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By R. E. Reed, R. D. Leggett, Paxton, H. W.

TECHNIQUES have been developed for growing monocrystals and bicrystals of Fe-20 Cr, Fe-20 Cr-20 Ni, and Fe-18 Cr-8 Ni alloys by both the strain-anneal and the Bridgeman techniques. None of the techniques are new but since they are simple and many people have expressed interest, they are described here quantitatively as they could be modified for other single-phase "commercial" materials of high melting point. CRYSTAL GROWTH BY STRAIN ANNEAL Flat tensile specimens with a tapered gage length were initially studied to deduce the approximate critical strain. Normal flat tensile specimens were then used. The optimum procedure for the austenitic steels (Fe-Cr-Ni) deduced from a variety of cold reductions, recrystallization treatments, tensile strain, and growth anneals was as follows: cold reduce 70 pct, recrystallize (after machining tensile specimens) at 1000°C for 1 hr, strain in tension 2.5 pct, and then heat to 1350°C as rapidly as possible. A time of 100 hr at 1350°C is usually sufficient to pro-

Jan 1, 1960

By J. W. Rutter, K. T. Aust

The motion of individual grain boundaries under a constant driving force was investi,qated for zone-refined lead, with and without solute tin additions. The rate of boundary migration was found to depend strongly on tin content and on the orientation relationship between the adjacent grains. The results are compared with the theory of impurity-controlled grain boundary miqration developed by Lucke and Detert. Evidence was found that grain boundaries separating grains which have the Kronberg-U&apos;ilson orientation relationships of 38 and 22 deg about <Ill> and 28 deg about <100>, correspond to boundaries of high mobility. The results are discussed in relation to the formation of annealing textures in metals and the structure of high-angle boundaries. It is generally known that small amounts of impurities in solid solution greatly influence the re-crystallization behavior of metals. For example, the addition of 0.005 at. pct of tellurium to copper,&apos; or 0.005 at. pct of silver to lead,2or 0.01 at. pct of manganese or nickel to aluminum3 greatly decreases the rate of recrystallization of these metals. However, this effect may be the combined result of a decrease in the rates of both nucleation and growth; recrystallization experiments do not separate these two factors. Bolling and winegard4 determined the effects of small quantities of tin, silver, and gold on grain growth in polycrystalline zone-refined lead.

Jan 1, 1960

By R. O. Williams

A recent article by Chernock, Singer, Mueller, and Beck 1 which supports the use of the integral of I sin $ d$ for comparing fiber texture data does not settle what happens to I sin ø as ø approaches zero, where I is the diffraction intensity for poles oriented 0 deg from the fiber axis. They indicate that they believe that it should approach some constant value (that is, I increases without bound) and the fact that in reality it does not was a result of the diffraction

Jan 1, 1960

By W. J. Wenger

THIRTY-FOUR analyses of crude oils from the fields of the Four Corners Area of Arizona, Colorado, New Mexico, and Utah are presented and compared. The samples, taken from formations in four geological time periods, have high gravity and low-sulfur, -nitrogen, and -asphalt content. Generally, the oils are paraffinic in the low-boiling fractions, with increasing naphthenicity in the higher-boiling fractions. Oils from Cretaceous formations resemble other Cretaceous oils in the Rocky Mountains, but oils from Permian and Pennsylvania formations are unlike other oils of these ages in the Rooky Mountains. The differences in the oils are minor and cannot be used to distinguish between fields or between producing formations. With minimum special processing, the oils should yield large amounts of good-quality motor fuels. INTRODUCTION The only place in the United States where four States have a common junction is known as the Four Corners Area. This area (fig. 1) includes the northeast corner of Arizona, the southwest corner of Colorado, the northwest corner of New Mexico, and the southeast corner of Utah. It includes three major geological basins: The Black Mesa, the San Juan, and the Paradox. Major oil developments have occurred in both the San Juan and Paradox basins, but no discovery of commercial importance has been made in the Black Mesa basin.

Jan 1, 1960

By H. H. Heady

A naphtha obtained by destructive, recycle hydrogenation of crude shale oil, produced by gas-combustion retorting of Colorado oil shale, was found by the Bureau of Mines to contain 49.1 percent paraffins, 20.3 percent cycloparaffins, 7.8 percent olefins, and 22.8 percent aromatics. The naphtha contained only minor amounts of sulfur, nitrogen, and oxygen compounds. Compounds containing less than 5 carbon-atoms per molecule were removed by distillation before analysis. The paraffins where predominantly straight-chain compounds; n-Hexane was present in the largest quantity, and the other straight-chain paraffins decreased in amount as the molecular weight increased. The cycloparaffins, which contained both cyclopentanes and cyclohexanes, were evenly distributed throughout the boiling range. Although the naphtha had been produced by hydrogenation, it contained a small quantity of olefins. Straight-chain olefins with a terminal double bond comprised about two-thirds of these compounds. Among olefins with an internal double bond, those having trans configuration were present in three times the quantity of those in the cis form. In the aromatics all but one of the alkylbenzenes having nine or less carbon-atoms per molecule were identified; toluene was present in the greatest quantity. Only a few of the higher molecular-weight homologs were identified. The composition of the naphtha was computed from analyses of 105 narrow¬boiling distillation fractions. Volume, density, refractive indices, bromine number, and an ultraviolet spectrum were determined on each fraction. From these data the hydrocarbon-group composition of each fraction was estimated. A silica gel adsorption analysis was used to check the values of nearly one-third of the fraction calculated from physical-property data. Mass and infrared spectra were obtained on some fractions for identifying individual compounds or types of compounds, such as terminal olefins.

Jan 1, 1960

By J. R. Mihalisin, J. S. Iwanski

The response of Inconel "700" to heat treatment has been studied by light and electron microscopy combined with X-ray and electron diffraction techniques. A heat treatment which vesults in low ductility for this alloy appears to be associated with the formation of MC carbide in a Widmanstdtten distribution. This type of precipitation can be suppressed by suitable heat treatment with concurrent increase in ductility. Various other phases precipitated in this alloy are also identified. RECENT studies of commercial nickel base su peralloys have demonstrated the importance of the morphology of carbide phases upon physical properties.&apos; For example, empirical heat treatment studies applied to Nimonic "80" and Inconel "X" have resulted in prescribing double aging treatments for optimum physical properties. These treatments have subsequently been related micro-structurally to grain boundary carbide morphology.2 The purpose of this study was to obtain information about the morphology and identity of some of the phases precipitated in Inconel "700" after heat treatment. It was hoped that some correlation could be made of micro structure with heat treatment similar to that observed with Inconel "X" and Nimonic "80." EXPERIMENTAL PROCEDURE Specimens were obtained from a hot-rolled bar of Inconel "700" of the following composition: C Mn Fe S Si 0.10 0707 0.42 0.007 0.12 Cu Cr -A1 -Ti- Co Mo Ni 0.02 -14.90 TM 2.22 27.61 2.92-- Bal. Specimens were prepared in the following heat-treated conditions: (A) 2275°F for 2 hr WQ (B) 2275°F for 2 hr WQ + 2000°F for 1 hr (C) 2275°F for 2 hr WQ + 1600°F for 48 hr. (D) 2275°F for 2 hr WQ + 2000°F for 1 hr + 1600°F for 48 hr. Empirical stress-rupture studies had shown that treatment (D) resulted in optimum stress-rupture life and ductility. Treatment (C), although giving a good aging response, resulted in low ductility. Treatments (A) and (B), respresenting individual. steps in treatments (C) and (D) were added here for microstructural comparison studies. The procedure was to make an optical and electron microscopic investigation supplemented by X-ray diffraction analysis of electrolytically extracted residues. Electron diffraction studies were made utilizing selected area diffraction techniques with extraction

Jan 1, 1960

By C. G. Dunn, J. L. Walter

SILICON-iron .under certain conditions of processing and annealing will form a cube texture. The occurrence of this texture in thin tapes of silicon iron was first reported by Assmus, Detert, and Ibe.&apos; They concluded that the cube texture in their material formed by a secondary re crystallization process. In the course of present investigations on the development of the cube texture and the mechanisms involved in its formation by secondary re-crystallization it was found that under certain conditions the cube texture was replaced by a cube-on-edge or (110) [001] texture. We call this phenomenon tertiary re crystallization since it follows secondary recrystallization. The secondary recrystallization occurs after primary recrystallization and a substantial amount of normal grain growth. It is the purpose of this paper to describe briefly the occurrence of tertiary recrystallization and the structure and texture prior to and after tertiary recrystallization. The primary and secondary recrystallization structures and textures are the subject of another study and will be referred to briefly in the discussion of results. Evidence will be presented for the view that the dominant driving force for tertiary recrystallization is derived from the surface free energy which depends on the crystallographic planes presented to the gas-metal interface. In the absence of boundary restraining forces (dispersed phases, thermal grooves, and so forth) a sufficiently large difference in surface free energy across a grain boundary would produce boundary migration away from the center of curvature of the boundary intersection line in the surface of the sample according to risher.2 Therefore, particular attention was paid to observation of the direction of motion of these surface boundary lines. Furthermore, measurements of the actual boundary curvatures could be used to estimate the driving force supplied by surface free energy. EXPERIMENTAL PROCEDURE Samples were prepared by hot and cold-rolling vacuum-melted ingots of iron containing 3 pct Si to strips 0.012 and 0.006 in. thick. The ingots contained less than 0.005 wt pct impurities. The rolled strips were cut into samples approximately 1 in. wide by 3 in. long and were electropolished to remove surface imperfections. All samples were annealed in a vacuum at a pressure of approxi-

Jan 1, 1960

By M. M. Wong

A brief investigation was made to determine the feasibility of electro-refining beryllium in a KCI-LiCI-BeC12 bath. Thin, platelike crystals of beryllium metal were produced by electrolyzing technical-grade beryllium metal beads (about 94-percent purity) as the soluble anode. Operating cell conditions were: Temperatures of 450° to 600° C.; an inert atmosphere; bath compositions of (1) 38.1 mol. percent KC1, 54.8 mol. percent LiCl, and 7.1 mol. percent BeC12 and (2) 36.7 mol. percent KC1, 52.7 mol. percent LiCl, and 10.6 mol. percent BeC12; cell voltages of 0.30 to 0.80; and initial cathode current densities of 50 to 435 a./sq, ft. Current efficiencies ranging from 87 to 96 percent were obtained. Qualitative spectrographic analyses of the metal products indicated that impurities were reduced. This technique offers the possibility of producing a grade of beryllium purer than that now generally available, which may have better mechanical properties.

Jan 1, 1960

By G. R. Wilms

In a recent investigation1 on the properties of chromium, and of Cr-10 wt pct W and Cr-5 wt pct Mo alloys at elevated temperatures, it was found that intercrystalline cavities developed in all of these materials during tensile creep at 950°C, and that the cavities led to intercrystalline fracture. There were some interesting differences, however, between the cavities produced in the pure metal and those in the alloys; these differences, moreover, were associated with a difference in ductility. The relevant conditions of creep testing are specified in the captions to Figs. 1 and 3. Chromium showed the presence of quite large intercrystalline cavities, Fig. 1, and these were more or less randomly distributed around the boundaries. The chromium alloys, on the other hand, showed the presence of both small cavities and cracks at the grain boundaries, Fig. 3; it is apparent that the cracks are formed by the linking together of the small cavities. Moreover, the cavities and

Jan 1, 1960

By Harold W. Lipper

BUREAU OF MINES helium plants produced a. record-breaking 477 million cubic feet of this essential element in 1959. The supply of helium was less than the demand before operations were resumed at the Navajo plant in July and begun Sit a. new plant at Keyes, Okla., in August. Helium was in abundant supply after August, and the informal allocation system which had been in use intermittently since 1955 was discontinued Delivery of 26 new tank cars in August and September increased the total in the tank-car pool to 163. Defense and space agencies and the Atomic Energy Commission continued to use more helium in their operations and research.

Jan 1, 1960

By F. C. Langenberg, J. Chipman

New data on the distribution of silicon between slag and carbon-saturated iron at 1600oand 1700oC are presented which, in combination with previously published data, permit the determination of silica activities over a broad range of compositions in the CaO-Al2O3-SiO2 system. The distribution of silicon between graphite-saturated Fe-Si-C alloys and blast furnace-type slags in equilibrium with CO has been described in previous publications.1"3 In this past work the silica-silicon relation was established at temperatures of 1425" to 1700°C for slags containing up to 20 pct Al2O3. This paper presents the results of additional studies at 1600" and 1700° C which extend the silicon distribution data at these temperatures for CaO-A1203-SiO2 slags over a range from zero pct A12O3 to saturation with A12O3, or CaO.2A12O3. The upper limit of SiO, is set by the occurrence of Sic as a stable phase when the metal contains 23.0 or 23.7 pct Si at 1600" or 1700°C, respectively. The activity of silica over the expanded range is determined directly from the distribution data.3 Recently, 4-7 other investigators have studied the activities of SiO, and CaO, principally in the binary system, using different methods and obtaining somewhat different results. EXPERIMENTAL STUDY The experimental apparatus and procedure have been fully described in previous publications.1, 3 Six new series of experimental heats have been made, four at 1600° and two at 1700°C. Master slags of several fixed CaO/A12O3 ratios were pre-melted in graphite crucibles, and these were used with additions of silica to prepare the initial slag for each experiment. Slag and metal were stirred at 100 rpm and CO was passed through the furnace at 150 cc per min. The initial sample was taken 1 hr after addition of slag at 1600°C or 1/2 hr after addition at 1700°C. The run was normally continued for 8 hr at 1600°C or 7 hr at 1700°C, and the final sample was taken at the end of this period. Changes in Si and SiO2 content indicate the direction of approach to equilibrium, and in a series of runs where the approach is from both sides this permits approximate location of the equilibrium line. Fig. 1 shows the results of such a series of 15 runs at 1600°C for slags of CaO/Al2O3 = 1.50 by weight. Figs. 2 and 3 record other series at 1600°C and Fig. 5 a series at 1700°C with fixed CaO/Al2O3 ratios. The results of the experiments at 162003°C have been reported in part in a preliminary note.3 In the experiments recorded in Figs. 4 and 6, the slags were saturated with A12O3 (or with CaO.2A12O3 within its field of stability) by suspending a pure alumina tube in the melt during the course of the run. The final slag analyses were used to establish the liquidus boundaries8 in the stability fields of CaO.2Al,O3 and of A120,. ACTIVITY OF SILICA The free-energy change in the reaction has been calculated by Fulton and chipman2 from recent and trustworthy data including heats of formation, entropies, and heat capacities. The more recent determination by Olette of the high-temperature enthalpy of liquid silicon is in satisfactory agreement with the values used and therefore requires no revision of the result which is expressed in the equation: SiO, (crist) + 2C (graph) = Si + 2CO(g.) [1] &F° = + 161,500 - 87.4T The standard state for silica is taken as pure cristobalite and that of Si as the pure liquid metal. Since the melts were made under 1 atm of CO and were graphite-saturated, the equilibrium constant for Eq. [I] reduces to K1 = asi /asio2 The value of this constant is 1.77 at 1600°C and 16.2 at 1700°C. Through K1, the activity of silica in the slag is directly related to the activity of silicon in the equilibrium metal.

Jan 1, 1960

By John W. Barnes

In seeking cost reductions, control methods are a fertile field because they significantly affect labor and other costs. While process control in uranium mills is excellent by the evidence of high recovery, the costs seem high to those familiar with extractive operations for other metals. To some extent this high cost is inevitable, because of exacting quality control-, the technically complicated recovery processes; poor control over grade and nature of mill feed- special problems arising out of the radioactive property of the material. Practices used in uranium mills and the limitations indicated for instrumentation and automation are discussed. It is concluded that any large investment in automatic controls should be preceded by a careful study of their reliability and maintainability, and an estimate of the net income after taxes smaller plants my find it more profitable, or at least less risky, to concentrate their efforts on the possible reduction of some control problems and to development of a stable force of skilled employees. The observed experience does not inspire optimism that ore-dressing plants can be extensively automated although certain unit operations offer a challenge for improvements in instrumentation and machine design.

Jan 1, 1960

By T. A. Henrie

The Federal Bureau of Mines has investigated methods of sodium reduction of titanium chlorides to produce high purity titanium metal (14).4/ This investigation was made to obtain a better understanding of the reactions involved in sodium reduction of titanium chlorides and was part of the Bureau&apos;s activities toward improving the technology of titanium. Theoretical and experimental evidence show that sodium reduction of titanium tetrachloride occurs by stepwise reactions. The first stage reduction between sodium vapor and vapors of titanium chlorides produces titanium di-and trichlorides which subsequently condense with sodium chloride to form a salt mixture. The second stage reduction takes place in the condensed salt mixture between sodium and titanium subchlorides. Final reduction is a heterogeneous reaction between two separate phases, the a phase which consisted of sodium dissolved in sodium chloride and the ß phase titanium subchlorides dissolved in sodium chloride. The mechanism of the heterogeneous reaction between these phases is electrochemical in nature. The model proposed is a galvanic reaction at the interfacial region.

Jan 1, 1960

By Niles E. Grosvenor

Several methods have been proposed for determining the tensile strength of rock. These have been tried out over the past several years, but the results have been erratic and of doubtful value. The tensile strength of rock is its weakest property, and this property apparently enters into all failure phenomena whether underground or on the slope of an open pit. Therefore, it is essential that detailed quantitative information is known about the tensile strength of rock if the design engineer is going to select the proper pit&apos; slope, pit orientation, or orientation of underground workings so as to give the most economical and safest mining condition. This quantitative information may be used to orient the pit in such a manner as to allow steep slopes along two sides. This information may possibly be used to orient the direction of either underground workings or open pits so as to decrease powder consumption and to increase blasting efficiency. Hence it is of prime importance that a method of determining accurately the tensile strength of rocks be developed.

Jan 1, 1960

By R. E. Morgan, D. L. Douglass

The determination of phase relationships and solid-solubility limits can be performed by quantitative metallography in addition to the usual X-ray and metallographic techniques. For example, Beck and smith1 redetermined the ß/ß + ?, ß + ?/?, a/a + ß and a + ß/ß boundaries in the Cu-Zn system by measuring the volume fraction of second phase of several alloys and extrapolating the volume fraction-composition curves to 0 and 100 pct. A modification of this technique is suggested for certain alloy systems, in which it is not necessary to use several alloy compositions but merely one. A single two-phase alloy may be used to determine terminal solubilities in the following manner. The method consists of equilibrating samples of the alloy in a two-phase region adjacent to the desired solid solution, at three or more temperatures, quenching, measuring the volume fraction of second phase present, and applying an analytical treatment to calculate the unknown solid solution. However, two restrictions are inherent in this technique. They are: 1) only certain types of alloy systems are amenable to it, and 2) the general features of the system must be known. The first drawback to the new technique, i.e., that only certain types of systems may be studied, necessitates that the composition at one end of the tieline must either be constant with temperature or well established as a function of temperature. Either a pure metal or some intermetallic compounds fulfill the former. If it is assumed that the volume per gram-atom of a dilute solution is unchanged by the addition of element B to element A, the composition of the solid solution in equilibrium with the second phase may be determined by a material balance and is given by where X, = volume fraction of B in a solid solution Xc = volume fraction of B in compound c X = volume fraction of B in alloy f = volume fraction of second phase The composition by weight may then be determined by the use of tables in the Metals Handbook2 when the density ratio of the solid solution constituents is known. A possible alternative treatment involving the use of the lever rule is less precise than the above tech- nique. This may be used when the density of the solid solution is either known or may be calculated from X-ray data for several compositions. The following analysis is then made. The ratio of compound to solid solution (by weight) may be expressed as follows: x0 - x wc = xr-x = x0 - x r2i Xc -X where Wc = weight of compound w = weight of solid solution x, - alloy composition, weight percent x = unknown composition Xe = compound composition but where V, = volume of compound VA = volume of solid solution pc = density of compound p, = density of solid solution fc = volume fraction of compound fB = volume fraction of solid solution and fs = l -fc then If pc and xc are known, and f, is measured, then pB is the only unknown on the right side of Eq. [4]. The known densities of the solid solution can be plotted for various compositions and can then be expressed mathematically as a function of composition. The use of an expression of pB = f(x)reduces the equation to one unknown—the desired solubility. In the event that the densities are unknown, they may be calculated for various compositions from Vegard&apos;s law. The calculated values are then plotted and expressed analytically. The most accurate results are obtained for Eq. [4] when fc<< 1, i.c., when (x, -x,) - 0, &/l-f, - m; but as fc/l -fc - 0, (xl-x,)- (x, - x), and x - x,,. However, the accuracy with which fc can be measured decreases as f, decreases.3 Alloys for investigation must be selected by a compromise, which is based upon an error analysis of Eq. [4] and knowledge of the accuracy of volume fraction measurements. An examination of phase diagrams in the literature showed many which were amenable to the technique described here. The zirconium-copper system was selected in order to determine the solubility of copper in beta zirconium. Pieces of an alloy which was arc-melted three times were wrapped in tantalum foil and sealed under an argon atmosphere in Vycor tubes. The sealed samples were equilibrated at temperatures from 850" to 960°C for 3 weeks and quenched to room temperature by smashing the capsule in water. Several planes of polish were examined, and

Jan 1, 1960

By I. Iwasaki

In recent years the rapid depletion of high-grade iron ores and the demand by blast furnace operators for increasingly low-silica ores have stimulated interest in flotation studies of low-grade iron ores, such as wash-ore tailings and oxidized taconites. Four processes have been reported for the flotation separation of these iron ores--anionic and cationic collection of the iron oxides, cationic collection of siliceous gangue, and anionic collection of activated siliceous gangue (5).5/ The effectiveness of any one method, however, depends largely on the mineralogical composition and on the physical structure of the sample; hence, a comprehensive study of the floatability of the individual minerals occurring in these materials is essential. A review of the literature shows that the floatability of hematite and magnetite has been frequently investigated, whereas very little corresponding information is available for goethite, or for its more earthy form, limonite, both of which are abundant in the Mesabi and Cuyuna ores (19). The purpose of this investigation was to formulate general information on the floatability of goethite. Vacuum flotation, contact angle measurement, and simplified flotation tests using a modified Hallimond tube were used. The experimental results were correlated with the electrokinetic properties of goethite as determined by streaming potential measurement. The results were used to interpret the batch flotation tests made on an artificial mixture of quartz and goethite.

Jan 1, 1960

By J. Chipman, J. C. Fulton

Reduction of Si from slag to carbon-saturated iron is a very slow reaction. The rate is nearly independent of stirring but is accelerated markedly by increased temperature. In a slag containing 45 pct SiO2, 38 pct CaO, 17 pct Al2O3, the energy of activation is approximately 130 kcal. AT temperatures of 1450" to 1600°C occurring in the hearth of the iron blast furnace, chemical reactions are normally expected to proceed with great rapidity. Many of the reactions of iron making are indeed quite rapid and attain a condition corresponding roughly to a state of equilibrium before metal and slag are tapped from the furnace. The one conspicuous exception is the reaction by which carbon in the coke or metal reacts with silica in the slag to deliver silicon to the metal. From the practical viewpoint the slowness of this reaction is indeed fortunate, for if it were fast enough to reach equilibrium during the time of contact, it would be difficult to produce pig iron of the desired low silicon content. The one other reaction which under certain circumstances can also be very slow is the transfer of sulfur from blast-furnace metal to slag. In their laboratory exeriments on this reaction, Hatch and Chipman found that at least 5 hr were required for the attainment of equilibrium in a small crucible and that the reaction was not accelerated by increasing the rate of stirring. Subsequently it was shown2 that the presence of a reducible oxide MnO greatly inhibited sulfur removal, and finally that SiO2 itself3 under some conditions has sufficient oxidizing Dower to interfere with sulfur transfer. The kinetics of sulfur removal are now rather well understood,4 and it has been shown3,5 that when the silicon content of the metal is high enough to prevent reduction of SiO,, the desulfurizing process is rapid. Thus the observations of slow removal of sulfur are associated with the coincident slow reduction of SiO2, a process which transfers both silicon and oxygen to the metal phase. It is, of course, the oxygen which interferes with sulfur removal. An explanation of the slowness of the silica reduction reaction has not been obtained. The sulfur transfer process has been shown by the authors5 to be at least partially transport-controlled in the absence of interference by silica. Under the experimental conditions. 99 pct of the total transfer at 1600" was accomplished within an hour. Under similar conditions the reduction of silica may not proceed half-way to equilibrium6 in 8 hr. It is scarcely imaginable that silica reduction could be transport-controlled when the slag contains 44 pct SiO2 and the metal about 1.4 pct C. The experiments reported here show definitely that it is controlled by a slow step or steps in the chemical reaction. One might expect to find such a slow step in the breaking of SiO bonds or in the slow removal of oxygen by carbon at the slag-metal or metal-crucible interface or by bubble formation. EXPERIMENTAL PROCEDURE The experimental procedure used in this investigation was similar to that used in the study of the kinetics of desulfurization.5 A sketch of the graphite crucible and stirrer used in the current work is shown in Fig. 1. The quantity of metal and slag used was adjusted so that the slag-metal interface was located between the top and bottom blades on the stirrer; the top of the slag layer was above the top blade. The stirrer shaft was hollow down to the metal level and served as thermocouple well or optical pyrometer target. Stirring speeds of 0 to 500 rpm were used. A carbon monoxide atmosphere was maintained in the furnace by flushing the gas over the slag surface, except in run No. 220 when it was bubbled

Jan 1, 1960

By A. E. Dwight

Lattice parameters were determined for eighteen equiatornic alloys of the CsCl-type structure, ten of which were previously un-reported. It was found that fomation of the CsCl-type structure in binary alloys of the transition elements is largely dependent on position of the elements in the periodic table. The relative size of the two elements was not found to be a controlling factor. A recent paper by Beck, Darby, and Arora1 corre-lates the occurrence of CsC1-type ordered structures with the position of the constituent elements in the periodic table for the first long period. It was also suggested that a definite increase in relative bond strength between unlike atoms occurred when, in binary alloys of iron-group elements, the other component is changed from a chromium-group element, to a vanadium-group element, to titanium. A later paper by Philip and Beck2 noted that the lattice contraction increased in the order CrFe, VFe, and TiFe. It was also noted by Philip and Beck2 that the lattice contractions of CsC1-type alloys decreased in the order: TiFe, TiCo, and TiNi, which is an apparent reversal of the contractions expected from the position in the periodic table. It was suggested that the increasing lattice contraction is an indication of increased stability, i.e., greater A-Bbond strength. The present investigation was carried out to determine whether the relation of the position in the periodic table to the formation of the CsC1-type structure was also correct for alloys involving the second and third long-period elements. A systematic search was made for CsC1-type structures among equiatomic alloys and for those found, the lattice contraction was determined. EXPERIMENTAL TECHNIQUE The elements Y, Gd, Ti, Zr, Hf, V, and Cb are designated the A group and the elements Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, and Au are designated the B group. Equiatomic alloys were prepared for 57 AB combinations. The alloys were arc melted in a multicrucible furnace3 in buttons ranging from 5 to 20 g. Chemical analyses were not made, as the charge weights agreed closely with those of the buttons after melting. The alloy buttons were homogenized at 800° to 900°C. Metal log raphic and X-ray specimens were prepared and heat treated at temperatures from 600° to 1200°C. Specimens for X-ray diffraction were usually ground to a powder in an agate mortar; however, needle-shaped solid specimens were used when the alloy was sufficiently ductile to permit their preparation. Diffraction patterns were taken with a Straumanistype Debye-Scherrer camera using filtered Cu or Co radiation. The lattice parameters were obtained in A by plotting the calculated a0 values against the cos29/sin 0 + cos2?/? function and extrapolating linearly to ?= 900. Metallographic control specimens were polished on cloth wheels with diamond paste and etched with various phosphoric and nitric acid reagents. RESULTS The eighteen equiatomic alloys listed in Table I gave evidence of a cubic structure with two atoms in the unit cell, although two of these cubic structures exist only at elevated temperatures and transform to a tetragonal structure on quenching. Nine of these eighteen alloys gave diffraction patterns with super-lattice lines showing that the structure is of the CsC1-type. The lack of superlattice lines in patterns of the other nine alloys may be attributed to the small difference in atomic scattering power of the components. Metallographic study indicates the occurrence of nine narrow single-phase fields at the AB composition. Any or all of these nine may also have a CsC1-type structure. The VFe alloy was found to have a CsCl-type structure by Philip and Beck2 through the use of CrKa radiation (for which the scattering factor of V is anomalously low), whereas the Cu radiation used

Jan 1, 1960

By C. H. Li, R. J. Stokes, S. H. Bendel, J. A. Sartell, T. L. Johnston

The mechanism of the oxidation of high-purity copper has been studied at temperatures from 500° to 981°C employing gravimetric, high-temperature microscopic and inert marker techniques. An investigation of the adhesion of copper oxides was also made. The oxidation of copper is found to be parabolic at all temperatures. It is concluded that the controlling mechanism is the outward diffusion of CU+ ions through the Cu2O layer, but the mechanism of diffusion is modified by the state of compressive stress in the oxide layer at the oxidation temperature. At temperatures below the transition from elastic to plastic behavior of Cu2O the growth stresses reach a value sufficiently high to cause CuO whiskers to be extruded. The extrusion of whiskers results in the injection of a large number of vacancies into the CuO. The Cu20 layer grows by the advance of the CuzO/CuO interface into vacancy-rich CuO. Since there is an adequate supply of non -thermally created vacancies, the activation energy for oxidation is that required to move the Cu+ ion through the appropriate saddle point to a neighboring vacancy, which has been determined to be 20,000 cal per mole. At temperatures at which the Cu20 can deform plastically the stresses are never high enough to cause whiskers to form. thus vacancies must be supplied by themal activation and as a result the activation energy increases to 40.000 cal per mole. ALTHOUGH extensive studies of the oxidation kinetics of pure copper have been made in the past. the mechanism has received relatively little attention. As a result, certain features of the kinetic data have not been satisfactorily explained&apos; For example, several workers1,2 have reported that the activation energy for oxidation in the range from 500° to 700° C was about 20,000 cal per mole whereas that above

Jan 1, 1960

By Oliver Bowles

Slate is a fine-grained rock that has a more or less perfect natural cleavage, permitting it to be split readily into thin, smooth sheets. According to a definition established by the American Society for Testing Materials, slate is "a microgranular crystalline rock derived from argillaceous sediments by regional metamorphism and characterized by a perfect cleavage entirely independent of original bedding, which cleavage has been induced by pressure within the earth." Origin and Character Slates have originated from sedimentary deposits consisting largely of clay. Such materials were carried by streams and deposited in seas or lakes in successive horizontal beds. Other materials such as calcium carbonate, sand, or gravel may have been deposited over the clays, and the pressure of these superimposed materials gradually consolidated the materials below into bedded deposits of shale. Shale is a stratified rock formed by recrystallization of the clay plus adsorbed potash into the mica, sericite. Shale has neither the strength nor the splitting properties of slate since the mica is fine and the flakes unoriented, and the quartz grains do not interlock. Many shales, however, have been subjected to intense metamorphism. Mountain-building forces ever at work in the earth&apos;s crust may crumple, squeeze, and fold the shales. At the same time, accompanying high pressures and temperatures changed the original minerals into mica, interlocking quartz, or chlorite. Both mica and chlorite consist of minute tabular sheets or flakes with perfect cleavage. The intense pressure and movement tend to orient these flakes in parallel positions normal to the direction of pressure. The parallelism of the flakes results in the tendency to split with ease in one direction, which has been termed "slaty cleavage," and which is the outstanding characteristic of slate. Actually, the cleavage is through the cleavages of the individual micaceous plates. The original bedding of the slate is often folded and contorted, and the slaty cleavage commonly cuts across it at sharp angles. Composition MINERALOGICAL COMPOSITION The most abundant mineral in most slates is white mica (sericite), a hydrous silicate of potash and aluminum. It is present in very small flakes recognizable only with a microscope. Small grains of quartz (silicon dioxide) are also abundant and are regularly distributed among the mica flakes. The mica-like mineral, chlorite, is usually present in considerable quantities. Chlorites are of several kinds, the more common being hydrous silicates of aluminum and iron or magnesium. Other common minerals present in small quantities are rutile, clay, hematite, pyrite, carbonaceous matter, feldspar, zircon, tourmaline, calcite, dolomite, and siderite. The general range of the chief constituents is about as follows: Sericite, 38 to 40; quartz, 31 to 45; chlorite, 6 to 18; hematite, 3 to 6; and rutile, 1 to 1 ½ pct. CHEMICAL COMPOSITION Results of many analyses indicate that clays, shales, and slates differ little in chemical composition. The changes that take place during metamorphism are confined largely to rearrangement of the elements into new minerals with accompanying changes in physical properties such as hardness and cleavage. The general

Jan 1, 1960