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By Arne Bergholm

Australian rutile was chlorinated in the presence of CO or carbon. The chlorination velocity in CO was found to be strongly influenced by temperature and proportional to the CO concentration, but independent of the Cl, concentration. In the presence of carbon, the reaction velocity is much higher. The reactivity of the carbon and the distance between the carbon and the rutile surfaces are important variables. The reaction velocity is approximately proportional to the Cl, concentration and independent of the CO concentration of the surrounding atmosphere. Experiments with fluidized-bed chlorination of carbon-rutile mixtures indicate that the motion of the bed has little influence on the reaction velocity. At low temperatures, the chlorination velocity of dense tablets is much greater than that of TiO, coke mixtures suitable for fluidization. The reaction mechanism is discussed. In the industrial production of TiCl, rutile is chlorinated in the presence of carbon. Disregarding intermediate steps, the reaction may be expressed by the following equations: The ultimate object of this study was to find out whether the reaction velocity was higher in fluidized bed operation compared with chlorination of pelle-tized carbon-rutile mixtures. From a literature survey and preliminary experiments it was learned that some basic knowledge about the reaction mechanism was needed for a good experimental design. Therefore the following sets of experiments were carried out: 1) Studies on the reaction velocity in the chlorination of rutile with CO as the only reducing agent. 2) Chlorination of separate rutile-carbon tablets. 3) Chlorination of rutile-carbon tablets at different temperatures with various kinds of carbon, various grain sizes, and various tablet-making techniques. This series of experiments was carried out not only with pure chlorine but also with mixtures of chlorine with argon, CO and CO,. 4) Chlorination of rutile-carbon tablets made in a strictly standardized manner. 5) Chlorination of static-bed rutile-carbon mixtures. 6) Fluidized-bed chlorination of the same mixture. The experiments 4 to 6 formed the final and direct test of the main question: Static bed vs fluidized bedo. Although there are many patents and papers dealing with the general aspects of chlorination, only few experiments from which detailed information can be obtained have been reported in the literature. Pamfilov and coworkersl3 have studied chlorination of TiO, with CO or carbon as the reducing agent. They found that the weight decrease per hour at 600o to 800°C amounted to 11 to 14 pct with CO and 45 to 51 pct with carbon. They suggest that phosgene might be an intermediate in the chlorination of TiO,. Takimoto and Hattori have chlorinated reduced titanium oxide (TiO) and found a very high rate of TiC1, -production. They proved that the composition of the gas from the chlorination of rutile-carbon mixtures contained mainly CO. They reported for instance 74.7 pct CO, and 5.6 pct CO at 800°C at which temperature the Boudouard equilibrium composition is 12 pct CO and 88 pct CO. Seligman and Segerchano6 have studied the chlorination of TiO. They proved that Ti0 and chlorine react rather rapidly at temperatures as low as 300°C. Above 400°C, the reaction was complete. At 500°C the velocity of this reaction was much higher than was chlorination of TiO, + C. McTaggart,7 Nishimura, et al. and Wilskam have chlorinated mixtures of carbon and various kinds of rutile or beneficated ilmenite. Nishimura, et al. also report the results from reduction of TiO, with H2, CO, or carbon. At 900°C only 1 pct Ti O is formed in 2 hrs. At 1100°C 23.1 pct Ti, 0, was formed if elementary carbon was present. No carbide formation occurred below 1400°C. McIntosh and Cofferll have observed that the CO, content of the exit gases from chlorination of rutile and calcined petroleum coke is appreciably higher than found in the Boudouard equilibrium. At 900°C the ratio (CO, /CO + CO) is about 80 pct, whereas the equilibrium value is about 2 pct. W. E. Dunn12 has studied the chlorination rates of several TiO,-bearing minerals with CO + Cl, or COCl . Chlorinations were carried out either in a fluidized reactor or a fixed-bed reactor, both having a 30-mm diameter. The results obtained in both reactors were comparable. It was proved that benefi-ciated ilmenite (i.e., ilmenite from which the iron oxide had been removed by chlorination) was chlorinated 10 times faster thanrutile. Sore1 slag showed an intermediate rate. When phosgene is used, the

Jan 1, 1962

By E. G. King

The literature contains little thermodynamic information regarding inter-oxidic compounds of the ferroalloy elements and, as a result, thermodynamic considerations of extractive and utilization processes involving these elements have been hampered. As part of a Bureau of Mines program to improve this situation, this paper reports the heats of formation of three calcium vanadates and two magnesium vanadates. There were no previous similar data for any of these compounds. The experimental method was hydrochloric acid solution calorimetry, using calorimetric reaction schemes involving the vanadates and their component oxides. The results were expressed as heats of formation from the component oxides and from the elements. Corresponding free energy of formation values were calculated. The data show that the calcium and magnesium vanadates are stable with respect to all possible decompositions in which vanadium remains pentavalent. This conclusion is similar to the one drawn by Koehler6 for three sodium vanadates.

Jan 1, 1962

By D. G. Westlake, E. S. Fisher

The habit planes for zirconium hydride precipitation in crystals of a zirconium have been determined at various hydrogen concentrations. The (10 • 0)planes are the predominant habit planes; some (10 • 5) and (10 -1) planes were observed after charging conditions which pevmitted formation of a surface layer of hydride. No platelets zrlere observed parallel to any of the twinning planes. Mechanisms for em-brittlement due to hydride precipitation are discussed. LANGERON and Lehr1 found, in 1956, that zirconium hydride precipitates in zirconium in platelets lying parallel to (10.0) slip planes. In 1960, Kunz and Bibbz reported observing the platelets in three different families of twinning planes, (10.2) {11.1), and {11.2), but never in the slip planes. The present study was undertaken to ascertain the cause of these seemingly contradictory results. EXPERIMENTAL Two specimens of iodide zirconium were used in the experiments. Specimen I was a single crystal, while specimen II contained three grains. Grain growth was accomplished by the technique of Lange-ron and Lehr. Three faces were ground on specimen I; the first was 2 deg from the (00.1) basal plane, a second was 2 deg from the (10.0) prism plane, and a third was 4 deg from the (12.0) plane. One face was ground on specimen II such that the poles of the surfaces of crystals A, B, and C were as shown in Fig. 1. After the faces were ground on 600 grit silicon carbide paper, they were chemically polished by dipping in a solution of 8 parts hydrofluoric acid, 50 parts nitric acid, and 50 parts water. This removed all cold worked metal from the surface. The samples were charged to various levels of hydrogen content by heating in hydrogen gas which had been purified by reaction with uranium powder. The various charging conditions are shown in Table I. Specimen I was heated to the reaction temperature at the indicated hydrogen pressure and allowed to react until essentially all the hydrogen was used up. Then the temperature was raised for homogenization. Specimen II was charged by making periodic addi-

Jan 1, 1962

By David Turnbull

STAFF: Editor, Gerhard Derge Carnegie Institute of Technology Schenley Park Pittsburgh 13, Pa. Editorial Assistant, M. A. Redmerski Production Editor, Otto T. Johnson THE METALLURGICAL SOCIETY: J. S. Smart, Jr., President; C. C. Long, Past-President; K. L. Fetters, Vice President; T. D. Jones, Treasurer; R. W, Shearman, Secretary. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: C. L. McCabe, Chairman; H. L. Bishop, K. L. Fetters, J. J. Harwood, W. A. Krivsky, F. C. Langenberg, R. E. Lund, W. O. Philbrook, L. L. Seigle, R. L. Smith, and F. L. Vogel. Review and selection of monuscripts is under the supervision of the following Publications Committees: Extractive Metallurgy Division: C. L. McCabe, Chairman; R. E. Lund, Vice-Chairman; D. H. Baker, Jr., W. A. Krivsky, R. A. Lewis, Paul Queneau, A. S. Russell, R. E. Shinkoskey, W, W. Stephens, and M. E. Wadsworth. Institute of Metals Division: L. L. Seigle, Chairman, Paul A. Beck, I. I. Bessen, J. 0. Better-ton, Jr., J. B. Clark, R. S. Davis, A. E. Dwight, R. W. Fountain, R. B. Gordon, C. D. Graham, Jr., R. W. Guard, J. C. Gurland, E. L. Harmon, J. J. Heger, A. A. Hendricksan, M. Herman, J. N. Hobstetter, H. H. Johnson, Jr., R. R. Nash, T- N. Rhodin, R. H. Richman, W. Ros-toker, P. G. Shewmon, C. W. Spencer, L.SIifkin, J. K. Stanley, C. D. Starr, and H. C. Stumpf. Iron and Steel Division: H. L. Bishop, Chairman; R. E. Boni, F. C. Langenberg, J. B. Wagstaff, and T. V. Wainwright. Published bimonthly by the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc., 29 West 39th Street, New York 18, N. Y. Telephone: PEnnsylvania 6-9220. Subscription $20 per year for non-AIME members in United States and North, South, and Central America; $25, foreign; $5 for AIME members. Single copies, $4.00, single copies foreign, $5.00. The AIME is not responsible for any statement made or opinion expressed in its publications . . . Copyright 1961 by the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc. . . . Registered cable address, AIME New York .. . Indexed in Engineering Index, Industrial Arts Index, and Chemical Abstracts . . . Second class postage paid at New York, N. Y., and Ann Arbor, Mich. Volume 221, Number 3.

Jan 1, 1962

By Y. L. Yao

It is suggested that the binary alloy systems of transition metals may be classified into groups according to "excess energy"E. For systems with positive ?E, the Laves phase, the TiNi3-, the TiCu3- and the Cudu-type rich in the smaller atom and the TizNi-type rich in the larger atom may exist. For systems with negative ?E and composed of two components of different crystal structures, the X, the Cr3O and the phase may exist on the side of the phase digrattz rich in the component with the higher "solubility factor" value am! the Cudu-type and the disordered hcp phase on the other side; if the crystal structure of two components is the same, the Cudu-type may exist on both sides. For systems with weakly positive ?E and cotnposed of different crystal structures, the u phase and the MgCd3-type may replace the Laves phase and the other types; the X, the Cr3O and the a phase may also exist. Finally, the equirnolar compounds of the CuAu- and the CsC1-type may exist irrespective of the sign of ?E. THERE are many factors which play a major role in the formation of binary intermediate phases in alloys, such as the crystal structure, the electronic structure, the atomic size and the electrochemical factor. To find the simultaneous effects of all these factors on the formation of intermediate phases of every metal would be a difficult task, especially because only a small fraction of experimental facts necessary for the complete formulation is known at present. Thus the past surveys of intermediate phases have been usually confined to few metals, several types of intermediate phases and some but not all controlling factors. In a previous paper1 the idea of "solubility factor" of metals was introduced. Although the suggested values are tentative and empirical, the formation of a continuous series of solid solutions in metals could be correlated with the interplay among the atomic size factor, the solubility factor and the crystal structure factor. The purpose of this paper is to demonstrate qualitatively the interplay of these factors in the formation of binary intermediate phases among transition metals. FACTORS CONSIDERED The Crystal Structure Factor. With rare earths excluded, the transition metals are classified into three common crystal structures listed in Table I. There is arbitrariness in the present classification of several allotropic elements. However, out of seventy-odd continuous solid solutions formed among transition metals, only six of them, namely, those

Jan 1, 1962

By J. F. Butler

The degree and type of carbide dispersion resulting from changes in the cooling rate from austenite determine the amount of carbon remaining in solution after slow cooling- from a subsequent subcritical annealing treatment. A difjusion model has been proposecl to explain the effect of carbide dispersion on the amount of carbon retained in solution and the amount of carbon in solution has been related to the degree of carbon strain aging. COTTRELL and Leak' have shown that the rate of strain aging in low-carbon steels is dependent upon the amount of carbon and nitrogen in solution. Carbon can be effectively removed from solution as Fe , C by quench aging at temperatures of 200" C or lower; however, the relatively higher solubility of nitrogen at these temperatures prevents sufficient removal of nitrogen as iron nitrides. For this reason, nitrogen in solution has been considered the major cause of strain aging in rimming grades of commercial low-carbon steels. Nitrogen can be effectively removed from solution and nonaging steel produced through the addition of aluminum to form the stable nitride, AlN; however, the aluminum also causes deoxidation resulting in a killed steel. III an attempt to produce a rimmed steel which was also nonaging, Morgan and Shyne 2 investigated tile strain-aging properties of low-carban steels containing boron and found that strain aging was suplx-essed in steels containing as little as 0.007 pet B. The original purpose of this investigation was to determine the mechanism of strain-aging suppression by boron. Early in the study, the function of boron was discovered to be much like that of aluminum in that the formation of a nitride, BN, removed the nitrogen from solution.' However, during the course of the investigation, an effect of heat treatment upon the strain-aging properties and the amount of carbon in solution was found which could be related to the microstructure of the steel. The purpose of this paper is to examine these relationships among heat treatment, microstructure, carbon in solution, and strain aging in steels where nondetectable amounts of nitrogen are present in solution. EXPERIMENTAL PROCEDURE The investigation was carried out using 0.030 in. by 12. in wire specimens which had been cold swaged and drawn to the final diameter. Table I lists the compositions of the low-carbon steels used. Those with 'V' designations were vacuum melted and cast; the alloys designated 'AISI' were prepared from high-purity iron obtained from the American

Jan 1, 1962

By Ursula E. Wolff

Il.lechanica1 twins have been observed in brigsten single crystals of a variety of axial orientations defornzed at room temperature in tension or bending. The twins formed near the final fracture and were up to 3 p thick. The twinning plane was always of the type (113). Twinning at room ternperature occurred only after considerable prior slip. Twins usually preceded fracture and nucleated cracks. The crack surfaces often alternated between a (001) plane and the twin interfaces. Secondary twins could also nucleate from cracks. In the absence of twinning tensile samples failed by shear; twinned samples failed by cleavage. On the assumption that observed sudden load drops in the stress-strain curves are associated with twinning, a critical resolved stress for twinning of 60, 000 to 65, 000 psi was calculated. MeCHANICAL twinning has been observed in iron and iron alloys at low temperature by a number of investigators.'-7 Similarly, for high-purity tungsten, twinning has been reported for deformation temperatures below 211°K.8-10 In W-Re and Mo-Re alloys, 20 pct Re was determined as the lower limit for twin formation at room temperature." Since the twins are generally very narrow, they are usually identified only by etching techniques. The expected (112) habit plane has always been confirmed by angular analysis of the surface traces. Recently, however, a complete identification by X-ray analysis has been performed on twins in a Mo-35 pct Re alloy.12 During an investigation of the deformation charac- teristics of tungsten single crystals, twins were revealed in tensile and bend samples deformed at room temperature. This paper deals with the conditions for such twinning and the relation of twinning to fracture. EXPERIMENTAL PROCEDURE Tungsten single crystals, 1/8 in. in diam, of a variety of axial orientations were grown from un-doped material by four-pass electron-beam zone melting. A representative analysis is given in the following table: From these crqstals, tensile samples with 1 in. gage lengths were made by surface grinding, leaving shoulders for gripping. The diameter after grinding was 0.082 in. The distorted surface layer was then removed by ele1:trolytic polishing which reduced the diameter of the gage length to 0.080 in. Tensile tests were carried out at room temperature in an Instron machine under two different sets of conditions: a) Rigid mounting; strain rate 0.02 in. per in. per min. b) Gimbal mounting; strain rate 0.002 in. per in. per min up to a total strain of approximately 0.2 pct, then 0.01 in. per in. per min to fracture. Stress axis and growth direction coincided in all samples and are subsequently called orientation.

Jan 1, 1962

By George J. Carter

Data obtained from field and laboratory examinations were used by the Bureau of Mines to evaluate 82 silica deposits in the Pacific Northwest. A total of 94 field samples was taken from 64 deposits, and an additional 18 deposits were investigated that did not warrant sampling. Of the 37 deposits found to be of high quality, only 16 were large enough to be classified as industrial silica resources. Another 27 deposits did not meet quality requirements. Methods of simple low-cost beneficiation and rapid classification of a large number of samples were investigated in the laboratory. These tests indicated that high-intensity electromagnetic separation was equal or superior to either high-or low-intensity electrostatic separation. In general, the electromagnetic method gave higher recoveries and produced equal or better grade concentrates. A glass button method developed for estimating iron oxide content of silica samples proved to be highly satisfactory as a means of classifying field samples and evaluating beneficiation tests.

Jan 1, 1962

By W. W. Krysko

In order to calculate the critical particle size of lead oxide entrapped in lead, Stoke's Formula may be applied. All data were available except figures for the density of lead oxide at elevated temperatwes. The density of lead oxide was determined by means of dilatometmetrc and volumetric methods up to 1010°C. Graphs of the density of lead and lead oxide as well as the viscosity of lead are given and discussed, with the conclusion that the most unfavorable region for the separation of lead oxide from molten lead lies just above the melting point of lead. DURING previous investigations, particularly on the dedrossing of lead with aluminum1 and the oxygen solubility in lead,' the critical particle size of lead oxide which could be entrapped in solidifying lead was estimated by calculation, and it was shown that high values found for the oxygen content of lead may be due to the method of sampling and the entrapped particles of dross. Unfortunately, due to lack of data, an exact mathematical solution was not possible. The particle size which will separate under a given condition can be estimated from Stoke's Law, which states that where: d = diameter of the critical particle size ¦q = viscosity of lead in Poise V = constant velocity in cm sec-I g = 981 cm sec-2 61= specific gravity of lead 62= specific gravity of lead oxide The depth of the lead bath and the time before solidifying define the velocity. The viscosity of molten lead is known from earlier work by Krysko and is given in Table I. The specific gravity of lead is also known, see Table II. These values are according to Hofmann. A careful survey of literature revealed no values for the density of lead oxide at elevated temperatures. The present investigation was therefore conducted to provide this information. RESEARCH INVESTIGATIONS The density of lead oxide was determined from the following experiments: 1) Determination of the density of lead oxide at room temperature. 2) Dilatometric investigations on the same samples. 3) Determination of the shrinkage at the liquid-solid trans£ormation. 4) Density determinations on liquid lead oxide. 5) Time temperature curves during cooling. 1) The samples for the determination of the density of lead oxide in the solid state were prepared in the following manner. Molten lead oxide was cast into I hot mold which could be opened along the longitudinal (vertical) axis. The cast samples were cylinders of approximately 10 mm diam and approximately 80 mm length. The cylindrical hot mold was open at both ends and was placed on a large copper chill plate shortly before casting. The solidification of the lead oxides proceeded upwards without any formation of internal cavities. The sample was carefully checked with respect to density and crystalline appearance, and only the lower portions which were crystalline and free from porosity were used. The density was determined in a specially made pyknometer-like container, where the surplus liquid was squeezed out through an orifice approximately 1/10 mm in diameter. Mercury or water was used as the liquid. The densities of the samples were calculated from the weight, volume, and mean specific gravity of eight samples was 9.62 * 0.05 g cm"3 at 22"~. 2) The samples were machined to approximately 1 1/2 in. in length and fitted into a dilatometer. A

Jan 1, 1962

By Howard P. Hamlin

This Bureau of Mines report is concerned with the testing procedures for evaluating clays, shales, and slates for lightweight aggregates using the rotary-kiln method of production. To meet the increasing demand for light-weight concrete, rapid, accurate methods for appraising raw materials for light-weight aggregate are needed. Preliminary tests were made on samples of clay, shale, and slate, using laboratory equipment, and the data were used to establish operating conditions for pilot-plant-size rotary-kiln tests. Lightweight concrete was made from the processed aggregates and the properties determined. The results show that the laboratory data can be used to guide rotary-kiln testing, and, with the exception of sampling, a complete appraisal of a raw material for lightweight aggregate concrete can be made in 3 days by the methods described in this report.

Jan 1, 1962

By A. G. Loomis

METHODS for measuring relative permeability as a valid function of saturation were compared by the. Bureau of Mines, using core samples from representative oil-productive California formations, from the Bartlesville sand in Oklahoma, and from synthetic samples. Measurements for gas-oil systems were made by steady-state dynamic, unsteady-state displacement and two stationary-phase methods. Measurements for water-oil systems were made by the unsteady-state displacement method. As the ratio rather than individual relative permeabilities is measured by the last method, three methods for calculating individual relative permeabilites from their measured ratio were compared for gas-oil systems and two methods for water-oil systems. Errors arising from capillary discontinuities, such as the end effect and stabilized-zone flow, are discussed and evaluated; possible errors rocs arising from turbulant flow are also examined. The inapplicability of non-steady-state methods for water-oil systems that are not definitely oil-wet is discussed in detail. Measurements of relative permeability to both gas and oil can be made quickly and accurately by the steady-state dynamic method when rates of flow of the two phases are sufficient to minimize the capillary discontinuity at the outflow end of the sample. At such rates relative permeability-saturation measurements are essentially independent of the rate of flow. The steady-state method wits modified by a dispersion section at the inflow end of the sample acid designated tie dispersed-feed method.

Jan 1, 1962

By Heinz W. Sternberg

The literature on electrochemical treatment of coal is reviewed, and possible avenues of further research in this field are discussed in this report. Electrolytic reduction of finely distributed coal resulted in the addition of as many as 9 atoms of hydrogen to 100 atoms of carbon. Reduction of coal extracts at controlled potentials indicated the presence of condensed aromatic hydrocarbons and reducible quinones in coal. As much as 65 percent of low-rank coal can be made alkali soluble by electrochemical treatment. Higher rank coals gave smaller yields of alkali-soluble products. However, the nature of this reaction is not clear. The difficulty of reducing coal electrolytically is probably due to the insolubility of coal and not to any structural peculiarity. Reduction of coal by electrolytically generated radical anions appears to be a promising approach for further research.

Jan 1, 1962

By L. M. Irwin

This Bureau of Mines investigation relates the physical properties of copper reverberatory furnace slags to changes in composition, The smelting of upper Michigan copper ore presents some problems that probably differ from those of other copper smelting areas. The study of these problems has, however, provided important data regarding slags in general and therefore will be of value to other operations as well. Conclusions reached from this study were: (1) Slag fluidity and refractive indices varied directly with the iron content and inversely with silica, lime, and alumina, and (2) there was no apparent correlation between slag fluidity and its copper content.

Jan 1, 1962

By J. Mote, P. Ward Flynn, J. E. Dorn

The effect of strain and strain rate on the critical resolved shear stress for prismatic slip in specially oriented single magnesium crystals was determined over a range of temperatures in an effort to identify the thermally activated strain-rate controlling dislocation process. Below about 450°K prismatic slip was preceded by twinning and fracturing. Above 450°K extensive prismatic slip was obtained followed by fracturing. Neither the Peierls&apos; mechanism nor the dislocation intersection mechanism can account for the observations. The data, however, are in good agreement with the dictates of Friedel&apos;s theory for cross slip to the prismatic plane. PREVIOUS investigations on single and polycrys-talline magnesium have resulted in the identification of the mechanisms of plastic deformation summarized in Table I. The-only well-confirmed mechanisms are {0001}, (1010}, (1011) slip plus (1012) twinning. The other twinning modes were only tentatively established and additional investigations are required to further confirm their operation. As noted in Table I, slip in this hexagonal close-packed metal invariably occurs in the direction of greatest atomic density, revealing that the Burger&apos;s vector for-active slip dislocations is always given by b = a/3<1210>. Slip is easily induced on the basal plane, and recent investigations have shown that the strain-rate controlling mechanism at low temperatures is the thermally activated intersection of the glide dislocations with dislocations threading the basal plane. In contrast, very little is known about prismatic slip. It has been reported to be active at points of stress concentration in polycrystals below

Jan 1, 1962

By Elmars Ence, Harold Margolin

The partial isothermal section of the Ti-Cu-Zr system at 750°C has been studied. The crystal structure of Ti2Cu has been detevnlined as tetragonal and when expressed as face-centered tetragonal, a = 4.164, c = 3.611 A, and c/a = 0.867. TITANIUM systems in which ß-titanium decomposes eutectoidally into a and a compound rather readily are known as active eutectoid systems. Recently in active eutectoid alloys based on the Ti-Cu system, and containing additionally A1 and Zr, it has been found that zirconium may produce both moderate weakening and marked strengthening at elevated temperatures.&apos; In order to obtain some insight into the behavior of zirconium, an attempt was made to determine whether compounds of the type Tix Zr and TixZryCu exist. Only results of the Ti-Zr-Cu studies are reported here since data on Ti-Zr alloys will be presented in a separate publication. EXPERIMENTAL PROCEDURE Alloys were nonconsumably arc melted in argon atmosphere as 15-g buttons, prepared from materials of the following purities: Bureau of Mines electrolytic Ti — Bhn 63 OFHC copper Reactor Grade Zirconium Bhn .C 150 Prior to alloy preparation the electrolytic titanium was premelted to avoid excessive spattering of the charges during melting. The weight losses during melting did not exceed 1 pct of the total weight of the charge. The alloys prepared are listed in Table I together with analyzed compositions. in cases where they were determined. Specimens for heat treatment were wrapped in molybdenum sheet, annealed in argon-filled quartz capsules, and quenched by breaking the capsules under iced brine. About 1 to 2 sec are required to remove the capsule from the furnace, drop it into the iced brine and break it. Because of the insulation effect of the quartz, this delay in quenching should not produce a large drop in temperature. In many instances, no difference or little difference has been detected between the same specimen quartz capsule quenched or directly quenched in vacuum by an impinging stream of water.&apos; Ti-Cu-Zr alloys were homogenized for 48 hr at 825°C prior to annealing at 750°C. Annealing for 5 days at 750°C produced the same results as 11 days at temperature and it was therefore assumed that 5 days was sufficient to establish equilibrium. Titanium-copper alloys were homogenized for 40 hr at 900°C prior to heat treatment for 6 days at 750°C. Specimens for metallographic examination were electropolished and etched with the following solution:

Jan 1, 1962

By O. D. Gonzalez, H. A. Wriedt

Alloys ranging from pure iron to pure nickel were saturated with nitrogen gas at 918°, 999°, and 1217°C and analyzed. The solubility of nitrogen at 1-atm pressure was obtained as a function of nickel content for the whole range of iron-nickel alloys and the temperature dependence of solubility is shown for the experimental alloy compositions. The heat of solution and the entropy of solution of nitrogen in the alloys as func-tiom of composition up to 41 pct Ni are given. 1 HE acquisition of more exact thermodynamic information for systems composed of iron with various alloying elements continues to interest ferrous metallurgists. The interstitial alloying elements, especially carbon, hydrogen, and nitrogen, comprise a field of particularly intense study. A recent investigation of carbon solubility in Fe-Ni alloys held at 1000°C in gases of fixed carbon activity showed an unpredicted minimum in the solubility near 72 pct Ni.1 The present investigation was undertaken to see if a similar anomaly in solubility existed for nitrogen in Fe-Ni alloys. The solubility of nitrogen in ? iron at known nitrogen activities has been measured several times.&apos;-&apos; Corresponding information for the solubility of nitrogen in solid Ni and Fe-Ni alloys is not available. Juza and sachsze9 reported that metallic nickel dissolved 0.07 pct N in equilibrium with Ni3N at 445°C. This result was regarded as dubious by Turkdogan and Ignatowicz10 who found less than 0.0004 pct N in nickel specimens equilibrated at 600°C with ammonia-hydrogen mixtures having fugacities of N2 gas up to 35,000 atm. Such fragmentary reports indicate only that nitrogen gas has a very much lower solubility in nickel than in iron. MATERIALS A purified iron from Battelle Memorial Institute was used for solubility measurements. This grade contained more than 99.95 pct Fe, the highest content of any measured individual impurity being 50 ppm for each of As, C, Cu, and Pb. The nickel and iron-nickel alloys, supplied by the International Nickel Co., contained 0.02 to 0.04 pct C, 0.17 to 0.19 pct Mn, 0.04 to 0.08 pct Si, < 0.01 pct P, <0.03 pct S, and <0.20 pct Co as principal impurities. The Fe-0.59 pct Mn alloy was of zone-melted quality, the highest concentration of any individual impurity being 15 ppm Al. The "prepurified" grade of nitrogen gas from Matheson Co. had a nominal nitrogen content of 99.996 pct. An "electrolytic" grade of hydrogen gas from National Cylinder Gas. CO. in which the principal impurity is water vapor was admixed with the nitrogen to prevent oxidation of these specimens. This grade was preferred to a purer grade because the presence of some oxygen helps in suppressing contamination of the specimens, for instance, by silicon from the porcelain furnace tube. EXPERIMENTAL PROCEDURE The specimens were equilibrated in vertical tube furnaces through which a 99 pct N2-1 pct H2 gas was passed at ambient pressure. For the 915", 918", and 999°C runs, a wound-resistance furnace was used, and for the 1217°C runs, a furnace with a tubular silicon carbide element was used. The temperature control system on both furnaces was similar: a Weston "Celectray" controller with a modulator, responding to the electromotive force of a thermocouple with its hot junction in the furnace, switched the furnace current between high and low settings. The temperature distributions in the working zones of the furnaces were determined with calibrated Pt/Pt-10 pct Rh thermocouples. The overall uncertainty in temperature was estimated to be ±3° at 915° to 999°C and ±5° at 1217°C . Consideration of the small temperature coefficients of the equilibria studied, together with the error limits in the method of analyzing for nitrogen, showed that further refinement in temperature uniformity would give no improvement in resultant accuracy. The reactive gas was generated by mixing together "prepurified" nitrogen and "electrolytic" hydrogen directly from cylinders commercially supplied. The flow rates of nitrogen and of hydrogen were fixed by setting with bleeders the pressure drops across the individual calibrated flow meters of constant resistance. For any given alloy, the solubility of nitrogen at 1-atm pressure (% N) was obtained from the analyzed nitrogen content of equilibrated specimens (% Na)according to Sieverts&apos; law, thus

Jan 1, 1962

By M. J. Langley

Zinc ores were first discovered in Tennessee in 1856 at Jefferson City where a deposit of oxidized ore became known as the Mossy Creek Mine. From that time until 1913 small scale attempts at prospecting and mining were made in various parts of the district. The actual systematic development of the zinc deposits dates from 1913 when the American Zinc Company started operations at Mascot. Six mines are in operation by three companies and a seventh mine is being developed by a fourth company. The total daily production from the field is 11,000 tons of crude ore, which grades from 3 to 6 per cent zinc. Most of the ore bodies are large and ramiform, resembling asyrmetrical networks in which the ore shoots form channel like branches with areas of non-comercia1 rock, called blank islands. Most of the orebodies are adapted to large scale mechanization.

Jan 1, 1962

By R. Ward Stahl

The underground junction or intersection is analogous to the doorway or window in a building in that the continuous wall or support for the overhead structure has been weakened by making the opening. Some type of bridge or support seems necessary to prevent roof sag and possibly eventual failure at this point, although frequently it appears that little is done until a fatal accident induces action. The intersection generally represents less than 15 percent of the exposed roof area. As a result of recent multiple fatalities, some of which occurred at or near intersections, the Bureau of Mines was asked to examine the junction-support problem more thoroughly and to report its findings. A national survey of the junction-support systems in use has been made by correspondence, and the local area has been canvassed rather thoroughly to determine just what and how much is being done.

Jan 1, 1962

By P. Greenfield, C. C. Smith, A. M. Taylor

The Mg-Zr alloy ZA and Mg-Mn alloy AM503(S) are shown to have a markedly improved resistance to creep deformation after suitable heat treatments. This improvement makes them suitable for certain stress-bearing fuel element components in nuclear reactors. The extent of strengthening is described and an explanation of the behavior of both materials is given, based on a combination of strain-aging and grain growth. The increase in operating temperatures of fuel element components in Calder Hall type nuclear reactors has necessitated the development of magnesium base alloys with a very high resistance to creep at temperatures up to 500°C. Such alloys are not required for fuel element cans, which require high-creep ductility rather than strength, but for can supporting and stabilizing components, which are needed to support the imposed loads without deforming more than about 1 pct in times of up to 40,000 hr. The amount and type of alloying addition made to magnesium for these parts is limited by the necessity of keeping the cross-section to thermal neutrons as low as possible. The alloys must also possess a high resistance to oxidation in CO2. Alloys which have been developed for this application include ZA, an alloy of magnesium with 0.5 to 0.7 pct Zr and AM503(S), an alloy of magnesium with 0.5 to 0.75 pct Mn. In the as-extruded condition these alloys are very weak and ductile in creep but it has been found that they can be strengthened to a significant extent by heat treatment. This paper describes the method of developing a high-creep resistance in ZA and AM503(S), the extent of the strengthening produced and discusses the probable mechanisms of strengthening. TEST MATERIALS Specimens were taken from typical casts of ZA and AM503(S) alloys extruded into 2 1/4-in.-diam bars, supplied by Magnesium Elektron Ltd. Typical analyses of the bars were as follows: The as-extruded mean grain diameter was 0.001 to 0.002 in. for the ZA alloy and 0.003 in. for the AM503(S) alloy. EXPERIMENTAL METHODS Extruded bars of ZA alloy, 2 1/4 in. in diameter and 9 in. long, were heat treated in electrical resistance furnaces in an atmosphere of flowing CO2 containing 50 to 300 ppm water, thereby reducing the extent of oxidation compared with that which would have occurred in air. Heat treatments were carried out at 600oc for times of 8, 24, 48, 72, and 96 hr and material was subsequently both furnace cooled and water quenched. In order to measure the effect of time of heat treatment, specimens were creep tested at 400°C and 336 psi for about 1000 hr. Subsequently, the behavior of material heat treated for 96 hr at 600°C and furnace cooled was tested at a variety of stresses from 200° to 500°C. Tests were also conducted at 200o and 400°C on material in the as-extruded condition for comparative purposes. With the AM503(S) alloy, only the effect of heat treatment at 565°C for 4 hr was examined. It has been shown1 that such a heat treatment produces marked strengthening in this alloy. Tests on this material were conducted at a variety of stresses at 200°, 300°, and 400oc with comparative tests on as-extruded material at 200o and 400°C. The creep tests were carried out on machines using dead-weight loading and direct micrometer strain measurements on specimens 5 in. long and 0.357 in. diameter. At temperatures of 400° C and below, the creep tests were conducted in air, but at higher temperatures an atmosphere of CO2 was used. Grain size measurements were made on ZA in the extruded and heat treated states and on each specimen after creep testing. This was done by a line count of a minimum of 20 grains in two or three random fields in the longitudinal and transverse directions. The same method was used for measuring the grain size of as-extruded AM503(S), but the grain size of the heat treated material was so large that this method could not be employed. For heat-treated AM503(S) the large grained characteristics (between 0.1 and 1 in.) were confirmed by the measurement of individual grains. In the case of the ZA alloy, specimens taken from various stages in the program were analysed for hydrogen by a combustion method. Material in various states was also analysed for the soluble and insoluble zirconium content by dissolving in dilute hydrochloric acid. This technique has been useda for the determination of amounts of zirconium present

Jan 1, 1962

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

Competitive growth of recrystallized grains into striated single crystals of zone-refined lead produced preferred orientations of the coincidence type after annealing at 175°C, but not at 300°C. This preferred orientation development was found to result from the higher mobility and lower energy of large -angle coincidence boundaries compared to large-angle noncoincidence boundaries. These mobility and energy difference provide a useful basis for explaining many cases of preferred orientation observed in annealed metals. DURING a study1 of the mobility of grain boundaries in zone refined lead, it was observed that the temperature dependence of the grain boundary migration rate is smaller for large-angle, coincidence-type grain boundaries than for large-angle noncoincidence ("random") boundaries. This observation is illustrated schematically in Fig. 1, which shows log rate of grain boundary migration vs reciprocal absolute temperature for two large-angle boundaries. The upper curve refers to a coincidence-type boundary of the sort discussed by Kronberg and Wilson.2 While the mobilities of these two boundaries are similar at 300°C, the coincidence-type boundary has a greater mobility, by a factor of about: four, at 175°C than does the noncoincidence boundary illustrated in the lower curve. The observation described above suggested a simple experiment for testing the role of grain boundary mobility in the development of preferred orientation in annealed, high-purity lead. On the basis of this observation, it would be expected that if a large number of grains of different orientations are growing competitively, and if relative grain boundary mobility is a controlling factor, then the specimen procluced by boundary migration will contain crystals having random orientations if annealing is done at 300°C, while preferred orientations of

Jan 1, 1962