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By R. A. Vandermeer, J. C. Ogle

Two distinct types of depth-dependent variations in texture have been observed in niobium cold-rolled various amounts up to 99.5 pct reduction in thickness. These nonuniformities are thought to be the results of nonhomogeneous plastic dewmation during rolling. The first type is characterized by a zone at intermediate depths that tends to lack certain strong orientations which are present in the surface and center layers of the rolled stock. This type of texture modification seemed to be associuted with "high" body rolling and may be related to the shape of the zone of deformation in rolling. The second type of texture inhomogeneity found involved the formation of a unique texture in the surface layers of heavily rolled strip. High fiiction forces between work piece and rolls appear to be needed to generate and maintain this texture. We believe that this unique surface texture results from a shear mode of deformation in the surface layers. THE evolution of texture in both the surface and center regions of cold-rolled niobium as a function of increasing deformation from 43 to 99.5 pct reduction in thickness was reported in a previous paper.' It was noted that for strips rolled between 95 and 98 pct reduction a distinctly different texture appeared in the surface layers which was unlike the center texture. Certain other layer to layer textural variations were also detected during the experimental phase of that work but were not described in the paper. Surface textures have been reported previously for the bcc materials iron and Steel2-4 and are well known in the fcc metals.5 It is usually stated that these are shear textures which arise under conditions of high friction between specimen and rolls. Work by Mayer-Rosa and Haessner5 n niobium rolled under conditions presumed to be high roll friction gave no indication, however, of a surface texture in that material. This is indeed puzzling in view of our results.' Thus we undertook additional experiments designed to study the stability of the surface texture for certain rolling variables. The variables investigated were the presence or absence of lubrication, amount of reduction per pass, and reverse vs unidirectional rolling. It is the purpose of the present paper to describe the kinds of depth-dependent textural inhomogeneities that we have observed in rolled niobium as well as to present the results of our recent experiments on the stability of the surface texture. Possible explanations for the depth-dependent texture variations will be discussed in terms of nonhomogeneous plastic deformation during rolling. EXPERIMENTAL Specimens cut from the niobium rolled to different reductions in the previous study1 were examined at various layer levels throughout the strip thickness for textural inhomogeneity. The specimen surfaces were either etched or machine ground and etched to remove material to a specific depth. Textures were determined by means of the Schulz X-ray reflection pole figure method with a Siemens texture goniometer and Cum X radiation. Since the important intensity peaks of the textures in niobium are usually located on the normal direction (N.D.) to rolling direction (R.D.) radius of the (110) pole figures, it was sufficient in many cases to scan only along this radius. At selected depths or where additional information was required the entire (110) pole figure was also obtained. In studying the stability and formation of the surface texture, experiments were conducted on 0.400-in.-thick, fine-grained, randomly oriented niobium specimens extracted from the same starting stock as that used in the earlier study.' Two of these specimens were rolled at room temperature to a total reduction of 96.4 pct. One was rolled between cleaned and degreased rolls with no lubrication. The other was lubricated between passes with Welch Duo Seal vacuum pump oil. The rolling schedules of each were kept as nearly identical as possible. Drafts were of the order of 0.006 to 0.012 in. per pass. Other experiments consisted of rolling specimens at constant fractional reduction per pass, i.e., (ta- tb)/ta equals a constant where ta and tb are the entrance and exit thickness of the rolled stock, rather than at a constant draft, i.e., ta- tb equals a constant. Ten specimens were rolled at room temperature on a two-high, motor-driven rolling mill with 8-in.-diam rolls. These specimens were rolled to thicknesses of between 0.041 and 0.073 in. (82 to 90 pct total reduction) at approximately constant reductions per pass ranging from 9 to 45 pct. Kerosene was used as a lubricant. Half of the specimens were always rolled in the same direction while the other half were reversed end to end at each pass. The texture in the surface regions was determined with the X-ray technique described above. RESULTS The textural inhomogeneities noted in niobium rolled from fine-grained, randomly oriented stock 1.5 in. long by 0.75 in. wide by 0.40 in. thick can be classified into two types. The first may be discussed with the aid of Figs. 1 to 3. Fig. 1 is a three-dimensional plot of the X-ray intensity in units of times random vs f , the angle from the N.D. to any point along the N.D. to R.D. radius of the (110) pole figure, and depth, given as percent of the thickness (?t/to X 100, where at is the thickness of material removed and to is the as-rolled

Jan 1, 1970

By A. G. Guy, T. B. Lindemer

A second intepation of the Fick law has been developed and applied to three-place data generated from the Gosting and Fujita solution of the diffusion equation. This integration provides new mathematical techniques for the analysis of experimental data. Through use of the synthetic data it is shown that for concentration-independent interdifiusion coefficients these techniques permit a more accurate determination of the coefficients than does the usual Boltzmann-Alatano analysis. Another technique, applicable to the most general concentration-dependent diffusion coefficients , can be used to determine whether given sets of coefficients are consistent with the experimental ternary concentration-distance curves. DURING the past 10 years the subject of three-component diffusion has advanced from the stage of a laboratory curiosity to the status of an accepted portion of physical metallurgy.1 In the course of this development the underlying treatment for two-component sys- tems was extended and generalized to accommodate the added component, but fundamentally the analyses currently employed for ternary systems are analogous to those previously developed for binary systems. There are several indications that an improved analysis is needed for the ternary case. First, the two cross coefficients, D312 and D321 are typically an order of magnitude smaller than the direct coefficients and consequently are difficult to determine with adequate precision. Second, instead of a single concentration-penetration curve (as in binary diffusion), there are four such curves in the usual determination of ternary diffusion coefficients. These curves have definite theoretical interrelationships, but actual experimental curves exhibit significant departures from these relationships. Finally, the amount of data needed to adequately describe the diffusion behavior of a ternary system is so large that radically new methods are needed to facilitate the gathering of these data. ICirkaldy2j4 has proposed several possible analyses of ternary diffusion data, including some of the methods in current use. A "second-integration" procedure proposed by him4 differed in important respects from that presented here and was not carried to the point of application. Two other methods have been explored by the authors and will be published separately; these are a numerical analysis technique and a method for the analysis of a single ternary diffusion couple. Still other analyses are being explored by various investigators. At present it seems likely that the final analysis of ternary diffusion that evolves will be a composite

Jan 1, 1968

By JOHN R. SUMAN

I WOULD like to spend a few minutes describing to you the present condition which exists in the oil industry and then point out some aspects of this deplorable situation in which I think petroleum engineers can be helpful. As you know, the oil business at this time is in a very critical condition, .due to the tremendous potential production in excess of current demand. This is a world-wide condition as well as a national problem, as it is estimated that the surplus production available for the market in foreign countries is of about the same proportion as that existing in the United States. Due to the inability within the United States to hold production within the bounds of demand prices have been slumping for the last four years and at this time have reached the point where the sales value of the average barrel of crude oil in the United States, is far below the cost, of production. In addition to the large amount of potential production available for the market in excess of demand we have in storage in the United States about six hundred fifty millions of barrels 'of oil. Unless something can be done to limit the amount of oil coming onto the market to a point well below the demand, which point will permit the reduction of stocks, it looks as though the 'oil business is facing demoralization.

Jan 1, 1931

By John R. Gould

A mathematical treatment of multiple-pass floating-zone refining of semiconductors, including the evaporation of solutes from the melt at reduced pressure, is presented. Vapor pressures and evaporation rate constants for phosphorus, arsenic, and antimony in germanium have been determined from floating-zone experiments conducted at 10 mm Hg. Rate sensi-tivity of arsenic in germanium has been examined over the range of 1 to 10 in. per hr growth rate. The equilibrium value of the segregation coefficient of arsenic in germanium, as determined by an extrapolation of these data, was found to be 0.09. PFANN has treated the segregation of nonvolatile solutes in the zone-melting process, Bradshaw and Mlavsky2 considered the evaporation of solutes in a vacuum during the growth of crystals by pulling from the melt, and van den Boomgaard3 has shown that it is possible to bring a volatile impurity element homogeneously into an ingot by means of zone-melting under a constant pressure of that element. This paper is concerned with the volatilization of solutes during zone - melting in a vacuum. The mathematical analysis by Lord4 of multiple-pass zone melting is extended to include evaporation of solutes. A method is presented in which evaluations of vapor pressures, evaporation rate constants, and distribution coefficients may be derived from the variation of solute concentration in the floating-zone refining of germanium at 105 mm Hg. EXPERIMENTAL Ingots of zone refined germanium, approximately 1/4 in. in diam and 10 to 12 in. in length, were subjected to several floating-zone passes at 105 mm Hg in order to provide intrinsic material for these studies. These ingots were then seeded in a [Ill] direction and solid-doped to a constant impurity concentration of approximately 1015 atoms per cmS in a forming gas ambient (10 pct H - 90 pct A) at 1/2 atm gage. The resulting crystals were subjected to repeated floating-zone passes at 105 mm Hg and a concentration profile along the length made after termination of each pass. Concentrations were determined from four-point probe resistivity measurements, and proper precautions were taken to prevent contamination during handling. A constant zone length, crystal cross section, and growth rate were maintained during zoning. A stationary coil and moving crystal system were employed for floating-zone growth with neither the section of crystal above nor below the melt rotated.

Jan 1, 1962

By AIME AIME

THERE is a constant reiteration in some quarters that technical societies are autocratic and that democracy is utterly lacking and that members would welcome democratic societies in which they had full, control of affairs. While we may not speak for other societies, than our own, in so far as th's Institute is concerned such charges- can only come from people uninformed as to the circumstances. It. is no curtailment of the democratic privileges of the members that a -slate is prepared by the Nominating Committee to be voted on at the annual meeting. The Constitution of the, institute stipulates how the nominating committee shall; be chosen and who shall compose it, which prevents anything like- a- clique controlling- the situation. The Constitution further provides how the nominees shall be distributed geographically and the by-laws specify geographical boundaries: for-these nomination districts. Further more, any man or complete ticket can be placed in nomination by means of a petition signed-by only; twenty-five members,- and three or four times such an independent slate has been so nominated and elected.

Jan 1, 1920

By M. B. Bever, A. M. Reti, A. K. Jena

The results of this investigation show that in the system SnTe-PbTe l) the solid solutions have small exothermic heats of formation relative to the binary compounds, 2) solid-solution hardening is almost absent, 3) the tin and lead atoms are .randomly distributed on the sublattice occupied by them and do not undergo an ordering transition during a thermal treatment designed to promote such a transition, and 4) the lattice parameter changes linearly with composition. These findings suggest that the solid solutions of tin telluride and lead telluride approach ideal behavior. THE binary compounds SnTe and PbTe form a continuous series of solid solutions.' Information on several physical properties of these solid-solution alloys has been published.1"3 In the work reported here, the heats of formation, microhardness, and lattice parameters of these alloys have been measured and the possibility of an order-disorder transition has been investigated. Order-disorder transitions occur in some solid solutions of binary compounds. In the system Bi2Te3-BizSes, for example, the electropositive bismuth atoms and the electronegative tellurium and selenium atoms always occupy separate layers. In the disordered alloy Bi2Te2Se, the tellurium and selenium atoms are randomly distributed on the layers occupied by them, while in the ordered alloy they occupy distinct layers.4 The NaC1-type (Bl) structure of SnTe-PbTe alloys consists of two sublattices, one of which is occupied by the electropositive tin and lead atoms and the other by the electronegative tellurium atoms; any ordering would be expected to occur in the sublattice occupied by the tin and lead atoms. PREPARATION OF SPECIMENS Polycrystalline specimens of PbTe and Sn1-xPbxTe (x = 0.25, 0.50, and 0.75) were prepared by melting stoichiometric amounts of lead (99.999 pct), tin (99.98 pct), and tellurium (99.999 pct) in evacuated and sealed Vycor tubes. Because of the deviation of tin telluride from the stoichiometric composition5 this compound was prepared by melting 49.8 at. pct Sn and 50.2 pct Te. The tubes containing the melts were quenched into water; the solidified ingots were removed from the tubes and annealed for 2 weeks in vacuum (PbTe approximately 100°C below its melting point, the three alloys 100°C below their solidus tem-

Jan 1, 1969

By Rustum Roy, E. F. Osborn

THE investigation discussed in this paper concerns phase equilibria in the alumina-silica-water system. Studies in this system are part of a re¬search project sponsored by the Geophysics Branch of the Office of Naval Research2 directed toward increasing knowledge of the stability relations of metamorphic mineral assemblages. Inasmuch as metamorphic rocks consist largely of aluminosilicate struc¬tures, many of them hydrated, the system alumina-silica-water is a logical starting point for the systematic laboratory study of metamorphic mineral systems. Although logical, this is not, however, an easy approach to the problem because of the very great difficulty of obtaining transformations among structures in response to changes in temperature, pressure, and con¬centration. Commonly equilibrium among the phases in this system is exceed¬ingly difficult to attain. New laboratory techniques are required to produce certain structural rearrangements, such as inversion of diaspore to boehmite or the transformation of alumina-silica mixtures to andalusite or kyanite. Phase equilibrium data for the alumina-silica-water system are consequently only partly complete, and only a summary progress report is presented here. Crystalline phases in the alumina-silica-water system are numerous and many are common minerals. The oxide components exist as: quartz, tridymite, cristobalite, corundum, water, and ice. Binary compounds occurring naturally are: sillimanite, andalusite, kyanite, and mullite in the alumina-silica system and gibbsite, boehmite, and diaspore in the alumina-water system. The most abundant among the ternary compounds is the composition A12O3.2SiO2.¬2H2O, existing in the four structural modifications, kaolinite, nacrite, dickite, and halloysite. The hydrated form of halloysite, A12O3.2SiO2.4H2O, is here called endellite. Pyrophyllite, A12O3.4SiO2.H2O, is the third ternary compound of natural occurrence. In addition to these minerals, two other ternary crystalline phases have been encountered in this study. The first is a structure resembling montmorillonite and corresponding perhaps to the pure aluminian end member of the beidellite series. The other has a composition approximating A12O3.2SiO2.H2O but its composition and structure are still in doubt. LABORATORY PROCEDURE In these laboratory studies, a starting material such as an alumina-silica gel or one or more of the crystalline phases is wrapped in platinum foil,

Jan 1, 1952

By completing a double-track railroad cut-off, involving a large volume of cut and fill, in addition to a half-mile bridge spanning an important French river, engineers in the zone of the Services of Supply have opened up a route by means of which hours of valuable time are being saved in transporting men and materials to combat areas. Its most valuable feature is that it provides a means for by-passing a certain city where several, French railroad lines converge and where, consequently, congestion of traffic has been responsible for delayed train movements. To avoid a double-track turnout, which would have involved a cross-over cutting one of the French tracks, the two track connections of the cut-off are taken off from opposite sides of the French right-of-way. This involved running one of the new lines of the cut-off out from the main line track on a fill to a point where it could be brought back and over the French track on a steel girder bridge. Beyond this bridge the two tracks of the cut-off converge and straighten out in the standard type of double-track construction. The new cut-off is about 5 3/4 mi. (9 km.) long and has required 160,000 cu. yd. of cut (122,329 cu. m.) and 414,000 cu. yd. (316,527 cu. m.) of fill. In the biggest continuous fill a-yardage of 180,000 has been placed; the road-bed in this section-being-about 40-ft. (12 m.) above the original ground surface. The bridge portion of the cut-off, 2190 ft. (667.5 in.) long, is made up of ninety-nine 14-ft. (4.3 m.) timber spans and sixteen 50-ft. (15.3 m.) steel girder spans. This is the longest bridge which engineers of the American Expeditionary Forces have built in France. The timber spans are supported by pile trestle bents, while the longer steel girders rest on clusters of 43 piles. Two pile drivers of the steam-hammer type worked from each -end of the bridge toward the center of the river, while a drop hammer worked westward from the shore end. In this structure nearly two thousand piles 50 ft. or so in length had to be driven.

Jan 12, 1918

By T. H. Alden

In several recent studies of fatigue fracture in single-phase metals, tests have been made using the condition of essentially constant plastic strain amplitude.1-4 This procedure departs from the more common practice of holding the amplitude of stress constant. From these studies have emerged two important generalizations about the behavior of metals during cyclic straining. First, measurements of the stress amplitude, required to impose the fixed plastic strain amplitude, have shown that the rate of cyclic strain hardening in annealed metals is rapid in the early cycles but decays quickly to a very low value.1"5 This behavior is displayed particularly for a range of strain amplitudes below about 2 pct and at low and high temperature. Frequently, the hardening rate becomes so low that one can determine a "saturation" stress. This stress increases with strain amplitude. In addition, an experimental relation between fracture life and plastic strain amplitude was obtained by Coffin and Taternelli,' namely N 1/2 ep = constant. For several metal:;, this equation has been shown to hold down to a strain amplitude of 0.1 pct. Whether it also holds in the "low amplitude" range (lives of more than about 105 cycles) has not been established. The importance of the saturation stress level (a value derived from strain hardening measurements) to the question of fracture life (the usual quantity of interest of fatigue testing) lies in the observation that cracks start to form when the cyclic hardening rate is essentially zero, and not before.4"5 This point suggests immediately a means of relating tests at constant stress and constant strain amplitudes. When making comparison, the stress in a constant stress test is to be identified with the saturation stress in a constant strain test. If these ideas are correct, then it should be possible, using the relation between fracture life and strain amplitude and experimental curves of saturation stress versus strain amplitude, to predict the fracture life as a function of stress, i.e. predict the S -N curve, for low stress fatigue. Saturation stress amplitude-plastic strain amplitude data, obtained in tension-compression, exist only for a few metals and for relatively high amplitudes of strain. Comparable S -N curves (push-pull loading) were known by the author only for OFHC copper. Values for this metal taken from Ref. 2 are shown in Fig. 1. The strain amplitudes, the lowest

Jan 1, 1962

By Edna A. Dancy, Gerhard J. Derge

The specific conductance of FeOx,-CaO melts in contact with iron was found to decrease from 200 ohm-1 cm-1 for FeO, to 40 ohm-1 cm-1 for a melt containing 26.3 pct CaO at 1400°C. The temperature coefficient was positive at all compositions, but became smaller at high CaO contents. Current efficiencies for electrolysis increased from 2.5 pct in FeOx to 17.3 pct at the high CaO composition, indicating a change from predominantly electronic conduction to conduction with a substantial ionic contribution. It was shown that Ca++ ions as well as Fe++ ions carry the ionic current. A subsidiary investigation on the apparent effect of atmospheres of argon, helium, and nitrogen on the electrical conductivity showed that this could be correlated with surface temperature losses, which varied with the thermal conductivities of the gases and resulted in precipitation of metal by the reaction 3 Fe++ = 2 Fe+++ + Fe. The work described in this paper is offered as a contribution to the general fund of knowledge concerning metallurgical slags. Measurement of electrical conductivity and electrolysis are comparatively trouble -free methods for investigating molten materials, but, although these methods had been used for complex slags, it was not until the work of Bockris et al.1 that the approach of examining simple binary slag systems was employed, and CaO-SiO2, MnO-SiO2, and Al2O3-Si9 were studied. Two groups have performed work of particular relevance to the present investigation. Inouye, Tomlinson, and chipman2 studied the conductivity of wustite as a function of temperature and of the addition of 5 mol pct of a number of oxides, including CaO. They concluded that molten FeOx in equilibrium with iron is a semiconductor. Simnad, Derge, and ceorge3 demonstrated the ionic nature of liquid iron silicate slags and also concluded that, although the conductivity of FeOx in equilibrium with iron is predominantly electronic in nature, there is a small ionic contribution. The work reported here on FeOx,-CaO slags consists of three main parts, namely, the determination of the specific conductance over a wide composition range, an investigation into the nature of the conductivity through current-efficiency measurements over the same composition range, and an attempt to identify the current-carrying ions, as well as a subsidiary investigation on the apparent effect of the nature of the inert atmosphere on the conductivity. EXPERIMENTAL Materials. The slags, varying in composition from FeOx to 27 pct CaO, were prepared by heating reagent- grade Fe2O3 in an ingot iron crucible with a suitable amount of CaCO3 and, in some cases, powdered iron, in air. This prefused material was then used for the runs. At the end of each run the cell was removed from the furnace and quenched by immersing the bottom half in water. After crushing, the slags were analyzed for calcium and total iron by the usual wet methods. The oxygen content was obtained by difference. Specific Conductance: Apparatus and Method. Fig. shows the experimental setup, with the conductivity cell and leads of ingot iron. The standard four-probe method for measuring high conductivities was used. In this, the potential drop across the unknown resistance is compared with the potential drop across a known resistance connected in series, i .e., same current through both resistances. Thus there are both current and potential leads to the center electrode and to the crucible, which acts as th other electrode. Both ac and dc circuits were available for the measurements; they have been described in earlier work performed in this laboratory.4,5 The geometry of the cell was such that the center electrode was equidistant from the bottom and sides of the crucible. This ensured that the current path was the same irrespective of the magnitude of the conductivity of the material in the cell. Cell constant were measured with KC1 or NaCl solutions, which have considerably lower conductivities (0.0013 to 0.25 ohm-' cm) than the slags, and this precaution in design made sure that the determined cell constants applied to the cells with contents of any conductivity. The cell-constant determinations were made with the ac measuring circuit to prevent polarization. The four-probe method eliminates lead resistance but not the resistance of those parts of the center

Jan 1, 1967

By A. Ghosh, T. B. King

The kinetics of the discharge reaction: 20'- (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'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.1'8 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.' Esin and his coworkers5'10"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,'~ 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,'~ 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. "'~~ 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

By R. E. Hudrlik, G. W. Preckshot

The diffusion coefficients of silver from solid silver in molten lead were measured to within ± 0.8 pet in a columnar type diffusion cell ower, the temperature range of 326° to 530°C. Fick's law describes the process up to 530°C where the laminar mechanism appareltly breaks down. These is negligible resistance at the interface as shown by mathematical analyses. The diffusion coefficients are found concentration independent. IT would seem that diffusion in liquid metals would be free of such effects as molecular structure, dissociation. polarization. and compound formation. This view was taken by Gorman and preckshot in their study of diffusion of copper from solid copper into molten lead. They reported diffusion coefficients which were independent of the concentration over the range of 478° to 750°C. They found that the Stokes-Einstein equation with constant radius of the diffusing specie represented the diffusion data better than Eyring's rate theory equation and Sheibel's correlation. The radius of diffusion was found to be that of the doubly charged copper. There appeared to be no resistance across the solid-liquid boundary. In the present work the diffusion coefficients for silver in liquid lead were measured over a range of temperatures of 350° to 505°C. The solubility of silver in lead over the range of 303° to 630°C was also obtained. These results are compared with calculated or correlated values or with data in the literature. EXPERIMENTAL Procedure—The experimental equipment techniques and procedures were those reported in detail by Gorman and preckshot9 and will not be repeated here. Measured values of WT, Co, A. L were obtained for various diffusion times and the diffusion coefficient was computed for the case of no resistance at the interface9, 11 by: WT/CoAL = 1- 8/p2 n=1 1/(2n - 1)2 exp[-(2n - 1)2p2 Dt/4L2] [1] or where there was resistance at the interface by: WT = 1- ?n=1 2h2/ap2L [sxp [-Dan2t]/[(h2 + an2) L + h] The roots an are those of the transcendental equation3 tan (an L) = Iz/cun. The diffusion coefficient is that defined by Hartley and Crank.7 The total silver in the lead cylinder and equilibrium slug was determined by a cupellation technique' with proper correction for losses. Analysis of known samples showed that this method is surprisingly accurate. The amount of silver in the lead adhering to the silver cylinder was obtained in the same fashion as shown by Gorman and preckshot.9 The small errors involved in this determination are not critical since the silver in this adhering lead layer is only 3 to 15 pet of the total diffused. Materials—Electrolytic silver containing 99.9+ pet Ag obtained from General Refineries of Minneapolis, Minn. was used for all but runs 7 and 8. For the balance of the runs this silver was reduced with hydrogen at 1100°C and its oxygen content was found to be about 0.017 pet. For the runs. 7 and 8, phosphorous-reduced silver of the same purity was obtained from Handy and Harman Co. of Chicago, Ill. The densities of the phosphorus-reduced silver and the hydrogen-reduced electrolytic silver were 10.484 and 10.487 g per cm3, respectively. These values agree with those reported for pure silver. Silver which was reduced at 900 C had an average density of 9.998 g per cm3, indicating porosity. This silver was used for a number of runs which were not tabulated in Table I. These are indicated by crosses on Fig. 2. The 99.999 pet Pb was obtained from the National Lead Co. Research Laboratory of Brooklyn, New York. DISCUSSION OF RESULTS The diffusion and solubility results are reported in Table I for eleven runs using either phosphorus-reduced electrolytic silver or hydrogen-reduced silver at 1100° C. The solubility data shown in Fig. 1 show the excellent agreement with that reported by Heycock and Neville.8 The data of Friedrichs5 apparently are in error. The experimental solubility data of this work are reported to 0.3 pet. The experimental diffusion coefficients computed from Eq. [1] are reported within 1.2 pet of the mean and are plotted in Fig. 2. These are expressed within +0.8 pet of the experimental values over the entire temperature range by: D= 8.26 x 10 -5 e-1925/RT . [3] There appears to be little difference due to the

Jan 1, 1961

By Frank T. Weems

The basic operating properties of the DorrClone are discussed and certain metallurgical applications which exploit these properties are presented. An effective method of controlling the consistency of the DorrClone underflow is described. THIS paper presents in a general manner some of the applications of the DorrClone (Dutch States Mines cyclone) in the metallurgical and heavy chemical fields. Technical or mathematical analyses of the design factors and of the mechanism whereby the cyclone effects its separation have been capably treated in a series of previous papers.'-' Engineering and operational aspects of a few installations and laboratory tests have been chosen to emphasize the unique classification characteristics of the DorrClone and to illustrate its utility in certain difficult situations. Its use in coal washing and heavy-media operations are not considered. Some 25 or more industrial installations and applications of the DorrClone in the metallurgical fields are operating at present, ranging from single trial units to complete batteries composed of a multiplicity of units. The data were obtained in part from some of these, and in part from operations of units at the Westport Mill, the laboratories and testing plant of the Dorr Co. at Westport, Conn. The DorrClone was developed, in principle, by the research dept. of the State Mines, Limburg, Holland, during World War 11. Its first use was to dewater a —50 micron sand used as a dense medium in coal washing. The metallurgical wet cyclone was first publicized by Driessen and Yancey and Geer.6 ince then the cyclone has been studied as a means of de-watering, heavy media concentration, and fine size classification. The DorrClone is shown in Figs. 1 and 2. pulp to be treated is pumped through the feed nozzle, A, into the feed cylinder, B. The feed nozzle is of rectangular cross-section, the outermost edge being tangent to the feed cylinder walls. Feed shims, C, may be attached to the innermost walls to adjust the open area of the feed nozzle available to entering pulp. The tangential injection of feed under pressure supports the vortex action of the pulp that has been detained in the cyclone; the centrifugal forces of this vortex throw the coarse particles to the walls of the cone, D, where they collect and pass downward and out through the adjustable apex opening, E. The fine particles contained in most of the water that entered with the feed pulp move to the inner spiral of the vortex and flow out through the vortex finder, F, contained in the orifice plate, G, which forms the top of cyclone chamber. The overflow pulp may then spray freely into a spray chamber, H, surmounting the cyclone or pass directly into a 90' elbow, I, of somewhat larger diameter than the vortex finder. Installation Where more than one cyclone is to be installed, best overall efficiency and ease of control are obtained with equal distribution of both pulp volume and weight of solids among the cyclones, and with the same pressure being maintained at each cyclone feed nozzle. Fig. 3 is a suggested arrangement for feeding two or more cyclones in parallel. Feed pressure control: Under normal operating conditions it is not unusual for some surge to exist in the feed that is to be sent to the cyclone. As will be discussed later, surges in the solids content of the pulp are usually not of great operational consequence, but surges in feed volume are a problem. Several systems have been devised for absorbing surges in feed volume, each involving a surge tank. If the surges are small and fairly rhythmical, a tank of sufficient size might be installed to dampen out

Jan 1, 1952

By K. G. Wikle, J. G. Klein, W. W. Beaver

Consolidation of hydride process, electrolytic, calcium reduced, and comminuted thorium powder, as well as saw chips and lathe turnings, by vacuum hot pressing and by cold pressing-vacuum sintering was studied. The mechanical properties of the consolidated material in the extruded form are compared with those of wrought castings. AT present there little little industrial use for thorium metal, although it has some important though small scale applications in electronic equipment. Despite its high inelting point—about 1750°C —a low modulus of elasticity, 11.4xl0 si at 20°C;' relatively low mechanical properties coupled with a high density, 11.7 g per cu cm; and an unusually high chemical activity with normal atmospheres limit any structural applications. The metal is utilized as an alloying element principally in magnesium. Pure thorium finds utility as electrodes in gaseous discharge lamps such as the high intensity mercury lamp' because its low work function and high electron emissivity provide lower starting potentials and more uniform operating characteristics than other available materials. The metal is also found in photoelectric tubes used for the measurement of the ultraviolet spectrum." Thorium metal has been used in germicidal lamps of the cold cathode type as sputtered coatings on nickel in order to provide a low work function surface and a low starting voltage. Other applications have involved the radioactive properties of thorium for the production of ionized particles." The potential value of thorium is much greater than its present use pattern because of possible utility in the field of nuclear power. Th may be converted through nuclear reaction to a fissionable element U which should be capable of acting similarly to U in the g'eneration of atomic power. Thorium has been reported to be about three times as plentiful as uranium in the earth's crust, placing it in the order of abundance of lead and molybdenum." Thus, it is of interest in augmenting the potential supply of fissionable material for nuclear power. Because of its high melting point, thorium is usually produced as a powder through the calcium reduction of its oxide or thermal reduction of halides by sodium, magnesium, and calcium. It may also be produced in flake form by electrolysis of fused alkali or alkaline earth chloricles and fluorides. Therefore, powder metallurgy assumes importance in the fab- rication of thorium metal shapes. Furthermore, it is rather difficult to obtain pure thorium by melting, as the molten metal reacts readily with graphite as well as oxide, carbide, and nitride refractories. These contaminate the melt with oxides, carbides, and metallic impurities." The current investigation was undertaken to examine the fabrication of thorium by powder metallurgy methods which have been used for the commercial production of beryllium and other metals.' A sparcity of data concerning the comparative cold and hot compaction of thorium powders of different derivation existed. Therefore, all commercially available types were examined along with other experimentally produced thorium powders in order to round out the comparison of consolidated thorium powders with melted reguline metal. Review of the Literature By heating a mixture of ThC1, with potassium, Berzelius made the first thorium metal as an impure powder in 1828. Improvements in the basic process, increasing thorium assay to 99 pct, were made by several investigators including Arsem," Lely and Hamberger10 and Von Bolton." Calcium reduction of Tho, to make powders was investigated by Berger," Huppertz,'" Kroll," and Kuzel and Wedekind.'" A thorium powder produced by this method using a CaC1, fluxing agent assayed 99.7 pct, as reported by Marden and Rentschler.'" Compacted and sintered, this product was found to be ductile, and could be fabricated into wire and sheet. Improvements of the calcium reduction process were made later" wherein CaCl, was eliminated from the reaction, producing metal assaying 99.8 pct Th. Further work by Lilliendah118 howed that a coarser metal could be obtained by the substitution of ThC1, or ThOC1, for oxide with consequent advantage of stability to atmospheric reaction. Reports on the technology of thorium developed in Germany during World War II have been made by Espe."' Thorium powder of 99.5 pct Th was obtained by reduction of the oxide by calcium. Screening to —200 mesh, compacting with about 20 tsi, and sintering in vacuo at 1320" to 1360°C for 3 hr resulted in a porous sinter cake. The sinter cake was sufficiently ductile to be worked into bar, wire, and sheet which could be employed as electrode materials.

Jan 1, 1957

By C. E. Turner, J. R. Elenbaas, R. D. Grimm, J. A. Vary, D. L. Katz

A technique is presented by which well samples and core plugs of dolomite formations are classified by microscopic examination into seven different porosity grades. Quantitative values of porosity and permeability are determined for each grade by a statistical correlation of the core plug test data with the porosity grading system. These quantitative values are applied directly to the grades exhibited in the well samples for the purpose of estimating the reservoir void space for wells that were not cored. The procedure is described for estimating the gas reserves per unit area lor the South Hugoton gas field. but a reserve estimate for the field is not given. INTRODUCTION The miscroscopic examination of well sample; and the graphic recording of their lithologic qualities and other distinguishing characteristics of various geologic formations drilled is both a science and an art of long standing and wide application. Usually the primary objective of a geologist who "sits on the well" and examines the samples are: to identify the formation being drilled, determine the total depth, casing point. and completion interval. In most cases the porosity is described. if done at all, in general terms. such as: trace, scattered, fine, poor, fair, medium. good, excellent, or in some other relative terms. In fields where various geologists have examined samples and recorded observations on many wells considerable variations in lithologic terms and porosity descriptions occur unless there is primary effort to establish uniformity of logging observations and standards of recording observable porosity. When an estimate of the pore volume of a reservoir is made a geologic concept of the processes that control the magnitudes of porosity and permeability is developed by microscopic examination of well samples. The characeristics and appearances are then mentally related to rather general quantitative units of porosity based on physical core data from the same reservoir or on such data or experience in other reservoirs that have similar qualities. The reliability of such estimates depends largely on the variations of the lithology of the formations, the geometric properties of its void system. the extent of comparisons of sample appearances with porosity data, as well as the uniform recording of all relevant characteristics. This statement is particularly significant for dolo-mitized limestone formations of substantial thicknesses and heterogeneity such as the Permian Dolomites of the Hugoton gas field. Jn this field, as well as in most of the Permian Dolomite fields, the producing formations are of relatively great thicknesses in which the porosity and permeability of the reservoir varies substantially in all directions, depending on the crystalline structure. degree and kind of impurities, kind of fossils anti cementation thereof, degree of dissolution. and fracturing. The variations of the lithologic texture of the dolomites and post deposition alterations have resulted in porosities and permeabilities of such magnitudes that only a part of the gross thickness can be counted as "pay." At the time of this study insufficient gas production had been experienced to apply the pressure decline production method in the South Hugoton Field and the electric logs are not definitive enough. The problem of estimating gas reserves in the south part of the Hugoton Field is primarily one of determining the pay thickness and porosity from well samples and core data. The area studied embraced all that part of the field lying south of an east-west line through Guvmon, Okla., anti containing approximately 1.000,000 acres. This paper describes a technique of correlation of physical core data with well samples so that quantitative values of pay thickness, porosity. Permeability, and connate water may be assigned to well samples that are representative of a given interval, and thereby permitting the estimation of gas reserves lor a given unit area. The procedure was developed by a uniform microscopic qualitative porosity grading of the dolo. mite core plugs.. and relating these grades to the respective physical core data on a statistical basis The well sample-were also graded in a Similar manner in order that the quantitative values established lor the core plugs could be applied to the well Sample for wells that were not cored. GRADING OF DOLOMITE A group of experienced geologists was given the assignment of examining the samples on all wells in South Hugoton in order that they could log their observations in a uniform and standardized manner and grade the observed porosity so that it could be related quantitatively to the core data. The group initiated the study 011 chips from cores which bad been tested for porosity and permeability. This study continued until all of the geologists developed a common knowledge of lithologic terms and of the characteristic appearances of the samples and their relations to measured porosity. The characteristic appearances of the dolomite samples under twelve-power magnification as related to their qualitative porosities afforded a classification of the dolomite into :even grades of porosity, ranging from dolomite of no-visible porosity under twelve-power magnification to dolomite of excellent porosity. The assigned grade for a specific 10-ft interval is a weighted average of all visible grades of porosity exhibited by the cuttings representing that interval. The porosity characteristics were recorded by a color graph adjacent to the lithology column in conjunction with a numerical system for further definition of relative porosity as shown in Fig. 1. The three vertical lines to the right of the lithology column each represent 33 1/3 per cent. which lines were used to record the percentage of the samples, for any particular interval. that showed porosity under the microscope. The colors were used to denote actual pore size. i.e., orange. blue and I-ed for pore diameter of one-fourth or less. one-fourth to one-Ilalf. and greater than one-half millimeter, respectively. The area colored 1)). one or more colors represents the percentages of the samples exhibiting pores of the respective size or sizes. The numerals from one to six inclusive shown on the log in

Jan 1, 1952

By G. F. Jenkins

ASBESTOS is a general term embracing the fibrous varieties of a number of minerals. Of these, the hydrous magnesium silicate, chrysotile (H4Mg3Si209), a variety of serpentine, is the most abundant and useful to industry. All other types of asbestos belong to the amphibole group of minerals and are classified as: crocidolite, NaFe(SiO3), FeSiO3; anthophyllite, (MgFe)SiO3; amosite, also a ferromagnesium silicate but with iron content higher than that of anthophyllite; tremolite, CaMg3(SiO3)4; and, actinolite, Ca (MgFe)3(SiO3)4. PROPERTIES The commercial value of asbestos depends largely on the physical property that permits it to be readily separated into fine filaments of high tensile strength and flexibility, which, coupled with the fact that it has the quality of incombustibility of a mineral-in distinction to vegetable and animal fibers-makes it of unique usefulness for many purposes. To some extent, the value depends upon the length of the fiber, although extreme length is neither necessary nor desirable for most purposes. Chrysotile occurs as cross-fiber veins, in which the asbestos fibers are approximately' at right angles to the vein walls, with vein width- or fiber length-seldom exceeding 2 or 3 in.; also as slip-fiber, in which the fibers 'lie in the same plane as the vein or on slippage planes. A cleanly broken vein of cross-fiber has a pearly luster and may range from a deep green or brown color to light shades of yellowish green or cream. When of good quality, the fiber filaments forming the vein may be easily drawn away from their neighbors and exhibit a fine silkiness and pure white color. They may be twisted into a thread and when flexed between thumb and fingers are found to be strong and pliable. Chrysotile withstands comparatively high temperatures without breaking down completely or fusing but begins to lose water of crystalliza-

Jan 1, 1949

By Lee Morris, Charles E. Lawall

This paper represents the results of a study to determine the source, mode of occurrence and conditions influencing the flow and liberation of large volumes of inflammable gas in the Pocahontas No. 4 coal bed in southern West Virginia. A study of this kind is of interest in connection with mine ventilation, because in the removal of gases from coal mines it is very important to know the origin, the occurrence and laws of gas flow. The study was started in April, 1931, and the data and observations were obtained throughout a period of 15 months of field work. Geology The country where this study was made is mountainous and rugged; great cliffs, precipitous slopes and deep narrow gorges are found throughout the area. The outcropping rocks consist of stratified layers of sandstone, shale, limestone and deposits of coal of Carboniferous age. The Pottsville series of the Pennsylvanian, lying at the base of this period, cover the greater portion of the area. A stratigraphic section of the Pocahontas group of the Pottsville series is shown in Fig. 3. The older rocks outcrop in the extreme southeastern part of the area, but are under drainage in the central and northern parts due to the gradual northwest dip of the strata. The structure has a general northeast-southwest trend (Fig. 1). North of Dry Fork anticline the strata have been only slightly disturbed by movements of the earth's crust; it is now a long monocline. Southeast1 of Dry Fork anticline the strata are warped into great arches and deep troughs and are broken by overthrust faults. All of this folding is probably the result of the intense folding associated with the formation of the Appalachian Mountains. Pocahontas No. 4 Coal Bed The Pocahontas No. 4 bed, lying approximately 550 ft. above the base of the Pottsville series, is one of the thickest and most gassy coal beds in

Jan 1, 1934

By C. M. Young

Wherever salt is extracted from the ground as an artificial brine produced by pumping down fresh water to dissolve the salt, subsidence of the overburden is a possibility, though apparently few cases of such subsidence have been noted and detailed records are wanting. This description is intended as a record of subsidence that may permit the forcasting of similar occurrences in other cases; the data were supplied largely by R. B. Lee, city engineer of Hutchinson, Kans. About eleven years ago, ground movement occurred at a neighboring salt plant, when the surface assumed the form of a shallow funnel. Movement was probably due to a flow of sand into a well through a poor seal or a broken casing. The salt deposit increases in thickness from the east until at Hutchinson, where the subsidence occurred, it is about 310 ft. thick. The interbedded layers of shale vary in thickness from mere traces to about 7 ft. While knowledge of the shale content of the beds is not exact, the log of a shaft 3 miles east of Hutchinson indicates that shale forms about 25 per cent. of the total thickness. This shaft does not reach the bottom of the salt by about 60 ft., but there is no reason to think that the lower part of the bed is different from the upper. Logs of wells sunk to the bottom are not sufficiently detailed to be of much value. Above the salt is the shale of the well-known Red Beds. The thickness of this is variable, principally because of its eroded surface, but at the mine it is 340 ft. This shale is variable in character and strength, but contains no strong members of limestone or sandstone. If the support is removed, very probably it will subside. The Arkansas River flows across the salt district and Hutchinson is situated on the flood plain. Between the top soil, which is about 8 ft. thick, and the shale is 60 to 100 ft. of water-bearing sand and gravel. The process of removing salt, at least in the case of the earlier wells with which we are concerned, is as follows: An 8-in. hole is put down through the sand and gravel by means of a drive pipe, which is bedded in the shale. Prom the top of the shale, a 6411. hole is drilled through the shale, to, or nearly to, the bottom of the salt. Casing is put in to a depth of about 140 ft. to shut off a water-bearing layer in the shale.

Jan 1, 1927

By AIME AIME

THE Committee on Elimination of Waste in industry came into existence from a speech in Washington by Mr. ,Hoover, in November, in which, he said: It is primary to mention the three-phase waste in production: first, from intermittent employment; second, from unemployment that arises in shifting of industrial currents; and third; from strikes and lockouts. Beyond this elimination of waste there is another field of progress in the adoption of measures for positive improvement in production.

Jan 1, 1921

By Basil B. Zavoico

ALTHOUGH the American petroleum industry was affected by the Second World War from its early beginning it was not until Dec. 7, 1941- that the industry was placed on full war footing. Even throughout most of 1942 the American overseas operations were limited and not until late in the year did expansion of military activities, more particularly the offensive in North Africa, affect the domestic supplies to such an extent that critical deficiencies developed locally in this country, particularly along the East Coast. The definite outlook for greatly expanded offensive operations by the United States on both Atlantic and Pacific fronts makes certain that during 1943 the domestic situation will. not be alleviated; rather it may become even more critical even though additional transportation facilities, now being built and planned. will be completed from the southwestern producing states to the East Coast.

Jan 1, 1943