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By M. Yokoi, K. Yoshida, T. Ishihara

The solubility of aluminum in cryolite melts has been determined by measuring the weight loss of aluminum submerged in melts contained in closed silicon nitride crucibles. The solubility in pure cryolite has also been checked with radioactive isotopes. The solubility decreases with increasing A1203 concentration, decreasing temperature, and decreasing cryolite ratio. The change of aluminum solubility in pure cryolite with the activity controlled by using Al-Ag and A2-Cu alloys supported the assumption that aluminum would dissolve in the form of monovalent ions according to the reaction 2AI + A1' —3 A1'. DURING the electrolytic production of aluminum, the electrodeposited metal redissolves in the bath in some form and is subsequently oxidized back to the former ionic state. This dissolution is believed to cause a decrease in current efficiency. Reported data on the solubility of aluminum in cryolite melts are scattered. The mechanism of the dissolution has not yet been determined, although certain tentative interpretations have been proposed. Many previous studies were performed under different test conditions. Studies were performed in open Systems and closed systems,'o and some were apparently not given sufficient time to Saturate." The solubility can be determined either analytically or gravimetrically. The analytical determination involves measurement of hydrogen gas evolved when frozen cryolite bath saturated with aluminum is treated with sodium hydroxide or hydrochloric acid. The gravimetric determination, adopted by many investigators,'-37'3>14 involves measurement of weight loss of the metal after equilibration with a known amount of salt. It appears that the former technique yields much smaller values of solubility than the latter technique. This large difference in results strongly suggests that the dissolved metal in the cryolite melt is no longer in the metallic state. In the present study, the solubility was determined by the gravimetric technique at various activities of aluminum using A1-Ag and Al-Cu alloys. An attempt was also made to determine the ionic (or atomic) state of the dissolved metal from the solubility data. 1) EXPERIMENTAL Apparatus. Preliminary tests demonstrated that silicon nitride was suitable as a container material since it is compatible to both the fluoride melts and molten aluminum. Crucibles were made from silicon powder nitrided with Nz gas at 1600°C. The good compatibility between crucible and melts is due to the near perfect nitrogenation of silicon. Only small amounts of silicon were found in the aluminum metal after the experiments. The crucible dimensions were 90 mm inside height, 38 mm ID, 105 mm outside height, and 50 mm OD. Close-fitting lids made of silicon nitride were also prepared. The crucible was placed in a close-fitting graphite crucible heated by a vertical Kanthal furnace, Fig. l. The lid and crucible are fastened tightly together by the condensation of vaporized bath in the narrow gap between them. The temperature was measured in the wall of the graphite crucible and controlled within * 5°C. The temperature difference between the measuring point and the interior of the melts was initially determined. Materials. The materials used were: Greenland cryolite (impurities CaF,, 0.5 pct; AlzO3, 0.2 pct; high-purity aluminum metal (purity 99.99 pct); A1203 and AlF, (provided by Nippon Light Metal Co., Ltd); reagent-grade NaF and CaF2; and 99.9+ pct Ag and Cu. Powdered reagents were carefully dried before use. A1-Ag and A1-Cu alloys were prepared before the experiments; their composition was checked by analysis

Jan 1, 1969

By J. W. Downey, J. B. Darby, L. J. Norton

THE only previous investigation of the phase equilibria in the Ta-Pd system was reported by Greenfield and Beck.1 Their work (actually a portion of a much broader survey) was limited to the composition range 50 to 75 at. pct Ta and to a single temperature, 1000°C. The results indicated that no intermediate phases were present at this temperature. They pointed out that this was an unexpected result in view of the fact that niobium, which belongs to the same group in the periodic table as tantalum and has essentially the same atomic size, forms a o phase with palladium.' Also, tantalum in combination with rhodium,' iridium,' or platinum' stabilizes the s phase. By analogy, the Ta-Pd system would also be expected to contain a s phase. The present investigation was therefore undertaken to explore more fully the phase relationships in this system. Alloys were prepared by arc melting on a water-cooled copper hearth in an argon-helium atmosphere. The purity of the starting materials was greater than 99.9 pct. The weight losses on melting were less than 1 pct and therefore the alloys were not analyzed chemically. Specimens were wrapped in molybdenum foil, encapsulated in quartz capsules under a vacuum of at least 1 x 10-5 mm of Hg, annealed as indicated in Table I, and water quenched. Optical and X-ray metallography were used for identifying the phases present in the annealed and quenched alloys. The alloys were resistant to attack by several acids; however, a sodium cyanide electroetch and an immersion etch containing 1 part HF, 1 part HNO3, 2 parts H2SO4, and 5 parts H2O by volume were found satisfactory. The X-ray diffraction patterns were taken with a Straumanis-type Debye-Scherrer camera and filtered copper or chromium radiation. A summary of the phases found in this investigation is presented in Table I. No attempt was made to determine the composition limits of the various phases. The present results indicate that this system consists of two terminal solid solutions separated by at least four intermediate phases at the approximate compositions Ta3Pd, -TaPd, TaPd,, and TaPd3. The Ta-rich solid solution, containing less than 10 at. pct Pd at 1150°C, is in equilibrium with a o phase which is stable in the vicinity of 25 at. pct Pd. The latter phase is also in equilibrium with a bct phase at the equiatomic composition. At high temperatures it appears that the Pd-rich solid solution extends to at least 66.6 at. pct Pd and is in equilibrium with the bct phase. When annealed at 900°C, a sample containing 66.6 at. pct Pd transformed to an unidentified phase designated as X. An X-ray diffraction pattern of this phase contained sharp low-angle lines while the high-angle lines were characteristically diffuse. The observed d-spacings and relative intensities for lines in the low-angle region are presented in Table 11. In the vicinity of 70 at. pct Pd an intermediate phase having the TiA13-type structure is formed. It is stable to at least 1100°C, and presumably dissolves congruently into the ter-

Jan 1, 1963

By C. G. Dunn, F. W. Daniels

IN recent publications1-5 the existence and behavior of subgrain boundaries in high-purity metals has been clearly brought to light. Lacombe and Beaujardl by means of special etching methods disclosed in polycrystalline sheets of aluminum the existence of substructures differing in orientation by small amounts (about 1/4"). Boundaries of these structures at relatively high temperatures had the remarkable property' of moving about while the ordinary boundaries remained stationary. Cahn2 also observed substructures in bent and annealed single crystals of aluminum, zinc, magnesium, and rock salt. The position of subboundaries could be explained in terms of a dislocation mechanism of polygonization in which dislocations move into lines at right angles to the bent glide planes thereby relieving elastic stresses in these planes. Guinier and Tennevin8,6 disclosed the further interesting feature that polygonized structures coarsened significantly upon prolonged annealing. Somewhat similar subgrain phenomena have been observed in silicon iron of commercial purity. Although some evidence for the development of macro-mosaic structures in silicon iron already has been reported by one of the authors6,7 under the phenom-enological term "crystal recovery," much better evidence recently has been obtained due to improved etching techniques. In addition, phenomena regarding structural changes have been uncovered. The present investigation is divided into three parts: (1) The phenomenon of Laue spot sharpening on annealing cold-rolled crystals, (2) the phenomena of polygonization and subgrain coarsening The material used in the present investigation was high-grade commercial silicon iron sheet of nominal composition, 3.3 pct Si, 0.004 C, 0.011 P, 0.010 S, 0.04 Mn, 0.01 Al, 0.04 Cu, 0.01 Sn. Large single crystals of this material Were prepared for cold-rolling or bending as scheduled. Cold-rolling of 12 pct was carried out on a laboratory 8-in, diam rolling mill. The bending deformations were performed by pressing the crystals between a solid Fig. 2—lllustrative foue patterns to show Laue spot sharpening. a (Left)—Specimen as cold rolled, b (right)—After 48 hr at 1400°C. round bar and a mating half cylinder, both heavily greased. Individual specimens were cut from the deformed crystals, and the cut edges were deeply etched prior to annealing. Laue photographs were made using 40-kv tungsten radiation. The technique used to disclose the various subboundaries was an electropolish and electroetch in a bath of chrome-acetic acid.' The anodic polishing done at 22 v was immediately followed by etching at a reduced voltage, which was dependent upon the nature of the subboundaries. Phenomenon of Laue Spot Sharpening on Annealing Cold-Rolled Crystals Fig. 1 gives the initial and final orientations of the specimens cold-rolled 12 pct. Each specimen was annealed at a temperature and for a time which caused significant structural changes as evidenced by alterations in Laue patterns. Representative Laue patterns and micrographs showing the essential changes are given in Figs. 2, 3, and 4. The essential points to be derived from these illustrations follow: 1. Annealing at 950°C clearly develops a substructure with the orientation of the cold-rolled specimen. 2. The subboundaries formed obviously separate regions of nearly the same orientation. Some of the subboundaries appear as a sequence of dots similar to those observed in aluminum by Lacombe and Beaujard,' but whether this is due to extremely small differences in orientation is not known at present. 3. The substructure coarsens upon prolonged annealing. 4. Prolonged annealing also causes a decrease in orientation spread according to Laue spot sharpening'

Jan 1, 1952

By Robert E. Green

Experiments were performed in order to investigate the influence of magnitude of driving force, recouery, and previous heat treatment on grain boundary migration in deformed aluminum crystals. The frequency of occurrence of strain-free grains possessing Preferred crystallographic orientations was studied both as a function of heat treatment and as a function of amount of deformation of the matrix crystal. Aluminum of such composition as to exhibit precipitation-hardening behavior was used. CONSIDERABLE work has been devoted to the factors influencing grain boundary migration in metals.1'52 Aust and Rutterl-9 have studied grain boundary migration into matrix crystals containing a striation substructure, which provided a thermally stable driving force during the course of the migration experiments. These authors state that, while variations in the striation pattern were sometimes observed, it was possible to obtain reasonably uniform and reproducible striation structure by careful control of the solidification conditions. Admittedly, this source of driving force is a unique one and has served well in numerous experiments. However, although the striation substructure provides a thermally stable driving force, the subject of its reproducibility from crystal to crystal is questionable. In fact, Aust and Rutter3 attribute the scatter shown in some of their experimental points and several anomalies in boundary migration rates to variations in the substructure driving force along a single specimen. A further limitation on striation-induced driving force is that the driving force cannot be varied over wide ranges in a controlled manner. More often used as a source of driving force is the strain energy stored in a crystal during plastic deformation. This type of driving force has the disadvantage that it is not thermally stable due to recovery taking place simultaneously with the grain boundary mobility measurements. On the other hand, this strain-induced driving force is very reproducible from crystal to crystal since it is very easy to grow single crystals possessing the same purity and crystallographic orientation and then to strain them identically. In order to measure grain boundary migration rates two different methods are primarily used. Most often the technique employed is the heat-cool-etch method1' which involves thermal cycling, while the other technique, developed by Graham and Cahn11 using an X-ray diffractometer and goniometer furnace, involves continuous heating only. Thus the influence of thermal cycling vs continuous heating is a factor to be considered in grain boundary migration rate measurements, particularly in cases where the source of driving force is the strain energy stored in the deformed matrix, and recovery is likely to occur. Numerous recent investigations have shown that extremely small impurity additions to zone-refined metals exert a marked effect on grain boundary migration rates1-5, 9, 12-27 and a few have considered the effect of the distribution of impurities.28-35 The concentration of impurities and their distribution as influenced by heat treatment must also be taken into account in migration-rate studies. In the present article consideration is given to the influence of the magnitude of driving force, recovery, and previous heat treatment on grain boundary migration rates. In order to vary the driving force over a large range it was necessary to use as a source of driving force the energy stored in the matrix crystal during plastic deformation. A majority of the investigations were performed on aluminum specimens which were of such compositions as to exhibit precipitation-hardening behavior.

Jan 1, 1965

By Harvey Cline, Donald P. Ferriss

THE violent outgassing of commercial tungsten and other refractory metals when melted in an electron beam zone refining apparatus1"3 is dealt with experimentally by one or both of two approaches. One is to provide a suitable emission current control1,2 the other is to purify the metal in the solid state before melting.4 The first of these is usually sufficient, but the authors chose also to investigate the source of the troublesome gases and to devise means of solid-state purification. Some further insights into the use of tungsten as a structural material at temperatures near its melting point were also revealed in the course of the work. One may speculate on the causes of gas formation in tungsten at high temperature by inferences from the literature and an examination of the impurities in commercial wire. Davenport5 observed microporosity in both tungsten and molybdenum filaments heated to several hundred degrees below their melting points. Studying the function of oxygen in molybdenum welds, Perry, Spacil, and wulff8 attributed similar porosity to the disproportionation of Moo2 to molybdenum metal and Moo3. Tungsten dioxide also disproportionates7 above 2000oC to yield WO3 vapor at considerable pressure. Commercial tungsten contains some 5 to 20 wt ppm O and a similar concentration of carbon depending on the details and precautions of processing. Therefore, evolution of CO is also a strong possibility as a source of gas at high temperatures. Furthermore, even for activities in the order of 0.01, it may be calculated that the pressure of CO at 3000°C would be over 4000 psi, which is in excess of the tensile strength of tungsten at this temperature.9,10 Powder metallurgy tungsten contains some 0.02 pet Fe and 0.002 to 0.005 pet of the elements Ni, Si, Al, Ca, Mn, Mg, and Mo; at temperatures over 2800°c, therefore, these elements will exhibit appreciable vapor pressure, though small compared to that of WO3 and CO. Some of these impurities may react to form high-pressure monoxides such as SiO and A10. Finally, dissolved and occluded nitrogen is an ever-present source of high-pressure gas. Commercial Type 218, General Electric filament wires, 0.025 in. diam, were heated by resistance in 10 -4 mm of Hg and in argon or hydrogen at pressures from 50 µ to atmospheric. For temperature determinations in vacuo, the Jones - Langmuir8 current-temperature relationship was employed. For gaseous atmospheres, the burn-out temperature was assumed to be the same as in vacuo so that a small, constant correction could be made for temperatures below burn-out conditions (i.e., local heating to failure). Several dozen experiments may be summarized by pointing out some structural observations. At 3050oC in 1 atm of A, porosity is very evident after 30 min, as shown in Fig. 1. For the section in Fig. 2, failure occurred 200°C below the melting point and many voids have grown in the grain bound-

Jan 1, 1962

By L. R. Ingersoll, James Fisher, Harry Vivian

The copper mines of the Keweenaw Peninsula in northern Michigan have long been of interest in connection with deep earth-temperature measurements. The extraordinary low geothermal gradient of l° F. in 223.7 ft. announced by Agassiz1 as a result of measurements dating from 1886, although later2 stated as in error, served to focus attention on this region as one offering, because of the great depth of the mines, unusual opportunity along this line. Lane,3 Van Orstrand4 and others have made valuable contributions to this study. Fresh opportunities afforded by the constant deepening of the mines, improvements in the accuracy and reliability of temperature-measuring instruments together with increasing knowledge of the heat conductivities and specific heats of the rocks, led the Michigan College of Mining and Technology in cooperation with some of the mining companies to renew work on this problem. It is planned eventually to complete a survey which will make use of the favorable opportunities for deep rock-temperature measurements presented in these mines. This survey should include the determination of a depth-temperature gradient in both conglomerate and arnygdaloid mines, and also the variations in temperature at the same depth in different geological formations. The first problem has a direct bearing on the question of providing equipment for necessary ventilation with increased depth. The second may show that a relation exists between the natural rock temperature and the mineral content of the formation. The measurements in all cases are to be guided by heat conduction considerations, to the end that they may represent as closely as possible

Jan 1, 1934

By E. O. Kirkendall

The investigation reported herein was undertaken to obtain data to supplement those presented in an earlier paper,l particularly for longer times at a higher temperature. This information may further develop our knowledge of the mechanism of diffusion in substitutional solid solutions. Diffusion of solute atoms interstitially dissolved is not difficult to visualize: it can take place without much disturbance of the solvent atoms. The mechanism of diffusion of solute atoms substitutionally dissolved is not so easily understood. Many theories have been advanced. Rosen-hain,2,3 Frenkel,4 Smekal,5 Langmuir,3,6 Steigman, Shockley and Nix,' and Johnson8 all proposed theories to explain diffusion. Langmuir's proposed mechanism consisted of a simple cyclic interchange of atoms involving an interchange in lattice positions of four or more atoms. This mechanism, accepted by the author at the time of his previous publication,1 and apparently quite generally accepted, required a net exchange in positions of both solute and solvent atoms in equal numbers. In other words, the rate of diffusion of the solvent and solute atoms would be the same. That this cyclic interchange in lattice positions of solute and solvent atoms in equal numbers is the only true mechanism of diffusion is denied by the evidence presented in this paper. Experimental Procedure This modification of similar procedure1 will be outlined briefly. The method consisted of the following steps: I. A pure Muntz metal (60.6 per cent Cu, 0.1 per cent total impurities) that was almost all beta brass at 780°C. was chosen. 2. The brass was turned between centers in a lathe to a diameter of 0.5965 inches. 3. After the brass was cleaned, it was electroplated with pure copper to a diameter of about one inch. 4. The sample was heated slowly to 400°C. under reduced pressure and held at that temperature for 4 hr. to remove occluded gases. It was then cooled to room temperature. 5. The sample was heated to 780°C. ± 3°C. and held at that temperature for different lengths of time; then quenched. Samples were cut off each time after quenching. Metallographic samples 1/4 in. thick were removed at I hr., 6 hr., 24 hr., 96 hr. and 701 hr. After 96 and 701 hr. samples of about I in. were removed for X-ray analysis. 6. The metallographic samples were polished on the cross section and photomicrographs were taken. 7. The I-in. samples were polished and etched on both ends. With the aid of a microscope each was carefully mounted in a four-jaw chuck in a lathe, so that they could be accurately bored for an arbor. 8. Turnings were taken for each X-ray sample. After each set of turnings, the sample was heated in an oil bath for about 1/2 hr. at 300°C. It was then etched in 25

Jan 1, 1942

By Ronald C. Koo

SMALL additions of potassium, aluminum, and silicon as oxides (referred to as dope) to tungsten have been known for several decades to have a very large effect in raising the recrystallization temperature and altering the recrystallized grain morphology of heavily drawn wire. Previous investigations of this doping effect1 6 have led to various speculations but all failed to deduce unequivocally the physical state or the mechanistic influence of the dopant. Recently, walter7 has observed, by transmission electron microscopy, strings of "fine particles" in heavily rolled and annealed doped tungsten sheet and concluded that they were particles of mullite (Al6Si2013). His conclusion was inferred from the electron diffraction patterns of large particles ex-trated by carbon replication of fractured surfaces of slabs rolled from sintered ingots. That the strings of "fine particles" in heavily rolled and annealed sheet were also mullite was an assumption for which no evidence was presented. A similar investigation has been carried out in this laboratory over the past 2 years on a variety of tungsten wire: doped tungsten, and undoped tungsten, as well as 218 doped tungsten purchased from the Lamp Metals and Components Department of the G.E. Lamp Division. Although the electron microscope observations are similar to those reported by Walter, the writer has reached a different conclusion concerning the physical state of the dopant in annealed tungsten. The purpose of this communication is to present evidence that the strings of "fine particles" observed in transmission specimens are not mullite, but are voids. In the present investigation, tungsten wire, 0.88 mm in diam, was rolled into ribbon 0.2 mm by 125 µ thick. The ribbons were annealed in vacuo at a pressure of -1 x 10-5 Torr and then thinned electrolytically in a 2 pct KOH solution. Fig. 1 shows a typical transmissicjn electron micrograph of a sample annealed at 1700°C for 30 min which reveals rows of closely spaced voids having a light contrast (referred to as "fine particles" by Walter) aligned parallel to the working direction. Stereo micrographs (by D. Moon, Westinghouse Research and Development Center) have shown that these voids do not exist on the surfaces of the specimens as a result of thinning but are within the thin-foil specimens. The following experiments have been performed to verify that these are indeed voids. I) Effect of Annealing. Voids are absent in unannealed specimens and appear only after annealing. This behavior cannot be explained if they were solid particles such as mullite. Precipitation (in an unquenched specimen) upon annealing requires solute elements having decreasing solubilities with increasing temperature. Although the solubility of aluminum in tungsten does decrease with increasing temperature, precipitation requires a concentration in excess of 1.4 wt pct,8 which is at least two orders of magnitude higher than the aluminum content in doped tungsten. It is also unreasonable to assume that particles aligned in rows initially present in unannealed specimens were too

Jan 1, 1968

By E. O. Kirkendall

The investigation reported herein was undertaken to obtain data to supplement those presented in an earlier paper,l particularly for longer times at a higher temperature. This information may further develop our knowledge of the mechanism of diffusion in substitutional solid solutions. Diffusion of solute atoms interstitially dissolved is not difficult to visualize: it can take place without much disturbance of the solvent atoms. The mechanism of diffusion of solute atoms substitutionally dissolved is not so easily understood. Many theories have been advanced. Rosen-hain,2,3 Frenkel,4 Smekal,5 Langmuir,3,6 Steigman, Shockley and Nix,' and Johnson8 all proposed theories to explain diffusion. Langmuir's proposed mechanism consisted of a simple cyclic interchange of atoms involving an interchange in lattice positions of four or more atoms. This mechanism, accepted by the author at the time of his previous publication,1 and apparently quite generally accepted, required a net exchange in positions of both solute and solvent atoms in equal numbers. In other words, the rate of diffusion of the solvent and solute atoms would be the same. That this cyclic interchange in lattice positions of solute and solvent atoms in equal numbers is the only true mechanism of diffusion is denied by the evidence presented in this paper. Experimental Procedure This modification of similar procedure1 will be outlined briefly. The method consisted of the following steps: I. A pure Muntz metal (60.6 per cent Cu, 0.1 per cent total impurities) that was almost all beta brass at 780°C. was chosen. 2. The brass was turned between centers in a lathe to a diameter of 0.5965 inches. 3. After the brass was cleaned, it was electroplated with pure copper to a diameter of about one inch. 4. The sample was heated slowly to 400°C. under reduced pressure and held at that temperature for 4 hr. to remove occluded gases. It was then cooled to room temperature. 5. The sample was heated to 780°C. ± 3°C. and held at that temperature for different lengths of time; then quenched. Samples were cut off each time after quenching. Metallographic samples 1/4 in. thick were removed at I hr., 6 hr., 24 hr., 96 hr. and 701 hr. After 96 and 701 hr. samples of about I in. were removed for X-ray analysis. 6. The metallographic samples were polished on the cross section and photomicrographs were taken. 7. The I-in. samples were polished and etched on both ends. With the aid of a microscope each was carefully mounted in a four-jaw chuck in a lathe, so that they could be accurately bored for an arbor. 8. Turnings were taken for each X-ray sample. After each set of turnings, the sample was heated in an oil bath for about 1/2 hr. at 300°C. It was then etched in 25

Jan 1, 1942

By T. L. Joseph

THE invention of the Bessemer converter process in 1856 added great impetus to the manufacture of steel and is one of the outstanding contributions to process metallurgy. Although the process of refining pig iron by passing air through the molten metal bears the name of Henry Bessemer, it should be mentioned in passing that William Kelley of Eddysville, Ky., worked on the process as early as 1847. Kelley was granted a patent on the process in 1857, inasmuch as he was able to prove priority in discovery.1 After considerable litigation in 1865 the respective interests of Kelley and Bessemer were combined. On Sept. 10, 1856, Robert Mushet of England obtained his first patent on the application of manganese to cast steel. Mushet anticipated trouble in purifying iron by passing currents of air through it. His patent specified that steel made in this way often contained flaws and was red short or cold short. Mushet understood the refining of pig iron into steel well enough to realize the difficulties likely to be encountered from oxidation of the iron. Mushet was not only an inventor but he was also an investigator. He understood the principle of selective oxidation which takes place in the converter process, arid he realized therefore that the remedy for over-oxidation was attainable if a suitable metal could be found at a reasonable cost and in sufficient quantities. His first experiments were made in small crucibles holding a few ounces of metal. Later his work was conducted on a larger scale and with complete success. Manganese had been used in making steel a quarter of a century before the converter

Jan 5, 1927

By J. E. Gould, H. J. Hand

MANY independent studies are being made on slag-metal relationships in the open-hearth furnace, and these studies cannot help but result in an ultimate improvement in the quality of open-hearth steel of both the open and killed types In maintaining quality control at the National Tube Company's plant, emphasis has been placed on an evaluation of the iron oxide content of the steel in as quantitative a manner as possible, in order that the most desirable level of oxidation might be obtained for a given type of steel, and to secure a more precise basis for final deoxidation In the past, various methods were used for estimating FeO content of the metal at tap to ensure uniform and thorough deoxidation of killed steel, avoiding over-deoxidation to minimize the amount of inclusions present and to make as sound a steel as possible For the open-type steels, such control involves obtaining the necessary level of oxidation for the most suitable action of the steel in the molds to provide good surface quality and cross section for the specific grade involved While rapid analytical methods are available for determination of FeO in the liquid metal, such methods are still not sufficiently rapid for routine control on the open-hearth floor, nor do such analyses provide information as to what causes high or long FeO values The method of sampling can still be considered a problem in view of the variability encountered in taking simultaneous duplicate tests With the accurate rapid methods now available for determining carbon in the metal, estimating slag basicity and obtaining temperatures of liquid metal, it was believed possible to determine the influence of the various furnace reactions in establishing the state of oxidation at a given time Simultaneous slag and metal tests were used in this analysis, aided by statistical methods, to determine the factors that affect the metal FeO, and also to make a quantitative evaluation of these factors Data obtained are from actual furnace operations, the metal test being of the spoon, Herty type, and taken in duplicate. Metal temperatures were taken with the open-tube bath pyrometer developed by the Research Laboratory of the United States Steel Corporation This method of taking open-hearth metal temperature was invented by Collins and Oseland,1 and was developed into its present form by L 0 Sordahl,2 of the Research Laboratory The instrument and its mode of operation have been fully described by Sordahl and Sosman in three publications 3,4,5 Slag components were obtained by chemical analysis Data were taken from four 165-net-ton furnaces during the working period of the heat Recognizing that additions of ore affect the

Jan 1, 1942

By J. W. Taylor, E. G. Zukas

THE results of shock-loading studies on copper were reported several years ago by smith. In his experiments, Smith found that there was a correlation between the shock direction and the orientation of twins which the shock produced. By using free-surface-type shots in which the free surface of the specimen was not normal to the shock direction, he showed conclusively that twinning of copper in impulsive loading was caused by the rarefaction wave. Similar tests with iron, however, showed that it twinned during compression. More recent studies of iron2 and on Fe-Si single crystals3 have shown that twinning can be suppressed in these materials by shock loading at pressures high enough so that the velocity of the shock wave exceeds the elastic-wave velocity. From these observations, it appeared that twinning was caused by the shear stresses present in the zone undergoing adjustment from one-dimensional to three-dimensional loading. At high pressures, such a zone becomes so thin that there is insufficient time for the relatively ordered motion of atoms involved in twinning to occur. Twinning in copper, therefore, cannot be produced by a single compressive shock wave because resolved shear stress large enough to create twins exists only for a very short time (0.01 psec or less) before the pressure increases suddenly and loading becomes essentially hydrostatic. (A typical pressure vs time record for a copper shot, illustrating the short rise time of the compression wave, is shown in Fig. 1.) If, on the other hand, a second shock wave can be created in a precompressed sample, then the new elastic limit is several kilobars,4 and a resolved shear stress sufficient to cause twinning should be maintained for an adequate time period (0.1 psec or more). This experimental situation can, in fact, be realized. The experimental arrangement used to do so is shown in Fig. 2. By utilizing the pressure transformation in Fe-V alloys, it was possible to shock-load the copper in compression while the copper was already precompressed. In the first test, an 8 wt pct V-Fe sample was used as a driver for loading the copper, and the copper was exposed to the following series of compressive shocks: 1) an elastic wave of about 8 kbars, which is usually ignored in shock studies; 2) the pressure transformation wave for the driver of 200 kbars; and 3) the driving shock wave of 270 kbars pressure. Metallurgical determination of the angular twin distribution, shown in Fig. 3, with respect to the shock direction and the shock rarefaction direction (which was 23 deg from the shock direction) showed that twinning took place

Jan 1, 1965

By V. H. Wilhelm

The year 1941 in the California oil industry was marked by an increased market demand, drilling activity, and production of crude oil. Although seven new oil fields and two gas fields were discovered during the year, additions to reserves from these discoveries, as well as extensions and revaluations of previous discoveries, were approximately 100 million barrels, as against estimated withdrawals of 230,233,000 barrels. The year was remarkable for the very great increase in domestic demand for all products, which more than compensated for the loss in shipments to Japan, which averaged 60,041 bbl. Per day during 1940. Demand in terms of crude during 1941 was 648,967 bbl. per day as against 632,647 for the same period in 1940. This abnormal increase in demand is due to increased industrial activity, and especially increased railroad activity. Gasoline consumption for 1941 was 241,011 bbl. per day as against 217,744 in 1940. Demand for fuel oil increased from 259,806 bbl. per day in 1940 to 285,896 in 1941, and caused a withdrawal from stocks of more than 7,473,000 barrels. During 1941, total oil storage declined 9,153,000 bbl., but additions to storage of 1,754,000 bbl. of light oil and light oil products were offset by a withdrawal of 10,907,000 bbl. of heavier products. Production during the year is estimated at 230,233,000 bbl. as against 222,784,386 bbl. for 1940. TraNsportation For a short time, California was affected by lack of transportation due to the diversion of tankers. This shortage affected the movement of oil from the Sari Joaquin mated to the refineries, since a large percentage of this production is moved to the coast through pipe lines, and thence by tankers to Los Angeles and San Fran-,iSco, Return of the tanker fleet, which may be temporary, indicates that there is a possibility of ample supplies of petroleum products in the Pacific Northwest. Drilling Activity Contrary to general opinion, drilling activity increased in 1941 over the pre-vious Year, 942 wells being completed in 1941 as against 890 in 1940, an increase Of 6 per cent. This increase was due to the increased demands for fuel oil, and also to the decreased drilling costs, which made many former marginal locations economic. The main activity caused by increased demands for fuel oil was in the Mt. Poso, McKittrick, Midway and Santa Maria Valley oil fields. Dry-hole footage in 1941 was 655,354 ft. as against 583,537 ft. for 1940. Curtailment Voluntary curtailment succeeded in holding production considerably below demand, although it was above the state quota. During the year the top allotment

Jan 1, 1942

By Frederick L. Knouse

THE south border of Espirito Santo begins about 400 km. north of Rio de Janeiro and extends along the Atlantic Coast northward some 325 km. and inland 100 to 150 km. The area under consideration, where quartz crystal of strategic grades has been mined, extends from 19° to 21° and 30" south latitude; and from 40° to 41° and 30" west longitude. This includes the central part of Espirito Santo, chiefly south of the Rio Doce from the Atlantic ocean, and west across the border into Minas Gerais near the town of Aimores, in the municipalities of Aimores, Minas Gerais; Baixo Guandu, Santa Teresa, Santa Leopoldina, Colatina, Joao Neiva, Fundao and Domingo Martines, Espirito Santo (Fig. 1). During 1943 and the first half of 1944, this region accounted for approximately 3 to 5 per cent of the quartz crystal produced in Brazil. Shipments of crystal have been made chiefly by rail to Rio de Janeiro. This region is serviced by the E. F. Minas-Vitoria and E. F. Leopoldina to Rio de Janeiro through Vitoria; and by the E. F. Minas-Vitoria and E. F. Central do Brasil through Bello Horizonte, Minas Gerais to Rio de Janeiro. The major deposits are accessible from the railheads by dirt roads, some being 5 to 30 km. off the road, reached by trail. In 1943 and the first half of 1944, the bulk of the production was from inter mountain marshes and adjoining hillside alluvial placer deposits in the zone surrounding the town of Santa Teresa. Most of these deposits were formed from the erosion of pegmatites, quartz veins and pockets in the gneiss, with minor quantities produced from miarolitic cavity fillings in the granitic rock. EARLY OPERATIONS Mining of quartz crystal in this region began in 1928, and has been stimulated by the market demand for military uses. Before 1936 little attention was given to it, either in Espirito Santo or eastern Minas Gerais. From 1936 to 1941 the Japanese sent agents to various points of production or potential production to acquire quartz through purchase. They bought crystal as small as 10 grams. Since 1941 only the United States and Great Britain have received quartz from Brazil. The United States purchases crystals of loo grams and larger for strategic purposes. The first known discoveries were made either in the municipalities of Aimores, Minas Gerais, or in Baixo Guandu, or Domingos Martines, Espirito Santo. Marketable quartz crystal was first found either in the massive quartz replacement veins of the Victor Hugo mine in the municipality of Domingo Martines, or in the large cores of quartz in the pegmatites near Baixo Guandu, extending into Minas Gerais. PRODUCTION The production of quartz in Espirito Santo from 1936 through 1941 as recorded

Jan 1, 1946

By V. H. Wilhelm

The year 1941 in the California oil industry was marked by an increased market demand, drilling activity, and production of crude oil. Although seven new oil fields and two gas fields were discovered during the year, additions to reserves from these discoveries, as well as extensions and revaluations of previous discoveries, were approximately 100 million barrels, as against estimated withdrawals of 230,233,000 barrels. The year was remarkable for the very great increase in domestic demand for all products, which more than compensated for the loss in shipments to Japan, which averaged 60,041 bbl. Per day during 1940. Demand in terms of crude during 1941 was 648,967 bbl. per day as against 632,647 for the same period in 1940. This abnormal increase in demand is due to increased industrial activity, and especially increased railroad activity. Gasoline consumption for 1941 was 241,011 bbl. per day as against 217,744 in 1940. Demand for fuel oil increased from 259,806 bbl. per day in 1940 to 285,896 in 1941, and caused a withdrawal from stocks of more than 7,473,000 barrels. During 1941, total oil storage declined 9,153,000 bbl., but additions to storage of 1,754,000 bbl. of light oil and light oil products were offset by a withdrawal of 10,907,000 bbl. of heavier products. Production during the year is estimated at 230,233,000 bbl. as against 222,784,386 bbl. for 1940. TraNsportation For a short time, California was affected by lack of transportation due to the diversion of tankers. This shortage affected the movement of oil from the Sari Joaquin mated to the refineries, since a large percentage of this production is moved to the coast through pipe lines, and thence by tankers to Los Angeles and San Fran-,iSco, Return of the tanker fleet, which may be temporary, indicates that there is a possibility of ample supplies of petroleum products in the Pacific Northwest. Drilling Activity Contrary to general opinion, drilling activity increased in 1941 over the pre-vious Year, 942 wells being completed in 1941 as against 890 in 1940, an increase Of 6 per cent. This increase was due to the increased demands for fuel oil, and also to the decreased drilling costs, which made many former marginal locations economic. The main activity caused by increased demands for fuel oil was in the Mt. Poso, McKittrick, Midway and Santa Maria Valley oil fields. Dry-hole footage in 1941 was 655,354 ft. as against 583,537 ft. for 1940. Curtailment Voluntary curtailment succeeded in holding production considerably below demand, although it was above the state quota. During the year the top allotment

Jan 1, 1942

By H. L. Gilbert, C. Travis Anderson, W. J. Kroll

IN a previous paper,1 the use of a split graphite tube resistor as a heater element for high-temperature furnaces has been described. The principal advantages of this type of construction are: I. The quadruple resistance or voltage compared with the top-bottom clamp resistor furnace. 2. Free expansion of the resistor. 3. The ease of protection from oxidation by air. 4. The firmness by which it may be held in the compact split clamp. This construction appeared to be well adapted for the fusion of high melting metals which require fusion in a vacuum. Zirconium metal had previously been melted at the Albany Laboratory of the Bureau of Mines in a vacuum arc furnace on a water-cooled plate, using a movable tungsten top electrode.2 When larger furnace capacities were desired, this type of construction proved to have its limitations as the largest tungsten rods available were about 7/8in. in diameter. The supply of direct current of high amperage for producing the . desired arc characteristics was also not available. Considerable difficulty was also found in compensating the atmospheric pressure on the flexible tubing of the movable electrode, at the same time keeping its movement sufficiently free to enable the striking of an arc on any part of the metal briquet. Among the various materials used for the electrodes in conducting experiments in the vacuum arc furnace was graphite. It was found that zirconium fused in a graphite cup with a carbon arc was contaminated to only 0.2 pct carbon. It was therefore decided to melt zirconium directly in graphite crucibles. A high-frequency furnace was first used in the attempt to melt the zirconium in graphite crucibles. The high-frequency heating coil was placed outside a silica tube which was evacuated by means of an oil diffusion pump backed up by a mechanical pump. The graphite crucible was thoroughly degassed at 1900°C before use. Considerable difficulty was experienced in operating at such temperatures in vacuo because, as shown by Zintl,3 carbon vapor formed and reacted with silica according to the reaction: Si02 + C = SiO + CO. The silicon monoxide which is volatile at these high temperatures reacted with the zirconium, thereby contaminating it with silicon and oxygen. The presence of carbon monoxide was detected by means of a gas discharge tube placed in the vacuum system as indicated by the pale blue glow of the tube as soon as carbon vapor started to react with the hot silica. The reaction between the carbon vapor and hot silica was avoided by the use of split cylindrical molybdenum shields which were inserted between the graphite crucible

Jan 1, 1948

By H. E. McCoy, C. J. McHargue

Single crystals of columbium containing various levels of oxygen, nitrogen, carbon, or hydrogen were deformed by slaw compression and impact loading at -196°C. For the slow deformation rates. 1500 to 1900ppm oxygen, 500 pprn nitrogen, or 150 to 200 ppm carbon completely suppressed mechanical twinning. Hydrogen in concentrations to 1000 ppm had no apparent effect on ease of twinning. Impact loading caused twins to form at all levels of contamination studied, and cleavage mucking on (100) planes occurred in specimens having higher interstitial contents. It is well established that, under some conditions, the bcc metals vanadium, columbium, tantalum, chromium, molybdenum, tungsten, and iron deform by formation of mechanical twins. In general it has been accepted that high strain rates, low temperatures, and large grain sizes are conducive to this kind of deformation.' Since interstitial impurity atoms have a relatively large effect on slip in bcc metals, one might sus- pect a similar effect on twinning. This could occur directly by the interstitials affecting the nucleation or growth of the twins or indirectly from their effect on slip. It has often been argued that the large increase in yield stress caused by interstitial elements enables the effective stress to exceed that necessary to cause twinning. The twinning stress has always been thought to be higher than the stress necessary to cause slip in pure metals.2 simonsens and Tipper and Hall4 found profuse twinning in very pure a iron even at room temperature, whereas Low and Fueste15 and Churchman and tottrell' observed twins in a iron containing carbon but none in highly decarburized specimens. McHargue7 reported mechanical twins to form readily in vanadium which contained 390 ppm interstitigs, while Clough and Pavlovic8 found twins only in the one or two grains adjacent to the fracture surface in vanadium which contained 1500 to 1700 ppm interstitials. In columbium, McHargue9 found high-purity single crystals to twin easily whereas Churchman,10 Adams, Roberts, and mallman,11 and Johnson12 studied less pure material and found far fewer twins. Although the results of Leadbetter and Argent13 showed oxygen to inhibit twinning, a study by sheely14 indicated the opposite to be true. Chromium exhibits this mode of deformation15,16 but there are no data regarding impurity effects. Lawley, Van den Sype, and Maddin17 observed twins in very pure molybdenum single crystals deformed at 77°K but none in less pure crystals. The work by Cahn18 and

Jan 1, 1963

By E. C. W. Perryman

The recovery and recrystallization characteristics of superpurity aluminum have been investigated using electrical resistivity, X-ray line breadth, and hardness measurements for the former and the micrographic method for the latter. The three different properties recover at different rates and have different activation energies. The recrystallization results agree well with Avrami&apos;s theory and furthermore indicate that the perfect subgrains formed during recovery are not the nuclei for re-crystallization. WHEN a metal is plastically deformed, its physical and mechanical properties generally undergo considerable changes and by subsequent annealing these changes are partly or wholly annihilated. Thus, a recovery process can be discussed, taking this term in its general sense. In practice, however, there is reason to discriminate between two apparently different processes, one most easily followed at low temperatures, in which the properties return to an almost constant value between that of the cold worked and fully annealed material, and a second process in which the properties return to their original values before cold working and which is accompanied by the formation and growth of new grains having an orientation different from that of the matrix. In this paper the word recovery will be taken to mean the changes in some property as a function of annealing time which occur either without the appearance of new grains or under conditions such that the new re-crystallized grains are very small (= 2 microns), are very few in number, and substantially do not affect the property being measured. This definition is rather abitrary, for it will depend upon the sensitivity of the technique used for the observation of new recrystallized grains, which in the present work was about 1 to 2 microns. However, it is helpful to use the term recovery in this sense and to reserve the term recrystallization for the processes of nucle-ation and growth of new grains in the cold worked matrix. Although considerable work has been done on recovery and recrystallization, most workers have based their study on the measurement of one or perhaps two parameters. Since very small amounts of impurities have such a profound effect on the recrystallization characteristics of a pure metal, it becomes extremely difficult to correlate one piece of work with another. With this in mind, the present work on recovery and recrystallization was done on the same material. Experimental Procedure Material Used and Fabrication: The composition of the superpurity aluminum used throughout this investigation was 0.002 pct Cu, 0.003 pct Fe, 0.003 pct Si, and <0.001 pct Mg. The ingot was hot rolled to 0.250 in., annealed, and cold rolled to 0.034 in. A large number of reductions and intermediate anneals were carried out so as to produce material with a minimum of preferred orientation and maximum homogeneity. For the recovery part of the investigation, the final cold reduction was 20 and 80 pct and for the recrystallization part, 20 pct. After each pass in the cold rolling process, the material was quenched in cold water in order to keep the rolling temperature as near room temperature as possible. Annealing Procedure: For the recrystallization work, specimens 1x1 in. were cut from the 0.034 in. cold rolled sheet and a hole was drilled in each through which a wire was threaded to support it in the salt bath. The temperature of the salt bath was controlled to +2°C and the time taken for a specimen to reach temperature was approximately 5 sec. These 1 in. squares were then divided into three groups, one of which was given 5 min at 318°C and another 2 hr at 244°C. These treatments were such that recovery was almost complete and a well defined subgrain structure produced. Separate specimens of each group were annealed for different times at 301°, 318°, 355°, and 373°C, i.e., three specimens for each annealing time. The delay between finish of cold working and start of annealing was about 1 hr. For the recovery work, strips 0.062 in. thick were cut from the cold worked sheet, annealed, and then given the last cold rolling operation. This was done for each annealing temperature. By this means it was possible to minimize the delay between cold working and annealing. In general, all measurements were carried out within 1 hr of the last cold rolling operation. Annealing at low temperatures was done in an oil bath the temperature of which was maintained constant to +1°C. Electrical Resistivity Measurements: Strips 20x0.5x0.05 in. were machined and the electrical resistance measured using a Kelvin double bridge. Measurements were made in an oil bath maintained at 20rt0.1°C. The same specimen was used for the complete isothermal annealing curve.

Jan 1, 1956

By R. H. Johnson

All strata not yielding oil or gas in commereial quantities or a corresponding amount of water may be called dry in a wide sense. In petroleum geology, however, we may exclude all sands of too low or fine porosity to yield gaseous or fluid contents to the hole drilled in the sand before any original pressure that its contents may be under is disturbed. Most rocks are of this class and they are not reservoirs in our definition; their "dryness" is wholly a matter of course. What are the contents of the pores or what is the exact porosity of such rocks is of almost no concern to us, for economically they are "dry." What does interest us is the content of a rock having sufficient porosity and the pores of sufficient size to yield oil or gas in commercial quantities, if they were present under original pressure. Dryness of these reservoirs is a matter of supreme practical importance. Three views current as to such dryness seem, to me, to apply in a few cases only. It is the purpose of this paper to give reasons for this position and for believing that, in ordinary sedimentary rocks, there is only rarely a reservoir of competent porosity and undisturbed pressure that is dry in the sense of not yielding water, oil, or gas when first penetrated. 1. Gardnerl writes of some Kentucky sands, "There has never been present any salt water or other water in the sand." Absence of water cannot demonstrate this position. It is necessary to show that the rocks were not laid down in water, but in air, and that they became so enclosed, while still above the water-table of the ground water, that water has not been able to enter since. Most of these sands, and certainly the productive limestones, were deposited in water; and such sands as have been commercially productive show no reason for believing that the overlying shale or limestone was not laid down progressively from one direction and in water that would have flooded it. NO adequate explanation has been offered for this hypothesis, which is so inherently improbable. 2, Reeves2 urges that "sands originally water filled may have been drained of their water and not filled when later covered." It is difficult I James H. Gardner: Kentucky as an Oil State. Science, N. S. (1917) 46, 279-280. Reeves: Origin of the Natural Brines of Oil Fields. Johns Hopkins Univ. Circ., N. S. (1917) N. 3; Absence of Water in Certain Sandstones of the Appalachian Field. Econ. Geol. (1917) la, 354-378.

Jan 1, 1921

By R. I. Jaffee, R. W. Wood, H. R. Ogden, D. N. Williams

D. W. Morgan, D. H. Polonis,and R Taggart (Uuivevsity of Washington)—Dispersion hardening in titanium-copper alloys is of particular interest to us in view of our current research activities in phase transformations in this system. We should like to raise questions concerning several points in the paper. The flow sheet for fabrication and heat treatment (Authors&apos; Fig. 2) indicates that 0.045 in sheet is treated in air for a period of 30 min at 1625&apos; F. Were any surface coatings used to reduce oxygen contamination at this stage? One might ask the same question about the 8-hr annealing at 1400F. Contamination during fabrication and heat treatment of such thin sections could be considerable without some protection. Although the authors state that no analyses were made, they note that contamination masks the distinction between base strengths of the different alloys. In this connection, what fabrication and heat-treatment procedures were used in obtaining the comparison specimens of unalloyed titanium? It would seem that oxygen contamination must cast doubt on the reliability of the proposed strength-mean free path relationship deduced from the data (Authors&apos; Fig. 5). It is usual to evaluate dispersion hardening on the basis of yield strength rather than ultimate tensile strength, and accordingly we have replotted the authors&apos; Fig. 1 to include yield strength. The yield strength data do not justify a discontinuity of 3 p at either 70" or 1000 OF. Can the authors substantiate their conclusion 1) with additional evidence? Otherwise it seems that they have succeeded only in pointing out the possibility of a linear relationship between yield strength (or Uts) and the logarithm of the nleall free path, comparable with that demonstrated for iron-carbon alloys (Authors&apos; Ref. 2). Work in our own laboratories has shown that the hardness of the phase Ti,Cu is 235 Vpn, and that of a 1.5 pct (at.) (2 pct wt) supersaturated solid solution of copper in titanium is 190 Vpn. This small difference in hardness would suggest that Ti2Cu should not be a very effective dispersion-hardening phase. D. N. Williams, R. W. Wood, H. R Ogden, RI. L Jaffee (authors&apos; reply)— This discussion brings out some interesting points with respect to the interpretation of our results, and also raises some questions regarding the experimental technique. We shall consider the latter questions first. Contamination during heat treatment was prevented by performing all heat treatments in argon-filled Vycor capsules. Fabrication was done in air, with the usually observed scaling. Scale was removed

Jan 1, 1962