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By T. G. Digges, C. L. Vold, M. R. Achter

A study was made of the effect of the growth conditions on the perfection of single crystals of niobium (columbium). Dislocation densities, determined by means of double-crystal diffractometer measurements , were not greatly affected by the method of crystal preparation but could be reduced by annealing treatments. However, the size, sharpness, and tilt angles of the substructures, observed with X-ray reflection macrograph, were sensitive to variations in growth procedures as well as to subsequent thermal treatments. Although the dislocation density was the same in both types, there were more low-angle bound-aries in crystals grown by zone melting than in those prepared by strain anneal. Mechanisms to account for these observations are discussed in terms of dislocation movements. A planned study of the structure-sensitive properties of refractory metals required the use of single crystals of a high degree of structural perfection and, for ease of handling, of large cross section. It appeared that the strain-anneal technique could satisfy both of these requirements. First, crystals grown in the solid state have been reported to be more perfect than those obtained from the melt.' Second, the diameters of rods which may be produced by zone melting should have a theoretical limit determined by specific gravity, thermal conductivity, and surface tension, while the diameter of strain-annealed rods is limited only by practical considerations. Previously it was shown that niobium (columbium) single crystals of 1 in. diam2 may be grown by strain anneal, compared to the 0.5 in. maximum diameter achieved by zone melting, as reported for molybdenum by Belk.3 The current research was undertaken to investigate and optimize the effect of various process variables on the perfection of 1/4 and 1/2-in.-diam niobium single crystals grown by strain annealing and to compare their perfection to those grown by zone melting. Characterization of these crystals was more conveniently accomplished by means of X-ray than by metallo-graphic techniques. EXPERIMENTAL PROCEDURE Specimen Preparation. Zone-melted crystals of 1/4 in. diam were produced by the standard electron-beam zone-melting technique. The swaged and cleaned rods were outgassed, in the solid state at a temperature near its melting point, at a rate of 12 in. per hr, and single crystals were grown by making two molten passes at 2 in. per hr. By maintaining a zone length of 4 to % in., very uniform single crystals several inches long were obtained. For the strain-annealed crystals, an induction heater was used, in preference to other types of heating, to take advantage of the good penetration of large sections. A five-turn coil, 1 in. long, operating at 10 kc and powered by a motor generator, was contained in a vacuum chamber. The rod, suspended from the upper end, was raised through the coil for both recrystallization and crystal growth. In preliminary work single crystals of the same material were also grown with single and multiturn coils powered by a 450-kc generator. A vacuum of 2 X 10-6 Torr was maintained at temperatures up to 2400°C. Starting with electron-beam-melted ingots of 21/2 in. diam, the analysis for which is given in Table I, the material was cold-swaged to the desired cross section of 1/4 and 1/2 in. diam and then recrystallized. The rods were then strained in a tensile machine and converted to single crystals by passing through the induction coil. As with zone melting, control of orientation is possible by the use of special procedures. Other investigators, see for example Williamson and smallman,4 have reported that orientation control may be achieved by a bending technique. In the present work the strained rod is partially lowered through the coil to start the growth of the crystal. Then it is removed and bent at a point in the poly crystalline portion. Finally, it is returned to the chamber and growth is continued "around the corner". This procedure has certain limitations. If the bending operation exceeds the critical strain, recrystallization may take place. Also, the amount of bending which can be imparted to the rod is limited by coil geometry, and up to now has been 10 deg. However, by repeating the bending and growing operations it should be possible to attain any desired orientation. In preparation for X-ray examination, single crystals were sectioned and planed by means of the spark-erosion technique. To obtain the maximum reflected intensity, the (110) plane was exposed for examination. They were then etched 3 to 5 min in a mixture of con-

Jan 1, 1967

By R. L. Dalton, L. A. Rapoport, C. W. Carpenter

Procedures have been developed to study the performance characteristics of unconfined pilot water floods using scaled laboratory models. The effects of operating conditions on pilot performance for variozrs well patterns have been investigated. The limitations of the laboratory model studies are outlined. Relationships between the oil recoveries of pilots and large-scale floods have been established. The applications of model studies to the prediction of large-scale waterflood performance and pilot flood design are discussed. INTRODUCTION Pilot water floods are undertaken to evaluate operational procedures and to gain advance information about the performance of an extensive water flood. In general, however, the performance of a pilot flood is not directly indicative of what can be expected from a large-scale pattern water flood. This difference stems from the fact that the over-all flow configurations are not the same for the two systems. A water flood normally consists of an array of identical well patterns. In such an array, the perimeters of the well patterns are axes of symmetry and act as impermeable boundaries. Thus, an extensive, pattern water flood can be visualized as a repetition of "confined" floods. In contrast, a pilot water flood involving only one or a few well patterns is "unconfined". Here the well patterns are not balanced by other flood units; hence, the perimeter of the pilot area does not act as an effective boundary. Accordingly, only a portion of the fluids injected (and also of those originally contained within the pilot area) is captured by the producers of the pilot. The rest escapes into the surrounding reservoir. This usually causes the amounts of oil and water produced in the pilot to be different from those recovered by a producer in an extensive water flood. Moreover, the recovery observed in the pilot can be expected to be greatly influenced by operating conditions, i.e., by the bottom-hole pressures at the injection and producing wells. The above considerations show that full utilization of pilot test results and reliable prediction of large- scale water floods require a knowledge of the relationship between the recovery performance of confined and unconfined well patterns. To date, only limited basic information is available on the behavior of pilot water floods. Craig, et al,' have investigated the effects of initial gas saturation, oil-to-water mobility ratio, and well damage on the oil recovered from a single, "normal" five-spot pilot pattern (Fig. 1). Rosenbaum and Matthews2 studied the effect of initial gas saturation and mobility ratio on the ratio of production rate to injection rate for various groupings of five-spot patterns. Paulse113 investigated the effect of mobility ratio and distance from the pilot to the edge of the reservoir on the areal sweep in a single "inverted" five-spot (Fig. 1). However, none of these studies considered the effect of operating conditions on pilot flood behavior. Moreover, hardly any of the work to date dealt explicitly with the oil-recovery performance of the pilot floods. The purpose of this paper is to introduce the concept of interrelation between pilot flood behavior and operating conditions, to illustrate this interrelation by means of experimental data and to compare the recovery performances of dif-

By E. P. Abrahamson, S. L. Lopata

A general relalionship between the amount of glide shear (due to slip) and the macroscopic shape change has been developed. Since the deformation can be large, finite strain analysis is employed. In this treatnzent, the shape change is expressed by a deforlnation gradient matrix, F - [axi/aXj/ where X and x refer lo the initial and final positions of a particle. This matrix is readily evaluated in termas of the amounl of glide shear, a , and the direction cosines of the slip-plane normal and the slip direction for a single active slip systena. In the case of deforma tion from slip on several systems, the product F(a) of the several deformation gradient matrices is first calculated. Then, by assuming that the final configuration is reached by a long series of small shears of magnitude a, occurring more or less alternately in the several slip sys- IN problems of crystal plasticity, it is often necessary to relate the amount of glide in the operating slip systems to the macroscopic strain components. This relationship is relatively simple when only small strains are considered. In this case the separate strain contributions from several slip systems are additive. Such a procedure is incorrect in the case of large plastic deformation. To the authors' knowledge, no general treatment of the latter problem has appeared in the literature. In specific instances, Mark, Polanyi, and schmid3 have derived the relationship between glide and axial elongation during tensile pulling of a single crystal when only one slip system is active. A similar relationship for duplex slip was worked out by v. Göler and Sachs.4 Taylor and Elam1 have also studied in detail problems of large plastic deformation. Due to uncertainties as to the slip systems at the time, ! terns, the final deformation gradient matrix can be obtained. Mathematically, the problem is reduced to finding the limit of F(aN as N — m while a — 0 in such a way that the Product Na = a finite conslant designatzng the accumulated amount of shear. It turns out that this limit is simply eafF1, where F, is the matrix whose elements are the coefficients of a in the F(a) twatrzx. Application is made of the present treatment to a fcc crystal of Permalloy compressed on the (110) plane and contrained to elongate in the [112] directzon. In addition, it is shown that one rnay readily obtain from the general analyszs the well-known formulas relating elongation, amount of glide shear, and amount of lattice rotation for crystals deforming by single and double slip under tension. however, they were mainly concerned with proving that slip occurs on {111}(110) systems in fcc metals. The present general treatment arose out of recent investigations of magnetic anisotropy in cold-worked Fe-Ni alloys6 as well as some related problems in strength anisotropy of single crystals.' Detailed application of the general analysis will be provided in the case of a Permalloy single crystal compressed on the (110) plane and constrained to elongate only in the [112] direction. It will be seen that, as expected, the small strain approximation leads to significant errors after moderate straining. It will also be shown that the present general treatment yields the formulas of Mark et al. and of v. Goler and Sachs in those specific cases. GENERAL CONSIDERATIONS Consider a homogeneous deformation in which a material point initially at moves to (xl,xz,x3), both positions being referred to the same set of Cartesian axes. Such a deformation can be

Jan 1, 1967

By D. P. Harris

The construction of a model to associate probability of occurrence of some measure of mineral wealth with the geology for each subdivision (cell) of the area is postulated. The questions (1) are the observations made in reconnaissance geology sufficiently related to mineral wealth to distinguish the cells of high value from those of low value, and (2) can this geology be related mathematically to mineral wealth and probability are answered in a case study of 97,000 square miles in Arizona and New Mexico. Measurements on mineral wealth and geologic variables of 243 cells were made. The geologic variables, valued in counts, percentages and lengths, quantified the theoretical concepts of the model. It was found that multiple discriminant analysis and classification analysis by Bayesian statistics and multivariate normal probability function constitute a two-phase probability model that associates probabilities with geologic information and mineral wealth. The cells of explored area must be allotted the value class indicated by their cumulative production and estimate reserves (given well-defined geological relationships in a mineral wealth area), and a discriminant and classification analysis must be performed in which probabilities of the cell belonging to each of the value groups are generated as a function of the geologic variables. This determines whether high value cells can be distinguished from low value cells by their geology as well as indicating those cells misclassified by the model into a higher value group than warranted by their known mineral wealth. The second use of the model is for extrapolation. It is demonstrated how geologic information on an explored area can be utilized in guiding exploration in an unexplored area. Exploration decisions can be predicted on explicitly determined measures of uncertainty (the probabilities). SUMMARY This study postulates the construction of a model to associate probability of occurrence of some measure of mineral wealth with the geology for each subdivision (cell) of the area. Such a model will distinguish those cells deserving further exploration on the basis of their geology: The basic postulates of this study are as follows: v = Q(R,S,F,A) P(V) = G(R,S,F,A,V), where V = a measure of mineral wealth P(V) = the probability of occurrence of V R = age and type of rock F = rock fracturing A =age of igneous activity and contact relationships. There are really two questions to be answered: 1) are the observations made in reconnaissance geology sufficiently related to mineral wealth to distinguish the cells of high value from those of low value, and 2) can this geology be related mathematically to mineral wealth and probability? In order to answer these questions, an area of about 97,000 square miles situated chiefly in Arizona and New Mexico was selected as a case study. This case study area was divided into 243 cells, each 20 miles square, and measurements were made on mineral wealth and geologic variables. Crude geologic variables valued in counts, percentages and lengths are constructed to reflect the above postulated variables. These measurement variables thus provide quantified values defining the theoretical concepts of the model. It was found that multiple discriminant analysis and classification analysis by Bayesian statistics and the multivariate normal probability function constitute a two-phase probability model that associates probabilities with geologic information and mineral wealth. Given the availability of an area that is well explored and upon which the relationships of mineral wealth to geology can be adequately defined, there are two ways in which the analysis outlined in this paper can prove beneficial. First, the cells of the explored area must be allotted the value class indicated by their cumulative production and estimated reserves, and a discriminant and classification analysis must be performed in which probabilities of the cell belonging to each of the value groups are generated as a function of the geologic variables. Such an analysis determines whether cells of high

Jan 1, 1967

By J. E. Johnson

Charcoal-iron is quantitively so unimportant compared with coke-iron, that its qualitative importance for many industrial purposes is entirely unkriown to many coke-furnace-men, and to the great majority of the inembers of this Institute. To explain this qualitative importance, and explain some of the fact,ors that affect the quality, are the objects of this paper. A brief review of' the commercial conditions governing the charcoal-iron industry is a necessary preliminary to any adequate treatment of the subject. The advent of coke-iron, which transformed the whole iron industry commercially, left intact a limited production of charcoal-iron in the East and South, which has been conducted almays on the basis of high cost and high quality, with correspondingly high selling-price. In the Northwest, particularly in the Lake Superior district, the development has been along totally different lines, for which the close proximity of the great iron-ore deposits and the great forests of that region mere responsible. When the great white-pine forests were removed there were left behind large areas of hardwood and hemlock, to which little attention was paid in the prosperous years of the white-pine industry. But when the latter declined, the demand for lumber, and the presence of lumber-men, probably more skilled than any others in the world, caused the gradual introduction of these woods into commercial use. It was a matter of ancient knowledge that hardwood made an excellent charcoal, and to utilize the cordwood left after the saw-logs were removed, by converting it into charcoal and using it to smelt ore from the adjacent mines, mas an obvious step. In some cases the establishment of the furnace occurred in-

Jan 1, 1913

By E. T. Turkdogan, J. H. Swisher

bi the fivst part of the paper results ave given on the rate of decarburization of Fe-C melts ln CO2-CO atmospheres at 1580°C. The rate -controlling step is believed to he that irvlloluing dissociation of curbotz dioxide on the suvfuce of the melt. 4 genevral reaction mechanistm is poslnlated jor gels-t11eta1 veactions oc-curit~g on the surface of iron coutcotamncited with chemi-sovbed osygesL. Oxygen the present work on decavbuvization of liquid iron and previous studies on the kinetics of nitrogen absorption and desorplion are discussed in terms of the postulated mechanism, ManY of the early studies of rate of decarburization of liquid steel were of an exploratory nature and laboratory exppriments carried out pertained to open-hearth or oxygen steelmaking processes. References to previous work on this subject may be found in a literature survey made by Ward. Using more sophisticated experimental techniques, several investigators have recently studied the kinetics of decarburization of molten Fe-C alloys in oxygen-bearing gases. For example, Baker et al2.' reported their findings on the rate of decarburization of liquid iron, levitated by an electromagnetic field, in carbon dioxide-carbon monoxide-helium atmospheres. In these levitation experiments the samples used were small in size, e.g., -0.6-cm-diam spheres weighing -0.7 g, and the rates were measured for decarburization from about 5 to 1 pct C at 1660°C. The rates obtained under their experimental conditions were considered to be controlled primarily by gaseous diffusion through the boundary layer at the surface of the levitated melt. Parlee and coworkers3 measured the rate of absorption of carbon monoxide in liquid iron. The rates were found to follow first-order reaction kinetics, yielding a reaction velocity or a mass transfer coefficient in the range 0.2 to 0.4 cm per min. The coefficient was found to decrease with increasing carbon content of the melt. These investigators attributed the observed rates to the transfer of carbon or oxygen through the diffusion boundary layer adjacent to the surface of the melt. In the work to be reported in this paper, an attempt has been made to study the kinetics of gas-metal surface reactions involved in the decarburization of liquid iron. EXPERIMENTAL The experiments consisted of melting 80-g samples from an Fe-1 pct C master alloy in an induction furnace and decarburizing in controlled CO2-CO mixtures at 1 atm pressure and 1580°C. The master alloy was prepared by adding graphite to electrolytic "Plastiron" melted in racuo. None of the impurities in the master alloy exceeded 0.005 pct. The reacting gases were dried by passage through columns of anhydrone; in addition, CO2 impurity in carbon monoxide was removed by passage through a column of ascarite. A schematic diagram of the apparatus is shown in Fig. 1. A 1.25-in.-diam recrys-tallized alumina crucible containing the sample was placed inside a 3-in.-diam quartz reaction tube, all of which was surrounded by an induction coil. A 450-kcps induction generator was used as the power source. Water-cooled brass flanges, which contained the gas inlet, gas exit, and sight port, were sealed to the top of the reaction tube with epoxy resin. The reacting gases were metered with capillary flowmeters and passed through a platinum wire-wound alumina preheating tube, 0.25 in. ID and 11 in. long. The gases were preheated to about 1300°C. A disappearing-filament optical pyrometer was used to measure the melt temperature. The pyrometer was initially calibrated against a Pt-6 pct Rh/Pt-30 pct Rh thermocouple. The temperature was controlled to within +10°C by manually adjusting the power input to the induction coil. In a typical experiment, an 80-g sample of the master alloy was melted in a CO2-CO atmosphere having pcO2/pco = 0.02 and flowing at 1 liter per min. A negligible amount of carbon was lost and no significant reduction of alumina from the crucible occurred during melting, e.g., 0.005 pct Al in the metal. After reaching the experimental temperature of 1580°C, the gas composition was changed to that desired for a particular series of decarburization experiments. The duration of the transient period for obtaining the desired gas composition at the surface of the melt was about 20 sec . The flow rate of the reacting gas was maintained at 1 liter per min. After a predetermined reaction time, the power to the furnace was turned off. During freezing, which took about 10 sec, the amount of gas evolution was not sufficient to result in a significant loss of carbon. The samples were analyzed for carbon by combustion and in a few cases they were analyzed for oxygen by the vacuum-fusion method. RESULTS A marked increase in the rate of decarburization of iron with increasing pcO2/pco ratio in the gas stream is demonstrated by the experimental results given in Figs. 2 and 3 for pco2/pco ratios from 0.033 to 4.0. In one series of experiments, denoted by filled triangles in Fig. 2, the reacting gas was diluted with argon (48 vol pct) resulting in a slower rate of decarburization. Samples from two series of experiments with pco2/pco = 0.033 and pco2/pco = 0.10 (with argon dilufion) were analyzed for oxygen. In these Samples the oxygen content increased with reaction time

Jan 1, 1968

By G. Austin Schroter

ALTHOUGH there is now an extensive literature on the bleaching clays, not a great deal of material is to be found concerning the geological fea-tures of these deposits and their bearing on problems of exploration and development. At the same time, chemical and crystallographic research on the clay minerals during the past few years has laid a suitable founda-tion upon which to base conclusions of economic value drawn from field observations. All of the criteria and deductions herein presented are based upon extensive field work by the senior author, both in the United States and Canada, and when subjected to the ultimate tests of development and exploitation they have held up remarkably well, despite the fact that many of these conclusions apparently have not been reviewed in the litera-ture heretofore. The nomenclature of the bleaching clays is rather confusing in the light of present-day commercial standards and has even led to litigation." The old term "fuller's earth" is largely based upon trade usage and the definition of the term therefore is dependent upon the changing standards of commerce. For statistical purposes the Bureau of Mines81 classes as "fuller's earth" all natural bleaching or filtering claylike materials that possess high adsorptive capacity without previous chemical treat-ment or activation. Conversely, the so-called activated or acid activated clays are now generally recognized as any clay mineral or mixture of the clay minerals whose adsorptive capacity has been developed to commercial standards by chemical or physical treatment. Therefore, without attempting to propose any additions to the nomen-clature of bleaching clays, this paper will refer to naturally adsorptive clays and activable clays, respectively, for the two types indicated.

Jan 1, 1940

By G. Austin Schroter

ALTHOUGH there is now an extensive literature on the bleaching clays, not a great deal of material is to be found concerning the geological fea-tures of these deposits and their bearing on problems of exploration and development. At the same time, chemical and crystallographic research on the clay minerals during the past few years has laid a suitable founda-tion upon which to base conclusions of economic value drawn from field observations. All of the criteria and deductions herein presented are based upon extensive field work by the senior author, both in the United States and Canada, and when subjected to the ultimate tests of development and exploitation they have held up remarkably well, despite the fact that many of these conclusions apparently have not been reviewed in the litera-ture heretofore. The nomenclature of the bleaching clays is rather confusing in the light of present-day commercial standards and has even led to litigation.76 The old term "fuller's earth" is largely based upon trade usage and the definition of the term therefore is dependent upon the changing standards of commerce. For statistical purposes the Bureau of Mines81 classes as "fuller's earth" all natural bleaching or filtering claylike materials that possess high adsorptive capacity without previous chemical treat-ment or activation. Conversely, the so-called activated or acid activated clays are now generally recognized as any clay mineral or mixture of the clay minerals whose adsorptive capacity has been developed to commercial standards by chemical or physical treatment. Therefore, without attempting to propose any additions to the nomen-clature of bleaching clays, this paper will refer to naturally adsorptive clays and activable clays, respectively, for the two types indicated.

Jan 1, 1940

By A. L. Mincher, W. F. Sheely

Mechanical properties of columbium have been studied over the temperature range of -196 to 1093oC. The decreased strengthening influence of cold-work at temperatures below ambient has been interpreted in terms of the Peierls-Nabarro effect. Maxima in the rate of strain hardening observed during tensile testing in the range 250-600°C. have been correlated with interstitial impurities to indicate the temperature ranges at which carbon, oxygen, and nitrogen, respectively, are responsible for strain aging. THE growing need for structural materials for use above the useful service temperatures of the iron-, nickel-, or cobalt-base alloys has caused the refractory metals to be considered as potential engineering materials. These metals, which include columbium, tantalum, molybdenum, and tungsten, are called refractory because the lowest melting point among them,that of columbium, is about 1000°C higher than the average melting temperatures of conventional high-temperature alloys. They are all body-centered cubic transition metals and, as such, their mechanical properties have basic characteristics which distinguish them from the face-centered cubic metals. For example, all show a much steeper rise in strength with decreasing temperature below room temperature than do the face-centered cubic metals, and their mechanical properties are strongly influenced by interstitially dissolved impurities. In order that these new metals may be used efficiently, it is necessary that their characteristics of behavior be fully known. In this paper, the mechanical properties of columbium will be examined over a wide range of temperatures. In particular, the influences of cold-work and individual species of interstitial impurity atoms on mechanical properties will be described, and basic mechanisms which may control the observed characteristics will be explored. EXPERIMENTAL The material used in this investigation was Union Carbide Metals Co. columbium roundels consolidated to four 4-in. diam ingots, three by consumable-electrode arc melting and one ingot by electron beam melting. Impurity contents of the ingots and methods of ingot conversion and treatment are summarized in Table I. The only metallic impurity occurring in any significant quantity was tantalum at about 0.1 pct. Iron, silicon, titanium, and zirconium were each less than 0.015 pct; boron was 1 ppm or less. This should have no appreciable influence on properties. The electron beam melted material, being the purest, will be used as the basis for comparison in the discussions to follow. Tensile tests were conducted from-196 to 1093oC, on both cold-worked and fully recrystallized arc-melted and electron-beam melted columbium using standard 1/4-in. diam, 1-in. long gage length test specimens. A strain-rate of 0.005 in. per in. per min was employed until the 0.2 pct yield strength was achieved and then the strain-rate was increased to 0.05 in. per in. per min for the balance of the test. Samples were protected in an inert atmosphere at tests above 300°C. The tensile properties obtained on the electron-beam melted columbium, E, in both the cold-swaged and recrystallized conditions are given in Fig. 1. The yield strength data of Dyson, et al.,' obtained on recrystallized electron beam melted columbium and the tensile strength data reported by Tottle2 on powder metallurgy columbium are included in Fig. 1. The material used by Tottle had been purified by vacuum sintering. There is excellent agreement between Dyson's data and those obtained in the present investigation. The tensile strengths obtained by Tottle were slightly greater than those obtained in this investigation on electron-beam melted columbium but varied with temperature in a similar manner. Tottle's data showed a maximum in tensile strength near 500°C, as did our data on electron-beam melted material, and also showed a small maximum at 300°C. The significance of these maxima will become evident later in the discussion. The tensile properties of cold-swaged and recrys-tallized arc melted columbium are plotted in Fig. 2. It was found that the properties of the recrystallized arc-melted columbium from all three heats showed very close agreement except at temperatures between about 500" and 800°C. A reason for this range of disagreement will be suggested in the discussion. The generally good agreement, however, attests to the ability of cold-working and subsequent recrystal-lization to erase the effects of the three different primary breakdown procedures and to produce nearly equivalent structures in the samples derived from the three different heats. wesse13 reported tensile data on columbium having interstitial impurity contents between those of the

Jan 1, 1962

By C. W. Volek, G. Mandl

Steam-injection tests in the field have shoum that heat transport into the oil/water region, ahead of the steam zone, may have a significant effect on the production process. Earlier theoretical work on reservoir heating by hot-fluid injection can be used to describe the growth of the steam zone, but only if heat transport from steam zone into oil/water region is neglected. It therefore became necessary to re-examine and extend the earlier theory. It was found that this theory ceases to be consistent with the physical model of the process at a certain critical time, tc, which depends on reservoir thickness, temperature, and quality of the steam. The critical time marks an important change in the heat flow across the condensation frovt: the heat flow, which is purely conductive during 0 < t < tc&apos; becomes predominantly convective at t = tc. Accordingly, at t = tc, the equation which governs expansion of the steam zone changes. On the basis of the new equation, an approximate description for the steam-zone growth during t > tc is developed by making use of upper and lower bounds for the exact solution of the problem. The boundary conditions for heat and mass flow inside the oil/water region are established, and a simple method of detennining the saturation at the downstream side of the condensation front is presented. Experimental results show that the theory gives an accurate description of steam-zone expansion before the critical time. At times near critical time, and also after critical time, experimental data show theoretical steam-zone volumes to be high. Even so, the accuracy of the calculated steam-zone volumes is sufficient for practical purposes. THEORY OF STEAM-ZONE GROWTH INTRODUCTION The engineering evaluation of steam-drive processes is based mainly on a mathematical description of reservoir heating by hot fluid injection presented several years ago by Marx and Langenheim.l This theory can be used to determine the growth of the steam zone,2 provided the flow of heat from the steam zone into the liquid zone ahead of the condensation front (Fig. 1) is neglected. Since we must expect, however, that heat transport into and inside the liquid region (the region between condensation front and production wells) will affect both the water/oil flow and the growth of the steam zone, it is necessary to re-examine and to generalize the Marx and Langenheim theory as applied to steam drive, which will hereafter be termed the "old" theory. Observations made in several field tests emphasize the need to study the heat flow across the condensation front (CF). On several occasions it was discovered that heat was transported in the liquid zone far ahead of the advancing CF, resulting in an early breakthrough of warm water. This seems to occur most often when high injection pressures are applied, when "wet" kONINKLIJKE/SHELL EXPLORATIE EN PRODUKTIE LABORATORIUM RIJSWIJK, THE NETHERLANDS SHELL DEVELOPMENT CO. HOUSTON, TEX.

Jan 1, 1970

By Zay Jeffries

Page Introduction............................. 474 Nature of Experiments ........................ 476 Materials Used in Experiments..................... 476 Description of Samples........................ 476 Details of Tests and Apparatus .................... 486 Determination of Elongation...................... 488 Determination of Reduction of Area .................. 488 Results of Tests........................... 489 Quantity and Arrangement of Amorphous Phase............. 497 Properties of Amorphous and Crystalline Phases............. 501 Intercrystalline Fracture........................ 530 Trans-crystalline Fracture....................... 531 Rupture ............................... 535 Explanation of Beilby&apos;s Results..................... 536 Mechanical Properties of Copper Wires................. 537 Mechanical Properties of Tungsten Wires................ 542 Mechanical Properties of Iron Wire................... 546 Effect of Diameter of Wire on Mechanical Properties........... 554 General Considerations on Properties of Metals at Very Low Temperatures .. 556 General Considerations on Physical Properties of Complex Alloys...... 557 Summary.............................. 559 Discussion.............................. 562 Introduction DuRing the period 1914 to 1916. the writer observed many times that tungsten wire could be drawn hot until it became brittle but on cooling to room temperature it became ductile again. In searching the literature for parallel cases. it was found that Beilbyl had produced hard-drawn wires of gold. silver. and copper that showed less than 1 per cent.

Jan 1, 1919

By Wm. Reuben Webster

THE greatly enlarged demand for small sizes of seamless copper tube which has recently occurred, due particularly to the rapid growth of the electric household-refrigerator industry, has emphasized the superiority of phosphorized to tough pitch copper for the purpose of producing this commodity. In the manufacture of this material exceedingly heavy reductions by cold drawing are employed, customary practice involving as much as 90 per cent. reduction of cross-sectional area in four runs without intermediate annealing. Although this superiority has long been recognized by tube makers, no quantitative expression of it has heretofore been published. It is believed that the data herewith presented will serve this purpose. Recent investigators are not in agreement as to the relative mechanical properties of copper containing small amounts of oxygen as compared with copper containing sufficient oxygen to produce that condition known as tough pitch. Hanson, Marryat and Ford&apos; found that "oxygen has a relatively small effect on the properties of copper." Johnson,2 on the contrary, states "it cannot be denied that it (tough pitch copper) is inferior, to deoxidized copper where severe mechanical manipulation is concerned." These authorities in the reports of their investigations, as might be expected from their conclusions, do not present data of a character requisite to a conclusive determination of the question.

Jan 1, 1927

By C. E. Sims, C. A. Zapffe

MANY hundreds of publications have appeared during the past 78 years that treat the subject of hydrogen in iron and steel,105 but conclusions regarding the functions of hydrogen in causing some important defects in steel are still unsatisfactory to many; and other hydrogen-caused phenomena yet remain to be identified with this gas. The most widely discussed of these defects is hydrogen embrittlement, but the conception, perhaps the popular one, that embrittlement is due to hydride formation does not conform to the known facts.104 The true identity of hydrogen embrittlement seems instead to lie in a mosaic nature of metal crystals, which is a concept not yet accepted by most metallurgists. A study of hydrogen embrittlement therefore provides new viewpoints in regard to the crystalline substructure of steel. A second widely discussed hydrogen-caused defect is the "flake" or "shatter crack." Although it is generally agreed that the presence of hydrogen is a prerequisite for their appearance, it is also realized that internal stress plays a decisive part. The relationship of hydrogen to internal stress has not been explained very clearly; nor is it always clear what the relationship is between a "flake" and a "snowflake," or between a "fish eye" and a "shatter crack." More importantly, the relationships among hydrogen embrittlement, hydrogen-caused fissures such as "flakes" and the ultramicroscopic structure of steel have scarcely been recognized. The present investigation attempts to provide an explanation for the embrittlement of steel by hydrogen by showing cause for accepting the "block" concept of metal crystals, and then to show how the numerous hydrogen-caused defects are interrelated in the light of this concept. EVIDENCE OF SUBSTRUCTURE IN METAL CRYSTALS It appears that the concept of a crystal as an aggregate of smaller multi-atom units must be accepted in some form if the behavior of metals is to be understood. The abundant literature on the evidence of an ultramicroscopic "mosaic" structure in metals and other crystalline substances suggests that the physicist has provided the metallurgist with an invaluable new insight. The exact picturization that any one physicist provides may be open to question, but the fact that there is some such fundamental substructure seems undeniable. The present work makes no pretense of comprehensively treating the imperfection structure theories. Nor will conclusions be drawn here regarding the exact nature of the substructure of crystals. However, the acceptance of some imperfection theory of fundamental attributes seems so necessary to an understanding of the behavior of hydrogen in steel that the following brief

Jan 1, 1941

By R. E. Somers

1. INTRODUCTION 1. Location, Topography, and Climate The Burro Mountains are located in the southwestern part of New Mexico, in Grant County. The group is made up of two distinct moun-tain masses, known as the Little Burros and the Big Burros, the former lying about 6 miles southwest of Silver City-, and the latter about 9 miles farther in the same direction. They are separated by the valley of the Mangas River, a tributary of the Gila, and a stream only in name, except after a heavy down-pour of rain. . The Little Burros attain an elevation of 6,625 ft. above sea level, and the Big Burros 8,054 ft., with the surrounding country averaging about 6,000 ft. To the south of these mountains stretches the desert plain, while to the north are the more frequent elevations of the mountainous country.

Jan 5, 1915

By W. A. Anderson

IN the pressure die-casting of zinc alloys it is customary to force the molten alloy under high pressure into a permanent steel die by means of a plunger moving in a bushing that has a clearance on the diameter of the order of 0.002 in. Successful operation of the plunger type of machine requires the presence in the zinc alloy of certain percentages of aluminum. Without these aluminum additions, the normal reaction of molten zinc on ferrous materials causes sticking of the plunger and a complete shutdown of the equipment. All of the zinc alloys used for pressure die-casting today contain approximately 4 per cent of aluminum, which is more than sufficient to make plunger operation feasible. The clearance between the plunger and its bushing is an important matter. As the space becomes larger, there is a loss in effective metal pressure. Ordinary gray cast iron served fairly well and is still used in some machines. However, the rate at which the plunger clearance increases with this material is considered by many to be far too great. There is, therefore, a serious interest in finding new materials more capable of retaining the desired clearance during long periods of use. Today many die casters are using special materials for plungers and bushings selected by the somewhat expensive and time-consuming test of actual experience. An analysis of the problem reveals two possible end points of plunger operation: (1) the building up of zinc-alloy plunger-material reaction products in sufficient bulk to cause sticking and (2) rapid solution, wear or erosion, all of which will increase the clearance to an undesirable extent. If neither of these takes place, the plunger will operate for a long time, of course. The authors have developed a laboratory apparatus in which the action of a plunger moving in a bushing immersed in molten zinc alloy could be simulated closely. Such a machine made possible a more rapid and less expensive survey of the available construction materials and an analysis of the specific alloying reactions taking place in the clear-ance area.

Jan 1, 1939

By A. S. Odeh

The mechanism of two-phase flow in porous media has been a subject of wide controversy. One of the properties essential for understanding the dynamic behavior of two-phase flow is relalive permeability. Relative permeability to a certain phase is defined as the ratio of the effective permeability of that phase to its permeability when it is the only fluid present and powing. In this research, a theoretical analysis was made to determine the effect of viscosity ratio between the non-wetting and the wetting phase on relative permeability. Experimental work was conducted to test the validity of the derived equations. The experiment was conducted on four natural cores. Four oils were used as the non-wetting phases with a viscosity range of 0.42 to 71.30 cp and two wetting phases with a viscosity range of 0.86 to 0.96 cp. Oil and bring were made to flow simultaneously at various ratios, and relative permeability curves were constructed. A total of eight relative pertileability cycles representing eight viscosity ratios were run oil each sample. It was found that relative permeability to the non-~cletting phase varies with viscosity ratio. The relative effect of this variation on relative permeability values was a function of the sample&apos;s single-phase permeability, decreasing with its increase. It was concluded that, for .samples of single-phase permeability over I darcy. the effect of viscosity ratio could be disregarded, and relative permeability would be, in effect, a function of satrtration only. INTRODUCTION Two-phase as well as multiphase flow occurs in many fields of science. This type of flow is of particular interest in petroleum production. The knowledge of relative permeability, which describes the dynamic behavior of two-phasc as well as multiphase flow, is essential for solution of problems arising in that field. Thc relative permeability ot a porous medium to a given phase in multiphase flow. is generally considered to be only a function of the saturation of that phase, independent of the properties of fluids involved and ranging in value from zero to unity. Work by Leverett&apos; and Leverett and Lewis&apos; apparently supports this concept. In his experiments Leverett used a clean, packed unconsolidated sand of high permeability (3.2 to 6.2 darcies) with two phases (water and oil) flowing and a viscosity ratio range of 0.057 to 90.0. His results showed that the wide range of viscosity had practically no effect on relative permeability-saturation relationship. Recently accumulated evidence from work performed by several laboratories and a paper by Nowak and Krueger,2 in which relative permeability to oil of a few core samples in the presence of interstitial water was considerably greater than single-phase permeability to water, cast some doubt on the conclusions reached by Leverett&apos; and subscribed to by a large number of individuals in the oil industry. One explanation advanced to explain this behavior states that it is caused by the variable extent of hydra-tion of clay minerals present in the sand. The greater the water saturation, the greater will be the area of contact between water and clay minerals; therefore, the greater will be the extent of swelling with corresponding reduction in permeability. Yuster4 presents another explanation for the recently accumulated evidence. Utilizing Poiseuille&apos;s law, he analyzed concentric flow in a single capillary where the non-wetting phase flows in a cylindrical portion of the capillary and concentric with it. The wetting phase flows in the annulus between the non-wetting phase and the capillary wall. The equations obtained indicate that relative permeability to the non-wetting phase is a function of saturation and viscosity ratio. Although Yuster&apos;s equations show that fractional rel-ative permeability to oil could be greater than unity, as was indicated by the data of Nowak and Krueger,1 they failed to present an explanation to the experimental data of early investigators such as Leverett.1 Due to the importance of relative permeability in understanding the flow behavior of petroleum reservoir fluids, this work—theoretical as well as experimental —was undertaken to determine whether relative permeability is a function of saturation only as was concluded by Leverett1 or a function of saturation and viscosity ratio as was theorized by Yuster.4 THEORETICAL ANALYSIS An equation will be derived for the rate of oil flow through a porous medium that is initially filled with water. Based on this equation, an analytic expression for relative permeability will be developed. The porous medium will be assumed to consist of .straight circular capillaries of different radii. It will also be assumed that there are no interconnections among the capillaries and no mass transfer across the oil-water interface. Consider a porous sample initially saturated with a wetting phase (water). As a non-wetting phase (oil) is

By C. F. Tolman

In February 1913, Prof. L. C. Graton and Dr. Joseph Murdochl presented to the American Institute of Mining Engineers a notable contribution to economic geology under the title The Sulphide Ores of Copper. The value of the work was recognized by mine operators, and Mr. Graton was assisted in his plan to extend his investigations, by the organization of a commission to undertake a "secondary enrichment investigation." In this work he secured the cooperation of the Geophysical Laboratory of the Carnegie Institution of Washington. The report2 on the chemical phascs of the investigation has just been published. Incidental to investigations3 carried on in our laboratory of Economic

Jan 1, 1916

By H. S. Price, R. L. Reed, J. E. Warren

The behavior of the reverse-combustion process in a linear adiabatic system is theoretically investigated by means of an idealized physical model. T his model is described by a pair of non-linear equations involving heat and mass transfer which are coupled by a concentration-dependent reaction-rate function of the Ar-rhenius type. The differential equations governing the quasi steady-state temperature and concentration distributions are approximately solved by using either physical or mathematical simplifications. It is shown that the reverse -combustion process can be mechanistically described by simple physical models whose behavior equations can be solved formally. It is further demonstrated that the derived reverse-combustion equations can be solved numerically within the error limits for the experimental data. The theoretically predicted peak temperature-flux-velocity relationship exhibits reasonable agreement with experimental data obtained from Athabasca tar sand. The principal contribution of this work lies in its usefulness as a starting point for developing a more comprehensive theory. A description of the vaporization-coking process must be obtained; then, the theory must be extended to three dimensions to include geometrical effects and heat losses. INTRODUCTION In another paper,&apos;" he physical processes visualized as occurring during reverse combustion have been described. In this paper, the extent to which an elementary theory can account for experimental observations is determined. Theoretical results that can be used to estimate some of the behavior characteristics of importance to this process are also presented. Since it is not possible to include all the features of the combustion mechanism of which we are currently aware, the mathematical formulation refers to the highly idealized system developed herein. This simplified physical model is based on the simultaneous transfer of mass and heat accompanied by a chemical reaction: it is described mathematically by a pair of coupled, nonlinear differential equations. Similar sets of equations have been studied extensively in the field of flame propagation; an excellent review of these investigations has been published by Evans.1 FORMULATION OF THE PROBLEM It will be recalled that the experiments are performed with a thin-walled cylindrical tube that is uniformly packed with sand and oil. The system is maintained substantially adiabatic by means of heat supplied externally in such a way that the radial temperature gradient in any plane normal to the axis of the tube approaches zero. Initially, the tube is at ambient temperature, except at one end where it is rapidly heated to a predetermined temperature. When the prescribed temperature is achieved, air is caused to flow into the cold end of the tube. As the oxygen in the air stream contacts the hot oil, a localized exothermic reaction takes place. The generated heat is conducted and convected away from the reaction zone so that definite temperature and concentration profiles are rapidly established and move uniformly in a direction opposite to that of the air flow (Fig. 1). As a consequence of this mode of oxidation, all of the oxygen in the air is consumed; then, the remaining nitrogen and the gaseous combustion products sweep out all vaporized hydrocarbons and leave an immobile hydrocarbon-coke on the sand.

By W. H. Bassett

A 10-year, sea-water, corrosion test of tubes of several copper alloys has shown that many alloys withstood attack by solution, pitting, and dezinkification; a 1-year, salt-spray test of sheet-metal specimens of the same composition showed the same results. THE late J. P. Sparrow, chief operating engineer of the New York Edison Co., carried out a series of practical tests on condenser tubes of several copper alloys and reported on the results to the Association of Edison Illuminating Companies at its meeting in&apos; September, 1913. In the preparation of these tubes the senior author had the pleasure of cooperating. Copper-zinc alloys in the proportions of 60-40, 70-30, 80-20, 90-10, and Admiralty metal, which is in effect 70-30 with 1 per cent. of tin, were tried. Monel metal and several copper-nickel alloys, and 8, 5, and 3 per cent. aluminum bronze were also tried. At the time of this report, the aluminum bronze had been in service for 4 1/2 years and seemed to be giving especially good results but later it began to fail and showed no substantial improvement over Admiralty metal. Monel metal was unsatisfactory and the nickel alloys apparently did not give better service than the Admiralty alloy. Previous to the publication of the report, and after considerable discussion, it was agreed that a test where tubes of different kinds could be under laboratory observation would be advisable, so the apparatus described here was set up in The American Brass Co.&apos;s Waterbury Laboratory. This was fitted with tubes of copper, brass, bronze, nickel silver, cupro-nickel and other alloys, and the test started Oct. 11, 1912. Salt water from East River, New York harbor, was barrelled and transported to the laboratory for the test. A fresh supply, completely replacing the water in service, was obtained at the end of each six months period.

Jan 1, 1925

By H. H. Kellogg

A model of the slag-fuming process for recovery of zinc oxide fume from lead blast furnace slags, adapted to solution by a digital computer, is presented. The model incorporates the variaticm with time of the following: the fuming of zinc and lead, the change in the ferrous-ferric ratio in the slag, the transfer of sulfur to and from the slag, the temperature of the liquid slag, the temperature of the gases and fume which exit to the flue, the heat losses to the water jackets, and the amount of frozen slag on the water jackets. The assumptions which underlie the model-some of which are but crude approximations—are discussed. Despite some obvious shortcomings, the model simulates faithfully many of the important features of practical slag-fuming operations. The behavior of the model is compared with the operation of the American Smelting and Refining Co. fumzace at El Paso, Tex. The model is used to predict the effects on performance of changes in the coal rate, the temperature of the secondary air, and the composition of the coal. THE fuming of lead blast furnace slag for recovery of zinc oxide is standard practice today, and it has been the subject of several previous attempts at mathematical process analysis.&apos;-&apos; The mathematical process model described in this paper incorporates many of the features from the earlier studies, but it is a far more complete and realistic representation of the commercial process in that the following additional features have been included: the fuming of lead as well as zinc; the transfer of sulfur between slag and gas; the addition of slag feed in batches, over a period of time; tapping of the final slag over a period of time; the change of slag temperature with time. The additional features of the present model add greatly to the mathematical complexity, but this difficulty has been obviated by programming the model for solution by a digital computer. The IBM 7094 computer solves the model for one operating cycle of the fuming furnace in less than 1 min. It is doubtful if the same calculations could be completed with the aid of a desk calculator in less than a month. The computer program, written in the Fortran IV language, is too lengthy for presentation here.* Instead, this paper As shown in the sections which follow, it does simulate with remarkable faithfulness most of the known behavior of the industrial process. On the other hand, the model contains several gross simplifications of both the chemistry and heat balance, necessitated by the lack of more exact knowledge. In addition to these known weaknesses, it is not unlikely that those more intimately acquainted with industrial practice than the author will find other additions to or modifications of the model which will improve its utility and reliability. CHEMISTRY In brief outline, the present model treats the fuming furnace as two units, A and B, in series. In A the batch of slag reacts with the continuous stream of air (primary and secondary) and fuel injected at the tuyeres, to produce a stream of hot, reduced gases containing zinc vapor. The zinc content of both the slag and the product gas changes with time because of the batch nature of the process. Unit A is called the "lower furnace" in this paper; physically, it is considered to be that part of the fuming furnace which lies below the charge port. In B, the "upper furnace", the product gas from A is burned with the stream of "tertiary" air, to produce zinc oxide fume. The performance of B also depends on time because of the time dependence inherited from the product gas of A. The rate behavior in the lower furnace determines the important features of the process—the rate of elimination of zinc and lead from the slag, and the amount of fuel required for this purpose. Bell, Turner, and peters&apos; published the first useful model of the lower furnace. They employed the assumption that, at any instant of time, the slag and reduced gas reach a state of equilibrium, according to the reactions: They cited only indirect evidence in support of their assumption of slag-gas equilibrium, yet several more recent laboratory studies of the activity of zinc oxide in slags4-8 have produced evidence which supports their view. On first acquaintance it seems unlikely that a high-output "rate" process like slag fuming would even approach an equilibrium state. The author, in an earlier study,&apos; established, however, that the gas-slag interface in a fuming furnace was capable of such high mass-transfer rates that a close approach to equilibrium between gas and slag was quite probable. In devising the present model it was decided to assume a state of equilibrium between slag and gas at the outset, and then to modify this assumption as necessary in order to make the model agree with the be -havior of the actual process. Up to this time the assumption remains a part of the model, since no behavior

Jan 1, 1968