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By J. L. Gillson

In a brief summary of the many occurrences of fluorspar in our western states, it is not possible to go into detail in regard to the geology, mining and milling methods, and reserves about individual deposits. Rather a broad review is made of the occurrences and an analysis of how the western deposits may fit into our future domestic economy is presented. General Statement on Fluorspar Situation Fluorspar has been used for years as a flux in the manufacture of basic open-hearth steel, in foundry cupolas for melting pig iron, in the manufacture of opalescent glass and in the preparation of hydrofluoric acid. In 1880 the annual production of fluorspar in the United States was around 4000 tons per year. By 1900 it was up to 21,656 tons and between 1902 and 1908 it averaged about 40,000 tons annually. Prices were then so low, by present standards, that it seems impossible to believe now that mining could have been performed profitably at the price levels then prevailing. In 1890 fluorspar sold at the mines for $6.70 per ton, in 1901 for $5.81, in 1916 for 85.92. When the United States entered World War I, flyorspar production and price skyrocketed; the production reached 263,817 tons in 1918, with prices above $20.00 per ton, and prices were even higher in 1919 and 1920. After 1920, the domestic production fell from the 1918 level to about 125,000 tons annually and the average price dropped back to about $18.00 per ton. By 1935 the average price had fallen to $15.00, but in 1940 with a rising demand the average price of all grades had gone back up to $20.31. Today it is 75 per cent higher than in 1940 and presumably the price of acid grade at .least would be even higher if it were not for price ceilings. The first subsequent year that the domestic production exceeded that of 1918 was 1941, and the 1944 production is expected to exceed 400,000 tons, or over one and a half times that of 1918. In five-year periods, average production and imports were as are shown in Table I. Many people concerned with the consumption of fluorspar believe that the postwar period ahead will show a repetition of price trends of the last such period. They believe that imports will be again an important factor in the available supply and the price will fall back gradually toward the prewar level. The following basic factors are pertinent in analyzing this conclusion:

Jan 1, 1948

By F. E. Wood, H. W. Young, A. W. Buell

This paper summarizes the results of laboratory tests conducted to determine the properties of the paraffin or rod-wax encountered in the Salt Creek field, Wyoming. It also describes field tests and methods employed to cope with the paraffin problem. The conclusions to bo drawn from the laboratory work are: 1. Samples of Salt Creek paraffin range in consistency from soft lo hard, the melting points varying from 120" to 156" V. 2. Masses of soft paraffin are soluble to an appreciable extent in crude oil and its liquid fractions at temperatures somewhat below the melting point of the paraffin. Hard paraffin is very slightly soluble. under these conditions. 3. Agitation apparently increases the amount of paraffin that will go into solution. 4. Paraffin congeals from solutions upon cooling to the point of saturation ation, which is in all cnscs below thc melting point of the paraffin. 5. Crutltl oil is tlie most effective. of all the solvents for holding paraffin in solution. 6. Pressure alone does not appreciably affect the solubility of paraffin in crude oil nor does it aid materially in holding paraffin in solution when the temperature is reduced. 7. Natural gas in solution under pressure does not appreciably increase the solubility of paraffin in crude oil, hut is effective in holding paraffin in solution when the temperature is reduced. 8. A foreign body introduced into a solution of paraffin in oil is imrnediately coated with paraffin if the temperature of the solution is at or below the melting point of the paraffin, and the object is considerably cooler than the solution. It may not be entirely correct to ray that paraffin is taken into solution; it is impossible that the paraffin may be in suspension rather than in solution.

Jan 1, 1928

By Edmund Newton

The steel industry of the United States has depended in the past almost wholly upon imports for its supplies of manganese. Many of the important domestic sources yield ores leaner in their natural condition than the foreign ores the steel industry. has been accustomed to use. To make them available, therefore, either the ores must be concentrated or the practice of the steel industry modified. Roughly 25,000 T. annually of high-grade manganese ores are used for dry batteries for chemical purpose, and in other ways; while approximately 750,000 T. are required for making steel. , By present practice, every ton of steel takes an average of about 14 lb. (1.8 kg.) of metallic manganese. This is generally added to the steel in the form of an alloy, the standard alloys being the 80-per cent. ferro-manganese and the 20-per cent. spiegeleisen, During the year 1917, 286,000 T. of ferromanganese and 193,291 T. of spiegeleisen were made in this country, the former largely from imported ores; and 45,381 T. of ferromanganese. was imported. The metallic manganese represented by these alloys was 304,000 T., the product of roughly 800,000 T. of high-grade ore and 345,000 T. of low-grade ore. Manganese Deposits in the United States Before the war manganese ore was mined in relatively small quantities in the Appalachian region, including Virginia, Tennessee and Georgia, and in Arkansas, but owing to the increase in prices during the past three years manganese mining has been undertaken also in Montana, California, Arizona, New Mexico, Nevada, Utah, and Minnesota. From data now available it appears that in this country deposits of high-grade manganese ores are usually small, while materials lower in manganese and higher in iron occur in appreciable quantities. Our total quantity of manganese-bearing material is relatively large, but on

Jan 1, 1920

By Harold S. Morgan

INTRODUCTION The Waste Isolation Pilot Plant (WIPP) is being developed in southeastern New Mexico by the United States Department of Energy as a research and development (R&D) facility to demonstrate the safe disposal in salt of radioactive wastes resulting from defense activities. As part of the WIPP R&D program, a series of in situ tests will be performed to determine the behavior of drifts and storage rooms in the creeping salt medium (Matalucci, et al. 1982). Data obtained in these tests will be used to evaluate and improve numerical models used to compute the structural response of these drifts and rooms. Stress has been proposed as one of the parameters to be measured in the tests, and borehole inclusion stressmeters have been included in the instrumentation package. Cages of this type provide an indirect measurement of stress change in that they actually monitor borehole displacements which are then related to changes in the in situ stress away from the borehole. The relationship between stress and displacement is highly dependent upon the constitutive behavior of the rock in which the gage is emplaced. This relationship is well understood for rocks with linear stress-strain behavior (Fossum, et al, 1976), but, for creeping rocks like salt, the relationship has yet to be determined. Thus, inclusion gage response in salt must be investigated fully before stress measurements from the WIPP in situ tests can be used for comparisons with computed stresses The calculations presented in this paper were performed as part of an investigation of inclusion stressmeter performance in salt. They focus on the strain gaged stressmeter (SGS) (Cook and Ames, 1979) and on a hypothetical solid cylindrical inclusion with variable stiffness Issues addressed include the effects of creep and the effects of gage stiffness on stressmeter output for various loading conditions. The

Jan 1, 1984

By H. J. Snyder

Both the room-temperature and 600°F (315°C) primary solid-solution phase boundaries for the silver comer of the Ag-Cd-In temary system have been determined using X-ray diffraction and metallo-graphic techniques. Solid solubility of indium in silver at room temperature and 600°F (315°C) is shown to be between 20.3 and 21.7 wt pct, and corrects the previously extrapolated value of 18 wt pct appearing in the literature. The solid solubility of cadmium in silver at room temperature, not previously established, is shown to be between 34.9 and 41.3 wt pct. The solid solubility of cadmium in silver at 600°F (315°C) is confirmed as 43.2 wt pct. The shape of the primary phase boundary line for the subject temary system appears straight at room temperature and curves con-vexly towards the solvent (silver) comer at 600°F (315°C). THIS investigation was undertaken to initiate development of the Ag-Cd-In ternary diagram by establishing the primary solid-solution phase boundary in the silver corner of the diagram. At the present time, a diagram for this ternary system is not available, while this system appears to offer potential for a variety of uses. One alloy in the system has already proven to be useful as a control rod material in nuclear reactors.1"3 To encourage additional exploration of the potential of the system an understanding of its ternary diagram would be beneficial. It is towards this end that the present study is directed. LITERATURE SURVEY In undertaking this study, a comprehensive literature survey was first conducted to find information that would be useful for guidance. Useful knowledge did result from investigating the respective solubilities of indium and cadmium in silver as indicated in the binary constitutional diagrams of the systems Ag-In and Ag-Cd and also reviewing possible shapes of ternary primary phase boundaries. Weibke and Eggers~ used metallographic techniques to establish the system In-Ag as illustrated in Fig. Is This diagram shows that silver in the solid state is capable of dissolving approximately 18 wt pct In. This solid solubility of indium in silver holds true from room temperature up to 1276°F (691°C), then decreases continuously up to 1'761°F (960.5"C), the melting point of the silver. The solid-solubility limit of indium in silver established by Weibke and Eggers has been confirmed by Hume-Rothery and Reyno1ds. G Durrant' used a method which consisted of microscopic examination of quenched specimens to establish the Cd-Ag system as displayed in Fig. 2.' The primary phase boundary of Fig. 2 proved to be in good agreement (ie., within 1 wt pct) with other studies*'1' of the Ag-Cd system made using X-rays and metallog-

Jan 1, 1968

By M. J. Hordon, M. A. Wright

The well-defined increase in fatigue life observed o many metals cyclicly strained at vacuum levels below 10-1 to 10-3 torr has been attributed to the critical retardation of oxygen or water vapor chemisorption at the crack tip during crack propagation.1-3 In the absence of strongly adsorbed surface films, crack re-welding during cyclic compression or dislocation escape from the plastic zone around the crack tip has been proposed to account for the observed decrease in the rate of crack growth. The increase in the critical pressure required for the transition in crack growth rate with temperature experimentally determined for aluminum was found to be generally in accord with the adsorption rate model.4 However, although the adsorption mechanism would also predict an increase in transition pressure and fatigue life with increase in cyclic loading rate, and such effects were noted by Snowden5 for lead and Hordon3 for aluminum, the opposite results were reported by Kramer et al.B in studies on aluminum. The present note describes some recent measurements of the fatigue properties of 1100-H14 aluminum at low pressures to determine the specific effect of cyclic strain frequency in the transition pressure range. Flat cantilever-type specimens of 1100-H14 aluminum shaped to produce a uniform strain gradient along the gage length were tested in reverse plane bending at constant deflection amplitudes in two independent multi-specimen vacuum fatigue systems. One series of tests using 2-in. gage length specimens was conducted in an ion pumped apparatus with 107 torr and 50 cps capacity, denoted as Unit I, utilizing fixed mechanical cams to impose the strain amplitude. An independent test series using shorter 1-in. gage length specimens was conducted in a cryopumped apparatus designed for extremely low pressures below 10-10 torr, denoted as Unit II, using an electromechanical vibrator at non-resonant frequencies up to 150 cps to provide the deflection. Both vacuum fatigue units and associated test procedures have been described previously.3'7

Jan 1, 1969

By W. A. Wood, W. H. Reimann

A study is made of the creep that can be induced in armco iron at room temperature by superposing small amplitudes of alternating torsion on a tensile creep load. It is shown that the creep differs from that in comparable tests on copper in being trmsient only. At the same time, though transient, the creep can produce extensions of some 10 pct under creep loads less than the tensile yield stress of the material. The creep can be largely suppressed b$ applying cyclic strain of suitable amplitude before applying the creep load and the metal thereby stabilized. At room temperature, plastic flow in a metal under steady load is normally limited by strain-hardening processes. However, if a small cyclic stress is superposed on the steady load these processes may be more or less neutralized and, as shown in recent investigations,'-4 plastic flow may continue. In this way annealed copper, for example, can be induced to creep continuously to fracture under loads as small as 1 tsi. Dislocation mechanisms possibly responsible for this room-temperature creep have been usefully reviewed by Feltner.But discussion so far has been based mainly on creep as it is found in close-packed metals initially in the annealed state, and their behavior may not be general. In fact, recent work shows that the form of creep in annealed copper is different from that even in cold-worked copper;7 the creep thus depends on the dislocation pattern already in a metal as well as on the metal itself. This paper describes the creep in annealed armco iron, tested in the same way as the above-mentioned copper. One object was to see how creep in a typical bcc metal compared with that in the annealed close-packed metals. Another object was to utilize the fact that a bcc metal like iron has a more pronounced elastic range than close-packed metals like copper and to find to what extent the creep load or superposed cyclic stress had to exceed their re-

Jan 1, 1964

By Vittal S. Bhandary, B. D. Cullity

Swaged iron wire has a cylindrical {001} <110> texture. The texture is also cylindrical after re-crystallization in the absence of a magnetic field, but <111> and <112> components are added to this texture when recrystallization occurs in a field. The mecizanical properties in tension and in torsion are not greatly altered by these changes in texture. AS shown in a previous paper,1 cold-worked wires of the two fcc metals copper and aluminum can be made relatively strong in torsion and weak in tension, or vice versa, by proper control of preferred orientation (texture). The deformation texture can be controlled by selection of the starting texture (texture before deformation), because certain initial orientations are stable during deformation. The present paper reports on similar work performed on bcc iron. In this case it was clear at the outset that there was no hope of controlling the deformation texture, which is one in which <110> directions are aligned parallel to the wire axis. (1t has usually been regarded as a fiber texture, but Leber2 has recently shown that it is a cylindrical texture of the type {001} <110>. In either case, <110> directions are parallel to the wire axis.) There is general agreement on this texture among a large number of investigators, which in itself suggests that the starting texture has no influence on the deformation texture. More direct evidence was produced by Barrett and Levenson,3 who reported that iron single crystals of widely varying initial orientations all had a single <110> texture when cold-worked into wire. Thus <110> is a truly stable end orientation for iron and probably for other bcc metals as well. Under these circumstances attention was directed to the possibility of controlling the recrystallization texture. This texture is normally <110> in iron,4 just like the deformation texture. However, it is conceivable that this texture could be modified by a proper choice of the time, the temperature, and what might loosely be called the "environment" of the recrystallization heat treatment. In the present work the environmental factor studied was a magnetic field. The effect of heating in a magnetic field ("magnetic annealing") on recrystallization texture has been investigated by Smoluchowski and Turner.5 They found that a magnetic field produced certain changes in the recrystallization texture of a cold-rolled Fe-Co alloy. The texture of this material is normally a mixture of three components, and the effect of the field was to increase the amount of one component at the expense of the other two. Smoluchowski and Turner concluded that the effect was due to magnetostriction. With the applied field parallel to the rolling direction, the observed effect was an increase in the amount of the texture component which had <110> parallel to the rolling direction. In the Fe-Co alloy they studied, the magnetostriction is low in the <110> direction and high in the <100> direction. Thus nuclei oriented with <110> parallel to the rolling direction will have less strain energy than those with <100> orientations and will therefore be more likely to grow. In a later paper on the same subject, Sawyer and Smoluchowski6 ascribed the effect to magneto-crystalline anisotropy and made no mention of magnetostriction. In the papers of Smoluchowski et al. the intensity of the magnetic field was not reported but it was presumably large, inasmuch as it was produced by an electromagnet. In the second paper6 it is specifically mentioned that the specimens were magnetically saturated. But if magnetostriction has a selective action on the genesis of stable nuclei during recrystallization, that selectivity must depend only on differences in magneto-strictive strains between different crystal orientations and not on the absolute values of those strains. Thus the saturated state does not necessarily produce the greatest selectivity, because the relative difference in magnetostrictive strains between different crystal directions may be larger for partially magnetized crystals than for fully saturated ones.7 In the present work the specimens were subjected to relatively weak fields (0 to 100 oe) produced by solenoids. MATERIALS AND METHODS Armco ingot iron rod (containing 0.02 pct C and 0.19 pct other impurities) was swaged from 0.25 in. in diam. to 0.05 in., a reduction in area of 96 pct. The mechanical properties in tension and torsion were measured as described previously.&apos; Textures were measured quantitatively with chromium or iron radiation and an X-ray diffractometer,8,1 and

Jan 1, 1962

By A. McLean, D. W. Gomersall, R. G. Ward

An experimental study has been made of the solubility of nitrogen in liquid iron and liquid Fe-C alloys using levitation melting and a rapid quenching device. Iron alloy droplets were equilibrated with nitrogen gas at 1 atm pressure, quenched, and analyzed. Previous techniques for studying the Fe-C-N system have produced data which me in marked disagreement. This disagreement is due largely to errors caused by reaction between the molten alloy and the crucible material. With the levitation procedure, errors from this source have been eliminated and precise solubility data obtained for temperatures between 1450° and 1750°C. C-N interactions in molten iron have been expressed in terms of first- and second-order free energy, enthalpy, and entropy parameters. ALTHOUGH the solubility of nitrogen in iron base alloys is in general small, the effects of nitrogen on the properties of steel may be quite profound. For most purposes nitrogen in finished steels is undesirable, particularly in the low-carbon grades, since on cooling to room temperature the solubility limit of nitrogen in the steel may be exceeded and this can lead to embrittlement and loss of ductility on aging. On the other hand, nitrogen can improve the work-hardening properties and machinability of steels while in certain stainless grades nitrogen is important in order to stabilize the austenite phase. It is, therefore, desirable that one should be able to predict the solubility of nitrogen in liquid iron alloys. To do this, information is required concerning the interactions between nitrogen and the various alloying elements which may be present in liquid iron. There have been several investigations of these effects in recent years1"7 and the interactions between nitrogen and many elements dissolved in liquid iron are now known to a high degree of precision at steel-making temperatures. Unfortunately, a number of iron alloy systems which are of interest in steelmaking have been difficult to deal with by the experimental techniques generally used for this type of investigation. Among the most important of these are the Fe-C alloys. In the past, two methods have been widely used for determining nitrogen solubilities: the Sieverts&apos; technique, in which the amount of nitrogen required to saturate a given mass of liquid metal at a particular temperature and pressure is measured volumetrically, and the sampled-bath technique in which liquid metal held in a crucible is equilibrated with a gas phase containing a known partial pressure of nitrogen, and samples drawn from the melt are quenched and analyzed. These two methods have been discussed in detail elsewhere.5,8 With the Sieverts&apos; technique, errors may be introduced from the following sources: i) Gas adsorption on metal films which have condensed on the cooler parts of the reaction chamber. ii) Uncertainty in the determination of "hot volume" calibrations. iii) Crucible-melt interaction, particularly if a gaseous reaction product is formed or if the melt becomes contaminated with material from the crucible walls. The sampled-bath method may also suffer from errors due to reaction between the melt and the crucible material. In addition, there is the possibility that gas may be lost from the sample during solidification and cooling. In the present investigation, the solubility of nitrogen in liquid iron alloys has been studied by means of a new technique based on the use of levitation melting equipment and a rapid quenching device. In addition to the fact that problems of the type outlined above are avoided, this particular approach has the following advantages: i) The high-frequency current induces vigorous stirring within the levitated droplet so that gas-metal equilibration is rapidly attained. ii) The gas phase surrounding the melt can be changed very quickly and is easily controlled. For example, a droplet may be levitated in helium, deoxidized in hydrogen, equilibrated with nitrogen, and quenched, within a period of 15 min. ii) Melts can be readily under cooled or superheated, thus extending the effective temperature range of an investigation and allowing temperature-dependent data to be determined with a high degree of precision. Excellent reviews of levitation melting techniques and their application to physical-chemistry studies at high temperature have been published recently by Jenkins et al.,9 Peifer,10 and Rostron.11 In the present investigation a levitation melting technique has been used to obtain data for the solubility of nitrogen in pure liquid iron and liquid Fe-C alloys at temperatures between 1450° and 1750°C. The solution of nitrogen in liquid iron can be described by the reaction:

Jan 1, 1969

By W. J. Keep

Cast-iron, or pig-iron, is iron which contains all the carbon that it could absorb during its reduction in the blast-furnace. As is well-known to chemists, carbon exists in cast-iron in two distinct forms. In chemical union, as "combined" carbon, it cannot be discerned, except as it may increase the whiteness of the fracture, in so-called white iron, or carburetted iron (sp. gr. about 7.72). Carbon mechanically mixed with the iron as graphite is visible, varying in color from gray to black, while the fracture of the iron, according to the color and amount of graphite it contains, ranges from a light to a very dark gray. The specific gravity of graphitic iron is about 7.40. Silicon in cast-iron is evidently to some extent combined with the iron and the carbon ; but whether it exists also in a form corresponding with graphitic carbon, mechanically mixed with the remaining mass, is a question still in dispute, which we have not in this paper endeavored to answer. It has been the opinion of many writers on metallurgy, and many foundry men, that silicon is in every way injurious to cast-iron. Yet

Jan 1, 1889

By P. K. Foster, A. McNabb

A consideration of the literature shows the inadequacy of Fick&apos;s Laws to describe the diffusion of hydrogen in steels below 400°C. These laws are modified an the assumption that hydrogen is delayed at fixed sites in the lattice. Approximate and exact solutions of the resulting nonlinear system are derived for simple geometrical shapes. The results qualitatively account for the observed anomalous behavior. Experimental methods for verifying the theory are suggested. 1 HIS paper presents a new analysis of the diffusion behavior of hydrogen in steel based on a physical model which supposes that hydrogen atoms wander in a random manner through the crystal lattice, but tend to get trapped or delayed at certain fixed sites uniformly distributed throughout the metal. These sites, which will be called traps, are regarded merely as potential wells of significantly greater depth than those encountered in regular regions of the crystal lattices and no assumptions are made concerning their nature or origin. The results of experimental studies of the diffusion of hydrogen in iron and steel have usually been reported in the literature in terms of a diffusion constant D derived under the assumptions that the hydrogen concentration C is governed by Fick&apos;s laws.1 Fig. I is a composite of published graphs of the man. ner in which the values of D, so derived, vary with temperature. It is convenient to consider this material in two categories; the high temperature results above 400°C, and the results at lower temperatures. The graphs 2, 3, 4, 5 in the first class lie within a factor of three of each other and are relatively consistent compared with the low-temperature values. There is an increasing divergence in values of D with decreasing temperature till at room temperature they are spread over three orders of magnitude. Small values of D have been obtained for work-hardened specimens.&apos; It is evident that D is a function of other variables besides temperature in this range and that these neglected variables are in some way connected with the work hardening experienced by the specimen. In view of evidence for an interaction between hydrogen in solution and dislocations9&apos;10 and adsorption on crack surfaces,&apos; some doubts must be entertained about the validity of Fick&apos;s laws and their associated physical model of noninteracting particles in random motion through the medium. More direct evidence of their inapplicability to the diffusion of hydrogen in steel was first produced by Darken and smith." Consider the permeation of hydrogen through a plate of thickness a under a boundary concentration Co at the ingoing, and zero at the outgoing, face. If Fick&apos;s first law1 is valid, the steady state flux P, through unit area is DCo/a. In addition, the concentration C varies linearly throughout and Qo, the mean quantity of hydrogen in the medium, is co/2. Compare Qo with Q1 the mean quantity required to saturate the same specimen to a uniform concentration G. In this case Ql = Co and hence the ratio

Jan 1, 1963

By A. Ghosh, T. B. King

The kinetics of the discharge reaction: 20&apos;- (in silicate melt) = O,(g) + 4e- at a platinum anode in lithium silicate melts have been studied al 1350°C by galvanostatic methods. Plots of the sleady-state overpotential, q, as a function of the logarithm of the current density, i, showed injlections and were linear only at high current densities. The value of the overpotential was influenced by bubbling gas through the electrolyte. The ocer potential was also studied as a function of time. The rise and decay of overpotential were very slow processes. At low current densities transport is the likely rate-controlling process but at high current densities passivation of the electrode, Presumably by an oxide film on the surface, seems to be a contributory functor. IT is well-established that molten silicates behave as electrolytes&apos;5 and, except in a few cases,6 conduction is entirely ionic. Moreover, it is supposed that a possible, and perhaps predominant, mechanism for phase boundary reactions between metals and slags is similar to that in corrosion whereby anodic and cathodic processes occur at unrelated sites, the metal serving to conduct electrons.1&apos;8 Thus electrochemical studies of some slag-metal reactions would seem to be a useful way to diagnose the rate-controlling steps in the overall reaction. The electrochemical method is, in principle, a better diagnostic tool than the direct chemical method for the following reasons: 1) The partial electrochemical reactions, which are simpler than the overall reaction, may be studied individually. 2) The rate of reaction can be controlled at will and independently of the concentrations of reactants. 3) Fast reactions can be studied by relaxation methods.&apos; Esin and his coworkers5&apos;10"12 have pioneered such studies in silicates and have deviloped some ingenious techniques. Not all of their findings, however. can be accepted without a good deal of further work. In this investigation, the kinetics of the oxygen discharge reaction: 202- (in silicate melt) = Oz(g) + 4e- [I] at a platinum electrode were studied by both steady-state and transient galvanostatic techniques. Interest in this reaction was first developed as a result of the findings of Fulton and chipman13 that the reduction of silica, in a silicate slag, by carbon, dissolved in liquid iron, is a very slow reaction. Subsequent work, for example, by Rawling and ~lliott,&apos;~ has demonstrated that the reaction under these conditions must be slow, because the rate is limited by diffusion of oxygen in the iron to the metal-crucible phase boundary at which a CO bubble may be nucleated. Further work by Tarassof,&apos;~ in which the reduction of silica by aluminum dissolved in copper was studied, has shown that under these conditions, where carbon monoxide evolution is not involved, control of the reaction rate resides in diffusion of silica in the slag phase. However, there is no practical way of inducing sufficient convection in the system to make it clear that the phase boundary reaction is indeed fast. The overall reaction of silica reduction involves the discharge of silicon ions at cathodic sites and oxygen ions at anodic sites. In the examples cited, the discharged ions are dissolved in a liquid metal. In the present study of oxygen ion discharge, gaseous oxygen may be evolved at high current densities or oxygen may simply dissolve, possibly as oxygen molecules, in the silicate at very low current densities. The discharge of an oxygen ion at an anode must, in silicates less basic than the orthosilicate composition, be preceded by a reaction in the vicinity of the electrode, such as: which makes oxygen ions available. Platinum was chosen as the working electrode since it is comparatively inert to oxygen and is, therefore, expected to come rapidly into equilibrium with the electrolyte and with gaseous oxygen. Minenko, Petrov, and Ivanova16 have measured the electromotive force at a platinum electrode in molten silicates as a function of the partial pressure of oxygen in the atmosphere, the concentration of oxide ions in the melt, and the temperature. They found platinum to behave as a reversible oxygen electrode. At two different oxygen pressures, Po2 (I) and Pq (11). the electromotive force is given by: where F is the Faraday constant, equal to 23,060 cal per v equivalent, indicating that the electrode reaction is as written in Eq. [I.]. Platinum has been similarly used in molten silicates by other inve~ti~ators. "&apos;~~ In this investigation platinum was used only as an anode, since a current deposits other elements on its surface and changes its characteristics.

Jan 1, 1970

T. M. Drown, South Bethlehem, Pa.: Mr. Thackray&apos;s paper shows in a striking way the high degree of rapidity and ac curacy exhibited by the chemists of our steel-works in ordinary everyday practice. That determinations made in an hour should present only slight differences in the third place of deci male is certainly matter for surprise and congratulation. This remarkable result has been due, perhaps, in part, to a remark able cause. The managers of works, ignorant of all the diffi culties of the laboratory, have demanded "the impossible " of their chemists—and the chemists have done it! Andrew A. Blair, Philadelphia, Pa.: Mr. Thackray&apos;s paper is extremely interesting, especially in its bearing on the question of a standard method for the rapid determination of phosphorus in the laboratories of steel-works. Before discussing the re sults in general, I desire to explain the results obtained by me under method A&apos;. This is the method which I have used in the work of the sub-committee on Methods of the Interna tional Steel Standards Committee. It may be described briefly as follows: Solution in nitric acid; oxidation of carbonaceous matter by permanganate; precipitation of phosphoric acid by molybdate solution; reduction of molybdic acid in the reductor, and titra tion by permanganate. This method was used apparently by only three chemists, Dr. Dudley, Mr. Crowell, and myself. In determining phosphorus by this method, among the most essential points to be considered are the ratio of iron to molyb dic acid, or the reducing action of zinc on molybdic acid as compared to its reducing action on iron, and the ratio of molyb dic acid to phosphorus in the ammonium phospho-molybdate obtained by precipitation from the solution of the steel. In regard to the first point, the usually accepted ratio is 1 to 0.90756, or, as it is roughly stated, 0.9076, which is based on the assumed reduction of the molybdic acid to Mo12019,. This

Jan 1, 1896

By H. F. Webster, C. G. Dunn

Rolling md annealing procedures are described for developing the (110) preferred orientation in tantalum for use as a thermionic-emission materinl where electrodes of a uniform high work function are needed. The development of a (110) [001] annealing texture is also reported. A preferential growth process due to low (110) gas-metal surface energy is considered in explanation of the observed growth of (110) grains. ThE growth of (110)-oriented grains in thin strips of rolled zone-refined tantalum, previously discussed briefly,&apos; is reported together with more recent information on the formation of a (110)[001.] annealing texture, i.e., one where the [001] direction of each grain lies close to the rolling direction. The development of tantalum sheet with a (110) preferred orientation (position of [001 ] directions unspecified) is of importance as a thermionic-emission material in thermionic-energy converters. Since therm ionic-emission properties of cesium-coated crystals vary over a wide range depending on (hkl) a2-7 a single (hkl) preferred orientation is more useful than either several preferred orientations or none. Furthermore, the (110) preferred orientation yields the highest thermionic-emission density for a cesium coverage of less than a monolayer.5-7 A consideration of the stability of the grain structure needed at high operating temperatures suggests that the preferred orientation itself should be produced by annealing processes. Information on annealing textures in tantalum, however, is rather limited. Pugh and Hibbard 8 obtained (111)[112] and (lll)[112] components in a 1400°C recrystallization texture in 95 pct cold-rolled foil; these components were enhanced on annealing at 2500°C. Muller9 rolled 99.97 Ta to 90 pct reduction in thickness in the final stage and noted only a slight sharpening of the rolling texture, with some intensification of the (111)[112] component upon annealing at 1200°C. The experimental procedure followed in the present work stemmed from the idea of using possible differences in (hkl) surface energies to provide a small driving force for growth of grains having the lowest (hkl) surface energy.l0* This would mean using high-purity tantalum processed into thin sheet form and annealed at high temperatures either in a noncontaminating atmosphere or in one producing additional sample purification. EXPERIMENTAL Zone-Refined Tantalum. National Research Corp. tantalum in the form of 1/8-in.-diam rod and of 99.98 purity (53 ppm 0, 15 ppm N, and 8 ppm C) was zone-melted four times. The traversing speed was 4 mm per min. Such treatment increased the resistance ratio, R293k/R20K , where R293K is the resistance of the specimen at 20°C and R20K the re-resistance at liquid-hydrogen temperature, from a value of 25 for the initial rod to 175 for the zone-refined rod (the increase in the resistance ratio provides a measure of purification11,12). Part of a zone-refined rod was rolled unidirec-tionally to a strip 0.003 in. thick and 0.28 in. wide. Samples were given anneals in the range 1300" to 2100°C using ac conduction heating in an oil-free vacuum system. Recrystallization to small grains appeared to be complete at 1300°C. Large grains were formed at higher temperatures, but these were not entirely strain-free, some grains showing asterism in Laue X-ray patterns and some displaying a range in orientation. Part of the difficulty was caused by thermal expansion of the tantalum strip as it was held between fixed supports. However, in a different arrangement with the tantalum freely suspended in a tantalum can, high-frequency induction heating in vacuo at about l0-6 Torr produced

Jan 1, 1964

By A. G. Guy

In a special type of electrodiffusion experiment the entire specimen is at constant temperature. The vacancies are then created at one end of the specimen and flow to the other end where they are destroyed. The energy required to operate the corresponding sources and sinks results in a super saturation of vacancies at one end of the specimen and an under -saturation at the other end. This gradient in vacancy concentration produces a chemical-diffusion flux, J(D), of vacancies in addition to the flux, J(E), caused by the electric current. Using the experimental data of Ch. Herzig,5 it is shown that a super saturation of 1 pct can cause J(D) to be about 25 pct of J(E), and thus account for the anomalous behavior of short specimens. THERE are advantages in a phenomenological treatment as contrasted to an atomistic one. For example, there are many reactions involving the element copper that are quantitatively and usefully understood from a phenomenological viewpoint, even though electron theory is not yet able to predict whether copper should be fcc or cph.&apos; Similarly, the lack of a complete atomic theory of vacancies need not prevent the development of a treatment based on thermodynamics and chemical kinetics. In the following discussion, models will be used for the vacancies and for the mechanisms by which they move or are created or destroyed, but the phenomenological treatments are not dependent on the details of these models. The important product of a phenomenological analysis is an equation that describes the relation among the measurable quantities determining the behavior of the system. Based on such an equation, experiments can be performed to study these quantities in detail. Eventually atomic theory will supply an adequate theoretical base for the phenomena in question. A chemical species whose chemical potential was invariant during reactions in binary and ternary systems of varying composition would indeed be an anomaly. Yet this is the role that has frequently been assigned to the vacancies in pure metals, in dilute solutions, and even in ordinary alloys. The weight of available evidence supports the view that supersatu-rations of vacancies are on the order of 1 pct in usual diffusion processes.&apos; Although it may seem strange that such a small deviation from equilibrium could significantly affect the thermodynamic properties of the vacancies, it is well known that the driving force for an ordinary chemical reaction is the departure of the components from their equilibrium state. Similarly, the reaction of vacancies that results in the formation of pores in various types of diffusion3 can reasonably be attributed to the supersaturation of vacancies. In the present paper, it will be shown that small degrees of supersaturation can significantly affect the kinetics of the diffusion process itself. ISOTHERMAL ELECTRODIFFUSION Two different experimental techniques are convenient for studying the behavior of vacancies in a pure metal in the presence of an electric field. Gilder and Lazarus4 studied self-electrodiffusion in a gold specimen in which only the central portion was at high temperatures. In this case the significant vacancy sources operate inside the specimen in the presence of a temperature gradient. In the laboratory of Th. Heumann a method has been devised for studying self-electrodiffusion at constant temperature.5 In principle, there is then no effect of thermodiffusion. It will now be shown why in this case the significant ATungsten disks \^^ ^^ ^Gold disks^^ ^^"T>.... "TTZA ? Up Iy&apos;7 markers ///// ////// initial plane p I y/y/y of joining \I 7//// V7//A_________I_________V//// -I 0 +I Distance from center of specimen (a) -— Direction of flow of electrons —Direction of flw of vacancies %yy} Matano I z~irkendall /%W, vy/A inlerfacej "interface ///// -} HfiK- +/ 0 Distance from center of specimen (6) Fig. 1—-Schematic illustration of the essential features of isothermal self-electrodiffusion. (a) Initial condition of specimen. (b) Condition of specimen after electrodiffusion.

Jan 1, 1970

By N. L. Carwile, G. W. Geil

A metallographic study was made of deformation twinning (Neumann lamellae) in ingot iron slowly deformed in tension at —196O and —150°C. The results showed that twinning is initiated mainly during the initial stages of plastic deformation. However, the breadth of the twins generally increases with increase in strain up to fracture of the specimen. HE results of an investigation of the effect of low I temperatures on the flow, fracture, strain hardening, and strain aging characteristics, and the true stress-strain relationship for specimens of ingot iron deformed in tension were reported recently.1,2 In that study specimens of ingot iron, in different initial conditions, were slowly deformed in tension at various temperatures between —196" and +100°C. A phenomenon observed, but only briefly reported, was the formation of deformation twins (Neumann lamellae) in the specimens deformed at the lower temperatures. Preliminary metallographic examination of these specimens indicated that there was apparently some correlation between the deformation twinning and the strain of the specimen and that this factor merited further investigation. Some recent investigations have indicated a direct association of Neumann lamellae and the fracture of the metal. Bruckner".&apos; * postulated that the twinning immediately precedes the fracture and the latter is initiated by the stopping of the propagation of twins, either at subgrain boundaries or at other structural features. Tipper and Sullivan5 postulated that Neumann lamellae are initiated by the shock or a shock wave set up at fracture in the still highly stressed unbroken metal, and that a high rate of deformation is a necessary condition for their formation. An extensive metallographic examination, therefore, was made of many of the specimens used in the study of ingot iron at this Bureau and of additional specimens deformed to selected strains under various conditions. The present paper summarizes the effects of deformation under these conditions upon the breadth and scope of the deformation twins. Other features of twinning will be discussed in another paper. Material and Testing Procedure All of the specimens were prepared from one lot of ingot iron, as hot-rolled, of chemical composition other than iron as follows: C, 0.02 pct; Mn, 0.02; P, 0.005; S, 0.018; Si, 0.002; Cu, 0.10; 0, 0.058; and N, 0.002. Cylindrical tensile specimens with a 2 in. gage length were used. The reduced section was slightly tapered from each end; the diameter (0.438 in.) at the midsection of the gage length was about 0.003 in. less than at the ends. The specimens were finished to the final dimensions by grinding and polishing in the axial direction. The ends of the specimens were machined with 3/4 in. x 10 threads and the shoulder fillets were machined to a radius of 0.75 in. The specimens were extended slowly in tension (deformation rate less than 0.5 pct reduction in area per minute) while immersed in an appropriate cryogenic liquid maintained at the desired temperature. The minimum diameter of the specimen was measured during the test by means of a specially designed reduction of area gage accurate to 0.0001 in." A detailed description of the testing equipment and the method of maintaining the desired temperature is given in a previous paper.&apos; Each specimen, after deformation to a specified strain at a selected temperature, was sectioned longitudinally and examined metallographically. The preparation of specimens for metallographic examination was carried out in the usual manner by mechanical polishing and etching. Results and Discussion Deformation twins in specimens of ingot iron extended slowly in tension at —196" and —150°C are shown by the representative micrographs of Figs. 1

Jan 1, 1954

By E. W. Johnson, M. L. Hill

Cold working of iron-carbon alloys was found to increase greatly the hydrogen solubility and to decrease the diffusivity at temperatures up to 400° C. These effects are increasing functions of both the carbon content and the degree of deformation. The hydrogen behavior is consistent with the idea that cotd working creates "traps", which are concluded to be microcracks in which the hydrogen is chemisorbed. Hydrogen embrittlement is explained by the Petch theory of metal crack surface energy loss due to hydrogen adsorption. HYDROGEN embrittlement of steel has been studied for many years and has been the subject of an extensive literature, but the mechanism of the effect has not been completely understood. The embrittlement is unusual in that the ductility loss is not accompanied by an increase of the yield strength, being primarily a decrease of the fracture strength alone. The loss of fracture strength is usually most severe in the temperature range between 0°and 100°C. Here the solubility of hydrogen in the iron lattice at ordinary H2 pressures is extremely low while the diffusivity is still quite high. From the relationships between the ductility and the hydrogen content, test temperature and strain rate, it is apparent that the hydrogen atoms causing the ductility loss difbse to and concentrate in small regions of the metal which are especially susceptible to the initiation and propagation of fracture. This hydrogen segregation apparently occurs after plastic straining has begun. Below 0°C the ductility loss persists only at low strain rates in confirmation of the view that the embrittlement is diffusion .controlled. The tendency of the embrittlement to disappear above 100°C can be explained by the increasing lattice solubility of hydrogen with rising temperature. A common view of hydrogen embrittlement of steel is that the hydrogen initially dissolved in the metal lattice diffuses to structural discontinuities and there precipitates as H2 gas at very high pressures which assist the external stress in causing premature failure.1,2 The idea of a high H2 pressure in equilibrium with ordinary amounts of hydrogen in steel at room temperature is due to observations of hydrogen behavior in fully annealed material, for which the Sieverts&apos; law constant relating solute concentration to H2 pressure is extremely small. Hydrogen-embrittled steel, however, is always plastically deformed to some extent, and therefore it is important that hydrogen embrittlement be explained primarily in terms of hydrogen behavior in plastically deformed material. Such an explanation is attempted in this paper. Previous studies of hydrogen in cold-worked steel have shown that both the solubility and the diffusion rate are significantly chaned when the steel is cold worked. Darken and Smith discovered that the amount of hydrogen absorbed from acid by cold-rolled steel at 35°C is many times greater than that absorbed by hot-rolled steel. They found also that the hydrogen permeability of the steel is unaffected by cold working. Keeler and Davis4 confirmed the high apparent solubility of hydrogen in cold-worked iron-carbon alloys at temperatures up to and even beyond the recrystallization temperature. They also found that this solubility increase accompanying cold work is a sensitive function of the carbon content, being absent when no carbon is present. The present experimental study was undertaken primarily to obtain an improved understanding of the behavior of hydrogen in cold-worked steel. Data were obtained on the effects of temperature, H, pressure, carbon content, and degree of cold work on the hydrogen solubility and diffusivity in iron-carbon alloys. These data have been helpful in elucidating the nature of the cold-worked steel structure as well as in providing information on the mechanism of hydrogen embrittlement of steel. EXPERIMENTAL Cylindrical specimens for hydrogen absorption and diffusion rate measurements were prepared from three iron-carbon binary alloys and a commercial SAE 1010 steel. The iron-carbon alloys were prepared by vacuum melting electrolytic iron with graphite in a magnesia crucible. The alloys were cast in vacuum as 2 1/2-in. sq ingots weighing about 20 lb each. The ingots were hot rolled (above 1900°F) to 5/8-in.-diam round bars and then cooled in air to room temperature. The resulting metallographic structure consisted of islands of fine pearlite surrounded by free ferrite. Chemical analyses of the materials are given in Table I. The 5/8-in. diam bars were turned to diameters such that cold reduction to the desired final specimen diameters would result in either 30 or 60 pct reduction in area (RA). The machined bars were then cold worked by swaging at room temperature

Jan 1, 1960

By S. P. Kinney

Sulfur has been one of the most troublesome elements encountered since the earliest days of iron smelting, and this problem will become of increasing importance as the higher sulfur coke is used, because of the rapidly diminishing supply of low-sulfur coals suitable for the manufacture of metallurgical coke. The deleterious effect of sulfur in iron and steel is well known; therefore, except in special cases, it is desirable to make the iron produced by the blast furnace as low in sulfur as possible. Sulfur enters the furnace in all of the raw materials, but principally in the coke. It comes out of the blast furnace distributed between the iron and the slag; very little passes out of the furnace with the gases. The mechanism of the reactions that cause the sulfur of the coke to pass into the slag and iron has not been studied to any great extent, although the character of the end products, and the conditions controlling the distribution of the sulfur between the iron and slag, are fairly well known. In the iron, the sulfur occurs as ferrous sulfide; or manganese sulfide in case of iron high in manganese. In the slag, the sulfur is present mostly as calcium sulfide. The presence of free sulfur1 and sulfates in blast-furnace slags is to be accounted for on the basis of oxidation of the calcium sulfide after the slag is tapped. The generally accepted reaction for the relation between the ferrous sulfide in the iron and in the coke, and the calcium sulfide in the slag, is that given by Howe? FeS + CaO + CDFe + CaS + CO

Jan 1, 1923

By S. P. Kinney

Sulfur has been one of the most troublesome elements encountered since the earliest days of iron smelting, and this problem will become of increasing importance as the higher sulfur coke is used, because of the rapidly diminishing supply of low-sulfur coals suitable for the manufacture of metallurgical coke. The deleterious effect of sulfur in iron and steel is well known; therefore, except in special cases, it is desirable to make the iron produced by the blast furnace as low in sulfur as possible. Sulfur enters the furnace in all of the raw materials, but principally in the coke. It comes out of the blast furnace distributed between the iron and the slag; very little passes out of the furnace with the gases. The mechanism of the reactions that cause the sulfur of the coke to pass into the slag and iron has not been studied to any great extent, although the character of the end products, and the conditions controlling the distribution of the sulfur between the iron and slag, are fairly well known. In the iron, the sulfur occurs as ferrous sulfide; or manganese sulfide in case of iron high in manganese. In the slag, the sulfur is present mostly as calcium sulfide. The presence of free sulfur1 and sulfates in blast-furnace slags is to be accounted for on the basis of oxidation of the calcium sulfide after the slag is tapped. The generally accepted reaction for the relation between the ferrous sulfide in the iron and in the coke, and the calcium sulfide in the slag, is that given by Howe? FeS + CaO + CDFe + CaS + CO

Jan 1, 1923

By G. P. Gladis, R. H. Atkinson

PALLADIUM has been used for jewelry for many years, particularly in conjunction with gold. This use increased in amount during the war, as palladium and gold were only moderately used for war purposes while demands for platinum and some of the other members of the platinum group were so great that their use in jewelry was prohibited. Palladium hardened with a small percentage of ruthenium has the necessary technical properties and appearance for good jewelry, and it is sufficiently rare to be desirable for luxury items-at least 100 times as rare as gold. Although both visual and spectrophotometric examination demonstrated that the color of palladium was almost the same as that of platinum, a few jewelers found the surface of palladium, even after some polishing, rather dark in areas that had been repeatedly heated during the soldering necessary to assemble certain types of handmade ornaments. This phenomenon is not to be confused with the thin, bluish oxide film that can be produced by heating in air over the range 400° to 800°C., as that film is easily reduced by dipping in warm 5 per cent formic acid or in warm methanol. It was suspected that the difficulty arose from heating in atmospheres that were alternately oxidizing and reducing, as Wise and Vines1 had found that this opened the grain boundaries of palladium and palladium-silver alloys in the same manner as in pure silver, as reported by Martin and Parker.2 This damage is caused by the reaction between oxygen in solid solution in the metal, acquired when heated under oxidizing conditions, and hydrogen diffusing in from subsequent heating under reducing conditions; the steam cannot diffuse out and therefore builds up sufficient pressure to disrupt the metal near the surface. Copper and various other metals can be damaged similarly, but platinum is nearly immune; therefore the problem was new to the platinum jeweler. Sulphur in the fuel gas also can cause trouble but did not appear to be dominant in the present instance. Metallographic examination of both pure palladium and ruthenium-palladium showed that the usual torch using oxygen and city gas as normally operated did in fact cause the surface and subsurface damage that had been observed, and also disclosed that a reducing flame caused more damage than an oxidizing flame and was very damaging even in the absence of any intentional swing in atmosphere from oxidizing to reducing (Fig. 7); besides the surface damage, there was serious loss of ductility. A full explanation of the mechanism of attack is not evident at the moment, but may be allied to the attack that occurs on heating catalytically active metals in nonequilibrium atmospheres.

Jan 1, 1946