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By G. I. Madden, L. H. Van Vlack

WhEN basic refractories which contain peri-clase, MgO, are used in steel furnaces, they are altered by iron oxide to form magnesiowiistite, (Mg,Fe)O, and an iron-rich magnesioferrite, (Mg,Fe)Fe2O4. Silica, which is usually present, produces a silicate liquid that surrounds the solid phases. The individual crystalline grains of the above two solid phases grow at elevated temperatures. Previous papersL" showed that, if either periclase or magnesiowiistite is present as the only solid phase, its grain size increases in proportion to temperature and in proportion to the square root of time; the growth rate is reduced slightly if the amount of silicate liquid is increased. Similar results have been observed for iron-rich magnesioferrite.3 To determine the effect of the presence of two solid phases on the rate of grain growth, micro-structural studies have been made on samples containing both magnesiowustite and magnesioferrite. The experimental procedure was the same as that followed in the previous studies of this type.'12 Briefly, this included determination of compositions from the available phase relationships4 that would produce the two phases of interest at the firing temperature and using reagent-grade raw materials to prepare mixtures of these compositions. The mixtures were pressed into pellet-size samples and then fired at the desired time and temperature. The samples were water-quenched to preserve the microstructure present at the firing temperature. Standard reflected-light metallographic techniques were used for sample examination and sample analysis. Grain sizes were determined by measuring the mean diameter of a number of randomly selected grains in a two-dimensional microsection. A large cross section of the sample was covered to prevent biased data resulting from such effects as localized differences in the radius of curvature of the crystal grains. Examination indicates that grain growth is restricted when more than one solid phase is present. This is illustrated in Fig. 1 for: (a) magnesiowustite plus a silicate liquid; (b) magnesioferrite plus a silicate liquid; and (c) magnesiowiistite and magnesioferrite plus a silicate liquid. Fig. 2 plots the

Jan 1, 1964

By George W. Orton

i\- number of investigations have established that tungsten monocarbide (WC) forms throughout a wide range of temperatures (800° to 2200°C), but the di-tungsten carbide (W2C) forms only at the high end of this temperature range.1"7 In addition the decomposition of WC into WzC and C at elevated temperatures has been observed.8"10

Jan 1, 1964

By E. E. Thurlow

The Geology Div. of Northern Pacific Railway Co. has adapted to its exploration efforts field procedures for geochemical sampling and semi-quantitative analysis which have been developed through research by the U. S. Geological Survey. The sampling is done in conjunction with reconnaissance geologic mapping on aerial photographs or during field checking of maps which have been prepared largely by photo-geologic interpretation. Stream sediment or soil samples are taken and readily soluble combined heavy metals are extracted with ammonium citrate followed by colorimetric titration with dithizone at the sample site. The effectiveness of this approach has been demonstrated both in positive and negative results, thereby assisting in the elimination of large areas of land from further immediate attention and in providing targets for followup exploration. An occa sional sample is submitted for spectrographic analysis as a check on the possible presence of other elements of economic significance. Field laboratory procedures are also being implemented for determining molybdenum, mercury, and other metals which may be valuable in themselves or useful as pathfinder elements in outlining mineralized areas. A lead-zinc occurrence in Oregon and a copper deposit in Montana were readily detected and outlined by stream sediment and soil sampling and a heavy metal anomaly that lacks obvious interpretation has been found in northwestern Montana. Detailed mapping and additional sampling are followed by other exploration techniques if warranted. Northern Pacific's program of reconnaissance mineral evaluation of company-owned lands and adjoining areas was outlined in a paper presented at the American Mining Congress meeting in Las Vegas four years ago. That report included policies and procedures with respect to mineral development on Railway Co. lands and may be referred to for information on these matters.1 In a sense this paper is a progress report on the use of geochemical prospecting in Northern Pacific's continuing mineral evaluation program. At this time there are positive results but as yet there is no real success story in the form of a minable ore body. GEOCHEMICAL PROSPECTING PROCEDURES The decision to use geochemistry as a reconnaissance exploration tool must be followed by research into sampling and analytical methods and into the interpretation of results. Various analytical methods were tried and evaluated by the Geology Div., including hot and cold acid extraction with and without fusion of the sample, panning and magnetic separation followed by dithizone testing of the magnetite, and cold aqueous extraction of metallic ions followed by indicator tests. Samples were first sent to the laboratory for analysis; later field laboratories were established and now virtually all testing is done at the sample site. It was concluded that, where applicable, the quickest dependable methods for reconnaissance use are the dithizone field tests for readily extractable heavy metals. This involves the simultaneous treatment of a sample, usually of soil or stream sediment, with two immiscible liquids; one a cold aqueous extractant (ammonium citrate) and the other a solution of dithizone in toluene or xylene.2 Dithizone is a colorimetric indicator that reacts quantitatively with copper, lead, zinc, and several other metals to form colored complexes in organic solvents. Results may be expressed in ml of 0.001 pct dithizone that are required to reach the blue end point, or calibration of the test results can be carried out with standard solutions of zinc; conversion factors would then be expressed in ppm, zinc equivalent. Calibration of dithizone solution with zinc standards indicates that 1 ml of 0.001 pct dithizone is equivalent to approximately 0.25 ppm of zinc. An authoritative report on dithizone field tests authored by H. E. Hawkes in the June-July 1963 issue of Economic Geology* states "The appeal of these techniques has been the simplicity and speed of the determinations as compared with more tedious laboratory determinations of trace metals in weathered rocks, soils, or plant materials. This obvious appeal, however, has often been more than matched by misuse of the method in such a manner that the results are

Jan 1, 1964

Jan 1, 1964

By J. C. Cook

In solution-mining of underground salt and similar minerals, using drilled wells for access, it is desirable to monitor the lateral growth pattern of the resulting fluid-filled cavern. Therefore, a process of seismic surveying from the surface of the ground has been conceived in which the amplitudes of waves reflected from and transmitted through the soluble formation are measured. The large acoustic impedance contrast between solid and fluid should produce striking amplitude anomalies, especially if shear waves are employed, since thick fluid bodies are opaque to shear waves. Horizontally-polarized (SH) shear waves are best for preventing conversion to P waves at the numerous horizontal interfaces in the ground. Field tests to date have shown that a truck-mounted, half-ton hammer striking horizontally against the end of a trench produces usable SH-wave energy at lateral distances up to about 850 ft. Horizontally-directed explosive wave sources were effective to about 2000 ft. Conventional magnetic-tape recording and processing were used, but with the detecting geophones oriented to favor SH waves. An irregular solution cavity in bedded salt at 500-ft depth has apparently been located by SH-wave and SV-wave reflections. Further field work is planned to corroborate and extend this result. The Brine Cavity Research Group, an association of 11 chemical and salt producing companies, is supporting this work. Major deposits of salt in tabular beds lie beneath some 300,000 sq miles of land in the central and northeastern U.S. This salt is a basic source of soda ash and chlorine, and has been extracted as brine from drilled wells for about a century. During the past two decades, the U.S. solution-mining industry, following the lead of European operators, has greatly improved the extraction process through the application of engineering and science.' In 1957, the Brine Cavity Research Group, an association of 11 chemical and salt producing companies, was formed. This group proceeded to attack certain common problems through the support of research. An outstanding problem has been that of determining the shape and location of the growing solution cavities in the underground salt, so that measures can be taken to maintain operating efficiency. The problem has been partially solved by the Dowel1 sonar mapping service, which employs a pulse-echo device lowered into the cavity through the well.2 However, the working range of this equipment is at present insufficient for large cavities, and echoes are not returned from highly sloping walls nor from behind such obstructions as rock debris. Therefore, an independent means of mapping the cavity, for example, from the surface without interfering with operation of the well, would be desirable. THEORY OF THE METHOD Seismic waves are the only physical agent known to be capable of sufficient resolution and penetration to define typical solution cavities from the surface of the ground. The geometry is unfavorable: cavity widths are generally less than half their depths below the surface; resolution and lateral location of boundaries and channels to within 50 ft at depths of 500 to 3000 ft is desirable. Conventional seismic surveying, as used for petroleum prospecting, is probably not the answer: isopach mapping, for example, is not thought accurate enough to define the cavity by the slight additional delay time it would introduce (of the order of 0.005 sec for a 50 ft-thick cavity in hard Paleozoic rocks). Refraction surveying has also been considered, but seismic specialists see little promise in it for this problem. In 1957, in correspondence with industry personnel, the writer suggested a seismic method based upon careful measurement of reflection amplitudes. As Table I illustrates, seismic reflection coefficients r for typical brine-rock interfaces are considerably higher than those for typical interfaces between different kinds of solid rock. This fact can be utilized in two ways, illustrated in Fig. 1: 1) If the cavity roof is reasonably flat (which it may sometimes be since the unsaturated top brine will be in contact with an insoluble rock stratum), extra-strong seismic reflections will be received from the salt stratum where the solid has been replaced by liquid.

Jan 1, 1964

By Craig R. Barrett, Alan J. Ardell, Oleg D. Sherby

It is shown that the apparent activation energy for creep of pure poly crystalline metals increases with increasing temperature in the temperature range 0.5 to 1.0 of the absolute melting temperature. This increase is probably associated with the influence 0-f the elastic modulus on the creep rate. By accounting for the variation of Young&apos;s nodulus with temperature, the true activation energies for creep of pure cadmium and aluminuvl are shown to be equal to the activation energies for self-diffusion in these metals, within experimental error, at all temperatures above 0.5T,. New creep parameters are proposed for cmrelation of steady-state creep rate and time-to-rupture data. These are respectively, where u is the creep stress, E is Young&apos;s rrodulus, i,is the steady-state creep mte, t, is the time -to-rupture, and D is the self-diffusion coefficient [equal to Do exp (-QSd/RT)] . It has been established experimentally1 and theoreticallyZm4 that high-temperature creep of poly-crystalline pure metals is a thermally activated process and may be represented by the general expression where <, is the steady-state creep rate, A is a constant dependent on the internal structure of the material, f is some function of the applied stress (0) and test temperature (T), and D is the self-diffusion coefficient. If D is separated into its temperature-dependent and independent portions, then it is possible to rewrite Eq. [I] as where Qsd is the activation energy for self-diffusion. Assuming a simple Arrhenius-type relationship between creep rate and temperature at a given constant stress, the apparent activation energy for creep, Q,, is given by the expression It is obvious that if is not a function of temperature It has been shown that the steady-state creep rate for pure polycrystalline metals1 can be represented by where S is a constant, L is the grain diameter, E is the isotropic polycrystalline (unrelaxed) elastic modulus, and n is a constant equal to approximately 5 over a wide range of stress. The apparent activation energy for creep calculated from this expression at constant grain size and stress is given by

Jan 1, 1964

By P. Hadzeriga

There are two places in the world where potash, trade name for potassium chloride, is economically recovered from naturally occurring brines by solar evaporation. One is at the Dead Sea and the other at Wendover, Utah. American Potash and Chemical at Trona, Calif. recovers potash from natural brines, but uses fuel to accomplish evaporation. Solar evaporation is always desirable, because of low costs, however artificial evaporation may be economical if a group of very valuable salts are recovered. This is the case for the American Potash operations at Trona. Solar evaporation is limited by low working temperatures, which in most areas of the world is between 18 and 45°C. In many cases the average working temperature is about 25°C. However, solar evaporation will have to accommodate itself to the highs and lows of each 24 hour period, and to the different average temperatures during the months of the year. Therefore, solar evaporation, although more economical than artificial evaporation, has a tem- perature limit which greatly reduces the chances of its application. The feasibility of solar evaporation as a means of recovery of values from a particular brine, may be evaluated by the use of phase diagrams showing the several components present. This paper is restricted to the five component system: C1-, SO4=, Na+, K+, Mg++, and H2O, which correspond to brines found at Wendover, Utah, the Great Salt Lake, and sea water bitterns. THE BONNEVILLE OPERATION AT WENDOVER, UTAH For more than 25 years Bonneville, Ltd., now a division of Standard Magnesium and Chemical Co. (recently acquired by Kaiser Aluminum and Chemical Corp.), has been recovering potassium chloride from the brines found in the desert area just east of Wendover, Utah. Solar evaporation of the brines is possible as a consequence of relatively low precipitations (year average: 4.8 in.), and of dry and hot summer months. The brine, collected by a series of approximately 67 mi. of ditches crossing the desert, is fed into solar evaporation ponds. Evaporation which takes place from around the middle of May to about the end of September, permits the crystallization of approximately 90% of the originally present NaCl on what is called the "General Pond Area". Further evaporation,

Jan 1, 1964

By C. G. Durdaller, W. H. Robinson, G. M. Pound

The nucleation rate of the a (pay) to 0 (white) tin transformation was measured as a function of temperature and a tin particle size using an X-ray diffraction technique. The powder specimens of a tin were essentially monodisperse and the small dinzension of the particles of these specimens was varied from 13 to 75 p. Several types of nucleation sites of differing potency were fbund to be operative in the nucleation process, but it could not be determined whether these sites were on the free surface of the tin particles or within the volume. Assuming that they were on the free surface, the average density of the most potent sites was calculated to be 2.5 to 5.3 x 10&apos; sites per sq cnz through the application of a Poisson distribztion finction to the isothermal data. Analysis of the temperature dependence&apos; of the rate constmts at a given fraction transformed suggests that the active sites are regions of higher free energy and not catalytic interfaces. Appreciable induction periods were observed at the lower temperatures of transformation. Experimental studies1 of solid-solid phase transformations have led to the belief that the new phase nucleates at structural imperfections. The purpose of the present work was to learn more about the mechanism of nucleation in solids and the nature of the singularities at which nucleation occurs. In this investigation nucleation rates in the isothermal transformation of gray to white tin were measured by an X-ray diffraction technique using essentially monodisperse powders of gray tin. This particular phase transformation was chosen for study because it presented fewer experimental difficulties than most others. The experimental temperature-control problems were minimal because the two phases coexist in equilibrium at 13.3"C, and measurable transformation rates occur at temperatures only slightly above room temperature. The growth rate of the P phase into the a2 is sufficiently fast to make the measured transformation rate equivalent to the nucleation rate, provided that the particle size of the samples is small enough; for the experimental temperatures used in this study, the particle diameter must be less than 100 p. EXPERIMENTAL TECHNIQUE The P tin used in this study was obtained from Capper Pass and Son Ltd., North Ferriby, Yorkshire, England, and was of 99.999 pct purity. It was transformedS to the a phase and ground into a fine powder in an agate mortar. This powder was separated by a Roller air classifier into seven fractions whose dimensions, as determined by microscopic measurement of many thousands of particles, are given in Table I and whose distribution of size within each fraction is given in Figs. 1 and 2. The shape of the particles was roughly that of an oblate spheroid,

Jan 1, 1964

By D. D. Todd, W. A. Oates

THERMODYNAMIC data for solutions are best derived from a combination of equilibrium and calorimetric studies. However, the accurate measurement of heats of mixing of metallic solutions at high temperatures presents considerable experimental difficulties, simple calorimeters1-3 giving

Jan 1, 1964

By W. Rall, A. J. Birkle

The effect of fast-neutron irradiation on the micvo strcture of a common reactor pressure-vessel steel, A212 Grade B, was studied using thin-foil transmission electron microscopy. The dislocation density of the irradiated material is considerably greater than that of the nonirradiated control material. Annealing studies indicated that dislocations and hardness ill the irradiated material annealed out—as docs the radiation-induced embrittlement according to other- investigators— at temperatures STEELS in nuclear reactors are affected by neutron irradiation. In the American Society for Testing Materials (ASTM) A302B and A212B steels commonly specified by designers for reactor vessels, between 650° and 800°F. However, the dislocations and hardness in control samples cold-worked to 9 and 70 pct did not anneal out readily, and a high dis -location density was observed, even after a 1-hr anneal at 850°F. Based on the hypothesis that cllrster defects, rather than the increased dislocation density, are primarily responsible for mdicltiotz-iudziced e)nbriftlen7ent, reconzmendations are made for reducing the susceptibility to such ernbrittlement. exposures at a temperature of 550°F or lower to neutron dosages encountered during a 20- to 30-year life (-3 X 10&apos;&apos; nvt, >1 mev) may increase the nil-ductility transition temperature (NDT) as much as 300" or 400".&apos;9 Therefore, to prevent brittle failures in reactor structures, extreme caution is required to reduce thermally induced stresses during all reactor shutdowns and startups when the temperature is below the NDT of the pressure vessel.

Jan 1, 1964

By Evan Just

Government aid, regulation, and participation in the mineral industry are not new; they date back to the time when man first adopted communal living. Even in primitive tribal life, the obtaining of arrowhead or ceramic materials, washing of gold, or mining of copper were specialized activities, under tribal sponsorship. Later, when kingdoms, dynasties, and hierarchies developed, titles to mining properties were held by the sovereign or the state, work usually being done by slaves. Title acquisition through denouncement developed in Europe in the late Middle Ages and spread to the Western Hemisphere with the Spanish and Portuguese empires. Denouncements still recognized the rights of the sovereign in the requirement to pay royalties, which practice continues in many places today. Thus, anyone who views government participation in mineral activity as "encroachment" has no historical perspective. Only in a few countries and for a few generations have private interests enjoyed the right to exploit mineral deposits without the specific consent of the sovereign or without payment of royalty. Governments and the mineral industry have been linked together by other factors. Governments have had special interest in metals and minerals as stores of value and for armaments. Spanish conquests in the New World were energized by the lure of gold and silver. Pursuit of gold led to the American seizure of California in the days of the Forty-niners. The strategic importance of minerals in our own times has called for special steps to stimulate production in national emergencies and to prevent the enemy from acquiring mineral supplies. Our export controls to deny certain minerals to unfriendly countries, purchases for Government stockpile, and subsidies for domestic production are examples. Production regulation by state governments of oil and gas has become a well established routine. In brief, the mineral industry has never lacked aid, regulation, and participation by governments. The entrepreneur who wishes to explore for or develop minerals must deal with governments in most areas before he can begin, because mineral rights are reserved by them. He can proceed through discovery and de-

Jan 1, 1964

By I. J. Polmear

Earlier work revealed that small amounts of silver (< 0,l at. pct) may exert a marked effect on the structure and aging characteristics of certain a1loys based on the Al-Zn-Mg system. Silver additions have now been made to other age-hardening aluminum alloys, and significant effects have been observed in the Al-Mg system and in several Al-Cu-Mg and Al-Mg-Si alloys. Similarities exist between the behavior of alloys from all four systems, notably that in each case silver stimulates nucleation of an intermediate precipitate which forms when the alloys are aged in the medium temperature range (-120" to 220°C). The mechanism for this effect is uncer- IT has been shown that small additions of silver (<0.1 at. pct) may have a marked effect on the structure and age-hardening characteristics of tain although it is suggested it originates in a preferred affinity between magnesium and silver atoms. There is evidence to indicate that the effects of silver are unique to that element. It is suggested that silver atoms interact with vacancies during low-temperature aging of Al-4 pct Cu and certain Al-Cu-Mg alloys. Silver had little effect on Al-8 pct Zn aged at any temperature. Preliminary observations indicate that silver may have interesting effects on the strength properties of Al-Mg alloys, md a the commercial Al-Cu-Mg alloys designated as 2024 and 2618. many alloys based on the Al-Zn-Mg* system.1"&apos;*

Jan 1, 1964

By J. F. Martin, L. M. Melnick, R. Rapp, R. C. Takacs

Recent studies on the determination of hydrogen in steel have shown that the hot-extraction method for removing hydrogen from a solid sample is preferable to its removal from a molten sample by vacuum fusion or by fusion in vacuum with tin. A number of techniques are available, however, for determining the hydrogen so extracted. They include: thermal conductivity, gas chromatography, pressure measurement before and after catalytic oxidation of the hydrogen to water and removal of the water, and pressure measurement before and after diffusion of the hydrogen through a palladium membrane. These techniques have been evaluated on the basis of initial cost, maintenance, speed and accuracy of analysis, and applicable concentration range. The results of this study showed that the palladium-membrane technique is best suited for routine use. FOR some time investigators have been concerned with the origin, form, and effect of hydrogen in steel. In such stdies&apos;, the analysis for hydrogen constitutes one of the most important phases. It is quite apparent that the results for hydrogen concentrations in a given steel are dependent on the method of obtaining the sample, storage of the sample until analysis, preparation of the sample, and analysis of the sample, including all the facets inherent in the calibration and operation of an apparatus for gas analysis. There are a number of means available for determining hydrogen. This is a critical study of some of the more common techniques in use today. In most conventional melting and casting methods, hydrogen concentrations of 4 to 6 parts per million (ppm) in steel are quite common. Because of the undesirable effects of hydrogen on steel there has been increased use of techniques such as vacuum melting,&apos; vacuum casting, and ladle-to-ladle stream degassing, which lower the hydrogen content to levels on the order of 1 to 2 ppm. Therefore, the method used for determining hydrogen in steel must be sensitive and precise. In any analytical procedure for gases in metals there are two distinct operations—the extraction of the gas from the metal and the analysis of the extracted gas. To extract the gas from the steel, three methods have been employed: 1) fusion of the sample with graphite at high temperature; 2) fusion with a flux, such as tin, at a lower temperature; and 3) extraction of the hydrogen from the solid sample at a temperature below the melting point of the steel. Fusion with graphite is the least-acceptable method. The blank in this method is higher and more variable than in either of the other two methods. The hydrogen fraction of the total gas composition usually is between 10 and 50 pct; thus, a larger analytical error is possible. The vacuum-tin fusion4 extraction of hydrogen is probably the most rapid method in use today; the extraction time is usually about 10 min. However, with this system a bake-out of the freshly charged tin for 2 hr is necessary and a change of crucible and a charge of fresh tin are required after each day of operation whether one or thirty samples have been analyzed. In addition, frequent checks of blank rates are required since CO and Na are continually being given up by the steel samples dissolved in the tin bath. The composition of the gas in this method lends itself readily to analysis; although the hydroge concentration may fall to as low as 50 pct, more often it is above 90 pct, thus allowing a more precise analysis (because of less interference from other gases). In 1940 ewell&apos; published the hot-extraction method for extracting hydrogen from the solid sample, comparing analysis for hydrogen extracted at 600°C with similar analysis for the gas extracted at 1700°C by fusion with graphite. Good agreement for hydrogen was obtained between these two methods, provided sufficient time was allowed for extraction at the lower temperature. carsone obtained good results in his comparison of this hot-extraction method with vacuum-tin fusion. Subsequent work by Geller and sun7 and Hill and ohnson&apos; has shown that steel samples should be heated to at least 800°C to effect the release not only of the diffusible hydrogen but also of the "residual" hydrogen that may be present as methane. Since the rate of evolution of hydrogene9l0 depends on such factors as sample size and composition, thermal history, and extent of cold work, a fixed extraction time is not possible. Extraction times of 30 min are normal, but 2 hr are not unusual. Induction or resistance heating may be used in the hot-extraction method. With resistance heating the

Jan 1, 1964

By Nicholas J. Grant, Hanna Ibach, Bill C. Giessen

The system Ta-Rh was investigated over the entire comnposition range using metallogvaphic and X-ray techniques as well as thermal analysis. Terminal solubility limits, solidus temperatures, and the crystal structures of two new intermediate phases were determined. There are five intermediate phases: o, tetragonal, isostructural with o(Fe-Cr); a1, orthorhomnbic : a2, orthorhombic, isostructural with CozSi; 0 3, a high -temperature phase of unknozun structure; and a TaRh3, cubic, AuCu3 structure. a, aL, a,, and a melt peritectically; and a TaRh, has a maximum melting point. Five peritectic and one eutectic reactions occur. THE Ta-Rh phase diagram has not been fully treated in the literature; however, two inter metallic phases have been described.&apos;-&apos; This study attempts to work out the diagram covering the details of phase boundaries as well as the crystallography of the intermediate phases. EXPERIMENTAL METHODS Starting materials were tantalum powder of 99.8 pct purity, supplied by National Research Corp., Cambridge, Mass., and rhodium powder of 99.9 pct purity, supplied by Bishop Co., Malvern, Pa. Analyses as given by the manufacturers are presented in Table I. In addition to the spectroscopic analysis, an oxygen analysis has been made of the tantalum powder. After preliminary trials, the standard procedure employed in making the alloys was as follows (see Ref. 4 for further details). The powders were weighed, mixed manually, compacted under 16,000 psi, and arc-melted at not more than 500 amp under thoroughly titanium gettered welding-grade argon of 400 mm Hg pressure. The gettering process was repeated after each melt. It had been shown previously5 that under these conditions no oxygen pick-up exceeding 0.001 pct in a hafnium button could be detected. The buttons, ranging from 5 to 10 g in weight, were inverted or, if possible, crushed and remelted three times. Melting presented no difficulty, except for tantalum-rich al- loys, which showed considerable spashing during melting. The average weight loss of 1 wt pct rose to 2.5 wt pct in these cases. Subsequent melting, however, resulted in losses of less than 0.1 wt pct. The melts obtained frequently showed small in-homogeneities, mostly in the tantalum-rich part of the system below 25 at. pct Rh. This was not due to insufficient blending of the elements, but to crystallization taking place from the cooled bottom. This condition was not improved by further re-melting; therefore the following precautions were taken. Cross sections of as-cast buttons were made. For the investigation only buttons were used where these inhomogeneities did not exceed 1 at. pct (estimated from the amounts of haSeS resent). In addition, only the center portions of such buttdns were utilized to minimize errors. Smaller buttons showed smaller concentration gradients and were used as a check. Finally, all alloys were homogenized to eliminate coring (see below). After this, the error in alloy composition due to inhomogeneity was cl at. pct. In order to confirm the concentrations of the alloys and to provide an impurity check, wet-chemical analyses and oxygen-fusion analyses of four key alloys were carried out. The results, together with the concentrations as calculated with the weight balance method, are presented in Table 11. It was found that for three alloys the agreement is very good (< 0.2

Jan 1, 1964

By O. N. Carlson, K. E. Solie

The brittle-ductile transition temperatures of single and poly crystalline chromium metal were studied as a function of nitrogen concentration and chromium nitride distribution. It was observed that In recent years there has been an increasing interest in chromium-base alloys for high-temperature applications. The principal disadvantages, however, have been the difficulties of fabrication and the design problems associated with a material of such limited ductility. Various studies have been the effects noted in the poly crystalline material are essentially reversed in the single crystals. These observations are discussed in terms of existing theories for the brittleness of chromium. conducted recently directed toward a determination of the cause of this brittleness and to find ways for minimizing its effects. Allen et al.,&apos; Wain Abrahamson and rant,&apos; and weaver4 have carried out studies on the effects of interstitial impurities on the brittle-ductile transition of chromium metal of various degrees of purity. These investigations have shown that oxygen has little or no effect on the transition temperature of chromium in all conditions studied but that carbon increases the transition temperature under all conditions tested. Nitrogen was found to increase the transition temperature in the wrought condition and in the quenched or cast conditionS but reportedly has no effect in the furnace-cooled condition.

Jan 1, 1964

By E. T. Turkdogan, P. Grieveson

Experimental results are given for the rate of oxidation of ferrous iron to ferric iron in pure molten iron oxide by carbon dioxide + carbon moloxide mixtures at 1550°C. It is shown that the rate-controlling process is the interdiffusion of iron and oxygen atoms within the melt. The inter-diffusivity of iron and oxygen in the melt is obtained from the results and the value of (5.0 * 1.0) x 10-5sq cm per sec is recommended for the temperature of 1550°C. Similarly, it is also found that the rate of reduction of molten iron oxide is con -trolled by diffusion in the melt; however, apparent interdiffusivity values from these experiments are 10 to 20 pct higher than those obtained in the oxidation experiments, by virtue of convection arising from density difference. The results of the oxidation experintents are used to calculate an estimated self-diffusivity of iron in molten iron oxide of (1.5 * 0.5) x sq cm per sec. BECAUSE of the industrial importance of iron oxides, the study of the kinetics of both the reduction and oxidation of the solid oxides has received a great deal of attention. However, knowledge of the kinetics of similar reactions in the liquid state is very meager. Dancy 1 studied the kinetics of reduction of molten iron oxide by carbon in pig iron and found that the reaction is very fast. It was concluded from the results that the reduction of molten ferrous oxide is a first-order reaction up to 80 pct reduction, while

Jan 1, 1964

By J. L. Lytton, T. E. Tietz

The recovery of flour stress of recrylstallized are-cast molyhdenum after 10 pet prestrain at 150°C was studied for recovery temperatures of 725o 801o and 901oC. The yield phenomenon observed after recovery was such that the yield drop diminished and disappeared as recovery proceeded. A fractional flow-stress recovery parameter fr, was developed and it was shown that, independent of recovery ternperatzwe, equal f, values of about 0.16 produced superposition of stress-strain curves except for the initial yield phenomenon. The activation energy for low degrees oj recovery was found to he 32,600 cal per mole, in close agreement with a reported valzie for difjzdsion of carbon in molybdenum. For values of fr greater than about 0.15 where recovery was thought to predominate over strain aging, the activation energy varied from 43,600 to 82,500 cal per mole and increased with increasing recovery and recovery temperature. A 10 pet pre-strain shifted the ductile-brittle transition temperature, as indicated by tensile elongation, from 10°C. to about -22"C. A 100-hr recovery anneal at 801oC was shown to shift the transition temperature to about —5oC, the major shift occurring during the first hour of recovery. ThE recovery of cold-worked metals is accompanied by changes in the arrangement of the dislocations generated during cold work. In recent years, the use of transmission electron microscopy has allowed direct observation of some of the dislocation configurations formed, such as "tangles", networks, cells, subboundaries, and loops. These observations have recently been reviewed by Keh and Weissmann.&apos; Accordingly, some understanding has been gained concerning the nature of the dislocation rearrangements involved. The relationship between recovery and the decrease of mechanical strength, however, has only recently been explored. Previous efforts of the authors were directed toward investigating the decrease of tensile flow stress of aluminum and Al-1 pet Mg during recovery2 and the effects of concurrent elastic and plastic strain on the flow-stress recovery of aluminum.3 In addition, an investigation of the effect of four different solute additions on the tensile flow-stress recovery of aluminum has been made.4 Many important metals, however, have the bee crystal structure, e.g., iron, molybdenum, tungsten, vanadium, columbium, tantalum, and chromium. These metals might be expected to behave differently during recovery from those with other crystal structures for two reasons. First, the previous and present investigations of aluminum and its alloys have shown that tensile flow-stress recovery is strongly affected by foreign atoms in the lattice. In the bee metals, interstitial impurities are usually present and might be expected to have various effects upon both flow behavior and recovery. For example, heterogeneous yielding might occur during prestraining. The diffusion of these interstitials can also relock dislocations during recovery so that a yield point might be obtained upon restraining (strain aging). Second, some of the bee metals (e.g., iron, molybdenum, and tungsten) undergo the familiar structure-sensitive ductility transition and exhibit brittle fracture at suitably low temperatures. It is of considerable interest to determine the effects of recovery on the transition temperature of such metals. The purpose of the present investigation was to extend our knowledge of flow-stress recovery to the bee metals and to study the effects of recovery on the ductile-brittle transition temperature. Unalloyed recrystallized are-cast molybdenum was chosen as a test material, since it exhibits a well-defined ductility transition near room temperature. As in the previous studies, the degree of recovery was measured in terms of the decrease of tensile flow stress. Prestraining and restraining were carried out at 150°C to avoid the possibility of brittle fracture. EXPERIMENTAL PROCEDURE The are-cast molybdenum sheet used in this investigation was obtained from the Climax Molybdenum Co. of Michigan. It was 0.060 in. thick by 10

Jan 1, 1964

By F. D. Richardson

STAFF: Editor, Gerhard Derge Carnegie lnstitute of Technology Schenley Park Pittsburgh, Pa. 15213 Editorial Assistant, M. A. Redmerski Production Editor, Otto T. Johnson THE METALLURGICAL SOCIETY: Jack H. Scoff, President; Richard C. Cole, Past-President; Harold 0. Emerick, President-Elect; Ralph L. Hennebach, Treasurer; Robert W. Shearman, Secretary; Donald A. Parks, Assistant Secretary; Leslie S. Wilcoxson, Assistant Secretary. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: R. E. Lund, Chairman; T. E. Dancy, H. O. Emerick, P. R. Gouwens, R. E. Grace, J. H. Jackson, H. H. Johnson, A. E. Lee, Jr., R. R. Nosh, R. D. Pehlke, and Paul Queneau. Review and selection of manuscripts is under the supervision of the following Publications Committees: Extroctive Metallurgy Division: R. E. Grace, Choirmon; G. M. Bell, D. W. Bridges, J. M. Cigon, G. W. Heoly, T. A. Henrie, R. D. (Holli-doy, C. E. O&apos;Neill, C. S. Somis, A. W. Schlech-ten, and Charles Shull. Iron and Steel Division: R. D. Pehlke, Choirmon; T. P. Floridis, Arnulf Muon, G. R. St. Pierre, E. T. Turkdogan, L. H.Von Vlock, and J. M. Uys. lnstitute of Metals Division: H. H. Johnson, Jr., Chairman; J. B. Clark, Vice Choirmon; M. R. Achter, G. F. Bolling. J. O. Brittoin, G. P. Conard, II, R. S. Davis, L. A. Girifolco, G. T. Hohn, J. P. Hirth, L. Himmel, G.T.horn, George Krauss, J. D. Livingston, R. D. Manning, H. M. Otte, S. V. Rodcliffe, R. E. Reed-Hill, H. C. Rogers, E. ScaIa, O. Sherby, M. T. Simnad, G. R. Speich, E. A. Steigerwald, R. A. Swolin, W. A. Tiller, W. R. Upthegrove, J. B. Wagner, Jr., Derek Wolton, H. W. Weart, W. W. Webb, and D. Published seven times yearly in February, March, April, June, August, October, and December by the American lnstitute of Mining, Metallurgical, and Petroleum Engineers, Inc., 345 East 47th Street New York, N. Y. 10017. Telephone PLAZA 2 -6800. Subscription $30 per year for non-AtME members m United States and North, South, and Central America; $32, foreign; $7.50 for AlME members Single copies, $6.00, single copier foreign, $6.50. The AiME is not responsible for any statement made or opinion expressed in its publications . . . Copyright 1964 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 dost postaas poid ot New York, N. Y.,ond Ann Arbor, Mich. Volume 230, Number 6.

Jan 1, 1964

By R. S. Barneyback

Not much more is known about concrete today than was known to the Romans. For all the research only better tools have resulted to measure the quality of the materials that go into it." In this paper "some of the materials for lightweight concrete and their characteristics are considered and effort is made to indicate their effect on the end result — a structure of lightweight concrete." Lightweight concrete had noble beginnings. It is believed that the first specification for lightweight concrete was written by the Roman Emperor Hadrian in the early years of his reign, 117-138 AD. Hadrian, was an engineer by trade and an Emperor by adoption. He took considerable interest in the structures sponsored during his reign, even to the point of working out the structural details and preparing working drawings for some of the more prominent works in the vicinity of Rome. In order to reduce the dead weight of the 140 ft diam dome of the Pantheon he specified that the lightweight structural concrete members supporting this concrete and tile composite dome were to be fabricated from a concrete containing pumice and scoria. Still standing after 18 centuries of abuse, this structure has been described as the master effort of a great structural genius, the ultimate achievement of Roman engineering skill.&apos; The Romans were the first to employ many concrete techniques we think of as modem innovations. Some unnamed superintendent noted that when a carefully measured amount of pigs blood was measured into each batch of concrete during mixing, the concrete was more durable and exhibited much better resistance to freezing and thawing climates. He no doubt, attributed this success to the appeasement of one of the gods who in return provided protection for the building containing this sacrificial offering in its walls. It is known today that the blood-entrained air in the concrete tends to make mixtures more workable, resistant to moisture penetration and more resistant to frost damage.

Jan 1, 1964

By R. L. Stone, T. D. Tiemann

Jan 1, 1964