur electrophilic centers coupled with straight-chain saturated alkyl hydrocarbon radicals would hold the most promise for floating secondary uranium minerals. As the dithiocarbamate compounds can be made to combine these attributes they were selected for further study. The dithiocarbamates form a parallel structure to the xanthates, with the fortuitous exchange of

Jan 1, 1957

By Wallace Ralston

The East Texas district includes the northeast 38 counties of the State of Texas. It still remains one of the most important oil-and-gas-producing areas of the United States, since it includes within its boundaries the large East Texas field. Other fields of importance are: Van, Rodessa, Talco, Cayuga, Long Lake and Sulphur Bluff. Production is from the Nacatoch, Blossom, and Woodbine of the upper Cretaceous and the Paluxy and Glen Rose of the lower Cretaceous. Of these, the Woodbine is the most important, since it is the producing horizon iri the East Texas field. Fields East Texas Field.—There were 2471 oil wells, 1 gas well and 84 failures completed during the year of 1936 in the East Texas field; that is, 1565 fewer than in the year of 1935. The total number of producing wells is now 22,031, of which 50 are temporarily shut down; 18,435 wells flowing their production; 3150 pumping; 293 on gas-lift, and 82 operated by other methods. This shows an increase of 1642 wells on artificial lift over Jan. 1, 1935. The average daily salt-water production is estimated at 42,700 bbl. from 2327 wells—an increase of 1201 wells over the year of 1935. The field is now drilled to an average density of one well to 5.85 acres. Average bottom-hole pressure has dropped from 1193 Ib. to 1168 lb., approximately 1 lb. drop for each 6,600,000 bbl. of oil produced. During the month of December 1936, the estimated daily average production of illegal oil had dropped from 20,500 bbl. in December 1935 to 7500 bbl. The commercial gas production is of minor importance in the East Texas field, and figures for the amount of gas taken from the field are not available at the present time. Talco Field, Titus and Franklin Counties.—The discovery well was drilled by Housh, Thompson et al. on the C. M. Carr tract and completed in March 1936, as a pumping well making 552 bbl. per day of 24' gravity oil. This well was first completed at a total depth of 4208 ft., the top of the sand being 4190 ft. Later it was deepened to 4260 ft., which increased the production from 552 to 725 bbl. per day. This field is producing

Jan 1, 1937

By Arnulf Muan, R. W. Taylor

Activities of iron in Fe-Pt alloys have been dctermined by equilibrating mixtures of platinum metal and iron oxide at known oxygen Pressures in a thermobalance at 1300°C. Conzpositions and iron activities of the oxide phase at equilibrium are known from previous work, and compositions of the Fe-Pt alloy phase formed at equilibrium were detcvt?zined from the observed weight changes of the samples. The activity curve obtained shows a strow negative deviation from Raoult's law. THE present investigation was undertaken as part of a research program dealing with phase equilibrium relations existing among the oxides of iron and titanium at 1300°C. At low oxygen pressures of the gas phase in equilibrium with these oxides, the iron activity of the system is high, and considerable alloying of iron with the platinum used as a container material takes place. Thermodynamic data for Fe-Pt alloys at 1300°C are needed in order to evaluate quantitatively the extent of such reactions. Larson and chipmanlhave determined activities of iron in Fe-Pt alloys at 1550°C by equilibrating platinum metal with CaO-iron oxide-SiOzmelts in which the iron activities were known. Compositions of the resulting Fe-Pt alloys were determined by chemical analysis. Mundiath and Gerassimov2 have studied thermodynamic properties of Fe-Pt alloys by electromotive force measurements in the temperature range 550" to 1000°C. The experimental method used in the present investigation is a slight modification of that used by Grube and Ratsch3 in studies of NiCr-alloys. 1) EXPERIMENTAL METHOD 1) General. Mixtures of platinum metal and iron oxide were equilibrated at 1300°C in atmospheres of known oxygzn przssures, and the course of the reactions was followed by measuring the weight changes of the mixtures. The principles involved in the derivation of composition-activity relations from these measurements are illustrated by the composition triangle for the system Fe-FeZO3-Pt shown in Fig. 1. Take as an example a mixture of FeZO3 (hematite) and platinum such that the total composition is represented by point T. If this mixture is heated to 1300c in air (poz = 0.21 atm) and the oxygen pressure is then reduced gradually, the oxygen content of the oxide phase decreases and increasing amounts of iron enter the metal phase. As the oxide phase and the metal phase for all practical purposes are insoluble in each other, their compositions are represented by points moving toward Fe along the joins Fe-Fe,03 and Fe-Pt, respectively. The total composition of the mixture during this process also changes, but only with respect to oxygen content, because the vapor pressures of iron and platinum are negligible at 1300°C. Hence the change in total composition is described by a straight line (constant Fe/Pt ratio) radiating from the 0 apex of the composition triangle Fe-Pt-0, of which the triangle in Fig. 1 is a part. Only one such line ("oxygen reaction line", T-T",) is shown in Fig. 1. The total composition of the alloy-iron oxide mixture at any instant must, in addition, be located on the straight line (conjugation line) connecting the two points representing the compositions of the two coexisting phases. It therefore follows that the total composition of the mixture at any instant is represented by the point of intersection between the conjugation line and the oxygen reaction line. An example of the situation prevailing at a chosen oxygen pressure, po2, is shown in Fig. 1 by points a' (alloy composition), b' (oxide composition) and T' (total composition). Point b' is known from the work of Darken and Gurry,4 and point T' is experimentally determined by the observed weight change of the mixture (distance T-T). Hence, point a', the composition of the alloy, is determined from the above data as the intersection between the join Pt-Fe and the extension of the straight line bl-7'. The activity of iron in the alloy at equilibrium is identical to that of the iron oxide phase, if the same

Jan 1, 1962

By A. H. Larson, R. J. McClincy

ALTHOUGH arsenic has a very high vapor pressure and vacuum distillation appears to be a likely method for its removal from lead, the published literature contains virtually no information concerning the vacuum removal of arsenic from lead. Caldwell, Spendlove, and St. Claire1 mention arsenic in their investigation of the removal of volatile metals from lead by vacuum distillation. They do not, however, give any data for arsenic removal or refer to any actual experimental work involving arsenic dissolved in lead. Moriyama, Kozuka, and Miura2 have determined the activity of arsenic in dilute As-Pb alloys in the temperature range from 450" to 600°C using a closed galvanic cell. They found that the activities of both arsenic and lead showed a positive deviation from ideality at 600°C. In view of the lack of experimental data regarding the vaporization of arsenic from As-Pb alloys, a limited vapor pressure study was made on liquid alloys containing from 0.5 to 3.3 wt pct As in lead at 703°C. The pressure of As4(v) above the alloys studied was determined from weight-loss data collected by means of the inert-gas saturation method. The experimental apparatus and procedure used were similar to that discussed by Alcock and Hooper9 with modifications as described by the authors., The technique involved was one of passing a known volume of inert gas over the alloy to be studied in a known amount of time and determining the loss in weight of the sample. Because of the low vapor pressure of lead at 703"C, the observed weight loss could be attributed solely to the vaporization of arsenic as the tetratomic molecule AS43 Measurements of the apparent vapor pressure were repeated at different inert-gas flow rates until from three to five values were obtained which were independent of inert-gas flow rate. This value of the apparent vapor pressure was taken to be the equilibrium vapor pressure of the alloy under consideration. The vapor pressures measured in this investigation have been converted to the activities of arsenic in As-Pb alloys, Table I, by use of the data compiled by Elliott and Gleiser5 for the vapor pressure of pure arsenic. The standard state for arsenic was chosen as the pure, hypothetical, supercooled liquid. The activity of arsenic was calculated from the fourth root of the ratio PAs,/PAS,. The low magnitude of the vapor pressures given in Table I explains the difficulty en- countered by earlier workers in successfully vacuum distilling arsenic from very dilute As-Pb alloys. The data shown in Fig. 1 indicate that the As-Pb system behaves ideally. The apparent outlier represented by the alloy containing 1.43 mol pct As is a result of the fact that the pressure of As, above the alloy was barely detectable by the experimental procedure used in this investigation. Because of this, the apparent vapor pressure determined for this alloy could be in considerable error. Moriyama, Kozuka, and ~iura' have reported that arsenic shows a positive deviation from ideality in dilute solution in lead. However, details of their results have not been made available. This research was made possible by a grant from the National Science Foundation (GK-196) for which the authors are very appreciative.

Jan 1, 1970

By Ottar Dragge, C. Danielsson, Bo Kalling

DISCUSSION, T. L. Joseph presiding L. F. Reinartz (Armco Steel Corp., Middletown, Ohio) —I would like to know, in the practical application of the Kalling process, what kind of a lining was used, how thick was the lining, and how much metal was treated at one time? S. Fornander (author's reply)—The rotary furnace is lined with a course of fireclay bricks 6 in. thick. This course is backed by 5 in. of insulation. The furnace has a capacity of about 15 tons. Mr. Reinartz—How was the ladle preheated? Mr. Fornander—As pointed out in the paper, the furnace was heated by a gas flame in the beginning of the experiments. During these first tests, however, the desulphurization was inconsistent. We think that this was due to the fact that iron droplets sticking to the furnace walls were oxidized by the gas flame. Now, the furnace is operated without preheating of any kind, and the results are much better. T. L. Joseph (University of Minnesota, Minneapolis, Minn.)—I might add one comment. This furnace was heated with a flame and for a time they had a little difficulty due to some residual metal in the rotating drum that would oxidize in between treatments and they found therefore, that it was very essential to drain the drum completely of metal so that they would not build up any ferrous oxide between treatments and they eliminated some of their erratic heats by maintaining those more reducing conditions. It was interesting to watch this operation. As soon as the drum started to rotate there was considerable flame, at least, at the time I saw it, that came out around the flanges, indicating there was quite a little pressure on the inside of the drum. W. 0. Philbrook (Carnegie Institute of Technology, Pittsburgh)—Is the reaction slag in the Kalling process liquid or solid, and how is it separated from the metal? Mr. Fornander—In the process there is no slag in the usual sense of the word. The lime powder does not melt during the treatment. After the treatment the lime is still in the form of a fine powder. It is separated from the metal by means of a piece of wood of suitable size placed within the furnace before it is emptied. D. C. Hilty (Union Carbide & Carbon Research Laboratories, Niagara Falls, N. Y.)—Dr. Chipman has given us some of his ideas in connection with a specific effect of silicon and silica on sulphur elimination and how silicon might interfere with desulphuriz- ing in the blast furnace. I wonder if he would like to elaborate on the possibility of a similar effect of silicon in the Kalling process? J. Chipman (Massachusetts Institute of Technology, Cambridge, Mass.)—Silicon does not interfere with the Kalling process. Anything that has strong reducing action is good for desulphurization. In these tests where the temperature was low compared to blast furnace temperatures, the silicon that is in the metal is a better reducing agent than the carbon. At high temperatures, carbon is the better. It is not the silicon in the metal that interferes with desulphurization, it is the silica in the slag. Mr. Joseph—I might add that the metal that was tapped from the drum after desulphurization was really at quite a low temperature. It was not measured, but I think it was well under 1300 °C, probably 1200" or a little above that. That was one of the difficulties, and I think there is no question about the fact that the Kalling process—in that it affects desulphurization between powdered lime, solid and liquid iron— is a reaction definitely between the solid lime and the liquid iron. E. Spire (Canadian Liquid Air, Montreal, Canada) — This Kalling process seems very interesting to us and after all it is only a mixing action that is taking place between the iron and the slag. We have attempted to do the same thing in another way. We have placed at the bottom of the ladle a porous plug through which we injected an inert gas. It can be nitrogen or argon. This plug is placed at the bottom of the conventional ladle and gas injected through the plug. That has appeared in our patent. To define this new type of treatment, I use the word gasometallurgy. I do not know if you like it, but it is a way of defining methods of treating metal using gases. What we do is exactly what is done in the exchange process in another way. We have a porous plug at the bottom with a high lime slag on top of the metal. Using this method, we have very good agitation of metal and slag, and with a small flow of gas, we can achieve a very strong agitation. For instance, in the 500 lb ladle, we use only 5 liters of gas a minute. We have an agitation compared to very rapidly boiling water in a pail. Moreover, the agitation can be controlled to create any amount of mixing desired. In a few minutes, with this method, the sulphur dropped from 0.58 to 0.11. These results have been improved since, and we have obtained results like 0.08

Jan 1, 1952