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By J. F. Poland

B. C. Burgess-—Prior to hearing this paper presented at the San Francisco meeting, I travelled by car from Yuma, Ariz., across south-central California and up through the San Joaquin Valley. After hearing the paper I returned by the coast route to San Diego then along the Mexican border to Yuma. The striking feature of these trips, related to this paper, was the dry river and creek beds at a time of year not the dry season. Contrasted with this was the wasteful use of water in irrigation canals and laterals. Poland says "at least 90 pct of the ground water pumped is used for irrigation." That being the case, it would appear that first consideration should be given to conservation of this use. Probably a small part of this is actually reaching the plants. Some measure of this loss between pump and crops would be revealing. Methods that might be employed to reduce this loss are pipe lines and spraying of some crops such as the banana planters are using in Central America. Another idea which might be investigated is to line canals and ditches with some water-repelling mineral like pyro-phyllite. Perhaps a comparatively thin sprayed-on

Jan 1, 1951

By M. M. Rao, P. G. Winchell, R. J. Russell

A detailed analysis has been used to correlate the avalable thermodynami c da In on iron-ric11 Fe-Ni (41loys in the body-centered a, and the face-centered y phases. The inp ut injovrt~ation required by the a am lysis consists of tile heat of the a, to y transformation at 1123°K, the heat of mixing of y at 1123°K, tile specific heats of both a, and y (decomposed into Debye, electronic, and magnelic contributions), and the positional and magnetic entropies of both a, and y. PYLrrzary oirt.bul of the analysis is the free energy of each phase as a Junction of temperature and composition. FOr Fe-Ni alloys the adjustment of twenty-one parunletevs allows the accurate reproduction of enthalpy data for both phases, the heat of mixing- for y, the a/y equilibrinm compositions in the Fe-Ni phase diagram, and the usually accepted enthalpy and entropy of a and y iron. Also obtaitzed are fuirly accurate reproductions of electronic specific heat coefficients predicted from electron- to-atom ratio interpolations and To temperatuves eslimanted from transformation studies. Also considered in the calculation are the elastic constants, Curie temperatures, saturation magnlelizalion values, and indications of short- range order. The measnred activity coefficient of iron in anstetnite could not be accurately matched. The major source of uncertainty in the model is thought to be the magnetic contribution to the entropy of austenite. Calcrclations were extended to Fe-ni-C alloys using available carbon-acliuity data. The free energy of transformation from martensile to r at fixed composition was obtained as a function of nickel and carbon contetzt, and binary thetal-carbon phase diagrams Were estimaled as a function of nickel contenl. We needed thermodynamic information for Fe-Ni and Fe-Ni-C alloys at temperatures between 400" and 800°K in order to interpret the results of several phase-transformation studies. The most recent theoretical analysis of the thermodynamics of Fe-Nialloysl was based on a lumped-parameter, regular-solution model and used the Fe-Ni phase diagram available at that time.' Because significant difficulties were encountered in attempting to extend this analysis to Fe-Ni-C alloys, and because more experimental data has become available recently, we decided to attempt a new correlation. The analysis used here allows the extrapolation of measured and calculated thermodynamic values to lower temperatures and the extension of the thermodynamic analysis to Fe-Ni-C alloys. The structure of this correlation consists of expressions containing a total of twenty-one adjustable parameters. The forms of these expressions are discussed in the next section; however, a less formal summary is presented now to provide a physical overview of the model and to indicate its connections to prior work. Primary input information for this correlation is described below. The measured values of the specific heat of iron3 and its analysis475 and theoretical estimates of the specific heat of y* iron at low tempera- loys at 1123°K has been measured by solution calori-metry.7 The enthalpies of both a, and y have been measured most recently by Scheil and Saftig,B who used a dry-ice calorimeter. These data are used to formulate expressions for the heat of mixing of y and the heat of transformation of a, to y both at 1123°K. The a and y solubility limits in the Fe-Ni phase diagram have been redetermined recently9 by methods which assure a close approach to equilibrium. The a to y transformation can occur without change in nickel content or free energy at a temperature called TO; TO temperatures for various nickel contents have been estimated from transformation studies. The computed free-energy functions are adjusted by means of the parameters to fit both the phase diagram and the TO temperatures. Primary emphasis is placed on the phase diagram fit. Iron activities have been measured in Fe-Ni austenite10 between 973" and 1173°K. These activity data, which cannot be fitted accurately with our model, indicate that iron is substantially ideal in iron-rich austenite. Secondary, but helpful, information for the present correlation is provided by neutron diffraction and saturation magnetization measurements on both body-centered and face-centered Fe-Ni alloys."-'3 These results were interpreted11 in terms of composition-insensitive, localized magnetic moments on both iron

Jan 1, 1968

By N. W. Lord

The process of molten-zone refining is analyzed for long ingots and many zone passages. Formulas are derived which give the resultant impurity distribution in terms of finite series. A comparison with the approximate procedure of Hamming is given. HE physical principles and applications of an extremely physicalprinciple efficient form of metallurgical refinement has been described by Pfann. The purpose of the present paper is to describe a method of analyzing exactly the particular program used which enables the segregation effect to be predicted for any number of molten-zone passages in a long ingot. The method is applied to the particular case of refinement of an ingot whose impurity initially is uniformly distributed throughout its length. A number of molten zones of equal length are passed through the ingot effecting a radical redistribution of impurity. Pfann has indicated an approximate method, due to R. W. Hamming, of calculating the resultant concentration after each successive zone pass for a particular value of the segregation constant defined in his paper. Here a solution will be presented in terms of the number of zone passes and the segregation constant. The expression, though cumbersome, is exact and susceptible to ordinary numerical computation procedures. The results of a similar computation using the procedure of Hamming are presented in a table together with the exact results of the present method. The discrepancy in terms of absolute concentrations is tabulated for the first eight zone-lengths. To establish the notation (which follows that of Pfann1 as closely as possible) and physical basis of the analytical equations, the physical model and principal assumptions may be reviewed. An alloy of two elements, where there is formed a continuous range of solid solutions, usually does not melt as a simple compound. Rather, a temperature is reached where the solid solution is in heterogeneous phase equilibrium with a liquid solution of different composition. The temperature dependence of these equilibrium compositions forms part of the phase diagram. For very small concentrations of a solute B in a solvent A, this usually takes the form of Fig. 1. Sometimes the solidus and liquidus slope upward. This corresponds to a segregation constant (defined below) which is greater than unity. The segregation constant is now defined as k = Cn(x)/CnI(x) [1] where C,,(x) is the impurity concentration in the solid ingot at distance x during the nth passing of a molten zone and Cnl (x) is the impurity concentration of the liquid zone from which the solid at dis- tance x is formed (see Fig. 4 of ref. 1.) C (x) remains the same after passage of the zone. The constant k may be either greater or less than unity in general. Purification in the former case is effected only in a finite ingot and in the portion that is melted last. For k less than unity purification is effected even in an infinite ingot. The method which follows gives, in the former case, the successive increases in impurity concentration and, in the latter case, the successive decreases in concentration. The general case of impurity redistribution will be considered first, and purification will be discussed later on. The analysis rests on the following assumption: The movement of the zone is too rapid to allow appreciable atomic rearrangement in the solid sections and too slow to disturb the uniform impurity distribution in the liquid zone characteristic of equilibrium. Hence, the composition in the solid at the left solidifying interface will be determined by Eq. 1 while the impurity concentration of the liquid zone will be uniform throughout its length. The reasoning which follows closely parallels that of Appendix 11 in Pfann&apos;s paper. It is reviewed here for the case of the nth zone pass in order to make clear the meaning of an operator essential to the present method. Fig. 4 of ref. 1 shows the movement of a molten zone of length 1 in an ingot of total length d. Each Cn(x) can be determined from the condition that the amount of solute added to the zone during an incremental advance, dx, is due to the melting in of a solid portion C(x)dx and the freezing out of kCnl(x), that is d I —r- CnL (x) dx = Cn-1 (x+l)- kCnL (x) dx or, in terms of Cn(x) d k k —— C,(x) +—c.(x) =— Cn-1 (x + l). [2] dx l l This, of course, is derived from the main assumption, the fact that 1 is constant, and that the total impurity content previously present up to x + 1 is constant . A correction has to be made for the region (d — nl) < x < d. This is due to the zone length changing during the passage of the solidifying interface beyond x = d — 1. Since the general solution would be too complicated otherwise, only the region 0 < x < d — nl is considered. The general solution of Eq. 2 is

Jan 1, 1954

By George C. Bravner

WITH the great expansion currently being made in the aluminum output of the United States, not only by the company that has heretofore been the sole producer but by a now organization in the field it is only natural to wonder to what degree the; ore reserves of the United States can contribute to the growing consumption. For the three-year period 1937-&apos;39 the U.S. Bureau of Mine&apos;s figures indicate that the annual domestic production of bauxite averaged about 370,000 long tons, compared with average, annual import of about 194,000 long tons. About 85 per cent of the imports came from Surinam, nearly all of which went into aluminum manufacture. Not all of the or -kipped from mines in the United States is used to make alumimun however as Bureau figures indicate that in these three years an average of only 48 per cent of the domestic ore shipment were so used the abrasive chemical and other industries taking respectively 27, 21, and 4 per cent of the output. The recent increase in the demand for bauxite has been of course in it use for aluminum manufacture. This as is well known is largely attributable to the world race for supremacy in

Jan 1, 1941

G. D. Kneip, Jr., and J. 0. Betterton, Jr. (Union Carbide & Carbon Corp., Oak Ridge, Tenn.)—The authors have contributed to the theory of zone melting by considering the effects of the solidification of the final zone on the distribution curves for the finite length bar. However, they do not consider in sufficient detail the restrictions imposed by the particular metals involved. Eq. 4 has the analytical solution which is equivalent to Pfann&apos;s&apos; equation for normal solidification of the final zone. For distribution coefficients less than one, it is apparent from this form of the equation that, as the solidification approaches completion, the concentration attains extremely large values which are inconsistent with the density of physical materials. The necessary restrictions then are that the solute concentration cannot exceed the density of the alloy, or more frequently, the solubility limit in the solid phase. Secondly, the distribution coefficient cannot be constant from 0 to 100 pet solute unless the liquidus and solidus coincide over this whole region. It would thus be more correct to impose limits on the solubility such as would be indicated by a typical eutectic diagram. Furthermore, in this case the assumption that the distribution coefficient remains constant is more likely to be realized. Eq. 4 should then be replaced by the following C,,(x) =k/L-x [ ?11 3 C11 (x)Ddx - ?11 4 Cn(x)dx= k[Cn (L-l)/k] [ L-x/l]x-1 L-l = x = L-l [kCenterlie/Cn (L-l)]1/k-1 The typical shape for the distribution curve in the final zone is indicated schematically in Fig. 12 for the simple eutectic case. The solidification proceeds according to Pfann&apos;s&apos; expression until the concentration reaches the maximum solubility in the solid phasc. At this point, the concentration changes abruptly to the eutectic composition and remains at this value for the duration of the solidification. The width of the flat region, and the back reflection of this effect into the concentration curve on subsequent passes, depends upon the ratio of the eutectic concentration to the original concentration, upon the distribution coefficient, and upon the number of passes. Similar effects on the concentration curves in the first zone length would be expected in many systems for which the distribution coefficient is greater than one, and where the maximum solubility is not too much larger than the original concentration. The discussers agree with the authors that the assumption that the liquid is uniform in concentration should be considered with caution. Kneip and Better-ton&apos; have shown, however, that in floating zone refining of zirconium, using induction heating, the distribution of iron agrees with theory which assumes a uniform liquid composition. Hence, in this case, the experimentally realized distribution coefficient agrees with the present phase diagram within the experimental uncertainty. L. Burris, Jr., C. H. Stockman, and I. G. Dillon (authors&apos; reply)—The authors are happy to have received the comments of G. D. Kneip, Jr., and J. 0. Betterton, Jr., which provide additional insight into the zone refining process. It is true that the equations developed are inapplicable if the solute solubility in the solid phase is exceeded. However, this restriction on the use of the equations was clearly stated in the paper. A closer approach to

Jan 1, 1957

By L. A. Bromley, R. L. McKisson

A high temperature calorimeter designed for use up to 1500°K is described and the theory of its operation presented. This calorimeter was used to measure the heats of formation of Na-Sn alloys ranging in composition from tin to Na2Sn. The values tend to support those reported by Kubaschewski and Seith. ONE method of obtaining the heat of formation of an alloy is to measure the heat of mixing of the elements at high temperature. The principal advantage of this method is that the desired quantity is measured directly, while in conventional room temperature methods the differences of the heats of solution of the elements and the alloy in a suitable solvent are measured. A method of improving the accuracy of the high temperature measurements, when the precision of the measurement is lower than that of the heat capacity values for the elements, is to add one component at room temperature to the other at the high temperature, so that part of the heat of reaction is dissipated in heating the cold component to the high temperature. Thus, only a fraction of the heat of reaction is measured, and a result of higher precision is obtained. The limitations of the high temperature technique are that volatile systems cannot be studied, and that many alloys melt at temperatures higher than those at which the calorimetric apparatus operates readily. Nevertheless, a calorimeter operating at 1500°K would be useful in investigating many of the lower melting alloy systems and the low melting mixed oxide systems. A unit designed for these applications was built and is described here. The Na-Sn system was chosen for investigation because the temperature involved, 880°K, would adequately test the operation of the calorimeter. Further, the data reported in the literature for the various alloys of sodium and tin differ markedly, and it was hoped that this investigation would help to fix the values of the heats of formation in this system. Design of Apparatus A detailed discussion of the considerations involved in the calorimeter design is given by Mc-Kisson and Bromley,&apos; and a brief summary follows. Fig. 1 shows a sectional view of the calorimeter. The inner graphite chamber is maintained at constant temperature by means of the circulating molten tin bath in which it is submerged. The tin is contained in a graphite vat. This unit comprises a thermostat whose heat capacity is about 7000 cal per "C. The main heating element consists of a machined graphite spiral with a room temperature resistance of about 1/2 ohm. These parts are separated from the powdered carbon external insulation by the cage, a cylindrical graphite chamber. The electrical insulators and separators, the auxiliary heater spool, and the loading tube liner are made of sintered alumina. The tin vat stirrers, the sample stir-rer, the melt thermocouple well, and the power leads are made of molybdenum. The auxiliary heater is wound with molybdenum wire and serves to compensate for the heat loss up the loading tube. All of the individual components in the high temperature region of the calorimeter will withstand at least 2000°K, and the various contacting materials should easily withstand 1500°K. The external container for the insulating carbon powder is a copper shell upon which copper tubes are soldered to serve as cooling coils.

Jan 1, 1953

By F. H. Buttner, E. R. Funk, H. Udin

Gold wires, 5 mil in diam, are found to creep viscously up to approximately 5.5x106 dynes per sq cm around 1300°K. Beyond this point, an additional slip mechanism appears. The average coefficient in the viscous range at these temperatures is 18.9 ± 7x10 12 poises. This observation and other visual observations made during the experiments agree with Herring&apos;s predictions. EARLY creep studies by Chalmers on single crystals of tin produced some of the first experimental evidence to suggest that metals deform viscously under very light stresses. That is to say, over a small initial stress range up to 150 g per sq mm, the single crystals of tin elongated at a rate proportional to the stress. The proportionality constant between strain rate and stress is by definition the coefficient of viscosity. Chalmers named this range of proportionality the microcreep range. One of the first theoretical attempts to explain the microcreep phenomenon was given by Kauzman,&apos; who applied Eyring&apos;sQ eneral statistical mechanical theory of shear rates to creep data then available. From the rate theory, he deduced the general hyperbolic sine law for shear rate on the assumption that the distortion of the reaction path due to stress is negligible and that the system is an infinite continuum. In order to fit the available data to the equation, it was necessary to assume that creep occurs by shear of rather large blocks of material, rather than by an atomistic shear process as in diffusion. The size of the shear units was shown to increase with increasing temperatures and lower stress, or lower strain rates. In applying the hyperbolic sine law equation to the microcreep data of tin, it was shown by Kauzman that the unit shear blocks became quite small, which suggested to him that microcreep might be a self-diffusion process. Making this an assumption, Kauz- man reworked the rate theory and arrived at an equation where the shear rate is proportional to the stress. In the form of viscosity coefficient, the equation is: o- _ \LkT V = 2qAlA where u is the stress; S, the shear rate; X, the distance in shear direction moved by flow units relative to one another in the unit process; L, the distance between layers of units of flow; T, the absolute temperature; k, Boltzmann&apos;s constant; qAL, a constant proportional to the size of flow units; and kT A, the diffusion coefficient = ------kTe-Q/RT = K X2 h Kauzman applied the expression to molten lead with a fair degree of success, the calculated viscosity being low by a factor of four. For solid lead the result is 5000 times too high. Taking q = 1, and X = dA = L = 21 = nearest neighbor distance, Udin, Shaler and Wulff8 found the equation low by a factor of lo7 for solid copper. On the basis of the discrepancy in lead, Kauzman indicated that microcreep is probably not a simple diffusion process of molecular shear units, but one involving preferential diffusion paths, or even that diffusion in solids does not involve shear at all. Cottrell and Jaswon4 treat the microcreep phenomenon on the basis of slow moving dislocations and apply it to Chalmers&apos; data on tin with fair success. Nabarro Suggested a microcreep model in which mass movement in the direction of pull is effected by the diffusion of holes. The tension on the crystal effectively creates a greater hole concentration at regions near the crystal surfaces perpendicular to

Jan 1, 1953

By W. A. Backofen, G. Y. Chin, W. F. Hosford

The effect of machine stiffness on discontinuous flow and fracture of the 2024 aluminum alloy was studied in tension at 4.2OK. An increase of machine stiffness was found to decrease the amount of elongation and drop in load during discontinuous flow, thereby postponing fracture to larger strains and higher stresses. The possibility of utilizing stiffened tools in deformation processing to suppress shear fracture originating from unstable flow was indicated. The problem of nucleating discontinuous flow and the role of the effective mass of the system in discontinuous flow were also considered. AT low temperatures the plastic flow of metals is often discontinuous, with sudden load drops and elongations.1,3 Basinski1,4 has presented strong evidence that discontinuous flow, at least in aluminum alloys, occurs under nearly adiabatic conditions. During testing the load may drop suddenly and flow become localized when the thermal softening, due to heat generated in plastic straining, is greater than the strain and strain-rate hardening. This instability criterion is more easily satisfied at low temperatures because 1) the volume specific heat is reduced so that relatively large temperature increases are possible in straining, and 2) the flow stress is relatively temperature-dependent. The important role of adiabatic shear in ductile fracture processes has been emphasized,5-1 and consideration has already been given to the influences of thermal and mechanical properties on the tendency of a material to undergo adiabatic shear.17677 By focusing attention on how the mechanical loading system influences low-temperature discontinuous flow, additional insight into adiabatic shear and its effect on fracture may be gained. EXPERIMENTAL PROCEDURE Because of its low thermal conductivity, the 2024 aluminum alloy exhibits a highly consistent discon- tinuous-flow behavior at 4.2°K and was therefore chosen as the material for study. Machined specimens of 0.113 in. diam and 1.125 in. gage length were solution heat-treated at 490°C for 3 hr, quenched into cold water, and immediately immersed in liquid nitrogen until just before testing. Testing was done at 4.2°K by immersion in liquid helium at a crosshead drive rate of 0.03 in. per min. As normally used (hard-machine basis), the spring constant of the testing machine was k = 25,000 lb per in. By inserting beam springs in series with the specimen, this value could be lowered by a factor of about 100. Details can be found elsewhere.? As a result of variable machine stiffness, the actual strain rate ranged from about 3 x 10 5 to 3 x 10-4 per sec from one test to another, as well as within any one test. However, preliminary tests had established that the tensile curves were not altered significantly by this strain-rate variation. Fig. 1 shows a typical load vs plastic-elongation curve for a solution heat-treated 2024 aluminum alloy specimen pulled in the standard hard machine (k = 25,000 lb per in.) at 4.2"K. The elastic extension has been subtracted. Plastic flow proceeded smoothly from yielding at approximately 22,000 psi (load = 220 lb) to a strain of about 4 pct at which point the flow became discontinuous. The magnitude of the load drops as well as the plastic elongation per drop increased with increasing strain until the specimen finally broke abruptly. The load-elongation behavior of a sample tested with a relatively soft machine under otherwise identical conditions is given in Fig. 2. In general, there

Jan 1, 1964

By A. T. Aldred, K. M. Myles

The vapor pressure of chromium over solid V-Cr alloys has been measured by the torsion-effusion method in the temperature range 1450" to 1650°K. The chemical activities as well as the free energies, entropies, and enthalpies of formation of the alloys have hem computed from the vapor-pressure data. The activities of both chromium and vanadium exhibit fairly small negative deviations from Raoult&apos;s law over the entire composition range. The values of the excess entropies and the enthalpies of formation found at 1550°K are considered in terms of the changes in the clzaracteristic properties of vanadium and chromium that occur upon alloying. RECENT interest in the theory and properties of transition-metal alloys has shown the need for relevant thermodynamic data. The present investigation of the V-Cr system was undertaken as part of a more general study of thermodynamic properties of transition-metal alloys. The system was chosen because of the reported complete solid solubility of the components at all temperatures1 and because the difference in magnitude of the vapor pressures of vanadium and chromium allowed a simple effusion technique to be used. The torsion-effusion method was employed to minimize compositional changes in the alloys during the experiments. EXPERIMENTAL Equipment. The torsion-effusion apparatus, shown diagrammatic ally in Fig. 1, consists of a torsion system suspended inside a vertical vacuum chamber whose lower end is surrounded by a high-temperature vacuum furnace. An auxiliary optical lever and screen are used to determine the angle of rotation of the effusion cell. The torsion fiber is an annealed, high-purity, tungsten wire usually between 0.003 and 0.007 cm in diameter and about 43 cm long. The wire supports a concave mirror and a rigid tantalum connector tube. The effusion cell is fastened to the lower end of the connector tube by a dovetailed yoke and har- ness arrangement. The cells, which are 1.27 cm in diameter and 4.4 cm long, were made by electron-beam welding tantalum endcaps onto a 0.025-cm-wall tantalum tube. The two orifices, formed by drilling, have similar areas ranging from 0.011 to 0.031 sq cm. The noninductive sheath-type furnace consists of a single-phase tantalum heating element 6.35 cm in diameter, 15 cm high, and 0.013 cm thick; the element is completely surrounded by radiation shields in an evacuated chamber. The power system includes a 17-kva self-saturating saturable core reactor with an integral magnetic amplifier and a water-cooled, 15-kva, step-down power transformer with a multitap secondary. Temperatures are controlled to within ±1/2o at 1600°K by means of a unit that includes a reference voltage source, a dc electronic null detector, a current-adjusting proportional band relay, and the self - saturating reactor. At 1650°K the temperature variation within the cell, vertically and horizontally, is 3/4oK. Unwanted motions of the torsion system are damped by the movement of an aluminum vane, which is mounted on the connector tube, between the poles of an electromagnet. When not in use the magnet is withdrawn and rotated 90 deg to prevent its interaction with the rotation of the system. Measurements. The vapor pressure, p, is re-

Jan 1, 1964

By R. M. Rose, D. P. Ferriss, J. Wulff

Single crystals of tantalum were grown by multipass zone melting in an electron beam apparatus. Tension tests of these crystals at 4.2 x 10&apos;* per sec-gave a resolved louler yield stress of 7300 psi at with a chisel edge; total uniform deformation increased from 1 to 2 pct at 77°K to over 20 pct at 300°K. This, and slip traces, indicated that deformation is more inhomogeneous at lower temperatures. Deformation occurred exclusively by slip in <III> directions, on planes in the <111> zones. Cross slip was frequent, particularly for those orientations where the resolved shear stress on the cross system was comparable with that on the primary plane. The existence and magnitude of the upper yield point were found to be sensitive to orientation. This effect was related to the circumvention of dislocations which were "locked" by interstitial atoms, by double cross slip, or composite slip, of screw dislocations. Prestrainirg at 300°K did not remove the upper yield point in subsequent tension at 77°K. Also, this treatment was found to cause yield points, where none existed for the unprestrained material. This behavior was also rationalized in terms of the circumvention mechanism. The mechanical properties of polycrystalline tantalum have been investigated by several workers,1"4 and may be summarized by pointing out the following features: a) Sharp rise of yield stress with decreasing temperature below room temperature. b) Response to strain aging at 300" to 400"C. c) Yielding with upper and lower yield-point phenomenon at and below room temperature. d) Low strain hardening below room temperature. e) Reluctance to twin except at very high strain rate. Furthermore, tantalum is ductile at ordinary strain rates as low as 4.2"K.&apos; This feature, in particular, makes tantalum unique among the high melting point, bee transition metals of Groups V and VI in the periodic system. Therefore, a more fundamental and detailed knowledge of the low-tempera- ture deformation of tantalum is required. Since high purity and the absence of grain boundary effects make such a study most productive and unambiguous, the method of electron beam zone melting was selected for the preparation of test specimens. This technique has the further advantage that crystals may be seeded in order to obtain any desired orientation. EXPERIMENTAL The electron beam zone-melting equipment was constructed as a modification of that described by Calverley, Davis, and Lever? All crystals were made by three passes of the molten zone at 4 mm per min to achieve an optimum purity commensurate with economy of time and material. Table I reports the chemical analyses of the starting and refined metal. It will be noted that there remain some 50 to 70 wt ppm of interstitial elements, while all substi-tutional elements have been removed by evaporation. Tungsten is picked up by evaporation of the cathode filament wire. Crystal seeding was normally successful within 3 deg, and the orientation of all crystals are given in the standard stereographic triangle in Fig. 1. Tensile bars were prepared from the crystals by centerless grinding to the shape in Fig. 2. Specimens were then electropolished to remove 10 pct of the diameter in order to remove worked material and to prepare a metallographic surface for subsequent deformation trace observations. All specimens were held in the split bushing grips as indicated in the cross section view of Fig. 2. All tests were made at a strain rate of 2 112 pct per min in an Instron testing machine.

Jan 1, 1962

By M. R. J. Wyllie

Eight laboratory-prepared aqueous base drilling muds representing common mud types, and 15 aqueous base drilling muds sampled in the field, have been used in an experimental investigation of the relationship between the streaming potential developed across a mud filter cake and the differential pressure causing filtrate flow. It has been established that the relationship is of the form, ES = kPy, where Es is the streaming potential, P the differential pressure and k and y are constants for any particular mud system at constant temperature. Beyond a certain minimum thickness this relationship is independent of filter cake thickness. Experiment has shown that both k and y are temperature dependent parameters and that in certain mud systems there is a critical value of P above which the simple relationship Es = kPY ceases to hold. The constant k tends to be a function of the mud resistivity at 77ºF, but the exponent y has not been found to be related to any commonly measured mud property. Certain field experiments are described which serve to demonstrate that the total SP (self potential) developed opposite a formation may be quantitatively accounted for as the algebraic sum of an electrochemical potential and an electrokinetic potential. A chart to permit the simple use of mean solution activities in the interpretation of electrochemical SP data is given and its use described. Various field methods for computing the electrokinetic SP component of the total SP are considered and rejected as being unduly complicated and inaccurate. It is shown that the employment of low resistivity drilling muds is essential if optimum accuracy is desired in the use of the S.P. curve for the purpose of computing connate water salinities by the electrochemical SP method. The use of such low resistivity drilling muds is accordingly recommended. INTRODUCTION In a previous paper&apos; a quantitative analysis of the electrochemical compovent of the SP (self potential) curve was made and it was shown that the electrochemical* emf, E, could be expressed as E = ZtRT/F In a,/a,, where t is the transference number of the chloride ion, R is the gas constant, T the absolute temperature of the formation water and mud, a, the mean activity of the connate water (assumed to be sodium chloride) and a, the mean activity of the mud (as sodium chloride). The essential accuracy of this expression was confirmed by an investigation 2 of the SP kicks opposite sands of known water salinity. The logs examined had been routine runs in oil wells in a number of Mid-Continent states. Further confirmation of the original analysis of the electrochemical SP is implicit in the paper by Tixier3 wherein a relationship between the SP and the ratio of connate water and mud resistivities, based only on field data, is given. Allowing for the fact that mud and connate water resistivities were used instead of activities, and that electrokinetic effects were ignored, the constant reported by Tixier is essentially 2tRT/F. The error involved in the universal substitution of resistivities for activities will receive further reference below. Possible reasons for the fact that the electrochemical properties of shales do not appear to be significantly dependent upon either the nature or the quantity of cation exchange materials, such as clays, they contain has been considered at some length by Wyllie and Patnode.4 In the same paper, the probable effects of shale thickness and compaction on electrochemical efficiency, and hence the inherent difficulty of obtaining reliable laboratory-scale data, were also pointed out. However, it is

Jan 1, 1951

By M. R. J. Wyllie

Eight laboratory-prepared aqueous base drilling muds representing common mud types, and 15 aqueous base drilling muds sampled in the field, have been used in an experimental investigation of the relationship between the streaming potential developed across a mud filter cake and the differential pressure causing filtrate flow. It has been established that the relationship is of the form, ES = kPy, where Es is the streaming potential, P the differential pressure and k and y are constants for any particular mud system at constant temperature. Beyond a certain minimum thickness this relationship is independent of filter cake thickness. Experiment has shown that both k and y are temperature dependent parameters and that in certain mud systems there is a critical value of P above which the simple relationship Es = kPY ceases to hold. The constant k tends to be a function of the mud resistivity at 77ºF, but the exponent y has not been found to be related to any commonly measured mud property. Certain field experiments are described which serve to demonstrate that the total SP (self potential) developed opposite a formation may be quantitatively accounted for as the algebraic sum of an electrochemical potential and an electrokinetic potential. A chart to permit the simple use of mean solution activities in the interpretation of electrochemical SP data is given and its use described. Various field methods for computing the electrokinetic SP component of the total SP are considered and rejected as being unduly complicated and inaccurate. It is shown that the employment of low resistivity drilling muds is essential if optimum accuracy is desired in the use of the S.P. curve for the purpose of computing connate water salinities by the electrochemical SP method. The use of such low resistivity drilling muds is accordingly recommended. INTRODUCTION In a previous paper&apos; a quantitative analysis of the electrochemical compovent of the SP (self potential) curve was made and it was shown that the electrochemical* emf, E, could be expressed as E = ZtRT/F In a,/a,, where t is the transference number of the chloride ion, R is the gas constant, T the absolute temperature of the formation water and mud, a, the mean activity of the connate water (assumed to be sodium chloride) and a, the mean activity of the mud (as sodium chloride). The essential accuracy of this expression was confirmed by an investigation 2 of the SP kicks opposite sands of known water salinity. The logs examined had been routine runs in oil wells in a number of Mid-Continent states. Further confirmation of the original analysis of the electrochemical SP is implicit in the paper by Tixier3 wherein a relationship between the SP and the ratio of connate water and mud resistivities, based only on field data, is given. Allowing for the fact that mud and connate water resistivities were used instead of activities, and that electrokinetic effects were ignored, the constant reported by Tixier is essentially 2tRT/F. The error involved in the universal substitution of resistivities for activities will receive further reference below. Possible reasons for the fact that the electrochemical properties of shales do not appear to be significantly dependent upon either the nature or the quantity of cation exchange materials, such as clays, they contain has been considered at some length by Wyllie and Patnode.4 In the same paper, the probable effects of shale thickness and compaction on electrochemical efficiency, and hence the inherent difficulty of obtaining reliable laboratory-scale data, were also pointed out. However, it is

Jan 1, 1951

By D. K. Bose, C. K. Gupta, K. U. Nair

A new approach to processing an indigenously available low grade molysulfide concentrate by chlorination with elemental chlorine in presence of oxygen is reported. Recovery of nickel and copper values associated with the sulfide concentrate by suitably treating the residue obtained after chlorination is also reported. In the chlorination process, a gaseous mixture of chlorine and oxygen in the volume ratio bf 2:5 has been passed at 1.66 x 10- 5 m3/s for 1800 s over a 0.01 kg batch of molysulfide concentrate at a temperature of 573°K. Most of the molybdenum has been volatilized as molybdenum oxychloride which has subsequently been extracted in water. The molybdenum value from the aqueous solution has been recovered in the form of calcium molybdate (CaO.MoO3) by treatment with calcium chloride (CaCI2). In an alternative processing scheme, the molybdenum rich solution has been treated with an oxidizing agent (K2S20f.J) and allowed to boil to recover a major portion of the molybdenum value in the form of molybdic oxide (MOOS). The spent charge obtained after molysulfide chlorination has been mixed with about 1 wt % sodium chloride and heated at 773K under an oxygen atmosphere. The reacted mass has been water-leached to yield a nickel-copper bearing solution with limited iron. The process liquor appears to be well suited for further processing by known hydrometallurgical recovery processes for nickel and copper. In the conventional process of molybdenum extraction, the molysulfide concentrate (-59% Mo) is first subjected to roasting to produce molybdic oxide. The oxide is then further processed in sequential steps involving vacuum distillation, ammonia leaching, and calcination to higher purity prior to hydrogen reduction to metal. In India there is at present some small tonnage production of molysulfide concentrate from a byproduct recovery plant of the M/s. Uranium Corp. of India Ltd. (M/s UCIL), Bihar. Efforts are being made at this laboratory to process the low grade fraction of the concentrate which contains sulfides of copper, nickel, and iron; quartz; and chlorites. Here, the conventional routes involving roasting and vacuum distillation appear unsuitable to produce an acceptable quality of molybdic oxide at high recoveries. Formation during roasting molybdates of some of the impurities present in the sulfide concentrate make subsequent vacuum distillation less efficient. In view of these problems, in earlier work reported from this laboratory the low grade concentrate has been processed hydrometallurgically to P. produce calcium molybdate. Starting from this molybdenum intermediate, processes have also been developed for the production of molybdenum and ferromolybdenum. Chlorination as an alternative to roasting for metal sulfides has been drawing considerable interest. The high reactivity of chlorine, the relatively low temperature of operation, the suitability of application to low grade resources, the convenience of recovering sulfur in non-polluting form, and the purity of chlorides which are separated by distillation all favor chlorination. In recent years, considerable work has been reported on the chlorination of common metal sulfides. In the field of molybdenum extraction from its sulfide resource, use of chlorination technology has been rather limited. Senderoff and Labrie3 were the first to chlorinate molysulfide concentrate with elemental chlorine at about 823°K to molybdenum pentachloride for use in the electrolytic preparation of molybdenum. The only other reported work, by Haver, Uchida and Wong, involved reaction between molysulfide and chlorine at 673°K to recover sulfur. The reaction products were, however, identified as molybdenum pentachloride and sulfur monochloride.

Jan 1, 1979

By R. W. Coughlin, W. U. Ault

Experiments in laboratory and mine have clearly demonstrated the usefulness of radioactivity detection for directly measuring the potassium content of potash ore as mined. This paper presents the results of these tests and documents the design of a system for automatically grading and sorting potash ore on the basis of radiation detection. It is shown how the experimental results in the subject mine lead directly to the design of this kind of an automatic control system. The system is capable of grading the ore with an accuracy of approximately ±2% K20 content or better. Due to the usual stratification of the ore body, mining potash seldom presents an extreme problem of gangue separation. Nevertheless, it is frequently necessary to transport within a potash mine and even hoist to the surface considerable quantities of halite and other valueless materials. Up to recent times it has been customary to recognize and route these materials by simple visual and manual techniques. However, the work reported here clearly demonstrates that it is now practical and economical to improve upon these techniques by continuous measurement1 of the naturally occurring radioactive isotope, potassium-40. It was the purpose of the work reported here to investigate this technique and assess its applicability. LOCALE OF EXPERIMENTS The work described here was carried out in a potash mine in Carlsbad, N.M. At the working face of this mine the potash ore is freed by blasting; it is then transported a short distance by shuttle car to a moving-belt system which conveys it to the main shaft where it is hoisted to the surface. Quantities of gangue which are also produced in the mining operation are disposed of in mined-out sections of the mine where possible. Otherwise, this material which contains only a small percentage of potassium (as K2O) must also be transported by the conveyor-belt system to the main shaft and then hoisted to the surface and discarded. With this situation, any measuring device for automatic control purposes must be capable of clearly distinguishing between gangue containing insignificant amounts of K2O and ore containing larger percentages of the same mineral. The conveyor-belt system transports the material from the mine face to a rotary crusher and then to temporary storage pits at the main shaft. This is shown in Fig. 1. Upon leaving the conveyor belt the material enters either one of the two storage pits according to the position of a manually operated gate. It was decided that all experiments should be carried out at the conveyor belt between the crusher and gate with a view to the possibility of providing a signal which could operate the gate automatically. THEORETICAL BASIS AND LABORATORY EXPERIMENTS In principle it is possible to grade potassium-bearing ore on the basis of radioactivity. Natural potassium contains 0.012% K40, which is radioactive with a half-life of 1.3 x 10&apos; years. Although about 89% of the K40 disintegrates to Ca40 by beta decay, the other 11% changes to Ar40 by electron capture and the emission of gamma rays. Unlike the ß-rays which are readily absorbed in the first few millimeters of ore surrounding the disintegrating nucleus, the y-ray photons will escape from an ore sample several inches in size. A detector rigidly mounted under a conveyor belt loaded with potash ore will intercept some constant fraction of all the photons emitted from the ore within its field of view. Under these

Jan 1, 1968

United Engineering Trustees, Inc. GEORGE D. BARRON WILLIAM H. BASSETT R. M. ROOSEVELT The Engineering Foundation GEORGE D. BARRON H. C. BELLINGER E. DEGOLYER Engineering Societies Library Board ROBERT PEELE PHILIP W. HENRY H. K. MASTERS A. B. PARSONS, Ex-officio R. H. SWEETSER

Jan 1, 1932

Truman H. Aldrich &apos;78 W. S. Ayres &apos;73 Andrew A. Blair &apos;75 Walter M. Brodie &apos;72 H. M. Chance &apos;74 Fred&apos;k G. Corning &apos;77 Ralph Crooker &apos;81 A. W. Crookston &apos;80 George M. Davidson &apos;81 W. B. Devereaux &apos;80 H. S. Drinker Founder

Jan 1, 1929

By W. C. Leslie, R. M. Fisher, K. G. Carroll

J. S. Bowles and J. K. Mackenzie (Commonwealth Scientific and Industrial Research Organization, Mel- bourne, Australia)—The authors are to be congratulated for giving the first direct experimental proof that the observed macroscopic strain accompanying marten-site transformations is not necessarily a shear. We

Jan 1, 1953

United Engineering Trustees, Inc. GEORGE A. EASLEY H. G. MOULTON A. L. QUENEAU The Engineering Foundation GEORGE D. BARRON E. DEGOLYER A. L. QUENEAU Engineering Societies Library Board H. K. MASTERS A. B. PARSONS, Ex-officio F. F. SHARPLESS H. H. SWEETSER ARTHUR L. WALKER

Jan 1, 1934

By AIME AIME

AN unusually interesting meeting devoted to the discussion of the ways and means of improving coal mining practice, through the larger use of machinery underground, was held in the Auditorium of the Engineering Societies Building on March 11. The meeting was organized by the Materials Handling Division of the A. S. M. E. and held under the auspices of the Metropolitan Section of that Society and the National Coal Association. The New York Section of the A. I. M. E., which had been invited to participate, found itself unable to do so formally because of a conflicting date for its March meeting but informally did its part to aasure the success of the meeting. As a result of the discussion at and preceding the meeting, the National Coal Association, through Walter Barnum, chairman of its research committee, has asked the A. S. M. E. and A. I. M. E. to join the Association in a study of the present problems of the bituminous coal industry. Messrs. Harry L. Gandy, Calvin W. Rice and H. Foster Bain have been selected to act as a committee which shall develop plans for a joint program.

Jan 1, 1926

By W. Joseph Schlitt

The characteristics of successful heap and dump leach operations are first reviewed in a general sense. Then attention is focussed on solution management as the key operating parameter in leaching. The first part of this study includes a detailed conceptual analysis of fluid flow. This identifies the relationships between the flow parameters and the chemical and physical properties of the rock. Then these relationships are extended to practical systems in order to establish optimum application rates and solution distribution methods for heaps and dumps. The study shows that there is a maximum effective application rate, qmax, that can be used without causing solution short circuiting. This rate is a function of the minimum permeability in the heap or dump. The expression for qmax is qmax (gal/ft2/hr)[~]0.9 k (darcies). Here k is the appropriate permeability coefficient. Using this equation, qmax is found to be on the order of 1 gal/ft2/hr (4 cm/hr) for a typical heap or dump leach operation.

Jan 1, 1984