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By Waynw P. Myers

Electricity, as normally thought of by a layman's definition, is a man- made force that has no color, no odor, is not visible, cannot be heard, yet man can control it and make it perform his work for him. A person dare not cheat on it, for it then will master him. It has laws, rules, and regulations that must be strictly adhered to if it is to perform in the safest, most reliable, and economical manner. In the early days of coal mining the power source was man himself. Later man employed steam and compressed air to reduce his muscle power requirements needed in the extraction of coal. By the turn of the 20th century, electricity had become the most common source of power for the coal industry. Steam and compressed air are still found in use in isolated cases today for specific applications; however, they are rapidly being replaced by electricity. Electrical laws and regulations are quite extensive and somewhat complex for the proper generation and use of electricity. Man-made laws, rules, and regulations for the care and handling of electricity, designed for man's safety, are rigidly enforced by Mine Safety and Health Ad- ministration (MSHA), as well as the various state departments of mines. BACKGROUND Until recent years most underground coal mines used direct current exclusively for all movable and for some stationary equipment. Exceptions were for permanent pumps, tipple, fan, and outside buildings where alternating current was normally employed. However, over 60 years ago there were mines with dual systems. Alternating current was used for cutting machines, drills, and pumps ; direct current for locomotives. There were no other machines as these were hand-loading mines. Later, during early mechanization in the 1920s, alternating current was also applied to loading machines at some mines. Use of dual electric systems then declined until fairly recently when

Jan 1, 1981

By Francis H. Brownell

During the 1920's lead consumption in the United States reached the highest average total ever known. For the ten-year period 1921-'30, it was slightly over 600,000 tons per year, or say 50,000 tons per month, and the price averaged 6.81 per lb. But the I930's witnessed a severe drop in the consumption of lead is in other business activities. The average U.S. consumption for the ten-year period 1930-'40 was slightly less than 380,000 tons per year, or under 32,000 per month, with the average price dropping to 1.191c. per lb. The outlook in early 1939 was for a continuation of this average consumption and price a demand of 35,000 to 40,000 tons per month, and a price level of 4 1/2 to 5c. in the United States.

Jan 1, 1941

By Yoichi Ishida, Ching-Yao Cheng, John E. Dorn

Tile creep behavior of a iron was investigated over the range of temperatures from 375° to 1150°K. Apparent activation energies for creep, obtained by the effect of sudden changes in temperature on the creep rate, revealed the presence of- four distinguishable regions. The creep behavior of a iron in Regions II (480° to 774°K) and 111 (775° to 1045°K) was found to correlate well with a model where the creep rate is controlled by the nonconsevualive motion. of jogged screw dislocations. An anomalous increase in the apparent activation energy fur creep in Region III was found to be in harmony with the known decrease in the free activation energy for self-diffusion over the Curie transformation range. Furthermore, the creep rates in Regions II and III were found to increase with stress due not only to the effect of stress on the activation energy but also to an increase in density of mobile dislocations. The evidence suggests that pipe diffusion along moving dislocations could be a significant factor over the lower temperatures of Region II. ALTHOUGH the creep properties of iron and steel have been of interest to metallurgists for some time and an extensive literature is now available, most of the published information has not produced much toward understanding the fundamental dislocation processes controlling the creep behavior of these materials. Whereas the activation energy for high-temperature creep of metals usually agrees well with that for self-diffusion, Sherby, Orr, and Dorn1 deduced from the data of Tapsell -and c1enshaw2 that the activation energy for creep of Armco iron is about 78,000 cal per mole and more recently Lytton and sherby3 reviewed the data of Jenkins and Mellor4 and found an activation energy for creep of a iron of 80,000 cal per mole. Both values are substantially greater than the activation energy for self-diffusion in a iron. Because of the limited data suitable for purposes of identifying the controlling dislocation mechanisms of creep and the unusually high activation energies for creep quoted above, it was considered desirable to reinvestigate in detail the creep of a iron by more reliable techniques which would provide sufficient data for determination of the creep mechanisms. EXPERIMENTAL TECHNIQUE Creep specimens were prepared from 3/8 by 4 in. iron bar stock of the following composition by weight percent: 0.001 C, 0.0120 0, 0.001 N, 0.004 S, and 0.003 P. The as-received bars were cold-rolled to a thickness of 0.100 in., annealed under argon for 30 min at 1113°K, cold-rolled to a final thickness of 0.063 in., and machined into tensile specimens having gage section 0.250 in. wide and 1.70 in. long. Finally they were recrystallized under argon at 1113°K. Specimens to be crept above 1060°K were recrystallized at 1173°K. Both recrystallization treatments gave the same reproducible equiaxed ASTM No. 4 grain size. Creep testing was conducted in machines fitted with Andrade-Chalmers arms that maintained a constant stress to within ±0.2 pct of the reported values. Deformation over the specimen gage section was sensed with a linear differential transformer and recorded auto-graphically as a function of time. The strains deduced from these measurements were sensitive to ±5 x 10-5. During creep the specimens were contained in an argon-filled chamber which was immersed in a temperature-controlled molten tin bath. Creep temperatures, as measured by thermocouples attached to the specimen, were maintained to within ±10.25°K of the reported values. For activation-energy determinations rapid changes in temperature of about 12°K were obtained within 30 sec by direct resistance heating of the creep specimen, and maintained to ±1°K of the reported values. Observations of structural details of specimens before and after creep tests were made by electrolytic polishing and etching in acqueous ammonium persulfate. EXPERIMENTAL RESULTS A typical example of the determination of apparent activation energies, Q, by the effect of small changes in temperature is illustrated in Fig. 1. Q is defined by

Jan 1, 1967

By V.K. Zworykin

Throughout its development the science of electronics, like so many other branches of science and industry, has been indebted to the metallurgist. Metallurgy has provided the electronic engineer with conductors to furnish passage for electrons outside of his evacuated tubes: it has developed tungsten and tantalum wires for emitting electrons and various refractory metals and alloys suitable for electrodes, which receive them and guide them within the tube; finally it has supplied ferromagnetic materials both for shielding electronic apparatus from magnetic fields and for forming highly concentrated fields for deflecting electron . Today I hope to show you that electronics has not been altogether ungrateful for this assistance. More specifically, I wish to indicate the role that the electron microscope, a relatively recent product of electronic engineering, is playing even now in the study of metals. Every metallographer is aware that his standard metallographic microscope will not reveal structural detail involving separations smaller than a certain fraction —at the very best a tenth—of a micron. This limitation, he knows, is a consequence of the fact that the wave length of the light employed for forming the image has this order of magnitude. It is, thus, a property of all light microscopes. TO overcome it, a different imaging medium must be employed, The existence of such a medium became evident when it was demonstrated1 that electrons were affected by magnetic and electric fields with axial symmetry just as light is affected by glass lenses; these fields, or "electron lenses," curve the paths of electrons reaching them from an object located on the axis of symmetry in such a manner that, at some distance from the lens, a true image of the object is formed. Furthermore, although a wave length may . be ascribed to electron beams just as to light, this wave length is much shorter; for electrons accelerated through a difference of potential of 50 kilovolts, the wave length is only about one hundred-thousandth of that of visible light. Actually, the elcctron microscopes of today resolve detail one hundred times as fine as light microscopes; if the maximum useful magnification of the latter is taken to be a thousand, that of electron microscopes is one hundred thousand. The Electron Microscope Since electrons are readily scattered and absorbed by matter, specimens to be observed in the electron microscope must be prepared to be less than one micron in thickness; furthermore, the interior of the microscope must be carefully evacuated to prevent collisions between the clectrons and the molecules of the air. Finally, as already mentioned, the lenses are formed by axially symmetric magnetic or electric fields, and not by any material medium such as glass. Apart from these basic differences, the electron microscope closely

Jan 1, 1943

By V. K. Zworykin

Throughout its development the science of electronics, like so many other branches of science and industry, has been indebted to the metallurgist. Metallurgy has provided the electronic engineer with conductors to furnish passage for electrons outside of his evacuated tubes: it has developed tungsten and tantalum wires for emitting electrons and various refractory metals and alloys suitable for electrodes, which receive them and guide them within the tube; finally it has supplied ferromagnetic materials both for shielding electronic apparatus from magnetic fields and for forming highly concentrated fields for deflecting electron . Today I hope to show you that electronics has not been altogether ungrateful for this assistance. More specifically, I wish to indicate the role that the electron microscope, a relatively recent product of electronic engineering, is playing even now in the study of metals. Every metallographer is aware that his standard metallographic microscope will not reveal structural detail involving separations smaller than a certain fraction —at the very best a tenth—of a micron. This limitation, he knows, is a consequence of the fact that the wave length of the light employed for forming the image has this order of magnitude. It is, thus, a property of all light microscopes. TO overcome it, a different imaging medium must be employed, The existence of such a medium became evident when it was demonstrated1 that electrons were affected by magnetic and electric fields with axial symmetry just as light is affected by glass lenses; these fields, or "electron lenses," curve the paths of electrons reaching them from an object located on the axis of symmetry in such a manner that, at some distance from the lens, a true image of the object is formed. Furthermore, although a wave length may . be ascribed to electron beams just as to light, this wave length is much shorter; for electrons accelerated through a difference of potential of 50 kilovolts, the wave length is only about one hundred-thousandth of that of visible light. Actually, the elcctron microscopes of today resolve detail one hundred times as fine as light microscopes; if the maximum useful magnification of the latter is taken to be a thousand, that of electron microscopes is one hundred thousand. The Electron Microscope Since electrons are readily scattered and absorbed by matter, specimens to be observed in the electron microscope must be prepared to be less than one micron in thickness; furthermore, the interior of the microscope must be carefully evacuated to prevent collisions between the clectrons and the molecules of the air. Finally, as already mentioned, the lenses are formed by axially symmetric magnetic or electric fields, and not by any material medium such as glass. Apart from these basic differences, the electron microscope closely

Jan 1, 1943

By S. V. Krusiewski, J. W. Gabelman

Regional metallogenic zones and areas of equal paragenetic range have been interpreted from a compiled metallogenic map. of Mexico. Mineralization gradients of the pattern subsequently identified extend inland from coastal zones of high-temperature mineralization, and join in a central longitudinal zone of relatively low-temperature mineralization, apparently leaving no zonal room for lowest temperature deposits. The striking regional zoning pattern can be correlated with regional deformation gradients of similar position and orientation. The gradients represent at least three major orogenic cycles in two structural belts. Paleozoic structural belts existed along each coast with deformation gradients diminishing inland toward a narrow, central peninsular craton. The Mesozoic-Tertiary Mexican (Cordilleran) belt covered the entire country with a gradient oriented toward the Gulf of Mexico. Most ore deposits in this belt are of Tertiary age, although Tertiary mineralization gradients seem to have "inherited" the pattern left by Paleozoic tectonic gradients. Mineralization gradients can be used to identify the regions most favorable for the occurrence of selected metals. A metallogenic province is characterized by particular proportions of various metals, and the relative proportions can vary from province to province; but within any province the same intensity of mineralization would produce similar deposits in different places. Declining intensity of minetalization produces different kinds and sizes of deposits in zones that are concentrically arranged around sites of strongest rock alteration. On a regional basis, districts of similar average intensity of mineralization occur in zones that generally parallel some tectonic grain with the result that tectonic deformation has been designated a principal cause of mineralization. Variations in the type and intensity of deformation would determine the type as well as size of metal deposits. Mexico is especially favorable for such a study be- cause of its great abundance and variety of epi-genetic mineral deposits in various lithologic, structural and tectonic environments. The concept is also useful in recognizing portions of Mexico favorable for the occurrence of specific metals. METALLOTECTONIC ZONING IN MEXICO Theory: In studies of individual districts and groups of districts throughout North and South America, areal zoning of metal deposits generally seemed to respond to the paragenetic sequence of iron, gold, copper, zinc, lead, silver, antimony and arsenic, gold and fluorite. However, the definition of district zones is greatly obscured by contemporaneous or rhythmic deposition of metals, especially in the middle of the paragenetic range, and by the common superimposi-tions of different generations of metals. Zones could usually be distinguished only for groups of metals, such as early precious metals, base-metal sulfides, sulfosalts and late precious metals. The best defined zoning in a district is normally the spatial separation of the greatest volumes of altered and metallized rocks.' Exceptions are districts representing the high- and low-temperature extremes of the mineralization range where the former creates a matrix for the latter. In most districts the total quantity of alteration products is greatly in excess of, and appears to be roughly proportional to, the total quantity of metallization products. Subsequent to the bicomponent nature of each district, the most important mineralogical feature is the great excess of one to several metals or minerals which results in a district identifiable as one of predominantly gold, copper, lead-zinc, fluorite, etc., although a great variety of other elements may be present. The para-genetic range for the abundant elements in any district is only a portion of the entire possible range for all the elements representing the complete process throughout the region. Early during investigations of this type, it became apparent that the consistent bicomponent character of districts allows two methods for studying epi-genetic mineralization patterns. One is to identify and plot altered rock "pipes,"* which are easily recognizable in the landscape by their anomalous

Jan 1, 1969

By C. E. Ells, A. Sawatzky

The effect of neutron irradiation on tensile properties of the Zr-2.5 wt pet Nb-0.5 wt pet Cu alloy has been evaluated for integrated neutron fluxes up to 3 x 1020 n per sq cm (E > 1 Mev). Specimen temperature during irradiation was normally 300°C. The material was studied both in annealed and in quenched and aged conditions. When the alloy (fab-ricatedfrom sponge zirconium) is quenched from a temperature =40°C below the a + ß/ß transformation and aged 6 hr at 535oC, neutron irradiation up to the maximum studied has little effect 071 reduction in area, although there is a drop in uniform elongation and the yield strength is increased by = 25 pct. Conversely, irradiation of the alloy in an annealed condition can result in much greater changes in properties, with yield-strength increases of up to 200 pet. The dose dependence of irradiation hardening obeys the saturation equntion proposed by Makin and Minter to explain hardening in copper and nickel: Act = C[1 - exp(-Døt)/1/2 A rnodel is proposed to explain the effect of niobium content and metallurgical condition on irradiatiotz behavior. THE Zr-Nb alloys form a class of material susceptible to marked strengthening by quench and age heat treatment. With niobium concentrations as low as 2.5 wt pet, strengths can be developed which are double those of annealed zircaloy-2.1 Since the neutron-capture cross section of the Zr-2.5 wt pet Nb alloy is nearly identical to that of Zircaloy-2, significant gains in power-reactor neutron economy could be obtained by replacing stressed in-reactor components of Zircaloy-2 with the heat-treated Zr-Nb alloy. When the solution heat-treatment temperature is in the high (a + ß) phase, then the tensile properties of the quenched (and aged at 500°C) material have been shown to be relatively insensitive to neutron irradiation.1-3 Addition of small quantities of copper to the binary Zr-2.5 wt pet Nb alloy gives a useful reduction to the corrosion rate in air and carbon di- oxide,&apos; and a ternary alloy of composition Zr-2.5 wt pet Nb-0.5 wt pet Cu was chosen for one component in the Douglas Point Reactor. This application utilizes both the corrosion resistance to a moist air-carbon dioxide environment and the strength developed by a quench and age heat treatment. By suitable choice of solution heat treatment and aging temperatures, tensile properties of the ternary alloy can be made nearly identical to those considered as optimum for the binary alloy. One effect of the copper addition, however, is to give marked changes in the aging kinetics of the alloy.&apos; For this reason, it appeared that neutron irradiation might promote overaging in the ternary alloy, particularly at the elevated service temperature (=300°C). This paper describes the effect of neutron irradiation on the tensile behavior of the Zr-2.5 wt pet Nb-0.5 wt pet Cu alloy in several metallurgical conditions pertinent to its use as a reactor material. The metallurgical conditions included those for which aging occurs in the unirradiated material, and fully annealed conditions for which a higher degree of thermal stability could be expected. 1) EXPERIMENTAL Two batches of alloy were used, both made from sponge zirconium. The fabricator&apos;s analysis of principle constituents showed no significant difference between the two batches, Table I. The rod material was rolled to 1.5 in. diam, and then swaged to final sizes of 0.5 to 0.375 in. diam at nominal temperatures of 785" and 625°C for the AM and AS batches, respectively. Subsequent hydrogen analyses at CRNL confirmed that the hydrogen concentration of the as-received rod was indeed <20 ppm. However, it was found that the (a + ß)/ß transus for the AM material was approximately 25°C lower than that of the AS material, indicating rather more difference in oxygen concentration than given in Table I. Except for a small difference in yield-point behavior, the tensile prop-

Jan 1, 1965

By N. J. Olson, G. W. Toop

A series of equations previously derived for calculating ternary thermodynamic properties using binary data has been applied to the problem of predicting ternary phase diagrams and quaternary excess free energy. The methods are considered to be rigorous for regular ternary and quaternary systerns and empirical for nonregular systems. The equations have been used to predict ternary phase boundaries in the Pb-Sn-Zn system at 926°K and the Ag-Pd-Cu system at 1000ºK. Calculated quaternary excess free-energy values are presented for the Pb-Sn-Cd-Bi system at 773°K. A method for predicting the location of ternary phase boundaries would be a useful supplement to experimental measurements in ternary systems. This has been recognized with the considerable work that has been done to find models to predict or extend thermodynamic properties and phase diagrams in binary and ternary systems1-18 for which direct experimental measurements are limited. With the access to highspeed digital computers and mechanical plotting devices, it is currently rather easy to compare mathematical models with experimental data. The regular-solution model is consistent with systems which exhibit negative heats of mixing, positive heats of mixing, and miscibility gaps, and therefore it is applicable to simple phase diagrams. The purpose of this paper is to illustrate the use of regular-solution equations to predict, empirically, phase equilibria in some types of nonregular ternary systems. Corresponding equations for regular quaternary systems are given and used to calculate empirical quaternary excess free-energy data. METHOD FOR PREDICTING THE LOCATION OF TERNARY PHASE BOUNDARIES USING BINARY DATA Meijerin1,6 has used the regular-solution model to calculate common tangent points to ternary free energy of mixing surfaces and hence to determine phase boundaries in ternary systems involving miscibility gaps. He used the following equation to calculate ternary excess free energy of mixing values: stants characteristic of the binary solutions, and Ni is the mole fraction of component i. An alternate expression which gives for regular solutions as a function of binary values of along composition paths with constant N1/N2, N2lN3, and N1/N3 may also be derived:15 ternary r xs 1 ?c-*n.Ti*.U*. This expression for is more useful for the empirical calculation of ternary excess free-energy values for nonregular systems because actual binary AFXS data may be used in the expression rather than attempting to find suitable constants for Eq. [I]. The results of this feature of Eq. [2] are illustrated in Table I where calculated excess free-energy values for the Ni-Mn-Fe system at 1232°K are compared with experimental data of Smith, Paxton, and McCabe.19 Although regular-solution equations have been shown to give calculated thermodynamic quantities which agree quite well with experiment for single-phase nonregular ternary systems,14,15 care should be exercised in the use of the equations to predict thermo-dynamic properties of multiphase ternary systems in which strong compound formation is suspected. This precaution is consistent with the simple regular-solution model which for negative values of ai_j will indicate a tendency toward compound formation but even for very large negative values of ai-jwill not give multiphase binary or ternary systems involving a distinct stable compound. Hence, calculated ternary free-energy data using Eq. [2] might be expected to vary between being rigorous and poor, in the following order, for ternary systems which are: a) regular solutions, b) nonregular single-phase liquids in which random mixing is nearly realized, c) nonregular single-phase solids, d) nonregular multiphase systems exhibiting miscibility gaps, e) nonregular multiphase systems with binary compounds but no ternary compounds, f) nonregular multiphase systems with highly stable binary and ternary compounds. The calculated data will be expected to be least accurate for the last two cases. The general method adopted in this paper involves two-dimensional plots of ternary activity curves. The principle used is that tie lines indicating two-phase equilibria join conjugate phases a and B for example, for which a1(a) = a1(B), a2(a) = a2(B), and a3(a) = a3(B). Tie lines may be determined by plotting the ternary activities of two components along an isoactivity line for the third component and the unique points where the above equalities hold may be found graphically.

Jan 1, 1970

By Hsun Hu, B. B. Ruth

The rates of migration of high-angle boundaries in zone-refined aluminum crystals rolled 20 to 70 pct in the (110)[i12/ orientation were studied. Following a recovery anneal at an appropriate temperature to stabilize the polygonized structure, boundary migration rates of artificially nucleated grains were measwed isothermally at several temperatures. Results indicate that the rate of boundary migration depends strongly on the amount of deformation and on the cell size of the polygonized matrix, and is related to the driving free energy by a power function. The degree of anisotropy in growth 0.f the re crystallized grains nn&apos;th preferred mientation is independent of deformation; the migration rates of the fast-moving and the slow-moping boundary segments of a gowing grain differ by as much as one order of magnitude. The actir\ation energy fm a grain boundary migration, although nearly the same for both the fast-moving and the slow-moving boundaries for a given deformalion, decreases from 45 to 30 kcal per mole with an increase in deformation from 20 to 70 pct reduction. Re crstallization by the growth of the artificially nucleated grains results in preferred orientation. The Percentuge of&apos; grains favorably oriented for growth increases with increasing deformation. None of these grains corresponds to the ideal Kronberg-Wilson orientation relationship. The observed growth aniso-tropy is discussed in terms of boundary structure. The boundary velocity as a function of the cell inter -facial area, or the driving free energy, is discussed in the light of current theories of boundary migration. It is well established that recrystallization with re-orientation occurs by the migration of high-angle boundaries of strain-free grains. The driving force for this process is provided by the free energy stored in the metal during deformation. A quantitative study of the effect of varying driving force on grain boundary migration in deformed metals has not been possible heretofore, primarily because of: 1) concurrent recovery steadily decreasing the available driving free energy for boundary migration, &apos;-3 and 2) in-homogeneity of strain in the deformed metal.4 Aust and Rutter3 studied grain boundary migration in striated single crystals of zone-refined lead. Although the driving free energy in such crystals remains unaltered during annealing, this method does not provide a range of driving free energies over which measurements of grain boundary migration can be made. In the present investigation, the rates of migration of high-angle boundaries in deformed aluminum zone- refined single crystals were studied at various temperatures, after deformation ranging from 20 to 70 pct reduction by rolling at -78°C in the (ll0)[i12] orientation. The boundary migration rates along different crystallographic directions were determined under steady-state conditions, i.e., in the absence of competing recovery processes or impingement of recrystallized grains growing into the deformed single crystal matrix. Simultaneous recovery was eliminated by suitable anneals prior to the boundary migration measurements. The recrystallized grains, which grew a ni so tropically into the homogeneously polygonized matrix, developed flat boundary segments during early stages of growth. These boundary segments subsequently migrated along a direction approximately normal to the boundary plane into the matrix rystal. Increasing deformation over the range employed was estimated to increase the driving free energy for boundary migration by about five times. The kinetics of the boundary migration process, examined under these conditions, indicate that the boundary velocity is greatly affected by a small change of the driving free energy in the matrix crystals. These results were examined in the light of the current theories of grain boundary migration. EXPERIMENTAL PROCEDURES Single crystal strips (9 by 1 by 0.125 in.) of zone-refined aluminum, were seed-grown by the Bridgman method in a high-purity graphite mold (<lo ppm ash) at 1 in. per hr. Precautions were taken to minimize contamination of the metal during crystal preparation and subsequent handling. Spectrographic analysis of the metallic impurities in the grown crystals is Qven in Table I. The crystals were rolled in the (110)[112] orientation at -78°C to various reductions in thickness, ranging from 20 to 70 pct, in 10 pct increments. The desired reduction was achieved by many rolling passes, each being no more than 0.002 in. To minimize surface friction, the crystal was rolled between two thin layers of teflon. For those crystals rolled more than 40 pct, it was necessary to remove the disturbed surface layers by electropolishing at -5" to -10°C at an intermediate stage of rolling. The edges of deformed crystals were removed by a jeweler&apos;s saw while submerged in alcohol at -78° C to obtain samples of about ? by i in. The distorted metal at the cut edges and the surface layers were then removed by electropolishing, with removal of a minimum of 0.004 in. from each surface. The thickness of the crystals prior to rolling was chosen so that the final thickness was 0.025 in. for all samples. These deformed single crystals were each prean-nealed for 1 hr at an appropriate temperature in the range of 130" to 280°C, depending upon the amount of deformation. The purpose of this preannealing was to

Jan 1, 1970

By K. A. Jackson, J. D. Hunt

A general theory for the growth of lamellar and rod eutectics is presented. These modes of growth depend on the interplay between the diffusion required for phase separation and the formation of interphase boundaries. The present analysis of these factors provides a justification for earlier approximate theovies. The conditions for stability of rod and Lanlellar structures are consitleved in terms of the mechanisms by which the structure can change. The mechanisms considered include both small adjustments to the lnnzellar spacing due to the motion of lamellar faults, and catastrophic changes due to instabilities. It is concluded that stable growth occurs at or near the minimum interface undevcooling for a gizierz growth rate. The conseqrlences of the existence of a diffusion boundary layer at the interface are discussed. The experimental results for the variation of growth rate, undercooling, and Lanzellar spacing are cornpared with the theory. We believe that the theory presented in this paper provides an adequate basis for understanding the complex phenomena of lanzellar and rod eutectic growth. The growth of lamellar eutectics has been the subject of several theoretical and many experimental studies. The foundations for the theoretical work were laid by zenerl and Brandt2 in their analyses of the growth of pearlite. Zener estimated the effect cf diffusion, and took into account the surface energy of the lamellar structure. He found that the lamellar structure could grow in a range of growth rates at a given undercooling provided the lamellar spacing was appropriate for the growth rate. Since pearlite grows with only one growth rate and one lamellar spacing at a given undercooling, there is clearly an ambiguity in the theory. Zener removed this ambiguity by postulating that the growth rate was the maximum possible at the given undercooling. He predicted then that the product of the growth velocity v and the square of the lamellar spacing A should be constant, i.e., A2v = const. Brandt2 started out by assuming that the interface between the lamellae and austenite was sinusoidal. Because of this, the ambiguity encountered by Zener did not arise. Brandt was able to obtain an approximate solution to the diffusion equation, but, since he did not take into account the surface energy, his considerations are incomplete. Tiller3 applied some of these ideas to the growth of eutectics, and proposed a minimum undercooling condition to replace the maximum velocity condition used by Zener. These conditions are formally identical. Hillert4 extended the work of Zener. He found a solution to the diffusion equation assuming the interface to be plane. Taking surface energy into account, and applying Zener&apos;s maximum condition, he was able to calculate an approximate shape of the interface. Jackson et al.5 used an iterative method employing an electric analog to the diffusion problem to refine the calculation of interface shape. It was found that the interface shape calculated from a plane-interface solution to the diffusion equation was negligibly different from the exact solution. The method provided an analog only for eutectics for which the volumes of the two phases are equal, growing from a melt of exactly eu-tectic composition. There has also been considerable experimental work on eutectics, Several experimenters8-10 found that A2v is constant as predicted by Zener.1 Hunt and chilton10 demonstrated that ?T/v1/2 is also a constant for the Pb-Sn system as predicted. Lemkey et al.11have recently found A2v to be constant for a rod eutectic. In the present paper, we present the steady-state solution for the diffusion equation for a lamellar eutectic growing with a plane interface, for the general case, that is, with no restriction on the relative volumes of the two phases, and with the melt on or off eutectic composition. A similar solution is also found for a rod-type eutectic. Expressions are obtained for the average composition at the interface and the average curvature of the interface. These equations for the average composition and curvature are similar in form to those derived by Zener1 and Tiller,3 and provide a justification for some of the approximations made by these authors. The mechanisms by which the spacing in a lamellar structure can change are considered. The important mechanism for small changes in lamellar spacing involves a lamellar fault. Examination of the stability of lamellar faults leads to the conclusion that the growth occurs at or near the extremum.* The insta- bilities which can develop in a rodlike structure are also discussed, resulting in the conclusion that this structure also grows at or near the extremum. Comparison of the conditions for rod and lamellar growth permits a prediction of the surface-energy anisotropy required to produce rods or lamellae for various volume-fraction ratios. The diffusion equation predicts the existence of a diffusion boundary layer at the eutectic interface unless the eutectic has 0.5 volume fraction of each phase and is growing into a liquid of eutectic composition. This boundary layer is such as to make the composition in the liquid at the interface approximately equal to the eutectic composition. This boundary layer permits changes in composition during the zone refining of eutectics. Photographs of the eutectic interface of a growing transparent organic eutectic system have been made. Both the components of this eutectic are transparent organic compounds that freeze as metals do.12 The in-

Jan 1, 1967

By L. D. Jaffe, J. H. Hollomon

The effect of tempering temperature and time upon the properties of quenched steel is clearly a subject of great practical importance, as well as of considerable theoretical interest. It would be very desirable to be able to predict the properties of a quenched steel when given any selected tempering cycle, with a minimum of experimental work upon that heat or even type of steel. Two problems are involved: one consists of relating the structure obtained to the physical properties, and will not be discussed here; the other, with which this paper deals, involves the relations of time, temperature and composition with the structure obtained 011 tempering. Indentation hardness is perhaps the most convenient quantitative measure of the tempered structure, or of what might be called the "degree of tempering." Undoubtedly, it is not an exact measure, and in some cases (as when temper-brittleness occurs) pieces of the same quenched and tempered steel may have widely differing properties at the same hardness. However, hardness has the advantage of being simple to determine and is certainly the most widely used indication of the degree of tempering. Moreover, for fully quenched steels that are not temper-brittle and do not contain retained austenite when quenched, it appears that, in general, if the hardness of the steel is the same, the tensile and impact properties will also be identical, whether a high or a low tempering temperature is used. The tempering charts available in the metallurgical literature usually give the hardness as a function of tempering temperature for only one tempering time. However, in practice, tempering times frequently vary, and a method of converting tempering curves for one time to tempering curves for some other time would be very valuable. It is also advantageous, in determining the tempering treatment necessary for a given part, not to have to temper samples at several temperatures for the time used for the commercial tempering operation. A more satisfactory procedure would be to employ times of the order of 10 to 30 min., rather than 5 or 10 hr., and if possible to use only one temperature. Furthermore, it is frequently desirable, for reasons such as temper-brittleness,* to obtain a given hardness with short times at relatively high temperatures, and it would be convenient to be able to compute without tests the time required to produce this hardness. Remarkably few quantitative studies of the hardness of quenched steel tempered over wide ranges of temperature and time

Jan 1, 1945

By M. Muskat, M. O. Taylor

Theoretical calculations have been made on the performance to be expected of gas-drive reservoirs for various characteristics of the oil and gas and the producing rock. Such performante has been expressed graphically as curves for the reservoir pressure and gas-oil ratios of the production as functions of the cumulative oil recovery. The latter has been expressed in terms of percentage of pore space of the reservoir rock. Such curves automatically give values for the ultimate physical recovery, if the latter is interpreted as the recovery obtained when the reservoir pressure has declined to atmospheric, or to any other pressure chosen as defining the state of practical complete depletion. Calculations of these pressure and gas-oil ratio histories have been made for conditions in which the oil viscosity, the gas solubility and shrinkage, the size of an overlying gas cap, if present, the permeability-saturation characteristics of the rock, and the amount of connate water, have been individually varied, The results serve to show the extent to which the ultimate recoveries are sensitive to the important physical parameters characterizing the oil reservoir. As is to be expected, the ultimate recoveries are found to decrease with increasing oil viscosity. Because of the predominant effect of the oil shrinkage associated with the liberation of the gas in solution, the ultimate recovery will decrease with increasing gas solubility. Increasing gas-cap volumes lead to higher recoveries, although the contribution made by the gas-cap gas is small as compared with the oil expulsion by the equivalent amount of solution gas. As a whole, the oil recovery when expressed in percentage of the pore space is not very sensitive to the details of the permeability-saturation relationship. However, if the rocks possess an equilibrium free-gas saturation, the rise in gas-oil ratio will be retarded, and the &apos;ultimate recovery somewhat increased&apos; The oil shrinkage associated with the liberation of the dissolved gas also leads to the result that as long as the connate water is immobile and the permeability ratio curve for the rock is a function only of the total liquid saturation, the stock-tank oil recovery will be less for a sand containing no connate water than for One with an Original water content as high as 3&apos; per cent. The space voidage in the former case will be somewhat greater, but the effect of oil shrinkage will lead to smaller values for the equivalent stock-tank recovery. These calculations also give data showing how the productivity indexes for the producing wells will vary during the reservoir history. Because of decreasing Permeability to the oil and increasing oil viscosity, the productivity index will fall continuously as Production proceeds, and may finally reach values as low as 10 per cent of the initial productivity index. Introduction In a previous paper1 was developed the basic theory for the prediction of the production histories of gas-drive reservoirs. The data required for the application of this theory included the characteristics of the petroleum fluids, such as the viscosity of the Oil and gas phases, the solubility of the gas in the oil, and the oil shrinkage— all expressed as functions of the reservoir pressure—and the permeability-saturation characteristics of the producing rock, as

Jan 1, 1946

By M. Muskat, M. O. Taylor

Theoretical calculations have been made on the performance to be expected of gas-drive reservoirs for various characteristics of the oil and gas and the producing rock. Such performante has been expressed graphically as curves for the reservoir pressure and gas-oil ratios of the production as functions of the cumulative oil recovery. The latter has been expressed in terms of percentage of pore space of the reservoir rock. Such curves automatically give values for the ultimate physical recovery, if the latter is interpreted as the recovery obtained when the reservoir pressure has declined to atmospheric, or to any other pressure chosen as defining the state of practical complete depletion. Calculations of these pressure and gas-oil ratio histories have been made for conditions in which the oil viscosity, the gas solubility and shrinkage, the size of an overlying gas cap, if present, the permeability-saturation characteristics of the rock, and the amount of connate water, have been individually varied, The results serve to show the extent to which the ultimate recoveries are sensitive to the important physical parameters characterizing the oil reservoir. As is to be expected, the ultimate recoveries are found to decrease with increasing oil viscosity. Because of the predominant effect of the oil shrinkage associated with the liberation of the gas in solution, the ultimate recovery will decrease with increasing gas solubility. Increasing gas-cap volumes lead to higher recoveries, although the contribution made by the gas-cap gas is small as compared with the oil expulsion by the equivalent amount of solution gas. As a whole, the oil recovery when expressed in percentage of the pore space is not very sensitive to the details of the permeability-saturation relationship. However, if the rocks possess an equilibrium free-gas saturation, the rise in gas-oil ratio will be retarded, and the &apos;ultimate recovery somewhat increased&apos; The oil shrinkage associated with the liberation of the dissolved gas also leads to the result that as long as the connate water is immobile and the permeability ratio curve for the rock is a function only of the total liquid saturation, the stock-tank oil recovery will be less for a sand containing no connate water than for One with an Original water content as high as 3&apos; per cent. The space voidage in the former case will be somewhat greater, but the effect of oil shrinkage will lead to smaller values for the equivalent stock-tank recovery. These calculations also give data showing how the productivity indexes for the producing wells will vary during the reservoir history. Because of decreasing Permeability to the oil and increasing oil viscosity, the productivity index will fall continuously as Production proceeds, and may finally reach values as low as 10 per cent of the initial productivity index. Introduction In a previous paper1 was developed the basic theory for the prediction of the production histories of gas-drive reservoirs. The data required for the application of this theory included the characteristics of the petroleum fluids, such as the viscosity of the Oil and gas phases, the solubility of the gas in the oil, and the oil shrinkage— all expressed as functions of the reservoir pressure—and the permeability-saturation characteristics of the producing rock, as

Jan 1, 1946

By R. E. Cook

This paper presents results of a study to determine to what extent errors in estimated free gas saturation affect the results of static pressure calculations from build-up curves in two-phase systems. Use is made of the method of pressure build-up curve analysis developed by Miller, Dyes and Hutchinson1 , with modifications for two-phase flow advanced by Perrine2. Cornhined fluid compressibility of gas-oil mixtures is included, with special attention given to the discontinuity that occurs in fluid compressibility at the saturation pressure and its effect on static pressure calculations from build-up curves. The sensitivity of static pressure calculations to errors in gas saturation is considered over wide ranges of formation and fluid properties and reservoir pressure conditions. It is concluded from this study that for analyses of two-phase pressure build-up curves (I) the use of under-saturated crude compressibility data, even when producing GOR&apos;s are at or near solution values, will result in very significant negative errors in calculated static pressrrre, and (2) except for large values of buildup curve .slope and/or very low crude gravities, rather large errors in calculated gas saturation can he tolerated without .significant effect on calculated static pressures. The conc1usions arc qualified as referring only to the effects of gas saturation and excludc possible errors in the nuumerous other factors that enter into the ancllysis of pressure build-up curves. INTRODUCTION As part of the analysis of basic data for several major Eocene reservoirs in the Bolivar Coastal field (Western Venezuela), it was necessary to analyze a large number of pressure build-up curves for oil permeability and static reservoir pressure. From performance data it became apparent that gravity segregation is very active in these reservoirs. As a result of this performance it was recognized that the free gas saturation within the oil leg of the reservoirs would be small but would be subject to certain errors in calculation due to the inaccuracy of relative permeability data in the low gas saturation region. Since all of the various methods of build-up curve analysis were originally derived for sin- gle-phase, constant compressibility systems, and since the presence of a small but rather indeterminate gas saturation would greatly affect the reservoir fluid compressibility, a study was undertaken to investigate the effect of gas saturation on the results of two-phase pressure build-up analyses. TWO-PHASE BUILD-UP CURVE ANALYSIS The method of analysis used in this investigation is basically that originally developed by Miller, Dyes and Hutchinson1, with modifications for two-phase flow advanced by Perrine2. Miller, et al, showed that the original equation for single-phase permeability away from the well bore, held for two-phase flow except that the calculated permeability is the effective permeability to oil away from the wellbore. This finding was acknowledged by Per-rine, who also presented the equation for effective gas permeability* as Since Eqs. 1 and 2 contain no terms influenced by fluid compressibility, no distinct problem should develop in calculating permeability from two-phase build-up curves. In regard to the calculation of static reservoir pressure from build-up curves in single-phase systems, the modified Miller, et al, method as presented by Perrine is briefly as follows. 1. From build-up curve data, PVT data for the reservoir fluid and the well spacing and sand thickness, calculate the climensionless shut-in time corresponding to the highest value of actual shut-in time (t, hrs) on the straight-line portion of a semi-log build-up curve. Dimenrsionless shut-in time is related to actual shut-in time by the relation, t- 0.000264 kt 2. From a graph of dimension less shut-in time vs dimensionless pressure difference (Fig. 1 1 ) find the value of dimensionless pressure difference corresponding to the value of 7 calculated under (1) above. Dimen-

By H. K. Birnbaum

The effect of 1ow-temperature stabilization anneals on the structure of the 0 phase Au-Cd alloys and on the diffusionless transformations observed in these alloys was examined by X-yay diffraction techniques. A phase separation in the ß-phase region was proposed to account for the experimenta1 results. The effects of quenching from elevated temperatures on the transformation behavior of these alloys were shown to be consistent with the proposed mechanism. IT has been shown that the high-temperature ß phase (CsCl structure) of the Au-Cd alloy system transforms to a phase having an orthorhombic (D2) ß&apos; structurel1-3 for compositions near 47.5 at. pct Cd and a tetragonal (4/m, m, m) ß" structure* in the vicinity of 50.0 at. pct Cd. Both transformations are diffusionless, crystallographically reversible, and occur on cooling at about 60° and 30°C respectively. The temperature interval from the beginning to the end of the transformation is of the order of 5°C in each case. Although the transformations are normally athermal, some of them have been reported to occur isothermally.= wechsler6,7 has shown that the effects of quenching a 49.0 at. pct Cd alloy from elevated temperatures are consistent with the retention of a nonequilibrium number of lattice vacancies. Annealing of these quench effects results in a broadening of the X-ray reflections.8 After a suitable quench, the 47.5 at. pct Cd alloy transforms to a phase having not the p&apos; orthorhombic structure but another structure which has properties similar to that of the ß" tetragonal structure.5.9 This change in the type of transformation has also been obtained after long anneals in the ß-phase region at about 70oC10 The present investigation was primarily concerned with the structural changes accompanying the above transformation phenomena. The change in transformation product and accompanying physical changes during an anneal in the ß phase have been termed stabilization effects. Experimental Procedure —The results reported in this investigation were obtained with the use of a Norelco diffractometer fitted with a temperature-controlled cryostat. The specimen temperature was controlled to better than ± 0.l°C during the measurements. CrKa radiation monochromated electronically with the use of a scintillation counter and pulse height analyzer was utilized. Specimens containing 47.5 and 50.0 at. pct Cd were prepared by sintering filings obtained from homogenized ingots of the proper alloy composition. (Gold of 99.999 pct purity and cadmium of 99.98 pct purity were used). All heat treatments were carried out with the specimens capsulated in vacuum ( < 10 % mm Hg) or in a He-H gas mixture. The quenching technique used in these experiments was to drop the pyrex capsule which contained the specimen from the annealing furnace into water, the temperature of which was controlled. The pyrex capsule shattered on contacting the water resulting in a relatively rapid quench. After the heat treatment, the specimens were mounted in the diffractometer and were left undisturbed in the diffractometer specimen holder during each sequence of measurements. EXPERIMENTAL RESULTS A) Low-Temperature Annealing—The transformations which were considered "normal" for these alloys were those obtained athermally during furnace cooling at approximately 50°C per hr after an elevated temperature anneal. Under these experimental conditions, the specimens were observed to transform to phases having structures whose diffraction patterns could be indexed as the ß&apos; orthorhombic structure for the 47.5 at. pct Cd and as the 0" tetragonal structure for the 50.0 at. pct Cd alloys. The transformation temperatures on cooling were approximately 60" and 30°C, respectively. Under the "normal" conditions both transformations were observed to go to completion, i.e., the entire volume of the ß phase was transformed to the product phase. In some specimens an extremely weak ß 110 reflection was observed at 20°C indicating that a small amount of retained ß was present. The effect of low-temperature annealing on the nature of the diffusionless transformations was examined for the 47.5 and 50.0 at, pct Cd alloy. The specimens were annealed in evacuated capsules at temperatures in the vicinity of 600°C (as specified in Table I) for 24 hr and were then cooled to 100°C at a rate of 50°C per hr. The specimens were then removed from the capsules and mounted in the diffractometer without allowing the specimen temperature to drop below 80°C. Annealing at the low temperatures was accomplished in the diffractometer by means of the cryostat which was mounted around the specimen. During the low-temperature anneals the lattice parameter, integral breadth of the reflections, and ratios of the integrated intensities of the fundamental and super lattice reflections for the 0 cubic phase were periodically determined. After annealing for the required time, the specimens were slowly cooled in the diffractometer and the diffraction patterns were recorded as a function of temperature. The specimens were cooled until the phase transformations were completed, following which the specimens were heated and diffraction

Jan 1, 1960

By Sherwin F. Kelly

THE principal interest in the meeting sings arranged by the Geophysical Committee this year centered around the many papers dealing with the practical applications of geophysical methods to solving geological problems in many other parts of the world. The program Wednesday morning dealt with work in South Africa, Poland, and South America. Rudolph Krahmann&apos;s first paper gave a perspective of the geophysical investigations upon mineral deposits in South Africa. A striking point in his story was the tremendous increase in magnetic work during the last two or three years. This is largely accounted for by the intensive exploration for the extension of the Witwatersrand gold mining area. The author mentioned many surveys in which other methods were used for the search for ores of copper, lead, and zinc, and in the study of water-bearing and oil-bearing structures.

Jan 1, 1935

By S. K. Tarby, W. O. Philbrook

The rate of FeO and MnO reduction from silicate and aluminate slags by carbon-saturated iron is dependent on both slag composition and temperature. Owing to variable stirring rules during- the course of reaction, the reduction processes occur in two stages in stationary graphite crucibles. In the first stage the slirring caused by CO evolution results in forced convection conditions in the slag. As the boiling action subsides during reduction, the flow conditions within the system become those defined by natural convection. Analysis of the data by an unsteady-state penetration model indicates that the rate of reduction is controlled by the rate of cocur-rent flow of&apos; cations and anions from the bulk slag to the interface during both stages of reduction. The hearth reactions of the blast furnace have been extensively investigated from the viewpoint of equilibrium by deductions from controlled laboratory experiments. However, the literature contains relatively few studies that have been directed toward the area of slag-metal reaction kinetics, and the majority of these have been concerned with the rate and mechanism of sulfur transfer between iron and slag. More recently, attention has turned to the kinetic factors in the reduction of oxides from liquid slags. One of the first investigations in this field was conducted by Dancy1 on the reduction of pure liquid FeO and pure liquid Fe3O4 by carbon-saturated iron. The integrated form of the rate equation indicated that the reduction of FeO was of the first order up to 80 pct reduction. Over the initial 30 pct of reduction, the magnetite reaction was also interpreted as a first-order process. The rates of reaction were extremely rapid as indicated by a 30 pct reduction of the liquid magnetite in a time interval of about 1 to 2 sec. Phil-brook and irkbbride&apos; studied the reduction of FeO from a lime-alumina-silica slag by carbon-saturated iron and solid graphite in stationary crucible assemblies. With the use of the differential form of the rate equation, the rate of the reduction reaction was found to be proportional to the second power of the concentration of the reactant FeO for both the slag-metal and slag-graphite reactions. These authors presented a number of comments in an effort to explain the difference between the molecularity of the above reaction and the observed second-order relation. One such argument, recently extended by Wagner,3 was that the rate-limiting step may well be one of transport control. A complete discussion of the proposed mass-transport control mechanism of this reduction reaction will be presented in a later section of this paper. Kinetic studies of the reduction of other oxide species, namely chromous oxide, titania, and silica, have also been reported. McCoy and philbrook4 used rotating crucible assemblies to investigate chromium reduction from Ca0-SiO2-A12O3 slags. First-order kinetic law was obeyed for the slag-metal reduction reaction as determined by the integration method of data analysis. Due to scatter of the data, any dependence of the rate constant on temperature or slag composition was obscured. Concentration-time data for the reduction of titania from blast-furnace type slags under reducing conditions were obtained by Delve, Meyer, and Lander.&apos; The data were too few, however, for a formal kinetic interpretation. Kinetic data for the very slow reaction of silica reduction have been observed by McCoy and Philbrook6 and Fulton and chipman.7 The former experimenters found the reaction-rate constant for silica reduction by carbon-saturated iron to be 20 to 60 times less than the rate constant for chromium reduction. In their work on the reduction of SiO2 in mechanically stirred systems, Fulton and Chipman also found small values for the specific reaction rate and derived a high value for the energy of activation for the reaction. In both of these investigations, the reduction process was assumed to follow first-order behavior. schuhmann8 proposed that the rate-limiting step in this reaction is the diffusion of oxygen from the interface through a boundary-layer film to the bulk metal phase, and Rawling and Elliott9 have reported experimental confirmation of this hypothesis for temperatures below 1600°C. Turkdogan et a1.10 have also concluded that the rate of reduction of silica is a slow process and controlled by the diffusion of oxygen in the metal, but only in the absence of carbon monoxide bubbles at the slag-metal interface. In the presence of bubbles, achieved either by injecting carbon monoxide at the slag-metal interface or by blowing it through the metal and slag, these investigators found a rather rapid reduction of silica which appeared to be controlled by an interfacial reaction involving the de-sorption of silicate ions from the slag-metal interface to the metal phase as silicon and oxygen atoms. In view of the unresolved nature of the kinetics of FeO reduction and the lack of kinetic data for the manganese reaction,

Jan 1, 1968

By Ulf S. Landergren

Diffusion coefficients and marker movements have been determined in brass using welded couples. Three different concentration ranges were employed at 750°C, while a fourth concentration range was measured at 500°, 600°, 700°, and 800°C. Marker displacements toward and porosity development in the high zinc side of the couple were observed in all cases. The results were interpreted as favoring a vacancy diffusion mechanism. IN the large amount of diffusion literature which has accumulated during the past half century, very few experimental data have been presented on body-centered-cubic metallic phases. The impressive combination of experimental and theoretical studies which has given the vacancy mechanism a fairly secure position as the preferred mechanism for most face-centered-cubic metals has no counterpart for body-centered-cubic phases, although the theoretical picture seems to be in a better state than the experimental work. The attempts to select diffusion mechanisms by the theoretical calculation of the activation energy for the various conceivable unit diffusion processes and the energy of formation of the type of lattice defect required have been based on models of two kinds. The first kind utilizes potential functions fitted for certain properties of pure crystalline copper; the second kind is fitted for sodium. The latter is an example of an open metal in which the metallic ion is small compared with interatomic distance,&apos; while the former is characteristic of the larger class of metals in which the ions have diameters about as large as the interatomic distance. brass should resemble copper in this fundamental property. It should be evident that results on the mechanism of diffusion obtained for one of these classes need not necessarily apply to the other. Huntington and Seitz, using a model of the copper type, showed that the activation energies to be expected for interstitial migration or a two-atom direct interchange were much higher than that for vacancy diffusion. Zener pointed out that a four-atom ring rotation would involve an activation energy considerably lower than the two unlikely mechanisms although still higher than the vacancy mechanism in the face-centered-cubic structure. Furthermore, he argued, the four-atom rotation would be relatively easier in a body-centered-cubic lattice and might be competitive with the vacancy mechanism. Paneth showed that a body-centered-cubic crystal-like sodium could form interstitial defects of special type, called a crowdion, by crowding an extra atom into < 111 > directions where the defects would affect a line of about eight atoms. The defect was constrained to move along the defining line. Unlike the face-centered-cubic case, therefore, the theoretical calculations for the body-centered-cubic mechanism do not provide a very clear-cut answer, and the absence of adequate experimental studies is the more serious. This investigation was undertaken for the purpose of obtaining useful information on diffusion in body-centered-cubic phases. brass was chosen for several reasons: 1—the phase field is sufficiently wide at high temperatures to permit the use of diffusion couples with adequate concentration ranges for satisfactory chemical analysis, 2-—thermodynamic activity data are available for the calculation of mobilities from diffusion coefficients, 3—the phase is as close to the theoretical model of the copper -type on which the calculations have been done as any body-centered-cubic metallic phase is likely to be. Measurements of the movements (if found) of inert markers during the diffusion process would indicate that a vacancy or Or mechanism played a major role in diffusion in brass. If no marker movement should be found, a ring mechanism would be indicated but not assured. Experimental Procedure The alloys used in these experiments, listed in Table I with analyses, were supplied by the Naval Research Laboratory. They were from ingots of 3x3 in. cross-section, heated to 760°C, reduced under a

Jan 1, 1957

By H. J. Morel-Seytoux

Methods of predicting the influence of pattern geometry and mobility ratio on water flooding recovery predictions are discussed. Two methods of calculation are used separately or concurrently. The analytical method yields exact solutions in a convenient form for a unit mobility ratio piston-like displacement. A few typical pressure distributions, sweep efficiencies and oil recoveries are presented for various patterns. For non-unit mobility ratio, one may resort to a numerical method, such as that of Sheldon and Douherty. 1,2 Because the domains of applicability of the analytical and numerical techniques overlap, the exact solutions provide estimates of the errors in the numerical procedures. The advantages of the analytical and numerical methods can be combined. To develop a numerical technique as independent of geometry as possible, the physical space is transformed into a standard rectangle. The entire effect of geometry is rendered through one term, the "scale-factor", derived from mapping relations. The scale factor can be calcu-lated from the exact unit-mobility ratio solution for the particular pattern of interest. By this means recovery performances for arbitrary mobility ratio con be obtained for many patterns. A sample of tesults obtained in this manner is presented. INTRODUCTION Pattern geometry and mobility ratio are two major factors in making a waterflood recovery prediction. Because assisted recovery has become increasingly important to the oil industry, pattern configuration and mobility ratio also assume a greater significance in the assessment of the economic value of recovery projects. The influence of pattern geometry and mobility ratio in shaping a recovery curve and on the other quantities of interest to the reservoir engineer is the main subject of this paper. Much effort has already been spent on estimating quantitatively the influence of either pattern or mobility ratio or both on oil recovery. The literature reports many investigations of this nature. 3-9 However, many results or methods of recovery prediction presented in the literature cannot be considered fully satisfactory. Even for unit mobility ratio and piston-like displacement, where analytical solutions are available, the literature shows discrepancies. For non-unit mobility ratio, the divergence in the results is extreme. For infinite mobility ratio in a repeated five-spot, depending on the investigator, the sweep efficiency ranges from 0 per cent to 60 per cent. With respect to the influence of pattern on recovery, only the repeated five-spot has received much attention. Other confined patterns and pilot configurations have received very little attention. Two calculation methods are presented in this paper, either separately or concurrently: the analytical method of potential theory and the numerical method of finite-difference approximation. The analytical method is more restricted in scope than the finite-difference method, but it has the definite advantage of providing exact solutions within its range of applicability. If a unit-mobility ratio piston-like displacement is assumed, the analytical approach is possible. A few typical results are reported in this paper; the detailed description of the general method and of a great variety of results will be the subject of other articles. Fornon-unity mobility ratio, we must resort to a numerical scheme. The numerical technique is that which was described by Sheldon and Dougherty.l,2 It is not limited to piston-like displacement. However, mainly single interface results will be presented here. Because the respective domains of applicability of the analytical and the numerical method overlap, useful comparisons of exact and numerical solutions can be made for a variety of patterns. The advantages of the analytical and numerical approaches can be combined. The reason for the success of this analytical-numerical approach can be summarized in the following two points: 1. The numerical solution for arbitrary mobility ratio can be programmed most efficiently when the physical space in which the displacement actually takes place is transformed into a standard shape; and 2. This can be done with remarkable simplicity whenever an analytical expression for the pressure

Jan 1, 1966

By T. K. Redden

Protective coatings based on the formation of a surface coating of nickel aluminide (NiAl) were applied to the nickel-base superalloys IN 100, SEL 15, and U-700. Coated specimens were exposed to an oxidizing environment at temperatures between 1600 and 2200 F for times up to 1000 hr. The oxidation resistance and stability of the coating were evaluated by weight gain measurements, metallographic examination, and X-ray diffraction study of surface oxides and coating. The composition of the coating and diffusion zone was determined by electron microprobe traverse of samples before and after high-temperature exposure. Intermediate phases formed in the coating and diffusion zone were identified by X-ray diffraction in situ and after electrolytic extraction. The outer coating was found to consist of the inter-metallic compound, NiAl, while the diffusion zone contained MC, M23C6 or M6C carbides, and a phase in a matrix of NiAl + Nidl. Oxidation resulted in formation of an A1203 n&apos;ch scale containing some Tz02. Depletion of aluminum during oxidation resulted in degradation of the outer coating to Ni3Al and the nickel alloy matrix. Diffusion of aluminum into the base metal was found to be slight and did not influence coating life significantly. The o formed in the diffusion zone during coating decomposed during elevated-temperature exposure to form stable carbide phases characteristic of the base metal. Diffusion zone phase changes were found to have no effect on the life of the aluminide coating in the oxidizing envzron?nent. THE oxidation resistance of many high-strength nickel-base superalloys is inadequate for extended exposure at temperatures above about 1600°F. In addition, some applications for these materials require that they be exposed to environments containing sulfur compounds and sodium salts which can cause surface attalk known as sulfidation or hot corrosion. In order to provide the necessary corrosion resistance to the high-strength alloys, protective coatings based on an aluminizing process have been developed. These processes, usually based on a pack cementation technique, result in the formation of a NiAl-rich outer coating layer either during the coating process or by a subsequent diffusion treatment. The performance of the aluminide coatings is affected by interactions between the coating layer and the base metal both during the coating process and during subsequent exposure at elevated temperatures. Knowledge of these interactions is required to guide the development of coatings capable of longer life and improved reliability. Goward et al.&apos; recently reported the metallurgical factors which influence coating per- formance on MAR-M200. The present work is concerned with correlating the interactions and performance of coating compositions on several representative materials. EXPERIMENTAL PROCEDURES Materials. Three cast nickel-base superalloys which are used for turbine buckets in air-breathing engines were studied: IN 100, U-700, and SEL 15. Their chemical compositions are given in Table I. The alloys were vacuum-induction-melted and cast to slabs approximately 0.3 in. thick from which rectangular specimens 0.25 by 0.5 by 1 in. were machined. Coating Procedures. The machined specimens were coated by CODEP processes which were developed at the author&apos;s laboratory. These are based on pack cementation in various media to deposit either aluminum or aluminum in combination with titanium. The coating process which deposits only aluminum is designated CODEP-C, while the CODEP-D process deposits titanium in combination with aluminum. The CODEP-D process was applied only to IN 100. Both CODEP processes are applied at 1950" or 2000°F for 4 hr without need for a subsequent diffusion treatment. An outer coating about 1 mil in thickness is produced by these processes. Test Procedures. Coated specimens were exposed to static oxidation for periods ranging from 24 to 1000 hr at temperatures of 1600" to 2200°F. Terminal weight gain measurements and visual examination were used to evaluate oxidation resistance. including oxide spalling and coating failure. Both as-coated and exposed specimens of each alloy were studied by metallographic examination, electron microprobe analysis (EMA), and X-ray diffraction analysis either of the exposed surfaces or of phases extracted from the coating and diffusion zone. RESULTS As-Coated Condition. The microstructures of as-coated conditions were generally similar, irrespective of base materials or the particular coating process. They are typified by IN 100 coated by CODEP-D as shown in Fig. 1. The predominately single-phase outer layer, area A, Fig. 1, was identified by X-ray diffraction as the intermetallic compound NiA1. The NiAl zone extended inward to the original base metal interface. The diffusion zone, area B, Fig. 1, included carbide phases, a lamellar phase oriented perpendicular to the base metal surface, and a matrix phase consisting of a mixture of NiAl and Ni3Al. The phases in the diffusion zone were electrolytically extracted using a 10 pct HCl in methanol solution at approximately 1.3 amp per sq cm. The extracted phases were found to be M6C, MC, or M=C6 carbides and o as shown in Table I1 for each of the alloys. The d spacings from a typical diffraction pattern are

Jan 1, 1969