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By H. Y. Hunsicker

A graphic method has been devised for three-di-mensional analysis of hot deformation and for correlating the amount and directionality of the deformation with resulting directional properties. Deformation is evaluated in terms of dimensional change ratios referred to three orthogonal axes. Since all combinations of the three ratios can be represented in a triangular coordinate field with logarithmic scales, a two-dimensional chart of extent of deformation and degree of asymetry is possible. The entire gamut of shape changes from upsetting through flat-rolling to rod-rolling is accommodated. The resulting coordinate system is a base upon which can be represented the properties of the wrought products measured in the directions of the axes employed fir evaluating the deformation. When property data are available for many types and amounts of deformation, a three-dimensional figure can be constructed, and the projection of this figure is referred to as a ''3d'' chart. Experience in using such charts to plan fabricating operations for a variety of thick-section forged and rolled products of heat-treated aluminum alloys has verified its practical value for optimizing directionality relationships. MechANICAL anisotropy of thick section products of heat-treatable aluminum alloys is recognized by producers and users of these products, and the extent of the directional differences is apparent in property tabulations included in handbooks, standards, and specifications.' Attention has also been directed to the existence of important directional differences in the resistance of these products to stress-corrosion cracking. Metallurgical structure factors responsible for these directional differences include, among other possibilities, shape and alignment of grains, voids and nonmetallic inclusions (when present), volume fraction and spatial distribution of secondary phase particles and solid-state precipitates, crystal-lographic textures, and Bauschinger effect. The contributions of the individual factors vary with alloy composition, heat-treated temper, type of working process (forging, rolling, extrusion), and the amount and directional nature of the deformation. In general, the cast ingot used as the starting material for producing these wrought products exhibits only a modest degree of directionality. A monotonic and continuous transition from this nearly isotropic state with progressive hot deformation would appear probable, assuming that the working temperature is sufficiently high to cause continuous dynamic recovery. Several years ago a project was undertaken to evaluate the effects of hot deformation and metallurgical structures on the directionality of thick wrought aluminum alloy products, and the method to be described was developed as an analytical tool in this investigation. DIRECTION NOMENCLATURE The nomenclature system adopted by industry for the three mutually perpendicular directions employed in testing aluminum alloy products includes four terms: "longitudinal", "transverse", "long transverse", and "short transverse". These terms are conventionally related to the external geometry of the product but also by implication to the deformation and resulting metallurgical structure. Occasions arise in which through use of unusual fabricating methods, intentional or otherwise, the structure does not have the usual relationship to external geometry or may be very complex because of inhomogeneity of deformation throughout the piece. The longitudinal direction is generally parallel to the primary rolling direction or to the direction of extrusion. In the case of forging, it is parallel to the direction of maximum extension (not maximum "working" or "flow", as frequently stated). The term transverse is applied to any direction perpendicular to the longitudinal direction in a product having symmetry about the longitudinal axis, and generally, although not always, the deformation to produce these forms is nearly symmetrical in the transverse plane. This term then may be applied to a round, square, hexagon, or other polygonal, symmetrical shape produced by extrusion or rolling or by forging, if produced by a simple, symmetrical drawing procedure. The type of microstructure generally associated

Jan 1, 1970

By H. H. Evinger, M. Muskat

A methoD of calculating productivity factors for oil, gas, and water systems in the steady state is presented as an illustration of the quantitative application of the fundamental data on the flow properties of heterogeneous fluid systems. While the numerical results of the calculations cannot be applied directly to field conditions, because they are based on permea-bility data for unconsolidated sands and involve specific assumptions regarding the nature of the reservoir fluids, the methods of analysis and interpretation should havc significance in considering certain specific field situations when the necessary field and laboratory data become available. Moreover, it is felt that even under the idealized conditions to which the numerical calculations refer they should serve to give at least the orders of magnitude of the effects of gas-oil ratio and connate water on observed productivity factors. Within the indicated limitations, the computations imply that the foregoing factors can explain only a part of the apparent discrepancy between the homogeneous fluid productivity factors and those obtained recently in field measurements on the West Coast. IntroductioN Sufficient laboratory research has been carried out in the last several years on the fundamental features of the flow of heterogeneous fluids through porous media to call for consideration of what can be done with this type of information. It has, of course, already led to a, much clearer general understanding of the mechanics of oil production. However, examples of the quantitative application of the results of such laboratory studies are few in the literature. part of the explanation for this fact lies undoubtedly in the lack of sufficient laboratory data relating to practical fluids and sand systems such as would occur ill actual oil reservoirs. However, unless it can be shown that if such data were obtained quantitative applications could be made, serious doubt may be cast upon the desirability of carrying on further extensive experimental research work on fluid flow. The purpose of this paper is to present one approach to the problem of quantitative application of laboratory data to practical field problems. Because the published results on the basic experiments with three-phase fluid systems in porous media are limited entirely to uncon-solidated sands, the numerical applications made here will not pertain directly to any actual field situation. However, they should serve to illustrate what could be done with fundamental laboratory data if they were extended to cover the field of consolidated sands. From this point of view, it is hoped it will serve to encourage further laboratory research on this problem. The particular application to be treated here relates to the calculation of the productivity factors for oil-gas-water systems in the steady state. This specific problem seems especially appropriate for discussion in view of the recent publication by Johnston1 of the results of produc-

Jan 1, 1942

By M. Muskat, H. H. Evinger

A methoD of calculating productivity factors for oil, gas, and water systems in the steady state is presented as an illustration of the quantitative application of the fundamental data on the flow properties of heterogeneous fluid systems. While the numerical results of the calculations cannot be applied directly to field conditions, because they are based on permea-bility data for unconsolidated sands and involve specific assumptions regarding the nature of the reservoir fluids, the methods of analysis and interpretation should havc significance in considering certain specific field situations when the necessary field and laboratory data become available. Moreover, it is felt that even under the idealized conditions to which the numerical calculations refer they should serve to give at least the orders of magnitude of the effects of gas-oil ratio and connate water on observed productivity factors. Within the indicated limitations, the computations imply that the foregoing factors can explain only a part of the apparent discrepancy between the homogeneous fluid productivity factors and those obtained recently in field measurements on the West Coast. IntroductioN Sufficient laboratory research has been carried out in the last several years on the fundamental features of the flow of heterogeneous fluids through porous media to call for consideration of what can be done with this type of information. It has, of course, already led to a, much clearer general understanding of the mechanics of oil production. However, examples of the quantitative application of the results of such laboratory studies are few in the literature. part of the explanation for this fact lies undoubtedly in the lack of sufficient laboratory data relating to practical fluids and sand systems such as would occur ill actual oil reservoirs. However, unless it can be shown that if such data were obtained quantitative applications could be made, serious doubt may be cast upon the desirability of carrying on further extensive experimental research work on fluid flow. The purpose of this paper is to present one approach to the problem of quantitative application of laboratory data to practical field problems. Because the published results on the basic experiments with three-phase fluid systems in porous media are limited entirely to uncon-solidated sands, the numerical applications made here will not pertain directly to any actual field situation. However, they should serve to illustrate what could be done with fundamental laboratory data if they were extended to cover the field of consolidated sands. From this point of view, it is hoped it will serve to encourage further laboratory research on this problem. The particular application to be treated here relates to the calculation of the productivity factors for oil-gas-water systems in the steady state. This specific problem seems especially appropriate for discussion in view of the recent publication by Johnston1 of the results of produc-

Jan 1, 1942

By D. Walton

The effect of small solute additions of Cu on the activation energies for creep A1 single crystals were determined over the range from 78° to 850° K. Below 240°K and above 800°K activation energies were unchanged. Between 240°K and 400°K strain aging causes the creep rate to become vanishingly small and the flow stress was independent of the temperature. Between 500° and 50°K the activation energy was increased to 41,000 cal per mole. NUMEROUS investigationsL have shown that solid solution alloying invariably increases the flow stress. A typical example is documented in Fig. 1. Such increases in flow stress can arise from two general effects: Alloying can increase the long-range stress fields through which dislocations must move by causing appropriate clustering; modification of dislocation densities, and so forth. Alloying can also modify the short-range stress fields that determine the activation energies for thermally stimulated migration of dislocations, such as occurs in some solute atom pinning processes, and so forth. Actually both long- and short-range stress-field effects can occur simultaneously. It was the purpose of this investigation to evaluate the effect of alloying on the short-range stress fields by determining the effect of alloying on the activation energies for creep. The resulting observations also shed some light on the effect of long-range stress fields on dislocation processes. EXPERIMENTAL TECHNIQUE Single-crystal bars (6 in. long 3/8 in. wide and l/4 in. thick) of dilute solutions of Cu in A1 were seeded, so as to provide extensive single slip, with the pole of the tensile axis located in the standard stereographic projection as shown in Fig. 2. Each crystal was grown under an argon atmosphere in a graphite mold containing a large reservoir of molten alloy for the purpose of obtaining rather uniform composition of Cu along the length of the bar. The nominal compositions of the alloys which were produced from 99.99 pct Cu and high-purity A1 containing 0.001 pct Fe and 0.001 pct Si, are given in Table I. Strains, measured by linear variable transformers attached by quartz rods to a 3 in. gage section were sensitive to and the stresses were ap- plied by direct loading of the specimen. Temperatures were determined by thermocouples attached to the gage section of the specimens. Below 400°K the apparent activation energies for creep, Q, were determined by the effect of small, rapid changes in temperature of about + 10°K from T1 to T2 on the corresponding creep rates ?1 and ?2 during primary creep according to where R is the gas constant.' Above 400°K, Q was evaluated from Eq. [1] for the secondary creep rate using temperature changes of about ±20K. A typical set of results is shown in Fig. 3. RESULTS AND DISCUSSION The previously obtained effect of temperature on the apparent activation energy for creep of single crystals of high-purity A12 is shown by the broken curve of Fig. 4. The datum points on the same graph illustrate the effect of dilute a solid solution alloying with Cu on the activation energy between 600" and 750°K. Each plotted point is the average of not less than five independent test values between 600° and 750°K and not less than three at other tempera-

Jan 1, 1962

By G. G. Marino, J. W. Mahar

This paper provides an understanding of the behavior and potential damage of homes resulting from sag-type mine subsidence. This is done with extensive research of numerous case histories in Illinois collected by the authors. The house response to subsidence-induced ground displacements are summarized and evaluated. A damage level criteria, specifically developed for residential structures, is presented based primarily on repair costs. Damage levels and the associated subsidence profile characteristics for each case history are compared.

Jan 1, 1986

By D. B. Crouch, D. A. Poulter

The engineering and metallurgical assessment of the McLaughlin Project ore body concluded that an open-pit mine and cyanide leach mill process would be feasible, producing both waste rock and residual mill tailings. As a part of the planning and permitting process, site selection studies were conducted for the tailings and waste rock disposal. The site selection process began with a regional identification of potential disposal sites and proceeded through 1) regional screening, 2) elimination of sites with obvious fatal flaws, 3) qualitative ranking of site evaluation criteria, 4) quantitative ranking of sites, 5) field investigation, 6) evaluations of field data, and 7) selection of preferred sites. Based on this approach of site rankings and field evaluations, tailings and waste rock disposal sites were selected and recommended for the preliminary design phase of the permitting and project development process. The site selection study provided the documentation necessary to justify the use of these sites for waste disposal and enabled Homestake Mining Co. to anticipate and integrate environmental concerns with agency requirements into the planning process.

Jan 1, 1986

By A. G. Taylor, H. P. Ehrlinger, U. C. Tainton

FOR the last 15 years lead has been the standard material for anodes in electrolytic zinc production and it has been generally accepted that this lead should be as free as possible from impurities. Laistl says, "Next in importance to the purity of solution is the purity of the electrodes and tank lining material. The purest lead obtainable should be used for anodes." The same conclusion is expressed by Ingalls2 and by two German investigators who say that experiments have demonstrated that the purer the lead, the greater is its resistance to corrosion during electrolysis.3 Pure lead, however, while the best material hitherto available for anodes, is not entirely free from objection. The plain lead anode gradually disintegrates under electrolysis, so that the life of an anode, say 1/4 in. thick, is frequently not more than two years. Part of the lead from the anode finds its way to the cathode, lowering the purity of the deposited zinc and decreasing the hydrogen overvoltage. The rest of the lead that comes from the disintegration of the anode goes into the manganese dioxide which is precipitated in the cells, rendering unsaleable what might otherwise be a valuable by-product. Yet a further disadvantage of plain lead anodes comes from their tendency to bend or buckle during electrolysis, as a result of intercrystalline oxidation. This makes it necessary to use a fairly aide spacing between anode and cathode to avoid short circuits, and thus leads to a higher power consurnption than would otherwise be necessary. The power consumption is also affected by the high decomposition voltage at a lead peroxide surface.

Jan 1, 1929

By Robert F. Mehl

Jan 1, 1944

By Robert F. Mehl

Jan 1, 1944

By P. L. Weston, S. E. Khalafalla

A systematic study was made by the Bureau of Mines on the effect of so me hypothesized accelerators for the process of wustite reduction in carbon monoxide. When small concentrations of promoter materials in the order of 0.69 at. pct were added to the reducible charge, the rate of reduction to iron was increased. Promotion phenomenon prediction was made in light of a suyface reduction mechanism with the aid of Vol'kenshtein's effect regarding the propagation of crystal lattice disturbances by small amounts of relatively larger interstitial ions. The acceleration produced by a typical promotor, such as potassiunl, increases with protnoter concentration up to a maximum, beyond which the reduction rate decreases. Concentration for maximum promotion depends on the nature and physicochemical properties of the promoter. The extent of reduction rate enhancement is found to be directly proportional to the atomic volume and electronic charge of the additive. DESPITE the enormous volume of literature on iron oxide reduction, very little is reported concerning additive or impurity effects on this important metallurgical process. The beneficial effect bf calcium compound additions on the reducibility of iron oxide sinters has been reported by Tigerschiold,1 vor dem Esche,2 and Edstrom. Doi and Kasai~ found that the addition of lime or limestone to iron ores helps to break up any unreducible compounds, such as fayalite or ilmen-ite. and thus free the combined iron for reduction. Schenck et al. 5 suggested that the increased reduction rate obtained when adding lime could be accounted for by the instability of wustite in the presence of lime. Acid-base slagging reactions resulted in wustite disproportionation according to The dicalcium ferrite formed will yield iron and calcium oxide during reduction. Regenerated calcium oxide dissociates more wustite. This mechanism has been used by Seths and white7 to explain their experimental results. Recently, Strangway and ROSS' attributed the calcium carbonate acceleration of iron oxide agglomerate reduction to increased porosity, both initial as well as that developed during reduction. Aside from calcium carbonate, or oxide, no other promoter was noted in the literature, except for a brief mention by Barrett and woodg on the effect of sodium carbonate and aluminate as activators for the hydrogen reduction of magnetite at 600°C. The present investigation systematically studied a host of other promoters, including calcium and sodium, in an attempt to elucidate the mechanism by which promotion takes place and to fit the results into a simple chemical model. To attain this goal, the effect of promoter physical properties, such as atomic volume, electronic charge, and concentration are related to wustite reduction kinetics in this paper. Wustite reduction to iron, rather than the overall hematite reduction, was chosen since this reaction is known to be the slowest, and hence the rate-deter mining step for the overall iron oxide reduction process. EXPERIMENTAL PROCEDURE Raw Materials and Their Preparation. The pure or impregnated wustite pellets were prepared from minus 400-mesh chemically pure hematite powders. A known weight of hematite was thoroughly and uniformly mixed with a calculated weight of the additive. The mixed paste containing 35 wt pct water was gradually heated from 400" to 1200° C and fired at 1200°C for approximately 4 hr in an air atmosphere. After cooling, the sinter was pulverized to minus 100 mesh and pelletized into minus 4- plus 5-mesh spheres. Pellets were fired, similarly to the paste mix, air-cooled, sized, and stored. An appropriate weight of the charge (20 g) was placed in a zirconia reduction tube maintaining a uniform oxide bed height of 1 cm and a cross section of 7.1 sq cm for all of the test runs. The samples were supported in the vertical reaction tube by a bed of fragmented insulating firebrick plus 3- to 6-mesh alumina beads. The hematite was then transformed to wustite by reduction with a 30 pct CO2-70 pct CO gas mixture at 1000°C in a globar furnace. Complete conversion to wustite was ascertained by a continuous infrared gas analyzer recording the CO-CO2 content of the effluent gas until no carbon monoxide was absorbed from the inlet gas, and inlet-outlet gas analysis remained constant for 30 min. The wustite sample was then reduced with 100 pct CO at 100WC. From the recorded data, an initial rate of reduction was determined by the initial slope of the graph percent reduction vs time. In order to estimate the accuracy of the data, five separate determinations of the reduction curve of pure wustite, under otherwise identical conditions, were performed. The maximum deviation from the average reduction at 14 min amounted to 2 2 pct reduction. This deviation corresponds to 3.8 pct variation based on the percent reduction of the sample. Aiiy impurity effect below the limits of this maximum deviation was considered a spurious result. If the effect exceeded + 4 pct, then it was considered as a positive one. Considerable care was exercised in determining the initial rate from the slope of the initial segments of the curve. Each reduction curve was examined separately on large graph paper and the best tangent to the curve at zero time was drawn. The slope of this tangent was taken as a measure of the initial fractional reduction per minute. Although the time required to reach 50 pct reduction may be of special practical significance, initial rate measurements are invaluable in fundamental studies. These rates provide a measure of the process kinetics on the initial

Jan 1, 1968

By K. BRUCE DAVIDSON

-The North Central Texas area includes the following counties in Railroad Commission of Texas District 7-B: Brown, Callahan, Coleman, Comanche, Coryell, Eastland, Erath, Fisher, Hamilton, Haskell, Hood, Jones, Lampasas, Mills, Nolan, Palo Pinto, Parker, S

Jan 1, 1946

By B. L. Averbach, M. F. Comerford, M. B. Rough

The volume fraction of ß phase was determined in a Ti-6Al-4V alloy by measurements of integrated diffraction intensities. The (0002), and (100)ß diffraction lines were chosen because this combination minimizes the errors resulting from preferred orientation. The difficulties arising from fluorescence radiation were eliminated by use of a diffracted beam monochromator. A specimen quenched from 1475OF (800°C) contained approximately 5 pct ß, but in specimens quenched from higher temperatures no ß was found. The ß phase formed during aging, and in specimens solution treated at 1570oF (855oC) approximately 10 pct ß was present after aging at 1000°F (540°C) for 24 hr. This ß appears to form by decomposition of martensitic a'. ThE kinetics of the reactions which occur during the heat treatment of titanium alloys are complex ' and not completely understood. It has been proposed that hardening occurs in some alloys' on aging by the precipitation of a transition phase w followed by the formation of the stable a and ß phases. It has been proposed for other alloys2 that the a' marten-site decomposes by precipitating finely dispersed a particles. Most investigations have been hampered by the difficulties of determining quantitatively the amounts of the various phases present. This paper is concerned with the measurement of the amount of ß phase by an X-ray method, similar to one developed for the determination of retained austenite. The principal new feature was the use of a mono-chromator in the diffracted beam in order to reduce the fluorescence arising from the sample. EXPERIMENTAL PROCEDURE The experiments were carried out on an alloy of nominal composition Ti-6Al-4V (actual weight percentages: 6.2 Al, 4.1 V, 0.02 Mn, 0.17 Fe, 0.005 H, 0.03 C, and 0.02 N). The material was received as 5/8-in.-diam centerless ground rods in the annealed condition. The heat treatments were carried out in a vacuum of approximately 0.03µHg. The X-ray intensity measurements were made on 3/8-in. thick discs. The surface was prepared by grinding off about 0.060 in. and electropolishing in a solution af 60 ml (70 to 72 pct) perchloric acid in 1000 ml glacial acetic acid with a current density of 0.5 amp per sq cm.q The X-ray determination is based on the proportionality of the diffracted intensity of each line to the volume fraction of the corresponding phase. In calculating the intensities for a powder sample it is assumed that a large number of grains con- tributes to the diffracted intensity and that the grains are oriented at random. The presence of preferred orientation introduces serious errors in the relative intensities. The material used in this investigation exhibited a strong preferred orientation, which could not be removed by heat treatment. Other investigators have also found that preferred orientation may be retained after phase transformations. Glen and pugh5 performed a detailed analysis of the randomness expected after several allotropic transformations, but stated that this is not observed. Burgers,6 and Burgers and Ploos van Amstel,7 found that, in zirconium, the original orientation is retained after two phase transformations. Newkirk and Geisler8 observed similar behavior in titanium. On the basis of this evidence, it appears that, in the absence of plastic deformation, textures present in annealed titanium alloys are retained. Heating an a-ß alloy to the all-ß region and subsequent cooling to room temperature do not make the orientation of the mar-tensite different from that of the original a phase. In the present investigation it was possible to take advantage of the crystallographic relationships involved in the martensitic transformation to minimize the errors associated with preferred orientation. The relative orientation for titaniu-m marten-site9 takes the form (0001), 11 (110)ß; [1120], 11 [lll]ß. The same relationship has been proposed for zirconium' and certain titanium-base alloys.10-12 Additional sets of approximately parallel planes have been determined for titanium-nickel alloys." The influence of preferred orientation can be minimized by comparing intensities from parallel planes in the two related phases. If it is assumed that each family of planes in a given phase is equally well populated, the effect of preferred orientation can be eliminated by using the normal multiplicity for the family of planes since each set of parallel planes is equally preferred for any orientation of the sample relative to the X-ray beam. The most suitable combination of reflections in the Ti-6A1-4V alloy appeared to be (0002), and (110)ß It must be recognized that the ß formed during aging of the Ti-6A1-4V alloy is a precipitate rather

Jan 1, 1960

By James K. Gluck, William E. Galloway, Gary E. Smith, John P. Morton, Christopher D. Henry

INTRODUCTION Surface mining and in situ leaching of uranium have the potential to alter ground-water quality around mines and leach sites. Of particular concern is the fate of uranium and its associated trace elements: molybdenum, arsenic, and selenium. We wish to under- stand the natural processes that control trace element concentrations in ground water and how these processes will influence dispersion of the elements from a mineralized zone, both naturally and during and after mining or restoration. For example, it is commonly recognized that the trace elements are soluble in oxidizing ground water but are insoluble, and can be precipitated, in reducing ground water. Thus oxidizing, metal-bearing water leaving a deposit could re- enter reduced ground, causing the water to be re- reduced and the trace elements to be, reprecipitated. In a sense, this is recreating the original mineralization process. To accomplish the above goals, we have (1) examined the theoretical controls of concentrations based on the available geochemical and thermodynamic data, (2) determined the major ion composition and oxidation-reduction status of Oakville waters because of the influence of these factors on trace element solubility, and (3) determined trace element concentrations and distribution in Oakville ground water. The last approach is used to evaluate how well actual behavior follows predicted behavior. This report focuses on two elements, uranium and molybdenum, because they exemplify the results obtained. The report also is restricted to a regional study of Oakville ground water. Results of more de- tailed study in and around major uranium districts in the Oakville and much of the raw data that support the conclusions in this report are presented in Galloway, Henry and Smith (1980). This report is part of that larger study, which concerned the depositional systems, hydrology, and geochemistry of the Oakville. The U.S. Environmental Protection Agency funded the study, under grant numbers R-805357-01 and R-805357-02. Theoretical controls were determined by reviewing the available literature on aqueous chemistry and behavior of uranium and molybdenum. To aid in under- standing water chemistry, Oakville water analyses were run through a modified version of the computer model WATEQF (Plumer, Jones, and Truesdell, 1976). WATEQF calculates speciation of dissolved ions and determines saturation with respect to a variety of minerals. In the discussion below, ion activity products (IAP) are compared with the equilibrium constant (KT) for various reactions and mineral products. Values of log IAP/KT near zero indicate that the water is in equilibrium with a mineral. Values less than -1 indicate considerable undersaturation and values greater than +1 indicate oversaturation. Galloway, Henry, and Smith (1980) give a more complete discussion of the application of this approach to Oakville water chemistry. Eh-pH diagrams have been constructed or adapted from the literature to predict what form -- dissolved ion or stable mineral species -- uranium and molybdenum assume under various conditions. Construction of the diagrams has followed procedures described by Garrels and Christ (1965). This approach is particularly appropriate because the solubility of the elements is Eh-dependent, and Eh varies greatly within the Oakville aquifer. A number of assumptions or approximations are inherent in the use of Eh-pH diagrams and chemical models such as WATEQF and in the interpretation of water chemistry in general. Both Eh-pH diagrams and chemical modeling rely entirely upon available thermo- dynamic data, including free energies of formation and dissociation constants for various reactions. These values are known to varying degrees of accuracy. Most major ions and minerals are relatively well control- led; however, data for trace metals are much poorer. Thermodynamic data are not available for some minerals, and for other minerals, two or more divergent values exist. By necessity, we have relied on the judgment of others to evaluate thermodynamic data. Calculations by WATEQF and constructions of Eh-pH diagrams are based on an assumption of equi1ibrium. Equilibrium may not be comnon in low-temperature aqueous environments; at best, ground-water composi tion may be in a state of dynamic equilibrium, continuously changing due to changes in environmental conditions. Eh-pH diagrams show what phases are stable at equilibrium under given conditions; they do not prove that the phases actually exist. Many minerals persist or form metastably under conditions outside their equilibrium stability field. The kinetics of reactions, which cannot be evaluated here, are important in determining what phases occur. Kinetics may be less of a problem for ground water that travels and evolves slowly through a semihomogeneous matrix than for many other natural systems. Eh-pH diagrams show equilibrium fields only of phases included. They do not indicate anything about stability relative to phases not included in the diagram. WATEQF, obviously, cannot calculate the degree of saturation of a mineral not included in the program or for which the appropriate ions were not analyzed. Thus, a mineral that was not considered may be the most stable phase under a given set of conditions and may control the solubility of a trace element. Also, this study is limited exclusively to in- organic compounds. Organic material is known to be an

Jan 1, 1980

By Thomas L. Wright

Exploration activities were maintained at a high level throughout 1966. Numerous significant discoveries and developments in which geologists played an important part were announced. Although the complete results of exploration activities carried out during the year by private companies have not been announced, the following are among the more important developments that have been made public knowledge. In the western states, exploration for practically all of the metals continued at a high rate. Substantially increased interest in uranium occurred this year, and it is felt by many that a real boom in the demand for uranium may come about in the near future. The reasons have been the more rapid acceptance of atomic power than had been anticipated, and that uranium producers can now sell their product to private interests and even foreign countries. A tremendous demand for uranium is anticipated by many, and this has rekindled exploration activity. On the Colorado Plateau, in Wyoming, and in the area around Grants, N. M., a number of companies have undertaken uranium exploration programs, among which are Kerr-McGee, Homestake, Anaconda and Utah Construction. A new uranium orebody in Texas was brought into production early in 1966 by Susquehanna Western.

Jan 2, 1967

By D. E. Hawk, R. F. Burdyn, F. D. Patchen

Earlier work on a mud separator for barite recovery is extended to the design and construct ion of a rugged field unit. Problems associated with scale-up for field use include the me of dilution water and its effect on capacity, power requirements and pressures developed. Equations for these quantities are derived and applied in maximizing the beneficial effects of dilution and minimizing the power required. Tests on the full-size rotor show that its performance can be predicted by theory. The completed unit is compact and lighter than current decanting types. Its capacity is from 10 to 22 gal/min with corresponding barite recovery efficiencies of 92 to 86 per cent. INTRODUC'TION In an earlier publication a new type of centrifugal device was described for solid-liquid separations.l In that paper an operating equation was derived, and its validity demonstrated in laboratory scale experimentation. Some of the features apparent in this new device seem particularly well suited to the conservation of barite in field drilling-mud systems, hence the development was extended to the design and construction of a field unit. In the present paper the design problems associated with scale-up are considered. A full-scale, rugged self-contained field unit is described, and test results discussed which verify that the performance of the large field unit can be described by a simple operating equation. PRINCIPLE OF OPERATION OF SEPARATOR In principle, the new device is simply a perforated cylinder rotating within a body of fluid which is contained within a stationary case, as in Fig. 1. The frictional drag generated by the rotating cylinder causes part of the fluid to rotate. At the surface of the cylinder, assuming no slip occurs, the angular velocity of fluid and of the cylinder are identical. If there are suspended particles present of greater density than the fluid, the centrifugal force acting on these particles causes them to move radially away from the cylinder at some velocity vp . Where the Stokes settling equation holds, this velocity may be expressed as:2 d2 ?p rw2 If the case is provided with openings at both ends, a suspension can be pumped in at one end at a fixed rate. Part of the suspension can then be removed at a fixed rate at the other end of the case as underflow, and the remainder forced through the perforations and hollow shaft of the rotor to appear as effluent, also at a fixed rate. The radial component of the flow velocity of this stream as it reaches the rotor surface, is simply effluent flow rate divided by cylindrical surface area: Because up is a function of particle size, for some particular particle size, the velocities vp and v, will be equal in magnitude. This is defined as the critical particle size and represents the size above which all particles appear in the underflow and below which all particles appear in the effluent. For this equilibrium condition at the rotor surface, Eqs. 1 and 2 combined give

Jan 1, 1966

By G. Vaux, M. L. Fuller

AN apparatus and procedure for the determination by X-ray reflection of preferred orientation of crystals in rolled metal with the Geiger counter X-ray spectrometer was described by Schulz.' This is an excellent procedure and we have used it continually for several years. In our use of the procedure, two modifications have been made and used during most of this period. One of these provides for automatic scanning and recording of the reflections, and the other makes possible the application of the procedure to coarse-grained specimens and permits measurement of almost all orientations without resort to the transmission technique. The automatic scanning and recording are accomplished by a motor drive of the inner ring of the Schulz apparatus (see R, in Fig. 2 of his paper and R2 in Fig. 1 of this note) in synchronism with the chart recorder of the North American Philips 90" X-ray spectrometer. A rate of 10" per min is used. A scan of 180" is obtained corresponding to poles on the stereographic projection whose locus is a great circle. The modification for coarse-grained material is accomplished by allowing a larger area of the specimen to contribute to the X-ray diffraction. In the Schulz apparatus the incident X-ray beam is confined by a slit system to rays in the plane of the spectrometer. Schulz demonstrated that this restriction of the X-ray beam permits a survey of the X-ray reflections without correction up to about 80" on either side of that specimen position in which the specimen is perpendicular to the plane of the spectrometer. This is the angle + of rotation of the inner ring R2. One of these slits is horizontal and extends across the X-ray source side of the specimen. In the modification this slit is removed, thus permitting greater divergence in the X-ray beam and the irradiation of a larger area of the specimen surface. Fig. 1 shows the apparatus with the motor drive and with the slit removed. Discontinuities in the recorded X-ray intensity plot due to the few participating crystals in coarse-grained metal are much lessened. The increased divergence does not cause reflections from other crystal planes to enter the Geiger counter slit. An important advantage of the original Schulz scheme is thus lost and a system for correction is required. To do this, a compact of atomized copper powder was prepared and tested by the original Schulz method for the absence of preferred orientation. The horizontal slit was then removed and a curve recorded showing the variation of intensity with angle +. In our arrangement the intensity was uniform within the range + equals ±30°. Beyond this the intensity fell off rapidly reaching zero at ±90°. The curve thus produced is then used to correct measurements made on preferred orientation specimens. In practice this is accomplished by constructing from this calibration curve a family of curves which, as a transparency, can be superimposed on the recorder chart to read corrected intensity directly. Not only does this method permit the handling of coarse-grained material but it also makes possible the plotting of intensities almost to the circumference of the stereographic pole figure projection. Thus, nearly the entire pole figure can be plotted without the necessity of using the transmission technique. Moreover, intensities are much greater, an advantage when surveying crystal planes of poor reflecting power.

Jan 1, 1954

By E. M. Cox, A. S. Skapski, N. H. Nachtrieb, M. C. Bachelder

As a result of using copper-containing scrap in the steelmaking process, the copper content of steels has been steadily increasing for years. Consequently the possible role copper may play in the steelmaking process and in the finished product begins to attract the metallurgists' attention. Some time ago one of the present authors forwarded the idea—based on the results of the analysis of nonmetallic inclusions extracted electrolytically from steels—that sulphur in plain carbon steels is distributed mainly between copper and manganese, the amount of iron sulphide being very small; and that, consequently, the problem of copper and that of sulphur in steel cannot be treated separately.' At the time of the publication of the quoted paper little was known about the relative affinities of copper and manganese for sulphur at high temperatures except that at moderate temperatures (below 1000°C) the affinity of manganese for sulphur is much greater. To gather more experimental data on this subject, the present authors undertook the investigation of the equilibrium constants of the reactions: 2Mn(8 or 1) + S2(g) = 2MnS(s) 4Cu(s or 1) + S2(g) = 2Cu2S (S or I)* 2Fe(s) + S2(g) = 2FeS (s or 1) over a range of temperatures wide enough to establish the dependence of these equilibrium constants on temperature. From the equilibrium constants (K = l/Ps2) the free energy of formation (affinity) can be calculated from F° = -RTln 1/PSt (1) where the standard conditions chosen are: 1 atm of sulphur pressure and the activities of condensed components equal one. The decomposition pressure, Ps2, of sulphur over the respective sulphides is too small to be measured directly, but there is a way of eliminating this difficulty by measuring the equilibrium constant of the reaction between the sulphide and hydrogen. From the latter and from the equilibrium constant of the thermal dissociation of H2S we then calculate Ps2 for the respective sulphide. 2Mn + 2H2S = 2MnS + 2H, 2H2 + S2 = 2H2S_________ 2Mn + S2 = 2MnS The numerical values of the equilibrium constant of the thermal dissociation of H2S at different temperatures were taken from Kelley's paper, "The Thermodynamic Properties of Sulfur and its Inorganic Compounds."² In previous experimental work published by Jellinek and Zakowski3 and by Britzke and Kapustinsky4 the equilibrium constants of the reactions Metal sulphide + H2 = H2S + metal were determined by passing hydrogen, at different rates of flow, over the sulphide, analyzing the resulting H2S + H2 mixture and then extrapolating the H2S/H2 ratio (which is a function of the rate of flow) to the zero speed of flow, a method necessarily involving considerable uncertainty. In the present work the equilibrium ratio was actually measured instead of being extrapolated. The apparatus is shown in Fig 1. Experimental Procedure The sulphides were prepared by the following methods: FeS Powdered iron which had been reduced with hydrogen (ferrum reduc-tum) was mixed in stoichiometric ratio with sublimed sulphur and carefully ground. The mixture was put into an alundum crucible, covered with pure sulphur, and the reaction started by touching the mixture with a glowing iron rod. After the reaction was completed the product (still containing some metallic iron) was again ground with sulphur, put into a Rose crucible, covered with sulphur, and heated in a strong current of pure hydrogen. Analysis of the final product showed 62.46 pct Fe and 36.59 pct S. Theoretical for FeS: 63.53 pct Fe and 36.47 pct S. MnS Manganese sulphide (precipitated and carefully washed with distilled water containing H2S) was dried in a Rose crucible in an atmosphere of H2S and heated in a current of hydrogen for 2 hr at red heat. The product was then ground and ignited for several hours at 1000°C in a current of hydrogen sulphide. Analysis showed 64.53 pct Mn and 36.63 pct S. Theoretical: 63.15 pct Mn and 36.85 pct S. Some MnS samples were prepared from metallic manganese and sublimed sulphur by mixing and grinding them and then heating in a current of hydrogen sulphide in an alundum tube.

Jan 1, 1950

By T. P. Papazoglou, N. A. D. Parlee, W. C. Phelps

HE high vapor pressures of metals such as lead, calcium, lithium, bismuth, and magnesium at steel-making temperatures present experimental problems which have thus far rendered it almost impossible to obtain really reliable data for their solubilities in liquid iron. Many investigators have attempted to equilibrate liquid iron in the same crucible with the undissolved liquid phase of such volatile metals. The published results,l-6 although useful, are often questionable on the grounds of not being obtained under true equilibrium conditions. Such information is not always of practical value in any case since the equilibrium vapor pressure is often several atmospheres and steel is not currently made at these pressures. Solubility measurements at lower partial pressures (< 1 atm) appeared to be more practical and easier to make. These data could be used to calculate solubilities at other pressures where Henry&apos;s Law is obeyed, and to estimate solubilities under other conditions of temperature and pressure with useful accuracy. This note outlines the development of a general technique for the measurement of solubilities in systems of this kind. The method involves equilibration of the high-boiling metal at known temperatures with the vapors of a low-boiling metal at known partial pressures. Analyses of quenched samples provide vapor pressure-solubility data and make calculations of alloy thermodynamics possible. The principle involved is similar to the closed-system diffusion-transport method which is difficult to apply with most high-melting liquid metals like iron, due to closure problems. A two-zone horizontal (molybdenum wire element) tube furnace, Fig. 1, provides two constant-temperature zones in a reaction tuve (3/4 in. ID by 1 in. OD by 36 in.). A high-boiling metal sample, 9, introduced in the higher-temperature zone, is maintained at temperature T1, and a volatile metal sample, 7, in the lower-temperature zone, is held at T2. A stream of argon with 10 pct hydrogen is passed via flowmeters, 1, and mixing-drying towers, 2 and 3. through the reaction tube at a favorable flowrate and acts as a carrier gas which entrains vapor from the volatile liquid metal at a specific constant partial pressure. The gas mixture passes through a system of constrictions, 6 and 8, to the higher-temperature zone, establishes intimate contact with the high-boiling liquid sample, 9, and exits through a small condenser tube. The entire system is at (nearly) atmospheric pressure and the volume of carrier gas passed is measured with a wet gas meter. When the high-boiling sample attains equilibrium with the vapor phase, both samples are removed and quenched. Analysis of the high-boiling sample for solute content reveals its solubility for the low-boiling metal at a vapor pressure calculated from carrier-gas volume and either a) weight loss of volatile metal or 6) weight gain of high-boiling sample plus condenser (which collects the undissolved vapors). To test the capabilities of the method, liquid silver at 1403&apos;C was equilibrated with lead vapor at various partial pressures. The relatively simple Pb-Ag system was particularly suitable for uncovering experimental problems and providing the first step toward investigations with more volatile metals and more difficult combinations.

Jan 1, 1965

By W. E. Newell

The basic principles and assumptions involved in D. L. White&apos;s solution5 for ultrasonic wave amplification in piezoelectric semiconductors are summarized. If the gain per unit length is maximized at each frequency without regard to the drift-field power density, the gain increases linearly with frequency. Therefore it would seem that very high gain is possible for frequencies in the hundreds of megacycles. However, with present materials the resulting drift-field power density is so large that cooling would be a major problem. For this reason it is more realistic to judge the capabilities of an ultrasonic amplifier in terms of the gain that is possible with a specified power density. In this case the gain at high frequencies does not increase but decreases more rapidly than l/f. The calculation of the gain us frequency at a fixed power level involves the repeated solution of a cubic equation and is therefore tedious. For the purpose of comparing different materials, sufficient accuracy can be obtained from an approximate solution which may easily be plotted as three straight lines on logarithmic graph paper. This method is used to compare the Performances of CdS, CdSe, ZnO, and GaAs. At a power density of 10 watts per cu cm, the first three give maximum gains of 60 to 80 db per cm in the vicinity of 60 megacycles. At the same power density, GaAs has a maximum gain of about 7 db per cm near 150 megacycles. Although an increase in mobility usually increases the gain for a specified power density, it is shown that there is an optimum mobility above which the gain decreases. An approximate expression for the optimum mobility is established. It is well-known that the interaction between charged particles and an electromagnetic wave can be used to amplify the electromagnetic wave. In the conventional traveling-wave tube, electrons in a vacuum are caused to move at a velocity slightly greater than the wave velocity, thereby coupling energy into the wave.&apos; In principle, the same effect would be evident in a solid except that repeated collisions prevent the electrons from attaining a velocity greater than that of an electromagnetic wave. However, the drift velocity of electrons can be made to exceed the velocity of an acoustic wave in a solid. In 1956, weinreich2 noted that the deformation potential provided one means of coupling energy from drifting electrons into an acoustic wave, but the effect was too small to be of any practical importance. It was not until 1961 that White and Hutson demonstrated that the piezoelectric effect provided a strong enough coupling to give appreciable amplification of an ultrasonic wave and awakened wide interest in electron-phonon interactions. Qualitatively the effect may be described as follows. An acoustic wave propagating through a piezoelectric material is accompanied by an electric-field wave. If the vibrations are properly oriented with respect to the crystal axes of a piezoelectric semiconductor, the local electric fields are axially directed and cause bunching of the charged carriers. If the drift velocity of these carriers is less than the velocity of sound, they tend to be dragged along by the acoustic wave. This electroacoustic effect results in a net potential appearing across the material and in attenuation of the acoustic wave. On the other hand, if the drift velocity exceeds the velocity of sound, energy is coupled from the carriers to the acoustic wave and amplification results. Related effects which are being investigated include ultrasonic amplification in semimetals6-&apos; and semi-conductor, and current saturation in piezoelectric semiconductors.&apos;4-17 There are various problems which hinder the immediate application of ultrasonic amplification in a practical device. First, there are the traditional problems encountered in the design of acoustic delay lines: attenuation in the electromechanical transducers, reflected waves (which can lead to self-oscillation in an amplifying device), mechanical tolerances necessary to maintain phase coherence, and so forth. Second, there is the problem of selecting the best material from among the various piezoelectric semiconductors as they become available in single-crystal form with a wide choice of characteristics. This paper deals with the second problem and shows that the most realistic way of comparing materials is in terms of the gain which can be obtained without exceeding a

Jan 1, 1964

By T. D. Yensen, R. K. McGeary

While we have not been primarily interested in the determination of hydrogen in the alloys that we have been dealing with, we arc very glad to cooperate in this symposium on sampling and analysis for hydrogen, as we can never tell when we may find it desirable to perform such analyses. Vacuum-fusion Method Our primary interest has been oxygen and carbon, in the analysis of which we think we have become very proficient. Our oxygen-analyzing apparatus is of the vacuum-fusion type (Fig. I). This employs Dr. Derge&apos;s type of graphite cruciblc and slit sleeve, with graphite powder between, for heat insulation (Fig. 2) supported in a clear quartz bulb connected to the Pyrex glass system by means of a carefully made ground joint. The latter is kept cool by means of an air blast from a circular copper tube surrounding the joint. The crucible is heated by high-frequency induction and the 24 one-gram samples successively dropped in from the horizontal tube at the top by means of a magnet. The gases (H², CO, N2) are passed through the CuO catalyst held at 300°C. (converting CO to CO²I, H² to H²O) and the CO² and H2O frozen out in the main liquid air trap, while N2 is evacuated. At the end of the operation, shown by the termocouple vacuum gauge indicating a pressure of 10-4 mm. Hg, the analyzing system is isolated by means of the mercury cutoffs, and the CO² and H2oare determined by transferring first the CO2 and then the HzO to the small trap at the right. This is done by placing liquid air on the small trap, then removing the liquid air from the large trap for one minute, which is sufficient to evaporate the Co2 and transfer it to the small trap. The CO2 is then measured by closing the mercury cutoff at the extreme right, removing the liquid air from the small trap, warming it up to room temperature, adjusting the mercury level to one of the three marks on the glass tube (corresponding to three volumes calibrated so that I mm. Hg of CO² corresponds to 0.001, 0.002 and 0.010 mg., respectively, of oxygen) and finally reading the pressure. Liquid air is now replaced on the large trap, the mercury cutoff at the right opened, transferring the COz back to the large trap. The cutoff to the pumps is then opened, the liquid air removed for one minute, thus evacuating the CO², the pumps again cut off and the H2 O transferred to the small trap as before, except that it is now necessary to warm the large trap with a Bunsen burner in order to evaporate all the H2O. This requires about three minutes, as the inner tube must be heated to at least 100°C. In order to prevent H²O from being adsorbed on the glass walls, the glass tubing beyond the catalyst (i.e., to the right in Figs. I and 3) is kept heated to about 150°C. by means of Nichrome ribbon as shown in Fig. 3. For a I-gram sample the above amounts of oxygen (0.001, 0.002 and 0.010 mg.) 35

Jan 1, 1945